Coordination Chemistry Reviews 372 (2018) 1–30

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Coordination Chemistry Reviews

journal homepage: www.elsevier.com/locate/ccr

Review

Coordination polymers and metal-organic frameworks built up with

poly(tetrazolate) ligands
Aurel Tăbăcaru a, Claudio Pettinari b, Simona Galli c,d,⇑
a
Department of Chemistry, Physics and Environment, Faculty of Sciences and Environment, ‘‘Dunarea de Jos” University of Galati, 111 Domneasca Street, 800201 Galati, Romania
b
Scuola di Scienze del Farmaco e dei Prodotti della Salute, Università di Camerino, Via S. Agostino 1, 62032 Camerino, Italy
c
Dipartimento di Scienza e Alta Tecnologia, Università dell’Insubria, Via Valleggio 11, 22100 Como, Italy
d
Consorzio Interuniversitario Nazionale per la Scienza e Tecnologia dei Materiali, Via Giusti 9, 50121 Firenze, Italy

a r t i c l e i n f o a b s t r a c t

Article history: In the past two decades the chemistry of coordination polymers (CPs) and metal-organic frameworks
Received 23 March 2018 (MOFs) has known an incessant development at both the academic and industrial level: the diversity they
Accepted 27 May 2018 show in chemical composition, structural features and chemico-physical properties makes them attrac-
tive for a wide range of applications of technological, economical and/or environmental interest. Within
this scenario, this review focuses the attention on the transition-metal-ion CPs and MOFs built up with
Keywords: bis-, tris- and tetrakis(5-substituted tetrazolate) ligands. After a short introduction on CPs and MOFs,
Poly(tetrazole) ligand
and the chemistry of tetrazole and its derivatives, the reader is provided with a brief description of the
Coordination polymer
Metal-organic framework
synthesis, structural aspects and, whenever studied, functional properties of the numerous transition-
Synthesis metal poly(5-substituted tetrazolate) frameworks appeared in the literature to the end of 2017.
Crystal structure Ó 2018 Elsevier B.V. All rights reserved.
Functional properties

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
2. Tetrazole and its derivatives – a brief overview . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
3. Zinc(II) poly(tetrazolates) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
3.1. Ditopic ligands. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
3.2. Tritopic ligands . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
3.3. Tetratopic ligands . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12

Abbreviations: Alq3, tris(8-hydroxyquinoline)aluminum; BCEE, bis(2-cyanoethyl)ether; BET, Brunauer-Emmett-Teller; bpe, 1,2-bis(4-pyridyl)ethane; 4,40 -bpy, 4,40 -
bipyridine; CP, coordination polymer; DCA, 9,10-dicyanoanthracene; dcbipy, 6,60 -dicyano-2,20 -bipyridine; DEF, N,N0 -diethylformamide; DMA, N,N0 -dimethylacetamide; DMF,
N,N0 -dimethylformamide; DMSO, dimethylsulfoxide; EtOH, ethanol; Htz, 1H-tetrazole; H2Andolast, N-4-(1H-tetrazol-5-yl)phenyl-4-(1H-tetrazol-5-yl)benzamide; H2BDMPX,
1,4-bis((3,5-dimethyl-1H-pyrazol-4-yl)methyl)benzene); 1,4-H2BDP, 1,4-bis(1H-pyrazol-4-yl)benzene; 1,2-H2BDT, 1,2-bis(1H-tetrazol-5-yl)benzene; 1,3-H2BDT, 1,3-bis(1H-
tetrazol-5-yl)benzene; 1,4-H2BDT, 1,4-bis(1H-tetrazol-5-yl)benzene; H2BDTM, 1,2-bis((1H-tetrazol-5-yl)methyl)benzene; H2BDTri, 1,4-bis(1H-1,2,3-triazol-5-yl)benzene;
H2BPDT, 4,40 -biphenyl-bis(1H-tetrazol-5-yl); H2BPZ, 4,40 -bipyrazole; H2bta, N,N-bis(1(2)H-tetrazol-5-yl)amine; H2btzb, 1,2-bis(1H-tetrazol-5-yl)butane; H2btzbp, 6,60 -bis
(1H-tetrazol-5-yl)-2,20 -bipyridine; H2btze, 1,2-bis(1H-tetrazol-5-yl)ethane; H2btzop, 1,5-bis(1H-tetrazol-5yl)-3-oxapentane; H2btzp, 1,2-bis(1H-tetrazol-5-yl)propane; H2-
BTZPX, xylene-bis(1H-tetrazol-5-yl); H2cdtp, 2,3-camphoryl-5,6-bis(1H-tetrazol-5-yl)pyrazine; H2DMPMB, 4,40 -bis((3,5-dimethyl-1H-pyrazol-4-yl)methyl)biphenyl; H2DTA,
9,10-bis(1H-tetrazol-5-yl)anthracene; H2dtp, 2,3-bis(1H-tetrazol-5-yl)pyrazine; H2MeBDT, 2-methyl-1,4-bis(1H-tetrazol-5-yl)benzene; H2ox, oxalic acid; H2ptp, 2,3-bis
(pyridin-2-yl)-5,6-bis(1H-tetrazol-5-yl)pyrazine; H3BTC, 1,3,5-benzenetricarboxylic acid; H3BTP, 1,3,5-tris(1H-pyrazol-4-yl)benzene; H3BTT, 1,3,5-tris(1H-tetrazol-5-yl)
benzene; H3BTT2HCl, 1,3,5-tris(1H-tetrazol-5-yl)benzene dihydrochloride; H3BTTri, 1,3,5-tris(1H-1,2,3-triazol-5-yl)benzene; H3tatb, 4,40 ,400 -s-triazine-2,4,6-triylbenzoic
acid; H3TPB-3tz, 1,3,5-tri-p-(1H-tetrazol-5-yl)phenylbenzene; H3TPT-3tz, 2,4,6-tri-p-(1H-tetrazol-5-yl)-phenyl-s-triazine; H4btc, biphenyl-3,30 ,4,40 -tetracarboxylic acid;
H4tta, 1,3,5,7-tetrakis(1H-tetrazol-5-yl)adamantane; H4ttpa, 1,3,5,7-tetrakis((1H-tetrazol-5-yl)phenyl)adamantane; H4ttpm, tetrakis(4-tetrazolylphenyl)methane; H4TTPP,
5,10,15,20-tetrakis(4-(1H-tetrazol-5-yl)phenyl)porphyrin; H4ttps, tetrakis(4-tetrazolylphenyl)silane; IPN, isophthalonitrile; MeOH, methanol; Mn(III)Cl-ttzpp, 5,10,15,20-
tetrakis[4-(2,3,4,5-tetrazolyl)phenyl]-porphyrinato manganese(III) chloride; MOF, metal-organic framework; OLEDs, organic light emitting diodes; PCP, porous coordination
polymer; PPh3, triphenylphosphine; py, pyridine; pyz, pyrazine; PXRD, powder X-ray diffraction; UV–Vis, ultraviolet–visible; XPS, X-ray photoelectron spectroscopy.
⇑ Corresponding author at: Dipartimento di Scienza e Alta Tecnologia, Università dell’Insubria, Via Valleggio 11, 22100 Como, Italy.
E-mail address: simona.galli@uninsubria.it (S. Galli).

https://doi.org/10.1016/j.ccr.2018.05.024
0010-8545/Ó 2018 Elsevier B.V. All rights reserved.
2 A. Tăbăcaru et al. / Coordination Chemistry Reviews 372 (2018) 1–30

4. Copper poly(tetrazolates). . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
4.1. Ditopic ligands. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
4.2. Tritopic ligands . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
4.3. Tetratopic ligands . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
5. Manganese poly(tetrazolates) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
5.1. Ditopic ligands. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
5.2. Tritopic ligands . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
5.3. Tetratopic ligands . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
6. Cadmium poly(tetrazolates) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
6.1. Ditopic spacers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
6.2. Tritopic spacers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
6.3. Tetratopic spacers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
7. Cobalt poly(tetrazolates) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
7.1. Ditopic ligands. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
7.2. Tritopic ligands . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23
8. Iron poly(tetrazolates) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23
8.1. Ditopic ligands. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23
8.2. Tritopic ligands . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25
8.3. Tetratopic ligands . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25
9. Other metal poly(tetrazolates) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25
10. Conclusions and outlook . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 28
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 28
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 28

1. Introduction node-and-spacer connectivity, structural motif and functional

Coordination polymers (CPs) [1–3] and metal-organic frame-
works (MOFs) [4–9] are hybrid inorganic/organic compounds with
extended crystal structures built up by metal ions or metal-
containing clusters bridged, through coordination bonds, by poly(-
dentate) spacers. Both classes of compounds have known an inces-
sant growth during the past two decades, raising the interest of
chemists, material scientists and physicists at the academic and
industrial level.
The variety of chemical composition, crystal structures and
functional properties they show makes CPs and MOFs powerful
platforms for their exploitation in fields of economical, technolog-
ical and/or environmental interest ranging from luminescence
[10–15] to microelectronics [16], conductivity [17–20], electro-
chemistry [21], high-energy materials [22], catalysis [23–29], mag-
netism [30–34], capture, storage and separation [35–43], sensing
[15,16,44–46], drug delivery [47–49] or biomedicine [50–52].
The structural and functional diversity is granted by a careful
selection of inorganic and organic building blocks [53–57], also
under the guidance of computational chemistry methods [58–
62]: main-group metal ions [1,4,63], transition metal ions and lan-
thanides [64,65] have been coupled to a great variety of organic
ligands [66] typically containing oxygen [67], nitrogen [67–76]
and phosphorus [77] as donor atoms.
Within this vast and appealing scenario, this review is aimed at
gathering the transition-metal-ion CPs and MOFs built up with
poly(tetrazolate) ligands that have been reported to the end of
2017. Together with poly(pyrazolates) and poly(imidazolates),
poly(tetrazolates) are one of the three most employed classes of
azolates in the synthesis of coordination polymers [67–-76]. There
is a vast number of tetrazole ligands used as spacers to build up
coordination frameworks [71,73,75]. In the following, we will sys-
tematically concentrate on CPs and MOFs with linkers possessing
two to four 5-substituted tetrazoles. As detailed in Section 2, 5-
substituted tetrazoles can be prepared following a safe, convenient
and environmentally friendly synthetic path. In addition, 5-
substituted tetrazolates bear four nitrogen donor atoms per
heteroaromatic ring, this occurrence increasing the coordination
modes of the ligand, hence enriching and diversifying the class of
poly(tetrazolate) 1D to 3D coordination frameworks in terms of
properties.
Charts 1 and 2 collect the molecular structure and the acronym
of the bis-, tris- and tetrakis(tetrazoles) employed in the prepara-
tion of the CPs and MOFs briefly described hereafter. To facilitate
consultation, comparison and grouping, Table 1 provides the
reader with the list of compounds presented in this review,
together with details on network dimensionality, metal center
stereochemistry and ligand hapticity. In the text, for each deriva-
tive a brief description is reported on the synthesis, structural
aspects, thermal behaviour and, whenever studied, functional
properties. To increase legibility, the investigated functional prop-
erties are collectively highlighted in Table 2. The compounds have
been organized according to the transition metal ion, starting from
the most populated family, namely: zinc(II), copper(I,II), man-
ganese(II,III), cadmium(II), cobalt(II) and iron(II). The last section
collects the few derivatives isolated with other metal centers
[chromium(II,III), nickel(II), silver(I) and mercury(II)]. Schemes
have been introduced to highlight the role of reaction conditions
modulation. Figures are provided to illustrate the reader the most
recurrent or fascinating structural units or topologies, or pictorially
describe frequently studied functional properties.
Before briefly introducing the chemistry of tetrazole, the follow-
ing advice appears to us necessary: rigorously, CPs are coordina-
tion compounds in which the building blocks – metal ions or
metal-containing clusters, acting as nodes, and organic ligands,
acting as spacers – are reciprocally linked by means of coordina-
tion bonds and develop repetitively into one, two or three dimen-
sions [78]. When (permanent) porosity is present, they are referred
to as either metal-organic frameworks (MOFs) or porous coordina-
tion polymers (PCPs). There exists a long-lasting debate in the sci-
entific community (see e.g. [79,80]) about the use of these terms.
Entering into or detailing upon such a debate is out of the scope
of this review. In the following, we will use CP when dealing with
non-porous compounds, MOF in all of the cases in which the mate-
rial is porous.
2. Tetrazole and its derivatives – a brief overview
Since the accidental discovery of the first tetrazole-containing
metal complex in 1885 by Bladin [81], who proposed the term
 A. Tăbăcaru et al. / Coordination Chemistry Reviews 372 (2018) 1–30
Chart 1.
‘tetrazole’ for the five-membered heteroaromatic ring bearing four
nitrogen atoms, the chemistry of tetrazoles has known an inces-
sant development, as witnessed by the numerous reviews pub-
lished on this topic in approximately one century: as
representative examples, the reader is referred to [82–90]. The
continuous interest into tetrazoles and tetrazolates is justified by
their application in the preparation of different classes of com-
pounds, ranging from coordination complexes (see e.g. [91,92])
to functional coordination polymers (see e.g. [71,73,75]), active
pharmaceutical ingredients (see e.g. [93–96]) or green high-
energy materials (see e.g. [97]).
The extensive use of 5-substituted tetrazoles and tetrazolates
has certainly benefited from the introduction, by Demko and
Sharpless (see e.g. [98–100]), of a convenient, straightforward
and environmentally friendly preparation protocol based onto a
[2+3] dipolar cycloaddition reaction between an organonitrile
and an azide, carried out in water and catalyzed by Zn(II) salts
(Chart 3), and by the fact that they exhibit numerous coordination
modes (Chart 4).
Tetrazole is a very weak base (pKa in DMSO 8.3 [101]): this typ-
ically implies that the precipitation of tetrazolate coordination
compounds is driven by crystal growth rather than nucleation,
and the formation of single crystals over microcrystalline powders
is consequently favoured. As a concomitant drawback, tetrazolate
3
forms metal-to-ligand coordinative bonds weaker than those
involving other azolates, such as 1,2,3-triazolate, 1,2,4-triazolate,
imidazolate and pyrazolate (pKa in DMSO 13.9, 14.8, 18.2 and
19.8, respectively [101]), with a non negligible impact on the ther-
mal stability of its derivatives, as also shown by the compounds
presented in the following.
3. Zinc(II) poly(tetrazolates)
The one based on Zn(II) is the most populated group of
transition-metal poly(tetrazolate) coordination frameworks. In
the majority of cases, the metal centres show the expected tetrahe-
dral and octahedral stereochemistry [102,103] (Table 1), though
five-coordination is also observed. Due to the presence of a d10
metal ion (see e.g. [104–106]), luminescence is the most investi-
gated functional property of Zn(II) poly(tetrazolates) (Table 2).
CPs and MOFs are versatile luminescent materials as their emission
may have different origin [10,11], e.g.: ligand-based, metal-based
[12], (metal-to-ligand or ligand-to-metal) charge-transfer, or
guest-induced (Fig. 1), this justifying the deep attention raised by
these materials in this applicative context [10–15]. In the presence
of permanent porosity, Zn(II) poly(tetrazolates) gas adsorption,
with particular attention to H2 storage (see e.g. [107,108,42]), has
4 A. Tăbăcaru et al. / Coordination Chemistry Reviews 372 (2018) 1–30
Chart 2.
been invariably studied (Table 2). In the past decade, MOFs have
been extensively investigated as H2 adsorbents, as potential alter-
native to metal hydrides and activated carbons: hydrogen-fueled
vehicles and portable electronics need small-volume and low-
weight adsorbents storing large amounts of H2 at mild conditions
with fast recharging kinetics [109].
3.1. Ditopic ligands
To the best of our knowledge, the first zinc(II) poly(tetrazolate)-
based CP ever isolated is [Zn(1,3-BDT)] [110], which was obtained
upon reacting zinc(II) nitrate hexahydrate and 1,3-H2BDT. The
crystal structure of [Zn(1,3-BDT)], stable up to 300 °C, features
{ZnN4} tetrahedral nodes and l4-BDT2 ligands arranged within a
3D open framework with small cavities, the topology of which
resembles that of the Al net in SrAl2 [111]. In the solid state and
at room temperature, upon coordination to zinc(II) the emission
maximum of the ligand (471 nm) is blue-shifted (to 323 nm) with-
out intensity enhancement, an occurrence which was attributed to
the existence of less efficient conjugation paths in the CP in com-
parison to those at work in the free ligand, as reported for other
coordination polymers with nitrogen-donor ligands [112].
Lately [113], 1,3-H2BDT was prepared in situ through a [2+3]
cycloaddition reaction between isophthalonitrile, sodium azide,
1H-tetrazole and zinc(II) chloride, concomitant to the formation
of [Zn2(OH)2(1,3-BDT)]. Ligand in situ synthesis is a rather popular
approach (see e.g. [114,115]), employed also in the case of tetrazo-
late coordination polymers [75], as shown by the examples
reported in this review (Scheme 1).
The crystal structure of [Zn2(OH)2(1,3-BDT)] is built up by {Zn
(OH)} 1D chains along which the Zn(II) ions are bridged by l2-
OH groups. l4-Spacers bridge the chains within a non porous 3D
(4,6)-connected network. Also in the present case, in the solid state
and at room temperature, upon coordination to zinc(II) the emis-
sion maximum of the ligand is largely blue-shifted (326 nm),
which was explained as for [Zn(1,3-BDT)] [110].
With the higher-symmetry ligand 1,4-H2BDT, Dincă and
coworkers [116] obtained [Zn3(1,4-BDT)3(DMF)4(H2O)2]3.5MeOH
by 4-day evaporation at room temperature of a MeOH:DMF solu-
tion containing zinc(II) nitrate hexahydrate and 1,4-H2BDT. The
crystal structure of this MOF is characterized by Zn3 linear units
with octahedral nodes (Fig. 2a) bridged by l4-spacers within a
3D porous framework (Fig. 2b).
At the time, together with [Mn4(1,4-BDT)3(NO3)2(DEF)6] [116]
and [Mn3(1,4-BDT)3(DMF)4(H2O)2]2H2O3MeOHDMF [116] (see
Section 5), this was the first example of three-bladed paddlewheel
unit in MOFs, though a geometrically related moiety had been
already encountered in [MnI2(CO)6(N4CR)3] (R = CF3, F2NCF2) [117].
As also shown by the compounds described in this review, this struc-
tural motif is nowadays rather popular in MOFs, as much as the two-
bladed paddlewheel unit. [Zn3(1,4-BDT)3] shows a BET specific sur-
face area of 640 m2/g and adsorbs a maximum of 1.46 wt H2 % at
77 K and 1.2 atm. The initial steep slope observed along the H2
adsorption isotherm is indicative of strong H2 adsorption sites, sug-
gesting that removal of coordinated solvent molecules upon activa-
tion makes the unsaturated Zn(II) ions accessible to H2. As also
shown below, since 2007 numerous studies appeared highlighting
the role of exposed metal sites in MOFs for H2 adsorption
enhancement [118].
 A. Tăbăcaru et al. / Coordination Chemistry Reviews 372 (2018) 1–30 5

Table 1
Synoptic collection of the poly(tetrazolate) CPs and MOFs presented in this review. For each compound, the framework dimensionality, metal ion (M) stereochemistry and ligand
(L) hapticity are reported.

M Compound Dima M Coordination L Hapticity Refs.

Zn [Zn(1,3-BDT)] 3D {ZnN4} l4-j N1:j N3:j N10 :j N40 [110]
[Zn2(OH)2(1,3-BDT)] 3D {ZnN2O2} l4-j N1:j N3:j N10 :j N40 [113]
[Zn3(1,4-BDT)3(DMF)4(H2O)2]3.5MeOH 3D {ZnN6}, fac-{ZnN3O3} l4-j N2:j N3:j N20 :j N30 [116]
[Zn(1,4-BDT)] 3D {ZnN4} l4-j N1:j N3:j N10 :j N30 [119]
[Zn7(OH)8(DTA)3]H2O 3D {ZnO4}, {ZnN2O2}, {ZnN3O} l4-j N1:j N4:j N10 :j N40 [120]
[Zn(dtp)] 3D {ZnN6} l3-j2N1,N10 :j2N4,Npyz:j2N40 :Npyz0 [127]
[Zn2(btze)2]H2O 3D {ZnN4} l4-j N1:j N3:j N10 :j N40 and l3-j2N1,N10 : [133]
j N4:j N40
[Zn(btzp)] 3D {ZnN4} l4-j N1:j N3:j N10 :j N40 [133]
[Zn(btzb)(H2O)2]4H2O 1D {ZnN2O2} l2-j N1:j N10 [133]
[Zn(btze)] 3D {ZnN5} l4-j2N1,N10 :j N4:j N20 :j N40 [134]
[Zn(btze)(H2O)] 2D {ZnN4O} l4-j2N1,N10 :j N4:j N30 [134]
(3D)
[Zn2(BDTM)2(H2O)2]28H2O 1D {ZnN3O} l2-j2N1,N10 :j N4 [136]
(3D)
[Zn4(BDTM)4] 3D {ZnN4} l3-j N1,N1 :j N3:j N3 and l3-j N1,N1 :j
2 0 0 2 0
[136]
N4:j N40
[Zn(BTZPX)] 3D {ZnN4} l4-j N1:j N3:j N10 :j N40 [137]
[Zn(ptp)(H2O)]2 0D {ZnN4O} l2-j3Npy,Npyz,N1:j N10 [141]
[Zn(ptp)(MeOH)] 1D {ZnN5O} l2-j3Npy,Npyz,N1:j2N4,N10 [141]
(2D)
[Zn(ptp)] 2D {ZnN6} l3-j3Npy,Npyz,N1:j2N4,N10 :j N30 [141]
[Zn3(ptp)3(DMF)2(H2O)] 3D {ZnN5} l3-j3Npy,Npyz,N1:j N10 :j N30 and l3-j3Npy, [141]
Npyz,N1:j N10 :j N40
[Zn3(cdtp)3(H2O)]H2O 3D {ZnN4}, {ZnN5}, {ZnN4O} l2-j2N1,N10 :j2N4,Npyz and l3-j2N1,Npyz: [142]
j2N4,N40 :j N10
[Zn(HBTT)]2DMA 3D {ZnN4} l4-j N2:j N20 :j N200 :j N300 [143,145]
[Zn(DMA)6][Zn6H4(HBTT)6]5MeOH12DMA 3D {ZnN4} l4-j N2:j N20 :j N200 :j N300 [143]
[Zn2(HBTT)Cl2]MeOH3DMA 3D {ZnN3Cl} l6-j N1:j N4:j N20 :j N30 :j N200 :j N300 [143]
[Zn3Cl2(tta)(DMF)4]2DMF 3D trans-{ZnN2O4}, {ZnCl2N2} l8-j N1:j N3:j N10 :j N30 :j N200 :j N300 :j [146]
N2000 :j N3000
Cu [Cu(1,4-BDT)(DMF)]MeOH0.25DMF 3D trans-{CuN4O2} l4-j N2:j N3:j N20 :j N30 [116]
[Cu(MeBDT)(DMF)] 3D trans-{CuN4O2} l4-j N2:j N3:j N20 :j N30 [161]
[Cu(BPDT)(DMF)] 3D trans-{CuN4O2} l4-j N2:j N3:j N20 :j N30 [161]
[Cu2(OH)2(1,4-BDT)] 3D cis-{CuN2O2} l4-j N2:j N3:j N20 :j N30 [163]
[Cu(btzop)]0.5H2O 3D {CuN4O} l3-j3N1,N10 ,O:j N4:j N40 [164]
[CuIICuI2(btzop)2] 3D {CuIN4}, trans-{CuIIN4O2} l5-j3N1,N10 ,O:j N3:j N4:j N30 :j N40 [164]
H[Cu(DMF)6][(Cu4Cl)3(BTT)8(H2O)12] 3D trans-{CuClN4O}b l6-j N2:j N3:j N20 :j N30 :j N200 :j N300 [167]
3.5HCl12H2O16MeOH
Cu3[(Cu4Cl)3(TPB-3tz)8]211CuCl28H2O120DMF 3D {CuClN4}b l6-j N2:j N3:j N20 :j N30 :j N200 :j N300 [172]
Cu3[(Cu4Cl)3(TPT-3tz)8]2xsolvent 3D {CuClN4}b l6-j N2:j N3:j N20 :j N30 :j N200 :j N300 [172]
(NC2H8)4[Cu5(BTT)3]xG (G = DMF or H2O) 3D {CuN4} l6-j N1:j N2:j N10 :j N20 :j N100 :j N200 and [173]
l8-j N1:j N2:j N10 :j N20 :j N100 :j N200 :j
N300 :j N400
Cu[(Cu4Cl)(ttpm)2]2CuCl25DMF11H2O 3D {CuClN4} l8-j N2:j N3:j N20 :j N30 :j N200 :j N300 :j [174]
N2000 :j N3000
[H(Cu4Cl)(ttps)2(DMF)4]18DMF 3D trans-{CuClN4O} l8-j N2:j N3:j N20 :j N30 :j N200 :j N300 :j [175]
N2000 :j N3000
[Cu6(ttps)3(DMF)6] 3D {CuN6}, fac-{CuN3O3} l8-j N2:j N3:j N20 :j N30 :j N200 :j N300 :j [176]
N2000 :j N3000
Cu[(Cu4Cl)(tta)2]29DMF 3D {CuClN4}b l8-j N2:j N3:j N20 :j N30 :j N200 :j N300 :j [177]
N2000 :j N3000
[(Cu4Cl)(ttpa)2Cu2Cl3]6DMA4MeOH2H2O 3D {CuClN4} b
l8-j N2:j N3:j N20 :j N30 :j N200 :j N300 :j [177]
N2000 :j N3000 b
[Cu4Cl4(tta)(DMF)5]DMF 3D {CuCl2N3O}, {Cu Cl2N2O} l10-j N2:j N3:j N20 :j N30 :j N100 :j N200 :j [146]
N300 :j N1000 :j N2000 :j N3000
Mn [Mn3(1,4-BDT)2Cl2(DEF)6] 2D trans-{MnCl2N4}, fac-{MnClN2O3} l4-j N1:j N2:j N10 :j N20 [116]
[Mn4(1,4-BDT)3(DEF)6](NO3)2 2D fac-{MnN3O3} l4-j N1:j N2:j N20 :j N30 [116]
[Mn3(1,4-BDT)3(DMF)4(H2O)2]2H2O3MeOHDMF 3D {MnN6}, fac-{MnN3O3} l4-j N2:j N3:j N20 :j N30 [116]
[Mn2(1,4-BDT)Cl2(DMF)2]H2O1.5MeOH 3D mer-{MnCl2N3O} l6-j N1:j N2:j N3:j N10 :j N20 :j N30 [116]
[Mn(Andolast)(H2O)] 1D {MnN3O2} l3-j N1:j N4:j N20 [182]
(2D)
[Mn(btze)(H2O)4]2H2O 1D trans-{MnN2O4} l2-j N1:j N10 [134]
(3D)
[Mn{Mn3(l3-F)(bta)3(H2O)6}2] 2D {MnN6}, mer-{MnFN3O2} l3-j2N1,N10 :j N2:j N40 [183]
[Mn3(Hbta)4(l2-OH)2(H2O)]2H2O 2D trans-{MnN4O2}, cis-{MnN4O2} l2-j2N1,N10 :j N3 [185]
[Mn(bta)(H2O)] 2D {MnN5O} l4-j2N1,N10 :j N2:j N4:j N30 [185]
[Mn 3D trans-{MnClN4O}b l6-j N2:j N3:j N20 :j N30 :j N200 :j N300 [186]
(DMF)6]3[(Mn4Cl)3(BTT)8(H2O)12]242DMF11H2O20MeOH
Mn3[(Mn4Cl)3(TPT-3tz)8]225H2O15MeOH95DMF 3D {MnClN4}b l6-j N2:j N3:j N20 :j N30 :j N200 :j N300 [172]
[Mn6(ttpm)3]Solv 3D {MnN6}, fac-{MnN3O3} l8-j N2:j N3:j N20 :j N30 :j N200 :j N300 :j [174]
N2000 :j N3000

(continued on next page)

6 A. Tăbăcaru et al. / Coordination Chemistry Reviews 372 (2018) 1–30

Table 1 (continued)

M Compound Dima M Coordination L Hapticity Refs.

[H(Mn4Cl)(ttps)2(DMF)4]20DMF 3D trans-{MnClN4O} l8-j N2:j N3:j N20 :j N30 :j N200 :j N300 :j [176]
N2000 :j N3000
[Mn6(ttps)3(DMF)6] 3D {CuN6}, fac-{CuN3O3} l8-j N2:j N3:j N20 :j N30 :j N200 :j N300 :j [176]
N2000 :j N3000
[Mn2(tta)(DMF)2(MeOH)4]DMF2MeOH2H2O 2D fac-{MnN3O3} l6-j N2:j N3:j N20 :j N30 :j N200 :j N300 [146]
[Mn5Cl2(ttpa)2(H2O)4(DMF)4]3H2O7DMF 3D fac-{MnClN2O3}, cis-{MnClN4O}, {MnN6} l9-j N1:j N2:j N3:j N10 :j N20 :j N200 :j [194]
N300 :j N2000 :j N3000
Mn0.5[Mn4Cl(MnCl-ttzpp)2(H2O)4]20DEF18MeOH12H2O 3D trans-{MnClN4O}b l8-j N2:j N3:j N20 :j N30 :j N200 :j N300 :j [196]
N2000 :j N3000
Cd [Cd(1,2-BDT)(NH3)3]2H2O 1D mer-{CdN3(Nammonia)3} l3-j2N1,N10 :j N3 [136]
(3D)
[Cd(1,3-BDT)2(Py)2(H2O)2][Cd[Cd(Py)(H2O)]2(1,3-BDT)2] 2D {CdN5O}, {CdN6}, trans-{CdN4O2} l4-j N1:j N2:j N20 :j N30 and l4-j N1:j N3: [110]
j N20 :j N30
[Cd3(1,4-BDT)3(DMF)4(H2O)2]4DMF4H2O 3D {CdN6}, fac-{CdN3O3} l4-j N2:j N3:j N20 :j N30 [197]
[Cd2(btze)Cl2(H2O)] 3D cis-{CdCl2N4}, mer-{CdCl3N2O} l3-j N1:j N2:j N3, l3-j N1:j N2:j N4 [133]
[Cd3(btze)3(H2O)12] 2D {CdN6}, fac-{CdN3O3} l4-j N1:j N2:j N10 :j N20 [133]
[Cd2(btzp)Cl2] 3D trans-{CdCl2N4}, mer-{CdCl3N3} l7-j N1:j N2:j N3:j N4:j N10 :j N20 :j N30 [133]
[Cd3(btzb)2Cl2]4H2O 3D trans-{CdCl2N4}, trans-{CdN4O2} l6-j N1:j N2:j N4:j N10 :j N20 :j N40 [133]
[Cd5(N3)6(btzop)2] 3D fac-{CdN2(Nazide)3O}, fac-{CdN3(Nazide)3}, l6-j3N1,N10 ,O:j N2:j N3:j N4:j N20 :j N30 [198]
trans-{CdN4(Nazide)2}
[Cd5X2(N3)4(btzop)2] (X = Cl, Br) 3D fac-{CdN2(Nazide)OX2}, fac- l6-j3N1,N10 ,O:j N2:j N3:j N4:j N20 :j N30 [198]
{CdN3(Nazide)3}, trans-{CdN4(Nazide)2}
[Cd3(N3)2(btzop)2] 3D trans-{CdN4(Nazide)2}, l4-j3N1,N10 ,O:j N4:j N30 :j N40 [198]
{CdN3(Nazide)O}
[Cd3X2(btzop)2] (X = Cl, Br) 3D trans-{CdN4X2}, {CdN3XO} l4-j N1,N1 ,O:j N4:j N2 :j N4
3 0 0 0
[198]
(Me2NH2)3[Cd12Cl3(BTT)8(DMF)12]12DMF5MeOH 3D trans-{CdClN4O} l6-j N2:j N3:j N20 :j N30 :j N200 :j N300 [119]
Cd3[(Cd4Cl)3(BTT)8(DMF)12]219DMF129H2O 3D trans-{CdClN4O}b l6-j N2:j N3:j N20 :j N30 :j N200 :j N300 [199]
[Cd2(BTT)Cl(H2O)2] 3D trans-{CdClN4O}, mer-{CdCl2N3O} l7-j N1:j N2:j N3:j N10 :j N20 :j N100 :j N300 [200]
[Cd6(ttps)3(DMF)6] 3D {CdN6}, fac-{CdN3O3} l8-j N2:j N3:j N20 :j N30 :j N200 :j N300 :j [176]
N2000 :j N3000
[Cd4Cl4(tta)(DMF)7]DMF 3D {CdCl2N3O}, {CdCl2N2O} l10-j N2:j N3:j N20 :j N30 :j N100 :j N200 :j [146]
N300 :j N1000 :j N2000 :j N3000
[(Cd4Cl)(ttpa)2Cd2Cl3]Solv 3D {CdClN4} b
l8-j N2:j N3:jj N20 :j N30 :j N200 :j N300 :j [177]
N2000 :j N3000
[(Cd4Cl)(TTPP)2(CdCl)4]Solv 3D {CdClN4}b l8-j N2:jj N3:j N20 :j N30 :j N200 :j N300 :j [201]
N2000 :j N3000
Co [Co2(1,4-H0.67BDT)3]20H2O 3D {CoN6} l4-j N2:j N3:j N20 :j N30 [203]
[Co4(OH)2(SO4)(1,4-BDT)2(H2O)4] 3D mer-{CoN3O3}, cis-{CoN2O4} l5-j N1:j N2:j N3:j N4:j N10 [119]
[Co5F2(BPDT)4(H2O)6]2H2O 3D mer-{CoFN3O2}, cis-{CoFN4O}, trans- l4-jj N1:j N2:jj N3:j N20 [119]
{CoF2N4}
[Co3(OH)(SO4)(BTT)(H2O)4]3H2O 3D trans-{CoN2O4} l4-j N2:j N3:j N20 :j N30 [119]
Co3[(Co4Cl)3(BTT)8(DMF)12]2Solv 3D trans-{CoClN4O}b l6-j N2:j N3:j N20 :j N30 :j N200 :j N300 [199]
[Co(btzbp)] 2D {CoN6} l3-j4N1,N10 ,(N,N)2,2 -bpy:j N4:j N30
0 [214]
Fe [Fe2(1,4-H0.67BDT)3]13H2O 3D {FeN6} l4-j N2:j N3:j N2 :j N30
0
[205,219]
[Fe3(ox)(1,4-H0.67BDT)3(H2O)2]10H2O9MeOH 3D {FeN6}, fac-{FeN3(Oox)2Owater} l4-j N2:j N3:j N20 :j N30 [219]
[Fe2(1,4-H0.67BDT)3]4H2O 3D {FeN6} l4-j N1:j N2:j N10 :j N20 [205]
[Fe2(1,4-H0.67BDT)3]15H2O 3D {FeN6} l4-j N2:j N3:j N20 :j N30 [205]
Fe3[(Fe4Cl)3(BTT)8]222DMF32DMSO11H2O 3D {FeClN4}b l6-j N2:j N3:j N20 :j N30 :j N200 :j N300 [222]
[(Fe4Cl)(TTPP)2(FeCl)4]Solv 3D {FeClN4}b l8-j N2:j N3:j N20 :j N30 :j N200 :j N300 :j [202]
N2000 :j N3000
[Cr3O(1,4-HBDT)2(1,4-BDT)Cl3)]DMF 3D trans-{CrClN4O} l4-j N2:j N3:j N20 :j N30 [223]
[Cr(1,4-BDT)(DEF)]DEF 3D trans-{CrN4O2} l4-j N2:j N3:j N20 :j N30 [223]
[Ni2(1,4-BDT)3]10.5H2O 3D {NiN6} l4-j N2:j N3:j N20 :j N30 [119]
Ni3[(Ni4Cl)3(BTT)8(DMF)12]2Solv 3D trans-{NiClN4O}b l6-j N2:j N3:j N20 :j N30 :j N200 :j N300 [199]
[Ag2(1,4-BDT)] 3D {AgN4} l8-j N1:j N2:j N3:j N4:j N10 :j N20 :j N30 : [163]
j N40
[Ag2(BTZPX)] 2D {AgN3} l6-j N1:j N2:j N3:j N10 :j N20 :j N30 [137]
[Hg(BTZPX)] 2D {HgN4} l4-j N1:j N3:j N10 :j N40 [137]
[Hg(H2ptp)Cl2]2H2O 1D {HgCl2N2} l2-j N1:j N10 [142]
a
In parenthesis, the dimensionality of the supramolecular framework created by non-bonding interactions.
b
Information on the coordination sphere of extra-framework metal cations omitted.

More recently, by using 1,4-H2BDT along a different synthetic
route than in [116], Ouellette et al. [119] prepared [Zn(1,4-BDT)],
the non porous crystal structure of which is characterized by
{ZnN4} tetrahedral nodes linked to twelve surrounding ones by
l4-spacers within a complex 3D architecture.
Another, earlier example of in situ preparation of the
spacer (Scheme 1) is the solvothermal reaction of 9,10-
dicyanoanthracene with zinc(II) chloride and sodium azide, which
afforded [Zn7(OH)8(DTA)3]H2O [120]. Its crystal structure features
[Zn7(OH)8]6+ spindle clusters (Fig. 3a) linked by l4-spacers within
a 3D non porous framework (Fig. 3b) of pcu topology [121]. Opti-
cal diffuse reflectance showed that [Zn7(OH)8(DTA)3]H2O has an
optical band gap of about 2.9 eV, typical of a semi-conductor,
though impedance spectroscopy between 20 and 220 °C clearly
indicated that it is an insulator with a very high resistance (>109
ohm at room temperature). Upon excitation at 396 nm, in the
solid state and at room temperature [Zn7(OH)8(DTA)3]H2O exhi-
bits an intense photoluminescence centered at 483 nm with a
 A. Tăbăcaru et al. / Coordination Chemistry Reviews 372 (2018) 1–30 7

Table 2
Synoptic collection of the functional properties studied for the CPs and MOFs presented in this review.

M Compound Functional properties Refs.

Zn [Zn(1,3-BDT)] Luminescence [110]
[Zn2(OH)2(1,3-BDT)] Luminescence [113]
[Zn3(1,4-BDT)3(DMF)4(H2O)2]3.5MeOH N2 and H2 adsorption [116]
[Zn(1,4-BDT)] n.a. [119]
[Zn7(OH)8(DTA)3]H2O UV–Vis absorption; luminescence [120]
[Zn(dtp)] O2 and CO2 adsorption [127]
[Zn2(btze)2]H2O Luminescence [133]
[Zn(btzp)] Luminescence [133]
[Zn(btzb)(H2O)2]4H2O Luminescence [133]
[Zn(btze)] Luminescence [134]
[Zn(btze)(H2O)] Luminescence [134]
[Zn2(BDTM)2(H2O)2]28H2O Luminescence [136]
[Zn4(BDTM)4] Luminescence [136]
[Zn(BTZPX)] UV–Vis absorption; luminescence [137]
[Zn(ptp)(H2O)]2 Luminescence [141]
[Zn(ptp)(MeOH)] Luminescence [141]
[Zn(ptp)] Luminescence [141]
[Zn3(ptp)3(DMF)2(H2O)] Luminescence; N2, O2, H2, CO2 and CH4 adsorption [141]
[Zn3(cdtp)3(H2O)]H2O Luminescence [142]
[Zn(HBTT)]2DMA N2, H2 and CO2 adsorption [143,145]
[Zn(DMA)6][Zn6H4(HBTT)6]5MeOH12DMA n.a. [143]
[Zn2(HBTT)Cl2]MeOH3DMA Luminescence [143]
[Zn3Cl2(tta)(DMF)4]2DMF N2 and H2 adsorption [146]
Cu [Cu(1,4-BDT)(DMF)]MeOH0.25DMF H2 and O2 adsorption [116]
[Cu(MeBDT)(DMF)] n.a. [161]
[Cu(BPDT)(DMF)] n.a. [161]
[Cu2(OH)2(1,4-BDT)] Magnetism [163]
[Cu(btzop)]0.5H2O I2 adsorption [164]
[CuIICuI2(btzop)2] n.a. [164]
H[Cu(DMF)6][(Cu4Cl)3(BTT)8(H2O)12]3.5HCl12H2O16MeOH N2 and H2 adsorption [167]
Cu3[(Cu4Cl)3(TPB-3tz)8]211CuCl28H2O120DMF N2 and H2 adsorption [172]
Cu3[(Cu4Cl)3(TPT-3tz)8]2xsolvent N2 and H2 adsorption [172]
(NC2H8)4[Cu5(BTT)3]xG (G = DMF or H2O) CO2, N2, CH4 and H2 adsorption [173]
Cu[(Cu4Cl)(ttpm)2]2CuCl25DMF11H2O H2 adsorption [174]
[H(Cu4Cl)(ttps)2(DMF)4]18DMF N2 adsorption [175]
[Cu6(ttps)3(DMF)6] n.a. [176]
Cu[(Cu4Cl)(tta)2]29DMF n.a. [177]
[(Cu4Cl)(ttpa)2Cu2Cl3]6DMA4MeOH2H2O n.a. [177]
[Cu4Cl4(tta)(DMF)5]DMF N2 and H2 adsorption; magnetism [146]
Mn [Mn3(1,4-BDT)2Cl2(DEF)6] n.a. [116]
[Mn4(1,4-BDT)3(DEF)6](NO3)2 n.a. [116]
[Mn3(1,4-BDT)3(DMF)4(H2O)2]2H2O3MeOHDMF N2 and H2 adsorption [116]
[Mn2(1,4-BDT)Cl2(DMF)2]H2O1.5MeOH N2 and H2 adsorption [116]
[Mn(Andolast)(H2O)] Luminescence [182]
[Mn(btze)(H2O)4]2H2O Luminescence [134]
[Mn{Mn3(l3-F)(bta)3(H2O)6}2] Magnetism [183]
[Mn3(Hbta)4(l2-OH)2(H2O)]2H2O Magnetism [185]
[Mn(bta)(H2O)] Magnetism [185]
[Mn(DMF)6]3[(Mn4Cl)3(BTT)8(H2O)12]242DMF11H2O20MeOH N2 and H2 adsorption; catalysis [186]
Mn3[(Mn4Cl)3(TPT-3tz)8]225H2O15MeOH95DMF N2 and H2 adsorption [172]
[Mn6(ttpm)3]Solv N2 adsorption [174]
[H(Mn4Cl)(ttps)2(DMF)4]20DMF N2 adsorption [176]
[Mn6(ttps)3(DMF)6] n.a. [176]
[Mn2(tta)(DMF)2(MeOH)4]DMF2MeOH2H2O Magnetism [146]
[Mn5Cl2(ttpa)2(H2O)4(DMF)4]3H2O7DMF Magnetism [194]
Mn0.5[Mn4Cl(MnCl-ttzpp)2(H2O)4]20DEF18MeOH12H2O CO2, CH4 and C2H2 adsorption [196]
Cd [Cd(1,2-BDT)(NH3)3]2H2O Luminescence [136]
[Cd(1,3-BDT)2(Py)2(H2O)2][Cd[Cd(Py)(H2O)]2(1,3-BDT)2] Luminescence [110]
[Cd3(1,4-BDT)3(DMF)4(H2O)2]4DMF4H2O Luminescence [197]
(Me2NH2)3[Cd12Cl3(BTT)8(DMF)12]12DMF5MeOH N2 adsorption [119]
[Cd2(btze)Cl2(H2O)] Luminescence [133]
[Cd3(btze)3(H2O)12] Luminescence [133]
[Cd2(btzp)Cl2] Luminescence [133]
[Cd3(btzb)2Cl2]4H2O Luminescence [133]
[Cd5(N3)6(btzop)2] Luminescence [198]
[Cd5X2(N3)4(btzop)2] (X = Cl, Br) Luminescence [198]
[Cd3(N3)2(btzop)2] Luminescence [198]
[Cd3X2(btzop)2] (X = Cl, Br) Luminescence [198]
Cd3[(Cd4Cl)3(BTT)8(DMF)12]219DMF129H2O N2 and H2 adsorption [199]
[Cd2(BTT)Cl(H2O)2] n.a. [200]
[Cd6(ttps)3(DMF)6] n.a. [176]
[Cd4Cl4(tta)(DMF)7]DMF N2 and H2 adsorption [146]
[(Cd4Cl)(ttpa)2Cd2Cl3]Solv n.a. [177]

(continued on next page)

8 A. Tăbăcaru et al. / Coordination Chemistry Reviews 372 (2018) 1–30

Table 2 (continued)

M Compound Functional properties Refs.

[(Cd4Cl)(TTPP)2(CdCl)4]Solv Luminescence; catalysis [201]
Co [Co2(1,4-H0.67BDT)3]20H2O N2 and H2 adsorption; magnetism [203]
[Co4(OH)2(SO4)(1,4-BDT)2(H2O)4] Magnetism [119]
[Co5F2(BPDT)4(H2O)6]2H2O Magnetism [119]
[Co3(OH)(SO4)(BTT)(H2O)4]3H2O Magnetism [119]
Co3[(Co4Cl)3(BTT)8(DMF)12]2Solv N2 and H2 adsorption [199]
[Co(btzbp)] Magnetism [214]
Fe [Fe2(1,4-H0.67BDT)3]13H2O Magnetism [205,219]
[Fe3(ox)(1,4-H0.67BDT)3(H2O)2]10H2O9MeOH Magnetism [219]
[Fe2(1,4-H0.67BDT)3]4H2O Magnetism [205]
[Fe2(1,4-H0.67BDT)3]15H2O Magnetism [205]
Fe3[(Fe4Cl)3(BTT)8]222DMF32DMSO11H2O N2, CO2 and H2 adsorption [222]
[(Fe4Cl)(TTPP)2(FeCl)4]Solv Catalysis [202]
[Cr3O(1,4-HBDT)2(1,4-BDT)Cl3)]DMF N2, O2 and CO2 adsorption [223]
[Cr(1,4-BDT)(DEF)]DEF N2, O2 and CO2 adsorption [223]
[Ni2(1,4-BDT)3]10.5H2O Magnetism [119]
Ni3[(Ni4Cl)3(BTT)8(DMF)12]2Solv N2 and H2 adsorption [199]
[Ag2(1,4-BDT)] Reactivity [163]
[Ag2(BTZPX)] UV–Vis absorption; luminescence [137]
[Hg(BTZPX)] UV–Vis absorption; luminescence [137]
[Hg(H2ptp)Cl2]2H2O Luminescence [142]

[Zn7(OH)8(DTA)3]H2O doping with cobalt(II) [126] by reacting

NaN3, ZnX2
H2O, reflux
Chart 3.
Chart 4.
long lifetime (4.042 ns), showing potentiality as a photoactive
material.
To design the functional properties of a coordination compound
by concomitant incorporation of different metal ions into a given
network, a recently emerging strategy is based on in situ doping
a known derivative with the desired metal ion (see e.g.
[122–125]). An interesting example in this respect is
9,10-dicyanoanthracene with zinc(II) chloride, cobalt(II) chloride
hexahydrate and sodium azide. The Co(II)-doped MOF [Co2Zn5(-
OH)8(DTA)3]H2O is isostructural to the parent all-Zn derivative
but exhibits canted antiferromagnetism and weaker fluorescence
emission, which highlights the feasibility of metal doping to tune
the properties of a compound.
[Zn(dtp)] was isolated through the solvothermal reaction of zinc
(II) chloride with H2dtp [127]. {ZnN6} octahedral nodes and l3-j2:
j2:j2-spacers define a 3D (8,3)-connected chiral network of etd
topology [128]. Deliberate synthesis of chiral MOFs, to be applied
e.g. in heterogeneous catalysis [4,5,129–132], continues to be a
hot topic. In [Zn(dtp)] chiral, closed-packed channels (Fig. 4a) are
lined with nitrogen atoms, which provide basic adsorption sites
potentially useful for the interaction with guest molecules (see
e.g. [132]). This MOF is stable up to 380 °C, does not adsorb N2
at 77 K, but adsorbs 79.3 cm3/g of O2 and 98.8 cm3/g of CO2 at 77
and 195 K, respectively, and 1 atm. Such a selective adsorption
behavior was ascribed to the restricted size of the channels.
Bis(tetrazolyl) ligands bearing alkyl -(CH2)n- spacers between
the tetrazolyl rings have been successfully employed to build func-
tional CPs and MOFs showing different dimensionality and lumi-
nescence properties. For example, [Zn2(btze)2(H2O)], [Zn(btzp)]
and [Zn(btzb)(H2O)2]4H2O were prepared from the bis(1H-
tetrazol-5-yl)alkanes H2btze, H2btzp and H2btzb, respectively,
and zinc(II) chloride [133]. Both [Zn2(btze)2(H2O)] and [Zn(btzp)]
are characterized by 3D non porous frameworks built by {ZnN4}
tetrahedral nodes bridged by l4- and l3-j2:j:j-spacers in the for-
mer, l4-spacers in the latter. At variance, [Zn(btzb)(H2O)2]4H2O
features 1D chains of {ZnN2O2} tetrahedral nodes bridged by l2-
spacers. The three CPs have decomposition temperatures in the
range 330–380 °C. The photoluminescence spectrum of [Zn2(-
btze)2(H2O)] shows emission bands centered at 475, 485 and
496 nm, red-shifted with respect to that of H2btze (323 nm), sug-
gesting the occurrence of metal-to-ligand and/or ligand-to-metal
charge transfers. At variance, [Zn(btzp)] and [Zn(btzb)(H2O)2]
4H2O emit at 473 and 495 nm, and at 472 and 488 nm, respec-
tively, which was tentatively assigned to intraligand (p-p⁄ or n-
p⁄) charge transfers.
By using synthetic conditions differing from those in [133],
Shen et al. [134] employed H2btze to prepare [Zn(btze)] and [Zn
(btze)(H2O)]. In the crystal structure of the former, stable up to
440 °C, l4-j2:j:j:j-spacers and {ZnN5} square pyramidal nodes
 A. Tăbăcaru et al. / Coordination Chemistry Reviews 372 (2018) 1–30 9

Fig. 1. Pictorial representation of the most recurrent mechanisms beyond CPs and MOFs luminescence (fractional coordinates from [196]).

H2O/EtOH associated to the specific structural features of the two CPs, as

IPN + NaN3 + Htz + ZnCl2 [Zn2(OH)2(1,3-BDT)]
160 °C, 3 d [113]
already observed, e.g., in zinc(II) coordination polymers containing
the ligands H4btc, 4,40 -bpy and bpe [135].
Reacting H2BDTM with Zn(II) in different conditions (Scheme 2)
H2O/EtOH
DCA + NaN3 + ZnCl2 [Zn7(OH)8(DTA)3]·H2O afforded [Zn2(BDTM)2(H2O)2]28H2O and [Zn4(BDTM)4] [136].
160 °C, 2 d
[120] In the crystal structure of the former, {ZnN3O} tetrahedral nodes
are bridged by l2-j2:j-spacers along 1D zig-zag chains connected
H2O through a complex net of hydrogen bonds within a 3D supramolec-
NaN(CN)2 + NaN3 + KF+ MnCl2·4H2O [Mn{Mn3(F)(bta)3(H2O)6}2]
115 °C, 3 d ular network. At variance, the 3D crystal structure of [Zn4(BDTM)4]
[183]
is characterized by {ZnN4} tetrahedral nodes and l3-j2:j:j-
Cd(NO3)2 spacers. At room temperature and in the solid state, upon excita-
[Cd5(N3)6(btzop)2]
tion at 291 nm [Zn2(BDTM)2(H2O)2]28H2O and [Zn4(BDTM)4] exhi-
CdCl2 bit a weak fluorescence emission centered at 384 and 397 nm,
[Cd5Cl2(N3)4(btzop)2]
130 °C respectively. The red-shift observed for the latter CP with respect
BCEE + NaN3 [198]
to the emission of the free ligand (384 nm) was ascribed to a
CdBr2 [Cd5Br2(N3)4(btzop)2]
ligand-to-metal charge transfer.
Coupling H2BTZPX to Zn(II) chloride led to the isolation of [Zn
CdSO4 [Cd3(N3)2(btzop)2] (BTZPX)], stable up to 350 °C [137]. In the crystal structure of this
CP zig-zag chains of tetrahedral metal ions are connected by l4-
H2O
dcbipy + NaN3 + Co(ClO4)2·6H2O [Co(btzbp)] spacers within a 3D non porous network. The linkers adopt a chair
120 °C, 2 d [214] conformation, as already observed, e.g., with the bis(pyrazolyl)
ligands H2BDMPX [138], H2DMPMB [139], 4,40 -((2,3,5,6-tetrame
Scheme 1. The examples presented in this review of in situ synthesis of the ligand
concomitant to the formation of the CP or MOF. thyl-1,4-phenylene)bis(methylene))bis(3,5-dimethyl-1H-pyrazole)
[140] and 4,40 -((2,3,5,6-tetramethyl-1,4-phenylene)bis-(methy
lene))bis(3,5-diphenyl-1H-pyrazole) [140]. Solid-state UV–Vis
absorption revealed a bathochromic shift for both the ligand
form a 3D non porous network. [Zn(btze)(H2O)], decomposing at (330 nm) and [Zn(BTZPX)] (330 nm) with respect to the absorp-
250 °C, features 2D layers built up by {ZnN4O} square pyramidal tion of the main chromophore of the ligand (the benzene ring,
nodes and l3-j2:j:j-spacers, and connected by hydrogen bonds 260 nm).
within a 3D supramolecular framework. In the solid state and at By using the same reactants along different synthetic paths
room temperature, [Zn(btze)] and [Zn(btze)(H2O)] display emis- (Scheme 3), Bu and coworkers [141] obtained four coordination
sion bands at 458 and 396 nm upon excitation at 276 and 367 compounds of different dimensionality (0D to 3D) and photophys-
nm, respectively, which were assigned to intraligand charge trans- ical behaviour, namely: [Zn(ptp)(H2O)]2, [Zn(ptp)(MeOH)], [Zn
fers. The decreased luminescence, compared to the free ligand, was (ptp)] and [Zn3(ptp)3(DMF)2(H2O)]. [Zn(ptp)(H2O)]2 is composed
10 A. Tăbăcaru et al. / Coordination Chemistry Reviews 372 (2018) 1–30

(a)

(b)
Fig. 2. Three-bladed paddlewheel units in poly(tetrazolate) MOFs, as exemplified by the crystal structure of [Zn3(1,4-BDT)3(DMF)4(H2O)2]3.5MeOH (fractional coordinates
from [116]): (a) the Zn3 linear unit; (b) portion of the crystal packing, viewed in perspective along the [1 0 0] direction. Horizontal axis, c; vertical axis, b. The hydrogen atoms,
the clathrated solvent and the coordinated solvent (but the oxygen atoms) have been omitted for clarity. The skeleton of the ligand has been represented with a cyan segment.
Atom colour code: carbon, grey; nitrogen, blue; oxygen, red; zinc, orange.

by {Zn2(ptp)2(H2O)2} units with square pyramidal nodes, held
together by N  H-O hydrogen bonds within a 3D supramolecular
framework showing 1D channels. In [Zn(ptp)(MeOH)] [141] octa-
hedral metal centers are bridged by l2-j3:j2-spacers along helices
which are connected by N  H-O hydrogen bonds within
supramolecular 2D chiral sheets. In the solid state and at room
temperature, upon excitation at 372 and 255 nm [Zn(ptp)(H2O)]2
and [Zn(ptp)(MeOH)] show blue-shifted (to 431 and 436 nm,
respectively) and more intense emissions than the ligand (490
nm), which were ascribed to a decreased nonradiative decay of
intraligand excited states through coordination to the Zn(II) ions.
In [Zn(ptp)] [141], octahedral metal centers are linked by l3-j3:
j :j-spacers within 2D sheets of (6,3)-net topology. Upon excita-
2
tion at 446 nm, [Zn(ptp)] shows a red-shifted (to 491 nm) and
more intense emission band with respect to the ligand, which sug-
gested an enhancement of p-conjugation: indeed, p-p stacking
interactions are present between the pyridine rings of adjacent
ptp2 spacers. Finally, in the crystal structure of [Zn3(ptp)3(-
DMF)2(H2O)] [141], penta-coordinated Zn(II) ions are bridged by
l3-spacers within a 3D porous framework featuring 1D restricted
channels occupied by solvent molecules. This MOF is stable up to
300 °C and, upon excitation at 383 nm, it shows a blue-shifted
(to 431 nm) and more intense emission vs. that of the ligand. Acti-
vated [Zn3(ptp)3] was tested as an adsorbent towards N2 and O2 at
77 K, H2 at 77 and 87 K, CO2 and CH4 at 273 K. Noteworthy, it
adsorbs 11.21 wt CO2 % and 1.02 wt CH4 % at 1.1 bar, highlighting
a high selectivity towards CO2 over CH4.
Substitution of the two pyridyl rings in positions 2 and 3 of the
pyrazine ring of H2ptp with a camphoryl group led to the chiral
ligand H2cdtp, which was used in the synthesis of [Zn3(cdtp)3(H2-
O)]H2O [142], featuring a 3D non porous chiral framework where
tetrahedral, square-pyramidal and trigonal–bipyramidal nodes are
linked by l2-j2:j2- and l3-j2:j2:j-spacers. Upon excitation at
342 nm, this CP displays a strong emission peaking at 406 nm,
blue-shifted with respect to that of the ligand (426 nm, kex = 375
nm), and ascribed to intraligand (p-p⁄ or n-p⁄) transitions.
3.2. Tritopic ligands
Upon modifying the metal:ligand ratio (Scheme 4), H3BTT
hydrochloride and zinc(II) chloride yielded [Zn(HBTT)]2DMA
(IFMC-6), [Zn(DMA)6][Zn6H4(HBTT)6]5MeOH12DMA (IFMC-7)
and [Zn2(HBTT)Cl2]MeOH3DMA (IFMC-8) [143].
In the crystal structure of both IFMC-6 and IFMC-7, {ZnN4}
tetrahedral nodes are bridged by l4-HBTT2 spacers within 3D
(3,6)-connected neutral and anionic porous frameworks. While
IFMC-6 shows 1D square channels, IFMC-7 features mesoporous
cages connected by microporous channels. In IFMC-8, {ZnN3Cl}
tetrahedral nodes are connected by l6-HBTT2 spacers within a
3D (4,4)-connected framework with hexagonal channels (Fig. 3b).
IFMC-8 appeared an efficient host for Alq3, one of the most suc-
cessful chromophores ever used as electron injection layer in
OLEDs (see e.g. [144]), in order to attain modulated photolumines-
cence. Alq3@IFMC-8 composites exhibit a large ipso-chromic shift
of the emission band from green (517 nm) to blue (462 nm) as a
function of the concentration of the Alq3 solution used to prepare
them. IFMC-6 was also obtained (and labelled CPF-6) by Lin et al.
[145] starting from zinc(II) nitrate hexahydrate and H3BTT. These
 A. Tăbăcaru et al. / Coordination Chemistry Reviews 372 (2018) 1–30 11

(a)

(b)
Fig. 3. Uncommon clusters in poly(tetrazolate) MOFs, as exemplified by the crystal structure of [Zn7(OH)8(DTA)3]H2O (fractional coordinates from [120]): (a) the
[Zn7(OH)8]6+ spindle cluster. Also shown the tetrazolate moieties completing the octahedral coordination sphere of the Zn(II) ions. Atom colour code: carbon, grey; nitrogen,
blue; oxygen, red; zinc, orange. (b) Portion of the crystal packing, viewed in perspective along the [1 0 0] direction. Horizontal axis, b; vertical axis, c. The clusters have been
represented in orange, while the ligand has been simplified for clarity and depicted in blue.

(a) (b)

Fig. 4. Hexagonal channels in MOFs: (a) the chiral channel lined with nitrogen atoms in [Zn(dtp)] (fractional coordinates from [127]), viewed in perspective along the [0 0 1]
direction; (b) the achiral channel lined with chlorine and nitrogen atoms in [Zn2(HBTT)Cl2]MeOH3DMA (IFMC-8) (fractional coordinates from [143]), viewed in perspective
along the [0 0 1] direction. Atom colour code: carbon, grey; chlorine, green; nitrogen, blue; zinc, orange. The hydrogen atoms have been omitted for clarity.
12 A. Tăbăcaru et al. / Coordination Chemistry Reviews 372 (2018) 1–30

metal:ligand 1:1 mol/mol

[Zn2(BDTM)2(H2O)2]2·8H2O
NH4OH, rt, slow evaporation
ZnCl2 + H2bdtm
metal:ligand 2:1 mol/mol [Zn4(BDTM)4]
H2O, 140 °C, 1 d

Scheme 2. Influence of the reaction conditions: the reaction paths yielding [Zn2(-
BDTM)2(H2O)2]28H2O and [Zn4(BDTM)4] [136].

H2O/MeOH
[Zn(ptp)(H2O)]
180 °C, 3 d
H2O/MeOH
[Zn(ptp)(MeOH)]
120 °C, 3 d
Zn(NO3)2·6H2O + H2ptp
H2O/MeOH
[Zn(ptp)] STORAGE SEPARATION
170 °C, 3 d
Fig. 5. Pictorial representation of gas storage and separation in MOFs (fractional
H2O/DMF coordinates from [167]).
[Zn(ptp)(DMF)2(H2O)]
100 °C, 1 d

Scheme 3. Influence of the reaction conditions: the different solvothermal paths
employed to isolate the Zn(II) derivatives of H2ptp [141].
authors reported the adsorption of 1.89 wt H2 % at 77 K and 1 atm,
and 98 cm3/g of CO2 at 273 K and 1 atm.
3.3. Tetratopic ligands
and functionalization has allowed for the differential recognition
of small gas molecules [148]. MOFs gas storage and separation
[35–43] (Fig. 5) are at the basis, e.g., of greenhouse effect decrease,
clean energy usage [149–151], toxic compounds capture [152]. Gas
separation is one of the most critical passages in many industrial
processes, and metal–organic frameworks, in the form of mem-
branes, are potentially applicable in this context [38].

The coordination and structural chemistry of poly(5-substituted

tetrazolate)-based frameworks has attained an even higher degree
of richness by employing tetrahedral ligands. An example in this
sense is the use of H4tta and zinc(II) chloride in the formation of
[Zn3Cl2(tta)(DMF)4]2DMF [146]. The crystal structure of this
MOF shows trans-{ZnN2O4} octahedra and {Zn2(tetrazolate)4Cl2}
dimers with {ZnCl2N2} tetrahedral nodes. The dimers are con-
nected by l8-tta4 spacers leading to the formation of 2D layers.
The tetrazolate rings bridging the dimers form coordination bonds
also with the octahedral nodes, connecting the layers into a 3D
porous framework of fsc topology [147]. Coordinated and non-
coordinated DMF occupy the space between the layers. This MOF
does not adsorb N2 at 77 K, while it adsorbs 23.3 cm3/g (STP) of
H2 at 77 K.
4. Copper poly(tetrazolates)
Copper poly(tetrazolates) have been built up with di- to tetrato-
pic ligands. With only two exceptions, where a Cu(I) derivative and
a mixed valence Cu(I,II) compound have been synthesized, copper
is invariably in +2 oxidation state and is tetra- to hexa-coordinated
with stereochemistry ranging from square planar to tetrahedral,
square pyramidal, trigonal bipyramidal and octahedral [102,103]
(Table 1). As for the functional characterization (Table 2), in the
case of MOFs with permanent porosity gas adsorption and separa-
tion were typically investigated. MOFs have shown great potential
for gas separation and purification, as the tunability of pore size
4.1. Ditopic ligands
To the best of our knowledge, the first copper poly(tetrazolate)
ever appeared is [Cu(1,4-BDT)(DMF)]MeOH0.25DMF [116],
obtained upon coupling 1,4-H2BDT and copper(II) nitrate hemipen-
tahydrate. The crystal structure of this MOF, stable up to 210 °C, is
built up by Jahn-Teller distorted octahedral nodes. l2-Tetrazolates
and l2-DMF molecules bridge the nodes along 1D linear chains
(Fig. 6a) that are linked by the spacers within a 3D framework fea-
turing rhombic channels (Fig. 6b).
This structural motif is quite recurrent for MOFs built up with
ditopic [poly(carboxylate) or poly(azolate)] spacers, as exemplified
by MIL-53(M) (M = Al, Cr, Fe) (see e.g. [153–155]), [M(BPZ)] (M =
Cu, Ni) [156], [Ni(1,4-BDP-X)] [157,158] or [Cu(BDTri)(DMF)]
1.2H2O [159]. [Cu(1,4-BDT)(DMF)] does not adsorb N2 at 77 K
and uptakes only 0.66 wt H2 % at 77 K and 1.2 bar: this perfor-
mance, worse than expected based on the room conditions crystal
structure, is due to the formation of a closed-pore form upon acti-
vation, as proved by powder X-ray diffraction. At 77 K, O2 adsorp-
tion proceeds along a two-step hysteretic isotherm, suggesting a
gate-opening phenomenon, demonstrating the flexibility [160] of
this MOF and its selectivity towards O2 (14 mmol/g at 77 K and
a relative pressure of 0.9) over N2 and H2.
With the aim of extending the library of Cu(II) azolates known
at the time, the same research group coupled 1,4-H2MeBDT and
H2BPDT, showing either different functionality or length vs. 1,4-
H2BDT, with copper(II) chloride dihydrate, obtaining [Cu(MeBDT)

metal:ligand 3:1 mol/mol [Zn(HBTT)]·2DMA

(IFMC-6)

metal:ligand 4:1 mol/mol [Zn(DMA)6][Zn6H4(HBTT)6]·5MeOH·12DMA

ZnCl2 + H3BTT·2HCl MeOH/DMA 1:4 v/v
85 °C, 4d (IFMC-7)

metal:ligand 5:1 mol/mol [Zn (HBTT)Cl ]·MeOH·3DMA

2 2
(IFMC-8)

Scheme 4. Influence of the reaction conditions: the different metal to ligand ratios employed to isolate IFMC-6, IFMC-7 and IFMC-8 [143].
 A. Tăbăcaru et al. / Coordination Chemistry Reviews 372 (2018) 1–30 13

(a)

(b)
Fig. 6. Rhombic channels in poly(tetrazolate) MOFs, as exemplified by the crystal structure of [Cu(1,4-BDT)(DMF)]MeOH0.25DMF (fractional coordinates from [116]): (a)
portion of the 1D chains of trans-CuN4O2 octahedral nodes. Only the oxygen atoms of the coordinated DMF molecules have been depicted. Atom colour code: carbon, grey;
copper, orange; nitrogen, blue; oxygen red. (b) Portion of the crystal packing, viewed in perspective along the [1 0 0] direction. Horizontal axis, c; vertical axis, b. The hydrogen
atoms and the coordinated and clathrated solvent molecules have been omitted for clarity.

Fig. 7. 1D ladders in poly(tetrazolate) coordination polymers, as exemplified by the

crystal structure of [Cu2(OH)2(1,4-BDT)] (fractional coordinates from [163]) viewed
in perspective along the [1 0 0] direction. Horizontal axis, c; vertical axis, b. Atom
colour code: carbon, grey; copper, orange; nitrogen, blue; oxygen red. The hydrogen
atoms have been omitted for clarity.

80-140 °C, 3 d [Cu(btzop)]·0.5H2O

H2O:EtOH 2:1 v/v
Cu(ClO4)2·6H2O + H2btzop
160-180 °C, 4 d
Scheme 5. Influence of the reaction conditions: the solvothermal paths followed to
isolate [Cu(btzop)]0.5H2O and [CuIICuI2(btzop)2] [164].
(DMF)] and [Cu(BPDT)(DMF)] [161], which possess the same struc-
tural motif of [Cu(1,4-BDT)(DMF)] [116]. Upon immersion in a vari-
ety of solvents (MeOH, EtOH, DEF, DMSO) to promote solvent
exchange, the two frameworks showed a different, linker-
dependent response, a phenomenon which had been already
[CuIICuI2(btzop)2]
Fig. 8. Octagonal channels in poly(tetrazolate) MOFs, as exemplified by the crystal
structure of [Cu(btzop)]0.5H2O (fractional coordinates from [164]): portion of the
crystal packing viewed in perspective along the [0 0 1] direction. Horizontal axis, a;
vertical axis, b. Atom colour code: carbon, grey; copper, orange; nitrogen, blue. The
ligands (but the tetrazolate rings) and the clathrated water molecules have been
omitted for clarity.
observed, e.g., with the MIL-53(Fe) system [162]: indeed, while
[Cu(MeBDT)] is flexible, [Cu(BPDT)] is rigid irrespective of the sol-
vent employed.
14 A. Tăbăcaru et al. / Coordination Chemistry Reviews 372 (2018) 1–30

(a)

(b)

Fig. 9. Sodalite-type poly(tetrazolate) MOFs, as exemplified by the crystal structure of H[Cu(DMF)6][(Cu4Cl)3(BTT)8(H2O)12]3.5HCl12H2O16MeOH (Cu-BTT) (fractional
coordinates from [167]): (a) the {Cu4Cl}7+ chloride-centered square. Also shown the tetrazolate moieties and the oxygen atoms of the coordinated water molecules that
complete the coordination sphere of the Cu(II) ions. Atom colour code: carbon, grey; chlorine, green; copper, orange; nitrogen, blue; oxygen red. (b) Portion of the crystal
packing, viewed in perspective along the [1 0 0] direction. Horizontal axis, b; vertical axis, c. The hydrogen atoms, the coordinated and clathrated solvent molecules and the
[Cu(DMF)6]2+ cations have been omitted for clarity. The cyan sphere helps visualizing one of the truncated-octahedral cages.

1,4-H2BDT was coupled also with copper(II) perchlorate hex-
ahydrate, affording [Cu2(OH)2(1,4-BDT)] [163]. In its crystal struc-
ture, square planar nodes are bridged by l2-OH moieties along
{Cu(OH)} parallel ladders linked by l4-spacers within a 3D non
porous network (Fig. 7). The behavior of vMT as a function of
temperature suggested the existence, in this CP, of a strong antifer-
romagnetic exchange between the copper(II) centres.
[Cu(btzop)]0.5H2O and [CuIICuI2(btzop)2] [164] have been
obtained from copper(II) perchlorate hexahydrate and H2btzop
upon tuning the reaction temperature (Scheme 5), selectively
directing the achiral ligand within an achiral or a chiral framework,
respectively.
In the crystal structure of the former compound, stable up to
290 °C, trigonal-bipyramidal nodes are bridged by l3-j3:j:j-
ligands within a 3D network in which two types of channels are
present (Fig. 8): wider channels with octagonal section occupied
by water molecules and smaller, helical channels with square
section. Soaking thermally activated crystals of [Cu(btzop)] in an
iodine solution afforded [Cu(btzop)]0.5I2, showing the same
structural motif of the unloaded parent. As unveiled by X-ray
diffraction, I2 molecules occupy the wider channels with a head-
to-tail disposition and are involved into intermolecular
interactions with the unbound nitrogen atoms of the ligands point-
ing into the channels. Locating the adsorption sites within a MOF
pores, e.g. with crystallographic studies [165,166], is of utmost
importance as it enables the identification of the host–guest inter-
actions favouring the adsorption of a specific guest and the design
and synthesis of improved, next-generation adsorbents. Finally, the
crystal structure of the mixed-valence MOF [CuIICuI2(btzop)2] [164],
stable up to 340 °C, features tetrahedral and octahedral nodes
connected by l5-j3:j:j:j:j-spacers within a 3D (3,4,4)-connected
framework.
4.2. Tritopic ligands
The sodalite-type [121] MOF H[Cu(DMF)6][(Cu4Cl)3(BTT)8(H2-
O)12]3.5HCl12H2O16MeOH (Cu-BTT) was isolated by Dincă and
coworkers [167] upon reacting H3BTT and copper(II) chloride dihy-
drate. In its crystal structure, {Cu4Cl}7+ chloride-centered squares
(Fig. 9a), defined by eight l2-tetrazolates, are linked to eight
nearby ones by the spacers within a (3,8)-connected network
showing 1-D channels and truncated octahedral cages (Fig. 9b)
hosting the [Cu(DMF)6]2+ cations. As it will become evident in
the following, the {M4Cl(tetrazolate)8} node characterizes other
poly(tetrazolate) derivatives sharing the same (M = Mn, Cd, Fe) or
different (M = Cu, Mn, Cd) topology. As demonstrated also by this
review, sodalite-type frameworks are rather recurrent in MOFs:
they have been obtained with tritopic poly(carboxylates), e.g.
[Cu3(BTC)2] [168] and H6[(Co4O)3(tatb)8] [169], poly(pyrazolates),
e.g. [M3(BTP)2] (M = Ni, Cu) [170], and poly(triazolates), e.g. H3-
[(Cu4Cl)3(BTTri)8] [171]. Methanol-exchanged Cu-BTT (Cu-BTTm)
starts decomposing at only 190 °C. After thermal activation, N2
adsorption at 77 K revealed BET and Langmuir specific surface
areas of 1710 and 1770 m2/g, respectively. At 77 K, 2.42 wt H2 %
is reversibly adsorbed at 1.2 bar, along with an excess uptake of
4.2 wt H2 % (38 g/L) at 30 bar and a total uptake of 5.7 wt H2 %
(53 g/L) at 90 bar. Powder neutron diffraction experiments at 4 K
and different D2 loadings enabled the authors to identify the stron-
gest adsorption sites and confirm the relevance of unsaturated
metal ions [118] for H2 adsorption.
Aiming at obtaining expanded sodalite-type frameworks,
Dincă and coworkers [172] employed also the larger H3TPB-3tz
and H3TPT-3tz spacers, isolating Cu3[(Cu4Cl)3 (TPB-3tz)8]2
11CuCl28H2O120DMF and Cu3[(Cu4Cl)3 (TPT-3tz)8]2xsolvent,
respectively. While the former features a non-interpenetrated
 A. Tăbăcaru et al. / Coordination Chemistry Reviews 372 (2018) 1–30
Fig. 10. (4,8)-Connected networks in poly(tetrazolate) MOFs, as exemplified by the
crystal packing of Cu[(Cu4Cl)(ttpm)2]2CuCl25DMF11H2O (fractional coordinates
from [174]), viewed in perspective along the [0 0 1] direction. Horizontal axis, a;
vertical axis, b. Atom colour code: carbon, grey; chlorine, green; copper, orange;
nitrogen, blue; oxygen red. The hydrogen atoms, coordinated and clathrated solvent
molecules and CuCl2 extra-framework moieties have been omitted for clarity. The
skeleton of the ligand has been depicted with a blue segment. The cyan sphere help
guiding the eye.
sodalite-type structure, as Cu-BTT, the latter exhibits two interpen-
etrated sodalite-type networks. The selective formation of two dis-
tinct frameworks was ascribed to the distortion from planarity of
the sterically hindered spacer H3TPB-3tz. After mild thermal acti-
vation, the non-interpenetrated derivative adsorbs 300 cm3/g of
N2 at 77 K and 1 bar, with BET and Langmuir specific surface areas
of 1120 and 1200 m2/g, respectively: this performance, worse than
that of Cu-BTT, was attributed to the partial degradation of the
framework upon activation. Indeed, interpenetration helps stabi-
lizing the framework toward collapse upon desolvation, leading
to an increase of the BET specific surface area to 1580 m2/g and
the H2 excess uptake from 2.8 to 3.7 wt % at 77 K.
Coupled to copper(II) chloride dihydrate, H3BTT2HCl yielded
the Cu(I)-based MOF (NC2H8)4[Cu5(BTT)3]xG [173] (NC2H8 = dime
thylammonium cation, G = DMF and H2O), where the dimethylam-
monium cation was formed from solvent (DMA) decomposition in
the reaction medium. The crystal structure of this MOF is charac-
terized by two clusters of different nuclearity, Cu3 and Cu2, in
which the metal centers show tetrahedral geometry. The clusters
are linked by l6- and l8-spacers along left- and right-handed
helices, which are bridged within a 3D achiral framework. Giant
nanocages are present, in which large cavities are interlinked with
small windows lined by nitrogen atoms. After acetone exchange
followed by mild thermal activation, N2 adsorption at 77 K
revealed BET and Langmuir specific surface areas of 701 and 801
m2/g, respectively. The adsorption selectivity shown by this MOF
at 273 and 298 K towards CO2 over N2, CH4 and H2 was explained
with the presence of nitrogen atoms available for dipole-
quadrupole interactions with CO2: at the time, the CO2/N2 selectiv-
ity of 40 for a CO2:N2 = 0.15:0.75 mixture at 298 K and low pres-
sure placed (NC2H8)4[Cu5(BTT)3] among the top MOFs exhibiting
selectivities > 40.
15
Fig. 11. Garnet-like frameworks in poly(tetrazolate) MOFs, as exemplified by the
crystal structure of [Cu6(ttps)3(DMF)6] (IMP-17Cu) (fractional coordinates from
[176]) viewed in perspective along the [1 0 0] direction. Horizontal axis, b; vertical
axis, c. Atom colour code: carbon, grey; copper, orange; nitrogen, blue; silicon, beje.
The coordinated and clathrated solvent molecules have been omitted for clarity.
The skeleton of the ligand has been depicted with a blue segment.
4.3. Tetratopic ligands
Reaction of H4ttpm with copper(II) chloride hemipentahydrate
afforded Cu[(Cu4Cl)(ttpm)2]2CuCl25DMF11H2O [174]. Its 3D
framework contains {Cu4Cl}7+ chloride-centered squares, as the
M-BTT series, bridged to eight adjacent ones by ttpm4 spacers.
The combination of {Cu4Cl}7+ eight-connected nodes with ttmp2
four-connected nodes gives rise to a (4,8)-connected network
(Fig. 10) with flu [121] topology. Extraction of CuCl2 led to
[Cu4(ttpm)2]0.7CuCl2, showing deficiency of chloride anions
within the {Cu4Cl}7+ squares. This chloride-deficient phase shows
BET and Langmuir specific surface areas of 2506 and 2745 m2/g,
respectively, and reversibly adsorbs 2.8 wt H2 % at 77 K and 1.2 bar,
along with a total uptake of 5.6 wt H2 % at 77 K and 70 bar.
Replacing the central carbon atom in H4ttpm with a silicon
atom, as in H4ttps, Timokhin and co-workers unveiled a unique
influence on the crystal structure of [H(Cu4Cl)(ttps)2(DMF)4]
18DMF (IMP-16Cu) [175]. Although the structure of this MOF is
similar to that of pristine and chloride-deficient Cu[(Cu4Cl)
(ttpm)2]2CuCl25DMF11H2O [174], the rotational freedom about
the Si-Ar bonds in ttps4 (vs. the conformationally restricted rota-
tion about the C–Ar bonds in ttpm4) imparts a different orienta-
tion to the Cu(II)-based nodes, along with an increase of guest-
accessible empty volume: indeed, N2 adsorption at 77 K showed
BET and Langmuir specific surface areas of 2665 and 3123 m2/g,
respectively, which are the highest values reported so far for
tetrazolate-based MOFs.
By using copper(II) nitrate instead of copper(II) chloride along
reaction conditions similar to those adopted for IMP-16Cu, Timo-
khin and co-workers obtained [Cu6(ttps)3(DMF)6] (IMP-17Cu)
[176]. Its crystal structure contains linear trinuclear units, as in
[Zn3(1,4-BDT)3(DMF)4(H2O)2]3.5MeOH [116] (Fig. 2a), in which
the Cu(II) ions show octahedral stereochemistry. The nodes are
bridged by l8-ttps4 spacers within a 3D (4,6)-connected frame-
work (Fig. 11) with gar topology [121].
16 A. Tăbăcaru et al. / Coordination Chemistry Reviews 372 (2018) 1–30

(a)

(b)
Fig. 12. Gismondine-like poly(tetrazolate) MOFs, as exemplified by the crystal structure of [Cu4Cl4(tta)(DMF)5]DMF (fractional coordinates from [146]): (a) the tetranuclear
cluster. Atom colour code: carbon, grey; chlorine, green; copper, orange; nitrogen, blue; oxygen, red. The hydrogen atoms and the solvent molecules (but the oxygen atoms)
have been omitted for clarity. (b) Portion of the crystal packing viewed in perspective along the [1 0 0] direction. Horizontal axis, c; vertical axis, b. The hydrogen and chlorine
atoms and the solvent molecules have been omitted for clarity.

DEF, N2
[Mn3(1,4-BDT)2Cl2(DEF)6]
120 °C, 1 d
MnCl2·4H2O + 1,4-H2BDT
DMF/MeOH
[Mn2(1,4-BDT)Cl2(DMF)2]·H2O·1.5MeOH
70 °C, 1 d

DEF, N2
[Mn4(1,4-BDT)3(DEF)6](NO3)2
130 °C, 2 d
Mn(NO3)2·4H2O + 1,4-H2BDT
DMF/MeOH
[Mn3(1,4-BDT)3(DMF)4(H2O)2]·2H2O·3MeOH·DMF
Diffusion in EtOac
rt, 2 d

Scheme 6. The different reaction conditions employed to isolate the Mn(II) derivatives of 1,4-H2BDT [116].

Despite the fact that the room conditions solvent-accessible
volume amounts to 72%, upon thermal activation IMP-17Cu
decomposes, making it unsuitable for gas adsorption or separation.
Reaction of H4tta or its extended homologue H4ttpa with copper
(II) chloride afforded Cu[(Cu4Cl)(tta)2]29DMF and [(Cu4Cl)(ttpa)2
Cu2Cl3]6DMA4MeOH2H2O [177], which are isoreticular [178] to
Cu[(Cu4Cl)(ttpm)2]2CuCl25DMF11H2O [174].
Reacting copper(II) chloride and H4tta in different reaction con-
ditions than in [177], Boldog et al. isolated [Cu4Cl4(tta)(DMF)5]
DMF [146], stable up to 200 °C. Its crystal structure shows
{Cu4Cl4}4+ tetranuclear clusters (Fig. 12a) bridged by l10-spacers
within a 3D zeolitic framework (Fig. 12b) with gis topology [121].
N2 adsorption at 77 K revealed BET and Langmuir specific sur-
face areas of 505.5 and 594 m2/g, respectively, while the H2 uptake
at 77 K and 1 bar amounted to 0.72–0.79 wt %. vMT, 1.61 cm3
mol1 K at room temperature, decreases upon decreasing the tem-
perature to 1.9 K, suggesting the insurgence of weak antiferromag-
netic interactions.
5. Manganese poly(tetrazolates)
2D and 3D Mn(II) poly(tetrazolates) have been prepared with di-
to tetratopic ligands. In all of the cases but one, the metal centre
shows octahedral stereochemistry [102,103] (Table 1). The func-
tional characterization of the CPs has privileged the investigation
of spectroscopic and magnetic properties (Table 2). As also evinced
by the examples below, most of the studies on coordination poly-
mers magnetism have concentrated on the phenomena of long-
rage order or spin crossover [179,180]. In the case of Mn(II) tetrazo-
late MOFs with permanent porosity, due to the presence of exposed
metal sites [118] H2 adsorption has been typically studied (Table 2).
5.1. Ditopic ligands
In different reaction conditions (Scheme 6), 1,4-H2BDT was
employed to prepare [Mn3(1,4-BDT)2Cl2(DEF)6], [Mn4(1,4-BDT)3
(DEF)6](NO3)2, [Mn3(1,4-BDT)3(DMF)4(H2O)2]2H2O3MeOHDMF
 A. Tăbăcaru et al. / Coordination Chemistry Reviews 372 (2018) 1–30 17

(b)

(a)
(c)

Fig. 13. Dinuclear three-bladed paddlewheel unit (a) and honeycomb 2D layers in poly(tetrazolate) MOFs, as exemplified by the crystal structure of (b) [Mn4(1,4-
BDT)3(DEF)6](NO3)2 (fractional coordinates from [116]) viewed in perspective along the [1 0 0] direction and (c) [Mn2(tta)(DMF)2(MeOH)4]DMF2MeOH2H2O (fractional
coordinates from [146]) viewed in perspective along the [0 0 1] direction. Horizontal axis, a; vertical axis, b. Atom colour code: carbon, grey; manganese, orange; nitrogen,
blue; oxygen, red. The solvent molecules (but the oxygen atoms of coordinated solvent), nitrate anions and hydrogen atoms have been omitted for clarity.

and [Mn2(1,4-BDT)Cl2(DMF)2]H2O1.5MeOH [116], showing differ-
ent dimensionality.
The crystal structure of the former features 2D layers in which
Mn3 linear units are bridged to four neighbouring ones by the spac-
ers. Considering the trinuclear units as four-connected nodes and
the 1,4-BDT2 spacers as linear connectors, the layers can be clas-
sified as (4,4)-plane nets [181]. Stacking of the layers gives rise to
1D channels. Despite this, no functional characterization was
carried out, due to the fact that as-synthesized crystals are stable
outside the mother liquor only for short periods. [Mn4(1,4-
BDT)3(DEF)6](NO3)2 [116] is characterized by 2D layers built up
by Mn2 three-bladed paddlewheel units (Fig. 13a) linked by the
spacers. Stacking of the layers yields hexagonal channels occupied
by nitrate anions and uncoordinated DEF molecules. Regarding the
Mn2 units as three-connected nodes and the BDT2 ligands as lin-
ear connectors, a (6,3)-plane (or hcb) net [181] can be envisaged
(Fig. 13b). Also in this case, the crystals are stable outside the
mother liquor only for short periods. [Mn3(1,4-
BDT)3(DMF)4(H2O)2]2H2O3MeOHDMF [116] is isomorphous to
[Zn3(1,4-BDT)3(DMF)4(H2O)2]3.5MeOH [116] (see Section 3).
Finally, the 3D porous network of [Mn2(1,4-BDT)Cl2(DMF)2]
H2O1.5MeOH [116] is built up by helical chains of opposed chirality.
1D channels are present, which are occupied by both coordinated
DMF molecules and uncoordinated methanol and water molecules.
Overall, the crystal structure of this MOF can be regarded as an (8,3)-
b net [181]. At 77 K, [Mn3(1,4-BDT)3] and [Mn2(1,4-BDT)Cl2] show
BET specific surface areas of 290 and 530 m2/g, respectively. The
higher-than-average H2 isosteric heats of adsorption (6.3–8.4 and
6.0–8.8 kJ/mol, respectively), combined with the structural features
and the steep initial slope of the H2 isotherms, indicated the pres-
ence of strong adsorption sites, suggesting that unsaturated Mn(II)
ions become accessible after solvent release.
[Mn(Andolast)(H2O)] [182], stable up to 300 °C, was isolated
treating manganese(II) acetate tetrahydrate with Na2Andolast. In
its crystal structure, square-pyramidal Mn(II) nodes are bridged
by l3-Andolast2 spacers along 1D double-chains packing in a her-
ringbone disposition. Water molecules are involved in intra- and
inter-chain N  H–O hydrogen bonds with the unbound nitrogen
atoms of the ligand. Upon excitation at 355 nm, at room tempera-
ture and in the solid state both Na2Andolast and the CP exhibit a
broad and structureless emission band peaked at 450 nm.
The solvothermal reaction of H2btze with manganese(II) chlo-
ride tetrahydrate afforded [Mn(btze)(H2O)4]2H2O [134], stable
above 300 °C. In its crystal structure, octahedral nodes are bridged
by l2-ligands along 1D chains that are connected through a net of
hydrogen bonds within a 3D supramolecular network. Upon exci-
18 A. Tăbăcaru et al. / Coordination Chemistry Reviews 372 (2018) 1–30
tation at 300 nm, at room temperature and in the solid state this CP
displays a strong emission centered at about 367 nm, blue-shifted
with respect to that of the ligand (404 nm, kex = 337 nm) and
rationalized in terms of perturbation of an intraligand transition
due to the coordination to the metal centre.
The hydrothermal reaction of manganese(II) chloride tetrahy-
drate, sodium dicyanamide, sodium azide and excess potassium
fluoride afforded [Mn{Mn3(l3-F)(bta)3(H2O)6}2] [183], with in situ
generation of the bta2 ligand (Scheme 1). [Mn{Mn3(l3-F)
(bta)3(H2O)6}2] is characterized by 2D (3,6)-connected layers built
up by {Mn3(l3-F)} triangular clusters, showing mer-{MnFN3O2}
octahedral vertices, and {MnN6} mononuclear nodes. Variable-
temperature magnetic measurements unveiled a rather complex
behavior, which was rationalized assuming that the compound is
a molecular-based antiferromagnet with an unusual 2D frustrated
lattice, in which frustrated triangles are separated by mononuclear
paramagnetic ions. Substitution of fluoride with the hydroxyl
group led to the isomorphous CP [Mn{Mn3(l3-OH)(bta)3(H2O)6}2]
[184], which features the same magnetic behaviour.
Coupling H2bta to Mn(II) in different reaction conditions than
above afforded either [Mn3(Hbta)4(l2-OH)2(H2O)]2H2O or [Mn
(bta)(H2O)] [185]. In the crystal structure of the former, stable up
to 200 °C, rhombic {Mn2(l2-OH)2(Hbta)4} dimers are linked to four
{MnN4O2} nodes (and viceversa) within a 2D (4,4)-connected net-
work. At 300 K, vMT (12.76 emu K mol1) is close to the spin-only
value for three magnetically isolated Mn(II) ions in high-spin. Upon
cooling, vMT decreases slowly until 100 K; below this tempera-
ture, it decreases sharply (to 1.04 emu K mol1 at 2 K), suggesting
an antiferromagnetic behavior. [Mn(bta)(H2O)], decomposing at
360 °C, features {Mn2(bta)2} dimers along two types of helical
chains with the same handness, which are interwoven within 2D
chiral layers with left- or right-handness stacking alternately to
yield a 3D framework with PtS topology [121]. Temperature-
dependent magnetic measurements disclosed a complex beha-
viour, which was ascribed to the coexistence of spin-canted anti-
ferromagnetic coupling and field-induced spin-flop transition.
5.2. Tritopic ligands
Coupling H3BTT to manganese(II) chloride tetrahydrate yielded
[Mn(DMF)6]3[(Mn4Cl)3(BTT)8(H2O)12]242DMF11H2O20MeOH
(Mn-BTT) [186], isomorphous to Cu-BTT [167] (see Section 4). Mn-
BTT can be desolvated only partially at 200 °C, temperature beyond
which decomposition occurs. Also methanol-exchanged Mn-BTT
(Mn-BTTm) can be activated only partially, though in a more com-
plete way. As a direct consequence, the performance of the two
activated materials (Mn-BTT0 and Mn-BTTm0 ) is markedly differ-
ent: as an example, they reversibly adsorb 310 and 550 cm3/g of
N2 at 77 K and 1.7 and 2.2 wt H2 % at 77 K and 1.2 bar, respectively.
CAT
(a)
CAT
(b)
Scheme 7. The organic syntheses catalized by Mn3[(Mn4Cl)3(BTT)8(MeOH)10]2
[188]: (a) cyanosilylation of aromatic aldehydes and ketones; (b) Mukaiyama-aldol
reaction.
Powder neutron diffraction experiments at 3.5 K and different D2
loadings revealed that the high heat of adsorption of Mn-BTTm0
(5.7–10.1 kJ/mol) is due to the coordination of H2 to unsaturated
Mn(II) sites. To achieve an even higher heat of adsorption, Mn-
BTTm0 was used as a substrate to exchange the Mn2+ ions with
Li+, Cu+, Fe2+, Co2+, Ni2+, Cu2+ or Zn2+ [187]. The resulting MOFs
and the methanol-exchanged and activated counterparts are
isostructural to the parent compound. Their BET and Langmuir
specific surface areas are in the range 1695(5)–2210(5) and 1778
(10)–2282(8) m2/g, respectively. The H2 isotherms at 77 K show
significantly different slopes at very low pressure. This occurrence
suggested that, at low coverage, when the H2 molecules are
expected to adsorb onto the strongest binding sites, the nature of
the metal cation has a marked influence. Due to the presence of
unsaturated Mn(II) sites on its pore surface, Mn3[(Mn4Cl)3(BTT)8(-
MeOH)10]2 was tested [188] as size-selective Lewis-acid heteroge-
neous catalyst in the cyanosilylation of aromatic aldehydes and
ketones and in the Mukaiyama-aldol reaction (Scheme 7). With
cyanotrimethylsilane at room temperature, a 11 mol % loading of
catalyst led to a 98% conversion of benzaldehyde after 9 h, much
higher than the best previous result, attained with a series of lan-
thanide bis(phosphonates) [189]. In the Mukaiyama-aldol reaction
of benzaldehyde with methyltrimethylsilyldimethylketene acetal,
performed at room temperature with 16 mol % loading of catalyst,
a maximum conversion of benzaldehyde of 63% was attained after
99 h, comparable to the yields obtained for cation-exchanged ZSM-
5 or Y-zeolites [190,191].
As much as done with Cu-BTT, aiming at expanding the sodalitic
framework of Mn-BTT Dincă and coworkers [172] coupled H3TPT-
3tz to manganese(II) chloride tetrahydrate, isolating Mn3[(Mn4-
Cl)3(TPT-3tz)8]225H2O15MeOH95DMF, which features an inter-
penetrated sodalite-type structure, like the Cu(II) analogue [172]
(see Section 4). This MOF undergoes framework collapse upon sol-
vent exchange with a number of volatile solvents. The partially
desolvated form adsorbs 440 cm3/g of N2 at 77 K and 1 atm and
exhibits BET and Langmuir specific surface areas of 1580 and
1700 m2/g, respectively. At 77 K, this MOF shows an excess uptake
of 3.7 wt H2 % at 25 bar and a total uptake of 4.5 wt H2 % (37 g/L) at
80 bar. Overall, these performances are similar to those of Mn-BTT0 ,
suggesting that activation is less effective if solvent exchange is not
preliminary performed to eliminate DMF. As a matter of fact, MOFs
activation procedures is still a hot topic [192,193].
5.3. Tetratopic ligands
H4ttpm was coupled not only to copper(II), but also to man-
ganese(II), affording [Mn6(ttpm)3(Solv)6]2Solv (Solv = DMF, H2O)
[174], which is isostructural to [M6(ttps)3(DMF)6] (M = Cu, IMP-
17Cu, see Section 4; M = Mn, IMP-17Mn, see below) [176]. Despite
solvent-exchange, this MOF collapses upon thermal activation and
shows no significant uptake of N2.
IMP-16Mn, [H(Mn4Cl)(ttps)2(DMF)4]20DMF [176], isostruc-
tural to IMP-16Cu [175] (see Section 4), was isolated upon coupling
H4ttps to manganese(II) chloride tetrahydrate. This MOF is stable
up to 200 °C and, at 77 K and 0.9 bar, it adsorbs 710 cm3/g of N2,
with BET and Langmuir specific surface areas of 2510 and 2956
m2/g, respectively.
By using manganese(II) nitrate instead of manganese(II) chlo-
ride along reaction conditions similar to those adopted for IMP-
16Cu [175], Timokhin and co-workers obtained [Mn6(ttps)3(-
DMF)6] (IMP-17Mn) [176], which is isostructural to IMP-17Cu
[176] (Section 4). Despite the fact that the room conditions
solvent-accessible volume amounts to 71.5%, IMP-17Mn decom-
poses upon thermal activation, thus making it unsuitable for gas
adsorption or separation.
 A. Tăbăcaru et al. / Coordination Chemistry Reviews 372 (2018) 1–30 19

(a)

(b)
Fig. 14. Representation of the crystal structure of [Mn5Cl2(ttpa)2(H2O)4(DMF)4]3H2O7DMF (fractional coordinates from [194]): (a) the {Mn5(l-Cl)2(H2O)4(DMF)4} cluster;
(b) portion of the crystal packing, viewed in perspective along the [1 0 0] direction. Horizonal axis, b; vertical axis, c. Atom colour code: carbon, grey; chlorine, green;
manganese, orange; nitrogen, blue; oxygen, red. Hydrogen atoms, clathrated solvent molecules and coordinated solvent molecules (but the oxygen atoms) have been omitted
for clarity. The cyan sphere helps guiding the eye.

(a) (b)
Fig. 15. Representation of the crystal structure of Mn(II)0.5[Mn(II)4Cl(Mn(III)Clttzpp)2(H2O)4]20DEF18MeOH12H2O (UTSA-57) (fractional coordinates from [196]): (a)
Portion of the crystal packing viewed in perspective along the [1 0 0] direction. Horizontal axis, b; vertical axis, c. (b) Portion of the crystal packing viewed in perspective along
the [0 0 1] direction. Horizontal axis, a; vertical axis, b. Atom colour code: carbon, grey; chlorine, green; manganese, orange; nitrogen, blue; oxygen, red. The extra-framework
Mn(II) ions, clathrated solvent molecules, coordinated solvent molecules (but the oxygen atoms) and hydrogen atoms have been omitted for clarity.
20 A. Tăbăcaru et al. / Coordination Chemistry Reviews 372 (2018) 1–30
Boldog and coworkers coupled H4tta not only with copper(II),
but also with manganese(II), isolating [Mn2(tta)(DMF)2(MeOH)4]
DMF2MeOH2H2O [146]. Its crystal structure is composed of
dinuclear three-bladed paddlewheel units (Fig. 13a) bridged by
l6-linkers within hcb [121] (6,3)-connected layers (Fig. 13c), as
in [Mn4(1,4-BDT)3(NO3)2(DEF)6] [116]. At room temperature, vMT
(8.85 cm3 mol1 K) is close to the value expected for two uncou-
pled Mn(II) ions, while it decreases from 100 K to 2 K with a trend
indicative of weak antiferromagnetic interactions between the din-
uclear units.
As much as done with copper(II), Boldog and coworkers reacted
the expanded ligand H4ttpa also with manganese(II), isolating
[Mn5Cl2(ttpa)2(H2O)4(DMF)4]3H2O7DMF [194]. Its 3D polymeric
network (Fig. 14) is based on almost linear {Mn5(l-
Cl)2(H2O)4(DMF)4} clusters. Regarding the clusters as 8-connected
nodes and the ligands as tetrahedral nodes, the framework shows
the (4,8)-connected alb topology [195]. Although at room condi-
tions this MOF shows 63% of empty volume, both thermal activa-
tion above 120 °C and solvent exchange procedures resulted in
framework collapse or incomplete framework evacuation, possibly
due to the hydrolysis of the Mn–Ntetrazolate and Mn–Cl bonds
induced by water residues which might trigger the fragmentation
of the clusters. At room temperature, vMT (20.9 cm3 mol1 K) is
slightly lower than expected for five high-spin Mn(II) ions; upon
cooling to 2 K it decreases to the limit value (4.3 cm3 mol1 K)
for antiferromagnetically coupled clusters with an odd number of
Mn(II) ions.
Reaction of the porphyrinato-based metalloligand MnIIICl-ttzpp
with manganese(II) chloride tetrahydrate yielded Mn(II)0.5[Mn
(II)4Cl(Mn(III)Cl-ttzpp)2(H2O)4]20DEF18MeOH12H2O (UTSA-57)
[196], decomposing at 400 °C. Its crystal structure features {Mn4-
Cl}7 clusters [see Fig. 9a for the Cu(II) analogue] linked by the
MnIIICl-ttzpp ligands (Fig. 15a) within a 3D MOF with large square
channels (Fig. 15b). Regarding MnIIICl-ttzpp as a four-connecting
node and the {Mn4Cl}7 cluster as a eight-connecting node,
UTSA-57 shows a 4,8-c binodal net with scu topology [121].
The potential application of UTSA-57 in gas separation was
tested towards CO2, CH4 and C2H2: at 273 K and 1 atm it adsorbs
15 cm3/g of CH4, 65 cm3/g of CO2 and 57 cm3/g of C2H2. Gas
adsorption selectivities of 58.7, 40.3, or 28.0 at 273 K, and 43.1,
25.7, or 20.0 at 296 K were estimated for the 50:50 mixtures
C2H2/CH4, C2H4/CH4, or CO2/CH4, respectively.
Fig. 16. Portion of the crystal packing of [Cd2(btze)Cl2(H2O)] (fractional coordinates
from [133]) viewed in perspective along the [0 1 0] direction. Horizontal axis, c;
vertical axis, a. Atom colour code: carbon, grey; cadmium, orange; chlorine, green;
nitrogen, blue; oxygen red. The hydrogen atoms have been omitted for clarity.
6. Cadmium poly(tetrazolates)
The Cd(II) poly(tetrazolate) coordination frameworks appeared
in the literature to date have been obtained with di- to tetratopic
spacers. In all of the cases but one the metal centre shows octahe-
dral stereochemistry [102,103] (Table 1). As expected in the pres-
ence of d10 transition metal ions [104–106], the functional
characterization of Cd(II) CPs has invariably focused on lumines-
cence (Table 2). In the case of MOFs showing permanent porosity,
due to the presence of unsaturated metal sites [118] H2 adsorption
has been investigated (Table 2).
6.1. Ditopic spacers
Coupling the ortho, meta and para isomers of bis(1H-tetrazol-5-
yl)benzene to a number of cadmium(II) salts in different synthetic
conditions allowed the preparation of [Cd(1,2-BDT)(NH3)3]2H2O
[136], [Cd(1,3-BDT)2(Py)2(H2O)2][Cd[Cd(Py)(H2O)]2(1,3-BDT)2]
[110] and [Cd3(1,4-BDT)3(DMF)4(H2O)2]4DMF4H2O [197]. In the
crystal structure of the former [136], {CdN6} octahedral nodes are
bridged by l2-j2:j-spacers along zig-zag chains connected within
a 3D supramolecular framework through a net of hydrogen bonds
involving water molecules and ligands. In the solid state and at
room temperature, upon excitation at 307 nm [Cd(1,2-BDT)
(NH3)3]2H2O shows an emission centered at 361 nm, slightly
blue-shifted with respect to that of the ligand (370 nm) and
assigned to a ligand-to-metal charge transfer. The crystal structure
of [Cd(1,3-BDT)2(Py)2(H2O)2][Cd[Cd(Py)(H2O)]2(1,3-BDT)2] [110]
consists of 2D (4,4)-connected layers stacking in such a way that
two sets of channels are formed. In the solid-state and at room
temperature, upon coordination to Cd(II) the emission maximum
of the ligand (471 nm) is shifted to 323 nm, which was explained
in terms of ligand-based electronic transitions; the large blue-
shift observed was ascribed to less efficient conjugation paths in
the coordination polymer compared to those in the ligand.
[Cd3(1,4-BDT)3(DMF)4(H2O)2]4DMF4H2O [197], isostructural to
[Zn3(1,4-BDT)3(DMF)4(H2O)2]3.5MeOH [116] and [Mn3(1,4-
BDT)3(DMF)4(H2O)2]2H2O3MeOHDMF [116] (see Sections 3 and
5, respectively), is stable only up to 150 °C: decomposition begins
immediately after water release, this occurrence preventing study
of its adsorption properties. In the solid state and at room temper-
ature, it exhibits a strong emission band centered at 326 nm, blue-
shifted with respect to that of the ligand (473 nm) and rationalized
in terms of a ligand-to-metal charge transfer.
The bis(1H-tetrazol-5-yl)alkanes H2btze, H2btzp and H2btzb
were coupled not only to zinc(II) (Section 3), but also to
cadmium(II), yielding [Cd2(btze)Cl2(H2O)], [Cd3(btze)3(H2O)12],
[Cd2(btzp)Cl2] and [Cd3(btzb)2Cl2]4H2O [133], which are stable
up to 330–380 °C. Also in this case, frameworks of different
(2D to 3D) dimensionality and emissive properties were formed.
In [Cd2(btze)Cl2(H2O)], octahedral nodes are bridged by
l3-tetrazolates and l3-chloride anions within a 3D non porous
framework (Fig. 16).
[Cd3(btze)3(H2O)12] [133] consists of linear {Cd3(tetrazolate)6-
O6} clusters linked by l4-btze2 ligands within 2D layers. In the
3D framework of [Cd2(btzp)Cl2] [133], Cd(II) octahedral nodes are
linked by l7-btzp2 spacers and l2-chloride anions within 2D grid
layers alternatively pillared by the linkers and chloride anions.
Finally, the 3D polymeric network of [Cd3(btzb)2Cl2]4H2O [133]
is built up by octahedral nodes bridged by l6-btzp2 ligands and
l2-chloride anions. The room temperature photoluminescence
spectra of [Cd2(btze)Cl2(H2O)] and [Cd3(btze)3(H2O)12] show two
main emission bands at 475 and 493 nm, and 473 and 492 nm,
respectively, red-shifted with respect to that of H2btze (323 nm),
suggesting the occurrence of metal-to-ligand and/or ligand-
 A. Tăbăcaru et al. / Coordination Chemistry Reviews 372 (2018) 1–30
to-metal charge transfers. [Cd2(btzp)Cl2] emit at 495 nm, while
[Cd3(btzb)2Cl2]4H2O show emission bands at 472 and 496 nm. In
both cases the emissions were tentatively assigned to intraligand
(p-p⁄ or n-p⁄) electronic transitions, since the two ligands emit
at 480 and 472 nm, respectively.
Coupling H2btzop to different Cd(II) salts in solvothermal con-
ditions led to the isolation of [Cd5(N3)6(btzop)2], [Cd5X2(N3)4(-
btzop)2], [Cd3(N3)2(btzop)2] and [Cd3X2(btzop)2] (X = Cl, Br)
[198], stable up to 325–375 °C. In the case of the first four com-
pounds, the ligand was prepared in situ by the Cd(II)-catalyzed [2
+3] cycloaddition reaction of BCEE with sodium azide (Scheme 1).
In the crystal structure of [Cd5(N3)6(btzop)2] and [Cd5X2(N3)4(-
btzop)2] (X = Cl, Br), l6-btzop2 ligands are coordinated to six
octahedral Cd(II) ions within 2D layers which embed l2- and
l3-azide anions. l2-Azide or l2-halide anions connect adjacent
layers to generate a 3D framework. In [Cd3(N3)2(btzop)2] and
[Cd3X2(btzop)2] (X = Cl, Br), the two independent Cd(II) ions
show square-pyramidal and octahedral geometry and are linked
by l2- and l3-tetrazolates as well as l2-azide/halide anions
within a 3D non porous framework. In the solid state and at
room temperature, upon excitation at 356 or 390 nm, these CPs
exhibit emission bands in the range 464–494 nm, interpreted
as intra-ligand (p-p⁄ or n-p⁄) electronic transitions. The shifts
observed with respect to the emission bands of the ligand (358
and 472 nm upon excitation at 290 nm) were tentatively
assigned to both ligand deprotonation and coordination effects
of the azide or halide anions on the metal centre coordination
sphere.
6.2. Tritopic spacers
Coupling H3BTT to cadmium(II) sulphate in the presence of
HClconc afforded (Me2NH2)3[Cd12Cl3(BTT)8(DMF)12]12DMF5MeOH
[119], where the Me2NH+2 cations derived from the thermal decom-
position of DMF in the reaction medium. As much as like the M-
BTT MOFs, this compound shows an anionic sodalitic-type frame-
work (Fig. 8). N2 adsorption at 77 K disclosed BET and Langmuir
specific surface areas of 525 and 575 m2/g, respectively, which
are about four times less than those found for Mn-BTT [186] (see
Section 5) and Cd-BTT [199] (see below) due to the presence of
the larger Me2NH+2 counterions in the pores.
The simpler sodalitic-type MOF Cd3[Cd12Cl3(BTT)8(DMF)12]2-
19DMF129H2O (Cd-BTT) [199], in which the charge of the anionic
framework is compensated by extra-framework Cd(II) ions, was
obtained by coupling cadmium(II) chloride with H3BTT2HCl. After
heating at 150 °C, mimicking activation conditions, single crystal
X-ray diffraction showed that solvent release induces migration
of extra-framework chloride anions in the coordination sites left
available by the solvent molecules, as well as migration of extra-
framework Cd(II) ions near the framework walls. After methanol-
exchange and subsequent thermal activation, this MOF shows a
BET specific surface area of 1266.1 m2/g and adsorbs 1.5 wt H2 %
at 77 K and 1 bar.
H3BTT2HCl was reacted also with cadmium(II) chloride dihy-
drate affording [Cd2(BTT)Cl(H2O)2] [200], characterized by a 3D
non porous network built up by octahedral metal centers bridged
by l7-linkers.
6.3. Tetratopic spacers
Timokhin and coworkers coupled H4ttps also with cadmium(II),
isolating [Cd6(ttps)3(DMF)6] (IMP-17Cd) [176], isostructural to the
Cu(II) and Mn(II) analogues IMP-17Cu and IMP-17Mn [176] (see
Sections 4 and 5, respectively). Although the solvent-accessible
21
CAT
Scheme 8. The deacetalization-Knoevenagel condensation reaction catalized by
PCN-527-Cd [202].
volume of IMP-17Cd is higher than 70%, it undergoes decomposi-
tion to an amorphous, non-porous phase if left in air for 24 h.
Boldog and coworkers reacted H4tta and H4ttpa also with cad-
mium(II), preparing [Cd4Cl4(tta)(DMF)7]DMF [146] and [(Cd4Cl)
(ttpa)2Cd2Cl3]Solv [177] (Solv = 4–6DMF2H2O0–4MeOH), respec-
tively. The former compound shows a gismondine-type frame-
work, as the Cu(II) analogue [146] (see Section 4). Despite the
62% of solvent-accessible volume, it is not pervious to N2 at 77
K in the relative pressure range 0–1, but adsorbs 7.5 cm3/g of H2
at 77 K and 1 bar. [(Cd4Cl)(ttpa)2Cd2Cl3]Solv is isostructural to
[(Cu4Cl)(ttpa)2Cu2Cl3]6DMA4MeOH2H2O [177] and, together
with Cu[(Cu4Cl)(tta)2]29DMF [177] and Cu[(Cu4Cl)(ttpm)2]2CuCl2-
5DMF11H2O [174] (Section 4), forms an isoreticular [178] family
of microporous MOFs with flu topology [121].
The solvothermal reaction between the porphyrinic ligand H4-
TTPP and cadmium(II) chloride dihydrate led to Cd0.5[(Cd4Cl)
(TTPP)2(CdCl)4]Solv (Solv = DMA, MeOH or H2O) (PCN-526-Cd)
[201], the crystal structure of which shows chloride-centered {Cd4-
Cl}7+ squares defined by eight l2-tetrazolates. Each square is
bridged to eight adjacent ones by the spacers within a 3D network
with scu topology [121] featuring square channels, as in UTSA-57
[196] (Fig. 15). The walls of the channels are lined with the por-
phyrinic rings, accommodating square-pyramidal Cd(II) ions. Upon
abrupt cooling at 110 K, the framework undergoes a single-crystal-
to-single-crystal (SC-SC) transformation, leading to a modification
of the channel shape from square to rectangular. To shed light on
the transformation mechanism, Liu and co-workers prepared
PCN-527-Cd [201], in which the pyrrolic rings of porphyrin do
not coordinate a metal center. The same SC-SC transformation
occurred even in PCN-527-Cd, this ruling out any influence of the
porphyrinic Cd(II) ion. After adsorption into PCN-526-Cd of a num-
ber of aromatic compounds (benzene, toluene, benzoic acid,
terephthaldialdehyde, diamminonaphtalene and biphenyl-4,40 -dic
arboxylic acid), the phase transition was observed only with ben-
zene and toluene, possibly more weakly interacting with the
framework. A systematic investigation demonstrated that incorpo-
ration of smaller aromatic molecules, like naphtalene and phenan-
threne, has a negligible impact on the emission bands of the host,
while larger molecules, like perylene and 1,10 -binaphtyl, influence
the energy transfer pathways, with the appearance of new emis-
sion bands.
The Lewis acidity imparted by the Cd(II) ions, along with the
Lewis basicity conveyed by the uncoordinated tetrazolate nitrogen
atoms, prompted Liu and coworkers [202] to test PCN-527-Cd as a
heterogenous catalyst for the deacetalization-Knoevenagel con-
densation reaction (Scheme 8): in the presence of PCN-527-Cd
(0.01:2 catalyst:substrate, mol/mol), dimethoxymethylbenzene
was converted only up to 22%, which was attributed by the authors
to the weak Lewis acidity of Cd(II).
22 A. Tăbăcaru et al. / Coordination Chemistry Reviews 372 (2018) 1–30

Fig. 17. Portion of the crystal packing of [Co2(1,4-H0.67BDT)3]20H2O (fractional coordinates from [203]) viewed in perspective along the [1 0 0] direction. Horizontal axis, b;
vertical axis, c. Atom colour code: carbon, grey; cobalt, orange; nitrogen, blue. The clathrated solvent molecules and hydrogen atoms have been omitted for clarity.

7. Cobalt poly(tetrazolates) -yl-phenyl)-1H-tetrazole) and [Fe2(1,4-H0.67BDT)3]15H2O [205]

The class of cobalt(II) poly(tetrazolates) is less populated than
those of Zn(II) and Cd(II), which share the same stereochemical
preferences [102,103] but possess a rather different redox chem-
istry. In the crystal structure of the cobalt(II) poly(tetrazolates)
characterized to date, built up with a restricted number of ditopic
and tritopic ligands (1,4-H2BDT, H2BPDT, H2btzbp and H3BTT), the
Co(II) centers invariably show octahedral stereochemistry (see
Table 1) and, as expected in the presence of ligand-bridged Co(II)
chains in the crystal structure, in all of the cases emphasis is given
to the magnetic properties [179,180] (Table 2).
7.1. Ditopic ligands
[Co2(1,4-H0.67BDT)3]20H2O [203] and [Co4(OH)2(SO4)(1,4-
BDT)2(H2O)4] [119] were isolated by coupling 1,4-H2BDT and
cobalt(II) sulphate heptahydrate in different reaction conditions.
The crystal structure of the former is built up by octahedral nodes
bridged by l2-tetrazolates along {Co(tetrazolate)3} chains charac-
terized by the three-bladed paddlewheel motif. Each chain is
linked to four adjacent ones by planar and bent ligands within a
3D oab network [204] featuring rectangular channels (Fig. 17).
Noteworthy, bent spacers have been rarely observed: the reader
is referred to, e.g., [Cu2(L2)3Cl]12H2O (HL2 = 5-(4-[1,2,4]triazol-4
(see Section 8). [Co2(1,4-H0.67BDT)3]20H2O is stable up to 290 °C
and its crystal structure is not affected by dehydration or rehydra-
tion. It shows BET and Langmuir specific surface areas of 729 and
833 m2/g, respectively, and adsorbs 1.49 wt H2 % at 77 K and
120 kPa. For the as-synthesized form, at 1000 Oe and 300 K the
value of vT (3.7 emu mol1 K) is indicative of spin-orbit coupling.
Upon cooling to 5 K, vT smoothly decreases due to spin-orbit cou-
pling and possible antiferromagnetic interactions.
For the desolvated form, at 1000 Oe and 300 K vT amounts to 1
emu mol1 K, indicating that 80% of the metal centers are in low-
spin state. Cooling to 2 K, vT smoothly decreases due to the insur-
gence of antiferromagnetic interactions. The results of zero-field ac
susceptibility measurements performed on the as-synthesized
form are comparable to those previously reported for Co(II)
single-chain magnets (see e.g. [206,207]). Upon desolvation and
resolvation, the single-chain magnetic properties are not restored,
a phenomenon already observed for the so-called ‘‘magnetic
sponges” (see e.g. [208–212]).
The 3D network of [Co4(OH)2(SO4)(1,4-BDT)2(H2O)4] [119] is
characterized by {Co4(OH)2(SO4)(tetrazolate)2(H2O)4} layers pil-
lared by the linkers and in which {Co4(OH)2(tetrazolate)2(H2O)4}
chains are bridged by sulphate anions. At 300 K vT (14.85 cm3
mol1 K) is higher than expected for four spin-only Co(II) ions.
Upon cooling, no long-range magnetic phase transitions take place.
 A. Tăbăcaru et al. / Coordination Chemistry Reviews 372 (2018) 1–30
MCl2 (M = Co, Ni)
Cd3[(Cd4Cl)3(BTT)8(DMF)12]2·Solv
MeOH, 80 °C, 30 d
Cd-BTT [203]
FeCl2
X[(Cd4Cl)(TTPP)]·Solv
DMF, N2, 85 °C, 4 h
PCN-527-Cd [205]
X = extraframework cations/anions
Scheme 9. The examples of metal-exchange in the synthesis of isoreticular MOFs reported in this review.
Fig. 18. Square-grid layers in poly(tetrazolate) CPs, as exemplified by the crystal
structure of [Co(btzbp)] (fractional coordinates from [214]), viewed in perspective
along the [0 0 1] direction. Horizontal direction, [1 1 0] . Atom colour code: carbon,
grey; cobalt, orange; nitrogen, blue. The hydrogen atoms have been omitted for
clarity.
The hydrothermal reaction of H2BPDT with cobalt(II) sulphate
heptahydrate afforded [Co5F2(BPDT)4(H2O)6]2H2O [119], in which
the fluoride anion derives from the fluoridric acid added in the
reaction medium as a mineralizer. The 3D crystal structure of this
CP consists of {Co5F2(tetrazolate)4(H2O)4} chains linked by l4-
BPDT2 ligands. vT is higher than expected for five spin-only Co
(II) ions at 300 K (13.19 cm3 mol–1 K) and decreases upon cooling
(to 1.38 cm3 mol–1 K at 2 K). Below 9 K, long-range magnetic order-
ing is observed: the Curie–Weiss constant of 64 K indicates anti-
ferromagnetic interactions between the Co(II) centers, together
with spin-orbit coupling.
7.2. Tritopic ligands
[Co3(OH)(SO4)(BTT)(H2O)4]3H2O [119] was isolated upon
reacting H3BTT with cobalt(II) sulphate heptahydrate. Its crystal
structure is composed by {Co3(l3-OH)(l3-SO4)2(l2-tetrazolate)3}
chains bridged by the BTT3 ligands within a 3D non porous frame-
work. At 300 K, vT is higher than expected for three spin-only Co
(II) ions (8.76 cm3 mol1 K) and decreases upon cooling (to 0.59
cm3 mol1 K at 2 K). At 10 K, weak ferromagnetic ordering is
observed.
Attempts to directly obtain the sodalitic-type framework Co-
BTT (Co3[(Co4Cl)3(BTT)8(DMF)12]2Solv) were unsuccessful. Inter-
estingly, Liao and coworkers [199] isolated it by metal exchange,
treating crystals of Cd-BTT with cobalt(II) chloride. As shown also
by the case-studies presented by this review (Scheme 9), metal
23
M3[(M4Cl)3(BTT)8(DMF)12]2·Solv
M-BTT [203]
X[(Fe4Cl)(TTPP)]·Solv
PCN-527-Fe [206]
X = extraframework cations/anions
exchange involving either nodes or metalated linkers in MOFs is
a rather popular approach [213] to synthesize isoreticular MOFs
with tailored functional properties. In Co-BTT, extra electron den-
sity was found near adjacent tetrazolates and described as partially
occupied Co(II) sites coordinated by tetrazolates and water mole-
cules. High-temperature single-crystal X-ray diffraction indicated
that, upon removal of solvent, the occupancy of these extra-
framework Co(II) sites increases and residual chloride anions rear-
range to fill the coordination vacancies left by the water molecules.
Co-BTT shows a BET specific surface area of 1157.5 m2/g and an
uptake of 1.8 wt H2 % at 77 K and 1 bar.
Another recent case of in situ preparation of a poly(tetrazolate)
ligand followed by formation of the CP is the [2+3] cycloaddition
reaction of 6,60 -dicyano-2,20 -bipyridine with sodium azide in the
presence of cobalt(II) perchlorate hexahydrate (Scheme 1), which
afforded [Co(btzbp)] [214]. In its crystal structure, octahedral
metal centers are bridged to four neighbours within 2D grid layers
(Fig. 18). [Co(btzbp)] exhibits spin canting (TN = 4.0 K) along with
metamagnetism (Hc = 300 G).
8. Iron poly(tetrazolates)
To the best of our knowledge, at the time of writing the only
ligands ever employed to synthesize iron(II) poly(tetrazolates)
are 1,4-H2BDT, H3BTT and H4TTPP. Contrarily to what reported
with poly(pyrazolates) (see e.g. [215,216]), no iron(III) poly(tetra-
zolates) have ever been prepared. As with the cobalt(II) derivatives
(see Section 7), also in the case of iron(II) poly(tetrazolates), the
presence of ligand-bridged Fe(II) chains in the crystal structure
prompted the investigation of magnetic properties [179,180]
(Table 2), with particular emphasis to spin-crossover phenomena,
due to their relevance in, e.g., molecular electronics, data storage,
display devices [217,218].
8.1. Ditopic ligands
Depending on the reaction conditions, coupling 1,4-H2BDT with
iron(II) chloride tetrahydrate afforded either [Fe2(1,4-H0.67BDT)3]
13H2O or [Fe3(ox)(1,4-H0.67BDT)3(H2O)2]10H2O9MeOH [219]. In
both cases ascorbic acid was added to the reaction medium to pre-
vent the oxidation of Fe(II) and the oxalate anion in the latter com-
pound was generated in situ, likely due to the oxidative
decomposition of ascorbic acid catalyzed by the iron/triethylamine
system [220,221]. The crystal structure of [Fe2(1,4-H0.67BDT)3]
13H2O, stable up to 250 °C, contains two independent metal cen-
ters, in high (Fe1) and low (Fe2) spin state, bridged by l2-
tetrazolates along {Fe(tetrazolate)3} chains characterized by the
three-bladed paddlewheels motif, as in [Co2(1,4-H0.67BDT)3]
20H2O [203]. Despite this similarity, as detailed in Section 7 in
the Co(II)-derivative each chain is bridged to four nearby ones by
planar and bent spacers with the formation of rectangular chan-
nels, while in the Fe(II)-derivative each chain is connected to six
24 A. Tăbăcaru et al. / Coordination Chemistry Reviews 372 (2018) 1–30

(a)
(b)

Fig. 19. Triangular channels in poly(tetrazolate) MOFs. (a) Portion of the crystal packing of [Fe2(1,4-H0.67BDT)3]13H2O (fractional coordinates from [219]) viewed in
perspective along the c-axis. An ordered model for the ligand has been adopted for clarity. (b) Portion of the crystal packing of [Fe2(1,4-H0.67BDT)3]4H2O (fractional
coordinates from [205]) viewed in perspective along the a-axis. Horizontal direction, [0 1 1]. Atom colour code: carbon, gray; iron, orange; nitrogen, blue. The solvent
molecules and hydrogen atoms have been omitted for clarity.

i-prOH/cy
[Fe2(1,4-H0.67BDT)3]·4H2O
3:1 v/v

160 °C, 3 d i-prOH/H2O

Fe(SO4)·7H2O + 1,4-H2BDT + NaSCN [Fe2(1,4-H0.67BDT)3]·13H2O
8:1 v/v

i-prOH/H2O [Fe2(1,4-H0.67BDT)3]·15H2O
5:3 v/v

Scheme 10. The different solvothermal conditions (in terms of solvent) employed to isolate the Fe(II) derivatives of 1,4-H2BDT [205].

adjacent ones by planar linkers within a 3D (4,6)-connected net-
work of wmf topology [204] featuring triangular channels
(Fig. 19a). Upon cooling from 298 to 100 K, the almost unchanged
Fe2-N average distance indicates no change in the spin state of this
metal centre, while the slight decrease of the Fe1-N average dis-
tance suggests the occurrence of incomplete spin-crossover
(SCO), as confirmed by magnetic measurements: the room temper-
ature value of vT (3.41 cm3 K mol1) is close to the value associ-
ated to HS Fe(II) ions in an octahedral ligand field.
Upon cooling down to 30 K, vT decreases due to a progressive
but incomplete SCO. Further decrease of vT below 30 K was
explained in terms of zero-field splitting and antiferromagnetic
interactions of the remaining HS Fe(II) ions. The crystal structure
of [Fe3(ox)(1,4-H0.67BDT)3(H2O)2]10H2O9MeOH [219] is charac-
terized by {Fe3(tetrazolate)6} linear units built up by l2-
tetrazolates. Adjacent trinuclear units are linked by l2-j2:j2-
oxalate anions along {Fe3(tetrazolate)3(ox)3} chains which are
bridged by the linkers within a 3D (4,6)-connected network featur-
ing square and triangular channels. These structural features are
preserved after solvent exchange (n-butanol vs. methanol). Both
solvates are unstable after thermal activation, possibly due to the
removal of coordinated water molecules. For the methanol solvate,
at 300 K vT (9.07 cm3 K mol1) is lower than expected for three HS
Fe(II) ions, suggesting that the central ion of the {Fe3(tetrazolate)6}
units is only partially in HS state. Upon cooling vT progressively
decreases (to 7.73 cm3 K mol1 at 150 K and 0.85 cm3 K mol1 at
2 K), which was ascribed to both antiferromagnetic interactions
propagating along the metal chains and magnetically anisotropic
HS Fe(II) ions. In the range 300–150 K, the not monotonic decrease
of vT suggested the coexistence of a small SCO process.
1,4-H2BDT was reacted also with iron(II) sulphate heptahydrate
under solvothermal conditions in different solvents (Scheme 10),
affording the three polymorphs [205] [Fe2(1,4-H0.67BDT)3]4H2O,
[Fe2(1,4-H0.67BDT)3]13H2O (the same phase described in the con-
comitant work by Liu et al. [219]), and [Fe2(1,4-H0.67BDT)3]15H2O.
As in [Fe2(1,4-H0.67BDT)3]13H2O, also in the crystal structure of
the other two MOFs {Fe(tetrazolate)3} chains are bridged to adja-
cent ones within 3D networks featuring 1D channels. Differences
in either hapticity or geometry of the ligands are responsible for
structural differences in the three cases: In [Fe2(1,4-H0.67BDT)3]
4H2O l2-jN1:jN2-tetrazolates impart a rhombohedral packing
of the chains (Fig. 19b) vs. the hexagonal one in [Fe2(1,4-
H0.67BDT)3]13H2O; in both cases, triangular channels are formed.
[Fe2(1,4-H0.67BDT)3]15H2O, isostructural to [Co2(1,4-H0.67BDT)3]
20H2O [203] (see Section 7), is characterized by rectangular chan-
nels. [Fe2(1,4-H0.67BDT)3]4H2O is stable up to 350 °C while, like
[Fe2(1,4-H0.67BDT)3]13H2O, also [Fe2(1,4-H0.67BDT)3]15H2O
decomposes starting from 250 °C. For [Fe2(1,4-H0.67BDT)3]4H2O,
at 300 K vT (4.14 cm3 K mol–1) is higher than expected for HS Fe
(II) ions located in an octahedral ligand field; upon cooling, it
remains constant down to 50 K, then it undergoes a sharp decrease
due to zero-field splitting of the S = 2 ground state of Fe(II). For
 A. Tăbăcaru et al. / Coordination Chemistry Reviews 372 (2018) 1–30
[Fe2(1,4-H0.67BDT)3]13H2O, different observations were carried
out vs. those published by Liu and coworkers [219]: vT decreases
from 4.02 cm3 K mol–1 at 300 K, suggestive of a mixed-spin popu-
lation, to 2.01 cm3 K mol–1 at 30 K, revealing a 50% HS-to-LS trans-
formation, as also supported by low-temperature structural
studies. Finally, for [Fe2(1,4-H0.67BDT)3]15H2O, vT suggests the
existance of a HS:LS = 1:2 population at 300 K (1.26 cm3 K mol–1),
while it steadily decreases to the diamagnetic (LS) form upon
cooling.
8.2. Tritopic ligands
The family of sodalite-type frameworks M-BTT also comprises
the iron(II)-based derivative Fe3[(Fe4Cl)3(BTT)8]222DMF32DMSO
11H2O (Fe-BTT) [222], which was isolated by reacting anhydrous
iron(II) chloride with H3BTT2HCl. Mössbauer spectroscopy on a
DMF-exchanged sample indicated the presence of HS Fe(II) ions
in different, solvent-influenced, local environments as well as
extra-framework Fe(II) ions. Methanol-exchanged Fe-BTT is stable
only up to 150 °C, which prevents complete evacuation. N2 adsorp-
tion at 77 K revealed BET and Langmuir specific surface areas of
2010 and 2200 m2/g, respectively. At 77 K, the H2 adsorption iso-
therm shows a steep rise corresponding to a zero-coverage isos-
teric heat of adsorption of 11.9 kJ/mol, leading to a total storage
capacity of 1.1 wt % (8.4 g/L) at 100 bar and 298 K. Powder neutron
diffraction at 4 K under different D2 loadings enabled individuation
of ten adsorption sites, the strongest ones near the framework Fe
(II) ions. Finally, the presence of exposed Fe(II) sites is responsible
for a selective adsorption of CO2 over N2, with uptake ratios of 30.7
or 10.8 wt % at 298 K and 0.1 or 1.0 bar, respectively.
8.3. Tetratopic ligands
Prompted by the not completely satisfactory catalytic perfor-
mance of PCN-527-Cd (see Section 6), Liu and coworkers [202] iso-
lated the Fe(II) analogue by metal-exchange of PCN-527-Cd with
iron(II) chloride (Scheme 2). Single-crystal X-ray diffraction and
EDS showed a 95% exchange of the Cd(II) ions with Fe(II) ions along
(a)
(b)
Fig. 20. Representation of the crystal structure of the first poly(tetrazolate) chromium MOF (fractional coordinates from [223]): the oxo-centered cluster (a); portion of the
crystal packing viewed in perspective along the [0 0 1] (b) and [1 0 0] (c) directions. Atom colour code: carbon, grey; chlorine, green; chromium, orange; nitrogen, blue;
oxygen, red. The skeleton of the ligand has been represented with a blue segment. The hydrogen atoms and clathrated solvent molecules have been omitted for clarity.
25
a single-crystal to single-crystal transformation. Due to the stron-
ger Lewis acidity of Fe(II) vs. Cd(II), the catalytic performance for
the deacetalization-Knoevenagel condensation reaction (Scheme 8)
improved: reaction of PCN-527-Fe with either dimethoxymethyl-
benzene or 4-bromobenzaldehyhde diethyl acetal (0.01:2 cata-
lyst:substrate, mol/mol) led to a conversion to the final product
as high as 100% after 12 h.
9. Other metal poly(tetrazolates)
This last section gathers the few poly(tetrazolate)-based coordi-
nation frameworks reported, at the time of writing, with chromium
(II), chromium(III), nickel(II), silver(I) and mercury(II).
Strange as it may appear, given the popularity of the poly(car-
boxylate) MOF MIL-53(Cr) (see e.g. [154]), the first chromium-
based MOFs built up with poly(azolate) ligands were reported only
rather recently by Kongpatpanich and coworkers [223]. The
authors isolated [Cr3O(1,4-HBDT)2(1,4-BDT)Cl3)]DMF by reacting
anhydrous chromium(II) chloride with 1,4-H2BDT. Not surprisingly
in view of the lability of Cr(II), the binding energy peak observed at
577.7 eV in the XPS spectrum of this MOF confirmed the +3 oxida-
tion state of the metal centre. The crystal structure consists of tri-
angular oxo-centered clusters (Fig. 20a) bridged by l4-1,4-BDT2
ligands within a 3D framework featuring two types of cavities,
namely: honeycomb (Fig. 20b) and rhombic (Fig. 20c) channels.
[Cr3O(1,4-HBDT)2(1,4-BDT)Cl3)]DMF is stable up to 300 °C. Upon
complete removal of the solvent molecules, it undergoes a reversi-
ble structural modification: in contact with a drop of DMF, it
restores the original crystal structure. The adsorption properties
of this MOF were studied with N2 and O2 at 77 K, and CO2 at
195 K. N2 adsorption revealed a BET specific surface area of 700
m2/g. The total N2 uptake was 235.8 mL/g at 100 kPa, vs. a total
O2 uptake of 243.6 mL/g at 18 kPa, and a total CO2 uptake of
181.3 mL/g at 101 kPa.
In different reaction conditions (Scheme 11), Kongpatpanich
and co-workers [223] isolated the Cr(II)-based MOF [Cr(1,4-BDT)
(DEF)]DEF. The binding energy peak at 576.5 eV in the XPS spec-
trum of a sample exposed to air highlighted the +3 oxidation state
(c)
26 A. Tăbăcaru et al. / Coordination Chemistry Reviews 372 (2018) 1–30

CrCl2, DMF
[CrIII3O(1,4-HBDT)2(1,4-BDT)Cl3)]·DMF
120 °C, 2 d
1,4-H2BDT
Cr(CH3CO2)2·2H2O, DEF
[CrII(1,4-BDT)(DEF)]·DEF
120 °C, 1 d

Scheme 11. The different solvothermal conditions employed to isolate the only known examples of Cr(III) and Cr(II) poly(tetrazolates) [223].

(a)

(b)

Fig. 21. Representation of the crystal structure of [Ag2(BTZPX)] (fractional coordinates from [137]): (a) portion of the 1-D ladder; (b) portion of the crystal packing viewed in
perspective along the [1 1 0] direction. Atom colour code: carbon, grey; nitrogen, blue; silver, orange. The hydrogen atoms have been omitted for clarity.

of chromium, clearly indicating the air-sensitivity of the as-
synthesized MOF. The colour change (from dark purple, to pink
and finally dark beige) observed upon heating from room temper-
ature to 180 °C was interpreted, on the basis of PXRD, in terms of
structural transformations. The adsorption properties were investi-
gated with N2 at 77 K, O2 at 77 and 298 K, and CO2 at 195 K. At 77
K, the two-step adsorption of O2 is reversible and the sample can
be reused without any marked decrease in the gas uptake, indicat-
ing the weak binding of O2 with the framework.
At 298 K, O2 adsorption revealed an irreversible type I isotherm
(with a total uptake of 15 mg/L), indicative of strong interactions
between the framework and the probe: IR spectroscopy on an
evacuated sample showed that, while the C@O stretching of
clathrated DEF molecules hosted in the channels disappears, the
C@O stretching of bound DEF molecules shifts from 1621 cm–1,
as in the as-synthesized sample, to 1631 cm–1. This occurrence
indicates partial breaking of the bonds between the solvent and
the metal centers prompted by the evacuation process, with the
formation of unsaturated metal sites potentially available for O2
binding.
The hydrothermal reaction of 1,4-H2BDT with nickel(II) sul-
phate hexahydrate yielded [Ni2(1,4-BDT)3]10.5H2O [119], which
is isomorphous to [Co2(1,4-H0.67BDT)3]20H2O [203] (Section 7)
and [Fe2(1,4-H0.67BDT)3]15H2O [205] (Section 8). High-
temperature single-crystal X-ray diffraction indicated that, upon
thermal activation, the water molecules bound to the metal cen-
ters are not removed. Temperature-dependent magnetic suscepti-
bility measurements showed that at 300 K vT (3.34 cm3 mol1 K)
is higher than expected for two spin-only Ni(II) ions and decreases
upon cooling (to 0.562 cm3 mol1 K at 2 K). No long-range mag-
netic ordering is observed.
The attempts carried out by Liao and coworkers to obtain a Ni
(II)-based sodalite-type framework isostructural to M-BTT (M =
Cu [167], Mn [186], Co and Cd [199]) by direct synthesis were
not successful. Nonetheless, the authors [199] prepared Ni-BTT in
the same way as they isolated Co-BTT, namely: by metal exchange,
upon exposing crystals of Cd-BTT to nickel(II) chloride in methanol
(Scheme 2). As in Co-BTT, extra electron density was found near
the tetrazolate rings and modelled as partially occupied Ni(II) sites
coordinated by tetrazolates, water molecules and chloride anions.
 A. Tăbăcaru et al. / Coordination Chemistry Reviews 372 (2018) 1–30 27

25 23,9 70 65,2

60
19,6
20
17,4 17,4
50
15 40

30
10
6,5 6,5 20 17,4 17,4

5
2,2 2,2 2,2 2,2 10

0 0
Zn Cd Cu Mn Co Fe Cr Ni Ag Hg di tri tetra
(a) (b)

Fig. 22. Statistical analysis on metal cation nature and ligand topicity in the coordination polymers and metal-organic frameworks reported in this review: (a) frequency with
which a given metal cation has been used. (b) Frequency with which the di-, tri- and-tetratopic poly(tetrazolates) of Charts 1 and 2 have been employed.

100 100 1,4

90
88,6 78,3
90 90 80
1,2,4
80 80 70
70 70
60
60 60
2,3 50
50 50
40
40 40
1,2,3
30
30 30
20 20 20 14,1
9,8 1,3 7,6
10 10 10
1,6 1,2
0 0 0
1D 2D 3D
(a) (b) (c)

Fig. 23. Statistical analysis on ligand hapticity and framework dimensionality of the coordination polymers and metal-organic frameworks reported in this review (see also
Table 1): (a) percentage of l2-, l3- and l4-coordination. Only the compounds in which chelation was not observed were taken into consideration. (b) Percentage of the
different l2- and l3-coordination modes. Only the compounds in which chelation was not observed were taken into consideration. (c) Percentage of 1D, 2D and 3D
frameworks.

High-temperature single-crystal X-ray diffraction indicated that,
upon solvent removal, the occupancy of these extra-framework
Ni(II) sites increases. As assessed by N2 adsorption at 77 K, Ni-
BTT shows a BET specific surface area of 927.1 m2/g. The uptake
of H2 at 77 K and 1 bar amounts to 1.5 wt %.
Reaction of 1,4-H2BDT with silver(I) nitrate yielded [Ag2(1,4-
BDT)] [163], stable up to 380 °C. In its crystal structure, the ligands
use all the nitrogen atoms to bridge eight tetrahedral Ag(I) ions,
forming a 3D non porous framework. The reactivity of [Ag2(1,4-
BDT)] was tested towards a number of Lewis bases: while it proved
chemically inert with pyrazine, treated with PPh3 it yielded the
dinuclear complex [(PPh3)Ag]2(1,4-BDT).
Coupling H2BTZPX to silver(I) nitrate afforded [Ag2(BTZPX)]
[137], stable up to 370 °C. The crystal structure is characterized
by trigonal Ag(I) ions bridged by l6-ligands adopting a chair con-
formation. In [Ag2(BTZPX)], 1D ladders (Fig. 21a) are intercon-
nected by the ligands within 2D (3,6)-connected corrugated
layers (Fig. 21b). As with the Zn(II) derivative (see Section 3),
UV–Vis absorption revealed a bathochromic shift in the absorption
of [Ag2(BTZPX)] with respect to that of the main chromophore of
the ligand.
Coupling H2BTZPX to mercury(II) acetate afforded [Hg(BTZPX)]
[137], stable up to 250 °C. Tetrahedral Hg(II) ions are linked by
N1,N3-bridging tetrazolates along 1D chains in which mer-
28 A. Tăbăcaru et al. / Coordination Chemistry Reviews 372 (2018) 1–30
curophilic interactions [224] are reasonably at work. The chains are
interconnected via N1,N4-bridging tetrazolates within corrugated
double layers. Solid state UV–Vis absorption revealed a bathochro-
mic shift in the absorption of [Hg(BTZPX)] with respect to that of
the main chromophore of the ligand.
Interaction of H2ptp with mercury(II) acetate led to [Hg(H2ptp)
Cl2]2H2O [142]. Tetrahedral Hg(II) ions are bridged by l2-spacers
along 1-D chains, which are interlaced by parallel water helices
formed through hydrogen-bond interactions. Circular dichroism
showed negative Cotton effects at 211, 267 and 350 nm and posi-
tive Cotton effects at 250 and 285 nm, indicating the homochiral
nature of this CP. Upon excitation at 389 nm, [Hg(H2ptp)Cl2]
2H2O exhibits a strong fluorescence emission centered at 476
nm, slightly blue-shifted with respect to that of the ligand (490
nm, kex = 360 nm), an occurrence ascribed to intraligand transi-
tions (p-p⁄ or n-p⁄) upon ligand coordination to the Hg(II) ions.
10. Conclusions and outlook
The examples presented in this review witness the richness in
the chemistry, structure and function of poly(5-substituted tetra-
zolate) coordination frameworks: more than ninety among coordi-
nation polymers and metal-organic frameworks (Table 1) could be
successfully prepared and characterized in the past fifteen years by
combining a non negligible number of transition metal ions
[namely: zinc(II), copper(I,II), manganese(II), cadmium(II), cobalt
(II), iron(II), chromium(II,III), nickel(II), silver(I) and mercury(II)]
with a library of 5-substituted bis-, tris- and tetrakis(tetrazolate)
ligands counting twenty-six entries (Charts 1 and 2). A strong pref-
erence has been given to Zn(II), Cd(II), Mn(II) and Cu(II) for the
nodes (Table 1 and Fig. 22a) and to ditopic ligands as spacers
(Chart 1 and Fig. 22b).
The brief description we have provided of the main structural
aspects demonstrates that the combination of poly(tetrazolate)
linkers, potentially showing different coordination modes (Chart 4),
with metal centres possessing known stereochemistry is a key fac-
tor to build ad hoc polymeric networks ranging from 1-D single- or
double-chains to 2-D layers and 3-D frameworks of different
topology.
Restricting the analysis only to the cases in which chelation was
not observed, in the compounds presented above tetrazolate
shows l2-coordination in the majority of cases (Fig. 23a), with a
marked preference for the 2,3-coordination mode (Fig. 23b), fol-
lowed by l3- and l4-coordination (Fig. 23a and b). A few cases
exist in which tetrazolate is mono-dentate. As for the polymer
dimensionality, disregarding the contribution of non bonding-
interactions, most of the derivatives reported above are character-
ized by 3D frameworks (Fig. 23c).
This structural diversity is mirrored by a wide range of func-
tional properties (Table 2). The extensive work carried out through
the years on poly(tetrazolate) frameworks has contributed to
knowledge advancements on the chemical and structural proper-
ties a material should possess for H2 adsorption, with specific ref-
erence to the presence of exposed metal sites, catalysis and
magnetism, as well as on the mechanisms beyond luminescence.
A significant contribution to the development of poly(tetrazo-
late) coordination frameworks has been certainly provided by the
straightforward synthesis of poly(5-substituted tetrazole) ligands
through the Demko-Sharpless protocol (Chart 3), at times carried
out in situ (Scheme 1), and by the different reaction conditions,
ranging from solvent evaporation at room temperature to reflux,
hydrothermal or solvothermal synthesis and metal exchange
(Scheme 2), which have been explored. Schemes 2–6 and 9–11
show that, upon changing metal salt, solvent, temperature or a
combination of these factors, it is possible to isolate different
derivatives of the same metal cation and ligand. Advancements
have been obtained in the fields of ligand in situ synthesis, followed
by self-assembly of the coordination framework, and of CP/MOF
synthesis by metal exchange. Also the field of thermal activation
has benefited from the numerous tests carried out on poly(tetrazo-
late) MOFs.
As shown by this review, many research groups have been and
are presently involved in the design, synthesis and study of
tetrazole-based coordination frameworks. Due to the straightfor-
ward access to this class of ligands, their polymeric derivatives
are continuously isolated by modulating reaction conditions, stere-
ochemical preferences of the metal ions and/or size and shape of
the tetrazolate spacers. The examples presented can be of inspira-
tion for the preparation and characterization of new (poly)tetrazo-
late spacers and coordination frameworks: one of the main
challenges in the realm of (porous) coordination polymers is the
isolation of the desired material for a given application, for which
efforts in design and synthesis are still required. Moreover, the
examples gathered within this review can inspire, on already
known poly(tetrazolates), further characterization of the func-
tional properties.
Summarizing, additional investigation on poly(tetrazolate)
coordination polymers and metal-organic frameworks will
undoubtedly contribute to the chemistry of these two classes of
compounds and of metal poly(azolates) in general, as well as to
the progress in developing practical applications.
Acknowledgements
Some of the compounds described in this review are the result
of the efforts and the enthusiasm of our colleagues and collabora-
tors, to whom we are deeply indebted. Acknowledgements are also
due to the Universities of Insubria, Camerino and Galati for finan-
cial support.
References
[1] A. Morsali, L. Hashemi, Main Group Metal Coordination Polymers: Structures
and Nanostructures, Wiley Scrivener Publishing, 2017.
[2] S.R. Batten, S.M. Neville, D.R. Turner, Coordination Polymers: Design, Analysis
and Application, Springer, New York, 2010.
[3] M.-C. Hong, L. Chen, Design and Construction of Coordination Polymers, John
Wiley & Sons, Hoboken, 2009.
[4] S. Kaskel (Ed.), The Chemistry of Metal-Organic Frameworks: Synthesis,
Characterization, and Applications, Wiley-VCH, Weinheim, Germany, 2016.
[5] Y. Cui, B. Li, H. He, W. Zhou, B. Chen, G. Qian, Acc. Chem. Res. 49 (2016) 483.
[6] L.R. MacGillivray, C.M. Lukehart, Metal-Organic Framework Materials, Wiley-
VCH, Weinheim, Germany, 2014.
[7] D. Farrusseng, Metal-Organic Frameworks: Applications from Catalysis to Gas
Storage, Wiley-VCH, New York, 2011.
[8] M. Schröder, Functional Metal-Organic Frameworks: Gas Storage, Springer-
Verlag, Berlin, Separation and Catalysis, 2010.
[9] C. Janiak, J.K. Vieth, New J. Chem. 34 (2010) 2366.
[10] Y. Zhang, S. Yuan, G. Day, X. Wang, X. Yang, H.-C. Zhou, Coord. Chem. Rev. 354
(2018) 28.
[11] W.P. Lustig, S. Mukherjee, N.D. Rudd, A.V. Desai, J.g Li, S.K. Ghosh, Chem. Soc.
Rev. 46 (2017) 3242.
[12] J. Heine, K. Müller-Buschbaum, Chem. Soc. Rev. 42 (2013) 9232.
[13] Y. Cui, Y. Yue, G. Qian, B. Chen, Chem. Rev. 112 (2012) 1126.
[14] K. Binnemans, Chem. Rev. 109 (2009) 4283.
[15] M.D. Allendorf, C.A. Bauer, R.K. Bhakta, R.J.T. Houk, Chem. Soc. Rev. 38 (2009)
1330.
[16] I. Stassen, N. Burtch, A. Talin, P. Falcaro, M. Allendorf, R. Ameloot, Chem. Soc.
Rev. 46 (2017) 3185.
[17] L. Sun, M.G. Cambell, M. Dincă, Angew. Chem. Int. Ed. 55 (2016) 3566.
[18] P. Ramaswamy, N.E. Wong, G.K.H. Shimizu, Chem. Soc. Rev. 43 (2014) 5913.
[19] S. Horike, D. Umeyama, S. Kitagawa, Acc. Chem. Res. 46 (2013) 2376.
[20] G. Givaja, P. Amo-Ochoa, C.J. Gómez-García, F. Zamora, Chem. Soc. Rev. 41
(2012) 115.
[21] A.S. Lytvynenko, S.V. Kolotilov, Theor. Exp. Chem. 52 (2016) 197.
[22] K.A. McDonald, S. Seth, A.J. Matzger, Cryst. Growth Des. 15 (2015) 5963.
[23] S.M.J. Rogge, A. Bavykina, J. Hajek, H. Garcia, A.I. Olivos-Suarez, A. Sepúlveda-
Escribano, A. Vimont, G. Clet, P. Bazin, F. Kapteijn, M. Daturi, E.V. Ramos-
Fernandez, F.X. Llabrés i Xamena, V. Van Speybroeck, J. Gascon Chem. Soc.
Rev. 46 (2017) 3134.
 A. Tăbăcaru et al. / Coordination Chemistry Reviews 372 (2018) 1–30 29

[24] L. Zhu, X.-Q. Liu, H.-L. Jiang, L.-B. Sun, Chem. Rev. 117 (2017) 8129. [80] K. Biradha, A. Ramanan, J.J. Vittal, Cryst. Growth Des. 9 (2009) 2969.
[25] V. Stavila, A.A. Talin, M.D. Allendorf, Chem. Soc. Rev. 43 (2014) 6011. [81] J.A. Bladin, Ber. Dtsch. Chem. Ges. 18 (1885) 1544.
[26] J. Liu, L. Chen, H. Cui, J. Zhang, L. Zhang, C.-Y. Su, Chem. Soc. Rev. 43 (2014) [82] F.R. Benson, Chem. Rev. 41 (1947) 1.
6011. [83] F.R. Benson, Heterocycl. Compd. 8 (1967) 1.
[27] J. Gascon, A. Corma, F. Kapteijnand, F.X. Llabrés I Xamena, ACS Catal. 4 (2013) [84] R.N. Butler, Adv. Heterocycl. Chem. 21 (1977) 323.
361. [85] G.I. Koldobskii, V.A. Ostrovskii, V.S. Popavskii, Chem. Heterocycl. Compd. 17
[28] J. Canivet, D. Farrusseng, Application of metal–organic frameworks in fine (1981) 965–988.
chemical synthesis, in: K. Wilson, A.F. Lee (Eds.), Heterogeneous Catalysts for [86] S.J. Wittenberger, Org. Prep. Proced. Int. 26 (1994) 499.
Clean Technology: Spectroscopy, Design, and Monitoring, Wiley-VCH Verlag [87] V.A. Ostrovskii, G.I. Goldobskii, Russ. Chem. Rev. 63 (1994) 797.
GmbH & Co. KGaA, Weinheim, Germany, 2013. [88] R.N. Butler, in: Comprehensive Heterocyclic Chemistry II, Pergamon Press,
[29] M. Yoon, R. Srirambalaji, K. Kim, Chem. Rev. 112 (2012) 1196. Oxford, 1996, pp. 621–678.
[30] G. Mínguez Espallargas, E. Coronado, Chem. Soc. Rev. 47 (2018) 533. [89] D. Moderhack, Adv. Synth. Catal. 340 (1998) 687–709.
[31] M.C. Munoz, J.A. Real, Spin-Crossover Materials: Properties and Applications, [90] V.A. Ostrovskii, E.A. Popova, R.E. Trifonov, Adv. Heterocycl. Chem. 123 (2017)
Chapter 4, John Wiley & Sons, Chichester, 2013. 1–62.
[32] D.-F. Weng, Z.-M. Wang, S. Gao, Chem. Soc. Rev. 40 (2011) 3157. [91] P.N. Gaponik, S.V. Voitekhovich, O.A. Ivashkevich, Russ. Chem. Rev. 75 (2006)
[33] D.R. Talham, M.W. Meisel, Chem. Soc. Rev. 40 (2011) 3356. 507.
[34] M. Kurmoo, Chem. Soc. Rev. 38 (2009) 1353. [92] E.A. Popova, R.E. Trifonov, V.A. Ostrovskii, ARKIVOC i (2012) 45.
[35] H. Li, K. Wang, Y. Sun, C.T. Lollar, J. Li, H.-C. Zhou, Mater. Today 21 (2018) 108. [93] H. Singh, A.S. Chawla, V.K. Kapoor, D. Paul, R.K. Malhotra, Prog. Med. Chem. 17
[36] N.S. Bobbitt, M.L. Mendonca, A.J. Howarth, T. Islamoglu, J.T. Hupp, O.K. Farha, (1980) 151.
R.Q. Snurr, Chem. Soc. Rev. 46 (2017) 3357. [94] V.A. Ostrovskii, R.E. Trifonov, E.A. Popova, Russ. Chem. Bull. 61 (2012)
[37] K. Adil, Y. Belmabkhout, R.S. Pillai, A. Cadiau, P.M. Bhatt, A.H. Assen, G. 768.
Maurin, M. Eddaoudi, Chem. Soc. Rev. 46 (2017) 3402. [95] J. Roh, K. Vávrová, A. Hrabálek, Eur. J. Org. Chem. 2012 (2012) 6101.
[38] Z. Kang, L. Fana, D. Sun, J. Mater. Chem. A 5 (2017) 10073. [96] L.-L. Dai, H.ui-Z. Zhang, S. Nagarajan, S. Rasheed, C.-H. Zhou, Med Chem.
[39] Y. He, W. Zhou, G. Qian, B. Chen, Chem. Soc. Rev. 43 (2014) 5657. Commun. 6 (2015) 147.
[40] J. Canivet, A. Fateeva, Y. Guo, B. Coasne, D. Farrusseng, Chem. Soc. Rev. 43 [97] S. Zhang, Q. Yang, X. Liu, X. Qu, Q. Wei, G. Xie, S. Chen, S. Gao, Coord. Chem.
(2014) 5594. Rev. 307 (2016) 292.
[41] H. Wu, Q. Gong, D.H. Olson, J. Li, Chem. Rev. 12 (2012) 836. [98] Z.P. Demko, K.B. Sharpless, Angew. Chem. Int. Ed. 41 (2002) 2113.
[42] M.P. Suh, H.J. Park, T.K. Prasad, D.-W. Lim, Chem. Rev. 112 (2012) 782. [99] F. Himo, Z.P. Demko, L. Noodleman, K.B. Sharpless, J. Am. Chem. Soc. 124
[43] K. Sumida, D.L. Rogow, J.A. Mason, T.M. McDonald, E.D. Bloch, Z.R. Herm, T.-H. (2002) 12210.
Bae, J.R. Long, Chem. Rev. 112 (2012) 724. [100] Z.P. Demko, K.B. Sharpless, J. Org. Chem. 66 (2001) 7945.
[44] W.P. Lustig, S. Mukherjee, N.D. Rudd, A.V. Desai, J. Li, S.K. Ghosh, Chem. Soc. [101] J. Catalan, J.L.M. Abboud, J. Elguero, Adv. Heterocycl. Chem. 41 (1987) 187.
Rev. 46 (2017) 3242. [102] A. von Zelewsky, Stereochemistry of Coordination Compounds, Wiley, 1996.
[45] Z. Hu, B.J. Deibert, J. Li, Chem. Soc. Rev. 43 (2014) 5815. [103] M. Gerloch, E.C. Constable, Transition Metal Chemistry: The Valence Shell in
[46] L.E. Kreno, K. Leong, O.K. Farha, M. Allendorf, R.P. Van Duyne, J.T. Hupp, Chem. d-Block Chemistry, Wiley, 1994.
Rev. 112 (2012) 1105. [104] V.W.-W. Yam, V.K.-M. Au, S.Y.-L. Leung, Chem. Rev. 115 (2015) 7589.
[47] M.-X. Wu, Y.-W. Yang, Adv. Mater. 29 (2017) 1606134. [105] V.W.-W. Yam, K.M.-C. Wong, Chem. Commun. 47 (2011) 11579.
[48] J.D. Rocca, D. Liu, W. Lin, Acc. Chem. Res. 44 (2011) 957. [106] A. Barbieri, G. Accorsi, N. Armaroli, Chem. Commun. (2008) 2185.
[49] P. Horcajada, T. Chalati, C. Serre, B. Gillet, C. Sebrie, T. Baati, J.F. Eubank, D. [107] N.S. Bobbitt, J. Chen, R.Q. Snurr, J. Phys. Chem. C 120 (2016) 27328.
Heurtaux, P. Clayette, C. Kreuz, J.-S. Chang, Y.K. Hwang, V. Marsaud, P.-N. [108] J. Sculley, D. Yuan, H.-C. Zhou, Energy Environ. Sci. 4 (2011) 2721.
Bories, L. Cynober, S. Gil, G. Férey, P. Couvreur, R. Gref, Nat. Mat. 9 (2010) 172. [109] G.D. Berry, S.M. Aceves, Energy Fuels 12 (1998) 49.
[50] M. Giménez-Marqués, T. Hidalgo, C. Serre, P. Horcajada, Coord. Chem. Rev. [110] C. Jiang, Z. Yu, C. Jiao, S. Wang, J. Li, Z. Wang, Y. Cui, Eur. J. Inorg. Chem. (2004)
307 (2016) 342. 4669.
[51] P. Horcajada, R. Gref, T. Baati, P.K. Allan, G. Maurin, P. Couvreur, R.E. Morris, C. [111] M. O’Keeffe, B.G. Hyde, Crystal Structures I: Patterns and Symmetry, Am.
Serre, Chem. Rev. 112 (2012) 1232. Mineral. Assoc, Washington, DC, 1996.
[52] S. Keskin, S. Kızılel, Ind. Eng. Chem. Res. 50 (2011) 1799. [112] S. Wang, Coord. Chem. Rev. 215 (2001) 79.
[53] B. Li, M. Chrzanowski, Y. Zhang, S. Ma, Coord. Chem. Rev. 307 (2016) 106. [113] Y.-W. Li, H.-Y. Ma, S.-N. Wang, J. Xu, D.-C. Li, J.-M. Dou, X.-H. Bu, RSC Adv. 5
[54] W. Lu, Z. Wei, Z.-Y. Gu, T.-F. Liu, J. Park, J. Tian, M. Zhang, Q. Zhang, T. Gentle (2015) 88809.
III, M. Bosch, H.-C. Zhou, Chem. Soc. Rev. 43 (2014) 5561. [114] X.M. Chen, M.L. Tong, Acc. Chem. Res. 40 (2007) 162.
[55] V. Guillerm, D. Kim, J.F. Eubank, R. Luebke, X. Liu, K. Adil, M.S. Lah, M. [115] X.M. Zhang, Coord. Chem. Rev. 249 (2005) 1201.
Eddaoudi, Chem. Soc. Rev. 43 (2014) 6141. [116] M. Dincă, A.F. Yu, J.R. Long, J. Am. Chem. Soc. 128 (2006) 8904.
[56] H.-L. Jiang, T.A. Makal, H.-C. Zhou, Coord. Chem. Rev. 257 (2013) 2232. [117] E.O. John, R.D. Willett, B. Scott, R.L. Kirchmeier, J.M. Shreeve, Inorg. Chem. 28
[57] D.J. Tranchemontagne, J.L. Mendoza-Cortés, M. O’Keeffe, O.M. Yaghi, Chem. (1989) 893.
Soc. Rev. 38 (2009) 1257. [118] A. Uzun, S. Keskin, Progr. Surf. Sci. 89 (2014) 56.
[58] J.D. Evans, K.E. Jelfs, G.M. Day, C.J. Doonan, Chem. Soc. Rev. 46 (2017) 3286. [119] W. Ouellette, K. Darling, A. Prosvirin, K. Whitenack, K.R. Dunbar, J. Zubieta,
[59] G. Maurin, Role of molecular simulations in the field of MOFs, in: S. Kaskel Dalton Trans. 40 (2011) 12288.
(Ed.), The Chemistry of Metal–Organic Frameworks: Synthesis, [120] J.-R. Li, Y. Tao, Q. Yu, X.-H. Bu, Chem. Commun. (2007) 1527.
Characterization, and Applications, Wiley-VCH, Weinheim, Germany, 2016. [121] O. Delgado-Friedrichs, M. O’Keeffe, O.M. Yaghi, Phys. Chem. Chem. Phys. 9
[60] F.-X. Coudert, A.H. Fuchs, Coord. Chem. Rev. 307 (2016) 211. (2007) 1035.
[61] J. Jiang, R. Babarao, Z. Hu, Chem. Soc. Rev. 40 (2011) 3599. [122] F. Kettner, C. Worch, J. Moellmer, R. Gläser, R. Staudt, H. Krautscheid, Inorg.
[62] T. Duren, Y.-S. Bae, R.Q. Snurr, Chem. Soc. Rev. 38 (2009) 1237. Chem. 52 (2013) 8738.
[63] L.M. Aguirre-Díaz, D. Reinares-Fisac, M. Iglesias, E. Gutiérrez-Puebla, F. [123] H. Yang, X.W. He, F. Wang, Y. Kang, J. Zhang, J. Mater. Chem. 22 (2012) 21849.
Gándara, N. Snejko, M.A. Monge, Coord. Chem. Rev. 335 (2017) 1. [124] W.C. Song, J.R. Li, P.C. Song, Y. Tao, Q. Yu, X.L. Tong, X.H. Bu, Inorg. Chem. 48
[64] B. Li, H.-M. Wen, Y. Cui, G. Qian, B. Chen, Progr. Polym. Sci. 48 (2015) 40. (2009) 3792.
[65] J.-C.G. Bünzli, J. Coord. Chem. 67 (2014) 3706. [125] S.R. Caskey, A.J. Matzger, Inorg. Chem. 47 (2008) 7942.
[66] F.A.A. Paz, J. Klinowski, S.M.F. Vilela, J.P.C. Tomé, J.A.S. Cavaleiro, J. Rocha, [126] Y.-W. Li, S.-J. Liu, T.-L. Hu, X.-H. Bu, Dalton Trans. 43 (2014) 11470.
Chem. Soc. Rev. 41 (2012) 1088. [127] J.-R. Li, Y. Tao, Q. Yu, X.-H. Bu, H. Sakamoto, S. Kitagawa, Chem. Eur. J. 14
[67] A.Y. Robin, K.M. Fromm, Coord. Chem. Rev. 250 (2006) 2127. (2008) 2771.
[68] P.-Q. Liao, C.-T. He, D.-D. Zhou, J.-P. Zhang, X.-M. Chen, Porous metal azolate [128] N.W. Ockwig, O. Delgado-Friedrichs, M. O’Keeffe, O.M. Yaghi, Acc. Chem. Res.
frameworks, in: S. Kaskel (Ed.), The Chemistry of Metal-Organic Frameworks: 38 (2005) 176.
Synthesis, Characterization, and Applications, Wiley-VCH, Weinheim, [129] Z. Han, W. Shi, P. Cheng, Chin. Chem. Lett. (2017), https://doi.org/10.1016/j.
Germany, 2016. cclet.2017.09.050.
[69] C. Pettinari, A. Tabacaru, S. Galli, Coord. Chem. Rev. 307 (2016) 1. [130] K.K. Bisht, B. Parmar, Y. Rachuri, A.C. Kathalikattilad, E. Suresh,
[70] M. Eddaoudi, D.F. Sava, J.F. Eubank, K. Adil, V. Guillerm, Chem. Soc. Rev. 44 CrystEngComm 17 (2015) 5341.
(2015) 228. [131] G. Nickerl, A. Henschel, R. Grünker, K. Gedrich, S. Kaskel, Chem. Ing. Tech. 83
[71] J.-P. Zhang, Y.-B. Zhang, J.-B. Lin, X.-M. Chen, Chem. Rev. 112 (2012) 1001. (2011) 90.
[72] M.P. Suh, H.J. Park, T.K. Prasad, D.-W. Lim, Chem. Rev. 112 (2012) 787. [132] R. Matsuda, R. Kitaura, S. Kitagawa, Y. Kubota, R.V. Belosludov, T.C. Kobayashi,
[73] G. Aromí, L.A. Barrios, O. Roubeau, P. Gamez, Coord. Chem. Rev. 255 (2011) H. Sakamoto, T. Chiba, M. Takata, Y. Kawazoe, Y. Mita, Nature 436 (2005) 238.
485. [133] X.-L. Tong, D.-Z. Wang, T.-L. Hu, W.-C. Song, Y. Tao, X.-H. Bu, Cryst. Growth
[74] S.Q. Bai, D.J. Young, T.S. Hor, Chem. Asian J. 6 (2011) 292. Des. 9 (2009) 2280.
[75] H. Zhao, Z.-R. Qu, H.-Y. Ye, R.-G. Xiong, Chem. Soc. Rev. 37 (2008) 84. [134] L. Shen, J. Yang, G.-W. Yang, Q.-Y. Li, X.-Y. Tang, F. Zhou, Z.-F. Miao, J.-N. Jin,
[76] P.J. Steel, Coord. Chem. Rev. 106 (1990) 227. W. Shen, Inorg. Chim. Acta 370 (2011) 150.
[77] K.J. Gagnon, H.P. Perry, A. Clearfield, Chem. Rev. 112 (2012) 1034. [135] J.-J. Wang, L. Gou, H.-M. Hu, Z.-X. Han, D.-S. Li, G.-L. Xue, M.-L. Yang, Q.-Z. Shi,
[78] S.R. Batten, N.R. Champness, X.-M. Chen, J. Garcia-Martinez, S. Kitagawa, L. Cryst. Growth Des. 7 (2007) 1514.
Ohrstrom, M. O’Keeffe, M.P. Suh, J. Reedijk, Pure Appl. Chem. 85 (2013) 1715. [136] D.-Z. Wang, Polyhedron 35 (2012) 142.
[79] S.R. Batten, N.R. Champness, X.-M. Chen, J. Garcia-Martinez, S. Kitagawa, L. [137] E. Lavigna, N. Xhaferaj, A. Tabacaru, M. Lamperti, L. Nardo, M. Mella, C.
Öhrström, M. O’Keeffe, M.P. Suh, J. Reedijk, CrystEngComm 14 (2012) 3001. Pettinari, S. Galli, Cryst. Growth Des. 16 (2016) 6390.
30 A. Tăbăcaru et al. / Coordination Chemistry Reviews 372 (2018) 1–30
[138] A. Tabacaru, C. Pettinari, N. Masciocchi, S. Galli, F. Marchetti, M. Angjellari,
Inorg. Chem. 50 (2011) 11506.
[139] A. Tabacaru, C. Pettinari, F. Marchetti, S. Galli, N. Masciocchi, Cryst. Growth
Des. 14 (2014) 3142.
[140] Z.-Y. Wang, J.-H. Chen, L.-F. Zhao, W.-H. Zhang, G. Yang, Transition Met.
Chem. 36 (2011) 731.
[141] T.-L. Hu, Y. Tao, Z. Chang, X.-H. Bu, Inorg. Chem. 50 (2011) 10994.
[142] Y.-W. Li, Y. Tao, L.-F. Wang, T.-L. Hu, X.-H. Bu, RSC Adv. 2 (2012) 4348.
[143] G.-S. Yang, M.-N. Li, S.-L. Li, Y.-Q. Lan, W.-W. He, X.-L. Wang, J.-S. Qin, Z.-M.
Su, J. Mater. Chem. 22 (2012) 17947.
[144] C. Tang, S. VanSlyke, Appl. Phys. Lett. 51 (1987) 913.
[145] Q. Lin, T. Wu, S.-T. Zheng, X. Bu, P. Feng, J. Am. Chem. Soc. 134 (2012)
784.
[146] I. Boldog, K.V. Domasevitch, J. Sanchiz, P. Mayer, C. Janiak, Dalton Trans. 43
(2014) 12590.
[147] O.V. Dolomanov, A.J. Blake, N.R. Champness, M. Schröder, J. Appl. Crystallogr.
36 (2003) 1283.
[148] R.-B. Lin, S. Xiang, H. Xing, W. Zhou, B. Chen, Coord. Chem. Rev. (2017),
https://doi.org/10.1016/j.ccr.2017.09.027.
[149] G. Xu, P. Nie, H. Dou, B. Ding, L. Li, X. Zhang, Mater. Today 20 (2017) 191.
[150] H. Wang, Q.-L. Zhu, R. Zou, Q. Xu, Chem 2 (2017) 52.
[151] H. Zhang, J. Nai, L. Yu, X.W. Lou, Joule 1 (2017) 77.
[152] N.S. Bobbitt, M.L. Mendonca, A.J. Howarth, T. Islamoglu, J.T. Hupp, O.K. Farha,
R.Q. Snur, Chem. Soc. Rev. 46 (2017) 3357.
[153] T. Loiseau, C. Serre, C. Huguenard, G. Fink, F. Taulelle, M. Henry, T. Bataille, G.
Férey, Chem. Eur. J. 10 (2004) 1373.
[154] C. Serre, F. Millange, C. Thouvenot, M. Noguès, G. Marsolier, D. Louër, G. Férey,
J. Am. Chem. Soc. 124 (2002) 13519.
[155] F. Millange, N. Guillou, M.E. Medina, G. Férey, A. Carlin-Sinclair, K.M. Golden,
R.I. Walton, Chem. Mater. 22 (2010) 4237.
[156] C. Pettinari, A. Tabacaru, I. Boldog, K.V. Domasevitch, S. Galli, N. Masciocchi,
Inorg. Chem. 51 (2012) 5235.
[157] S. Galli, N. Masciocchi, V. Colombo, A. Maspero, G. Palmisano, F.J. López-
Garzón, M. Domingo-García, I. Fernández-Morales, E. Barea, J.A.R. Navarro,
Chem. Mater. 22 (2010) 1664.
[158] V. Colombo, C. Montoro, A. Maspero, G. Palmisano, N. Masciocchi, S. Galli, E.
Barea, J.A.R. Navarro, J. Am. Chem. Soc. 134 (2012) 12830.
[159] A. Demessence, J.R. Long, Chem. Eur. J. 16 (2010) 5902.
[160] G. Férey, Dalton Trans. 45 (2016) 4073.
[161] K. Sumida, M.L. Foo, S. Horike, J.R. Long, Eur. J. Inorg. Chem. (2010) 3739.
[162] T. Devic, P. Horcajada, C. Serre, F. Salles, G. Maurin, B. Moulin, D. Heurtaux, G.
Clet, A. Vimont, J.-M. Grenèche, B. Le Ouay, F. Moreau, E. Magnier, Y.
Filinchuk, J. Marrot, J.-C. Lavalley, M. Daturi, G. Férey, J. Am. Chem. Soc. 132
(2010) 1127.
[163] A. Maspero, S. Galli, V. Colombo, G. Peli, N. Masciocchi, S. Stagni, E. Barea, J.A.
R. Navarro, Inorg. Chim. Acta 362 (2009) 4340.
[164] P. Cui, L. Ren, Z. Chen, H. Hu, B. Zhao, W. Shi, P. Cheng, Inorg. Chem. 51 (2012)
2303.
[165] E.J. Carrington, I.J. Vitórica-Yrezábal, L. Brammer, Acta Crystallogr. B B70
(2014) 404.
[166] P.M. Mazaj, V. Kaučič, N. Zabukovec Logar, Acta Chim. Slov. 63 (2016) 440.
[167] M. Dinca, W.S. Han, Y. Liu, A. Dailly, C.M. Brown, J.R. Long, Angew. Chem. Int.
Ed. 46 (2007) 1419.
[168] D. Britt, D. Tranchemontagne, O.M. Yaghi, Proc. Natl. Acad. Sci. U.S.A. 105
(2008) 11623.
[169] S. Ma, H.-C. Zhou, J. Am. Chem. Soc. 128 (2006) 11734.
[170] V. Colombo, S. Galli, H.J. Choi, G.D. Han, A. Maspero, G. Palmisano, N.
Masciocchi, J.R. Long, Chem. Sci. 2 (2011) 1311.
[171] A. Demessence, D.M. D’Alessandro, M.L. Foo, J.R. Long, J. Am. Chem. Soc. 131
(2009) 8784.
[172] M. Dinca, A. Dailly, C. Tsay, J.R. Long, Inorg. Chem. 47 (2008) 11.
[173] B.X. Dong, S.Y. Zhang, W.L. Liu, Y.C. Wu, J. Ge, L. Song, Y.L. Teng, Chem.
Commun. 51 (2015) 5691.
[174] M. Dinca, A. Dailly, J.R. Long, Chem. Eur. J. 14 (2008) 10280.
[175] I. Timokhin, J.B. Torres, A.J.P. White, P.D. Lickiss, C. Pettinari, R.P. Davies,
Dalton Trans. 42 (2013) 13806.
[176] I. Timokhin, A.J.P. White, P.D. Lickiss, C. Pettinari, R.P. Davies, CrystEngComm
16 (2014) 8094.
[177] I. Boldog, K.V. Domasevitch, J.K. Maclaren, C. Heering, G. Machloufi, C. Janiak,
CrystEngComm 16 (2014) 148.
[178] M. Eddaoudi, J. Kim, N.L. Rosi, D. Vodak, J. Wachter, M. O’Keeffe, O.M. Yaghi,
Science 295 (2002) 469.
[179] C. Benelli, D. Gatteschi, Introduction to Molecular Magnetism: From
Transition Metals to Lanthanides, John Wiley & Sons, 2015.
[180] S.R. Batten, S.M. Neville, D.R. Turner, Coordination Polymers: Design, Analysis
and Application, Springer, New York, 2010, chapter 9.
[181] A.F. Wells, Structural Inorganic Chemistry, 5th ed., Oxford University Press,
Oxford, 1984.
[182] V. Colombo, A. Maspero, L. Nardo, A. Aprea, F. Linares, A. Cimino, S. Galli,
Polyhedron 92 (2015) 130.
[183] E.-Q. Gao, N. Liu, A.-L. Cheng, S. Gao, Chem. Commun. (2007) 2470.
[184] N. Liu, Q. Yue, Y.-Q. Wang, A.-L. Cheng, E.-Q. Gao, Dalton Trans. (2008) 4621.
[185] Y.-B. Lu, M.-S. Wang, W.-W. Zhou, G. Xu, G.-C. Guo, J.-S. Huang, Inorg. Chem.
47 (2008) 8935.
[186] M. Dinca, A. Dailly, Y. Liu, C.M. Brown, D.A. Neumann, J.R. Long, J. Am. Chem.
Soc. 128 (2006) 16876.
[187] M. Dinca, J.R. Long, J. Am. Chem. Soc. 129 (2007) 11172.
[188] S. Horike, M. Dinca, K. Tamaki, J.R. Long, J. Am. Chem. Soc. 130 (2008) 5854.
[189] O.R. Evans, H.L. Ngo, W.B. Lin, J. Am. Chem. Soc. 123 (2001) 10395.
[190] M. Sasidharan, R.J. Kumar, J. Catal. 220 (2003) 326.
[191] R. Garro, M.T. Navarro, J. Primo, A.J. Corma, J. Catal. 233 (2005) 342.
[192] A.J. Howarth, A.W. Peters, N.A. Vermeulen, T.C. Wang, J.T. Hupp, O.K. Farha,
Chem. Mater. 29 (2017) 26.
[193] J.E. Mondloch, O. Karagiaridi, O.K. Farha, J.T. Hupp, CrystEngComm 15 (2013)
9258.
[194] I. Boldog, K.V. Domasevitch, I.A. Baburin, H. Ott, B. Gil-Hernandez, J. Sanchiz,
C. Janiak, CrystEngComm 15 (2013) 1235.
[195] V.A. Blatov, M. O’Keeffe, D.M. Proserpio, CrystEngComm 12 (2010) 44.
[196] Z. Guo, D. Yan, H. Wang, D. Tesfagaber, X. Li, Y. Chen, W. Huang, B. Chen,
Inorg. Chem. 54 (2015) 200.
[197] J. Tao, Z.-J. Ma, R.-B. Huang, L.-S. Zheng, Inorg. Chem. 43 (2004) 6133.
[198] P. Cui, Z. Chen, D. Gao, B. Zhao, W. Shi, P. Cheng, Cryst. Growth Des. 10 (2010)
4370.
[199] J.-H. Liao, W.-T. Chen, C.-S. Tsai, C.-C. Wang, CrystEngComm 15 (2013) 3377.
[200] H. Tian, Y.-C. Wu, S.-Y. Zhang, B.-X. Dong, C.-B. Liu, W.-L. Liu, Y.-L. Teng, Inorg.
Nano-Metal Chem. 47 (2017) 549.
[201] D. Liu, T.-F. Liu, Y.-P. Chen, L. Zou, D. Feng, K. Wang, Q. Zhang, S. Yuan, C.
Zhong, H.-C. Zhou, J. Am. Chem. Soc. 137 (2015) 7740.
[202] D. Liu, X. Wang, Y.-P. Chen, S. Yuan, C. Zhong, H.-C. Zhou, Sci. China Chem. 59
(2016) 975.
[203] W. Ouellette, A.V. Prosvirin, K. Whitenack, K.R. Dunbar, J. Zubieta, Angew.
Chem. Int. Ed. 48 (2009) 2140.
[204] M. O’Keeffe, O.M. Yaghi, Chem. Rev. 112 (2) (2012) 675.
[205] Z. Yan, M. Li, H.-L. Gao, X.-C. Huang, D. Li, Chem. Commun. 48 (2012) 3960.
[206] A. Caneschi, D. Gatteschi, N. Lalioti, C. Sangregorio, R. Sessoli, G. Venturi, A.
Vindigni, A. Rettori, M.G. Pini, M.A. Novak, Angew. Chem. 113 (2001) 1810.
[207] X.-M. Zhang, Z.-M. Hao, W.-X. Zhang, X.-M. Chen, Angew. Chem. Int. Ed. 119
(2007) 3526.
[208] O. Kahn, J. Larionova, J.V. Yakhmi, Chem. Eur. J. 5 (1999) 3443.
[209] G.J. Halder, C.J. Kepert, B. Moubaraki, K.S. Murray, J.D. Cashion, Science 298
(2002) 1762.
[210] G. Férey, Nat. Mater. 2 (2003) 136.
[211] N. Lopez, H. Zhao, A.V. Prosvirin, A. Chouai, K.R. Dunbar, Chem. Commun.
(2007) 4611.
[212] N. Yanai, W. Kaneko, K. Yoneda, M. Ohba, S. Kitagawa, J. Am. Chem. Soc. 129
(2007) 3496.
[213] M. Lalonde, W. Bury, O. Karagiaridi, Z. Brown, J.T. Hupp, O.K. Farha, J. Chem.
Mater. A 1 (2013) 5453.
[214] J.-D. Tsai, C.-I. Yang, Dalton Trans. 43 (2014) 15576.
[215] Z.R. Herm, B.M. Wiers, J.A. Mason, J.M. van Baten, M.R. Hudson, P. Zajdel, C.M.
Brown, N. Masciocchi, R. Krishna, J.R. Long, Science 340 (2013) 960.
[216] S. Galli, A. Maspero, C. Giacobbe, G. Palmisano, L. Nardo, A. Comotti, I.
Bassanetti, P. Sozzani, N. Masciocchi, J. Mater. Chem. A 2 (2014) 12208.
[217] M.A. Halcrow (Ed.), Spin-Crossover Materials. Properties and Applications,
John Wiley & Sons, Hoboken, 2013.
[218] J.-F. Létard, P. Guionneau, L. Goux-Capes, Towards spin crossover
applications, in: P. Gütlich, H.A. Goodwin (Eds.), Spin Crossover in
Transition Metal Compounds III, Springer-Verlag, Berlin, Hidelberg, 2004.
[219] W.-T. Liu, J.-Y. Li, Z.-P. Ni, X. Bao, Y.-C. Ou, J.-D. Leng, J.-L. Liu, M.-L. Tong,
Cryst. Growth. Des. 12 (2012) 1482.
[220] J. Mecinović, R.B. Hamed, C.J. Schofield, Angew. Chem. Int. Ed. 48 (2009) 2796.
[221] G. de Ruiter, J.S. Costa, K. Lappalainen, O. Roubeau, P. Gamez, J. Reedijk, Inorg.
Chem. Commun. 11 (2008) 787.
[222] K. Sumida, S. Horike, S.S. Kaye, Z.R. Herm, W.L. Queen, C.M. Brown, F.
Grandjean, G.J. Long, A. Dailly, J.R. Long, Chem. Sci. 1 (2010) 184.
[223] K. Kongpatpanich, S. Horike, M. Sugimoto, T. Fukushima, D. Umeyama, Y.
Tsutsumi, S. Kitagawa, Inorg. Chem. 53 (2014) 9870.
[224] H. Schmidbaur, A. Schier, Organometallics 34 (2015) 2048.