Coordination Chemistry Reviews 347 (2017) 23–47

Contents lists available at ScienceDirect

Coordination Chemistry Reviews

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

Review

A review of the structural chemistry and physical properties of metal

chalcogenide halides
Jin-Rong Xiao, Si-Han Yang, Fang Feng, Huai-Guo Xue, Sheng-Ping Guo ⇑
School of Chemistry and Chemical Engineering, Yangzhou University, Yangzhou, Jiangsu 225002, China

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

Article history: Given the collaborative effect between different anions, compounds containing two types of anions can
Received 16 March 2017 have improved physical performance compared with some aspects of those containing only one type of
Accepted 6 June 2017 anion. To date, many such compounds have been investigated. This review focuses on metal chalcogenide
Available online 16 June 2017
halides, namely, M–Q–X (M = metal element; Q = S, Se, Te; X = F, Cl, Br, I) compounds. Although they have
similar atomic radii, chalcogen atoms have much smaller electronegativities than those of its neighboring
Keywords: halogen atoms, which results in their different bonding styles. The inclusion of X
into chalcogenides can
Metal chalcogenide halide
move their optical band gaps to higher values and their coordination polyhedra can become more dis-
Crystal structure
Solid-state electrolyte
torted, albeit with little density change. These structural effects make metal chalcogenide halides a good
Second-order non-linear optics choice to fine-tune the structures and physical properties of chalcogenides or halides. Several hundreds of
metal chalcogenide halides already have been discovered. They demonstrate rich structures and versatile
physical properties, enabling their diverse applications in the fields of solid-state electrolytes, second-
order non-linear optics and thermoelectricity. Considering their flourishing development, this paper pro-
vides an overview of recent achievements in the structural chemistry and physical properties of metal
chalcogenide halides.
Ó 2017 Elsevier B.V. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24
2. Main-group metal chalcogenide halides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24
2.1. Alkali-metal chalcogenide halides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24
2.1.1. Lithium chalcogenide halide-type solid-state electrolytes. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24
2.1.2. Supramolecular-type chalcogenide halides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25
2.1.3. Other alkali-metal chalcogenide halides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 27
2.2. Sr, Ba-based chalcogenide halides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 27
2.2.1. Second-harmonic generation-active chalcogenide halides. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 27
2.2.2. Magnetic chalcogenide halides containing [A2F2]2+ (A = Sr, Ba) blocks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29
2.2.3. Other Sr, Ba-based chalcogenide halides. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30
2.3. MQX (M = Ga, In, Sb, Bi)2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 33
2.3.1. MQX (M = Ga, In) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 33
2.3.2. SbQX . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 33
2.3.3. BiQX . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 35
2.4. Tl–Q–X . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 35
2.4.1. Tl6QX4 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 35
2.4.2. Tl5Q2X . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 35
2.5. In5Q5X, TlIn4Se5X, and TlIn4S5Cl . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36
2.6. Sb, Bi-based chalcogenide halides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36
2.6.1. Supramolecular-type chalcogenide halides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36

⇑ Corresponding author.
E-mail address: spguo@yzu.edu.cn (S.-P. Guo).

http://dx.doi.org/10.1016/j.ccr.2017.06.010
0010-8545/Ó 2017 Elsevier B.V. All rights reserved.
24 J.-R. Xiao et al. / Coordination Chemistry Reviews 347 (2017) 23–47

2.6.2. Other Sb, Bi-based chalcogenide halides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 37

3. Transition-metal chalcogenide halides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 37
3.1. Coin-metal chalcogenide halides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 37
3.1.1. Ag5Te2Cl . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 37
3.1.2. Ag10Te4Br3 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 37
3.1.3. Supramolecular type chalcogenide halides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 37
3.1.4. Ag23Te12X . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 38
3.1.5. M19Q6X7 (M = Ag, Cu) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 38
3.1.6. Other transition-metal chalcogenide halides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 38
3.2. Zn, Cd and Hg-based chalcogenide halides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 38
3.2.1. Hg3Q2X2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 38
3.2.2. Supramolecular-type chalcogenide halides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 41
3.2.3. Other Zn, Cd, Hg-based chalcogenide halides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 41
3.3. V, Nb, Ta-based chalcogenide halides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 41
3.3.1. M3QX7 (M = Nb, Ta) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 41
3.3.2. Other V, Nb, Ta-based chalcogenide halides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 43
3.4. Mo, W-based chalcogenide halides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 43
3.4.1. MX4S (M = Mo, W) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 43
3.4.2. Other Mo, W-based chalcogenide halides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 43
3.5. Ir, Rh, Re, Ru, Pd-based chalcogenide halides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 44
3.5.1. Supramolecular-type chalcogenide halides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 44
3.5.2. Other Ir, Rh, Re, Ru, Pd-based chalcogenide halides. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 44
4. Rare-earth metal chalcogenide halides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 45
4.1. RE-Q-X (RE = rare-earth metal). . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 45
4.2. Eu3Bi2Q4F4 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 45
4.3. Other rare-earth metal chalcogenide halides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 45
5. Conclusions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 45
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 45
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 45

1. Introduction crystal structures and physical properties of these metal chalco-

genide halides.
Recently, the inclusion of two different types of anions into one
structure has been a popular strategy to design compounds with
diverse structures and improved physical properties. Two types 2. Main-group metal chalcogenide halides
of anions can endow these structures with more types of structure
building units (SBUs), and the mutual effects between these two 2.1. Alkali-metal chalcogenide halides
anions definitely influence the chemical bonds and distortion
levels of the SBUs, resulting in a more adjustable physical perfor- 2.1.1. Lithium chalcogenide halide-type solid-state electrolytes
mance than compounds containing only one type of anion. To date, The traditional electrolytes used in batteries usually are organic
many compounds containing two types of anions have been stud- liquids, which pose serious safety concerns. Comparatively, solid-
ied, including but not limit to sulfide borates [1,2], sulfide silicates state electrolytes not only provide improved safety, but also have
[3], oxychloride borates [4], oxide sulfides [5,6] and oxide halides increased energy density, higher voltage stability windows and
[7–10]. more versatility in the geometry of the battery. Employing inor-
In recent years, metal chalcogenide halides have been investi- ganic solid electrolytes to replace organic liquid ones is an impor-
gated extensively in view of their increasingly important applica- tant issue. In addition to their applications in batteries, solid-state
tions in the fields of optics and electrochemistry. Their most inorganic electrolytes also enable solid oxide fuel cells, sensors,
outstanding properties include their ability to be employed as solid
state electrolytes for batteries and as second-order non-linear opti-
cal materials in the middle and far-infrared (IR) regions, both of
which are hot topics in their respective fields. Because of their
importance, it is necessary to summarize their crystal structures
and properties, and as such an overview on topic has not been pro-
vided to date, this paper presents a detailed review. Several hun-
dreds of metal chalcogenide halides have been studied, so only
recent achievements in their crystal structures and physical prop-
erties are given. The contents are divided according to the com-
pounds’ chemical compositions, which are classified into three
groups, namely main-group, transition and rare-earth metal
chalcogenide halides. Furthermore, each group is divided into sev-
eral subgroups according to their most outstanding properties and
chemical compositions, demonstrating their respective commonal-
ities to the greatest extent. As most metal chalcogenide halides are
obtained using solid-state methods, this paper does not discuss
their syntheses. Moreover, this paper presents some theoretical Fig. 1. a) Crystal structure of Li6PS5I, showing the distribution of PS4 tetrahedra,
considerations to help understand the relationship between the S2
and I
ions. b) A face-sharing S3I2 double tetrahedron [14]. Ó 2008 Wiley.
 J.-R. Xiao et al. / Coordination Chemistry Reviews 347 (2017) 23–47
Fig. 2. Unit cell of (ClCs6)[Dy21Se34] with the imbedded ClCs6 octahedron outlined
(red). Cs, red; Dy, blue; Cl, black; Se1, Se2, Se4, Se7 in triangular pyramids, yellow;
Se3, Se5, Se6, Se8, Se9 in cis-divacant octahedra, orange yellow; Se10 in square
pyramids, green [19]. Ó 2012 American Chemical Society.
Fig. 3. Fragment packing of Cs11(H3O)[Re6Se4O4Cl6]34H2O along the c-axis [20].
Ó 2005 Royal Society of Chemistry.
smart windows and memristor technologies [11,12]. Recently,
some lithium-rich sulfide halides were discovered and explored
for use as electrolytes in batteries. For example, Li7P2S8I was
obtained using appropriate compositions of LiI and Li3PS4. Its crys-
tal structure is similar to that of Li3PS4 and it can be regarded as a
solid solution of LiI in Li3PS4. Its ionic conductivity is 6.3  10
4 S/
cm, four times greater than that of Li3PS4 and more than three
orders larger than that of LiI. When used as an electrolyte, it can
stabilize a Li anode and can enhance interfacial kinetics and ionic
conductivity. Moreover, its electrochemical stability can be up to
10 V (vs Li/Li+), which opens up a new avenue for safe all-solid-
state Li batteries [13]. Moreover, several Li-argyrodites, Li6PnQ5X
(Pn = P or As; Q = S, Se; X = Cl, Br, I), have received strong interest
in view of their high conductivities, reliable electrochemical stabil-
ities and low electronic conductivities. Deiseroth synthesized the
colorless and air-sensitive Li6PS5X (X = Cl, Br, I) at 550 °C using
Li2S, P2S5 and LiX as the raw-materials [14], which crystallize in
the cubic space group F43m, with similar structures to argyrodite
(Fig. 1). These Li-argyrodites belong to a class of crystalline
25
Fig. 4. Crystal structures of [Cs6Cl][Fe24Se26] (left) and TiAl3 (right) [21]. Ó 2016
Wiley.
Li-rich solids with unusually high Li+ mobilities. Specifically,
Li6PS5Cl and Li6PS5Br have high ionic conductivity at room
temperature [15]. Moreover, there are several orders of magnitude
differences for the Li ion conductivity between Li6PS5Cl and Li6PS5I
because of the distribution of the X
ions in the available crystal-
lographic sites [16].
Temperature has an important influence on the properties of
Li-argyrodite solid electrolytes. At high-temperatures, the Li atoms
are heavily disordered over the available tetrahedral cavities.
Comparatively, the Li atoms occupy crystallographic positions
without disorder at low temperature [17]. The P and S atoms in
Li6PS5X can be replaced by As and Se atoms, respectively [16]. In
view of the excellent Li ion conductivity, Yu et al. designed a
Li6PS5Cl–Li2S all-solid-state Li-ion battery. They studied the con-
ductivity in the Li6PS5Cl electrolyte by distinguishing local Li-ion
mobility, bulk diffusion, the impact of grain boundaries and the
charge transfer kinetics on the interface with the Li2S electrode.
The battery could deliver capacities higher than 300 mAh/g for
40 cycles [18]. Based on this progress, it seems one type of promis-
ing strategy to solve the problems of liquid electrolytes is to
explore lithium chalcogenide halides as potential solid electrolytes.
Meanwhile, some problems have to be settled before the practical
substitution of liquid electrolytes, such as the limitation of the
reactivity between solid electrolytes and electrodes [11].
2.1.2. Supramolecular-type chalcogenide halides
Supramolecular-type chalcogenide halides contain two or more
different building units with different structures and physicochem-
ical behaviors, and can also be called host-guest compounds. As
these compounds can be versatilely designed and they usually
can hold the structure and property traits of different components,
it is attractive to explore them as multifunctional materials. To
date, many such compounds have been discovered, including
(ClCs6)[RE21Q34] (RE = Dy, Ho), Cs11(H3O)[Re6Se4O4Cl6]34H2O,
[Cs6Cl][Fe24Se26], (Cs6Cl)6Cs3[Ga53Se96], Cs2CeCll2[AsS3], (Sb7Te8)
[Ga2Cl7]2[GaCl4]3, (Sb7Te8)[Ga2Cl7]3[GaCl4]2, Na(Sb7Te8)[GaCl4]6
and Na(Sb7Te8)[AlCl4]6.
As shown in Fig. 2, the compound (ClCs6)[RE21Q34] crystallize in
the monoclinic space group C2/m. The structure features a three-
dimensional (3D) RE
Q network that is embed with novel nesting
doll structure cavities of (ClCs6)@Se32 [19].
The compound Cs11(H3O)[Re6Se4O4Cl6]34H2O crystallizes in the
trigonal space group R3 and was synthesized by the reaction of
26 J.-R. Xiao et al. / Coordination Chemistry Reviews 347 (2017) 23–47

Fig. 5. (a) Crystal structure of (Cs6Cl)6Cs3[Ga53Se96] viewed slightly off the b-axis. (b) Intralayer linking details of the Ga2Se6 dimer via cis-linking in slab A (top) or trans-
linking in slab B (bottom) [22]. Ó 2016 American Chemical Society.

Fig. 6. Unit cell of K[Re6S8F3(H2O)3]7H2O [24]. Ó 2007 Elsevier.

Fig. 8. Unit cell of [Re6Q8F2(H2O)4]12H2O [24]. Ó 2007 Elsevier.

Fig. 7. Unit cell of (H3O)[Re6Se8F3(H2O)3]7H2O [24]. Ó 2007 Elsevier. Fig. 9. Crystal structure of Ba4MGa4Se10Cll2 [27]. Ó 2015 Wiley.
 J.-R. Xiao et al. / Coordination Chemistry Reviews 347 (2017) 23–47 27

Fig. 10. Crystal structures of Ba6Cs2InxGa10
xSe20Cl4 (x = 1, 2) [28]. Ó 2016 Royal

Society of Chemistry.

Fig. 11. Unit cell of Ba3CsGa5Se10Cl2 [29]. Ó 2012 American Chemical Society.

Re6Se8Br2 and KOH [20]. Its structure contains a novel [Re6Se4O4]

cluster core and features the main cluster unit [Re6Se4O4Cl6]4

(Fig. 3).
Recently, Valldor et al. discovered a host-guest compound with
a unique Fe–Se topology, the compound [Cs6Cl][Fe24Se26]. It crys-
tallizes in tetragonal space group I4/mmm. As shown in Fig. 4, its
structure consists of a host lattice built by octamers of fluorite-
type edge-sharing FeSe4 tetrahedra, which can be regarded as a
hierarchical derivate of the TiAl3-type structure, in which guest
[Cs6Cl]5+ ions and cubane [Fe8Se6Se8/3] units occupy the Ti and Al
positions, respectively [21]. The compound [Cs6Cl][Fe24Se26] shows
antiferromagnetic-type behavior below 221 K, and a structural dis-
tortion or a complex spin structure is suggested by the distribution
of the hyperfine field in the Mössbauer spectrum.
As shown in Fig. 5, (Cs6Cl)6Cs3[Ga53Se96] crystallizes in the trig-
onal space group R3m Its structure features a unique stacking
structure of layers built by a dimeric Ga2Se6 unit extending with
cis- or trans-intralayer linking. Its optical energy gap was deter-
mined to be 2.74 eV [22]. Fig. 12. Crystal structure of NaBa4Ge3S10Cl [30]. Ó 2014 Royal Society of Chemistry.
The compounds (Sb7Te8)[Ga2Cl7]2[GaCl4]3, (Sb7Te8)[Ga2Cl7]3
[GaCl4]2, Na(Sb7Te8)[GaCl4]6 and Na(Sb7Te8)[AlCl4]6 were obtained
by the reactions of Sb and Te in molten GaCl3 or AlCl3 in the pres- ied. Outstanding examples contain P-type transparent conductors,
ence of MCl (M = Li, Na, In, Cu) and the oxidant SbCl3. Their struc- Sr1
xNaxFCuS and SrF1
xOxCuS (x = 0.05, 0.1), both of which crystal-
tures are built by [GaCl4]
, [Ga2Cl7]
and [AlCl4]
anions, and lize in the tetragonal space group P4/nmm, adopting the ZrSiCuAs-
discrete (Sb7Te8)5+ cationic clusters [23]. The compound type structure. Density functional theory band structure calcula-
Na(Sb7Te8)[AlCl4]6 mainly shows a second-order phase transition tions revealed that partial substitution of Na by Sr could create
at 177 K. positively charged carriers [25].
Four octahedral fluoride rhenium cluster complexes, K[Re6S8- Other examples include the Cs3Mo6Ii6Ii2
xSeixIa6 series. They crys-
F3(H2O)3]7H2O, (H3O)[Re6Se8F3(H2O)3]7H2O and [Re6Q8F2(H2O)4]- tallize in the trigonal space group R3c, and their structures are based
12H2O (Q = S, Se), were synthesized using K4[Re6S8Br6]2H2O and on magnetic [Mo6Ii6Sei2Ia6]3
and diamagnetic [Mo6Ii7SeiIa6]3
units,
Cs3[Re6S8Br6]2H2O with molten KHF2, followed by crystallization with 23 and 24 valence electrons per Mo6 cluster, respectively
from aqueous solutions. The former two compounds crystallize [26]. The reciprocal double-integration intensity of the electron
in the monoclinic space group C2/c, whereas the latter two com- paramagnetic resonance signal versus T graph indicates typical
pounds crystallize in the trigonal space group R3m The complexes Curie’s law behavior.
K[Re6S8F3(H2O)3]7H2O (Fig. 6) and (H3O)[Re6Se8F3(H2O)3]7H2O
(Fig. 7) are isotypical. Their structures present a packing of cluster 2.2. Sr, Ba-based chalcogenide halides
anion layers and K+ or H3O+ cation layers. The structures of [Re6Q8-
F2(H2O)4]12H2O (Fig. 8) and [Re6Se8(OH)2(H2O)4]12H2O are simi- 2.2.1. Second-harmonic generation-active chalcogenide halides
lar and present a packing of honeycomb [Re6Q8F2(H2O)4] clusters. Second harmonic generation (SHG) is a NLO frequency-doubling
The oxygen atoms of H2O ligands coordinated with the Re atoms phenomenon caused by the interaction of photons in an acentric
and F
ions are included in the water framework [24]. material [27]. Recently, many alkali-earth metal chalcogenide
halides have been explored as NLO materials in the IR region. It
2.1.3. Other alkali-metal chalcogenide halides is well-known that chalcogenides have wide transparent ranges
In addition to the previous compounds that could be divided in the middle and far-IR regions, and the inclusion of halogen
into a special group, some other compounds also have been stud- atoms in chalcogenides can move their transparent ranges to
28 J.-R. Xiao et al. / Coordination Chemistry Reviews 347 (2017) 23–47

Table 1
Crystal data of chalcogenide fluorides containing [A2F2]2+ (A = Sr, Ba) blocks.

Compounds Space Group Z a (Å) b (Å) c (Å) V (Å3)

Ba2F2Fe1.96(6)S3 I41/acd 8 6.1446(9) 38.675(8) 1460.2(4)
Ba2F2Fe1.72(6)S3 Immm 2 4.3075(9) 4.3832(9) 19.189(4) 362.30(13)
Ba2F2Fe1.98(5)S3 I4/m 2 4.3464(6) 19.344(4) 365.42(10)
Ba2F2Fe1.78(5)Se3 I4/m 2 4.3464(6) 19.344(4) 365.42(10)
Ba2F2Fe1.78(5)Se3 I4/m 2 4.4929(6) 19.548(4) 394.60(11)
Ba2F2Fe2OSe2 I4/mmm 2 4.1946(6) 19.522(4) 343.49(10)
Sr2F2Fe2OS2 I4/mmm 2 4.0400(6) 17.998(4) 293.75(9)
Ba4F4CrGa2S6 Pnma 4 13.0153(11) 18.5286(16) 6.1583(4) 1485.1(2)
Ba4F4MnGa2S6 Cmca 4 18.834(2) 6.1565(8) 12.8039(16) 1484.6(3)
Ba4F4FeGa2S6 Pnma 4 12.694(8) 18.867(13) 6.116(4) 1464.8(17)
Ba4F4MnIn2S6 Pnma 4 12.926(6) 18.910(8) 6.363(3) 1555.3(12)
Ba2F2Fe1.5Se3 Pnma 8 12.9428(2) 19.221(5) 6.3286(8) 1574.4(5)
Ba2F2Fe1.5S3 Pnma 8 12.528(3) 18.852(4) 6.0896(12) 1438.3(5)

Fig. 14. Crystal structures of A2F2Fe2OQ2 (A = Sr, Ba) [32]. Ó 2008 American
Chemical Society.

polycrystalline samples showed strong SHG intensities, of around

Fig. 13. Crystal structure of (BaF)2Fe2
xQ3 viewed along the b-axis [31]. Ó 2015
American Chemical Society.
further IR regions. On the other hand, most of chalcogenides are
semiconductors, so their laser induced damage threshold (LIDT)
values usually are not satisfactory.1 Because of the larger elec-
tronegativities of the halogen elements than the chalcogen ones,
59 (M = Zn), 52 (M = Cd), 39 (M = Cu/Ga) and 30 (M = Mn) times
that of AgGaS2 (AGS, a benchmark IR NLO material). Specifically,
Ba4ZnGa4Se10Cl2 has a strong laser-induced damage threshold
(LIDT), around 17 times that of AGS [27].
As shown in Fig. 10, the compounds Ba6Cs2In2Ga8Se20Cl4 and
Ba6Cs2InGa9Se20Cl4 crystallize in the tetragonal space group I4,
with the Ba6Cs2Ga10Se20Cl4-type structure. Their 3D structures fea-
ture alternately stacking non-polar InyGa4
ySe4 tetrahedra and In4-
2+ +
zGa4(1
z)Se10 supertetrahedral clusters, in which Ba /Cs and Cl

halides often have higher optical band gaps than chalcogenides.
Therefore, the combination of chalcogenide and halide groups in one
system should produce some promising materials with superior IR
NLO performance than pure chalcogenide compounds. In this paper,
we introduce several important compounds that are SHG active, and
hope this brief summary can arouse more research on this topic.
As shown in Fig. 9, the compounds Ba4MGa4Se10Cl2 (M = Zn, Cd,
Mn, Cu/Ga, Co, Fe) crystallize in the tetragonal space group I4 with
a zinc-blende structure. Their structures are constructed from a T2
supertetrahedral cluster of Ga4Se10 and T1 tetrahedral clusters of
MSe4. Ba2+ and Cl
ions occupy the cavities in this network. Their
optical band gaps were measured to be around 1.88–3.08 eV. Their
1
LIDT values usually are evaluated by the NLO materials’ optical band gaps, and
larger band gaps mean higher LIDT values.
ions are located in the cavities [28]. The SHG intensities of Ba6Cs2-
In2Ga8Se20Cl4 and Ba6Cs2InGa9Se20Cl4 are 70 and 64 times that of
AGS, respectively, and their LIDT values are around 17 times that
of AGS.
As shown in Fig. 11, the compounds Ba3AGa5Se10Cl2 (A = Cs, Rb,
K) crystallize in the tetragonal space group I4, and their structures
feature polar 3D frameworks [(Ga5Se10)5
]1 built by a non-polar
(GaSe4)5
tetrahedron and a polar supertetrahedral cluster (Ga4-
Se10)8
in a zinc-blende type structure, similar to Ba4MGa4Se10Cl2
[29]. The Ba3AGa5Se10Cl2 compounds show SHG responses about
100 times that of AGS at 2.05 lm and represent the first open-
framework compounds with red photoluminescence.
As shown in Fig. 12, the compound NaBa4Ge3S10Cl crystallizes
in the hexagonal space group P63. Its structure contains a unique
[Ge3S9] ring built by three GeS4 tetrahedra via sharing corners.
 J.-R. Xiao et al. / Coordination Chemistry Reviews 347 (2017) 23–47
Fig. 15. Unit cells of Ba4F4CrGa2S6 and Ba4F4MnIn2S6 [33]. Ó 2013 Royal Society of Chemistry.
Fig. 16. Crystal structure of Ba2F2Fe1.5Se3 [34]. Ó 2016 Royal Society of Chemistry.
Its 3D structure is constructed by linkage between pseudo layers
formed by [Ge3S9] rings and Na–Cl–Ba chains. NLO measurement
indicated that its SHG response is around 0.3 times that of AGS
at 2.09 lm, and it has a much higher optical band gap of 3.49 eV
[30].
2.2.2. Magnetic chalcogenide halides containing [A2F2]2+ (A = Sr, Ba)
blocks
In recent years, metal chalcogenide halides featuring [A2F2]2+
cations have been studied thoroughly, and thus far, many such
compounds have been reported (see Table 1). As shown in
Fig. 13, the compounds (BaF)2Fe2
xQ3 (Q = S, Se) crystallize in the
orthorhombic space group Immm, and their two-dimensional
(2D) structures can be depicted as alternate stacking of PbO-type
[Ba2F2]2+ cationic layers and [Fe2
xQ3]2
anionic layers along the
c direction. For (BaF)2Fe2
xS3, both long-range ordered and disor-
dered polymorphs were observed. The [Fe2
xQ3]2
layers show a
strong Fe–Fe interaction, whereas the (BaF)2Fe2
xQ3 crystals
29
Fig. 17. Crystal structure of Ba18F18In8S21 viewed along the c-axis [36]. Ó 2014
Royal Society of Chemistry.
demonstrate ferromagnetic orders at 280–315 and 240–275 K for
the sulfide and selenide, respectively, which are attributed to dif-
ferent concentrations of vacancies on the Fe sites [31].
As shown in Fig. 14, the compounds A2F2Fe2OQ2 (A = Sr, Ba)
crystallize in the tetragonal space group I4/mmm, which is differ-
ent from (BaF)2Fe2
xQ3 in the orthorhombic space group Immm.
Their structures feature stacked layers of [Ba2F2] and [Fe2OSe2]
SBUs. They are magnetic semiconductors with long-range antifer-
romagnetic ordering at 83.6–106.2 K. The main antiferromagnetic
spin exchange interaction between the Fe2+ ions occurs through
Fe–O–Fe bridges. The calculated spin exchange interactions
indicate that they represented a rare frustrated antiferromagnetic
checkerboard lattice [32].
30 J.-R. Xiao et al. / Coordination Chemistry Reviews 347 (2017) 23–47
Fig. 18. Crystal structure of Ba9F10In4S10 (a) and projection of the [BaF2In4S10] block parallel to the ac plane (b) [36]. Ó 2014 Royal Society of Chemistry.
Fig. 19. Crystal structure of Ba3S4I2 [37]. Ó 2016 Royal Society of Chemistry.
Fig. 20. Crystal structure of Ba3GaS4Cl [38]. Ó 2013 American Chemical Society.
As shown in Fig. 15, the compounds Ba4F4MGa2S6 (M = Cr, Mn,
Fe) and Ba4F4MnIn2S6 crystallize in two different space groups:
Ba4F4MnGa2S6 crystallizes in the orthorhombic space group Cmca,
whereas the other compounds crystallize in the Pnma space group,
belonging to the Ba2F2Fe1.5S3 structure type. Their 2D structures
can be described as alternate stacking of [Ba2F2]2+ and [M0.5GaS3]2-


/[X0.5InS3]2
blocks. First principle electronic structure calcula-
tions indicate that these compounds have band gaps of 1.83,
3.21, 1.16 and 2.93 eV, respectively. Ba4F4FeGa2S6 behaves ferro-
Fig. 21. Crystal structure of Ba3InSe4Cl [38]. Ó 2013 American Chemical Society.
magnetically, whereas the other three compounds are antiferro-
magnetic. Ba4F4CrGa2S6 also demonstrates a magnetic order
transition at around 8 K [33].
As shown in Fig. 16, the compounds Ba2F2Fe1.5Q3 (Q = S, Se)
crystallize in the orthorhombic space group Pnma. Their structures
are built by the alternate stacking of [Ba2F2]2+ and [Fe1.5Q3]2

blocks. In the [Fe1.5Q3]2
blocks, the Fe atoms show mixed
valences, being divalent in octahedral cavities and trivalent in
tetrahedral cavities. Susceptibility measurements indicate that
both compounds are antiferromagnetic [34,35].
2.2.3. Other Sr, Ba-based chalcogenide halides
In addition to the previous compounds, other compounds have
been studied recently. Most of them contain alkali-earth metals as
the counter cations.
As shown in Figs. 17 and 18, Ba18F18In8S21 and Ba9F10In4S10
crystallize in the tetragonal P42/ncm and orthorhombic Pnma space
groups, respectively. Ba18F18In8S21 contains unusual one-
dimensional (1D) [Ba16F18] ionic and [BaIn8S21] covalent regions,
whereas Ba9F10In4S10 has a 2D [Ba2F2] block and a unique tetra-
nuclear [In4S10]8
anion. First principles electronic structure calcu-
lations indicate that both of compounds are semiconductors with
direct band gaps of 2.28 eV for Ba18F18In8S21 and 2.23 eV for
Ba9F10In4S10 [36].
As shown in Fig. 19, the compounds Ba3Q4I2 (Q = S, Se) crystal-
lize in the monoclinic space group C2/c. Their framework struc-
 J.-R. Xiao et al. / Coordination Chemistry Reviews 347 (2017) 23–47 31

Fig. 22. Crystal structure of Ba7In2Se6F8 [38]. Ó 2013 American Chemical Society.

Fig. 25. Atomic positions in the ab plane in the unit cell of SbSI [48]. Ó 2016
American Physical Society.

Fig. 23. Crystal structure of Ba2F2SnSe3 [40]. Ó 2006 American Chemical Society.

Fig. 24. Crystal structure of SbSeI [46]. Ó 2013 American Chemical Society.
Fig. 26. Crystal structures of BiSI (a) and Bi19S27I3 (b) viewed parallel to the ab plane
[50]. Ó 2014 Elsevier.

tures are built by (Q2)2
dumbbells and isolated I
anions. Ba3S4I2

is a semiconductor with a band gap of 2.45(5) eV [37]. types. Three Ba3GaQ4X compounds crystallize in the orthorhombic
Five chalcogenide halides, Ba3GaS4X (X = Cl, Br), Ba3MSe4Cl space group Pnma. In Ba3GaS4Cl, each Cl atom is surrounded by five
(M = Ga, In) and Ba7In2Se6F8, crystallize in three different structure Ba atoms to form a square pyramid with the Ba(1) atom as the apex
32 J.-R. Xiao et al. / Coordination Chemistry Reviews 347 (2017) 23–47

Fig. 27. Crystal structure of Tl6SI4 viewed along the c (a) and a (b) directions [54]. Ó 2013 American Chemical Society.

Fig. 30. Crystal structure of [Sb10Se10][AlCl4]2 [65]. Ó 2011 Wiley.

I4/mcm. As shown in Fig. 21, its structure features two kinds of

Fig. 28. Crystal structure of Tl6SeI4 [55]. Ó 2012 American Physical Society.
and four Ba(2) atoms as the corners of the square base. These quad-
rangular pyramids are linked via sharing corner Ba(2) atoms to
form a zig-zag BaCl pseudo-layer parallel to the bc plane (Fig. 20)
[38]. Ba3InSe4Cl crystallizes in the tetragonal space group
pseudo layers [38]. The compound Ba7In2Se6F8 crystallizes in
the monoclinic space group C2/m. Its structure is constructed
by [(InSe3)3
]1 and [Ba7F8]6+ chains (Fig. 22) [38]. The three
Ba3GaQ4X compounds have optical band gaps of 2.14, 1.80 and
2.05 eV, respectively.
A series of homologous Ae2M1+nQ3+nF2 (Ae = Sr, Ba; M = main
group metal) compounds crystallize in the triclinic space group
P1. Their structures are constructed by the alternate stacking of
[Ae2Fe2] and rock-salt [Sb2Se4] layered building blocks [39]. The

Fig. 29. Crystal structures of In5Q5Cl (left) and In5Q5Br (right) [60]. Ó 2004 Wiley.
 J.-R. Xiao et al. / Coordination Chemistry Reviews 347 (2017) 23–47
Fig. 31. Crystal structures of (Bi2Se2)Cl[GaCl4] (a), (Sb2Te2)I[AlI4] (b), (Sb3Te4)[GaCl4] (c) and (SbTe4)[Ga2Cl7] (d) [66]. Ó 2013 American Chemical Society.
Fig. 32. Crystal structure of [Bi2Te2Br](AlCl4) [67]. Ó 2010 American Chemical
Society.
four compounds Ae2F2SnQ3 crystallize in the orthorhombic space
group Pnma. Their structural features are similar to those of Ae2-
M1+nQ3+nF2, which are also built by alternate stacking of [Ae2F2]
and [SnX3] layered building blocks (Fig. 23). As shown by the
results of band structure calculations, these compounds have opti-
cal band gaps of 2.24, 2.49, 3.06 and 3.21 eV, respectively [40].
2.3. MQX (M = Ga, In, Sb, Bi)2
2.3.1. MQX (M = Ga, In)
This section discusses several compounds formulated as InQX.
Interestingly, these compounds can crystallize with different struc-
2
Q: S, Se, Te; X: F, Cl, Br, I.
33
tures. InTeI and InTeCl crystallize in the monoclinic space group
P21/c. Their structures feature layers parallel to the [100] plane,
which are composed of four- and eight-membered rings with alter-
nating In and Te atoms, or (InTe3I)/(InTe3Cl) tetrahedra linked by
Te corners and edges [41,42]. InSeI crystallizes in the tetragonal
space group I41/a. Its structure features a 1D infinite tube along
the 41 axis, which is composed of six-membered rings with alter-
nate In and Se atoms, and the I atoms bonded to the In atoms
are located outside of the tube [42].
The GaTeX compounds crystallize in the orthorhombic space
group with a tetrahedral layer structure. Other GaQX com-
pounds are isostructural with novel structures. Their optical
band gaps were determined to be 2.55 (GaTeI) and 4.20 eV
(GaSeCl) [43].
GaSBr and GaSeBr could be obtained using Ga[GaBr4] and S/Se
in toluene or tetrahydrofuran, respectively. Both compounds can
be easily dissolved in pyridine and substituted pyridines. The as-
prepared GaSBr and GaSeBr compounds show different structures
depending on the different solvents [44].
2.3.2. SbQX
All of the known Sb-Q-X compounds have almost the same
chemical formula, including SbTeI, SbSeI, SbSBr and SbSI. SbTeI
crystallizes in the triclinic space group P1 [45]. SbSeI crystallizes
in the orthorhombic Pnma with a chain structure, in which infinite
[Sb2Se4I8]n zig-zag chains run along the b-axis (Fig. 24). It has a
band gap of 1.70 eV, and demonstrates n-type semiconductor
behavior with a resistivity of around 108 X cm. Moreover, well-
aligned SbSeI crystals show a considerable response to Ag Ka
X-rays [46].
Ferroelectric SbSBr has two different polymorphs, namely,
orthorhombic Pnam and Pna21. A phase transition occurs at 22.8 K
(Tc), which was determined from the temperature dependence of
the intensity of the [055] reflections. In the ferroelectric phase,
34 J.-R. Xiao et al. / Coordination Chemistry Reviews 347 (2017) 23–47

Fig. 33. Crystal structures of Pb2BiS2I3 (A) and Sn2BiS2I3 (B) [71]. Ó 2016 American Chemical Society.

Fig. 34. Crystal structures of Sn2BiSI5 (A) and Pb5S2I6 (C). Isolated 2D structures derived from the grey shaded region of the crystal structure in part A (B). Part D represents the
common structural fragment [M4S2I4] (M = Pb, Bi, Sn) [71]. Ó 2016 American Chemical Society.
 J.-R. Xiao et al. / Coordination Chemistry Reviews 347 (2017) 23–47
the Sb and S atoms shift by 0.11 and 0.03 Å, respectively, corre-
sponding to the Br atom, along the c direction from Tc to 11 K [47].
Ferroelectric SbSI has the same two polymorphs as SbSBr. The
atoms are connected to form layers parallel to the ab plane and
extend along the c direction (Fig. 25) [48]. It has indirect band gaps
both in the antiferroelectric and ferroelectric phases, namely 1.42
and 1.36 eV, respectively [49].
2.3.3. BiQX
BiSI crystallizes in the orthorhombic space group Pnma. Its
structure features BiSI strands with an elongated Bi–I distance
(3.0 Å) along the c direction, and these strands link together to
form a 3D structure through non-covalent Bi–I bonds (3.7 Å)
(Fig. 26a). Bi19S27I3 crystallizes in the hexagonal space group
P63/m. Its structure features slabs built by covalent Bi–S bonds
along the c direction, which are further linked via Bi(1)–S bonds
(>3.5 Å), and I atoms are located in the voids (Fig. 26b) [50].
BiSCl crystallizes in the orthorhombic space group Pnma,
whereas BiSBr and BiSI crystallize in the space group Pnam [51].
BiSCl, BiSBr, BiSI, BiSeI and BiSeBr have optical band gaps of 1.89,
1.95, 1.56, 1.3 and 1.5 eV, respectively, which are suitable for their
application in the field of solar energy absorption [52].
The pressure effects on the crystal and electronic structures of
BiTeX were studied, and the results indicated that BiTeI, under a
pressure of around 3.7–3.9 GPa, converted to an intermediate
phase, a Weyl semimetal formed during the transition from a triv-
ial semimetal to a topological insulator. At low pressures, BiTeI
crystallizes with the P3m1 structure; however, under high
pressure, it crystallizes in the Pnma structure [53]. In addition their
Fig. 35. Crystal structures of a-, b- and c-Ag5Te2Cl [75]. Ó 2004 American Chemical Society.
35
rich structures, the MQX compounds also have been investigated
as promising optoelectronic materials, such as photovoltaic
and c-ray detection materials [52].
2.4. Tl–Q–X
2.4.1. Tl6QX4
All the Tl6QX4 compounds are isostructural and crystallize in
the tetragonal space group P4/mnc. We discuss here Tl6SI4 and
Tl6SeI4 as representative examples. Tl6SI4 is a congruently melting
and mechanically robust compound with a strong photoconductiv-
ity response and with a room-temperature structure of merit. The
Tl atoms are coordinated by one S and four I atoms to form a dis-
torted square pyramid, in which the top and bottom of the pyramid
are formed by the S atom and a square plane of four I atoms
(Fig. 27) [54].
When S in Tl6SI4 is replaced by Se, its structure changes to
tetragonal P4/mnc (Fig. 28). There are only two distinct crystallo-
graphic sites for the Tl cations, and each Tl+ ion is coordinated with
one Se2
and four I
ions [55]. Tl6I4Se is a promising wide band-gap
semiconductor for hard radiation detection at room temperature
[56]. The Tl6QX4 compounds should be one type of interesting
optoelectronic material because of their efficient carrier transport
by the contribution of the 6s2 lone electron pair for the Tl+ ions,
if the toxicity of Tl can be effectively controlled.
2.4.2. Tl5Q2X
The compound Tl5Se2Br crystallizes in the tetragonal space
group I4/mcm, whereas Tl5Se2CI crystallizes with the lower
36 J.-R. Xiao et al. / Coordination Chemistry Reviews 347 (2017) 23–47

symmetric tetragonal P4/ncc space group. Each Tl atom is coordi- TlIn4Se5X and TlIn4S5Cl crystallize in the mononclinic space group
nated by two X and four Se atoms to form a TlSe4X2 octahedron, P21/m with mixed-valent In ions [61].
which connect to one another via corner sharing to construct a
3D structure [57]. Recently, the thermodynamic properties of
Tl5Se2Cl [58] and Tl5Se2Br [59] also have been studied. 2.6. Sb, Bi-based chalcogenide halides

2.5. In5Q5X, TlIn4Se5X, and TlIn4S5Cl 2.6.1. Supramolecular-type chalcogenide halides

The In5Q5X compounds have two structural types. The In5Ch5Cl-
type has a monoclinic P21/m structure, whilst the In5Q5Br-type dis-
play an orthorhombic Pmn21 structure (Fig. 29). The anionic partial
structures in the two polymorphs are similar, when ignoring the X
atoms. The main difference between them is an exchange of In+ by
(In2)4+ in selected positions [60]. Additionally, the compounds
Supramolecular compounds are aggregates of a discrete num-
ber of assembled molecular subunits or components with well-
defined compositions and structures. In such aggregates, the sub-
units or components with different structures and functions can
be assembled into mixed framework compounds showing diverse
structures and designed properties [62,63]. To date, several Bi-
and Sb-containing compounds belong to the supramolecular type.

Fig. 36. Crystal structure of the polymorphic Ag10Te4Br3 [79]. Ó 2007 American Chemical Society.
 J.-R. Xiao et al. / Coordination Chemistry Reviews 347 (2017) 23–47 37

Bi4Te4[AlCl4]4 crystals were obtained using Te, Bi, TeCl4, and
BiCl3 in a Na[AlCl4]/AlCl3 melt. Its structure features polycationic
(Bi4Te4)4+ cube-like clusters [64]. As shown in Fig. 30, [Sb10Se10]
[AlCl4]2 crystallizes in the triclinic space group P1. Its structure
contains the first [Sb10Se10]2+ polycation, which contains two
realgar-like [Sb4Se4] cages [65].
As shown in Fig. 31, the compounds (Bi2Te2)Cl[GaCl4], (Bi2Se2)Cl
[GaCl4] and (Sb3Te4)[GaCl4] crystallize in the monoclinic space
group C2/m, in which the polycations consist of ladder-like
pnicogen-chalcogen dumbbells with zig-zag conformations. The
compound (Sb2Te2)[GaCl4] crystallizes in the triclinic space group
P1. Its structure consists of two symmetrically independent
[(Sb2Te2)+]n polycations and discrete [GaCl4]
anions. (Sb2Te2)I
[AlI4] and (SbTe4)[Ga2Cl7] crystallize in the monoclinic space group
P21/n. The former also contains ladder-like pnicogen-chalcogen
dumbbells and the latter contains [(Sb2Te2)+]n polycations and dis-
crete [Ga2Cl7]
anions. The (SbTe4)+ cation is a five-membered ring
[66].
As shown in Fig. 32, the compounds [M2Te2Br](AlCl4) (M = Bi,
Sb) crystallize in the monoclinic space group C2/c. Their structures
are constructed by the connection between cationic layers of
[(Bi2Te2Br)+]1 and tetrahedral [AlCl4]
anions. The [(Bi2Te2Br)+]1
layers are built via the linkage of [(Bi2Te2)2+]1 chains and Br ions
along the c direction [67].
The compound (Te4)(Te10)[Bi4Cl16] crystallizes in the triclinic
space group P1. Its structure contains two types of polymeric
cations, (Te10)2+ and (Te4)2+. The (Te2+
10)n cation consists of
planar Te10 groups formed by three corner-sharing Te4 rings.
The (Te4)2+ cation consists of a rectangular planar Te4 ring.
[Bi4Cl16]4
is formed from BiCl7 units by sharing edges and
corners [68].
ion dynamics were studied using 109Ag, 125Te, and 35Cl NMR spec-
troscopies [76]. Ag5Te2Cl is the first example with low-dimensional
partially covalent-bonded subunits in a solid induced by the inter-
action between d10 ions, which results in the switching of thermo-
electric and electronic properties [77].
3.1.2. Ag10Te4Br3
Ag10Te4Br3 (Fig. 36) is the first coin-metal chalcogenide halide
with Te–Te dumbbells and isolated Te2
ions [78]. Ag10Te4Br3 has
four polymorphs from 3 to 450 K, namely hexagonal P6/mmm a-,
hexagonal P63/mmc b-, orthorhombic Cmcm c- and orthorhombic
Cmc21 d-phases. These structures can be transformed at 355, 317
and 290 K for the a-b, b-c and c-d phase transitions, respectively
[79].
3.1.3. Supramolecular type chalcogenide halides
(CuI)3Cu2TeS3 crystallized in the trigonal space group P3121 and
was discovered in 1997. Its structure is composed of iodide and
[TeS3]2
ions, and all the [TeS3]2
units within one layer are paral-
lel [80].
The isostructural (AgI)2Ag3SbS3 and (CuI)2Cu3SbS3 crystallize in
the orthorhombic space group Pnnm [81,82]. The crystal structure
of (AgI)2Ag3SbS3 (Fig. 37) features polyanionic 1[Ag3SbS3I2]2
lay-
ers, which are constructed by [SbS3], [AgS2I] and [AgS2I2] units. The

2.6.2. Other Sb, Bi-based chalcogenide halides

In addition to the previous compounds, some other compounds
also have been studied, including Bi19S27Br3 [69],
MnBiS2Cl, FeSbS2Cl [70], Pb2BiS2I3, Sn2BiS2I3, Sn2BiSI5 [71],
Pb3+xSb3
xS7
xCl1+x (x  0.45) [72], Bi2CuSe3I, Bi6Cu3S10I [73],
In2Bi3Se7I and InBi2Se4I [74].
Pb2BiS2I3, Sn2BiS2I3 (Fig. 33) and Sn2BiSI5 (Fig. 34) are direct
band gap semiconductors. Pb2BiS2I3 and Sn2BiS2I3, crystallize in
the orthorhombic space group Cmcm. Their 3D crystal structures
are strongly anisotropic and are composed of parallel infinite rib-
bons of [M4S2I4] (M = Pb, Sn, Bi) along the c direction. The com-
pound Sn2BiSI5 crystallizes in the monoclinic space group C2/m.
Its structure contains two successive ribbons of [M4S2I4] separated
by two interstitial (Sn1
xBixI6) octahedral units [71]. Fig. 37. Crystal structure of (AgI)2Ag3SbS3 viewed along the c direction [81]. Ó 2002
Royal Society of Chemistry.
3. Transition-metal chalcogenide halides

3.1. Coin-metal chalcogenide halides

Aside from their versatile structures, the mixture of electrons

and Ag+/Cu+ ion conductivities makes coin-metal chalcogenide
halides a type of special optoelectronic material in many fields,
so their exploration as novel optoelectronic materials should be
attractive.

3.1.1. Ag5Te2Cl
Ag5Te2Cl has three polymorphs, namely tetragonal I4/mcm a-,
monoclinic P21/n b- and monoclinic P21/c c-phases. These phases
can be transformed reversibly at suitable temperatures. Their
structures are closely related by symmetry and systematic twin-
ning (Fig. 35). Ag5Te2Cl is a 1D ionic conductor with conductivities
of 1.51  10
3 and 4.30  10
1 X
1 cm
1 at 323 and 469 K, respec-
tively [75]. The relationship between their crystal structures and Fig. 38. Crystal structure of Cu(Sb7Te8)[GaCl4]6 [84]. Ó 2014 Wiley.
38 J.-R. Xiao et al. / Coordination Chemistry Reviews 347 (2017) 23–47
conductivity of (AgI)2Ag3SbS3 was determined to be 8.15  10
5
and 1.52  10
3 X
1 cm
1 at 332 and 478 K, respectively.
The crystal structures of (CuX)(As4S4)(PAs3S3) contain PAs3S3
cages and 1D (CuX)(As4S4) strands built by alternating As4S4 cages
and CuX dumbbells. The 3D structure of (CuI)3(As4S4)(PAs3S3) con-
tains PAs3S3 cages and (Cu3I3)n strands as backbones [83].
A family of compounds M(Sb7Te8)[M0 Cl4]6 (M = Na, Ag, Cu;
M0 = Al, Ga) were reported recently. We take Cu(Sb7Te8)[GaCl4]6
as an example to discuss their structures. Cu(Sb7Te8)[GaCl4]6 crys-
tallizes in the triclinic space group P1. Its structure contains
(GaCl4)
tetrahedra and (Sb7Te8)5+clusters (Fig. 38). Unlike Na+
and Ag+ ions, the Cu+ ion is immobilized in the cube-shaped coor-
dination polyhedron in view of two very short Cu–Cl bonds
induced by the linear [CuCl2]
ion [84].
3.1.4. Ag23Te12X
Partial anionic substitution in Ag23Te12X can be realized to form
the quaternary solid solutions of Ag23Te12Cl1
xBrx, Ag23Te12Br1
yIy
and Ag23Te12Cl1
zIz [85]. The isostructural compounds Ag23Te12X
crystallize in the orthorhombic space group Pnnm. Their crystal
structures can be depicted using a topological method [86]. The
Te substructure can be depicted as a honeycomb-like distorted 63
net, and the halide substructure consists of strands (Fig. 39).
3.1.5. M19Q6X7 (M = Ag, Cu)
Three different structure types can be identified for the
M19Q6X7 solid solutions, namely monoclinic C2/m and orthorhom-
Fig. 39. Crystal structure of Ag23Te12X [86]. Ó 2008 American Chemical Society.
bic Pnma and Pbam. This system demonstrates versatile structures
after partial substitution of either cations or anions [87]. Other
than the monoclinic phase, Ag19Te6Br7 can also crystallize in the
trigonal space group R3m Its solid solutions Ag19Te6Br5.4I1.6 and
Ag19Te5SeBr7 crystallize in the orthorhombic space groups Pnma
and Pbam, respectively. The anion substructure of trigonal Ag19Te6-
Br7 is built up by 63 Te2
net units, corrugated Te6 ring net units in
chair conformations and Kagomé-like Br
net units (Fig. 40). The
results of an impedance spectroscopic investigation indicate that
Ag19Te6Br5.4I1.6 has a conductivity as high as 1.1  10
2 X
1 cm
1
at 323 K [88].
3.1.6. Other transition-metal chalcogenide halides
In addition to the previous Cu, Ag and Au-chalcogenide halides,
Cu3Bi2S3I3 [89], Cu1.5Bi2.64S3.42Br2.58, Cu1.57Bi2.37Se2.68Br3.32, Cu1.57-
Bi4.69Se7.64I0.36, Cu2.31Bi5Se8.31I0.69 [90], Cu4
dBiSe4I [91] and Cu3+d-
Bi5
dSe8
2dX2+2d (X = Cl, Br) [92] have also been studied.
3.2. Zn, Cd and Hg-based chalcogenide halides
3.2.1. Hg3Q2X2
This section introduces the compounds Hg3S2I2, Hg3Se2I2, Hg3-
Se2Br2 and Hg3S2Cl2, which belong to the Hg3Q2X2 family. Their
most attractive application is from their strong potential to act as
hard radiation detection materials at room temperature, usually
having better energy resolution than scintillator detectors, and
they can be applied in the fields of medical imaging, cosmic ray
 J.-R. Xiao et al. / Coordination Chemistry Reviews 347 (2017) 23–47 39

Fig. 40. Crystal structure of trigonal Ag19Te6Br7 [88]. Ó 2008 American Chemical Society.

Fig. 42. Crystal structure of b-Hg3S2Cl2 [95]. Ó 2016 American Chemical Society.

Fig. 41. Crystal structure of Hg3Se2Br2 [93]. Ó 2016 American Chemical Society.
astronomy and national security. As candidates for hard radiation
detection materials at room temperature, there are several aspects
should be considered – the compounds need to have (1) band gaps
in the range of 1.5–2.5 eV, (2) high average atomic numbers (Z), (3)
high mobility-lifetime products and (4) be cost-effective and show
efficient growth of high quality single crystals. Metal chalcogenide
halides combine the attributes from both chalcogenides and
halides by a lattice hybridization approach, so they are one of the
most promising candidates for this application [93].
40 J.-R. Xiao et al. / Coordination Chemistry Reviews 347 (2017) 23–47

Fig. 43. Crystal structure of HgI2As4S4 [96]. Ó 2006 Wiley.

Isostructural Hg3S2I2 and Hg3Se2I2 crystallize in the orthorhom-

bic space group Imma. Their structures contain 1D (Hg3Q2)2+ poly-
cations with intercalated I
ions [94]. Hg3Se2Br2 crystallizes in the
monoclinic space group C2/m. As shown in Fig. 41, the structure of
Hg3Se2Br2 is built from [Hg3Se2] layers parallel to the ab plane, in
which these layers are bound loosely by interlayer Br atoms along
the c direction [93]. It has a resistivity of the order 1011 X cm, and
the mobility-lifetime products of the electron and hole carriers are
around 1.4  10
4 and 9.2  10
5 cm2/V, respectively. It is a
promising candidate for X-ray and c-ray radiation detection at
room temperature.
b-Hg3S2Cl2 is a potential material for X-ray and c-ray detection.
It crystallizes in the cubic space group Pm3n Its 3D structure is
composed of [Hg12S8] cubes, with Cl atoms located within and
between the cubes, and featuring a trigonal pyramidal SHg3 unit
as the main building block (Fig. 42) [95]. Its single crystal sample
has a resistivity of 1010 X cm and the mobility-lifetime products
of the electron and hole carriers are around 1.4(4)  10
4 and 7.5
Fig. 44. Crystal structure of (Hg2Cd2S2Br)Br [97]. Ó 2011 Royal Society of (3)  10
5 cm2/V, respectively. It also is a potential hard-
Chemistry. radiation detector material.

Fig. 45. Crystal structures of CdBiS2Cl (a) and CdBiS2Br (b) [98]. Ó 2006 American Chemical Society.
 J.-R. Xiao et al. / Coordination Chemistry Reviews 347 (2017) 23–47 41

3.2.2. Supramolecular-type chalcogenide halides In/S layers (Fig. 49). Hg7InS6Cl5 has an optical band gap of 2.54 eV
HgI2As4S4 crystallizes in the monoclinic space group P21/c. Its [105].
3D structure, shown in Fig. 43, indicates the arrangement of The compounds TlHg6Q4Br5 (Q = S, Se) crystallize in the tetrag-
dimeric units. The centers of the dimers form a distorted cubic onal space group I4/m. Their 3D structures can be depicted as
close packing [96]. The discovery of HgI2As4S4 indicated that it BrHg3 trigonal pyramids linked by cuboid Hg12Q8 units, and the
was possible to preserve the As4S4 cage for the first time in an Tl and Br atoms occupy the interstitial cavities (Fig. 50). The com-
undistorted manner. pounds TlHg6Q4Br5 (Q = S, Se) melt incongruently and have band
The compound (Hg2Cd2S2Br)Br crystallizes in the orthorhombic gaps of 3.03 and 2.80 eV, respectively [106].
space group Cmmm. Its structure features a 3D cationic network Hg5AsS2I3 [107], Hg2TeBr3 [108], Hg2Te2Br2 and Hg2Te2I2 [109],
built from polyhedral slabs stacked with an –ABAB– mode along and Zn6S5Cl2 and Hg3ZnS2Cl4 [110] have been also investigated.
the b direction via linearly coordinated Hg atoms (Fig. 44). Its opti-
cal gap was determined to be 2.41 e, and it has no obvious absorp- 3.3. V, Nb, Ta-based chalcogenide halides
tion in the IR range 4000–400 cm
1 [97].
A family of quaternary mixed-framework chalcogenide halides, 3.3.1. M3QX7 (M = Nb, Ta)
CdSbS2Cl (1), CdSbS2Br (2), CdBiS2Cl (3), CdBiS2Br (4), CdBiSe2Br (5) The M3QX7compounds consist of Nb3TeI7 [111], Nb3SBr7 [112],
and CdBiSe2I (6), have two types of crystal structures depending on Ta3SBr7 [113] and Ta3QI7 [114]. This section describes only Ta3QI7
the combination of chalcogen and halogen elements. Compounds (Q = Se, Te).
1, 3 and 5 crystallize in the orthorhombic space group Pnma (type The compounds Ta3QI7 (Q = Se, Te) are isostructural with Nb3-
I) and the other compounds crystallize in the monoclinic space SeI7, and crystallize in the hexagonal space group P63mc. Their
group C2/m (type II). Both structures have slabs built from Cd-
centered CdQ6
xXx (x = 0, 2, 4) octahedra via sharing corners or
edges. In both structures, each M3+ (M = Sb, Bi) cation in CdMQ2X
forms a distorted MQ5 square pyramid, which is coordinated
weakly to three X atoms to form a distorted MQ5X3 bicapped trig-
onal prism. The CdQ6
xXx and MQ5X3 units are solely connected via
sharing Q atoms to construct the 3D structure (Fig. 45). They have
band gaps of 1.3–2.2 eV [98].
CdSb2Se3Br2 and its isoelectronic In derivatives InSb2S4X and
InM2Se4Br (M = Sb, Bi) are isotypic. As shown in Fig. 46, CdSb2Se3-
Br2 crystallizes in the monoclinic crystal system C2/m. Its structure
contains CdBr2 and Sb2Se3 sublattices. The former consists of dual
octahedral chains built from [CdBr5Se] units via sharing cis-Br
edges, and the chains propagate along the b axis through shared
trans-Br edges. The latter consists of three edge-shared [SbSe5] Fig. 46. Crystal structure of CdSb2Se3Br2 [99]. Ó 2007 American Chemical Society.

square-pyramidal units. The apex Se atoms of the [CdBr5Se] units

share corners with the [SbSe5] units to construct a 2D slab parallel
to the [
1 0 1] plane [99]. Their band gaps are around 1.1–1.8 eV.
A series of Hg bismuth chalcogenide halides, Hg3Q2Bi2Cl8, have
recently been discovered. Interestingly, they demonstrate different
structure types. As shown in Fig. 47, Hg3S2Bi2Cl8 crystallizes in the
monoclinic space group C2/m and Hg3Te2Bi2Cl8 crystallizes in the
monoclinic space group C2/c. Hg3Se2Bi2Cl8, however, shows com-
plex modulations and structural disorder, which makes its struc-
tural refinement complicated. Their structures feature a sheet-
like network [Hg3Q2]2+ cations built from chair-like Hg6Q6 rings.
The [Bi2Cl8]2
anions are located at the interspaces between the
cationic layers. Hg3S2Bi2Cl8 and Hg3Te2Bi2Cl8 have band gaps of
3.26 and 2.80 eV, respectively [100].
As shown in Fig. 48, the compounds (Hg3S2)(MCl4) (M = Fe2+,
Co2+) crystallize in the orthorhombic space group C222. Their
structures are characterized by a (Hg3S2)2+ polycationic host layer
and a chiral (MCl4)2
chain. The (Hg3S2)2+ layer consists of edge-
shared chair-like Hg6S6 rings with linearly coordinated Hg2+
cations and trigonal pyramidal coordinated S2
anions. They exhi-
bit 3D long-range ordering caused by antiferromagnetically cou-
pled interchain partially lifted geometric frustration, which
results in field induced metamagnetic phase transitions [101].
Aside from the Zn, Cd, Hg chalcogenide halide supramolecules,
2HgSSnBr2 [102], ZnHg3Se2Cl4 [103] and Hg4In2Q3Cl8 [104], also
have been investigated.

3.2.3. Other Zn, Cd, Hg-based chalcogenide halides

Hg7InS6Cl5 is the first member in the family of Hg
IIIA
Q
X
compounds. It crystallizes in the triclinic space group P1. Its struc- Fig. 47. Crystal structure of Hg3S2Bi2Cl8 viewed along the c (a) and b (b) axes [100].
ture features a novel 3D network constructed from Hg-bridged Hg/ Ó 2013 American Chemical Society.
42 J.-R. Xiao et al. / Coordination Chemistry Reviews 347 (2017) 23–47

Fig. 48. Crystal structure of (Hg3S2)(FeCl4) viewed along the a (a) and c (b) directions, and its coordination geometry (c) [101]. Ó 2015 Nature Publishing Group.

Fig. 49. Coordination geometry of Hg7InS6Cl5 [105]. Ó 2012 American Chemical

Society.

Fig. 51. Approximate [100] view of two layers of the extended structure of Ta3QI7:
small white circles, I; large white circles, Se or Te; dark circles, Ta [114]. Ó 1996
American Chemical Society.

Fig. 50. Crystal structure of TlHg6S4Br5 along the c-axis [106]. Ó 2013 American
Chemical Society. Fig. 52. Crystal structure of WF4S [123]. Ó 2009 American Chemical Society.
 J.-R. Xiao et al. / Coordination Chemistry Reviews 347 (2017) 23–47 43

structures consist of layers of I and Q atoms interleaved by Ta
atoms in alternating layers. The Ta atoms are ordered in three
quarters of all the octahedral sites to form Ta3 clusters, which are
located in the layers and are capped by the Q atoms (Fig. 51) [114].
3.3.2. Other V, Nb, Ta-based chalcogenide halides
In addition to the previous V, Nb, Ta chalcogenide halides,
Ta4Se9I8 [115], Ta4S9Br8 [116], V4S9Br4 [117], Nb7S2I19 [118],
Nb6I9S [119], Nb2Te6I [120] and Ta4SI11 [121], also have been
studied, focusing on their crystal structures.
3.4. Mo, W-based chalcogenide halides
3.4.1. MX4S (M = Mo, W)
Until recently, only WSF4 [122,123], WSCl4S8 [124], and MoSF4
[125], belonging to the MX4S (M = Mo, W) family, have been stud-
ied. This section discusses WSF4 and MoSF4.
WSF4 crystallizes in the orthorhombic space group Pca21 [122].
Its structure consists of F-bridged chains (Fig. 52). The F-bridge is
asymmetric with one short bridging W-Fb distance and one long
bridging W- - -Fb distance [123].
MoSF4 also crystallizes in the orthorhombic space group Pca21,
featuring infinite helical chains of cis-F-bridged MoSF5 pseudo-
octahedra along the a-axis (Fig. 53) [125].
3.4.2. Other Mo, W-based chalcogenide halides
Other Mo, W-based chalcogenide halides include Mo6S9
xIx
[126], Mo3Tel0Il0 [127], MoQCl3 [128], [Mo3Se7(TeBr3)Br2]2
[Te2Br10], [Mo3Se7(TeI3)I2]I, [Mo3Te7(TeI3)3]2(I)(TeI3) [129] and
WS2X2 [130].
a-MoSCl3, b-MoSCl3 and MoSeCl3 were synthesized by the
chemical vapor transport method. a-MoSCl3 and MoSeCl3 crystal-
lize in the monoclinic space group C2/c and b-MoSCl3 crystallizes
in the orthorhombic space group Pnma. For the a-phase, an infinite

Fig. 53. Crystal structure of MoSF4 [125]. Ó 2010American Chemical Society.

Fig. 54. Crystal structures of a-MoSCl3 (A), MoSeCl3 (B) and b-MoSCl3(C) [128]. Ó 2014 American Chemical Society.
44 J.-R. Xiao et al. / Coordination Chemistry Reviews 347 (2017) 23–47
Fig. 55. Crystal structures of [Ru(Te9)](InCl4)2 (a), [Ru(Te8)]Cl2 (b) and [Rh(Te6)]Cl3 (c) [131]. Ó 2011 Wiley.
Fig. 56. Crystal structure of b-[Ru2Bi14Br4](AlCl4)4 [132]. Ó 2012 Wiley.
[Mo2(S2)Cl4Cl4/2]1 chain runs along the c direction. For the b-
phase, a [Mo2(S2)Cl3Cl6/2]1 chain runs along the b direction
(Fig. 54). b-MoSCl3 shows weak paramagnetic behavior, and a-
MoSCl3, b-MoSCl3 and MoSeCl3 have band gaps of around 1.2,
1.24 and 1.18 eV, respectively. Moreover, these compounds can
be used as precursors for the syntheses of Mo–S gels and aerogels
[128].
3.5. Ir, Rh, Re, Ru, Pd-based chalcogenide halides
3.5.1. Supramolecular-type chalcogenide halides
The compounds [Ru(Te9)](InCl4)2 and [Ru(Te8)]Cl2 crystallize in
the monoclinic space group C2/c and [Rh(Te6)]Cl3 crystallizes in the
rhombohedral space group R3c (Fig. 55). In their structures, linear
[Mm+(Te±0
n )] (M = Ru, m = 2; M = Rh, m = 3) polycationic chains run
along the c direction. Each of the Ten molecules (n = 6, 8, 9) coordi-
nates with two transition-metal atoms [131].
Fig. 57. Crystal structures of LaTeCl-I (left, PbClF type) and LaTeCl-II (right, PbCl2
type) [143]. Ó 2013Wiley.
The cluster compound [Ru2Bi14Br4](AlCl4)4 has two polymorphs,
and both its a and b phases crystallize in the monoclinic space
group P21/n, but with different unit cell parameters (Fig. 56). The
polycationic cluster [Ru2Bi14Br4] should be written as [(Bi5)Ru(Bi4-
Br4)Ru(Bi5)]4+, which features a binuclear complex of two Ru(I)
cations coordinated by terminal (Bi5)+ square pyramids and a cen-
tral Bi4Br4 ring [132].
In addition to the previous compounds, [Re2Br4(Te2)(TeBr)2
(TeBr2)2] [133], Re6Te6Cl6(TeCl2)2, [Re6Te8(TeBr2)6]Br2 [134],
Re4(l3-Q)4(TeCl2)4Cl8 [135] and [Ir2Te14Br12]2(InBr4)2 [136] also
have been investigated.
3.5.2. Other Ir, Rh, Re, Ru, Pd-based chalcogenide halides
As well as the supramolecular-type Ir, Rh, Re, Ru-based chalco-
genide halides, [IrBr3(SeBr2)3] [137], ReSCl3 [138], Re6X8Br2
 J.-R. Xiao et al. / Coordination Chemistry Reviews 347 (2017) 23–47
[139,140], PdTeI [141] and Pd4Br4Te3 [142] can be also classified
into this subgroup.
4. Rare-earth metal chalcogenide halides
4.1. RE-Q-X (RE = rare-earth metal)
Many compounds belong to the REQX family [143–149]. With
its 1:1:1 composition, La3Se4Cl [144] would be considered another
member. This section introduces some of these compounds as rep-
resentative examples. The compounds RETeCl (RE = La, Ce, Pr, Nd)
crystallize in the tetragonal space group P4/nnm and belong to
the PbFCl structure type. As shown in Fig. 57, LaTeCl and CeTeCl
crystallize in the orthorhombic space group Pnma, with the PbCl2
structure type [143].
4.2. Eu3Bi2Q4F4
Eu3Bi2S4F4 crystallizes in the tetragonal space group I4/mmm.
Its structure contains CaF2-type Eu3F4 layers and NaCl-like BiS2
bilayers, stacking alternately along the c direction (Fig. 58) [150].
The Eu ions in Eu3Bi2S4F4 have two types of oxidation state, Eu
(1) is divalent and Eu(2) has an average oxidation state of around
+2.64(5). These special Eu oxidation states were confirmed by
Mössbauer spectroscopy and magnetization measurements.
Specifically, Eu3Bi2S4F4 has a superconductive transition at 1.5 K.
This superconducting transition temperature can be enhanced by
Se doping to form a solid solution of Eu3Bi2(S, Se)4F4 [151].
Fig. 58. Crystal structure of Eu3Bi2S4F4 [150]. Ó 2014 American Chemical Society.
Fig. 59. The building block La3Te14Br4 in La3Te4Br [152]. Ó 2011 MDPI.
45
4.3. Other rare-earth metal chalcogenide halides
La3Te4Br [152], La2TeI2 [153], Eu3F4S2 [154], Sm2SCl4 [155], Yb3-
F4S2 [156], RESbS2Br2 (RE = La, Ce) [157], RE7S6Cl9 (RE = Pr, Nd)
[158] and RE3S2Cl5 (RE = Nd, Dy) [159] are the other rare-earth
chalcogenide halides.
The first lanthanide telluride bromide La3Te4Br crystallizes in
the orthorhombic space group Pnma. Its structure is built from
bicapped trigonal prisms of Te and Br atoms surrounding La in
two different ways. The bicapped trigonal prisms connect with
each other via sharing edges to construct the 3D structure of
La3Te4Br (Fig. 59) [152].
The compound La2TeI2 crystallizes in the rhombohedral space
group R3m with the 3R-Lu2CCl2 structure type. Its structure fea-
tures layers built by Te-centered La atom octahedra via sharing
edges and these layers are separated by I atoms. La2TeI2 is metallic
at room temperature and undergoes a resistivity anomaly at
around 140 K, corresponding to lattice parameter changes along
with temperature [153].
Rare-earth chalcogenide halides also have potential applica-
tions in the fields of photoluminescence and magnetism. However,
related studies are relatively insufficient. In our opinion, they may
be important research directions in the future.
5. Conclusions
It has become increasingly popular to design new complex
compounds with more functional moieties to obtain desirable
properties [160]. Halogen atoms have larger electronegativities
and smaller atomic radii than their neighboring chalcogen atoms.
Halogen atoms have only one valence electron to take part in a
reaction, whereas chalcogen atoms have two. Chalcogenide halides
demonstrate diverse SBUs with different coordination polyhedra
and polarity. These features are demonstrated in their rich chemi-
cal compositions and crystal structures. In addition to their versa-
tile structures, metal chalcogenide halides M–Q–X have been
studied extensively as important photoelectric materials, being
one of the most successful solid-state electrolytes for batteries
and one of the most promising IR second-order NLO materials.
For the former, a suitable combination of X
and Q2
anions can
fine-tune the chalcogenide halides’ electronic and ionic conductiv-
ities and can influence their electrochemical performance. For the
latter, the introduction of X
ions into the chalcogenides can effec-
tively enhance their optical band gaps, specifically improving their
laser damage threshold. It remains challenging to choose a suitable
combination of X and Q elements with different atomic radii and
ratios. The choice of cations also must be carefully considered. If
necessary, two or more kinds of cations can be introduced into
chalcogenide halides for the ideal chemical or physical
performance.
Acknowledgements
This work was supported by the National Science Foundation of
China (21673203), the Higher Education Science Foundation of
Jiangsu Province (15KJB150031), Natural Science Foundation of
Yangzhou (YZ2016122), Qing Lan Project and the Priority
Academic Program Development of Jiangsu Higher Education
Institutions.
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