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Temperature- and pressure-induced phase

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transitions in the niccolite-type formate

Cite this: J. Mater. Chem. C, 2016,
4, 3185 framework of [H3N(CH3)4NH3][Mn2(HCOO)6]†
Mirosław Ma˛czka,*a Anna Ga˛gor,a Nathalia Leal Marinho Costa,b
Waldeci Paraguassu,b Adam Sieradzkic and Adam Pikula

Received 10th February 2016,
Accepted 4th March 2016
DOI: 10.1039/c6tc00611f
www.rsc.org/MaterialsC
We report the synthesis, crystal structure, thermal, pyroelectric, Raman, infrared and magnetic properties
of [NH3(CH2)4NH3][Mn2(HCOO)6] niccolite. Our results show that this compound crystallizes in a trigonal
%
structure (space group P31c) with dynamically disordered [NH3(CH2)4NH3]2+ cations. It undergoes a
phase transition near Tc = 350 K. The low-temperature structure is polar (space group Cc) and
pyroelectric measurements confirm that it exhibits ferroelectric properties. Detailed analysis of the
structural changes shows that both the spatial arrangement of the [NH3(CH2)4NH3]2+ dipole moments
and distortion of the manganese formate framework contribute to the spontaneous polarization within
the (a, c) plane. Based on Raman and IR data, assignment of the observed modes to the respective
vibrations of atoms is also proposed. Dynamic disorder of organic cations in the high-temperature
phase manifests in the vibrational spectra through very large width of bands corresponding to vibrations
of the NH3 groups. Ordering of these cations is clearly observed in the spectra through a pronounced
decrease in their bandwidths below the phase transition temperatures. Low-temperature magnetic
studies show that this compound is a weak ferromagnet below 9.0 K. We also report high-pressure
Raman scattering studies of this compound, which reveal the presence of two pressure-induced phase
transitions between 0.5 and 0.9 GPa and between 1.3 and 1.9 GPa.

Introduction
Divalent metal formates with general formula [amineH+][M(HCOO)3]
have been extensively studied in recent years due to their interesting
structural, magnetic and dielectric properties. For small cations,
such as NH4+ and HONH3+, these metal organic frameworks
(MOFs) crystallize in the chiral structure and [NH4][M(HCOO)3]
a
Institute of Low Temperature and Structure Research, Polish Academy of Sciences,
Box 1410, 50-950 Wrocław 2, Poland. E-mail: m.maczka@int.pan.wroc.pl;
Fax: +48-713441029; Tel: +48-713954161
b
Faculdade de Fı́sica, Universidade Federal do Pará, 66075-110, Belém, PA, Brazil
c
Department of Experimental Physics, Wrocław University of Technology, Wybrzeże
Wyspiańskiego 27, 50-370, Wrocław, Poland
† Electronic supplementary information (ESI) available: Tables S1–S6: crystal data
and selected geometrical parameters for the studied compound at different
temperatures, the results of the mode analysis performed in Amplimodes, Raman
and IR wavenumbers together with the proposed assignments and wavenumber
intercepts at zero pressure (o0) and pressure coefficients (a = do/dP) for the three
phases of bnMn observed in the high pressure experiment. Fig. S1–S8: Le Bail fit
to the powder XRD pattern, DSC traces, IR and Raman spectra at different
temperatures, wavenumbers vs. pressure plots of the Raman modes observed in
bnMn crystals for the compression experiment and Raman spectra recorded
during the decompression experiment. CCDC 1446778–1446782. For ESI and
crystallographic data in CIF or other electronic format see DOI: 10.1039/c6tc00611f
compounds (M = Mg, Zn, Mn, Ni, Co, Fe) were shown to exhibit
ferroelectric order below 254–160 K.1–5 Furthermore, the analogues
with M = Mn, Ni, Co and Fe order magnetically within 30–8 K.3,4
Formates with larger cations such as dimethylammonium (DMA+),
ethylammonium, formamidinium as well as [NH4][Cd(HCOO)3]
crystallize in the perovskite structure,6–9 whereas formates with
hydrazinium cations (H2NNH3+) may crystallize in both the
chiral and perovskite structural types.10 Among the family of
perovskite formates, those with DMA+ cations have been most
extensively studied due to their multiferroic properties.7,8,11,12 It
is also worth adding that recent studies showed that the properties
of perovskite formates may be modified by A-site or B-site doping,
leading to the diffuse character of phase transitions.13,14
A metal formate framework templated by large protonated
di-, tri- and tetra-amines crystallizes in more complicated
topologies.15 We will focus here only on compounds with
protonated di-amines of general formula [amineH22+][M2(HCOO)6].
To the authors’ knowledge, compounds of this composition
were reported only for N,N 0 -dimethylethylenediamine and 1,4-
diaminobutane (NH2(CH2)4NH2) and they were shown to crystallize
in niccolite-type structure.16–18 Only two compounds with 1,4-
diaminobutane are known with M = Mg and Co. X-ray diffraction
data revealed that [NH3(CH2)4NH3][Mg2(HCOO)6] (bnMg) undergoes

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structural phase transition at 398–412 K from the centrosymmetric
trigonal structure (space group P3% 1c) to the polar monoclinic
structure (space group Cc).17 Recent studies showed that the
room-temperature crystal structure of bnCo can also be described
by the centrosymmetric space group P3% 1c and this compound
orders magnetically below 9.9 K.18 However, the presence of
electric order was not reported for this compound and any other
divalent metal formate crystallizing in the niccolite structure.
The studies of polymorphism in MOFs are very important for
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understanding the structure–property relationship.19 Therefore,
MOFs were often studied as a function of temperature. Pressure
is another thermodynamics variable but it was much less
explored in the studies of MOFs although high-pressure studies
can be useful in many ways relevant to potential technological
applications.20 In this respect, high-pressure studies of chiral
formates [NH4][Zn(HCOO)3] and [ND4][Zn(DCOO)3] revealed
that these compounds exhibit negative linear compressibility
and a pressure-induced phase transition into a monoclinic
phase at about 1.1–1.35 GPa.21 Pressure-induced phase transitions
were also found for azetidinium manganese (AzMn), guanidinium
manganese (GuaMn), azetidinium zinc (AzZn), dimethylammonium
magnesium (DMMg), dimethylammonium cadmium (DMCd) and
[NH4][Cd(HCOO)3] formates crystallizing in the perovskite-type
architecture.9,22–24 Interestingly, the performed studies suggested
that the polar character of [NH4][Cd(HCOO)3] can be greatly
enhanced by application of pressure.9 Very recent theoretical
studies of guanidinium chromium formate and ethylammonium
manganese formate also revealed that the ferroelectric polarization
of these compounds should enhance by application of compressive
strain.25 Among metal formates templated by protonated di-, tri- or
tetra-amines, high-pressure data were reported only for erbium
formate templated by N,N,N0 ,N0 -tetramethylethylenediammonium
cations.26
The most interesting feature of some metal formate frame-
works is the coexistence of magnetic and electric order in a
single phase. Single-phase multiferroics have become a hot
topic in recent years since such materials are promising for
applications in electromagnetic sensors, telecommunication
systems, data storage etc.27 However, such materials are very
rare and in the family of divalent metal formate frameworks the
coexistence of magnetic and electric order was reported only for
the above mentioned chiral and perovskite structures templated
by monoammonium cations.3,7,11 We decided, therefore, to search
for novel materials exhibiting the coexistence of magnetic and
electric order in the weakly studied niccolite-type frameworks
templated by diammonium cations. [NH3(CH2)4NH3][Mn2(HCOO)6]
(bnMn) was chosen as a promising candidate since very recent
reports on Mg analogue indicated a polar structure at room
temperature.17 We report temperature-dependent X-ray diffraction,
Raman, IR and dielectric studies of bnMn in order to understand
the origin of electric ordering, i.e., whether it is related to a peculiar
ordering of organic cations, as reported for chiral- and perovskite-
type formates, or it arises due to distortion of the Mn2[COOH]62
framework. Our aim was also to obtain information on the
stability of this compound under the application of hydrostatic
pressure and the effect of pressure on its ferroelectric properties.
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High-pressure studies have not yet been reported for any niccolite-
type formate framework and we will show that in contrast to the
reported perovskite-type frameworks, for which pressure enhances
the ferroelectric polarization,9,25 application of pressure leads to
the suppression of the ferroelectric properties of bnMn.
Experimental
Synthesis
MnCl2 (99%, Sigma-Aldrich), methanol (99.8%, Sigma-Aldrich),
1,4-diaminobutane (99%, Sigma-Aldrich) and formic acid (98%,
Fluka) were commercially available and used without further
purification. To obtain single crystals of bnMn, 16 mL of
methanol solution containing 5 mmol of 1,4-diaminobutane
and 20 mmol of formic acid was placed at the bottom of a glass
tube (9 mm inner diameter). To this solution, 16 mL of
methanol solution containing 2 mmol of MnCl2 was gently
added. The tube was sealed and kept undisturbed. Light pink
crystals were harvested after 3 days. Elemental analysis (C, H,
N) was performed on an Elementar Vario EL CHNS analyzer.
Anal. calcd for bnMn (%): C, 25.55; H, 4.29; N, 5.96; found (%):
C, 25.47; H, 4.34; N, 5.91. The results of the Le Bail refinement
confirm the phase purity of the obtained sample (Fig. S1, ESI†).
DSC
Heat capacity was measured using a Mettler Toledo DSC-1
calorimeter with a high resolution of 0.4 mW. Nitrogen was
used as a purging gas. The weight of the bnMn sample was
13.3 mg. The heating and cooling rates were 5 K min1. The
excess heat capacity associated with the phase transition in
bnMn was evaluated by subtraction from the data of the baseline
representing variation in the absence of the phase transitions.
X-ray powder diffraction
The powder XRD pattern was obtained for all samples on an
X’Pert PRO X-ray diffraction system equipped with a PIXcel
ultrafast line detector, focusing mirror, and Soller slits for
CuKa1 radiation (l = 1.54056 Å).
Single crystal X-ray diffraction
XRD data were collected using Xcalibur-Atlas (for low temperatures)
and Xcalibur-Sapphire1 (for room temperature and high tem-
peratures) diffractometers, both operating in k-geometry,
equipped with a two-dimensional CCD detector and a Mo Ka
radiation (0.71073 Å) source. Data were measured in a o-scan
mode with Do = 1.01. The CrysAlis PRO was used for data
collection and processing [CrysAlis PRO, Agilent Technologies,
Version 1.171.37.35h.]. The structures were solved by direct
methods and refined using full-matrix least-squares methods
using SHELXL2014/7.28 Empirical absorption correction using
spherical harmonics, implemented in the SCALE3 ABSPACK
scaling algorithm, was applied on all data. The restraints on C–C
distances (DFIX) were used to fix disordered [NH3(CH2)4NH3]2+
(bnH22+) cations to be chemically reasonable in the trigonal phase
at 360 K and in the monoclinic phase at 345 K. Hydrogen atoms
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were introduced in calculated positions and refined as riding
atoms. Thermal parameters of hydrogen atoms were set to be
equal to 1.2 times the thermal parameters of the corresponding
parent atoms. The high temperature was sustained with a hot-
air flow attachment (Kuma Diffraction, covering the temperature
range 300–770 K) while an open flow nitrogen cryosystem (Oxford
Cryosystem, covering the temperature range 90–320 K) was used
for experiments at low temperatures. Table S1, in the ESI,†
presents the results of the data collection and refinement together
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with the crystal description. Tables S2 and S3 (ESI†) show the
selected interatomic distances and hydrogen bond parameters.
Dielectric and pyroelectric measurements
Ambient pressure dielectric measurements of the examined
sample were carried out using a Novocontrol analyzer. Since the
obtained single crystals were not big enough to perform single
crystal dielectric measurements, pellets made of well-dried
samples were measured instead. The pellets were placed between
two copper, flat electrodes (diameter 6 mm) of the capacitor with a
gap of 0.3 mm. The small signal of amplitude 1 V was applied
across the sample. The temperature was controlled by the Novo-
Control Quattro system, with use of a nitrogen gas cryostat. The
measurements were taken every 1 deg over the temperature
range from 300 to 400 K. Temperature stability of the samples
was better than 0.1 K.
For the pyroelectric measurements, the pellet sample was
poled in an electric field of 1 kV cm1 from 400 to 310 K. After
removing the poling electric field and releasing space charges
for at least 20 minutes, the pyroelectric current was recorded
with heating and cooling at a constant rate of 2 K min1.
Magnetic measurements
The magnetic properties of a large number of freely oriented
single crystals of bnMn (about 70 mg in total) were studied
using a commercial superconducting quantum interference
device (SQUID) magnetometer equipped with an AC suscepto-
meter. Magnetization was measured in the temperature range
2–40 K and in the external magnetic field up to 50 kOe. The AC
magnetic susceptibility was measured in the zero applied
magnetic field using an alternate probing magnetic field with
an amplitude of 3.73 Oe and frequency varying from 1 Hz to
1.5 kHz. The background coming from a weakly diamagnetic
sample holder (not shown here) was found to be negligible in
comparison to the total signal measured. Therefore its subtraction
was omitted. Also no demagnetization corrections were made to
the data reported here.
Temperature-dependent Raman and IR studies
Temperature-dependent Raman spectra were measured using a
Renishaw InVia Raman spectrometer equipped with a confocal
DM 2500 Leica optical microscope, a thermoelectrically cooled
CCD as a detector, an argon laser operating at 488 nm and
a Linkam cryostat cell. Temperature-dependent IR spectra in
the 5–300 K range were measured using a Biorad 575C FT-IR
spectrometer and a helium-flow Oxford cryostat. Additional
measurements in the 300–450 K range were done using a
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homemade furnace. The spectral resolution of Raman and IR
spectra was 2 cm1.
High-pressure Raman scattering studies
The high-pressure Raman spectra were recorded in back-scattering
geometry using a microscope attached to a triple-grating spectro-
meter Jobin Yvon T64000. The 514.5 nm line of a solid-state ion
laser was used as excitation and the spectral resolution was
2 cm1. In order to reach high pressures, a diamond anvil cell
m-scope DAC HT(S) from Almax easyLab with a diamond of
0.4 mm of culets was used. The sample was loaded into a
100 mm hole drilled in a stainless steel gasket with a thickness
of 200 mm using an electric discharge machine from Almax
easyLab. The Nujol served as the pressure transmitting media.
Pressures were measured based on the shifts of the ruby R1 and
R2 fluorescence lines.
Results and discussion
DSC
The DSC measurements show the presence of one heat anomaly
at 355.2 K upon heating and 349.7 K upon cooling (Fig. S2, ESI†).
The relatively large thermal hysteresis (5.5 K) and symmetric shape
of the thermal anomaly (Fig. S2 (ESI†) and Fig. 1) suggest a first-
order character of the phase transition.
The associated change in enthalpy DH and entropy DS was
estimated to be B2.6 kJ mol1 and B7.4 J mol1 K1, respectively.
From the Boltzmann equation, DS = R ln(N), where R is the gas
constant and N is the number of sites for the disordered system,
which can be estimated to be 2.4. X-ray diffraction data reported in
the next paragraph show the trigonal disorder of the bnH22+
cations in the high-temperature phase. The value of N obtained
by us (2.4) is, therefore, lower than the expected N value (3) for a
complete ordering of the bnH22+ cations. It is worth noting that the
former study of the isostructural bnMg compound estimated N to
be 3.9, i.e. significantly larger than expected for the trigonal
disorder of bnH22+ cations.17 Furthermore, the phase transition
Fig. 1 The heat capacity of bnMn measured in a cooling mode. The insets
show the change in Cp and S related to the phase transition.
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into the disordered phase occurs at higher temperature for
bnMg (B412 K in heating mode) compared to bnMn (B355 K
in heating mode). This behavior shows that similarly as in
the case of perovskite-type divalent formates templated by
protonated amines,29 also for the niccolite-type formate Tc is
unusually high for the Mg analogue.
Single crystal X-ray diffraction
BnMn is isomorphic to the recently reported bnMg analogue.17
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It crystallizes in a niccolite-type structure, in the P3% 1c space
group, similar to several newly synthesized heterometallic and
mixed-valence metal formate framework materials.30 In this
trigonal structure the divalent manganese ions occupy two non-
equivalent positions of 3.2 (D3) and 3% (C3) symmetries, both are
octahedrally coordinated by the formate ligands. The Mn1/
Mn2–O distances are equal to 2.174(3)/2.173(2) Å at 360 K.
Significantly shorter distances of 2.0807(10)/2.0845(11) Å at
430 K were reported for bnMg.17 This behavior reflects the
smaller ionic radius of Mg2+ compared to Mn2+ and thus a
significantly smaller unit cell volume of bnMg (853.41(5) Å3 at
410 K)17 compared to bnMn (894.44(6) Å3 at 360 K). The metal
centers are connected through formate linkers in the anti–anti
mode configuration. The template counterions accommodate
the elongated crystal voids. The bnH22+ ions are dynamically
disordered within three symmetrically equivalent positions
around the three-fold axis, see Fig. 2. At 345 K the structural
Fig. 2 (a) Disorder and conformational changes of the bnH22+ ions in the trigonal (360 K) and monoclinic phases (345–90 K). The crosses mark the
positions of additional electron maxima related to the disordered mirror position. (b and c) Arrangement of the template ions in the crystal cavities in the
trigonal and monoclinic phase, respectively. Dashed lines stand for hydrogen bonds.
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phase transition leads to lowering of the crystal symmetry to
the monoclinic with the polar Cc space group. In the new
phase, the site symmetry of all atoms is reduced to C1. The
mechanism of the transformation is complex and involves both
ordering of the bnH22+ ions and distortion of the Mn2(COOH)62
framework. The metrics of the primitive monoclinic structure
corresponds to the trigonal unit cell. Due to the C centering the
volume of the monoclinic cell is doubled compared to the trigonal
cell. Fig. S3 (ESI†) presents the temperature evolution of the
monoclinic lattice parameters during heating. The most affected
by the transition are the a and b directions with Da/a and Db/b B
2% whereas the cmono = ctrigonal change only insignificantly.
Nevertheless, close to the transition temperature the monoclinic
lattice exposes noteworthy changes in the monoclinic structure
in the c direction in quite a wide temperature range (B15 K).
The second important anomaly refers to the volume, which
decreases after the transition to the hexagonal cell manifesting
small negative thermal expansion of the lattice. Small negative
thermal expansion was also noticed for isomorphic bnMg.17
The observed structure anomalies are most likely associated
with the ordering process and conformational changes of the
bnH22+ ions. The determinant factors of the conformational
preferences of this di-protonated linear polyamine are the
electrostatic forces and steric effects.31 Minimization of the
repulsive N–H  H–N steric interactions and formation of intra-
molecular hydrogen bonds with temperature decrease lead to
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the lattice distortion and conformational changes of template
ions in bnMn. In the high-temperature phase the counterions
have the eclipsed form with C–C–C–N dihedral angles of 1271
and 1271. The temperature lowering induces rearrangement
of the ions. In the monoclinic phase the dihedral angles change
to 741 and 721 at 345 K and 681 and 671 at 90 K indicating
gauche conformation which is, interestingly, less energetically
favored according to the ab initio calculations.31 Simultaneous
skeletal rearrangements and thermally activated positional
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disorder were observed also in other 1,4-diaminobutane hybrids,
e.g. in [NH3(CH2)4NH3][MnCl4].32
In the trigonal phase the bnH22+ ion may perform free
rotations along the c-axis changing the placement among
3 possible sites. In the monoclinic phase this dynamical disorder
is significantly reduced. The cation is stabilized through the
N–H  O hydrogen bonds of medium strength that involve all
amine hydrogen atoms and formate oxygens. The donor to
acceptor distances range from 2.823(8) Å to 3.138(8) Å, the
donor to hydrogen to acceptor angles range from 1571 to 1771
at 345 K and do not change considerably with temperature
decrease except that at room temperature and below additional
bifurcated contact appears (Table S3, ESI†). The corresponding
hydrogen bond parameters for bnMg just below Tc (at 390 K)
were 2.847(2)–3.220(2) Å and 158.0–174.81.17 Slightly larger
donor to acceptor distances for bnMg suggest slightly weaker
hydrogen bonds for this compound. X-ray diffraction data also
show that the hydrogen bond parameters of bnMg exhibit more
significant changes upon cooling compared to bnMn. As a result,
the donor to acceptor distances at low temperatures become
slightly shorter for bnMg (2.815(13)–3.1147(12) Å at 100 K)17
than bnMn (2.817(3)–3.160(4) Å at 90 K).
Despite the stabilization of –CH2–NH3+ terminal groups the
central ethylene is prone to temperature-induced rotations
within the additional mirror position, see Fig. 2(a). At 345 K,
very close to the phase transition, the main and the mirror
Fig. 3 Temperature dependence of complex dielectric permittivity: (a) real part and (b) loss tangent. The measurements were taken with increasing
frequency.
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setting are populated in the 0.7/0.3 ratio. The temperature
decrease reduces the movements. At 298 K this particular
disorder manifests as an additional maximum at the electron
density map with r B 1.7 e Å3. It is also present at 160 K where
r B 0.74 e Å3 and finally, disappears at 90 K. Fig. 2(a)
illustrates the change of the orientational states for bnH22+
with the temperature lowering. It is worth adding that partial
disorder was also reported for bnMg and the mirror setting
population decreased for this compound from 0.75/0.25 at
390 K to 0.85/0.15 at 290 K and 0.9/0.1 at 240 K.17
Below Tc, the ordering of the bnH2+ ions breaks the symmetry
and induces the spontaneous polarization in the (a, c) plane.
The symmetry mode analysis performed in AMPLIMODES33
shows, however, that non-trivial contribution to the induction
of the spontaneous polarization has also a polar distortion of
the Mn2[COOH]62 framework. Thus, the ferroelectric phase
transition has both order–disorder and displacive contributions.
The details concerning the atomic displacements between P3% 1c
and Cc phases are given in ESI,† in Table S4.
Dielectric and pyroelectric measurements
Fig. 3 shows the temperature dependence of the complex
dielectric permittivity for bnMn. The real part of the dielectric
permittivity shows a step-like change at about 350 K (Fig. 3(a)).
Nearly discontinuous-like anomaly in the dielectric permittivity
suggests a first-order type phase transition. Furthermore, the
real part of the dielectric permittivity is almost frequency
independent at frequencies higher than 1 KHz and some
deviation can be noticed only on the low temperature side.
The loss tangent also shows a distinct anomaly at the phase
transition temperature (Fig. 3(b)). It can be noticed that at low
frequencies (below 2 kHz) the real part of the dielectric permittivity
and the loss tangent exhibit a significant increase on the high
temperature side. Such behavior may indicate some conductivity
process, which is activated at higher temperatures and which
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Fig. 4 The pyroelectric current as a function of temperature for poly-
crystalline bnMn in heating and cooling modes. The sharp pyroelectric
peaks indicate a ferroelectric transition. The inset shows the estimated
electric polarization obtained by integrating the pyroelectric current with
time as a function of temperature.
can be most likely attributed to the presence of some amount of
water absorbed by the studied pellet. The dielectric properties of
bnMn differ significantly from those reported for the bnMg
analogue,17 i.e., the dielectric permittivity values of bnMn are an
order of magnitude smaller. Furthermore, whereas the Mg
analogue exhibited pronounced dielectric relaxation attributed
to the relaxor-like behavior of the sample, frequency dependence
of the tangent loss of bnMn shows the weak relaxor nature of the
electric ordering.
In order to clarify the ferroelectric nature of the phase transition,
we have performed the pyroelectric current measurements. As
seen in Fig. 4, a distinct pyroelectric peak is observed at the
phase transition temperature Tc = 350 K. The estimated electric
polarization value (inset in Fig. 4) is 5.8 mC m2, indicating
good ferroelectric properties. It is worth adding here that in the
family of metal formate frameworks pyroelectric current was
successfully measured only for perovskite-type [(CH3)2NH2]-
[Mn(HCOO)3].11 Ferroelectric properties were also experimen-
tally confirmed by observation of the dielectric hysteresis loops
for [NH4][M(HCOO)3] chiral formates.3 Thus bnMn is the third-
type of metal formate templated by protonated amine for which
ferroelectric properties are proved. In contrast to the previously
reported compounds templated by monovalent cations (NH4+
or DMA+), which crystallize in the chiral and perovskite architecture,
respectively, bnMn is templated by diammonium cation (bnH22+)
and it crystallizes in the niccolite architecture.
Magnetic properties
Temperature dependence of the magnetization M(T) of bnMn
measured in an external magnetic field H of 100 Oe is displayed
in the main panel of Fig. 5. A distinct anomaly visible in the
M(T) curve at low temperatures indicates that the compound
orders magnetically below Tm = 9.0(1) K. Bifurcation of M(T)
appearing in the ordered region upon changing the cooling
regime of the sample suggests the ferromagnetic character of
the phase transition at Tm. However, a small magnitude of that
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Fig. 5 Temperature dependence of magnetization M of bnMn measured
in zero-field-cooling (ZFC) and field-cooling (FC) regimes in the external
magnetic field H. Left inset: M vs. H measured at constant temperature
T upon increasing and decreasing field (closed and open symbols, respectively).
Right inset: Real (w 0 ) and imaginary (w00 ) parts of AC magnetic susceptibility wAC
measured as a function of temperature in the zero applied magnetic field for
different frequencies fAC of the probing magnetic field. Solid lines serve as a
guide to the eye, and the arrows mark the ordering temperature Tm.
bifurcation as well as very weak magnetic hysteresis (hardly
visible in the field dependence of the magnetization M(H)
plotted in the left inset to Fig. 5) shows that the ferromagnetism
is very weak in the compound studied.
In order to clarify the nature of magnetic ordering in bnMn
we measured its AC magnetic susceptibility wAC in the zero
magnetic field and in the ZFC regime. As can be inferred from
the right inset to Fig. 5 a distinct cusp visible in the real part w 0
of wAC at Tm is associated with featureless and temperature
independent imaginary part w00 . Moreover, there is no significant
difference between the wAC curves probed by an alternate
magnetic field of different frequencies fAC (for the sake of clarity
only the data collected at two terminal frequencies are plotted in
Fig. 5). Such behavior points out clearly at antiferromagnetic
character of the ordering at 0 Oe.
Taking into account the above findings one can conclude
that bnMn is most probably a weak ferromagnet, i.e. an anti-
ferromagnetically ordered compound with a small canting of
the spins in the underlying antiferromagnetic lattice. The origin
of the ferromagnetism in such systems is a small ferromagnetic
component of the magnetic moments, which is produced
perpendicular to the spin-axis of the antiferromagnet by an
antisymmetric exchange or single-ion anisotropy.34,35 The magnetic
behavior of bnMn is similar to that observed in other metal–
organic frameworks with Mn, e.g. [(CH3)2NH2][Mn(HCOO)3]
and [NH4][Mn(HCOO)3].3,11
Temperature-dependent Raman and IR studies
Temperature-dependent Raman and IR spectra are presented in
Fig. 6 and Fig. S4–S6 (ESI†). Table S5 (ESI†) lists the wavenumbers
of the observed modes together with the proposed assignment.
Assignment is proposed by comparison of the bnMn spectra with
the spectra of other formates,8,23,36 and experimental as well as
This journal is © The Royal Society of Chemistry 2016

Journal of Materials Chemistry C
theoretical studies of neutral bn and related 1,3-diaminopropane
molecules, bnH22+ cations in the C–H and N–H stretching
regions, [NH3(CH2)4NH3]BiCl5 and [NH3(CH2)4NH3]BiCl5H2O
compounds.37–42
Fig. 6 and Fig. S4 (ESI†) show that the Raman spectra remain
qualitatively the same in the 360–380 K range. The spectrum
measured at 350 K is, however, significantly different. Firstly,
the bands in the 2800–3050 cm1 range are narrower. As a
result, the band at 2862 cm1 visible only as a weak shoulder at
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360 K, is clearly observed as a well-resolved band at 350 K.
Secondly, some bands exhibit a sudden change in intensity. For
instance, at 360 K the 871 cm1 Raman band is much weaker
than the 790 cm1 band but at 350 K the intensity of this band
significantly increases (see Fig. 6b). Thirdly, the band at
1025 cm1 disappears. Clear narrowing of bands and a sudden
change in intensities are also observed in the IR spectra (Fig. S5
and S6, ESI†). For instance, the full width at half maximum
(FWHM) of the 441 cm1 IR band decreases from 49 cm1 at
440 K to 19.8 cm1 at 340 K. It is worth noting that the most
significant narrowing of bands is observed for the bands
related to the bnH22+ cation, for instance the ds(NH3) band
observed at 1516 cm1 (see Fig. S6a, ESI†). This behavior is
consistent with the postulated order–disorder mechanism of
the phase transition. Our data show, however, that many bands
exhibit further pronounced narrowing upon cooling the sample
below 340 K. This behavior indicates that the bnH22+ cations
have some degree of reorientational motions in the low-
temperature phase and a complete freezing of these motions
occurs below 140 K. Low-temperature data also reveal that the
phase transition leads to splitting of many bands related to
HCOO ions (see Fig. 6 and Fig. S6, and Table S5, ESI†). This
behavior shows that ordering of cations is associated also with
distortion of the manganese formate framework. It is interesting to
Fig. 6 Detail of the Raman spectra corresponding to the spectral ranges 1310–1400, 750–1100 and 50–500 cm1 at different temperatures in
heating run.
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note that some of the IR and Raman bands of the high-
temperature phase disappear in the low-temperature phase or
exhibit very pronounced changes in intensities and shifts. This
behavior is especially pronounced in the 850–1200 cm1 region
(see Fig. 6b and Fig. S6c, ESI†), where most bands can be
attributed to vibrations of the NH3+ groups and the skeleton.
This behavior can be attributed to the change in the conformation
of the bnH22+ ion during the phase transition. Indeed, former
studies of polyamines and sodium oleate showed that the n(CC)
bands are very sensitive to the conformational changes.43,44 For
instance, the antisymmetric n(CC) Raman band of sodium oleate
observed at 1063 cm1 for the all-trans conformer shifted to
1086 cm1 for the gauche conformer.43 The observed shift of
the n(CC) Raman bands of bnMn from 998 cm1 for the high-
temperature phase (at 380 K) to 1005 cm1 for the low-
temperature polymorph (at 350 K) is consistent with the change
from all-trans conformation in the high-temperature phase
to gauche conformation in the monoclinic phase. Finally, it is
worth noting that the IR spectra change very weakly when
temperature is lowered from 120 K to 5 K (Fig. S5 and S6, ESI†).
This behavior indicates that bnMn does not undergo any
temperature-induced phase transition below 120 K.
Pressure-dependent Raman scattering studies
The pressure-dependent Raman spectra are presented in Fig. 7.
Fig. S7 (ESI†) shows pressure dependence of the wavenumbers,
which can be well described using a linear function o(P) = o0 +
aP. Table S6 (ESI†) summarizes the values of wavenumber
intercepts at zero pressure (o0) and pressure coefficients (a =
do/dP), obtained from fitting of the experimental data by linear
functions.
When pressure increases, the spectra exhibit weak changes
up to 0.5 GPa. At 0.9 GPa, the intensity of the 877 cm1 band
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Fig. 7 Pressure-dependent Raman spectra of bnMn recorded during the compression experiment.
strongly decreases and a new band is clearly observed at
1038 cm1 (see Fig. 7). Furthermore, the bands in the 1350–
1420 and 100–250 cm1 regions exhibit large broadening.
These changes indicate that bnMn undergoes a structural phase
transition between 0.5 and 0.9 GPa. It is worth noting that the
observed changes in the Raman spectra are very similar to those
observed at the temperature-induced phase transition near
350 K. It is, therefore, very likely that pressure induced transition
into the trigonal disordered phase observed at ambient pressure
above 350 K. Since the phase transition has a first-order nature, the
change in Tc upon applying pressure can be described by the
Claussius–Clapeyron equation:
@Tc Tc ðDV=VÞ
¼ Vmolar (1)
@p DHmolar
where Tc is the transition temperature, DV/V is the relative volume
change at Tc, Vmolar is the molar unit cell volume and DHmolar
represents the change in the molar enthalpy. The negative
pressure dependence of Tc means that a negative change of
the volume takes place at the phase transition. Indeed, our
X-ray diffraction data show that DV/V is negative (about 0.002
according to Fig. S3, ESI†). Taking Tc as 350 K, DHmolar =
2.6 kJ mol1 and Vmolar = 0.0002704 m3 mol1 we can estimate
qTc/qp to be about 73 K GPa1. Thus one would expect to
observe the ferroelectric phase transition at about 0.7 GPa. As
can be noticed, the estimated value is in excellent agreement
with the high-pressure experiment showing the phase transition
between 0.5 and 0.9 GPa.
Upon further increase of pressure, significant changes occur
in the spectra when pressure changes from 1.3 to 1.9 GPa.
Firstly, new bands appear at 215, 295 and 988 cm1. Secondly,
the 787 and 793 cm1 bands merge into one band. Thirdly, the
intensity of the 1005 cm1 band (at 1.3 GPa) strongly increases
3192 | J. Mater. Chem. C, 2016, 4, 3185--3194
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Journal of Materials Chemistry C
when pressure reaches 1.9 GPa. A strong intensity increase can
also be noticed for the 1368 cm1 band. Fourthly, some modes
exhibit a weak but discontinuous shift. For instance, the 878,
1005 and 1072 cm1 bands shift towards higher wavenumbers
by nearly 5, 6 and 8 cm1, respectively. These changes indicate
that bnMn exhibits a second pressure-induced phase transition
between 1.3 and 1.9 GPa. A significant and abrupt shift of bands,
which can be attributed to vibrations of the bnH22+ cations,
indicates that bnMn undergoes a first-order phase transition that
leads to significant strengthening of the interactions between the
bnH22+ cations and the manganese formate framework. The
appearance of additional bands suggests the lowering of the crystal
symmetry. The observed shifts of bands corresponding to the
formate ions are weak and this result indicates that the transition
leads to weak distortion of the manganese formate framework.
When pressure increases beyond 1.9 GPa, Raman bands become
broader and less intense and the spectra become very weak above
3.4 GPa. This behavior suggests that bnMn starts to amorphize at
high pressures. It is worth noting that amorphization, irreversible or
reversible, was observed for many MOFs.20 For porous MOFs,
amorphization is sometimes observed at very low pressures. For
instance, the Sc2BDC3 MOF (BDC = 1,4-benzenedicarboxylate)
exhibits reversible amorphization already at 0.14 GPa.20,45
Raman spectra of bnMn during the decompression are presented
in Fig. S8 (ESI†). The observed changes in the Raman spectra are
similar to those observed upon compression indicating reversibility
of the amorphization-like behavior and phase transitions.
Conclusions
We report synthesis and characterization of bnMn niccolite.
DSC and detailed temperature-dependent X-ray diffraction,
dielectric, Raman and IR data show that this compound
This journal is © The Royal Society of Chemistry 2016

Journal of Materials Chemistry C
undergoes a first-order phase transition from the P3% 1c to Cc
phase near 350 K. Pyroelectric current shows a distinct peak
near 350 K proving that this formate has ferroelectric properties
below 350 K. X-ray diffraction and vibrational data also reveal
that the phase transition is associated with the change of the
bnH22+ conformation from all trans in the high-temperature
phase to gauche in the low-temperature phase. Detailed structural
analysis also shows that both organic cations and distortion of the
manganese formate framework contribute to the spontaneous
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polarization. Another interesting observation is that this com-
pound orders magnetically below 9.0 K.
In addition to the temperature-dependent studies, we also
performed high-pressure Raman studies of this compound.
The obtained data show strong evidence for two pressure-
induced phase transition near 0.5–0.9 and 1.3–1.9 GPa. The
first transition leads most likely to transformation of the crystal
into the trigonal paraelectric phase, observed at ambient pressure
above 350 K. Thus pressure leads to suppression of its ferro-
electric properties. The second transition is most likely associated
with some reorientation and/or conformational change of the
bnH22+ ion, which leads to strengthening of the hydrogen bonds
and lowering of crystal symmetry. We also observe partial
amorphization of the sample when pressure increases beyond
3 GPa. This process is, however, fully reversible when pressure
decreases from 4.2 GPa to ambient pressure.
Acknowledgements
The authors acknowledge the Brazilian National Research
Council (CNPq) for a fellowship and grant 401849/2013-9.
References
1 R. Shang, S. Chen, Z. M. Wang and S. Gao, in Metal-Organic
Framework Materials, ed. R. L. MacGillivray and C. M. Lukehart,
John Wiley & Sons Ltd., 2014, pp. 221–238.
2 (a) Z. Wang, B. Zhang, K. Inoue, H. Fujiwara, T. Otsuka,
H. Kobayashi and M. Kurmoo, Inorg. Chem., 2007, 46,
437–445; (b) M. Ma ˛czka, A. Pietraszko, B. Macalik and
K. Hermanowicz, Inorg. Chem., 2014, 53, 787–794; (c) M.
Ma ˛czka, K. Szymborska-Małek, A. Ciupa and J. Hanuza, Vib.
Spectrosc., 2015, 77, 17–24; (d) J. Xu, B. E. G. Lucier,
R. Sinelnikov, V. V. Terskikh, V. N. Staroverov and
Y. Huang, Chem. – Eur. J., 2015, 21, 14348–14361.
3 G. C. Xu, W. Zhang, X. M. Ma, Y. H. Hen, L. Zhang, H. L. Cai,
Z. M. Wang, R. G. Xiong and S. J. Gao, J. Am. Chem. Soc.,
2011, 133, 14948–14951.
4 J. M. M. Lawler, P. Manuel, A. L. Thompson and P. J. Saines,
Dalton Trans., 2015, 44, 11613–11620.
5 B. Liu, R. Shang, K.-L. Hu, Z.-M. Wang and S. Gao, Inorg.
Chem., 2012, 51, 13363–13372.
6 (a) Z. Wang, B. Zhang, T. Otsuka, K. Inoue, H. Kobayashi and
M. Kurmoo, Dalton Trans., 2004, 2209–2216; (b) M. Ma ˛czka,
A. Ciupa, A. Ga ˛gor, A. Sieradzki, A. Pikul, B. Macalik and
M. Drozd, Inorg. Chem., 2014, 53, 5260–5268.
This journal is © The Royal Society of Chemistry 2016
View Article Online
Paper
7 (a) P. Jain, V. Ramachandran, R. J. Clark, H. D. Zhou,
B. H. Toby, N. S. Dalal, H. W. Kroto and A. K. J. Cheetham,
J. Am. Chem. Soc., 2009, 131, 13625–13627; (b) M. Sánchez-
Andújar, S. Presedo, S. Yáñez-Vilar, S. Castro-Garcia,
J. Shamir and M. A. Señaris-Rodriguez, Inorg. Chem., 2010,
49, 1510–1516.
8 M. Ma ˛czka, A. Ga ˛gor, B. Macalik, A. Pikul, M. Ptak and
J. Hanuza, Inorg. Chem., 2014, 53, 457–467.
9 L. C. Gómez-Aguirre, B. Pato Dolán, A. Stroppa, S. Yáñez-
Vilar, L. Bayarjargal, B. Winkler, S. Castro-Garcia, J. Mira,
M. Sánchez-Andújar and M. A. Señaris-Rodriguez, Inorg.
Chem., 2015, 54, 2109–2116.
10 (a) S. Chen, R. Shang, K.-L. Hu, Z.-M. Wang and S. Gao, Inorg.
Chem. Front., 2014, 1, 83–98; (b) G. Kieslich, S. Kumagai, K. T.
Butler, T. Okamura, C. H. Hendon, S. Sun, M. Yamashita,
A. Walsh and A. C. Cheetham, Chem. Commun., 2015, 51,
15538–15541.
11 W. Wang, L.-Q. Yan, J.-Z. Cong, Y.-L. Zhao, F. Wang,
S.-P. Shen, T. Zhou, D. Zhang, S.-G. Wang, X.-F. Han and
Y. Sun, Sci. Rep., 2013, 3, 2024.
12 (a) M. Sánchez-Andújar, S. Presedo, S. Yáñez-Vilar, S. Castro-
Garcia, J. Shamir and M. A. Señaris-Rodriguez, Inorg. Chem.,
2010, 49, 1510–1516; (b) M. Sánchez-Andújar, L. C. Gómez-
Aguirre, P. Pato-Dolán, S. Yáñez-Vilar, R. Artiaga, A. L. Llamaz-
Saiz, R. S. Manna, F. Schnelle, M. Lang, F. Ritter, A. A.
Haghighirad and M. A. Señarı́s-Rodrı́guez, CrystEngComm,
2014, 16, 3558–3566; (c) M. Kosa and D. T. Major, CrystEng-
Comm, 2015, 17, 295–298.
13 S. Chen, R. Shang, B.-W. Wang, Z.-M. Wang and S. Gao,
Angew. Chem., Int. Ed., 2015, 54, 11093–11096.
14 M. Ma ˛czka, A. Sieradzki, B. Bondzior, P. Dereń, J. Hanuza
and K. Hermanowicz, J. Mater. Chem. C, 2015, 3, 9337–9345.
15 Z. Wang, K. Hu, S. Gao and H. Kobayashi, Adv. Mater., 2010,
22, 1526–1533.
16 (a) Z. Wang, X. Zhang, S. R. Batten, M. Kurmoo and S. Gao,
Inorg. Chem., 2007, 46, 8439–8441; (b) M.-Y. Li, M. Kurmoo,
Z.-M. Wang and S. Gao, Chem. – Asian J., 2011, 6, 3084–3096.
17 R. Shang, G.-C. Xu, Z.-M. Wang and S. Gao, Chem. – Eur. J.,
2014, 20, 1146–1158.
18 R. Shang, S. Chen, K.-L. Hu, Z.-C. Jiang, B.-W. Wang,
M. Kurmoo, Z.-M. Wang and S. Gao, APL Mater., 2014,
2, 124104.
19 D. Aulakh, J. R. Varghese and M. Wriedt, Inorg. Chem., 2015,
54, 8679–8684.
20 S. C. McKellar and S. A. Moggach, Acta Crystallogr., Sect. B:
Struct. Sci., Cryst. Eng. Mater., 2015, 71, 587–607.
21 (a) W. Li, M. R. Probert, M. Kosa, T. D. Bennett,
A. Thirumurugan, R. P. Burwood, M. Parinello, J. A. K. Howard
and A. K. Cheetham, J. Am. Chem. Soc., 2012, 134, 11940–11943;
(b) M. Ma ˛czka, P. Kadłubański, P. T. C. Freire, B. Macalik,
W. Paraguassu, K. Hermanowicz and J. Hanuza, Inorg. Chem.,
2014, 53, 9615–9624.
22 W. Li, A. Thirumurugan, P. T. Barton, Z. Lin, S. Henke,
H. H. M. Yeung, M. T. Wharmby, E. G. Bithell, J. A. K.
Howard and A. K. Cheetham, J. Am. Chem. Soc., 2014, 136,
7801–7804.
J. Mater. Chem. C, 2016, 4, 3185--3194 | 3193

Paper
23 M. Ma ˛czka, T. Almeida da Silva, W. Paraguassu, M. Ptak and
K. Hermanowicz, Inorg. Chem., 2014, 53, 12650–12657.
24 M. Ma ˛czka, T. Almeida da Silva, W. Paraguassu and K. Pereira
da Silva, Spectrochim. Acta, Part A, 2016, 156, 112–117.
25 S. Ghosh, D. Di Sante and A. Stroppa, J. Phys. Chem. Lett.,
2015, 6, 4553–4559.
26 E. C. Spencer, M. S. R. N. Kiran, W. Li, U. Ramamurty,
N. L. Ross and A. K. Cheetham, Angew. Chem., Int. Ed., 2014,
53, 5583–5586.
Published on 04 March 2016. Downloaded by Federal University of Ceará on 14/11/2016 13:22:43.
27 (a) K. F. Wang, J. M. Liu and Z. F. Ren, Adv. Phys., 2009, 58,
321–448; (b) N. A. Hill, J. Phys. Chem. B, 2000, 104, 6694–6709.
28 G. M. Sheldrick, Acta Crystallogr., Sect. A: Found. Crystallogr.,
2008, 64, 112–122.
29 B. Pato Dolán, M. Sánchez-Andújar, L. C. Gómez-Aguirre,
S. Yáñez-Vilar, J. Lopez-Beceiro, C. Gracia-Fernandez, A. A.
Haghighirad, F. Ritter, S. Castro-Garcia and M. A. Señaris-
Rodriguez, Phys. Chem. Chem. Phys., 2012, 14, 8498–8501.
30 (a) J.-P. Zhao, B.-W. Hu, F. Lloret, J. Tao, Q. Yang, X.-F. Zhang
and X.-H. Bu, Inorg. Chem., 2010, 49, 10390–10399;
(b) A. Ciupa, M. Ma ˛czka, A. Ga˛gor, A. Sieradzki, J. Trzmiel,
A. Pikul and M. Ptak, Dalton Trans., 2015, 44, 8846–8854;
(c) A. Ciupa, M. Ma ˛czka, A. Ga˛gor, A. Pikul and M. Ptak,
Dalton Trans., 2015, 44, 13234–13241; (d) M. Ma ˛czka,
A. Ciupa, A. Ga ˛gor, A. Sieradzki, A. Pikul and M. Ptak,
J. Mater. Chem. C, 2016, 4, 1186–1193.
31 M. P. M. Marques and L. A. E. Batista de Carvalho, COST 917:
Biogenically active amines in food, 2000, vol. IV, pp. 122–129.
32 K. Tichy, J. Benes, R. Kind and H. Arend, Acta Crystallogr.,
Sect. B: Struct. Crystallogr. Cryst. Chem., 1980, 36, 1355–1367.
3194 | J. Mater. Chem. C, 2016, 4, 3185--3194
View Article Online
Journal of Materials Chemistry C
33 D. Orobengoa, C. Capillas, M. I. Aroyo and J. M. Perez-Mato,
J. Appl. Crystallogr., 2009, 42, 820–833.
34 I. Dzyaloshinsky, J. Phys. Chem. Solids, 1958, 4, 241–255.
35 T. Moriya, Phys. Rev., 1960, 120, 91–97.
36 (a) M. Maczka, J. Hanuza and A. A. Kaminskii, J. Raman
Spectrosc., 2006, 37, 1257–1264; (b) A. L. Magalhaes, S. R. R. S.
Mandail and M. J. Ramos, Theor. Chem. Acc., 2000, 105, 68–76.
37 E. Kasap and S. Öscelik, J. Inclusion Phenom. Mol. Recognit.
Chem., 1997, 28, 259–267.
38 A. M. Amorim da Costa, M. P. M. Marques and L. A. E. Batista
de Carvalho, J. Raman Spectrosc., 2003, 34, 357–366.
39 M. P. M. Marques, L. A. E. Batista de Carvalho and
J. Tomkinson, J. Phys. Chem. A, 2002, 106, 2473–2482.
40 A. L. M. Batista de Carvalho, S. M. Fiuza, J. Tomkinson,
L. A. E. Batista de Carvalho and M. P. M. Marques, Spectrosc.
Int. J., 2012, 27, 403–413.
41 H. Jeghnou, A. Ouasri, A. Rhandour, M. C. Dhamelincourt,
P. Dhamelincourt, A. Mazzah and P. Roussel, J. Raman
Spectrosc., 2005, 36, 1023–1028.
42 A. Rhandour, A. Ouasri, P. Roussel and A. Mazzah, J. Mol.
Struct., 2011, 990, 95–101.
43 P. T. T. Wong and H. H. Mantsch, J. Phys. Chem., 1983, 87,
2436–2443.
44 J. P. Anastassopoulou, M. Berjot, J. Marx, C. M. Paleos,
T. Theophanides and A. J. P. Alix, J. Mol. Struct., 1997, 415,
225–237.
45 A. J. Graham, A. M. Banu, T. Düren, A. Greenaway, S. C.
McKellar, J. P. S. Mowat, K. Ward, P. A. Wright and S. A.
Moggach, J. Am. Chem. Soc., 2014, 136, 8606–8613.
This journal is © The Royal Society of Chemistry 2016