Article

Cite This: Cryst. Growth Des. 2018, 18, 6211−6220 pubs.acs.org/crystal

Field-Induced Slow Magnetic Relaxation and Anion/Solvent

Dependent Proton Conduction in Cobalt(II) Coordination Polymers
Partha Mondal,† Bijoy Dey, Subhadip Roy, Siba Prasad Bera, Rajendar Nasani, Atanu Santra,
and Sanjit Konar*
Department of Chemistry, Indian Institute of Science Education and Research Bhopal, Bhopal Bypass Road, Bhauri, Bhopal 462 066,
India
*
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ABSTRACT: Three new coordination polymers (CPs), namely, 2D {[Co-

(L)2(H2O)2](ClO4)2·3DMA·0.4H2O}n (1), 3D {[Co(L)2(H2O)2]·(Cl)2}n (2),
and 2D {[Co(L)2(NCS)2]}n (3) were obtained by the self-assembly of
corresponding cobalt(II) salts and a linear semirigid linker bis(4-imidazol-1-yl-
phenyl)diazene (L) designed with two terminal imidazole groups and an azo
moiety in the middle. CPs 1 and 2 are composed of a cationic framework which
leads to incorporation of anion in the framework along with solvent molecules
(only in 1), whereas CP 3 possesses a neutral framework. The cationic core adopts
a cis and trans configuration in 1 and 2, respectively. The structures consist of 2D
net with sql topology in 1, eightfold interpenetrating 3-periodic network with dia
topology in 2 and threefold interpenetrating 2-periodic network with sql (2,4L2) topology in 3. The structural diversity of CPs
1−3 is governed by several factors, including the different coordination ability of the anions, reaction conditions and
intermolecular interactions. Using the method of molecular Voronoi polyhedral, all intermolecular interactions in CPs 1−3 have
been analyzed. Magnetic susceptibility measurements in the range 2−300 K reveal that in these CPs Co(II) ions behave as
magnetically isolated centers with a significant orbital contribution to the magnetic moment. Alternating current (ac)
measurements show signature of slow magnetic relaxation in these CPs. Ab initio investigations on simplified model structures
indicate that CoII nodes in the CPs exhibit easy-plane magnetic anisotropy. Furthermore, CP 1 displays significant value of
proton conductivity which reaches up to 3.96 × 10−4 S cm−1 at 80 °C and 95% relative humidity (RH).

■ INTRODUCTION
The design and synthesis of coordination polymers are of
immense interest not only because of their intriguing
architectures and topologies, but also for their wide
applicability in various fields such as proton conduction, gas
storage and separation, and molecular magnetism.1−13 In
molecular magnetism, coordination polymers provide excellent
examples to better understand some fundamental magnetic
phenomena such as ferromagnetism, antiferromagnetism,
ferrimagnetism, spin-canting, and metamagnetic transi-
tion,14−27 and their correlation with structure. Magnetism of
metal−organic framework (MOF) materials containing para-
magnetic metal centers, which are separated by adequately
functionalized organic moieties, has emerged as a rapidly
growing field of research as these materials can easily give rise
to magnetic subnetworks of varied dimensions.28 In particular,
SCM (single chain magnet) and SMM (single molecule
magnet) based MOFs with slow magnetic relaxation have
found significance in the fields of high-density magnetic
memories and quantum computing devices.29−32
Following the finding of slow magnetic relaxation in a high-
spin iron(II) complex,33 several 3d metal complexes have been
investigated for SIM (single-ion magnet) behavior.34 Espe-
cially, Co(II) ion, which may exhibit large magnetic anisotropy
with a flexible zero-field splitting parameter depending on its
coordination geometry and the distortion degree of its
surroundings,35 has emerged as a promising candidate for
building SIMs. Our research group has actively pursued the
single-ion magnetism of Co(II) ions and reported mono-
nuclear complexes with different (tetrahedral,36 trigonal
bipyramidal,37 and square-pyramidal38,39) geometries, tetrahe-
dral binuclear double-stranded helicates,40 and even coordina-
tion polymer based on octahedral Co(II) building blocks.41
The 2D coordination polymer, [Co(L)2(SCN)2·2CH3CN·
2DMF]n (where L = 4′-(4-methoxyphenyl)-4,2′:6′,4″-terpyr-
idine]) represents a particularly interesting example where the
extended ligand-spacer prevents any magnetic interaction
among the metal nodes thereby leading to isolated single-ion
magnetic centers.41 Similar field-induced SIM behavior has
been also explored by other research groups in 1D,42−45
2D,46−53 and 3D54−56 Co(II) based coordination polymers
where the metal centers remain magnetically isolated.
On the other hand, proton conducting coordination
polymers have drawn great attention due to their potential
use in fuel-cells.57,58 Three approaches have been mainly
adopted to improve the proton conductivity of coordination
Received: July 17, 2018
Revised: August 29, 2018
Published: September 10, 2018

© 2018 American Chemical Society 6211 DOI: 10.1021/acs.cgd.8b01080

Cryst. Growth Des. 2018, 18, 6211−6220
Crystal Growth & Design
polymers: (1) utilization of functionalized organic ligands (e.g.,
−COOH, −OH, −SO3H) to tune the hydrophilicity and
acidity of the pore surface,59−61 (2) encapsulation of proton
carriers into the pores (e.g., NH4+, H3O+, HSO4−, H3PO4,
carboxylate, triazole, imidazole molecules),62−67 and (3) the
construction of ionic coordination polymers incorporating
well-organized counterions in the porous channels.68,69
Surprisingly, it has been observed that much less attention
has been paid in examining the proton conduction in cationic
frameworks,70 which hold immense potential for enhanced
proton conductivity due to the presence of counteranions and
trapped guest molecules in the channels of the framework.
Bearing the above points in mind and following our general
interest in Co(II) based SIMs, we aimed to generate
multidimensional frameworks ensuring the magnetic isolation
of the paramagnetic Co(II) centers. Moreover, we intended to
investigate the self-assembly regularity through variations in
the anion to modulate the coordination microenvironment
around Co(II) centers. We selected a linear semirigid ligand,
bis(4-imidazol-1-yl-phenyl)diazene (L) (Scheme 1) decorated
Scheme 1. Representation of the Ligand Bis(4-imidazol-1-
ylphenyl)-diazene (L)
with two terminal imidazole groups and an azo moiety in the
middle which can adopt bis(monodentate)bridging coordina-
tion mode71,72 to react with different Co(II) salts. Herein, we
report the syntheses, structural features, and topological
analysis of the following coordination polymers (CPs): 2D
{[Co(L)2(H2O)2](ClO4)2·3DMA·0.4H2O}n (1), 3D {[Co-
(L)2(H2O)2]·(Cl)2}n (2), and 2D {[Co(L)2(NCS)2]}n (3).
Magnetic measurements reveal that all the CPs display field-
supported slow magnetic relaxation behavior. In addition,
proton conduction behavior of CP 1 has been explored in
detail.
■
EXPERIMENTAL SECTION
Materials. All the reagents and solvents employed were
commercially available and used without further purification unless
otherwise noted. Bis(4-imidazol-1-yl-phenyl)diazene was synthesized
according to the literature method.71
Caution! Perchlorate salts of metal complexes with organic ligands
are potentially explosive. Only a small amount of material should be
prepared, and it should be handled with care.
Synthesis. {[Co(L)2(H2O)2](ClO4)2·3DMA·0.4H2O}n (1). A hot
DMA solution (3 mL) of ligand L (50 mg, 0.16 mmol) was added
to MeOH/H2O mixed solution (1:1, 2 mL) of Co(ClO4)2·6H2O (58
mg, 0.16 mmol). On slow evaporation of the filtrate at room
temperature, red colored crystals were obtained. The crystals were
separated and washed with methanol and air-dried (yield ∼49% based
on metal). Elemental analysis: Anal. Calcd for C48H57.8Cl2CoN15O13.4
(%): C, 48.48; H, 4.90; N, 17.67; Found (%): C, 48.56; H, 4.94; N,
17.63. FT-IR (KBr pellet, cm−1): 3404(br), 3138(m), 1603 (m),
1517(s), 1304(s), 1089(s), 1117(s), 963(m), 846(s), 623(s).
{[Co(L)2(H2O)2]·(Cl)2}n (2). A solution of CoCl2·6H2O (38 mg, 0.16
mmol) in acetonitrile (3 mL) was carefully layered over an DMA
solution (3 mL) of the ligand L (50 mg, 0.16 mmol) in a glass tube
using a mixture of DMA and acetonitrile as a buffer layer. Orange
colored single crystals were obtained from the junction of the layers
after 1 week. The crystals were separated and washed with acetonitrile
and air-dried (yield ∼45% based on metal). Elemental analysis: Anal.
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Calcd for C36H32Cl2CoN12O2 (%): C, 54.42; H, 4.06; N, 21.15;
Found (%): C, 54.37; H, 4.12; N, 21.11. FT-IR (KBr pellet, cm−1):
3407(br), 3110(m), 1712(s), 1602(m), 1516(s), 1303(s), 1117(m),
1063(m), 849(m), 655(m).
{[Co(L)2(NCS)2]}n (3). A mixture of Co(SCN)2 (28 mg, 0.16 mmol),
ligand L (50 mg, 0.16 mmol), and solvent mixture of MeOH/H2O/
DMA (1:1:3, 5 mL) was stirred at room temperature for 10 min.
Thereafter, the whole mixture was transferred into a 10 mL Teflon-
lined stainless steel vessel and heated at 160 °C for 3 days, followed
by cooling to room temperature. Orange-red colored single crystals
suitable for X-ray diffraction were collected by filtration, washed with
acetonitrile several times, and dried in air (yield ∼40% based on
metal). Elemental analysis: Anal. Calcd for C38H28CoN14S2 (%): C,
56.78; H, 3.51; N, 24.40; Found (%): C, 56.85; H, 3.58; N, 24.46.
FT-IR (KBr pellet, cm−1): 3120(m), 2077(s), 1599(s), 1515(s),
1304(s), 1057(m), 960(m), 846(m), 656(m).
Physical Measurements. The elemental analyses were carried
out on Elementar Micro Vario Cube elemental analyzer. FT−IR
spectra (4000−400 cm−1) were recorded on KBr pellets with a
PerkinElmer Spectrum BX spectrometer. Thermogravimetric analysis
(TGA) was carried out (PerkinElmer) in the temperature range of
30−900 °C (heating rate 5 °C min −1). Powder X−ray diffraction
(PXRD) data were collected on a PANalytical EMPYREAN
instrument using Cu Kα radiation. Alternating-current (AC)
impedance analysis measurements were carried out with a Solartron
SI 1260 impedance analyzer using the conventional quasi-four-probe
method on a pellet sample (diameter of 13 mm and thickness of
∼0.85−0.9 mm). The temperature and humidity were controlled by a
programmable humidification chamber (JEIOTECH, TH-PE series).
Water vapor adsorption studies were performed using a BELSORP
MAX (BEL JAPAN) volumetric adsorption analyzer.
Magnetic Measurements. Variable temperature (2−300 K)
direct current (dc) magnetic susceptibility measurements under an
applied field of 0.1 T and variable field (0−7 T) magnetization
measurements at low temperatures in the range of 2−10 K were
performed by using a SQUID VSM magnetometer (Quantum
Design). The measured values were corrected for the experimentally
measured contribution of the sample holder and the derived
susceptibilities were corrected for the diamagnetism of the samples,
estimated from Pascal’s tables.73 Variable temperature (2−10 K)
alternating current (ac) magnetic susceptibility measurements under 0
and 2000 Oe were carried out with SQUID VSM magnetometer. Ac
and dc measurements were performed by crushing the crystals and
restraining the sample in order to prevent any displacement due to its
magnetic anisotropy.
Crystal Data Collection and Structure Determination.
Intensity data were collected on a Brü k er APEX-II CCD
diffractometer using a graphite monochromated Mo Kα radiation
(λ = 0.71073 Å) at 120 K. Data collections were performed using φ
and ω scan. Olex274 was used as the graphical interface and the
structures were solved with the ShelXT75 structure solution program
using intrinsic phasing. The models were refined with ShelXL75 with
full matrix least-squares minimization on F2. All non-hydrogen atoms
were refined anisotropically. In CP 1, there is minor disorder in
perchlorate anions and one of the three DMA solvates, which has
been treated using standard techniques. Complete lists of the applied
restraints, the original diffraction file as well as the model itself are
embedded in the deposited CIF files. Crystallographic data for CPs
1−3 have been summerized in Table S1. Bond lengths and angles are
listed in Tables S2−S7.
Topological and Voronoi-Dirichlet Polyhedral Analysis.
Topological analysis was performed with the ToposPro program
package and the TTD collection of periodic network topologies.76
The RCSR three-letter codes77 were used to designate the network
topologies. Those nets that are absent in the RCSR are designated
with the TOPOS NDn nomenclature,78 where N is a sequence of
coordination numbers of all nonequivalent nodes of the net, D is
periodicity of the net (D = M, C, L, T for 0-, 1-, 2-, 3-periodic nets),
and n is the ordinal number of the net in the set of all nonisomorphic
nets with the given ND sequence.
DOI: 10.1021/acs.cgd.8b01080
Cryst. Growth Des. 2018, 18, 6211−6220
Crystal Growth & Design
The Voronoi-Dirichlet polyhedral analysis79−84 was also carried out
for CPs 1−3. The analysis was performed using the Dirichlet program
software package within ToposPro. Voronoi polyhedra were
calculated for each atom of the crystal structure. The belonging of
the atom to the valence-bound fragment was then determined.
Bonded fragments were the metal complex structure (ligands and
metal ions coordinating them), solvate molecules, and counterions.
Only contacts of fragments of the metal complex structure were
considered. Contacts were divided into valence and nonvalence
interactions.
■ RESULTS AND DISCUSSION
Structural and Topological Description. The com-
pound {[Co(L)2(H2O)2](ClO4)2·3DMA.0.4H2O}n (1) is a
2D coordination polymer, the structure of which is composed
of the repeating cationic [Co(L) 2 (H 2 O) 2 ] units and
perchlorate anions along with crystallization DMA and water
molecules. The six-coordinate Co(II) atom in the cationic
units in 1 shows a distorted octahedral {CoN4O2} environ-
ment filled by four N-atoms of the ligand L and two water
molecules (Figure 1). Out of four coordinated N-atoms, two
Figure 1. Structure of the fragment of the cationic core of CP 1.
Anion and solvent molecules are not shown. Coordination polyhedral
for Co(II) atom in 1 is shown in the inset.
N-atoms occupy the axial positions and two N-atoms occupy
equatorial positions, while the two O atoms of water molecules
occupy the equatorial positions. It is a cis-isomer. Crystal
chemical formula of the complex is AB22M12, where B
corresponds to L ligands and M corresponds to aqua ligands.85
The Co−N distances are in the 2.1129(19)−2.1523(19) Å
range; Co−O distances are 2.1240(17) and 2.1420(17) Å.
Using the Shape 2.1 program,86 the continuous shape measure
value (CShM) related to the ideal octahedron (Oh symmetry)
for the Co(II) center in 1 was calculated to be 0.151.
Examination of only valence bonds in the structure reveals
that aqua ligands are presented by 1-c nodes and they can be
removed from the underlying net. L ligands are bridging and
presented by 2-c nodes; the replacement of 2-c nodes by
straight edges leads to simplest underlying 2D net of sql
topology in standard representation (Figure 2a). H-bonding
pattern in 1 is complex in nature. One coordinated aqua ligand
is H-bonded to water molecule, perchlorate anion, and DMA
molecule. Another one is H-bonded to two DMA molecules
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Figure 2. (a) Fragment of the crystal structure merged with the
corresponding 4-c underlying net sql. H atoms are omitted for clarity.
(b) System of H-bonding in 1. Minor disordered components and H
atoms (which do not participate into forming H-bonds) are not
shown for clarity.
(Figure 2b). Considering H-bonds, it can be found that 2D
layers are additionally stitched by the edge, which corresponds
to the center of the mass of the outside molecules. The whole
topology of this network is 5-c SP 2-periodic net (4,4)Ia
(Figure 3a and b). Now, as layers are additionally stitched, the
Figure 3. (a) Fragment of the initial crystal structure. Layers are
shown by different colors. (b) Fragment of the corresponding 5-c
underlying net SP 2-periodic (4,4)Ia. (c,d) Different views on
polycatenated array.
whole structure can also be described as 2D+2D parallel
polycatenated array. Layers are oriented in [112] direction.
The pattern of catenation (Figure 3c and d) has been
characterized by topological type of extended ring net87 and
feature 12,16T2 topology. In 1, the shortest intranet Co···Co
distance is 10.338 Å, while the shortest internet Co···Co
distance is 7.309 Å.
The 3D structure of {[Co(L)2(H2O)2]·(Cl)2}n (2) bears
polymeric cationic [Co(L)2(H2O)2] units and chloride anions
(Figure 4). The cationic unit in 2 is very similar to 1, except
that it is a trans-isomer. Similar to 1, crystal chemical formula
of the complex is AB22M12.85 The six-coordinate Co(II) atom
in the cationic units in 2 reveals a less distorted octahedral
{CoN4O2} environment (minimum CShM value 0.039)
compared to 1, aqua ligands are located in axial positions
and L ligands occupy equatorial plane. The Co−N and Co−O
distances are ca. 2.125(2) Å and 2.130(2) Å, respectively.
Likewise, CP 1 in 2 aqua ligands is represented by 1-c nodes
and bridging L ligands act as 2-c nodes. The resulting
underlying 3D net is classified as dia in standard representation
DOI: 10.1021/acs.cgd.8b01080
Cryst. Growth Des. 2018, 18, 6211−6220
Crystal Growth & Design Article

Figure 4. Structure of the fragment of the cationic core of CP 2.

Coordination polyhedral for Co(II) atom in 2 is shown in inset.

(Figure 5a). The structure consists of eightfold interpenetrat-

ing 3-periodic coordination networks (Figure 5b).

Figure 6. (a) Fragment of the initial crystal structure. H atoms, which

do not participate in forming H-bonds, are not shown for clarity. (b)
Figure 5. (a) Fragment of the crystal structure and the corresponding
System of H-bonds forms additional edges of the underlying net. (c)
4-c underlying net dia. H atoms are omitted for clarity. (b)
Fragment of the underlying net with 6T4 topology in the standard
Interpenetrating array consists of dia frameworks.
representation and (d) its 6-c node.

By examining the pattern formed by H-bonds, it can be

found that aqua ligands and chlorine atoms participate in H-
bonding. This leads to the fact that frameworks are stitched by
additional edges. The topology of the 6-c underlying net is 6T4
(Figure 6). In 2, the shortest intranet and Internet Co···Co
distances are 19.477 and 8.042 Å, respectively.
The compound {[Co(L)2(NCS)2]}n (3) discloses a 2D
metal−organic network; it is however neutral and assembled
from the monocobalt(II) ions, thiocyanate ligands, and L
spacers (Figure 7). Likewise in 1 and 2, the crystal chemical
formula of the complex is AB22M12, where B corresponds to
inequivalent L ligands and M corresponds to thiocyanate
ligands.85 3 possesses six-coordinated Co(II) centers with a
distorted octahedral {CoN6} geometry (minimum CShM
value 0.144). Thiocyanate ligands occupy the axial positions
and L ligands are located in equatorial plane. The Co−N
distances range 2.133(3)−2.173(3) Å.
Terminal NCS− ligands are presented by 1-c nodes and can
be removed from the underlying net. L ligands are bridging
and presented by 2-c nodes; the replacement of 2-c nodes by Figure 7. Structure of the fragment of CP 3. Coordination polyhedral
straight edges leads to simplest underlying net of sql topology. for Co(II) atom in 3 is shown in the inset.
However, after removing 2-c nodes information about
entanglements is lost; the straight edges of entangled nets catenation for such systems. The nearest intranet and Internet
are crossed. Therefore, for characterization of the ring- Co···Co distances are 18.82 and 9.066 Å, respectively.
catenation pattern, 2-c nodes should be kept in the underlying Crystal Chemical Analysis by means of Voronoi-
net classified by 2,4L2 topological type (Figure 8a and b). The Dirichlet Polyhedral. Weak intermolecular interactions are
structure consists of threefold interpenetrating 2-periodic often instrumental in directing the self-assembly process in
coordination networks. Each ring of the net is catenated by coordination polymers.88,89 Hence, intermolecular interactions
four rings of the adjacent nets, and the pattern of catenation in the crystal structures of CPs 1−3 have been examined in
characterized by the topological type of the extended ring net87 detail by the method of molecular Voronoi−Dirichlet
has 8L1 topology (Figure 8c). This pattern of catenation polyhedral (VDP) which has been shown to be very effective
(8L1) was previously determined for 11 threefold inter- in the analysis of intermolecular interactions in crystal
penetrating 2D coordination polymers of sql (2,4L2) topology, structures of a variety of substances.82−84 In general, the
and it is second among the most widespread patterns of distribution of valence contacts by their type is similar in these
6214 DOI: 10.1021/acs.cgd.8b01080
Cryst. Growth Des. 2018, 18, 6211−6220
Crystal Growth & Design
Figure 8. (a) Fragment of the crystal structure merged with
underlying 2,4L2 nets. (b) Fragment of the interpenetrated
underlying nets 2,4L2 in the standard representation. 4-c nodes
correspond to Co(II) atoms, 2-c correspond to L ligands. (c) Mode of
interpenetration of three 2,4L2 underlying nets in the crystal
structure.
three CPs (Figure S1, Table S8). Due to the same set of
ligands in structures of CPs 1 and 2, the total contact areas are
almost identical. Contacts of H/O and O/Co disappear, and
C/S contacts appear in CP 3 from the replacement of water
with thiocyanate ion. Valence contacts C/C, H/C, and C/N
are the most probable.
The difference in the areas of nonvalence contacts turned
out to be more significant than for valence contacts (Figure 9,
Figure 9. Total areas of nonvalence contacts of the structures of CPs
1−3.
Table S9). In this case, the contacts H/H and H/C are the
most probable. An increase in the H/H contact area leads to a
decrease in the H/C contact area, as in CP 2. Conversely, a
decrease in the H/H contact area results in an increase in the
H/C contact area, as in CP 3. The presence of H···O hydrogen
bonds in CP 1 and H···Cl in CP 2 is clearly visible in Figure 9.
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The distribution of N/H contacts in each structure is
particularly unique (Figure 10). The smallest total area of
N/H contacts corresponds to CP 2 and the maximum total
contact area is realized in CP 3.
Figure 10. Intermolecular N/H contacts of a fragment from
structures of CPs 1 (a), 2 (b), and 3 (c). The total areas of the
intermolecular N−H contacts are 214.7, 200.9, and 290.9 Å2,
respectively. The faces of Voronoi-Dirichlet polyhedral are marked
in blue for contacts N/H, and in gray for contacts H/N.
Static Magnetic (dc) Measurements. Phase purity of
CPs 1−3 was checked by powder XRD (Figure S2).
Experimental powder XRD patterns matches well with the
PXRD patterns simulated from the respective single crystal X-
ray data, which indicates that the crystal structures are truly
representative of the bulk material. The temperature depend-
ence of the magnetic susceptibility for CPs 1−3 (Figure 11)
Figure 11. χMT versus T plot for CPs 1−3.
was measured in the 2−300 K temperature range under an
applied field of 0.1 T. The room temperature χMT products are
2.96, 2.8, and 3.04 cm3 K mol−1 for CPs 1−3, respectively.
These values are much higher than expected for an isolated
Co(II) high spin value for S = 3/2 of 1.875 cm3 K mol−1. This
mismatch indicates significant orbital contribution and spin−
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Crystal Growth & Design
orbit coupling (SOC) to the magnetic moment. Also, the
values fall in the range of other reported values (2.1−3.8 cm3 K
mol−1) for high spin octahedral Co(II) centers in distorted
octahedral geometry.47−52,54,55 The χMT remains fairly
constant up to 200 K, below which it decreases to reach a
minimum value of 1.66, 1.48, and 1.87 cm3 mol−1 K for CPs
1−3, respectively. In all these cases, the decrease in the
susceptibility below 200 K is more likely due to magnetic
anisotropy or thermal depopulation of the excited states rather
than antiferromagnetic interactions.54,90
The dc magnetization data in the form of the M vs H plots
(M being the magnetization per CoII unit and H being the
applied dc magnetic field) for CP 1 is given in Figure 12. In all
Figure 12. M vs H (a) and M vs H/T (b) plots for CP 1.
cases, the magnetization curves reveal a rapid and steady
increase of the magnetization at 2 K without clear indication of
saturation at 7 T. The nonsaturation, as well as the
nonsuperimposition of the isothermal lines in M vs H/T
(Figure S3) data at higher fields, clearly indicates the presence
of significant magnetic anisotropy. M vs H and M vs H/T plots
for CPs 2 and 3 are given in Figure S4.
Dynamic Magnetic Measurement Studies. As men-
tioned earlier, CoII based MOFs with larger separation
between the metal centers have gained interest recently due
to their SIM-like behavior.42−56 To study the slow relaxation of
the magnetization dynamics, temperature dependent ac
susceptibility measurements were done with 3.5 Oe ac field
in the 2−10 K temperature range. At zero applied dc field the
CPs show no peaks in the out of phase ac data, which can be
due to fast resonant zero-field quantum tunneling of the
magnetization (QTM) through the thermal relaxation barrier
Figure 13. Temperature dependence of out of phase (χM″) ac data for CPs 1 (a), 2 (b), and 3 (c) at 2000 Oe applied dc field. Plot of ln(χM″/χM′)
versus T−1 for CP 1 (d). Solid lines represent fit to the Debye model according to eq 1.
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between the degenerate ground ±3/2 levels, which dominates
other relaxation pathways in the absence of any applied field.
To suppress the quantum tunneling, an external dc field of
2000 Oe was applied upon which frequency dependency of in
phase and out of phase ac signals were observed (Figures 13a−
c and S5). There is no maximum in the temperature
dependence of out of phase ac data. Above 2 K, at frequencies
reaching 750 Hz the nature of out-of-phase ac signals indicated
slow relaxation of magnetization for all CPs. Temperature
dependency of in phase (χ′) and out of phase (χ″) ac data for
CPs 2 and 3 are presented in Figures S6 and S7. The energy
barrier is determined by assuming that there is only one
characteristic relaxation process with one energy barrier and
one time constant, which can be extracted from eq 1 (Figure
13d).90
ln(χ ″ /χ ′) = ln(ωτ0) + Ueff /KT (1)
The linear fitting of ln(χ″/χ′) vs 1/T allows extraction of the
energy barrier (Ueff) and relaxation time (τo) which are 4.29 K
and 1.1 × 10−5 s for CP 1, 4.11 K and 6.8 × 10−6 s for CP 2,
and 2.6 K and 6.3 × 10−5 s for CP 3. These values are in good
agreement with reported Co(II) MOF based SIMs. 54
Arrhenius plot for CPs 2 and 3 are given in Figure S8.
Proton Conductivity Studies. The presence of well-
organized hydrogen-bonded coordinated water molecules
along with lattice perchlorate ions and DMA molecules in
the channel of the framework make the CP 1 appropriate to be
screened for proton conduction. Although all the CPs 1−3
were investigated for proton conduction behavior, only CP 1
exhibited significant proton conductivity, thus confirming the
initial expectations. Hence, impedance data for 1 will be
described in detail.
The proton conductivity of the complex was evaluated by
the ac impedance measurements of pelletized sample at
anhydrous as well as controlled humidity conditions and
different temperatures. The thermal stability of the complex
was accessed from TGA (Figure S9). The proton conductivity
of sample was negligible in low humidity and room
temperature. However, after humidification at 95% relative
humidity (RH) for 24 h, CP 1 shows significant conductivity.
With increase of temperature at 95% RH, proton conductivity
increased with maximum value of 3.96 × 10−4 S cm−1 at 80 °C
(Figures 14 and S10) which is comparable to that of the high
conductive hydrated metal−organic framework (MOF) ma-
terial.63−65
The enhanced conductivity with an increase in humidity
(Figure 15) could be due to the improved intergrain
conduction by added surface water molecules, as the samples
are ground powders which have been pressed into pellets. It
DOI: 10.1021/acs.cgd.8b01080
Cryst. Growth Des. 2018, 18, 6211−6220
Crystal Growth & Design
Figure 14. Nyquist plot of CP 1 at different temperatures and 95%
RH.
Figure 15. Humidity dependent proton conduction in CP 1 at 30 °C.
suggests that conductivity value increases with the increase of
humidity as the number of water molecules significantly rises
inside the molecular structure which in turn can establish
strong hydrogen bonding with the coordinated aqua ligands,
perchlorate anion, and solvate molecules. Absorption of water
molecules in the framework was also supported by water vapor
adsorption study. From adsorption isotherm, the amount of
adsorbed water vapor was found to be 97.74 mL.g−1 (Figure
S11). The increase in the conductivity with the temperature is
certainly caused by thermal activation of the water molecules,
which helps with transport of protons in the channel.
Furthermore, movement of solvent molecules (DMA and
H2O) also tends to increase at high temperature facilitating
proton conductivity.91
To probe and gain more insight into the proton conduction
mechanism, we calculated the activation energy (Figures S12)
for proton conduction of CP 1 from the Arrhenius equation eq
iE y
2
σ T = σ 0expjjj a zzz
k kT {
(2)
where σ = conductivity and k = Boltzmann constant, which
was found to be Ea = 0.23 eV. It is well-known from the
literature that low activation energies (<0.4 eV) correspond to
the Grotthuss mechanism.5−7 The lack of proton conductivity
in other two CPs (2 and 3) under similar conditions may be
attributed to lack of guest solvent molecules particularly lattice
water.66
Ab Initio Studies. To gain a deeper insight into the
magnetic behavior of the CPs, ab initio calculations of zero-
field splitting parameters (D and E) have been carried out by
using MOLCAS 8.0 software package.92−94 In all the cases, the
structures have been reduced to simplified unit (the azo unit
6217
Article
has been replaced with capped NH2 group, Figure S13). ANO-
RCC basis sets have been utilized for all the calculations: Co
atoms (6s5p4d2f), N (4s3p2d1f), O (4s3p2d1f), S (5s4p3s2f),
C (3s2p), and H (2s). The calculations employed the second
order Douglas-Kroll-Hess Hamiltonian, where scalar relativistic
contractions were taken into account in the basis set. Two
electron cholesky decomposition approach has been adopted
to reduce computation time. After carrying out CASSCF
(Complete Active State Self Consistent Field) calculations,
spin−orbit coupling has been introduced as implemented in
the SO-RASSI (Restricted Active Space State Interaction)
approach. In all the cases, the active space is composed of
seven d electrons of Co(II) with 5d orbitals where all the
quadruplets (10) and doublet (40) states have been
considered. The computed zero-field splitting parameters
have been shown in Table 1. Computed low lying spin orbit
energy, g values and tensors, and D contributors and tensors
are presented in Tables S10−S12.
Table 1. Ab Initio (Molcas 8.0) Computed D, |E| (in cm−1),
and g Values for the Ground State of CPs 1−3
CP Dcalc |E|calc gXX gYY gZZ
1 157.6 7.4 1.88 2.21 2.78
2 85.9 23.7 2.03 2.27 2.93
3 109.5 8.9 2.74 2.57 1.94
The computed large and positive D values are indicative of
easy-plane magnetic anisotropy of the octahedral Co(II)
centers in 1−3. Moreover, it has been observed that 1D, 2D,
and 3D Co(II) coordination polymers reported in the
literature exhibiting SIM behavior with local Oh symmetry
only display an easy-plane type of magnetic anisotro-
py.41,47−49,51,52,54,55 In theory, large zero-splitting D parameters
should contribute toward a large energy barrier for reversal of
magnetization, but we need to consider the fact that spin
relaxation mechanisms also depend on lattice effects which can
lead to reduction of D values and can not be captured in
calculations done on single-molecule.54
■ CONCLUSIONS
In this article, three new Co(II) based coordination polymers
have been reported, which are based on the semirigid ligand
bis(4-imidazol-1-yl-phenyl)diazene (L). The structures of the
obtained compounds have been analyzed from topological
viewpoint, revealing 4-connected 2D layers with sql topology
in 1, eightfold interpenetrating 3D network with dia topology
in 2, and threefold interpenetrating 2D network with sql
(2,4L2) topology in 3. Employment of the long organic spacer
(L) leads to large intermolecular metal−metal separation in 1−
3 thereby generating magnetically isolated high-spin cobalt(II)
centers. Easy-plane anisotropy and field-supported slow
relaxation of magnetization behavior have been observed in
CPs 1−3. Investigation of proton conductivity of the CPs
discloses high conductivity at elevated temperature and
humidity exclusively for 1. In summary, the compounds
reported herein broaden a still very limited family of
coordination polymers exhibiting slow magnetic relaxation
with indication of bifunctional character.
DOI: 10.1021/acs.cgd.8b01080
Cryst. Growth Des. 2018, 18, 6211−6220
Crystal Growth & Design
■
ASSOCIATED CONTENT
*
S Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acs.cgd.8b01080.
Crystallographic Data and Structure Refinement, Bond
Lengths and Angles, Valence contacts, PXRD patterns of
compound, TGA, Nyquist, and Arrhenius plots, Model
structures PDF)
Accession Codes
CCDC 1852269−1852271 contain the supplementary crys-
tallographic data for this paper. These data can be obtained
free of charge via www.ccdc.cam.ac.uk/data_request/cif, or by
emailing data_request@ccdc.cam.ac.uk, or by contacting The
Cambridge Crystallographic Data Centre, 12 Union Road,
Cambridge CB2 1EZ, UK; fax: +44 1223 336033.
■
AUTHOR INFORMATION
Corresponding Author
*E-mail: skonar@iiserb.ac.in. Fax: +91-755-6692392. Tel: +91-
755-6692339.
ORCID
Bijoy Dey: 0000-0003-4185-4240
Sanjit Konar: 0000-0002-1584-6258
Author Contributions
† Rev. 2009, 38, 1353−1379.
Undergraduate Researcher.
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
S.K. acknowledges CSIR, Government of India and IISER
Bhopal for generous financial support. P. M. thanks to DST-
INSPIRE, India for fellowship. B.D. is thankful to IISER
Bhopal for PhD fellowship. S.R., R.N., and A.S. acknowledge
SERB, Government of India (file numbers PDF/2017/001188,
PDF/2015/0001032 and PDF/2015/000368, respectively) for
national postdoctoral fellowships. SPB thanks UGC, India for
fellowship. We acknowledge high performance computing
(HPC) facility of IISER Bhopal being utilized for computa-
tional work.
■
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