pubs.acs.

org/acsapm Article

Gram-Scale Synthesis and Multifunctional Properties of a Two-

Dimensional Layered Copper(II) Coordination Polymer
Sachin Ashok Bhat, Nani Babu Palakurthy, Nagaiah Kambhala, Angappane Subramanian,
Doddamane S. Shankar Rao, Subbarao Krishna Prasad, and Channabasaveshwar V. Yelamaggad*
Cite This: ACS Appl. Polym. Mater. 2020, 2, 1543−1552 Read Online

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ABSTRACT: Accomplishing an inexpensive and industrially scalable, robust multifunctional material exhibiting a range of
technologically significant phenomena is apparently essential for its projected use in a wide range of device applications. Herein we
report on the extremely simple, gram-scale synthesis, electrical conductivity, redox behavior, thermoelectric properties, and
magnetism of a two-dimensional (2D) layered copper(II) coordination polymer (COP) formed by treating the ligand 3,3′-
diaminobenzidine (DAB) with copper(II) acetate monohydrate, Cu(OAc)2·H2O. The experimental observations show that the
COP synthesized, hereafter termed Cu(DAB), and stored under ambient conditions remains intact, exhibiting resistance to air, light,
heat, water, and alkaline aqueous solution. FTIR spectroscopy, Raman spectral analyses, microanalytical data, SEM-EDX imaging,
surface analysis by XPS/AFM, powder X-ray diffraction, and HRTEM suggest a neutral 2D COP with Cu(DAB) repeating units.
While the AC experiments completely rule out ionic conductivity, two-probe DC electrical conductivity measurements on a pellet
(bulk sample) as a function of temperature (150−320 K) evidence the electrical conductivity of the COP. Notably, at room
temperature (298 K) the conductivity was found to be 0.01 S/m. The inherent p-type conduction was revealed by Hall effect
experiments. Apart from being redox-active, it shows thermoelectric behavior, and magnetic susceptibility vs temperature
measurements reveal the spin crossover from diamagnetic to the paramagnetic state upon cooling the bulk sample.
KEYWORDS: coordination polymer, facile synthesis, redox activity, electrical conductivity, p-type conduction,
thermoelectricity and magnetism

I. INTRODUCTION coordination segments in one, two, and three dimensions

In recent times, the metal−ligand coordination polymers1−20
and metal−organic frameworks (MOFs)21−27 have been the
subject of sustainable interest for chemists, biologists,
physicists, and material scientists because of their huge
promise for applications in gas storage, chemical sensing and
separation, heterogeneous catalysis, membrane and electronic
devices, magnetism, and so on. Coordination polymers
(COPs) have been especially regarded as next-generation,
feasible functional materials as they can be readily realized with
choice of the structural dimensionality through “bottom-up”
synthetic approach that essentially involves the appropriate
selection of coordination geometry of metal ion center and
guest ligands.1−9 Their infinite structures with repeating
manifest in the form of versatile arrays such as long chains,
sheets, and 3D networks.1−16 Moreover, such hierarchy
structured arrays, depending upon the chemical characteristics
of constituent inorganic and organic moieties, have the ability
to generate diverse supramolecular motifs resulting from H-
bonds, π-stacking, dipole−dipole, or van der Waals interaction;
Received: December 22, 2019
Accepted: March 24, 2020
Published: March 24, 2020

© 2020 American Chemical Society https://dx.doi.org/10.1021/acsapm.9b01219

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in fact, such secondary forces enable COPs to reversibly Thus, we intended to continue to work on this theme47
transform their structures.9 COPs, because of their diverse through the development of a new polymeric variant
topological order coupled with coordination geometries, incorporating Cu(II) and o-diimine ligand (N4 donor) as
display a wide range of promising phenomenon, viz., repeating units. This particular idea was conceived based on
adsorption/separation,6 catalysis,10 molecular recognition,12 the reported work that the Cu(II) complex Cu[C6H4(NH2)2]2,
magnetism, 13 nonlinear optics, 14 electrical conductiv- where C6H4(NH2) is the o-phenylenediamine ligand existing in
ity,8,20,21,28 host−guest behavior,19 thermoelectricity,16−19,29,30 semibenzoquinonediiminate form, displays paramagnetic be-
luminescence,15,31 and so on. havior along with promising redox behavior; the cyclic
However, one of the most noticeable shortcomings of COPs volammogram in acetonitrile shows two reversible electron
is their poor electrical conductivity (σ).8,20,21 Consequently, transfers and an irreversible phenomenon.40 While the
their projected usage as sustainable media in batteries, fuel iodinated product of the complex exhibits a high conductivity
cells, capacitors, molecular wires, and so on remains unex- (6.6 S/m) at room temperature and semiconducting property
plored. Analogously, their thermal conductivity, being the in the temperature range of 70−300 K, the complex fails to
outcome of heat mobility by charge carriers, is also exhibit the conductivity; furthermore, the iodinated complex
imperceptible, which is not surprising as this behavior is shows ferromagnetism with a magnetic moment of 1.23 μB.
interlinked with electrical conductivity as well as the Seebeck Herein we report on the exceedingly simple, hassle-free,
coefficient. Thus, the electrical conductivity needs to be multigram scale rapid synthesis at ambient temperature, and
improved adequately so as to enhance the thermal conduction characterization of a Cu(II) COP derived from an extended
of materials.15 In general, the intrinsic resistivity or lack of metal complex formation between 3,3′-diaminobenzidine
efficient signal transduction of COPs not only stems from the (DAB) and copper(II) acetate monohydrate, Cu(OAc)2·H2O
insulating nature of the organic part but also due to ineffective (Scheme 1 and Figure S1).
overlapping among the p-orbitals of organic moieties and metal
d-orbitals. Yet another very attractive phenomenon observed in Scheme 1. Facile Synthesis of the Cu(DAB) Which Involves
COPs is magnetism. Magnetically active frameworks generally the Room Temperature Addition of Cu(OAc)2 with 3,3′-
comprise magnetic moment carriers such as paramagnetic Diaminobenzidine Ligand (Top); A Space-Filling Model of
metals (V, Cr, Mn, Fe, Co, Ni, and Cu) and/or open-shell a Portion of the 2D Network (Top View) Formed by the
organic (radical) ligands. In the present day scenario, especially Self-Assembly of 1D Cu(DAB) Strands via H-Bond
in the context of microelectronics, spintronics, medical Interactions (Bottom)a
diagnosis, data storage devices, and so on, there is an obvious
demand for developing multifunctional COPs capable of
exhibiting long-range charge transport as well as magnetic
ordering. However, to our knowledge, the pristine (undoped)
COPs exhibiting such combined properties have not been
realized hitherto.6 Most importantly, multicharacteristic COPs
to be used in device applications obviously need to be highly
resistant to areal oxidation, heat, and moisture and be
inexpensive and industrially scalable.24,25 Thus, there is an
existent challenge to design and attain industrially scalable
multifunctional COPs.
On the other hand, the metal complexes derived from the
family of o-diimine ligands (N4 donors) and transition metals
(M = Cu, Ni, Zn, Pd, Pt, etc.) display a wide range of
properties/phenomena having high potential in many
applications.32−46 The delocalization of electrons between
the metal and the ligand has especially attracted the attention
of these novel transition-metal complexes.32−40 In these
complexes [M−N4], the electron transfer occurs at length,
and they undergo multiple reversible one-electron-transfer
reactions, attributable to the presence of the suspect/
noninnocent ligand L, the N4 donor.32,34,38−41 Thus, they
show prominent electrochemical features at mild poten-
tials.32−34,40,41,46 The mixing between the metal d-orbitals
and molecular (π/π*) orbitals of ligands, which determines the
electron distribution, plays a key role in ascertaining the overall
functional behavior of these complexes. Interestingly, it was
pointed out that the polymeric analogue of these complexes
(COPs) may have the ability to serve as molecular wires where
the switching is possible by varying the oxidation state of either
organic linker or the metal center; such COPs should be
yielding mixed valence species stemming from metal centers
and organic moieties.46 Besides, these complexes display not
only magnetic behavior32,40 but also the electrical conductiv-
ity5,9 and semiconducting property.40 a
Color codes: gray, C; yellow, H; red, Cu; blue, N.

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The comparison of the UV−vis spectra recorded for the

solutions/suspensions of DAB, Cu(OAc)2·H2O, and Cu(DAB)
(Figure S2) indicated the formation of the COP. Raman and
infrared spectroscopic data (Figure 1, Figure S3, and Table
S1), elemental analyses (Table S2), X-ray photoelectron
spectroscopy (XPS) surface study (Figure 2), scanning
electron microscopy (SEM) (Figure 3b,c), energy dispersive
X-ray analysis (EDX) (Figure 3f−h and Figure S4), atomic
force microscopy (AFM) (Figure 3d,e), high-resolution
transmission electron microscopy (HRTEM) (Figure 4), and
powder X-ray diffraction (XRD) (Figure S8) support the
formation of a 2D coordination polymer having Cu(DAB)
repeating units. The 2D layers originate from the secondary
interaction of linearly elongated metal complex strands formed
through H-bonds of NH-NH groups (see Scheme 1). As we
shall see later, the H-bonds appear to break when Cu(DAB) is
dispersed in N,N-dimethylformamide (DMF) solvent which is
an excellent H-bond acceptor according to the Hunter
solvation model. Notably, the 2D COP remains unaltered
even after exposing it deliberately to air, heat, light, moisture,
and aqueous alkaline solutions. However, the treatment with
dilute acid seems to protonate the COP. The experimental
studies clearly reveal that the Cu(DAB) displays p-type
conductivity, thermoelectric device characteristics with a
Seebeck coefficient of about 350 μV K−1 at 298 K, redox
activity, and magnetism. In the following sections, we present
the aforesaid aspects in detail.

II. EXPERIMENTAL SECTION

II.1. Chemicals. 3,3′-Diaminobenzidine (DAB) was purchased
from TCI Chemicals, whereas copper acetate monohydrate, Cu-
(OAc)2·H2O, was procured from Sigma-Aldrich. Analytical grade
solvents procured locally were dried as per well-known protocols
before use.
II.2. Synthesis of Cu(DAB). The Cu(DAB) was prepared by the
slow addition of a solution of Cu(OAc)2·H2O in water to an
equimolar ethanolic solution of DAB ligand (used in the range of
0.5−3 g) under ambient atmosphere and temperature, ∼30 °C
(Figures S1a,b). The black precipitate thus separated instantaneously
(Figure S1c) was stirred for 5 min and collected by filtration and
repeatedly washed with hot ethanol and water and again with ethanol.
The product obtained was poured into hot ethanol and heated to
reflux for 24 h. The Cu(DAB) thus obtained in the form of a free-
flowing black powder was filtered and dried in a vacuum for 6 h at
room temperature. The final dark compound, Cu(DAB) (Figure 3a),
was stored in ambient conditions. It was found that it is highly
resistant to air, moisture, light, heat, and alkaline aqueous solutions.
II.3. Characterization. II.3.A. General. X-ray diffraction (XRD)
experiments were performed with Cu Kα (λ = 0.15418 nm) radiation
using a PANalytical X’Pert PRO MP machine consisting of a focusing
elliptical mirror and a fast resolution detector (PIXCEL). The
chemical and elemental composition analysis was performed by using
a Kratos X-ray photoelectron spectrometer (Axis Ultra DLD). The
morphology, structure, and elemental distribution were studied by
transmission electron microscopy (TEM, Thermo Fisher Scientific Figure 1. FTIR spectra of ligand DAB (a) and Cu(DAB) (b)
Talos F200S G2) and field emission scanning electron microscopy recorded over KBr pellets. The inset in (b) shows a distinct band at
(FESEM, Tescan-Mira 3 LMH) with EDS (Bruker Quantax 200) and around 430 nm corresponding to Cu−N stretching vibration. (c)
atomic force microscopy (AFM, Agilent Technologies 5500). Raman Raman spectra recorded for the bulk sample (pellet) of the ligand
and FTIR spectroscopic data of the samples were respectively DAB (red trace) and Cu(DAB) (black trace). The inset of (c) shows
obtained from a confocal Raman spectroscope with 532 nm excitation the optical microscopic image of the portion of the Cu(DAB) pellet
(Horiba Jobin Yvon XploRA PLUS V1.2 MULTILINE) and a where the Raman spectrum was recorded.
PerkinElmer Spectrum 1000 FT-IR spectrometer. Thermal stability
was determined by using a thermogravimetric analyzer (TGA) where Ag/AgCl was used as reference electrode and platinum wire as
(Netzsch STA-2500). Electrochemical measurements to determine counter electrode. The requisite pellets (3 mm thickness) for
HOMO and LUMO gap were performed by using an electrochemical measurements were prepared by grinding Cu(DAB) (∼20 mg)
workstation (CH Instruments 660E) with a three-electrode system material using a mortar and pestle, and the resultant very fine black

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Figure 2. Plots of XPS studies performed on Cu(DAB). (a) A wide
scan showing the presence of different elements present, (b) C 1s
region, (c) N 1s region, and (d) Cu 2p region. The inset of (d) shows
the presence of two types of copper species.
Figure 3. Appearance, microstructural analysis by electron micros-
copy, and surface morphology study of the bulk sample Cu(DAB). (a)
Digital photograph of the microcrystalline solid as prepared; deep-
blackish appearance strongly implies the formation of coordination
polymer. (b, c) SEM images obtained for the increasing
magnifications. (d) AFM 2D micrograph. (e) AFM 3D surface
morphology. (f−h) EDX surface images. (f) Cross homogeneous
distribution of Cu and N elements. (g) Cu element and (h) N
element.
powder was then pressed for about 3 h using a 15 ton manual
hydraulic press of 0.6 cm diameter; this procedure was repeated if the
pellets comprise cracks/defects. The defect-free pellets were used for
AC conductivity and Hall effect experiments.
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Figure 4. (a, b) TEM images of two magnifications recorded for the
Cu(DAB) dispersed in water and drop-casted onto the carbon-coated
copper grid. These images clearly support the observations made by
Raman and SEM analysis that the COP forms a 2D sheet-like
arrangement. The high-magnification image (b) clearly depicts the
layers of COP stacked one over the other.
For thermoelectric measurements, a 3 mm pellet was sandwiched
between two thin (∼0.5 mm) copper plates, to which leads were
connected for determining the voltage and temperature. This device
was heated carefully a rate of 1 °C/min by using a hot stage, and the
difference in the temperature as well as voltage was measured; the
Seebeck coefficient was also obtained with the help of this
experimental setup.
II.3.B. Electrical and Magnetic Measurements. The DC electrical
resistivity measurements from 150 to 320 K were performed using a
Janis closed-cycle refrigerator with the conventional two-probe
method. The magnetic properties were measured by Quantum
Design MPMS-XL SQUID magnetometer. The AC conductivity
measurements were performed using an LCR meter (Agilent 4284A).
III. RESULTS AND DISCUSSION
The comparison of FTIR spectra of DAB (Figure 1a) and
Cu(DAB) (Figure 1b) measured over KBr pellets in the 4000−
400 cm−1 region indicated the formation of Cu(DAB). A
prominent band at 432 cm−1 seen in the far-IR region of
Cu(DAB) (Figure 1b; also see the inset) relates to ligand
coordination to the metal center, namely the Cu−N stretch;48
a broad band appearing at ca. 3000−3450 cm−1 can be
assigned to broadening of the −NH2 peak upon binding with
the metal center; the presence of two bands at 762 and 644
cm−1 may be assigned to rocking [ρr(H2O)] and wagging
[ρw(H2O)] (Figure 1b).50 The Raman scattering spectra,
which show vibrational frequencies as a shift from the incident
frequency, were obtained for the pellets of pristine ligand DAB
and Cu(DAB). Laser light with a wavelength of 540 nm
(green) was focused with a 20× objective lens and made
incident normal to the sample substrate. The spectra were
collected at room temperature in the region between 400 and
4000 cm−1. As can be seen in Figure 1c, striking differences
were seen among the spectra of DAB (see Table S1) and
Cu(DAB). The prominent Raman band observed in DAB at
1380 cm−1 due to the CN stretching/CNH plane bending
(Figure 1c, red trace)50 shifts to 1349 cm−1 in the spectrum of
Cu(DAB) (Figure 1c, black trace)this can be regarded as
the diagnostic for the formation of the Cu−N bond. A sharp
and intense band in the DAB spectrum at 1602 cm−1 due to
HNH stretching/NH2 scissoring (Figure 1c, red trace, and
Table S1)50 becomes broad and reduces its intensity with an
insignificant small shift in the spectrum of Cu(DAB)this can
perhaps be attributed to Cu−N bond formation (Figure 1c,
black trace). Interestingly, the Raman spectral pattern of
Cu(DAB) resembles those seen for the graphitic materials.
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ACS Applied Polymer Materials
XPS measurements were performed on a SiO2/Si substrate
to figure out the elemental composition as well as to determine
the chemical/electronic (oxidation) state of the elements
present. The XPS spectrum (Figure 2a) indicates the presence
of C 1s, N 1s, O 1s, and Cu 2p (2p1/2 and 2p3/2). The high-
resolution spectrum in these regions confirms the existence of
carbon in two different chemical environments (Figure 2b)
and of nitrogen in a single chemical environment (Figure 2c),
thus supporting the proposed chemical composition of
Cu(DAB). Importantly, these results clearly rule out the
presence of impurities (metal residues/cations/anions) which
may contribute to ionic conductivity of the material. In the
high-resolution Cu 2p spectrum, the Cu 2p1/2 and Cu 2p3/2
occur at 953.1 and 932.3 eV, respectively (Figure 2d), and the
latter can be considered for determining the chemical states of
copper. As can be seen in Figure 2d, the Cu 2p3/2 peak is
asymmetric, and its peak-fit profile shows two-component
peaks (Figure 2d, inset), implying the existence of copper in
two states with binding energies of 931.7 and 933.9 eV. The
peak at 931.7 eV is characteristic of the binding energy value of
a Cu 2p3/2 peak of Cu(I) species, implying the reduction of
Cu(II) to Cu(I) taking place during the preparation of
Cu(DAB) in the open air.51,52 The peak around 933.9 eV
showed a slight shift from the standard value of Cu(II) which
is observed around 934.2 eV.52 This shift can be attributed to
the formation of the Cu−N bond which lowers the binding
energy of Cu(II) slightly.
To understand the surface morphology of Cu(DAB),
FESEM and AFM techniques were employed where a pellet
∼3 mm thick was used. Needless to say, for AFM study the
entire pellet was used whereas for the FESEM technique, as
per the need, a portion of it was used. The images obtained
from FESEM and AFM studies are shown in Figure 3b−e. The
FESEM images obtained (Figure 3b,c) with the increased
magnification of the bulk sample show a 2D layered
morphology. The analysis of the phase contrast AFM image
and the topographic image in a 3D perspective illustrated in
Figures 3d and 3e, respectively, complement the results of the
aforementioned SEM study.
The composition of the Cu(DAB) was examined by both
SEM-EDX technique and elemental analysis. Figure 3f−h
depicts the EDX surface scanning images obtained for the
pristine sample. The images of Cu and N elements and the
homogeneous cross section show the distribution of Cu and N
elements on the sample surface. However, the EDX spectrum
of the bulk sample (Figure S4) indicates the presence of C, N,
Cu, and O with corresponding weight (normalized) percent of
48.18, 14.40, 24.47, and 12.95 (Table S2). Elemental analysis
revealed the sample Cu(DAB) to contain 47.58% carbon,
16.37% nitrogen, and 4.68% hydrogen. The results of both
EDX spectrum and microanalytical data deviate slightly from
the theoretical values (C, 46.52%; N, 18.08%; H, 4.554%; O,
10.328%; Cu, 20.509%) (Table S2) which can be attributed to
the polymeric nature of the sample1−4,50 and also due to
association of H2O/EtOH molecules adhering to Cu-
(DAB).1−4
TEM analysis was performed by drop-casting the well-
dispersed Cu(DAB) sample onto a carbon-coated copper grid.
The TEM images (Figure 4a,b) clearly indicate the formation
of a layered structure formed due to secondary interaction of
linearly elongated metal complex strands through H-bonds of
NH−NH groups, as mentioned earlier. The TEM data support
the 2D COP formation which is also evident from the Raman
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spectroscopic data and SEM analysis as noted earlier. The
Cu(DAB) suspended in DMF was investigated to know
influence of latter on the H-bond network. As is known, DMF
has two main H-bonding modes, viz., a weak H-bond donor
mode arising from CH3 groups and a strong hydrogen acceptor
in the form of the CO group which can be correlated to
Kamlet−Taft solvent parameters such as α (H-bond donor)
and β (H-bond acceptor).53−55 In particular, the parameter α
is zero, indicating the weak or nonexistent H-bond donor
ability, and the parameter β is much higher (0.69), indicating
very strong hydrogen bond acceptor ability. Owing to this
strong hydrogen bond acceptor feature, DMF was chosen to
disrupt the H-bonding network of the COP. The broadening
of IR (Figure S5a) and Raman (Figure S5b) signals clearly
indicates the disruption of hydrogen bond in the system. The
peak around 3200 cm−1 in the IR spectrum (Figure S5a) of
Cu(DAB) interacting with DMF gets broadened substantially;
this can be ascribed to the strong association of DMF
molecules and H atoms (N−H groups) of strands separated as
a result of partial disruption of the 2D network due to H-bond
breaking among the 1D strands. Similarly, in the Raman
spectra (Figure S5b), the peak around 1550 cm−1 gets
broadened, implying the disruption of 2D structure of
Cu(DAB). The UV spectrum (Figure S6) of Cu(DAB)
associated with DMF molecules, as compared with that of
the pristine sample, shows a slight red-shift. That is, the onset
UV peak ∼250 nm of the pristine Cu(DAB) sample was found
to occur at 262 nm when it was treated with DMF; this red-
shift of the onset peak by 12 nm can be ascribed to the strong
association of the CO group of DMF with the N−H group
of COP strands.54 FESM images (Figure S7a−c) recorded
substantiated this observation where the reduced dimensions
of the layers as compared with the pristine ones could be seen.
X-ray diffraction (XRD) study was performed on the powder
sample Cu(DAB). As shown in Figure S8, the XRD pattern
displays several prominent peaks indicative of long-range order
of a crystalline structure. Importantly, the XRD data rule out
the presence of Cu, Cu2O, and CuO traces that are expected to
be formed given the redox nature of DAB. Thermogravimetric
analysis (TGA) was used to test the thermal stability of the
COP. As shown in Figure S9, the TGA trace revealed the
weight loss of 2% and 15% at 90 and 300 °C, respectively; such
a trace was consistently obtained in any number of
experiments. The small (2%) loss can be attributed to the
traces of water−ethanol molecules adhering to the COP;
however, as we shall see later, the presence of such molecules
did not affect the electrical conductivity of the Cu(DAB). That
is, the pristine Cu(DAB) and the heated sample at 90 °C
showed identical conductivity values. The 15% loss suggests
that the COP begins to degrade at 300 °C. The TGA curve
indicates that the sample degrades completely at about 450 °C
where the organic part seems to have disappeared completely.
Cyclic voltammetry measurements of the Cu(DAB) were
performed in an aqueous solution using an Ag/AgCl reference
electrode, a platinum wire counter electrode, and a platinum
rod as a working electrode. The cyclic voltammogram (CV)
obtained is presented in Figure 5, and the corresponding data
derived from curves are summarized in Table S3. The presence
of two reversible peaks in a CV at the cathodic and anodic
region indicates the occurrence of two-electron processes.
E1/2(1) and E1/2(2) were found to be −0.059 and −0.084 V,
respectively. The bandgap (ΔE) was calculated by determining
EHOMO and ELUMO from the graph by using the expressions
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Figure 5. Cyclic voltammogram of Cu(DAB) obtained in an aqueous
solution with 1 M KCl as an electrolyte. A three-electrode system was
used with Ag/AgCl as reference and platinum wire as a counter
electrode. The redox plot obtained shows the variable oxidation states
of copper, which exhibit two transitions in both cathodic and anodic
sweeps.
−Eox − 4.75 (eV) and −Ered − 4.75 (eV), respectively. The
difference in energies between HOMO and LUMO gives a
bandgap which was found to be 0.693 eV.
The ability of Cu(DAB) to conduct electric current was
probed as a function of temperature by using a homogeneous
pellet of ∼3 mm thickness made by compressing the bulk
powder with a hydraulic press (Figure S10). Temperature-
dependent DC conductivity measured by using the two-probe
method in the range of 150−320 K is presented in Figure 6a. It
can be seen from the figure that the temperature-dependent
conductivity exhibits metal-to-insulator (M−I) transition
behavior which is analogous to the ones observed for
conducting polymeric systems.56−61 The M−I transition can
be attributed to various factors such as the sensitivity of doping
and level of disorder present in the system. But it is a well-
known fact that the M−I transition arises in polymers mainly
due to the phenomenon of disorder-induced localization.59−61
It may be mentioned here that the polymeric systems are
known to show partial crystallinity and their complex
morphologies. This can also be interpreted by using the
Ioffe−Regel criterion59 (KFI ∼ 1; KF is the Fermi number and I
is the mean free path) which states as the disorderness
increases in a system, the deviation can be seen from metallic
behavior due to the fact that the mean free path of electrons
becomes smaller than the interatomic spacing.57−60 According
to this expression, the metallic behavior is seen when KF is
much greater than one and the regime of M−I transition is
seen for the values KF less than one.57,60 Thus, the M−I
transition observed in COP Cu(DAB) synthesized in this
study can be attributed to its polymeric nature.
The current−voltage (I−V) study performed on the same
sample to confirm semiconductor behavior and the resulting
profile are shown in Figure 6b. Remarkably, the sample showed
a room temperature conductivity of a 0.01 S/m, one of the
highest reported values for the COPs derived from amine
ligands. Notably, the Hall effect experiments, showing positive
Hall voltage upon application of a variable magnetic field
(Figure S11), indicated the p-type semiconductor behavior of
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Figure 6. (a) Temperature-dependent conductivity reveals the
existence of metal−insulator transition occurring as a result of
disorderness in the COP material. (b) Current vs voltage (I−V) curve
and the nonlinear behavior of the I−V curve indicate the inherent
semiconducting behavior of the sample.
Cu(DAB)a feature further substantiated by Seebeck
coefficient measurements.
AC conductivity studies were performed not only to rule out
ionic contributions but also to know the mechanism of
electronic conduction. Besides, such an investigation provides
important information to understand the role of disorder on
the transport mechanisms.62−65 The films employed for these
measurements were prepared in the same manner as for the
DC conductivity studies. For establishing electrical contacts, a
conductive adhesive was applied on both sides of the film, thus
providing parallel-plate capacitor geometry for the experi-
ments. The universal feature observed is that at low
frequencies conductance is constant (taken to be GDC) while
becoming strongly frequency dependent (Gf) above a critical
frequency. Jonscher’s universal description62−64 considers a
distribution of hopping probabilities between sites distributed
randomly in space and in energy and relates G( f) with the
measuring frequency f,
G(f ) = G DC + kf n
where k is a constant and the exponent n is known to be in the
limits 0 < n < 1 for disordered solids. The frequency spectrum
for the COP studied here is well described by the
aforementioned equation, with the behavior being in
qualitative agreement with the expectation of universal
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behavior (Figure S12). The exponent obtained, 0.40 ± 0.01,
does fall in the expected window. The mechanism governing
the increase in G(f) with f can thus be attributed to hopping
conduction, with the weak temperature dependence associated
with GDC suggesting that the hopping is between localized
states in the vicinity of the Fermi level.
The temperature (T) dependence of the magnetic
susceptibilities (χm) of the Cu(DAB) was investigated on a
SQUID magnetometer in the temperature range of 10−300.0
K under an applied magnetic field of 0.1 T. Figure 7a depicts
Figure 7. χm (a) and 1/χm (b) plotted against temperature for
Cu(DAB); the latter fitting with Curie law yields the Curie constant at
high temperature. The Cu(DAB) shows temperature-dependent
magnetization behavior where magnetization (χm) increases with a
decrease in temperature and enters into the paramagnetic region
below 100 K.
the plot of χm vs T in which χm decreases with an increase in
temperature. At ∼10 K the χm value is 0.0135 emu/(mol Oe),
which initially decreases rapidly with increase in T and then
decreases gradually. Furthermore, the plot of 1/χm (Figure 7b)
against temperature (T) was fitted with Curie law and the
Curie constant (C) value obtained as the inverse of slope that
was found to be 4.4. Using the value of the Curie constant, the
magnetic moment at high temperature was calculated (see the
Supporting Information for calculations carried out). The value
of μeff is found to be 5.954, which is close to the spin-only value
of four uncoupled Cu(II) ions having S = 1/2 and g = 2, which
is 5.910
The thermoelectric behavior of the Cu(DAB) was examined
by using a homemade two-point configuration setup (Figure
1549
pubs.acs.org/acsapm Article
S13a−c). In particular, the Seebeck coefficient was determined
by using this setup. A schematic diagram of the two-point
configuration setup used for thermoelectric measurement is
shown in Figure S13a. The sample pellet was sandwiched
between two copper contact pads; both thermocouples and
voltage leads were imbedded in the contact pads (Figure S13b)
to determine the temperature and potential differences,
respectively.
The temperature difference was created by heating one side
of the sample at a constant rate. As shown in Figure 8, the
Figure 8. Plot of Seebeck coefficient as a function of temperature.
The Seebeck coefficient is obtained as the ratio between the change in
voltage with respect to change in temperature. A positive Seebeck
coefficient indicates the p-type semiconducting nature of the COP
which is also supported by Hall measurements.
Seebeck coefficient varies from 350 to 50 μV/K measured in
the temperature range of 300−440 K. The voltage thus
generated was measured with a voltmeter (Figure S13c). The
Seebeck coefficient obtained at 300 K (room temperature) is
350 μV/K. To the best of our knowledge, the Cu(DAB) is one
of the best semiconducting coordination polymers exhibiting
such a high Seebeck coefficient. The positive value of the
Seebeck coefficient, which occurs due to the establishment of
electrical potential in the same direction of the applied
temperature gradient, indicates that the majority of charge
carriers are the holes, implying that the Cu(DAB) is a p-type
semiconductor which agrees well with the results of the Hall
effect. The occurrence of higher Seebeck coefficient values
along with p-type behavior is rarely known in the literature,
especially in the case of coordination polymeric systems.66−69
IV. CONCLUSION
We have explored extremely simple gram-scale preparation,
electrical conductivity, thermoelectric behavior, redox activity
and magnetism of a two-dimensional copper(II) coordination
polymer which is inexpensive and stable. DC electrical
conductivity measurements on the pellet as a function of
temperature evidence a conductivity of 0.01 S/m at room
temperature. With the aid of AC conductivity studies, the
contribution of ionic species to the electrical conductivity has
been ruled out unambiguously. Hall effect experiments confirm
the p-type conduction of the material. It shows thermoelectric
behavior with high Seebeck coefficient value, besides redox
activity. Temperature-dependent magnetic susceptibility meas-
urements confirm the paramagnetic behavior of the Cu(DAB)
https://dx.doi.org/10.1021/acsapm.9b01219
ACS Appl. Polym. Mater. 2020, 2, 1543−1552
ACS Applied Polymer Materials
above 30 K. Thus, the COP reported herein can be regarded as
a novel material that has the potential to serve as an active
media in various technological applications. We are continuing
our work in this direction with the hope to have some
interesting outcomes.
■
ASSOCIATED CONTENT
*
sı Supporting Information
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acsapm.9b01219.
Experimental setup for synthesis, elemental composition,
bandgap, XRD of Cu(DAB), Hall effect measurements,
magnetic moment calculation, thermoelectric measure-
ment setup (PDF)
■
AUTHOR INFORMATION
Corresponding Author
Channabasaveshwar V. Yelamaggad − Centre for Nano and
Soft Matter Sciences (CeNS), Bengaluru 560 013, India;
orcid.org/0000-0003-3098-8358; Email: yelamaggad@
cens.res.in
Authors
Sachin Ashok Bhat − Centre for Nano and Soft Matter Sciences
(CeNS), Bengaluru 560 013, India; Department of Chemistry,
Mangalore University, Mangalagangotri 574 199, India
Nani Babu Palakurthy − Centre for Nano and Soft Matter
Sciences (CeNS), Bengaluru 560 013, India; Department of
Chemistry, Mangalore University, Mangalagangotri 574 199,
India
Nagaiah Kambhala − Centre for Nano and Soft Matter Sciences
(CeNS), Bengaluru 560 013, India; Department of Chemistry,
Mangalore University, Mangalagangotri 574 199, India
Angappane Subramanian − Centre for Nano and Soft Matter
Sciences (CeNS), Bengaluru 560 013, India
Doddamane S. Shankar Rao − Centre for Nano and Soft
Matter Sciences (CeNS), Bengaluru 560 013, India;
orcid.org/0000-0002-9643-6604
Subbarao Krishna Prasad − Centre for Nano and Soft Matter
Sciences (CeNS), Bengaluru 560 013, India
Complete contact information is available at:
https://pubs.acs.org/10.1021/acsapm.9b01219
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
C.V.Y. acknowledges DST - Nanomission Thematic Project
No. SR/NM/TP-25/2016 for funding the project.
■
REFERENCES
(1) Batten, S. R.; Neville, S. M.; Turner, D. R. Coordination Polymers:
Design, Analysis And Application; RSC: Cambridge, 2009.
(2) Janiak, C. Engineering Coordination Polymers Towards
Applications. Dalton Trans. 2003, 2781−2804. and references cited
therein.
(3) Robin, A. Y.; Fromm, K. M. Coordination Polymer Networks
With O- And N-Donors: What They Are, Why and How They are
Made. Coord. Chem. Rev. 2006, 250, 2127−2157.
(4) Czaja, A. U.; Trukhan, N.; Muller, U. Industrial Applications of
Metal−Organic Frameworks. Chem. Soc. Rev. 2009, 38, 1284−1293.
1550
pubs.acs.org/acsapm Article
(5) Yamada, T.; Otsubo, K.; Makiura, R.; Kitagawa, H. Designer
Coordination Polymers: Dimensional Crossover Architectures and
Proton Conduction. Chem. Soc. Rev. 2013, 42, 6655−6669.
(6) Cheetham, A. K.; Rao, C. N. R.; Feller, R. K. Structural Diversity
and Chemical Trends in Hybrid Inorganic−Organic Framework
Materials. Chem. Commun. 2006, 4780−4795.
(7) Spokoyny, A. M.; Kim, D.; Sumrein, A.; Mirkin, C. A. Infinite
Coordination Polymer Nano- and Microparticle Structures. Chem.
Soc. Rev. 2009, 38, 1218−1227.
(8) Givaja, G.; Amo-Ochoa, P.; Gomez-Garcia, C. J.; Zamora, F.
Electrical Conductive Coordination Polymers. Chem. Soc. Rev. 2012,
41, 115−147.
(9) Rurack, K.; Martinez-Manez, R. (Eds.). The Supramolecular
Chemistry of Organic-Inorganic Hybrid Materials; Wiley: Hoboken,
(2010).
(10) Kitagawa, S.; Kitaura, R.; Noro, S. Functional Porous
Coordination Polymers. Angew. Chem., Int. Ed. 2004, 43, 2334−2375.
(11) Maeda, H.; Sakamoto, R.; Nishihara, H. Coordination
Programming of Two-Dimensional Metal Complex Frameworks.
Langmuir 2016, 32, 2527−2538.
(12) Albrecht, M.; Lutz, M.; Spek, A. L.; Van Koten, G.
Organoplatinum Crystals for Gas-Triggered Switches. Nature 2000,
406, 970−974.
(13) Kou, H. Z.; Zhou, B. C.; Wang, R. J. Heterotrimetallic 4f-3d
Coordination Polymers: Synthesis, Crystal Structure, and Magnetic
Properties. Inorg. Chem. 2003, 42, 7658−7665.
(14) Hou, H.; Meng, X.; Song, Y.; Fan, Y.; Zhu, Y.; Lu, H.; Du, C.;
Shao, W. Two-Dimensional Rhombohedral Grid Coordination
Polymers [M(Bbbt)2(NCS)2]N (M = Co, Mn, or Cd; Bbbt) 1,1′-
(1,4-Butanediyl)Bis-1H-Benzotriazole): Synthesis, Crystal Structures,
and Third-Order Nonlinear Optical Properties. Inorg. Chem. 2002, 41,
4068−4075.
(15) Takaishi, S.; Takamura, M.; Kajiwara, T.; Miyasaka, H.;
Yamashita, M.; Iwata, M.; Matsuzaki, H.; Okamoto, H.; Tanaka, H.;
Kuroda, S.-i.; Nishikawa, H.; Oshio, H.; Kato, K.; Takata, M. Charge-
Density-Wave to Mott-Hubbard Phase Transition In Quasi-One-
Dimensional Bromo-Bridged Pd Compounds. J. Am. Chem. Soc. 2008,
130, 12080−12084.
(16) Zhang, Q.; Sun, Y.; Xu, W.; Zhu, D. Organic Thermoelectric
Materials: Emerging Green Energy Materials Converting Heat to
Electricity Directly and Efficiently. Adv. Mater. 2014, 26, 6829−6851.
(17) Rusu, M.; Airinei, A.; Butuc, E.; Rusu, G. G.; Baban, C.; Rusu,
G. I. On The Electrical Properties of some modified Polysulfones In
Thin Films. J. Macromol. Sci., Part B: Phys. 1998, 37, 73−82.
(18) Sun, Y.; Sheng, P.; Di, C.; Jiao, F.; Xu, W.; Qiu, D.; Zhu, D.
Organic Thermoelectric Materials and Devices Based on P- and N-
Type Poly(Metal 1,1,2,2-Ethenetetrathiolate)S. Adv. Mater. 2012, 24,
932−937.
(19) Kepert, C. J. Advanced Functional Properties in Nanoporous
Coordination Framework Materials. Chem. Commun. 2006, 695−700.
(20) Welte, L.; Calzolari, A.; Di Felice, R.; Zamora, F.; Gomez-
Herrero, J. Highly Conductive Self-Assembled Nanoribbons of
Coordination Polymers. Nat. Nanotechnol. 2010, 5, 110−115.
(21) Cristina, H.; Jose Vicente, Á .; Mohammad-Reza, A.; Carlos, G.;
Michelle, F.; Jose, S.; Gómez-H, J.; Cristina, G.; Félix, Z. Intrinsic
Electrical Conductivity of Nanostructured Metal-Organic Polymer
Chains. Nat. Commun. 2013, 4, 1709−1716.
(22) Batten, S. R.; Champness, N. R.; Chen, X.-M.; Garcia-Martinez,
J.; Kitagawa, S.; Ohrstrom, L.; O’Keeffe, M.; Paik Suh, M.; Reedijk, J.
Terminology Of Metal−Organic Frameworks and Coordination
Polymers (IUPAC Recommendations 2013). Pure Appl. Chem.
2013, 85, 1715−1724.
(23) Davis, M. E. Ordered Porous Materials for Emerging
Applications. Nature 2002, 417, 813−821.
(24) Stock, N.; Biswas, S. Synthesis Of Metal-Organic Frameworks
(Mofs): Routes to Various MOF topologies, Morphologies, and
Composites. Chem. Rev. 2012, 112, 933−969.
(25) Czaja, A. U.; Trukhan, N.; Müller, U. Industrial Applications of
Metal−Organic Frameworks. Chem. Soc. Rev. 2009, 38, 1284−1293.
https://dx.doi.org/10.1021/acsapm.9b01219
ACS Appl. Polym. Mater. 2020, 2, 1543−1552
ACS Applied Polymer Materials
(26) McGuire, C. V.; Forgan, R. S. The Surface Chemistry of
Metal−Organic Frameworks. Chem. Commun. 2015, 51, 5199−5217.
(27) Alexandrov, E. V.; Virovets, A. V.; Blatov, V. A.; Peresypkina, E.
V. Topological Motifs in Cyanometallates: From Building Units to
Three-Periodic Frameworks. Chem. Rev. 2015, 115, 12286−12319.
(28) Dutta, B.; Dey, A.; Sinha, C.; Ray, P. P.; Mir, M. H.
Photochemical Structural Transformation of a Linear 1D Coordina-
tion Polymer Impacts the Electrical Conductivity. Inorg. Chem. 2018,
57, 8029−8032.
(29) Huang, X.; Li, H.; Tu, Z.; Liu, L.; Wu, X.; Chen, J.; Liang, Y.;
Zou, Y.; Yi, Y.; Sun, J.; Xu, W.; Zhu, D. Highly Conducting Neutral
Coordination Polymer with Infinite Two-Dimensional Silver−Sulfur
Networks. J. Am. Chem. Soc. 2018, 140 (45), 15153−15156.
(30) Bai, S.-Q.; Wong, I. H. K.; Zhang, N.; Lin Ke, K.; Lin, M.;
Young, D. J.; Hor, T. S. A. A New 3-D Coordination Polymer as a
Precursor for Cui-Based Thermoelectric Composites. Dalton Trans.
2018, 47, 16292−16298.
(31) Chan-Navarro, R.; Elizondo, P.; Garcia-Lopez, M. C.; Jimenez-
Barrera, R. M.; Perez, N.; Guadalupe-Sanchez, M.; Garza, L. A.
Synthesis, Structural Characterization and Fluorescent Sensing
Properties of Terbium(Tb+3) Complex Derived from Dialdehyde
Ligand. Polyhedron 2018, 149, 66−72.
(32) Balch, A. L.; Holm, R. H. Complete Electron-Transfer Series of
The [M-N4,] Type. J. Am. Chem. Soc. 1966, 88, 5201−5209.
(33) Weiss, M. C.; Gordon, G.; Goedken, V. L. Crystal And
Molecular Structure of the Macrocyclic Nickel(II) Coplexni-
(C18H14N4)]:Dibenzo[B,I][1,4,8,11]Tetraaza[14]Annulenenickel(II).
Inorg. Chem. 1977, 16, 305−310.
(34) Belser, P.; Von Zelewsky, A.; Zehnder, M. Synthesis and
Properties of Ruthenium(II) Complexes with O-Quinodiimine
Ligands. Crystal and Molecular Structure of Ru(Bpy)2(C6H4(NH)2)-
(PF6)2. Inorg. Chem. 1981, 20, 3098−3103.
(35) Jacques, W.; Daul, C.; Van Zelewsky, A.; Goursot, A.;
Penigault, E. The Electronic Structure of Bis-(O-Phenylenedimido)
Nickel Ni [C6H4(NH2)2]2. Chem. Phys. Lett. 1982, 88, 78−83.
(36) Lelj, F.; Morelli, G.; Ricciardi, G.; Brigatti, M. F.; Rosa, A.
Chemical, Spectroscopic and Electrical Conduction Properties of
Iodinated Nickel Diimine Complexes. Polyhedron 1989, 8, 2603−
2610.
(37) Lelj, F.; Rosa, A.; Ricciardi, G. P.; Casarin, M.; Cristinziano, P.
L.; Morelli, G. On The Spectroscopic Behaviour of O-Bis(O-
Phenylendiimido) Nickel. Chem. Phys. Lett. 1989, 160, 39−42.
(38) Auburn, P. R.; Lever, A. B. P. Synthesis And Spectroscopic
Characterization of Bis[Bis(Bipyridine)Ruthenium(II)]-3,3′,4,4′-Tet-
raimino-3,3′,4,4′-Tetrahydrobiphenyl and its Redox Products. Inorg.
Chem. 1990, 29, 2551−2553.
(39) Masui, H.; Lever, A. B. P.; Auburn, P. R. Control of Orbital
Mixing in Ruthenium Complexes Containing Quinone-Related
Ligands. Inorg. Chem. 1991, 30, 2402−2410.
(40) Ricciardi, G.; Rosa, A.; Morelli, G.; Lelj, F. On The Synthesis
and Characterization of Cu[C6H4(NH2)2]2 (Cu[C6H4(NH2)2]2 =
Semi-Benzoquinonediiminate) As a Donor Precursor of The Semi-
conducting and Ferromagnetic Cu[C6H4(NH2)2]2(I3)1.66 Charge-
Transfer Complex. Polyhedron 1991, 10, 955−961.
(41) Masui, H.; Lever, A. B. P.; Dodsworth, E. S. Substituent Effects
and Bonding Characteristics in (O-Benzoquinone Diimine)Bis-
(Bipyridine)Ruthenium(II) Complexes. Inorg. Chem. 1993, 32,
258−267.
(42) Metcalfe, R. A.; Dodsworth, E. S.; Pietro, W. J.; Lever, A. B. P.;
Stufkens, D. J. Effect Of Donors and Acceptors on the Twist Angle of
a Ruthenium Complex Of Bis(Bipyridine)Ruthenium(II) 3,4-
Diamino-3′,4′-Diimino-3′,4′-Dihydrobiphenyl. A Bifunctional Bi-
phenyl Derivative and a Potential Molecular Switch. Inorg. Chem.
1993, 32, 3581−3582.
(43) Metcalfe, R. A.; Dodsworth, E. S.; Fielder, S. S.; Stufkens, D. J.;
Lever, A. B. P.; Pietro, W. Influence of Remote Ligand Lone Pairs on
the Electronic Structure and Spectrum of Bis(bipyridine)ruthenium-
(II) 3,4-Diamino-3′,4′-diimino-3′,4′-dihydrobiphenyl. Tuning by
External Donors and Acceptors. Inorg. Chem. 1996, 35, 7741−7751.
1551
pubs.acs.org/acsapm Article
(44) da Cunha, C. J.; Fielder, S. S.; Stynes, D. V.; Masui, H.; Auburn,
P. R.; Lever, A.B.P. Bis(2,2′-Bipyridine)(1,2-Diimino-9,10-
Anthraquinone)Ruthenium(II): A Complex Containing an Excep-
tionally Strong Π-Accepting A-A′ Diimine Ligand I. Synthesis, Crystal
and Electronic Structures. Inorg. Chim. Acta 1996, 242, 293−302.
(45) Metcalfe, R. A.; Lever, A. B. P. Tetraammineruthenium(II) and
-Ruthenium(III) Complexes of O-Benzoquinone Diimine and Their
Redox Series. Inorg. Chem. 1997, 36, 4762−4771.
(46) Metcalfe, R. A.; Vasconcellos, L. C. G.; Mirza, H.; Franco, D.
W.; Lever, A. B. P. Synthesis and Characterization of Dinuclear
Complexes of 3,3′,4,4′-Tetraminobiphenyl With Tetramminoruthe-
nium and Bis(Bipyridine)Ruthenium Residues and Their Two- And
Four-Electron Oxidized Products Including A ZINDO Study of
Orbital Mixing as a Function Of Ligand Oxidation State. J. Chem. Soc.,
Dalton Trans. 1999, 2653−2667.
(47) Alex, C.; Bhat, S. A.; John, N. S.; Yelamaggad, C. V. Highly
Efficient and Sustained Electrochemical Hydrogen Evolution by
Embedded Pd-Nanoparticles on a Coordination PolymerReduced
Graphene Oxide Composite. ACS Appl. Energy Mater. 2019, 2, 8098−
8106.
(48) Soylu, M. S.; Yesilel, O. Z.; Karabulut, B.; Buyukgungor, O. The
First Bis(Orotato−N,O) Complex: Synthesis, Crystal Structure,
Spectroscopic and Thermal Characterization of (Chah)2[Cu(Hor−
N,O)2(Cha)]·2H2O (Cha = Cyclohexylamine And Hor = Oro-
tate(2−)). Polyhedron 2009, 28, 2487−2766.
(49) Manna, S. C.; Mistri, S.; Jana, A. D. A Rare Supramolecular
Assembly Involving Ion Pairs of Coordination Complexes with a
Host−Guest Relationship: Synthesis, Crystal Structure, Photo-
luminescence and Thermal Study. CrystEngComm 2012, 14, 7415−
7422.
(50) Karabacak, M.; Bilgili, S.; Atac, A. Molecular Structure,
Spectroscopic Characterization, HOMO And LUMO Analysis Of
3,3′-Diaminobenzidine with DFT Quantum Chemical Calculations.
Spectrochim. Acta, Part A 2015, 150, 83−93.
(51) Khandwe, M.; Bajpai, A.; Bajpai, U. D. N. Synthesis And
Chara cter ization of C oordi nation Polymers of Poly-
(Butanethiooxamide) with Co(II), Ni(II), and Cu(II) Salts. Macro-
molecules 1991, 24, 5203−5207.
(52) Huang, X.; Sheng, P.; Tu, Z.; Zhang, F.; Wang, J.; Geng, H.;
Zou, Y.; Di, C.-a.; Yi, Y.; Sun, Y.; Xu, W.; Zhu, D. A Two-Dimensional
P−D Conjugated Coordination Polymer with Extremely High
Electrical Conductivity and Ambipolar Transport Behaviour. Nat.
Commun. 2015, 6, 7408.
(53) Lei, Y.; Li, H.; Pan, H.; Han, S. Structures and Hydrogen
Bonding Analysis of N,N-Dimethylformamide and N,N-Dimethylfor-
mamide−Water Mixtures by Molecular Dynamics Simulations. J.
Phys. Chem. A 2003, 107, 1574−1583.
(54) Huang, Z.; Yu, L.; Dai, Y.; Wang, H. Hydrogen Bonding
Interactions between N,N-Dimethyl Formamide and Cysteine: DFT
Studies of Structures, Properties, and Topologies. Struct. Chem. 2011,
22, 57−65.
(55) Zhang, C.; Ren, Z.; Liu, L.; Yin, Z. Modelling Hydrogen Bonds
in N, N-Dimethylformamide. Mol. Simul. 2013, 39, 875−881.
(56) Reghu, M.; Vakiparta, K.; Yoon, C. O.; Cao, Y.; Moses, D.;
Heeger, A. J. Tuning Through The Critical Regime of the Metal-
Insulator Transition in Conducting Polymers by Pressure and
Magnetic Field. Synth. Met. 1994, 65, 167−171.
(57) Heeger, A. J., Smith, P., Eds.; Conjugated Materials:
Opportunities in Electronics, Optoelectronics and Molecular Electronics;
Kluwer: Dordrecht, 1990; p 141.
(58) Ahlskog, M.; Reghu, M.; Heeger, A. J. The Temperature
Dependence of the Conductivity in the Critical Regime of the Metal−
Insulator Transition in Conducting Polymers. J. Phys.: Condens.
Matter 1997, 9, 4145−4156.
(59) Ioffe, A. F.; Regel, A. R. Non-Crystalline, Amorphous and
Liquid Electronic Semiconductors. Prog. Semicond. 1960, 4, 237−291.
(60) Mott, N. F.; Davis, E. A. Electronic Processes in Noncrystalline
Materials; Oxford University Press: Oxford, 1979.
https://dx.doi.org/10.1021/acsapm.9b01219
ACS Appl. Polym. Mater. 2020, 2, 1543−1552
ACS Applied Polymer Materials pubs.acs.org/acsapm Article

(61) Leong, W. L.; Vittal, J. J. One-Dimensional Coordination

Polymers: Complexity and Diversity in Structures, Properties, and
Applications. Chem. Rev. 2011, 111, 688−764.
(62) Jonscher, A. K. The Universal Dielectric Response. Nature
1977, 267, 673−679.
(63) Schroder, T. B.; Dyre, J. C. AC Hopping Conduction At
Extreme Disorder takes Place on the Percolating Cluster. Rev. Mod.
Phys. 2000, 72, 873−892.
(64) Sidebottom, D. L.; Roling, B.; Funke, K. Ionic conduction in
solids: Comparing Conductivity And Modulus Representations With
Regard To Scaling Properties. Phys. Rev. B: Condens. Matter Mater.
Phys. 2000, 63, 024301-01−07.
(65) Kamaliya, B.; Vijay Kumar, M.; Yelamaggad, C. V.; Krishna
Prasad, S. Enhancement of Electrical Conductivity of a Liquid Crystal-
Gold Nanoparticle Composite by a Gel Network of Aerosil Particles.
Appl. Phys. Lett. 2015, 106, 083110−05.
(66) Biswas, K.; He, J.; Wang, G.; Lo, S.-H.; Uher, C.; Dravid, V. P.;
Kanatzidis, M. G. High Thermoelectric Figure of Merit in
Nanostructured p-type PbTe−MTe (M = Ca, Ba). Energy Environ.
Sci. 2011, 4, 4675−4684.
(67) Lo, S.-H.; He, J.; Biswas, K.; Kanatzidis, M. G.; Dravid, V. P.
Phonon Scattering and Thermal Conductivity in p-Type Nano-
structured PbTe-BaTe Bulk Thermoelectric Materials. Adv. Funct.
Mater. 2012, 22, 5175−5184.
(68) Poehler, T. O.; Katz, H. E. Prospects for Polymer-based
Thermoelectrics: State of the Art and Theoretical Analysis. Energy
Environ. Sci. 2012, 5, 8110−8115.
(69) Sun, Y.; Sheng, P.; Di, C.; Jiao, F.; Xu, W.; Qiu, D.; Zhu, D.
Organic Thermoelectric Materials and Devices Based on p- and n-
Type Poly(metal 1,1,2,2-ethenetetrathiolate)s. Adv. Mater. 2012, 24,
932−937.

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