A Semiconducting Copper(II) Coordination Polymer with (4,4) Square Grid Topology: Synthesis, Characterization, and Application in the Formation of a Photoswitch

Article abstract of DOI:10.1021/acs.cgd.7b00830

A phenoxo and end-to-end thiocyanate bridged copper(II) coordination polymer (CP), [Cu₂L₂(μ-1,3-SCN)₂]_n, where HL is an potential tetradentate N₂O₂ donor Schiff base ligand, 2-(2-(ethylamin

Full text of DOI:10.1021/acs.cgd.7b00830

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Article
A semiconducting copper(II) Metal–Organic Framework
with (4,4) square grid topology: Synthesis, characterization
and application in the formation of a photo-switch
Samim Khan, Soumi Halder, Partha Pratim Ray, Santiago Herrero,
Rodrigo Gonzalez-Prieto, Michael G. B. Drew, and Shouvik Chattopadhyay
Cryst. Growth Des., Just Accepted Manuscript • DOI: 10.1021/acs.cgd.7b00830 • Publication Date (Web): 12 Dec 2017
Downloaded from http://pubs.acs.org on December 14, 2017
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A semiconducting copper(II) Metal–Organic Framework with (4,4)
square grid topology: Synthesis, characterization and application in
the formation of a photo-switch
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Samim Khana, Soumi Halderb, Partha Pratim Rayb, Santiago Herreroc,
Rodrigo González-Prietoc, Michael G. B. Drewd and Shouvik
Chattopadhyaya,*
aDepartment of Chemistry, Inorganic Section, Jadavpur University, Kolkata – 700 032, India. eꢀ
mail: shouvik.chem@gmail.com
b Department of Physics, Jadavpur University, Kolkata 700032, India.
c Departamento de Química Inorgánica, Facultad de Ciencias Químicas, Universidad
Complutense de Madrid, Ciudad Universitaria, 28040 Madrid, Spain.
dSchool of Chemistry, The University of Reading, P.O. Box 224, Whiteknights, Reading RG6
6AD, UK.
Abstract
A phenoxo and endꢀtoꢀend thiocyanate bridged copper(II) MOF, [Cu2L2(ꢀꢀ1,3ꢀSCN)2]n,
where HL is an potential tetradentate N2O2 donor Schiff base ligand, 2ꢀ(2ꢀ
(ethylamino)ethylimino)methyl)ꢀ6ꢀethoxyphenol, has been synthesized and characterized. The
band gap, bulk capacitance, electron lifetime, relaxation time, dielectric constant and DC
conductivity of the complex in the solid state have been studied. Variable temperature magnetic
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susceptibility measurement indicates the presence of weak antiferromagnetic interactions among
the copper (II) centres with J= ꢀ0.97 cmꢀ1. The complex shows increase in conductivity when
illuminated with visible light (photosensitivity ~2.833).
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Keywords: Copper(II); photoꢀsensitive, antiferromagnetic, band gap, DC conductivity, bulk
capacitance, dielectric constant
Introduction
The metal ions are denoted as nodes and ligands as linkers in multidimensional metal–organic
frameworks (MOFs).1ꢀ3 An appropriate metal–ligand complex could also be regarded as node in
place of a bare metal ion.4ꢀ5 The significance of the synthesis and characterization of these MOFs
lies in their promising potential applications as functional materials.6ꢀ8 Focusing to copper(II),
varieties of copper(II)ꢀMOFs are synthesized by various groups in order to understand the
structural and chemical factors that govern the exchange coupling between paramagnetic
copper(II) centres and also for developing new functional molecularꢀbased materials.9ꢀ11
A
variety of bridging groups have been employed for the synthesis of such systems; among them
the phenoxo oxygen atom of the salicylaldehyde derived Schiff bases deserves a special
mention.12ꢀ13 The magnetic properties (i.e. J values of the spin coupling) of only phenoxoꢀ
bridged complexes containing the Cu2O2 cores have been postulated to be dependent upon
various factors, such as the coordination geometry of the copper ions, the Cu–O–Cu angle, the
Cu–O bond lengths, the Cu···Cu distances, Addison parameter, etc. The study of magnetic
exchange mediated by this ligand is often complicated by the presence of additional bridging
ligands,14ꢀ17 e.g. pseudoꢀhalide, which may bind adjacent copper(II) centres in endꢀon (EO) and
endꢀtoꢀend (EE) modes.18 EO coordination mode of a pseudoꢀhalide is associated with
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ferromagnetic or antiferromagnetic coupling depending on various other factors,19ꢀ22 the EE
pseudoꢀhalide bridges, in general, propagate antiferromagnetic interactions,23ꢀ25 although there is
also a possibility of a ferromagnetic interaction between centres when the pseudoꢀhalide binds in
an endꢀtoꢀend fashion.26ꢀ27 The chemistry and magnetic properties of such complexes have been
the subject of several reviews.28ꢀ31 Interestingly, the dielectric property and conductivity of such
complexes are relatively less explored. For example, the semiconducting nature of a cadmium(II)
Schiff base complex having optical band gap values of 3.69 and 2.67 eV was characterized by
the distribution of electronic states in both valence and conduction bands with the partial density
of states.32 The use of such complexes in light harvesting and energy transfer is also a promising
area of research.
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In present work, the photosensitivity of a synthesized semiconducting complex with a
substantial on–off ratio has been demonstrated. Though several substances are reported to absorb
visible light and generate photocurrent with a quick response, probably this is the first example
of any coordination polymer constructed by copper(II) Schiff base complex and characterized by
single crystal Xꢀray crystallography. Herein, we would like to report the synthesis and Xꢀray
characterization of a novel 2D coordination polymer having copper(II) Schiff base building
block. The optical band gap of the complex in the solid state has been estimated experimentally.
The bulk capacitance, electron lifetime, relaxation time and dielectric constant of the complex
were also explored. The value of photosensitivity is calculated to be 2.833. The complex shows
increase in conductivity from 3.63 x 10ꢀ5 Scmꢀ1 to 4.13 x 10ꢀ5 Scmꢀ1 in presence of light.
Results and discussion
Synthesis
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The potential tetradentate Schiff base ligand, HL, was prepared by the condensation of Nꢀ
ethylꢀ1,2ꢀdiaminoethane with 3ꢀethoxysalicylaldehyde following the literature method.33ꢀ35 The
potential tetradentate Schiff base, HL, acted as a tridentate ligand and occupied three sites of the
octahedral copper(II). The remaining sites were occupied by one nitrogen and one sulpher atoms
from two end to end bridged thiocyanates and one phenoxo oxygen from a different ligand to
form a twoꢀdimensional coordination polymer, [Cu2L2(ꢀꢀ1,3ꢀSCN)2]n was formed. The
formation of the complex is shown in scheme 1.
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Scheme 1: Synthetic route to the complex.
Description of structure
The complex crystallizes in the orthorhombic space group, Pbca. The structure
determination reveals that the copper(II) centre is coordinated by one amine nitrogen atom,
N(22), one imine nitrogen atom, N(19), one phenoxo oxygen atom, O(11), of the deprotonated
Schiff base ligand, (L)ꢀ, and one nitrogen atom, N(1) and one sulfur atom, S(1) of two endꢀtoꢀend
bridging thiocyanate ligands. The sixth coordination site is occupied by a symmetry related (1ꢀ
x,ꢀy,1ꢀz) phenoxo oxygen atom, O(11)a, from a Schiff base ligand to complete its octahedral
geometry. The symmetry related phenoxo oxygen, O(11)a connect two copper(II) to form a
pseudoꢀdimer (Fig. 1). The pseudoꢀdimeric bridging unit Cu2O2 describes a rhombohedral plane.
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The rhombohedral angles of O(11)ꢀCu(1)ꢀO(11)a, Cu(1)ꢀO(11)aꢀCu(1)a, O(11)aꢀCu(1)aꢀO(11),
Cu(1)aꢀO(11)ꢀCu(1) are 91.78(11), 88.2(1), 91.8(1) and 88.2(1)º respectively. The saturated five
member ring, Cu(1)–N(22)–C(21)–C(20)–N(19) presents an envelope conformation with
puckering parameters q(2) = 0.409(5) and φ = 108.0(5)º.36 Selected bond angles are presented in
Table S1 (Supporting Information). Each copper(II) center of the pseudoꢀdimer is connected to
two neighboring copper(II) centers of two different pseudoꢀdimers through two endꢀtoꢀend
thiocyanate bridges to form a twoꢀdimensional polymeric layer along crystallographic ab plane
(Fig. 2a). Topology analysis reveals a (4,4)ꢀsquare grid topology (Fig. 2b) with copper(II)
occupying the nodes, where endꢀtoꢀend thiocyanate connectors take part in the formation of
edges.
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The complex shows intraꢀpseudoꢀdimeric hydrogen bonding (Fig. S1, Supporting
Information). The hydrogen atom, H(22), attached to the nitrogen atom, N(22), is participated in
hydrogen bonding interaction (Table S2, Supporting Information) with the symmetryꢀrelated
a
oxygen atom, O(13)a {symmetry transformation = 1ꢀx,ꢀy,1ꢀz }. The methyl hydrogen atom,
H(11D), attached to C(112), is involved in significant C–Hꢁꢁꢁπ interaction (Table S3, Supporting
Information) with the symmetry related (3/2ꢀx,ꢀ1/2+y,z) phenyl ring C(12)ꢀC(13)ꢀC(14)ꢀC(15)ꢀ
C(16)ꢀC(17). As the complex consists of centrosymmetric pseudoꢀdimeric building block, each
interaction is duplicated and the combination of these interactions creates a 2ꢀD supramolecular
structure (Fig. S2, Supporting Information).
Powder Xꢀray diffraction
The experimental PXRD pattern of the bulk product is in good agreement with the
simulated XRD pattern from singleꢀcrystal Xꢀray diffraction, indicating consistency of the bulk
sample (Fig. 3).
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Hirshfeld surfaces
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The Hirshfeld surfaces of the complex, mapped over dnorm, shape index and curvedness,
are illustrated in Fig. S3, Supporting Information. 2D fingerprint plots are shown in Fig. 4, where
intermolecular interactions appear as distinct spikes. Decomposition of fingerprint plots able us
to highlight particular atom pair close contacts.37 The proportion of C⋯H/H⋯C interaction
comprises 15.6%, where as O⋯H/H⋯O interaction comprises 6.1% of the Hirshfeld surfaces for
each molecule.
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IR and electronic spectra
In the IR spectrum of the complex, a band corresponding to the azomethine (C=N)
stretching vibration appears at 1649 cmꢀ1.38 The µꢀ1,3 bridging mode of the thiocyanate group is
confirmed by the splitting of the absorption band corresponding to the γC=N asymmetric
stretching that appears at 2102 and 2075 cmꢀ1 indicates the Sꢀ and Nꢀcoordination modes of the
thiocyanate ligand respectively.39 Two medium bands at 846 and 749 cmꢀ1 may be assigned to
υ(CS).40 The bands in the range of 2968ꢀ2865 cmꢀ1 are assigned due to alkyl CꢀH bond stretching
vibrations.41 A moderately strong, sharp peak at 3230 cmꢀ1, may be assigned to N–H stretching
vibration.42
The intense absorption bands at 276 and 372 nm may be assigned as intraligand π–π* and
ligand to metal charge transfer (LMCT) transitions respectively.43 The absorption band in the
visible range at 682 nm (Fig. 5) may be assigned as d–d transition.44
Morphology
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The FESEM image of the material is presented in Fig. S4 (Supporting Information)
which shows that the material has an arbitrary morphology.
Mass spectra
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The electrospray ionization mass spectra (ESIꢀMS positive) are performed to determine
molecular weight and study fragmentation pattern of possible complex adduct. The ESIꢀMS
positive spectrum of the complex is recorded in acetonitrile solution and the result is shown in
Fig. S5. In the mass spectrum of complex, the peak at m/z = 356.05 may be assigned to
[CuL(SCN)H]+ and the peak at m/z = 298.07 corresponds to the presence of monopositive
[Cu(L)]+.
Cyclic voltammetry
The cyclic voltammogram of the complex shows an oxidation peak (Epa) at about the
potential 1332 mV. This can be assigned as CuII/CuIII oxidation process. A wave (Epc) at 1265
mV is observed during the reverse scan (Fig. 6). The difference between the cathodic and anodic
peak is 67 mV for the complex, and this suggests the reversible nature of the electron transfer
processes. E1/2 is calculated as the average of anodic (Epa) and cathodic (Epc) peak potentials. The
value of E1/2 is 1.3 V. The criteria of reversibility were checked by observing the constancy of
the peak–peak separation (ꢂEp = EpaꢀEpc) and the ratio of peak heights (ipa/ipc ~1) with variation
of scan rates. The redox signal remains virtually invariant under different scan rates (0.01–1.0
Vsꢀ1) in the temperature range 300–280 K. Any solvent dependent shifts and changes in the
electrochemical reversibility of the redox couples are not noteworthy. Other peaks at negative
potentials may be due to the reduction to lower oxidation states of copper.
Band gap measurement
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The absorption spectra recorded is shown in the inset of Fig. 7. The spectra show
absorption in the visible region with absorption band edge at around 420 nm. The optical band
gap energy (Eg) of the complex was evaluated using the Tauc’s equation45
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Error! Reference source not found.
(1)
Where ‘α’ is the absorption coefficient, ‘Eg’ is the band gap, ‘h’ is Planck’s constant , ‘ ’ is the
frequency of light and the exponent ‘n’ is the electron transition process constant. ‘A’ is the
constant which is taken 1 for ideal case. To calculate the optical band gap energy, the value of n
is taken as ½ (The proof is given along with Fig. S6 in Supporting Information).
The Tauc’s plot of the complex is given in Fig. 7. The optical energy band gap (Eg) can
be determined by extrapolating the linear region of the plot of (αhError! Reference source not
found.)2 vs. hγ to α=0 absorption and the value is estimated to be about 2.95 eV. We tried to
perform the calculations of the crystal lattice within the GeneralizedꢀGradient approximation
(GGA) and the PerdewꢀBurkeꢀErnzerhof (PBE) formulation for the exchangeꢀcorrelation
functional. However, the presence of strong hybridization between the Cu 3d and N 2p orbitals
leads to the formation of isolated and intermediate bands in the crystal band gap. Therefore,
theoretical band gap in it cannot be determined.
The light absorption of the material in visible region indicate that the material has some
light induced properties and the optical band gap also suggests that there is semiconducting
nature which encourages us to further investigate the dielectric properties of the synthesized
material.
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Dielectric parameters
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The dielectric parameters were measured on pellet. The synthesized complex was
pelletized into a disc form of diameter 7.32 mm and thickness 1.8 mm.
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The complex plane impedance plot i.e. Nyquist plot of the sample is shown in Fig. 8a.
The plot shows a semicircle where the bulk resistance is evaluated from the diameter of the arc.
The Bode plot of the complex has been shown in Fig. 8b and the electron lifetime of the
material was calculated. The peak frequency is related to the inverse of the recombination
lifetime or electron lifetime. Electron lifetime is determined from the following equation46
(2)
Here τn is the electron lifetime and fmin is the peak frequency.
The impedance loss spectrum of the complex is represented in Fig. S7, Supporting
Information. It is used to determine the relaxation time of the complex47 using the following
equation.
(3)
τ is the relaxation time and fp is the peak frequency determined from the graph.
Fig. S7, ESI gives the curve showing the variation of the capacitance (C) as a function of
the frequency (f) at constant bias potential. The room temperature capacitance of the complex
shows frequency dependence at relatively low frequencies. The capacitance decreases with the
increase in frequency and becomes saturated at higher frequency (Fig. S8, Supporting
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Information). Using the value of capacitance at the saturation level the dielectric constant of the
complex was calculated using the following equation45:
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(4)
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Where, is the permittivity of free space, is the dielectric constant of the synthesized
material, is the capacitance (at saturation) and and are the thickness and effective area of
the pellet respectively. Using the above formula the dielectric constant (Error! Reference
source not found.) of the material was estimated and given in Table 2.
The above electrical parameters and the obtained band gap value indicate that the
synthesized product has a semiconducting nature. Hence, we have further studied its light
sensing behaviour to check the suitability of the synthesized material for electronic application.
Magnetic properties
The experimental χMT value at room temperature (0.86 cm3·molꢀ1) for the complex
corresponds to the presence of two independent copper(II) centres in the molecule (0.75
cm3·molꢀ1 considering g = 2) indicating an almost negligible interaction between the copper(II)
centres. However, although this value remains practically constant until around 50 K, then
decreases slowly and finally drops at 11 K, reaching a value of 0.54 cm3·molꢀ1 at 2K (Fig. 9).
This decrease at very low temperatures indicates a small antiferromagnetic interaction between
copper(II) atoms. Therefore, the magnetic behaviour of this complex has been simulated using
equation 5:
2J
Ng2ꢀB2
kT
2ekT
χ
=
×
+TIP
(5)
2J
1+3ekT
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Equation 5 was derived by Bleaney and Bowers48 from the Hamiltonian H = −2Jij SiSj . A
term considering a temperature independent paramagnetism (TIP) has also been included.
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The fit of the experimental data using equation 5 yields the following values: g = 2.14; J
= ꢀ0.97 cmꢀ1, TIP = 2.29x10ꢀ5 cm3 molꢀ1, with σ2 = 9.71x10ꢀ5. In the equation 5, the interactions
between copper(II) pseudoꢀdimers have not been considered despite that this type of interactions
could influence notably the magnetic behaviour of the compounds even through hydrogen
bonds.49 The introduction of one term to consider the interdimer interactions using the molecular
field approximation50 does not improve the fits showing a J value of the same order. Therefore,
the interdimer coupling in this complex seems to be negligible.
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It is well known that bis(ꢀꢀphenoxo)ꢀbridged dinuclear copper(II) complexes show
magnetic properties strongly dependent on structural factors. The CuꢀOꢀCu bridging angle, the
outꢀofꢀplane shift of the phenyl rings, the CuꢀO bond length, the planarity of the Cu2O2 core, and
the conformation and rotation of the phenyl groups can influence the magnetic behaviour of this
type of complexes. Although the majority of them show very strong antiferromagnetic coupling
constants (up to 2J = ꢀ905 cmꢀ1), small changes in these geometric parameters can make some of
the complexes present only weak antiferromagnetic, or even ferromagnetic, intradimer
interactions.15,31,51ꢀ55
The CuꢀOꢀCu bridging angle is one of the main parameters affecting these magnetic
properties. Thompson and col.52 found that the antiferromagnetic coupling increased linearly
with the increment of this angle for flat macrocyclic dinuclear copper(II) complexes derived
from 2,6ꢀdi(R)formylphenols. This tendency is similar to those described by Ruiz et al.56 for
similar hydroxoꢀ and alkoxoꢀbridged compounds. However, these later complexes show weaker
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antiferromagnetic couplings and even ferromagnetic for small CuꢀOꢀCu angles, while flat
macrocyclic phenoxoꢀbridged complexes show antiferromagnetic interactions in a broad range of
angles.52,56 High values of the outꢀofꢀplane angle (τ) of the phenyl rings, i.e. when the phenyl
groups are not in the Cu2O2 plane, favour the ferromagnetic contributions.31, 53,56,58 However, this
parameter has more influence in the variation of the coupling constants when the phenyl rings of
the phenoxo ligands present a syn conformation.31,53 In this case the antiferromagnetic coupling
is enhanced for values of τ in the range 0 – 20° whereas the contrary occurs for τ > 20°. On the
contrary, the outꢀofꢀplane angle does not have a very important effect if the phenyl rings show an
anti conformation, although the ferromagnetic contribution is slightly favoured for high values of
τ. Also, the rotation of the phenyl rings influences the magnetic coupling, since the
antiferromagnetic interactions increase with a perpendicular orientation of the ring with respect
to the Cu2O2 core. 31 Giapintzakis, and col.52 have also reported an important correlation of the
magnetic coupling with the CuꢀOphenolate bond length. Distances lower than 1.98 Å are associated
to strong antiferromagnetic coupling constants, whereas bond lengths higher than 1.98 Å can
show either weak antiferromagnetic or ferromagnetic behaviour. Deviations from the planarity of
the Cu2O2 framework, as a function of the CuꢀOꢀCuꢀO torsion angle, have also been studied for
these complexes31 and for the analogous hidroxoꢀbridged complexes.57 High torsion angles
reduce the antiferromagnetic couplings and favour the ferromagnetic contribution. Although in
copper(II) dimers with pentacoordinate environment, the magnetic exchange can be influenced
by the type of connection, such as axialꢀequatorial,15,51,54 basalꢀbasal,15,54 or basalꢀapical,54,58 this
variable is not considered for octahedral environments.
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Therefore, a magnetoꢀstructural analysis can be used to explain the weak
antiferromagnetic intradimer interaction (J = ꢀ0.97) cmꢀ1 found for the complex. First of all, its
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CuꢀOꢀCu bridging angle (88.22°) is very low. Although experimental values are found in a wide
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range (85.5ꢀ110.4°), most of them are in the 95ꢀ110.4° range.31 In addition, the τ value (45.06°)
is high and the CuꢀOphenolate distances are long (2.347 Å, in average). All those values are
consistent with very weak antiferromagnetic or even ferromagnetic coupling. Moreover, the anti
conformation of the phenyl groups for such a high value of τ makes weaker the
antiferromagnetic coupling. Nevertheless, there are other structural parameters that favour
antiferromagnetic coupling and, consequently, avoid reaching the ferromagnetic interactions: the
phenyl rings are almost perpendicular to the Cu2O2 core, which is completely flat (the CuꢀOꢀCuꢀ
O torsion angle is 0°). As a result of all these factors, the complex has very weak
antiferromagnetic coupling. Nevertheless, the existence of weak ferromagnetic interaction
through the phenoxo group and weak interdimers antiferromagnetic interactions through the
thiocyanate ligands cannot be discarded.
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Electrical properties
The presence of strong absorbance of the synthesized complex in the visible wavelength
region of light suggests that incident radiation has some influence on the charge transport
properties. Furthermore the value of optical band gap indicated semiconducting nature of the
complex. To elucidate charge transport mechanism, electrical current was measured at a bias
voltage of 2V.
The transient photocurrent response shown in Fig. 10 is generated by the transfer of
excited photoelectrons from the highest occupied molecular orbital (HOMO) to the lowest
unoccupied molecular orbital (LUMO). The transient photocurrent responses of the complex are
investigated for several onꢀoff cycles of irradiations. As shown in Fig. 10, the current falls
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rapidly to the initial value when illumination turns off. Photocurrent again goes back to the
maximum value as soon as the light turns on. This characteristic behaviour depicts that most of
the photogenerated electrons reach the ITO coated substrate to produce photocurrent under the
irradiation of visible light. The result suggests that photogenerated electron–hole pairs separated
efficiently for the complex. The photosensitivity of the material is 2.833 which is determined
from Fig. 10. This figure also tells that the material is very stable under the exposure of light.
The conductivity was measured from the currentꢀvoltage characteristics graph and it was
estimated as 3.63 x 10ꢀ5 Scmꢀ1 and 4.13 x 10ꢀ5 Scmꢀ1 under dark and light conditions. The
electrical transport parameters which are detrimental to device performance suggest that this
material can be a promising candidate for photoꢀswitch.
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Conclusion
In conclusion, we report the synthesis and Xꢀray characterization of a novel coordination
polymer based on a N2O2 donor potential tetradentate Schiff base ligand and µꢀ1,3ꢀthiocyanates
as linkers. The copper(II) MOF exhibit electrical conductivity that has been rationalised by band
gap measurement. The phenoxo bridged complex has very weak antiferromagnetic coupling.
Several dielectric parameters like bulk capacitance, electron lifetime, relaxation time and
dielectric constant of the complex in the solid state have also been studied. On irradiation with
visible light, there is a considerable increase in the conductivity of the present complex. The
photosensitivity of the material is 2.833 and the material is very stable under the exposure of
light which suggests that it can be used as photoꢀswitch.
Supporting Information
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Details experimental section, Theoretical methods, Hirshfeld Surfaces, Data Tables of
bond angles, hydrogen bond, CꢀH···π interactions (Table S1–S3); hydrogen bond, CꢀH···π
interactions (Fig. S1 to Fig. S2); Hirshfeld surfaces, FESEM image, ESIꢀMS (Fig. S3 to Fig. S5);
Plot of d[ln(αhν)]/d(hν) vs. hν and plot of ln(αhν) vs. ln(hνꢀEg) (Fig. S6); Impedance loss
spectrum, capacitance versus frequency graph (Fig. S7 to Fig. S8).
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Accession Codes
CCDC 1542881 contains the supplementary crystallographic 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.
Acknowledgments
Financial support received from the Spanish Ministerio de Economíay Competitividad
(CTQ2015ꢀ63858ꢀP, MINECO/FEDER) is gratefully acknowledged. PPR acknowledges UPE
programme of University Grants Commission and FIST programme of Department of Science
and Technology, Govt. of India.
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53. Biswas, A.; Drew, M. G. B.; Song, Y.; Ghosh, A. Effect of anionic coꢀligands on structure
and magnetic coupling of bis(ꢃꢀphenoxo)ꢀbridged dinuclear copper(II) complexes. Inorg. Chim.
Acta 2011, 376, 422ꢀ427.
54. Basak, S.; Sen, S.; Roy, P.; GómezꢀGarcía, C. J.; Hughes, D. L.; Butcher, R. J.; Garribba, E.;
Mitra, S. Structural Variation and MagnetoꢀStructural Correlation in Two New Dinuclear Bis(ꢃ2ꢀ
Phenoxo)ꢀBridged CuII SchiffꢀBase Complexes: Catalytic Potential for the Peroxidative
Oxidation of Cycloalkanes. Aust. J. Chem. 2010, 63, 479ꢀ489.
55. Archana V.; Imamura, Y.; Sakiyama, H.; Hada, M. Correlating Magnetic Exchange in
Dinuclear Bis(phenolate)ꢀBridged Complexes: A Computational Perspective. Bull. Chem. Soc.
Jpn. 2016, 89, 657ꢀ665.
56. Ruiz, E.; Alemany, P.; Alvarez, S.; Cano, J. Toward the Prediction of Magnetic Coupling in
Molecular Systems:ꢄ Hydroxoꢀ and AlkoxoꢀBridged Cu(II) Binuclear Complexes. J. Am. Chem.
Soc. 1997, 119, 1297ꢀ1303.
57. Ruiz, E.; Alemany, P.; Alvarez, S.; Cano. J. Structural Modeling and MagnetoꢀStructural
Correlations for HydroxoꢀBridged Copper(II) Binuclear Complexes. Inorg. Chem. 1997, 36,
3683ꢀ3688.
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58. Mashhun, A.; Zarei, S.A.; Piltan, M.; Chevreux, S.; Guillon, E. A binuclear copper(II)
complex with diphenoxidoꢀbridges: synthesis, characterisation, crystal structure and predicting
the magnetic coupling constant. J. Chem. Res. 2016, 40, 114ꢀ119.
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Table 1: Crystal data and refinement details of the complex.
Formula
Formula Weight
Temperature (K)
Crystal system
Space group
a(Å)
C14H19CuN3O2S
356.94
150
Orthorhombic
Pbca
13.3158(8)
10.3661(7)
22.9694(15)
8
b(Å)
c(Å)
Z
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dcalc (g cmꢀ3)
1.496
1.516
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8
ꢃ(mmꢀ1)
F(000)
1480
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Total Reflections
Unique Reflections
Observed data [I >2 σ (I)]
No. of parameters
R(int)
10650
4548
3108
192
0.062
R1, wR2 (all data)
R1, wR2 [I > 2 σ (I)]
0.1191, 0.1692
0.0797, 0.1549
Symmetry transformation a = 1ꢀx,ꢀy,1ꢀz; b = 3/2ꢀx,1/2+y,z.
Table 2: Dielectric parameters of the complex.
Complex
Bulk
Bulk
Electron
lifetime
Relaxation
time
Dielectric
constant
resistance
capacitance
2.74 kΩ
6.59 x 10ꢀ11 F
1.59 x 10ꢀ8
sec
1.81 x10ꢀ7
sec
0.858
1
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Fig. 1: (a) Perspective view of the complex with selective atomꢀnumbering scheme. Hydrogen
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a
atoms have been omitted for clarity. Symmetry transformation, = 1ꢀx, ꢀy, 1ꢀz. (b) Asymmetric
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unit of the complex. Selected bond lengths (Å): Cu(1)–O(11) = 1.924(3), Cu(1)–N(1) = 1.961(4),
Cu(1)–N(19) = 1.947(4), Cu(1)–N(22) = 2.036(4), Cu(1)–O(11)a = 2.770(3), Cu(1)–S(1)b =
2.886(14). Symmetry transformation a = 1ꢀx,ꢀy,1ꢀz; b = 3/2ꢀx,1/2+y,z.
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Fig. 2: (a) Twoꢀdimensional layer of the complex. Ethyl groups and hydrogen atoms are omitted
for clarity. (b) A perspective view of (4,4) Square grid topology of the complex.
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Fig. 3: Experimental and simulated powder XRD patterns of the complex confirming the purity
of bulk material.
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