Intercatenated Coordination Polymers - ACS Publications - American

Apr 18, 2017 - Department of Chemistry, Aliah University, New Town, Kolkata 700 156, India ... ABSTRACT: Three new coordination polymers (CPs) of...
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Intercatenated coordination polymers (ICPs) of carboxylato bridged Zn(II)-isoniazid and their electrical conductivity Kaushik Naskar, Chittaranjan Sinha, Arka Dey, Basudeb Dutta, Faruk Ahmed, Chandana Sen, MOHAMMAD HEDAYETULLAH MIR, and Partha Pratim Ray Cryst. Growth Des., Just Accepted Manuscript • Publication Date (Web): 18 Apr 2017 Downloaded from http://pubs.acs.org on April 19, 2017

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Table of Contents Intercatenated coordination polymers (ICPs) of carboxylato bridged Zn(II)isoniazid and their electrical conductivity Kaushik Naskar,† Arka Dey, Basudeb Dutta, Faruk Ahemed, Chandana Sen,† Mohammad Hedayetullah Mir,Partha Pratim Roy* and Chittaranjan Sinha†*

This is the schematic diagram of three new coordination polymers (CPs) [Zn(INH)(succ)]n (1), [Zn(INH)(fum)]n, (2) and [Zn(INH)(bdc)]n (3) based Schottky diode. The structural diagrams of the three complexes are presented here along with their characteristic Current – Voltage (I-V) graph.

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Intercatenated coordination polymers (ICPs) of carboxylato bridged Zn(II)isoniazid and their electrical conductivity Kaushik Naskar,† Arka Dey, Basudeb Dutta, Faruk Ahemed, Chandana Sen,† Mohammad Hedayetullah Mir, Partha Pratim Roy* and Chittaranjan Sinha†* †

Department of Chemistry, Jadavpur University, Kolkata 700 032, India.

Department

of Physics, Jadavpur University, Kolkata 700 032, India.

Department

of Chemistry, Aliah University, New Town, Kolkata 700 156, India

Abstract Three new coordination polymers (CPs)of coordinated isoniazid (INH) to Zn(II) with succinic acid (H2succ), fumaric acid (H2fum) and terephthalic acid (H2bdc) as organic linker, [Zn(INH)(succ)]n (1), [Zn(INH)(fum)]n, (2) and [Zn(INH)(bdc)]n,(3) respectively have been characterized. The structure determination by single crystal X-ray diffraction technique shows ZnN2O4 distorted octahedral geometry and the 1D chain is constituted via the INH and carboxylate coordination along with the hydrogen bonding (N–H---O) which comprises 2D structure. The CPs, 1 and 2, are isostructural and fabricate supramolecular networks by inclined intercatenation of two 2D layers while 3 shows parallel intercatenation. The electrical conductivity and Schottky barrier diode behaviour have been established by the charge transport mechanism of the compounds at quasi-Fermi level state. The analysis indicates that the compound, 1 has highest mobility (2.53 x 10

-10

m2V-1s-1) than 2 (1.86 x 10-10 m2 V-1s-1) and 3

(1.89 x 10-10 m2 V-1s-1) and highest electrical conductivity (2.26 x 10-4 Sm-1) than others (1.12 x

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10-4 Sm-1 (2) and 1.25 x 10-4 Sm-1 (3)). DFT computation of structural motif of CPs has calculated the band gap (E : 3.93 eV (1), 4.45 eV (2), 4.26 eV (3)) which supports the progression of conductivity.

Introduction An extensive research in the field of coordination polymers (CPs)1˗6 has attracted in the different branches of metal-organic framework (MOFs), coordination network (1D, 2D, 3D) etc. The field explores wide applications in gas storage,7˗9 separation,10˗13catalysis,14,15 ion exchange,16,17 drug delivery,18,19 sensing applications20˗22. N-Donor ligands in presence of bridging ‘linker’ are commonly used to fabricate CPs.23 The properties of CPs have been influenced by the metal ion type, flexibility and chemical functionality of the ligands. Dicarboxylates have been used as ‘linkers’ in the construction of major classes of CPs of various dimensionalities with different coordination modes and sizes.24˗27 Alkane/alkene dicarboxylates are more flexible than aromatic dicarboxylates and have been used to design CPs those are efficiently sensitive to external stimuli.28The electronic properties are influenced by the steric and electronic nature of organic linkers.24-27 Thus, the bulk electronic properties of the polymers may be harmonized by changing the linkers. For example, the CPs synthesized from d10 metal ions (Zn2+, Cd2+) with the conjugated carboxylate organic linkers are found to exhibit semiconductor properties29˗31 and may be the active components in the photonic and electronic devices.32,33 The band-gap in the polymer may be tuned by the size and the conjugation of the organic linker. Increase of the size or the π conjugation of the organic linkers can further narrow down the band gaps. Intercatenated/polycatenated34 features are very important in the context of

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semiconductivity of coordination polymers. The length of the bridging ligands is useful motif to incorporate catenation characteristics.35 Most CPs are electrical insulators, however, recently several classes of highly ordered CPs are demonstrated those assist band transport.36-43 Flexible ligand usually constitute architect to support charge mobility.36-44 Uses of CPs as semiconductor and as Schottky Barrier Diodes have recently been focused;44 because of their chemical stability and the structure-property relationship under the influence of external stimuli such as thermal, electric, magnetic and optical fields.45,46 We have recently focused our attention47-51 to the different aspects of CPs and exploration of their application potential. In this work we have used alkane/alkene dicarboxylates as bridging ligands and isoniazid (isonicotinylhydrazide, INH), a first line anti-mycobacterial drug,52 as another linker. Isoniazid and its derivatives have been used as linker to constitute hybrid materials.53-59Three different dicarboxylates, succinic acid (saturated) (H2succ), fumaric acid (single C=C bond) (H2fum) and terephthalic acid (aromatic dicarboxylic acid) have been used to synthesize bridging dicarboxylates of {Zn(isoniazid) or Zn(INH)} motif60 (Scheme 1).The CPs reported in this work display a surprising effect on the conductivity at an applied potential across it and [Zn(INH)(succ)]n shows highest activity in the switching applications. The structures of the compounds are supported by single crystal X-ray diffraction measurement and other spectroscopic data. The electrical conductivity of the clusters have been explained by DFT computation of coordination geometry of [Zn (isoniazide)(dicarboxylate)]n.

Experimental Section Materials and physical methods

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Isoniazid, (INH), succinic acid (H2succ), fumaric acid (H2fum), terephthalic acid (H2bdc) and Zn(NO3)2,6H2O were purchased from Sigma-Aldrich Chemical Co. Inc.and were used as received. All other chemicals and solvents were of reagent grade and purchased from Merck and used without further purification.Micro analytical data (C, H, N) were collected on Perkin- Elmer 2400 CHNS/O elemental analyzer. Spectroscopic data were obtained using the following instruments: IR spectra (KBr disk, 4000-400 cm−1) from a Perkin Elmer RX-1 FTIR spectrophotometer. Thermogravimetric analyses (TGA) were performed under a nitrogen atmosphere with a heating rate of 10°C/min using a Pyris Diamond TG/DTA instrument in the range of 30-500°C. X-ray powder diffraction was performed using a Bruker D8 ADVANCE Xray diffractometer.The field emission scanning electron microscopy (FESEM) images were taken by a FEI make Inspect F-50 scanning electron microscope.The optical characterization of all the synthesized compounds was carried out with the help of Shimadzu 2401 PC UV-Vis spectrophotometer, in the range 200-900 nm. The frequency dependent capacitance was recorded by the computer controlled Agilent make precision 4294A LCR meter. The electrical characterization was performed with the help of Keithley 2400 sourcemeter, interfaced with PC.

Synthesis of [Zn2(INH)2(succ)2]n (1) To aqueous solution (10 ml) of Zn(NO3)2. 6H2O (0.297 g, 1 mmol) was added succinic acid (H2succ) (0.118 g, 1 mmol) in ethanol (10 ml) neutralized with Et3N (0.212 g, 2 mmol) and isoniazid (0.137 g, 1 mmol) solution (10 ml ethanol) was injected carefullyto make undisturbed layer. It was then allowed to diffuse for a week. The colourless block shaped crystals were deposited on the glass wall. The crystals were separated mechanically under microscope and washed with methanol and water (1:1) mixture, and dried. The yield of [Zn(INH)(succ)]n (1) was

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72% (0.026 g). Elemental analysis calculated for (C10H11N3O5Zn)n(1): C, 37.72; H, 3.48; N, 13.19,Found: C, 37.58; H,3.44; N 13.05,. IR (KBr pellet, cm-1): 1670 νas(COO−), 1363 νs(COO−). Other two complexes, [Zn(INH)(fuma)]n (2) (79 %) and [Zn(INH)(bdc)]n (3) (82%) were also isolated following identical procedure. Microanalytical data for (C10H9N3O5Zn)n(2): C,37.93; H, 2.86; N, 13.27, Found: C, 37.78; H,2.80; N 13.18, IR (KBr pellet, cm-1): 1669 as(COO−), 1347 νs(COO−). (C14H11N3O5Zn)n(3): C,45.89; H, 3.02; N, 11.46, Found: C, 45.94; H, 2.97; N 11.36,. IR (KBr pellet, cm-1): 1671 νas(COO−), 1389 νs(COO−).

X-ray Crystallography Crystal data and experimental details for data collection and structure refinement are reported in Table 1. The crystal structures of compounds 1–3 were determined by X-ray diffraction methods. Suitable single crystal having appropriate dimensions were used for data collection via Bruker SMART APEX II diffractometer, having graphite-monochromated Mo-Kα radiation (λ = 0.71073 Å). The unit cell parameters and crystal-orientation matrices were determined for the complex by least squares refinements of all reflections within hkl range -11  h  24, -12  k  12, -16  l  16 (1); -12  h  12, -11  k  13, -18  l  18 (2); -25  h  27, -12  k  12, -25  l  16 (3). The intensity data were corrected for Lorentz and polarization effects61. Data were collected applying the condition I >2σ (I). The collected data were integrated using SAINT program and the absorption corrections were made with SADABS.Full matrix least squares refinements on F2were carried out using SHELXL-9762 with anisotropic displacement parameters for all non-hydrogen atoms. Hydrogen atoms were constrained to ride on the respective carbon or nitrogen atoms with isotropic displacement parameters equal to 1.2 times

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the equivalent isotropic displacement of their parent atom in all cases. All calculations were carried out using SHELXL 97 62, SHELXS 97 63, PLATON 99 64 and ORTEP-3 65 program. Table1: Crystal data and refinement parameters for 1-3 1

2

3

Formulae

C20H22N6O10Zn2

C20H18N6O10Zn2

C28H22N6O10Zn2

Formula weight

318.59

316.59

366.63

Crystal system

Monoclinic

Triclinic

Monoclinic

Space group

P2(1)/n

P-1

C2/c

a (Å)

9.1456(3)

9.2016(9)

19.6870(5)

b (Å)

9.7514(4)

9.8134(9)

9.1163(3)

c (Å)

13.5478(5)

13.7181(13)

19.0761(6)

α (o)

90.00

88.373(4)

90.00

β (o)

105.8180(10)

73.851(4)

112.608(2)

γ (o)

90.00

87.890(5)

90.00

V (Å3)

1162.47(7)

1188.8(2)

3160.55(16)

T (K)

297(2)

293(2)

273(2)

Z

4

4

8

Dcalcd (g/cm3)

1.820

1.780

1.541

 (mm-1)

2.134

2.087

1.582

 (Å)

0.71073

0.71073

0.71073

 range ()

3.13-26.34

2.077-28.256

2.50-28.76

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Total reflections

16401

22064

28303

Unique reflections

2349

5781

4422

Refine parameters

173

343

209

R1a [ I > 2 (I) ]

0.0491

0.0307

0.0296

wR2b

0.1342

0.0789

0.0780

Goodness-of-fit

1.074

1.032

1.051

1.263, −0.392

0.378, −0.387

Difference between peak and 1.612, −0.682 hole(e Å−3)

a

R1=Fo-Fc/Fo.

b

R2 = [w(Fo2-Fc2)2/ w(Fo2)2]/2. For 1, w = 1/[2(F0)2+

(0.0639P)2+4.7269P]; for 2, w = 1/[2(F0)2+ (0.0395P)2+0.7444P] and for 3, w = 1/[2(F0)2+ (0.0375P)2+2.7845P] where P = (F02 + 2Fc2) / 3. Theoretical Calculation GAUSSIAN-09 program package was used to generate optimized geometries and a molecular function of the CPs. Hybrid DFT-B3LYP functional was used throughout the calculations. For C, H and N the 6-31G (d) basis set was assigned. LanL2DZ basis set along with the corresponding pseudo-potential without any symmetry constrain for Zn were used. The vibrational frequency calculation was also executed for these three compounds to ensure that the optimized geometries represent the local minima and there were only positive Eigen values. The single crystal X-ray coordinates had been used in the calculations. To consign the low lying electronic transitions in the experimental spectra, TDDFT calculations of the complexes were done. We computed the lowest 25 singlet – singlet transition in methanol using the conductor-like polarizable continuum

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model and results of the TD-DFT calculations were qualitatively very similar. Gauss Sum66 was used to calculate the fractional contributions of various groups to each molecular orbital. Results and Discussion Synthesis and formulation Dicarboxylates serve as bridging groups to construct coordination polymer. Upon addition of isoniazid (INH) to aqueous solution of Zn(NO3)2 and succinic acid (H2succ) /fumaric acid

(H2fum)

/

terephthalic

acids

(H2bdc)the

complexes[Zn(INH)(succ)]n,

(1)

and

[Zn(INH)(fum)]n, (2) and [Zn(INH)(bdc)]n(3)are isolated.67,68 Infrared spectra of free isoniazid (Supplementary Materials, Fig. S1) show (C=O) at 1662 cm-1andin thefree carboxylic acids (Supplementary Materials, Fig. S2-S4) (COO) appear at 1697, 1676 and 1690 cm-1which shows shifting to lower frequency (Supplementary Materials, Fig. S5)in the complexes and support the coordination to Zn(II)69-71 and the difference in COO frequencies ( = as - s) larger than 200 cm-1maintainthe polymerisation. The TGA of the compounds determine thermal stability order 3 (350 °C) >2 (270 °C) >1(240 °C) (Supplementary Materials, Fig. S6). Powder X-ray diffraction (PXRD) patterns of as-synthesized 1, 2, and 3 exactly match with those simulated from single crystal data indicating phase purity of the bulk (Supplementary Materials, Figs. S7 – S9).The morphological study by FESEM of the compoundsis shown in Figure 1 and has revealed that the particle size of 1is smaller than 3, and in case of 2, it is largestin the series. This size dependent morphology of the material may influence some physical characteristics of the compounds.

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Fig. 1. FESEM images of compound (a) 1, (b) 2and (c) 3 respectively Structural descriptions of [Zn(INH)(dicarboxylates)]n, (dicarboxylates: succ (1) , fum (2), bdc (3)) The octahedral unit of CPs are shown in Scheme 1. The crystal structures of 1 (Fig. 2(i,ii)) and 2 (Fig. 2 (iii, iv)) are isotypical. The compound 1 crystallizes in the monoclinic space group P21/n with Z = 4. Its asymmetric unit contains distorted octahedral Zn(II) centre, bonded to one INH ligand, one succinate linker and each Zn(II) ion shows distorted octahedral geometry coordinated to two INH-N centres, one O donor from INH amide and three O atoms from two different succinate ligands, thus ZnN2O4 coordination arrangement (Scheme 1) is achieved. The compound 2 crystallizes in the triclinic space group Pī with Z = 4 with coordination arrangement as in 1, ZnN2O4 (Scheme 1). The connectivity of INH and succinate ligands in 1 and fumarate linker in 2 constitute the two dimensional (2D) sheet structure with (4,4)-grids as shown in Figures 2(ii), (iv). The lengths of the rectangles are 9.146 × 8.821 Å2 in 1and 9.444 × 9.202 Å2 in 2 (Supplementary Material, Fig. S10, S11).The cavity space is crowded and blocked by intercatenation of linker motif to generate an overall entanglement which is shown in Figures 2(i, iii). The catenation, considered as a disadvantage for construction of highly porous frameworks,72,73 is currently becoming very important because of enhancement of framework

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stability and generation of stimuli responsive properties.74 The Zn–Nbond lengths are in the range of 2.0990(18) ̶ 2.195(2) Å in 1 and 2.1042(16) - 2.1969(19) Å in 2; and Zn–O bond lengths are in the range of 1.9973(17) ̶ 2.3828(17) Å in 1 and 1.9989 (17) - 2.3855(16) Å in 2.

Scheme 1. Synthesis of CPs [Zn(INH)(succ)]n (1), [Zn(INH)(fum)]n (2),[Zn(INH)(bdc)]n (3) The compound 3 crystallizes in the monoclinic space group C2/c. The asymmetric unit of 3 consists of distorted octahedral Zn(II) centre in ZnN2O4coordination sphere (Fig. 2(v, vi)), bridged by both INH ligand and bdc linker and constitute (4,4)-gride of dimension 11.098 × 9.116 Å2 (Fig. 2(vi); Supplementary Material, Fig. S12). A report of Zn(II)-coordination

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polymer58 of INH with bdc shows no coordination of bdc to Zn(II) while it shows hydrogen bonded secondary interaction. So, we may applause that it is the first example of coordination polymer of Zn(II) with INH and bdc ligands.

(i)

(ii)

(iii)

(iv)

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(v)

(vi)

Fig. 2. 2D sheet constructed by INH linker and succ (i, 1), fum (iii, 2) and bdc (v, 3) as bridging ligand; inclined polycatenated of sql with doc 1/1 in [Zn(INH)(succ)]n (ii, 1), [Zn(INH)(fum)]n (iv, 2) and parallel polycatenated of sql with doc 1/1 in [Zn(INH)(bdc)]n (vi, 3).

The (INH-NH-)-N(H)–H---O(CO) (N---O, 2.840(3); H---O, 1.940(4) Å and N–H---O, 177.7(4), symmetry : -x, y, ½-z) of two different structural units form two hydrogen bonds and constitute eight member puckered ring and propagates to constitute supramolecule. Other hydrogen bonds are N(8)–H(8a)----O(5) (N---O, 2.824(3); H---O, 1.920(4) Å and N–H---O, 178.00, symmetry : -x, y, ½-z); N(8)–H(8b)----O(3) (N---O, 2.912(2); H---O, 2.250(4) Å and N–H---O, 130.00, symmetry : -x, y, ½-z) (Supplementary Materials, Figs. S10 (1); S11 (2), S12 (3)) enhance strength of molecular union.

UV-Vis spectroscopy, band gap and dielectric measurements

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The absorption spectra have been recorded for the compound deposited thin films of 1, 2, and 3 by preparing a well-dispersed solution in Dimethyl sulfoxide (DMSO) (inset, Fig. 3). The energy absorption is observed in the UV region such as 360 nm (1), 310 nm (2) and 320 nm (3). According to Tauc, the optical band gap of the material can be deduced from the absorption spectra of the material, by using the following equation:75 𝜶𝒉 = 𝑨(𝒉 − 𝑬𝒈 )𝒏

(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 processes dependent constant. ‘A’ is a constant which is considered as 1 for ideal case. Using this equation, the calculated optical band gap is 3.39 eV (1), 4.09 eV (2) and 3.98 eV (3). Here the value of the exponent ‘n’ in the above equation was considered as n = 1/2.1 The plot of (αh)2vs. h of the synthesized compounds are demonstrated in Fig.3.

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Fig: 3. UV-vis absorption spectra (inset) and Tuac’s plots for 1, 2 and 3.

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Theoretical calculations have shown that the band gap of CPs (the energy differences between the highest occupied orbitals (HOMOs) and the lowest unoccupied molecular orbitals (LUMOs)) between 1.0 and 5.5 eV serve as effective semiconductor and have largely been dependent on the ligand conjugation and the dimensions of the CPs.76The optical band gaps of present synthesized compounds are within the semiconductor limit. Moreover, the presence of strong absorbance in the UV and visible wavelength region predicts some conducting nature of the synthesized compounds. These results motivated us further to check the electrical conductivity of the synthesized compounds. Hence, we carried out the dielectric study of the compounds,1-3. Impedance spectroscopy has been widely used to study the charge transport behaviour of nano-crystalline materials. This analysis provides a correlation between the electrical and structural properties of the material. The transport properties of as-prepared CPs, 1, 2 and 3 have been evaluatedby the impedance measurement. The capacitance (C), impedance (Z), and phase angle () of the sample were evaluated as a function of frequency (40 Hz-11 MHz). For this purpose the polished pellets of the synthesized compounds were taken. High purity ultrafine silver paste was used as electrode on the opposite surfaces of the pellets. The plane impedance (Z) plots, i.e., the Nyquist plots (Z’ - Z’’) are shown in Fig. 4 and has revealed prominent arc of semicircles which have been contributed by semiconducting grains in the high-frequency region. Thesesemicircles at the high-frequency region are related to the electrode resistance and also reflect the charge transfer resistance at the electrode/composite interface. From Fig. 4, it is clear that the radius of 1is less than that of 2 and 3 and indicates that 1 facilitates the interfacial charge transfer.

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Fig. 4. Nyquest impedence plots for the 1, 2 and 3

Fig.5. Bode plotsfor the 1,2 and 3 The dependency of phase angle () with frequency (f) i.e; Bode phase plots of all three CPs (1-3) are demonstrated in Fig. 5. Comparing the Bode phase plots shows that the characteristic peak position of 1 shifts to a lower frequency rather than the characteristic peak position of 2 and 3. This characteristic frequency is related to the inverse of the recombination

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lifetime or electron lifetime (τn). From the curve peak of the characteristic graph the electron life time can be determined according to eqn (2).77 𝝉𝒏 =

𝟏

(2)

𝟐𝝅𝒇𝒎𝒊𝒏

The electron lifetime (τn) of 1, 2 and 3 are listed in Table 2. From these study it can be easily said, that the characteristic frequency is related to the electron lifetime. The longer electron lifetime corresponds to a smaller frequency. The AC conductivity measurements provide some information about the interior of the semiconductor which is a region of relatively low conductivity even when the conduction process is electrode-limited.78

Fig.6. Dependency of AC conductivity on frequency for 1, 2 and 3 Fig.6 shows the frequency (f) dependency of the AC conductivity of the compounds (13). The conductivity decreases with the increase in frequency when it depends on free

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carriers.79Thefrequency dependence of the conductivity obeyed the empirical law of frequency dependence given by the power law of the form (3): 𝝈(𝝎) = 𝝈𝑫𝑪 + 𝝈𝑨𝑪

(3)

where,σ(ω) is thetotalconductivity, σDCis the dc conductivity, and σAC is the dc conductivity. The frequency-dependent part of conductivity σAC has been observed to obey the relation, 𝝈𝑨𝑪 = 𝑨𝝎𝒔

(4)

where, A is a constant and s is a number depends upon frequencies at room temperature.

Fig.7. Capacitance versus frequency graph of 1,2 and 3 The relative dielectric constant was measured on pellet. As-synthesized compounds (1-3) have been pelletized into a disc of diameter 7.32 mm and thickness 1.8 mm. Fig.7 gives the plots showing the variation of the capacitance (C) as a function of the frequency (f) at constant bias potential. The room temperature capacitance of 1, 2 and 3 is shown to be frequency dependent at relatively low frequencies. The capacitance decreases with increasing of frequency and becomes

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saturated at higher frequency. From the saturation level the relative permittivity of the compounds was calculated employing following equation:75 𝜺𝒓 =

𝟏 𝜺𝟎

.

𝑪.𝒅

(5)

𝑨

where, ε0is the permittivity of free space, εris the dielectric constant of the synthesized material, 𝐶 is the capacitance (at saturation) and dandAare the thickness and effective area of the pellet. Using the above formula the dielectric constant (εr) of the materials were estimated and given in the Table 2 below. Table 2. Dielectric parameters of 1, 2 and 3 CPs

Charge Transfer

D.C. Conductivity

Electron Lifetime

Dielectric Constant

Resistance (Ω)

(10−4 Sm−1)

(10−8 s)

(Fm−1)

1

624

2.26

28.9

6.11

2

1264

1.12

3.6

2.68

3

1130

1.25

8.4

3.91

Literature review68,

80-83

suggests that the electrical conductivity of present Zn(II)-INH

intercatenated CPs of dicarboxylates appear in the higher range of conductivity data. All these parameters pointed out that 1 (2.26×10−4 Sm−1) is a better contender in the view of electrical conductivity than 2 and 3. Motivated from these results, we designed Schottky device of all synthesized compounds to check further the applicability in electrical field. Hence calculated the Schottky parameters and studied the electrical behaviour. Fabrication of Schottky device

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The Schottky devices of 1, 2 and 3 were fabricated in sandwich like ITO/1 and/or 2 and/or 3/Al configuration. Indium tin oxide (ITO) coated glass substrates was cleaned with soap solution, acetone, ethanol, and distilled water sequentially in an ultrasonic bath. The material was dispersed in DMSO medium and ultrasonicated well to form a stable dispersion. A thin film of the material was then prepared on the ITO coated glass by spin coating technique at 1200 rpm for 2 minutes and subsequently dried. Aluminium was chosen as the rectifier metal contact and deposited on the films by thermal evaporation technique to construct metal–semiconductor junction. The effective diode area was maintained at 7.065 x 10-6 m2 by shadow mask. Electrical properties of Schottky device The presence of strong absorbance in the UV and visible wavelength region of the synthesized compounds prophesies some impact of charge transport phenomena. Furthermore, the decreased value of optical band gap for 1 than the other two compounds interpreted some better possibility of formation of metal–semiconductor barrier with [Zn(INH)(succ)]n (1). Hence, for better understanding of the charge transport phenomenon, electrical characterization was accomplished by the thin films devices of the well-dispersed solution of compounds deposited on top of ITO coated glass substrates. To analyse the electrical properties, we have measured the current at corresponding applied bias voltage sequentially within the limit ±2V. Fig.8 represents the current-voltage (I-V) characteristics curve for 1, 2 and 3 based thin film devices under dark condition. Evidently, the current-voltage characteristics curve in Fig.8 shows that the devices based on the CPs (1-3) exhibit highly non-linear rectifying behaviour. The non-linearity of the I-V characteristic indicates that the prevalent conduction mechanism is non-ohmic in nature. The nature of the I-V curve represents the rectifying in nature, similar to the Schottky diode

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behaviour. The rectification ratio of 1 is 176 under dark condition and those of 2 and 3are 81.73 and 80.62, respectively.

Fig.8. I-V characteristics curve for ITO/(1)/Al, ITO/(2)/Al and ITO/(3)/Al structured thin film devices The curves have been quantitatively analyzed by considering the conventional I-V characteristics and all parameters are also verified using Cheung’s Equation (eq. 6). The currentvoltage characteristics of the Schottky junction can be analyzed by the following standard equations of thermoionic emission of Schottky diode:84 qV

-qV

I = I0 exp (ηKT) [1-exp (ηKT)]

(6)

Where I0 is the saturation current derived from the straight line intercept of ln (I) at V= 0 and is given by 𝑰𝟎 = 𝑨𝑨∗ 𝑻𝟐 𝒆𝒙𝒑 (

−𝒒∅𝑩 𝑲𝑻

)

(7)

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where q stands for the electronic charge, k is the Boltzmann constant, T is the temperature in Kelvin, V is the forward bias voltage, A is the effective diode area, ηis the ideality factor and A* is the effective Richardson constant respectively. The effective diode area was estimated as 7.065×10−2 cm2 and the effective Richardson constant was considered as 32 AK−2cm−2 for all the devices. From Cheung, in term of series resistance the forward bias I-V characteristics can be expressed as: 𝑰 = 𝑰𝟎 𝒆𝒙𝒑 [

𝒒(𝑽−𝑰𝑹𝑺 ) 𝜼𝒌𝑻

]

(8)

where the IRSterm is the voltage drop across series resistance of device. The values of the series resistance can be determined from following functions using equation (8) 𝒅𝑽

=( 𝒅𝒍𝒏(𝑰)

𝜼𝑲𝑻 𝒒

) + 𝑰𝑹𝑺

(9)

Equation (9) also can be expressed as a function of I as 𝑯(𝑰) = 𝑰𝑹𝑺 + 𝜼∅𝑩

(10)

and𝐻(𝐼) is given as follows: 𝜼𝑲𝑻

𝑯(𝑰) = 𝑽 − (

𝒒

𝑰

) 𝒍𝒏 (𝑨𝑨∗𝑻𝟐 )

(11)

The series resistance (RS) and ideality factor (η) for all devices under dark condition were determined from the slope and intercept of dV/dln(I) vs. I plot and the potential barrier heights were evaluated from the intercept of H(I) vs. I curve (Fig. 9). Equation (9) exhibits a straight line region where the series resistance dominates, for the data in the downward-curvature region of the forward bias I-V characteristics. Thus the plot of dV/d(lnI) versus I will give RS as the slope and ηkT/q as the y-intercept. The value of H can be calculated from the equation (10) using just

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obtained ideality factor (η) value. A plot of H(I) versus I will also lead to a straight line (Fig. 9) with the y-axis intercept being equal toηϕB. The measured potential height (ϕB), idealityfactor (η) and series resistance (RS) under dark condition for the Metal (Al)–Semiconductor (synthesized compounds) (MS) junctions were listed in Table 3. Table 3: Schottkydevice parameters of 1, 2 and 3 CPs

Rectification Ratio

Ideality Factor

Barrier Height (eV) Series Resistance (Ω)

1

176

1.43

0.368

567.22

2

80.62

1.94

0.511

1385.71

3

81.73

1.86

0.501

1133.96

Fig. 9. dV/dlnI vs. I and H vs. I curves in dark condition for all the compounds 1, 2 and 3 based device A good understanding of MS junction requires analysis of the charge transport phenomena of the material. So, for a better insight we investigated the I-V curves in the light of space charge limited current (SCLC) theory. Using this theorem the two important parameters of charge transport, effective carrier mobility (μeff) and transient response time (τ) was evaluated.

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Effectivecarrier mobility was estimated from higher voltage region of I vs V 2 graph (Fig. 10) by Mott-Gurney equation:85 𝑰=

𝟗µ𝒆𝒇𝒇 𝜺𝟎 𝜺𝒓 𝑨 𝑽𝟐

( 𝒅𝟑 )

𝟖

(12)

Here, dis the thickness of the film which was considered about ~1 μm for our device. Transit time (τ) of the charge carriers is one of the key parameters to analyze charge transport across the junction. For this purpose τ was evaluated from equation (13), by using the slope of forward I-V curve, shown in Fig.8.75 𝝉=

𝟗𝜺𝟎 𝜺𝒓 𝑨 𝑽 𝟖𝒅

(𝑰)

(13)

Estimated values of effective carrier mobility and lifetimes are presented in Table 4. The results demonstrate that the charge transport properties of the compound 1 are far better than the others two. The mobility implies higher transport through the MS junction and the life time reveals the average time of a free charge carrier before being recombined. All these factors corroborate the eventual superiority of 1 than 2 and 3.

Fig: 10. I vs. V2 curves in dark condition for the compounds 1, 2 and 3 based device

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Table 4: Charge conducting parameters of the CPS (1-3) CPs

Effective Mobility

Transient Time

Product

(m2/v.s)

(s)

(m2/v)

1

2.53 x10-10

1.7 x10-3

4.30 x10-13

2

1.86 x10-10

1.2 x10-3

2.24 x10-13

3

1.89 x10-10

1.6 x10-3

3.02 x10-13

DFT Computation and band gap Lattice matching and deformation potentials have been used to generate the Schottky electrical contact; the deformation commonly refers to the band gap which is commonly the energy difference between highest occupied and lowest unoccupied MOs (E = ELUMO - EHOMO, eV)86. In CPs the absolute deformation potentials (ADPs) is used to determine the band gap.87 The coordinated polymer has organic and inorganic hybrid nature,so the band gap may be influenced by the electronic feature of both. In CPs of d10 electronic configuration the band edges are often defined by electronic states on the organic ligand along with geometry strain of the network. 38

DFT optimization of the structure of coordination motif of CP has been used to calculate E

(the difference in energy of HOMO and LUMO) (Supplementary Materials, Tables S1, S2 (CP-1, 1); Tables S3, S4 (CP-2, 2); Tables S5, S6 (CP-3, 3)) which may match with band gap obtained from Tauc’s plot (Fig. 3). A small increment in calculated band gap may be assigned to geometry factor which has not been considered in the use of calculation using single motif. However, the movement in band gap follows the experimental results (Fig. 11).

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The trend observed in valence and conduction band in 1, 2 and 3 are attributed to the extended conjugation of bdc linker (3) to conjugation in 2 followed by no conjugation in 1. This also supports that CP-1, 1 shows highest activity in impedance plot (Fig. 4), Bode Plot (Fig. 5) and AC conductivity plot (Fig. 6).

Fig. 11. DFT computed energy of MOs and the energy difference between HOMO and LUMO of the compounds

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Conclusion Isoniazid bridges Zn(II) CPs with carboxylato linkers (succinic acid, fumaric acid, terephthalic acid), [Zn(INH)(succ)]n (1) [Zn(INH)(fum)]n (2) [Zn(INH)(bdc)]n (3) are characterized. The CPs exhibit electrical conductivity and reveal Schottky barrier diode behaviour. The analysis reports the best performance of [Zn(INH)(succ)]n (1) than others (2, 3). The conductivity has been rationalised by band gap measurement and has been supported by DFT computation of optimised geometry of motif. Highest mobility in 1may be due to lowest barrier height and series resistance than others. The subtle structural change from saturated in 1 (succ2-), one C=C bond in 2 (fum2-) to extended conjugation in C6H4 (3) (bdc2-) may be the reason of conductivity and charge mobility change in the CPs

Supplementary materials The

spectral

data

of

INH,

carboxylic

acids

(H2succ,

H2fum;

H2bdc),

[Zn(INH)(carboxylato)]n(FT-IR, Fig. S1 to Fig. S5); TGA Graph (Fig. S6), PXRD Plots (Figs. S7 to S9); H-bonded unit and 2D+2D interpenetrated CP (Figs. S10 (1), S11 (2), S12 (3)).Data Tables of frontier molecular orbitals of [Zn(INH)(carboxylato)]n (Table S1 – S6) are noted. This material is available free of charge via the Internet at http://pubs.acs.org.

Accession Codes CCDC

1450811

([Zn(INH)(succ)]n,

1);

1450813

([Zn(INH)(fum)]n,

2);

1450812

([Zn(INH)(bdc)]n, 3) contain 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 [email protected], or by contacting The Cambridge Crystallographic Data Centre, 12, Union Road, Cambridge CB2 1EZ, UK; fax: +441223 336033.

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Authors Information E-mails: [email protected] (C. Sinha); [email protected] (P. P. Ray)

Acknowledgments Financial support from the West Bengal Department of Science & Technology, Kolkata, India (Sanction No. 228/1(10)/(Sanc.)/ST/P/S&T/9G-16/2012) and the Council of Scientific and Industrial Research (CSIR, Sanction No. 01(2731)/13/EMR-II,), New Delhi, India are gratefully acknowledged. Authors thank to Centre for Advanced Studies (CAS-II, UGC), Department of Chemistry, Jadavpur University for generous help. We sincerely thank Dr. Suvendu Maity, Jadavpur University for his help.

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Table of Contents Intercatenated coordination polymers (ICPs) of carboxylato bridged Zn(II)isoniazid and their electrical conductivity Kaushik Naskar,† Arka Dey, Basudeb Dutta, Faruk Ahemed, Chandana Sen,† Mohammad Hedayetullah Mir,Partha Pratim Roy* and Chittaranjan Sinha†*

This is the schematic diagram of three new coordination polymers (CPs) [Zn(INH)(succ)]n (1), [Zn(INH)(fum)]n, (2) and [Zn(INH)(bdc)]n (3) based Schottky diode. The structural diagrams of the three complexes are presented here along with their characteristic Current – Voltage (I-V) graph.

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