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Coordination Polymers Containing Tubular, Layered and Diamondoid Networks: Redox, Luminescence and EPR Activities Kaustuv Banerjee, Sanidpan Roy, Moumita Kotal, and Kumar Biradha Cryst. Growth Des., Just Accepted Manuscript • DOI: 10.1021/acs.cgd.5b01329 • Publication Date (Web): 12 Oct 2015 Downloaded from http://pubs.acs.org on October 18, 2015

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Crystal Growth & Design

Coordination Polymers Containing Tubular, Layered and Diamondoid Networks: Redox, Luminescence and EPR Activities. Kaustuv Banerjee,a Sandipan Roy,a Moumita Kotal,b and Kumar Biradhaa* Department of Chemistry, Indian Institute of Technology Kharagpur, Kharagpur, India. Fax: +91-3222-282252; Tel+913222-283346; E-mail: [email protected] Department of Chemistry, Indian Institute of Technology Patna, India. KEYWORDS Coordination Polymers, Cyclic Voltammetry, Differential Pulse Voltammetry, EPR, Luminescence. ABSTRACT: The coordination polymeric (CP) materials are of interest due their versatile applications in various fields. The CPbased materials have a great potential to act as multifunctional materials given their diversified nature. A series of CPs found to exhibit combination of luminescence, redox and EPR activities with potential for multifunctional materials. In particular, four new CPs of Cu(II) and Co(II) containing bis(N-pyridyl amide) (L) and dicarboxylates have been synthesized and characterized by single-crystal X-ray and other techniques. The CPs found to exhibit two types of 2D-networks and one each of 1D and 3D networks. Interestingly the 1D-coordination polymer contains a tubular network which is formed by linking CoL2 macrocycles by 1,3benzene-dicarboxylate anions. In one of the 2D-layers, the Cu(II) centre found to form an interesting trimeric SBU via bridging of carboxylates and SO42- and propagates a 2D-layer that contains no cavities. The Co(II) complex also exhibits a 2D-layer containing rectangular cavities which are eventually filled by interdigitation of layers. The 3D-CP exhibits a pseudo diamondoid network containing two types of arms which differ in their length hugely and the networks are triply interpenetrated. Interestingly, two types of water tetramers were found in the 1D-tubular network and 2D-layer containing rectangular grids. The electrochemical measurements (CV & DPV), EPR and luminescence of CPs as well as ligands were explored. These studies indicate that all four CPs serve as redox active electrode materials. Among the four CPs, the CP containing interpenetrated diamondoid network found to exhibit higher electrochemical performance. The present work emphasizes that the interactions between metal ions and organic linkers play an important role in electrochemical performances of the materials. Further the EPR spectral properties and luminescence properties of CPs were found to follow the similar trends. The dimension of the network found to correlate with their observed properties, i.e. 3D>2D>1D.

Introduction The overwhelming interest in the studies of coordination polymers (CPs or MOFs) owes to their intriguing structures and functional properties and the field is very rapidly developing since last two decades. The main advantage of CPs is the linkers as well as nodes can be carefully selected depending on the targeted properties.1-5 Therefore, the CPs have become multidisciplinary field of research given their wide range of properties pertaining to chemistry, physics, biology, materials and environmental sciences.6-9 To date a significant part of the studies focused on the application of CPs as gas storage devices and heterogeneous catalysts, their potential to other applications such as luminescence, conductivity, proton conductivity and sensors just begun to realize in the recent past.10-14 Although, CPs have been extensively used for gas adsorption and other applications but yet remains largely unexplored on their utilization as supercapacitors. Recently, nanoporous carbon materials (NPC) obtained via carbonization of novel mesoporous CPs based materials were shown to act as an efficient supercapacitor electrode materials.15-19 However, to the best of our knowledge, very few CP based materials, as such, have been explored for their applications as redox-active electrode materials.20-27 Very recently, electronic and optical properties of redox active napthalenediimide based coordination polymers have been well

explored.23 Furthermore, Cu-based MOF was shown to act as an electrochemical biosensor for the selective detection of ascorbic acid.22 N

O

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Scheme 1. Structural drawing for L1, L2, SA and BDC

The carboxylate and bis-pyridyl linkers played a significant part in the growth of the literature of CPs. Also there is a considerable amount of literature in which both the linkers were used together. The use of these linkers together gives a better opportunity to fine tune the structure and nature of CPs. Such fine tuning can be done by functionalizing/changing the spacers

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between the pyridyl or carboxylate moieties.28-32 The introduction of functional group, which is capable of forming hydrogen bonding, in the spacer drastically changes the structure of CPs and therefore their properties. We have carried out extensive studies on CPs containing amide functional groups as spacers between the pyridyl groups. It was shown that the twodimensional coordination layers form N-H···O hydrogen bonds to convert the 2D-layers to 3D-networks and impart some control over the packing of the layers.33-37 In continuation to our earlier studies, in this paper we would like to present our studies on CPs of ligands L1 and L2 with dicarboxylates such as succinate (SA) and benzene-1,3-dicarboxylate (BDC) (Scheme 1). Notably, these CP based materials were found to exhibit significant redox activity, solid-sate photoluminescence and generation of radical signature. The ligand L1 contains two amide and three pyridyl functionalities, it can act as a distorted trigonal ligand if all three pyridines participate in coordination. It can also act as an angular ligand if only terminal pyridines participate in coordination. The aliphatic dicarboxylate SA can act as a linear linker while the aromatic BDC can act as an angular linker. Recently, the ligand L1 with the combination of trimesate or 1,4-benzene dicarboxylate was shown to form threedimensional CP.38-40 The ligand L2 was shown by us earlier to form 2D-layers with Cu(SCN)2 and exhibit amide-to-amide hydrogen bonds within the layers.41 Further, it was also shown to form 2D-layers in combination with 1,4benzenedicarboxylate.42 Although, the multifunctional nature of CPs is very well explored, very few studies exist on electrochemical performances on CPs containing amides.43-47 Recently, the exploration of electrochemical properties of Zn(II) and Cd(II) CPs containing N,N’-bis-(4-pyridyl)phthalamide and 4,4’biphenyldicarboxylate or 2,5-thiophenedicarboxylate revealed that they act as supercapacitor electrode materials.33 Further, a series of multifunctional Cu(II) coordination polymers based on flexible bis-pyridyl bis-amide ligands and carboxylates were found to exhibit good electrochemical behavior and significant emission properties.22,23 To date, some amide based CPs have been shown to exhibit redox activity, some have been shown to exhibit solid-state photoluminescence behavior but a few have been shown to be electron paramagnetic resonance (EPR) active.24,25 To the best of our knowledge, no CP was shown to exhibit all these three properties in combination. CPs exhibiting all these three properties may serve as excellent candidates for optoelectronic devices. In this manuscript, such examples of CPs of L1 and L2 with Cu(II) and Co(II) salts of carboxylates will be presented. Further, their synthesis, crystal structure analysis, exploration of their properties and structure-activity correlations will be presented.

Results and Discussion The ligands L1 and L2 were synthesized by following previously reported procedures.48-50 The single crystals of all the CPs were grown through hydrothermal process as the slow evaporation and layering techniques yielded in precipitates. In a typical experiment, the components in H2O were taken in a Teflon lined stainless steel reactor and they were kept for heating at 100 °C. In all cases, heating for two days and subsequently cooling at 5 °C per hour resulted in crystals CPs 1-4 suitable for single crystal X-ray diffraction. The crystals of complexes 2-4 were obtained by using sodium salt of corresponding diacids, whereas those of 1 were obtained by using succinic acid and equivalent amount of (N/20) dil. NaOH solution. We note here that the

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despite of several trails single crystals of CPs containing Co(II), L1/L2 and SA or those containing Cu(II), L1/L2 and BDC could not be obtained. An interesting trimeric Cu(II) cluster was found to be exhibited by complex 1 which further linked to twodimensional structure by L1 and SA. In case of 2, no such Cu(II) clusters were observed, it exhibits interpenetrated pseudodiamondoid network. Interestingly, in 3 the middle pyridyl unit of L1 does not coordinate as a result it forms Co2(L2)2 macrocyles which are linked further by BDC to form 1D-tubular network. 51-55The crystal structure 4 forms a two-dimensional layer containing rectangular grids of dimension 18.0×10.3 Å2. The carboxylate anions act as both chelating and monodentate ligands in all the cases and the coordination modes of SA and BDC observed in 1-4 are depicted in scheme 2. The pertinent crystallographic information for all the complexes 1-4 are given in Table-1. The electrochemical properties of L1, L2 and CPs 1-4 were measured using CV and DPV. Comparison of these properties of CPs with those of ligands reveals that, the overall properties exhibited by CPs is the manifestation of several factors but not just due to the ligands alone. The observed electrochemical properties were correlated with their luminescence properties as well as with their splitting of signals in X-band EPR spectra. {[Cu3(OH)2(L1)(SA)(SO4)]·4H2O}n, 1 {[Cu(L2)(SA)]}n, 2 {[Co(L1)(BDC)(H2O)]·3H2O}n, 3 {[Co(L2)(BDC)(H2O)]·4H2O}n, 4 M O

O M

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O

Scheme 2. The coordination modes displayed by SA and BDC ligand in 1-4.

Analyses of Crystal Structures: The complex 1 is crystallized in Pna21 space group and the asymmetric unit is constituted by one unit each of SA, SO42- and L1, three Cu(II) ions, two OH- ions, and four free water molecules. The three Cu(II) ions form a triangular cluster with Cu···Cu distances of 2.921(2), 3.163(3) and 3.215(3) Å. The cluster formed through the bridging of carboxylate, sulfate and two OH- ions: the edges are capped by two caboxylates (Cu-O: 1.970(13), 1.937(12), 1.920(11), 2.013(12) Å) and one OH(Cu-O: 1.920(13), 1.930(13) Å) while the faces of the triangle are capped by the second OH- (Cu-O: 1.983(11), 1.934(6), 2.012(11) Å) and SO42- ion (Cu-O: 2.310(12), 2.374(10), 2.443(10) Å) (Figure 1a). It is interesting to note that the within the cluster each Cu(II) forms a square pyramidal coordination geometry as they coordinate with four O-atoms and one pyridyl unit. On a whole, three anions (OH-, COO- of SA and SO42-) involved in stabilizing the Cu(II) triangular cluster in an unprecedented manner. Although there were a few trinuclear Cu(II) clusters reported in the literature, sulfate ion was not known to bridge such cluster, further there are very few exam-


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ples in which the Cu3 cluster was used as SBU for CPs. These clusters were linked into one-dimensional chains by SA and as well as by L1 (Figure 1b, c). The interconnection of the chains resulted in the formation of a two-dimensional layer with a thickness of 10 Å. These corrugated layers interdigitate in the crystal lattice along b-axis to form three-dimensional structure (Figure 1d, e). In case of 2, the asymmetric unit is constituted by half unit each of L2, Cu(II) and SA. The Cu(II) ion exhibits a distorted octahedral coordination geometry as it coordinates two carboxylates, in chelation mode (Cu···O: 1.963(4) and 2.461(4) Å), and two pyridine units (Cu···N: 1.987(5) Å). On a whole, the disposition of the ligand L2 and SA from Cu(II) generates a distorted tetrahedral node which leads to the formation of pseudo diamondoid network in which the Cu(II) centers are interconnected by SA and L2 with distances of 8.851 and 17.479 Å respectively. Three of such diamondoid networks interpenetrate in the crystal lattice to generate the overall packing. The NH···O hydrogen bond (H···O 2.076 Å, N···O 2.881(6) Å, and NH···O 155.54°) between amide N-H and one of the coordinated carboxylate O-atom play a significant role in the interpenetration. Apart from this hydrogen bond there are several other weak interactions exist between the interpenetrated networks.

a)

b)

c)

d)

a)

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e) c)

d) Figure 2. Illustrations for the crystal structure of 2: (a) Square planar coordination of Cu(II), (b) diamondoid network formed via coordination of L2 and SA to Cu(II), c) 3-fold interpenetrated diamondoid networks, the ligands were not shown, only the Cu(II) centers were connected for the sake of clarity (d) Interpenetrated 3D-networks containing channels, the interpenetration occurs through N-H···O hydrogen bonding, (e) hydrogen bonding interactions between neighboring networks. Color code: Cu, green; O, red; N, blue; C, grey.

e)

Figure 1. Illustrations for the crystal structure of 1: (a) Triangular copper(II) cluster capped by SO42- and carboxylates of SA; (b) 1Dchains by linking of Cu3 clusters via coordination of L1, note that L1 as well as Cu3 cluster act as three connecters, the -(CH2)2- of SA were not shown for the sake of clarity; (c) side view of the 1Dchains, (d) 2D-layer formed via linking of adjacent chains by carboxylates of SA, (e) side view of the 2D-layer. Color code: Cu, green; O, red; N, blue; C, grey; S, yellow.

The asymmetric unit of complex 3 contains one unit each of L1, BDC and Co(II) and four water molecules, one of which is coordinated to Co(II). The Co(II) ion exhibits an octahedral geometry which is composed of two pyridyl moieties (Co-N: 2.147(3) and 2.152 (3) Å), one water molecule (Co···Ow: 2.087(2) Å) and two carboxylates (Co-O: 2.046 (2) Å), one of which forms chelation (Co-O: 2.147(3) & 2.158 (2) Å).



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tahedral geometry, which is similar to that of complex 3, as it coordinates to two pyridyl units (Co-N: 2.168(8) and 2.171(8) Å), one water molecule (2.110(6) Å) and two carboxylates (2.018(6) Å), one of which forms chelation (2.153(6) & 2.204(6) Å). Such type of coordination leads to the formation of a 2D-layer containing rectangular grids 10.259x17.945 Å2 (Figure 4a, b). The water molecules form a tetramer such that one of the four connect to all other three water molecules with O···O···O bond angles of 135.82(4), 132.13(5) and 78.94(4)°.

a)

a) b)

c)

d)

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d) Figure 3. Illustrations for the crystal structure of 3 (a) 1D-tubular networks via linking of M2(L1)2 macrocycles by BDC units; notice water tetramers in the middle of macrocycles, (b) sideview of the 1D-tubular network; Interdigitation of tubular networks via OHw···N hydrogen bonds (c) top view, (d) side view. Color code: Co, green; O, red; N, blue; C, grey.

The central pyridine ring of L1 does not participate in any coordination, as a result it forms M2(L1)2 macrocylcle due to the angular nature of L1. Interestingly, these macrocyles are interconnected by BDC units to form a tubular structure in which the each macro-cycle is separated by a distance of 10.25 Å. Within the tube, the water molecules form cyclic tetramer (O···O: 2.803(4) & 2.915(4) Å) which are adhered to coordinated carboxylates of BDC via O-H···O hydrogen bonds (O···O 2.724(4) Å) (Figure 3a). These tubular structures interdigiate via OH···N (O···N: 2.752(4) Å, O-H···N: 57.58(9)°), between coordinated H2O and uncoordinated pyridine of the neighboring tube, and N-H···O hydrogen bonds, between one of the tetrameric water and the N-H group of the neighboring tube (H···O: 2.221 Å, N···O: 3.054(4) Å, and N-H···O: 163.29°). Such type of interdigitation leads to the formation of 2D-layer, mean plane of which runs perpendicular to the plane of M2(L1)2 macrocyle (Figure 3b, c). These layers pack in the crystal lattice with weak edge-to-face aromatic interactions between BDC and the terminal pyridyl group of L1 (Figure 3d). In case of 4, the asymmetric unit contains one each of Co(II) and BDC, two half units of L2, one coordinated and four non coordinated water molecules. The Co(II) exhibits distorted oc-

Figure 4. Illustrations for the crystal structure of 4: (a) 2D-layer of (4,4) topology containing rectangular grids, (b) side view of the 2Dlayer, (c) hydrogen bonding between four water molecules and carbonyl group of L2 (d) interdigitation of adjacent layers forming channels which are occupied by water molecules. Color code: Co, violet; O, red; N, blue; C, grey.

The central one further hydrogen bonds to the C=O (C=O···O: 2.717(11) Å) of BDC to complete a distorted hydrogen bonded tetrahedron around central H2O (Figure 4c). The 2D-layers interdigitate with adjacent layers such that there are continuous channels formed along direction of a-axis (Figure 4d). The above described water tetramers occupy these channels and play a significant role in binding the layers together via hydrogen bonding.

The electrochemical properties of CPs 1-4: Cyclic voltammograms (CVs) of individually modified CP materials 1-4 were measured on glassy carbon electrode (GCE) in 1M Li2SO4 aqueous solution in the range from −1.4 to 1.2 V vs. the saturated calomel electrode (SCE) at 10 mV/s (Fig. 5). Similarly CVs of ligands L1 and L2 were also measured on modified glassy carbon electrode (GCE) in 1M Li2SO4 aqueous solution in the range from −1.4 to 1.2 V vs. the saturated


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calomel electrode (SCE) at 10 mV/s. Bare glassy carbon electrode showed two irreversible peaks at -0.4 V and 0.8 V vs. SCE, which is associated with the evolution of bubbles, corresponding to the generation of H2 and O2 from water, respectively.56-58 However, CP modified GCE exhibited the similar potential for the generation of H2 and O2 from water but with the lower currents in CV suggesting increased electrode resistance of the CP materials. The 1 and 2 modified GCE showed strong pseudocapacitive behavior. In case of 1 modified GCE, cathodic peak potential (Epc) at 0.37 V and anodic peak potential (Epa) at 0.10 V were observed. In comparison with 1, modified GCE with 2 exhibited weak redox peak potentials at 0.71 V (Epc) and 0.28 V (Epa) respectively. Such redox peaks are ascribed to the redox of the C=O group of the ligand, which may originate from the redox-active ligand in the structure of the CPs.59-62 Additionally, the potential window, is unprecedentedly large (2.6 V vs SCE) in an aqueous electrolyte. According to Conway,63-64 the maximum operating voltage in an aqueous electrolyte is limited to 1.229 V by the electrolysis of water at ambient temperature.

Figure 5. Cyclic Voltammograms of CPs at 10 mV s-1

-1

Specific Capacitance (F g )

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the potential window using in an organic electrolyte (2.7 V).65-67 In order to compare the redox nature of L1 and L2 we calculated the areas under the CV curves for both L1 and L2 (Figure 7 & 8) and area under CV curves was higher in case of L2 than L1 revealing strong redox nature of L2 than L1. L1 shows oxidation peaks at 0.658 and 1.131 V and reduction peaks at -0.565V respectively. L2 shows oxidation peaks at 0.373, 0.598V and 1.131 V and reduction peaks at -0.565V respectively. The specific capacitance values for both L1 and L2 were found to be higher at lower scan rates. For L1 and L2 specific capacitance was found to be 0.069 and 0.02 F/g respectively at scan rate of 10 mV s-1. However, the area under the CV curve is found to be highest in 2 modified GCE indicating its highest specific capacitance 68-69 The CV curves at different scan rates (10, 20, 50 and 100 mV s-1) for 2 modified GCE are shown in Figure 6 and the corresponding electrochemical performance are presented in the inset of Figure 6. Both of the cathodic and anodic peak potentials are almost unchanged with increasing scan rate implies controlled diffusion of the redox process. For comparison, CV curves were measured by varying scan rates for 1, 3 and 4 modified GCE and their respective electrochemical performance are shown in the supporting information (Fig. S16-S19). The electrochemical properties of the redox active materials (CPs) were calculated in terms of specific capacitance (SC) from the area under the CV curve. The higher electrochemical performance of 2 modified GCE electrode is ascribed to the better charge transport pathway which arises from the combined effect of redox active metal ion, ligand and linker.70-72 The higher electrochemical behaviour observed for 2 is found to be comparable with those of porous CPs reported in the literature.48 Furthermore, the electrochemical impedance spectroscopic (EIS) response was analyzed in terms of Nyquist plots showing the frequency response characteristics at the electrode−electrolyte interface73-75 and is provided in Figure-9. Nyquist plot exhibits two distinct parts including semicircular arc in the high frequency region followed by almost linear spike in the low frequency region. A steep vertical line along the imaginary axis corresponds to the ideal capacitor. 45° -sloped portion in the Nyquist plots of the CPs 1-4 also known as the Warburg resistance,66,67 is larger in cases of 1, 3 and 4 than 2 suggesting greater variation in the ion diffusion path-lengths and increased obstruction to the ionic movement in 1, 3 and 4. Due to lowest interfacial charge transfer resistance and lowest variation in the ion diffusion path lengths of 2, it confirms the fast ion diffusion from electrolyte to the 2-modified electrode, leading to its highest electrochemical performance than other CPs. On the other hand, it might be due to presence of water tetramers within the tubular chains of 3, diffusion of ions did not show much variation and thus the vertical line in its Nyquist plot was little steeper than the others. Actually, the diameter of the semicircular loop for 1, 2, 3 and 4 are 91.2, 72.2, 591.3 and 170 Ω, respectively. Therefore, the charge transfer resistance is lower for 2 modified GCE compared to the other CP modified GCE indicating greater variations in transport pathway of electrons in 1, 3 and 4 modified GCE.

Figure 6. Cyclic voltammograms of 2 at different scan rates (10, 20, 50 and 100 mV/s); inset shows the variation of specific capacitance with scan rate.

Thus CP modified GCE provides a large potential window as high as 2.6 V in an aqueous electrolyte, which is comparable to



due to presence of amide functionality at 0.100 V and L2 shows redox peaks due to presence of similar functionality at 1.066 V. The presence of redox peaks corresponding to amide at higher potential for L2 compared to that of L1 signifies the greater extent of conjugation in L2 compared to L1. The greater conjugation in L2 compared to L1 can be attributed to its 1,4substitution of amido-pyridine groups on the central ring.

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0.04 0.03 0.02

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Figure 10. Differential pulse voltammograms of the three CPs at 10mV/s in 1 M Li2SO4

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1.5

Potential (V) Figure 8. Cyclic voltammograms of L2 at different scan rates in 1 M Li2SO4

Figure 9. Nyquist plots (Z’ vs. −Z’’) of the three-electrode systems in 1 M Li2SO4

Correlation electrochemical performance of 1-4 with those of L1 and L2 using differential pulse voltammetry: In order to correlate the electrochemical properties of CP based materials with those of L1 and L2 differential pulse voltammetric technique (DPV) was adopted (Figure 10). L1 showed peaks

The electrochemical performance of materials 1-4 over a precise range of different voltages not only states about their electrochemical robustness over this range but also depicts about the extent of redox activities. The measurements were carried out by depositing the powdered materials of 1-4 on glassy carbon electrode (GCE) with the aid of Nafion binder and DPV measurements were carried out using these GCEs in 1M Li2SO4 aqueous solution in the range of −1.4 to 1.2 V vs. the saturated calomel electrode (SCE) at 10 mV/s. Electrochemical performances of 1-4 were compared with the corresponding ligands (L1 or L2). The redox peaks in case of 1 appeared at 0.127 V revealing the incorporation of L1 into 1. The -0.013 V shift occurred due to the presence of Cu3 SBU within the lattice of 1. Similarly for both 2 and 4 redox peaks appeared at 1.027 and 0.969V respectively reflecting incorporation of L2 both in 2 and 4. the respective shifts of 0.044 V and -0.102 V in the redox peaks revealed their redox properties. This indicates that for shift in redox peak for 2 with respect to L2 was positive (0.044 V), whereas it is negative (-0.102 V) for 4 with respect to L2. These shifts are in correlation with their observed electrochemical performances (2>4). 3 followed similar redox patterns that of L1 and redox peak appeared at -0.110 V. The 0.237 V shift in the DPV of 3 revealed poor redox behaviors for 3. Thus amongst the CP based materials the trend for electrochemical performance followed the order 2>1>4>3. The observed trend in the electrochemical properties might be attributed to combined effects of incorporation of ligands L1 and L2 and network dimensionality of the CPs. 2 with 3D network topology showed strongest electrochemical property whereas 3 with 1D tubular network showed poorest electrochemical behavior.


EPR spectral analysis of the CP based materials 14 To understand further the electronic properties, the X-band EPR analysis at room temperature of all the powdered samples of CPs 1-4 (Figure 11). As shown in Figure 11, the EPR signal of samples 1, 2 & 4 displayed a distinct splitting at g ~ 2.00, corresponding to the formation of organic radicals. Whereas the solid sample of 3 displayed hyperfine splitting in X-band EPR spectrum to six peaks appeared in the range 104.5 to 489.2 mT with g = 2.00 for most prominent peak due to fine splitting centered at 311.3 mT (Figure 11b). In case of 1 sharp peaks centered around 315.4 and 318.3 mT for fine splitting of the orbitals involved in LMCT transitions. In case of 2 sharp peaks centering around 333.7 due to enhanced LMCT transitions. On the other hand for 3 peaks appeared centering around 311.3 mT due to fine splitting for labile electrons involved in LMCT transitions and the peaks due to hyperfine splitting centered around 107.5, 158.5, 210.9, 400.2 mT for labile electrons involved in considering very poor LMCT transition. For 4 EPR peaks centered around 162.3 mT considering direct transition of labile electrons and around 116.7 and 162.3 mT considering fine splitting electrons and around 301.5 mT considering hyperfine splitting for electron transfer.76-77 From the EPR spectra of 1, 2 and 4, it was evident that the LMCT transitions were prominent in all four as suggested by the fine splitting for electron transfer process. On the other hand, for 3 this type of LMCT transition was sluggish and thus it showed hyperfine splitting for electron transfer. Thus the EPR spectral analysis clearly demonstrated extent of electron transfer through LMCT follows the order 2 >1 > 4 >3. a)

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Figure 11. EPR spectra of the powdered samples of 1-4.

Luminescence properties of the CP based materials The emission profiles of grounded samples of 1-4 were recorded in the solid state to understand the effect of LMCT transitions on emission properties. Complexes 1, 2 and 4 showed λmax values in the green region at 501.4, 502.2 and 503.1 nm with intensities 9.864×104, 6.114×104 and 3.520×104 CPS respectively (Figure 12). Emission spectra of 3 exhibits a peak at 471.6 nm with intensity 1.735×104 CPS which is blue shifted com-

pared to 1, 2 and 4. The strong luminescence of these three CPs might be correlated to the observed fine splitting observed in their EPR spectra. Thus the close investigation of intensities (CPS) of emission profiles of CPs 1-4 reveals that 2 and 1 are highly luminescent given their strong LMCT and 3 is very poor luminescent given its weak LMCT. While 4 is moderately luminescent given its moderate LMCT property. The similarity of the trends of emission profiles of CPs with those of electrochemical and EPR activities reaffirm our results. From these it can be stated that the dimensionality of CP, LMCT, nature of the ligands and their interactions in the solid play a combined role in giving the resultant activities. 110000 100000 90000 80000 70000

Intensity (CPS)

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Wavelength (nm.) Figure 12 Solid state emission spectra of the powdered samples of 1-4.

Conclusions The ligands L1 and L2 in combination with dicarboxylates and Co(II)/Cu(II) were shown to form CPs containing diversified topologies. We note here that the 2D-layers are constituted by both metals Co(II) & Cu(II)), ligands L1 & L2 and anions SA & BDC. However, in case of Cu(II) complex, 1, the layers are propagated by a triangular SBU which is a rare phenomenon. Notably, Cu(I) forms several metallic clusters with the help of anion and ligand bridging, however it is not so common in case of Cu(II) complexes.78-86 The Co(II) complex, 4, contains an usual rectangular grid without any metal clusters. The 1Dcoordination polymer formed by the Co(II) complex, 3, is quite novel as there are very few reports that contain linking of macrocycles to form tubular networks. Interestingly, both these structures have two types of water tetramers that are being tapped in the cavities: in 3, it is a cyclic tetramer while in 4 it is a triangular tetramer in which one H2O is at the center and connects to three water molecules via hydrogen bonds. The complex 2 exemplifies the formation of 3D-diamondoid networks containing two types of arms that differ significantly in their lengths. Further, all four CPs were found to exhibit pronounced electrochemical behavior. Among the four complexes, the complex of 2 found to have higher electrochemical properties in terms of specific capacitance of 4.9 F g-1 at 10 mV s-1 compared to other three complexes. Importantly, in case of complex of 2, the combined effect of redox active metal ion, ligand and linker may have facilitated better charge transfer within the framework. The SC values found to correlate with dimensionality of the networks as 3D-network structure shows higher SC, twodimensional networks show moderate SC values and 1D-



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network shows lower SC value. Further the EPR spectra for the CP based materials also showed the mobile nature of electrons involved in LMCT transitions which was found to follow the observed trend in electrochemical properties. The observed trend in the electrochemical properties of 1-4 might be attributed to the network dimensionality, redox active ligands L1 and L2 and their interactions within the solid matrix. The present work opens up new opportunities for synthesis of redox active CP based materials as platforms for clean energy storage applications.

Experimental Section FTIR spectra were recorded with a Perkin-Elmer instrument, Spectrum Rx, serial no. 73713. 1H NMR (200 MHz) spectra were recorded on a BRUKER-AC 200 MHz spectrometer. Powder XRD data was determined by using a Bruker AXS Xray diffractometer (40 kV, 20 mA) using Cu Kα radiation (λ = 1.5418 Å) over the 5−50° (2θ) angular range and a fixed-time counting of 4 s at 25 °C. The diffuse reflectance spectra (DRS) of the crystalline materials were recorded with a Cary model 5000 UV-visible-NIR spectrophotometer. Elemental analyses were carried out with a Perkin-Elmer Series II 2400 apparatus, and melting points were taken using a Fisher Scientific melting point apparatus cat. No. 12-144-1. Single Crystal X-ray Determination. All the single crystal data were collected on a Bruker-APEX-II CCD X-ray diffractometer that uses graphite monochromated Mo Kα radiation (λ = 0.71073 Å) at room temperature (293 K) by the hemisphere method. The structures were solved by direct methods and refined by least-squares methods on F2 using SHELX-97.87 Non-hydrogen atoms were refined anisotropically, and hydrogen atoms were fixed at calculated positions and refined using a riding model. The H atoms attached to the O atom or N atoms are located wherever possible and refined using the riding model. Synthesis of Pyridine-3,5-dicarboxylic acid bispyridin-3-ylamide L1: To a 15 ml pyridine solution of pyridine-3,5-dicarboxylic acid (1.6 g, 0.005 mmol), 3-aminopyridine (1.18 g, 0.01mmol) was added and the mixture was vigorously stirred at room temperature. After 30 minutes of vigorous stirring P(OPh)3 (5.31 g, 0.017mmol) was added to the above mixture and the mixture was left for refluxing at 100 °C for 6 hours. After 6 hours of refluxing the mixture was cooled to room temperature and the pyridine was distilled out at 140 °C. To this solution 10 ml of CHCl3 was added and was taken in a separating funnel. To this solution 20 ml of water was added and shaken vigorously. Heavy yellowish white coloured precipitate appeared which was washed dried in air. Recrystallization from MeOH gave 1.8g, (Yield 65%) of L1. 1H NMR (DMSO-d6, ppm): d 7.96 (d, 4H), 8.34 (t, 1H), 8.44 (d, 2H), 8.58 (d, 4H), 11.26 (s, NH). Synthesis of N,N'-Di-pyridin-3-yl-terephthalamide L 2: The ligand L2 was synthesized in a similar procedure as that of L1 except instead of pyridine-3,5-dicarboxylic acid, terephthalic acid (1.6 g, 0.005mmol) was used for the reaction. After 6 hours of refluxing heavy white precipitate appeared which was recrystallized from ethanol to give 1.6 g, (Yield 58%) of L2. 1H NMR (DMSO-d6, ppm): 10.608 (s, 2H), 8.956 (d, 2H), 8.945 (d, 2H), 8.321 (t, 2H), 8.132 (t, 4H) 7.383 (t, 2H).

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Synthesis of Coordination Polymers of 1-4: Preparation of 1: A mixture of L1 (0.015 g, 0.05mmol), succinic acid (0.006 g, 0.05mmol), CuSO4 (0.025 g, 0.1mmol), 20 mL water and 3mL of (N/20) NaOH solution was sealed in a teflon lined stainless steel container and heated at 100 °C for 2 days. After 2 days the upon cooling to room temperature at a rate of 5 °C per hour light blue colored block shaped crystals of 1 were obtained and dried in air. Yield 0.0087 g, 58% based on L1. Elemental analysis (%) Calc. for C21H17Cu3N5O16S: C 30.8, H 2.1, N 8.6. Found C 28.12, H 2.02, N 8.44. IR (KBr, cm-1): 3899.15(s), 3848.73(s), 3753.50(s), 3647.05(s), 3384.24(b), 2935.57(m), 2862.74(m), 2374.30(s), 2344.59(s), 1617.07(s), 1376.35(s), 1144.65(s), 1001.39(s), 763.63(s), 720.04(s), 619.17(s). Preparation of 2: A mixture of L2 (0.015 g, 0.05mmol), Na-succinate (0.0081 g, 0.05mmol), CuSO4 (0.025 g, 0.1mmol) and 20 mL water was sealed in a teflon lined stainless steel container and heated at 100 °C for 2 days. After 2 days the upon cooling to room temperature at a rate of 5 °C per hour deep blue colored block shaped crystals of 2 were obtained and dried in air. Yield 0.0064 g, 43% based on L2. Elemental analysis (%) Calc. for C22H16CuN4O6: C 53.30, H 3.30, N 11.30. Found C 53.16, H 3.08, N.11.19 IR (KBr, cm-1): 3899.15(s), 3837.53(s), 3798.31(s), 3669.46(s), 3421.53(s), 3042.01(s), 2927.01(s), 2862.74(s), 2369.74(s), 2341.73(s), 1602.89(s), 1559.99(s), 1541.25(s), 1419.31(s), 1385.57(s), 1272.04(s), 1165.98(s), 1127.27(s), 1071.32(s), 1051.74(s), 970.55(s), 953.84(s), 827.97(s), 805.01(s), 755.10(s), 721.98(s), 693.87(s), 643.35(s), 548.19(s), 416.78(s). Preparation of 3: Complex 3 was prepared in a similar procedure as described for 1 except instead of succinic acid, CuSO4 and NaOH, Naisophthalate (0.011 g, 0.05mmol)and Co(NO3)2 (0.029 g, 0.1mmol) were taken. After 2 days of reaction and cooling to room temperature at a rate of 5 °C per hour purple colored crystals of 3 were obtained and dried in air. Yield 0.0092 g, 62% based on L1. Elemental analysis (%) Calc. for C26H24CoN4O10: C 53.20, H 3.30, N 9.50. Found C 53.04, H 3.18, N.9.29. IR (KBr, cm-1): 3904.76(s), 3848.73(s), 3798.31(s), 3820.72(s), 3747.89(s), 3310.22(b), 2369.74(s), 2344.18(s), 1636.52(s), 1610.64(s), 1424.27(s), 1384.61(s), 1328.67(s), 1286.71(s), 1224.11(s), 1179.98(s), 1110.83(s), 1065.73(s), 1025.15(s), 984.71(s), 931.68(s), 847.55(s), 823.80(s), 690.90(m), 618.01(s), 538.18(s). Preparation of 4: Complex 4 was prepared in a similar procedure as described for 2 except instead of Na-succinate and CuSO4, Na-isophthalate (0.011 g, 0.05mmol) and Co(NO3)2 (0.029 g, 0.1mmol) were taken. After 2 days of reaction and cooling to room temperature at a rate of 5 °C per hour pink colored crystals of 4 were obtained and dried in air. Yield 0.0068 g, 46% based on L2. Elemental analysis (%) Calc. for C26H18CoN4O11: C 50.30, H 2.90, N 9.00. Found C 50.14, H 2.78, N.9.29. IR (KBr, cm-1): 3899.15(s), 3848.73(s), 3803.92(s), 3747.89(s), 3245.03(b), 2369.74(s), 2344.23(s), 1609.87(s), 1544.05(s), 1454.54(s), 1427.70(s), 1331.72(s), 1286.71(s), 1227.86(s), 1180.78(s), 1108.15(s), 1021.78(s), 985.38(s), 935.69(s), 847.55(s), 820.66(s), 744.05(m), 710.48(m), 617.64(s), 537.31(s).


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Electrochemical measurements: CV analysis for the CPs 1-4. The electrochemical measurements were performed with a CH760D electrochemical workstation (CH Instruments, USA) using a standard three electrode cell set up. The CP materials were individually loaded on a glassy carbon electrode (GCE) acting as the working electrode. For this purpose, 4 mg of each CP materials were dispersed 1 mL ethanol with 50 µL Nafion solution by ultrasonicating for 6 min. 70 µL of the resultant homogeneous slurry was transferred on GCE followed by drying at 70 °C. A saturated calomel electrode (SCE) and a platinum wire were used as the reference and counter electrode, respectively, while 1M Li2SO4 aqueous solution used as the electrolyte. The amount of complexes 1, 2, 3 and 4 loadings were calculated to be 1.52 mg, 1.62 mg, 1.65 mg and 1.57 mg, respectively. The electroactive area of the glassy carbon electrode was 0.07065 cm2. All the measurements were recorded in 20 mL of N2 degassed solution at 25 °C. The applied potential range for cyclic voltammetry and galvanostatic chargedischarge was carried out from -1.4 to 1.2 V at varying scan rate (10-100 mV s-1). Electrochemical impedance spectroscopy (EIS) was recorded under sweep frequency range of 1MHz to 1.0 Hz, AC voltage amplitude of 5 mV against open circuit potential. EPR analysis for the CPs 1-4. The CPs 1-4 were grinded into fine powder and the EPR spectra were measured using JEOL-EPR spectrometer.

AUTHOR INFORMATION Corresponding Author * Department of Chemistry, Indian Institute of Technology, Kharagpur-721302, India. Fax: 91-3222-282252; Tel: 91-3222283346; E-mail: [email protected]. PresentAddresses

Author Contributions The manuscript was written through contributions of all authors

Funding Sources We acknowledge DST, New Delhi, India for financial support.

ACKNOWLEDGMENT We acknowledge, DST-FIST for single crystal X-ray diffractometer and K. Banerjee acknowledges CSIR for a research fellowship.

ABBREVIATIONS CV, Cyclic Voltammetry; DPV, Differetial Pulse Voltammetry, EPR, Electron Paramagnetic Resonance; CP, Coordination Polymer; GCE, Glassy Carbon Electrode; SCE, Saturated Calomel Electrode, LMCT, Ligand to Metal Charge Transfer.

REFERENCES 1. 2. 3.

DPV analysis for the CPs 1-4. Differential pulse voltammetry (DPV) was used for comparative study of the electrochemical properties of the CPs 1-4 and L1 and L2. They are measured using CH760D electrochemical workstation (CH Instruments, USA) with a standard three electrode cell set up in the potential range −1.4 to 1.2 V vs. the saturated calomel electrode (SCE) at 10 mV/ using 1M Li2SO4 aqueous solution as internal electrolyte. The CP materials 1-4 and L1 and L2 were individually loaded on a glassy carbon electrode (GCE). For the measurements of CPs, 4 mg of each CP material was dispersed in 1 mL ethanol and 50 µL Nafion solution by ultrasonicating for 6 min. 70 µL of the resultant homogeneous slurry was transferred on GCE followed by drying at 70 °C. A saturated calomel electrode (SCE) and a platinum wire were used as the reference and counter electrode, respectively, while 1M Li2SO4 aqueous solution used as the electrolyte. Similar measurements of ligands were carried using same procedure except the ligands were dispersed on dilute NMP (N-Methyl Pyrrolidone) solutions. Solid State Emission studies for the CPs 1-4. All the CPs 1-4 were grinded into fine powders and the emission studies were carried on these powdered materials using excitation wavelength of 325 nm. with Spex Fluorolog-3 (model FL3-22) spectrofluorimeter.

ASSOCIATED CONTENT Supporting Information. NMR of ligand L1, L2 FT-IR of ligand, L1, and complexes 1-4 and DRS, CVs of CPs 1-4 . The crystal structure depository numbers for. 1-4 are CCDC 1026220 – CCDC 1026223 respectively. “This material is available free of charge via the Internet at http://pubs.acs.org.”

4. 5. 6. 7. 8. 9.

10. 11. 12. 13. 14.

15. 16.

17. 18. 19. 20. 21.

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Table-1. Crystallographic parameters for the crystal struc

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

tures of 1−4.

Compound Formula

1

2

3

4

C21H17Cu3N5O

C22H18CuN4O6

C25H17CoN5O10

C26H18CoN4O11

16S

M.Wt.

818.16

497.94

614.43

631.45

T (K)

293(2)

273(2)

273(2)

293(2)

System

Orthorhombic

Monoclinic

Monoclinic

Triclinic

Space Group

Pna21

P-1

P21/c

P-1

a(Å)

7.269(2)

24.083(2)

13.129(5)

10.259(3)

b(Å)

20.125(4)

7.345(4)

19.681(7)

12.726(4)

c(Å)

18.948(3)

13.568(7)

10.247(4)

12.728(6)

α(°)

90.00

90.00

90.00

110.367(1)

β(°)

90.00

121.785(1)

91.348(7)

102.914(1)

γ(°)

90.00

90.00

90.00

108.996(9)

Vol. (Å3)

2772.2(9)

2040(2)

2647.1(16)

1362.5(9)

4

4

4

2

Z 3

Dcalc(mg/m )

1.6950

1.6213

1.5216

1.5147

R1(I>2σ(I))

0.0662

0.0581

0.0529

0.0853

wR2 (on F2 , all data)

0.1399

0.1411

0.1382

0.1199



1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 12 of 12

For Table of Contents Use Only Coordination Polymers Containing Tubular, Layered and Diamondoid Networks: Redox, Luminescence and EPR Activities. Kaustuv Banerjee, Sandipan Roy, Moumita Kotal, and Kumar Biradha*

Four types of coordination polymers were shown to exhibit electrochemical and EPR activities and the dimensions of the networks found to correlate with their observed properties i.e. 3D> 2D>1D.


Coordination Polymers Containing Tubular ... - ACS Publications

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