Articles written in Journal of Chemical Sciences

    • Bridging function mediated intermetallic coupling in diruthenium-bis(bipyridine) complexes

      Soma Chakraborty Biplab Mondal Biprajit Sarkar Goutam Kumar Lahiri

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      The interactions of potentially dinucleating bridging functionalities (I–VI) with the ruthenium-bis(bypyridine) precursor [RuII(bpy)2(EtOH)2]2+have been explored. The bridging functionsI,II andVI directly result in the expected dinuclear complexes of the type [(bpy)2RuIILnRuII(bpy)2]z+ (1,2,7 and 8) (n = 0,z =4 andn = -2,z = 2). The bridging ligandIII undergoes N-N or N-C bond cleavage reaction on coordination to the RuII(bpy)2 core which eventually yields a mononuclear complex of the type [(bpy)2RuII(L)]+,3, where L =-OC6H3(R)C(R′)=N-H. However, the electrogenerated mononuclear ruthenium(III) congener, 3+in acetonitrile dimerises to [(bpy)2RuIII {-OC6H3(R)C(R′)=N-N=(R′)C(R)C6H3O-}RuIII(bpy)2]4+ (4). In the presence of a slight amount of water content in the acetonitrile solvent the dimeric species (4) reduces back to the starting ruthenium(II) monomer (3). The preformed bridging ligandIV undergoes multiple transformations on coordination to the Ru(bpy)2 core, such as hydrolysis of the imine groups ofIV followed by intermolecular head-to-tail oxidative coupling of the resultant amino phenol moieties, which in turn results in a new class of dimeric complex of the type [(bpy)2RuII-OC6H4-N=C6H3(=NH)O-RuII(bpy)2]2+ (5). In5, the bridging ligand comprises of twoN,O chelating binding sites each formally in the semiquinone level and there is ap-benzoquinonediimine bridge between the metal centres. In complex6, the preformed bridging ligand, 3,6-bis(3,5-dimethylpyrazol-1-yl)-1,2-dihydro-1,2,4,5-tetrazine, H2L (V) undergoes oxidative dehydrogenation to aromatic tetrazine based bridging unit, 3,6-bis(3,5-dimethylpyrazol-1-yl)-1,2,4,5-tetrazine, L. The detailed spectroelectrochemical aspects of the complexes have been studied in order to understand the role of the bridging units towards the intermetallic electronic coupling in the dinuclear complexes.

    • A dysprosium-based metal-organic framework: Synthesis, characterization, crystal structure and interaction with calf thymus-DNA and bovine serum albumin

      Biplab Mondal Buddhadeb Sen Ennio Zangrando Pabitra Chattopadhyay

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      A dysprosium-based metallo-organic framework (MOF) containing calcium ions formulated as {Dy(pyda)3Ca1.5(H2O)6} · 5.5H2O (1) (H2pyda = pyridine-2,6-dicarboxylic acid) was solvothermally synthesized in ethanolic medium and characterized by physico-chemical and spectroscopic tools. A detailed structural analysis of the solid state structure of 1 by single crystal X-ray diffraction study showed a tricapped trigonal prism geometry for lanthanide in the [Dy(pyda)3]3− fragment. The mode of interaction of 1 with calf thymus- DNA and with protein bovine serum albumin (BSA) was investigated by using absorption and emission spectroscopic tools. The apparent association constant of complex 1 with CT-DNA was deduced from an absorption spectral study ($K_b = 4.08 \times 10^4$ M-1). Spectral and viscosity measurements indicated a groove-binding mode of 1 with CT-DNA, and from spectroscopic study the formation of a metal complex-BSA adduct was assumed to be the result of the interaction of 1 with BSA.

    • Zinc(II) complexes of carboxamide derivatives: Crystal structures and interaction with calf thymus DNA

      Biplab Mondal Buddhadeb Sen Ennio Zangrando Pabitra Chattopadhyay

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      Two mononuclear zinc(II) complexes of newly designed carboxamide derivatives, formulated as [Zn(L1)3](ClO4)2 (1) and [Zn(L2)3](ClO4)2 (2) [where L1 = 𝑁-(furan-2-ylmethyl)-2-pyridinecarboxamide and L2 = 𝑁-(thiophen-2-ylmethyl)-2-pyridine-carboxamide], have been isolated in pure form in the reaction of perchlorate salts of Zn(II) with ligands L1 and L2, respectively. The two complexes were characterized by physicochemical and spectroscopic tools, and by X-ray crystal structures of both ligands and the complex 1. In complex 1, zinc(II) is chelated by three ligands with a distorted octahedral geometry. The DNA-binding properties of zinc complexes 1 and 2 have been investigated by spectroscopic methods and viscosity measurements. The results suggest that both complexes 1 and 2 bind to DNA in an intercalation mode between the uncoordinated furan or thiophene chromophore and the base pairs of DNA.

    • Nickel(II) complexes of N2S2 donor set ligand and halide/pseudohalides: Synthesis, crystal structure, DNA and bovine/human serum albumin interaction

      Animesh Patra Biplab Mondal Buddhadeb Sen Ennio Zangrando Pabitra Chattopadhyay

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      A series of neutral hexacoordinated nickel(II) complexes of formula [NiII (L)X2] (where L = 3,4-bis(2-pyridylmethylthio)toluene with tetradentate N2S2 donor set and X = chloride (1), azide (2), cyanate (3) and isothiocyanate anion (4)) have been synthesized and isolated in pure form. The complexes were characterized by physicochemical and spectroscopic methods along with detailed structural characterization of 1,2 and 3 by single crystal X-ray diffraction analyses. The structural study showed that the nickel(II) ion has a distorted octahedral geometry being chelated by the tetradentate N2S2 ligand and bound to cis- located choride or pseudohalide anions. In dimethylformamide solution the complexes showed quasi-reversible NiII/NiIII redox couples in cyclic voltammograms with E1/2 values of +0.723, +0.749, +0.768 and +0.868 V for 1, 2, 3 and 4, respectively. The study of interaction of the complexes with calf thymus DNA, bovine serum albumin (BSA) and human serum albumin (HSA) using spectroscopic and physicochemical tools clearly indicates that the complexes interact with DNA via groove binding mode.

    • Synthesis, characterization, crystal structure and DNA-binding study of four cadmium(II) pyridine-carboxamide complexes


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      Treatment of perchlorate or nitrate salt of cadmium(II) with carboxamide derivatives (L) generated four novel mononuclear metal complexes, represented as [Cd(L)₄](ClO₄)₂ (1a and 1b) and [Cd(L)₂(ONO₂)₂] (2a and 2b) in appreciable yields (L = L¹ = N-(furan-2-ylmethyl)-2-pyridine carboxamide and L = L² = N-(thiophen-2-ylmethyl)-2-pyridine carboxamide). The complexes have been characterized by FT-IR, UVVisible, elemental analysis and single crystal X-ray crystallographic analysis which revealed eight coordinated cadmium ions, but in different coordination environments, depending on the counter anion used. In addition,electronic absorption, fluorescence spectroscopy and viscosity measurements revealed a significant interaction of the four complexes with CT-DNA via intercalative/groove binding mode. The intrinsic binding constant Kbobtained varies from 0.4 × 10⁴ to 1.11 × 10⁵ M⁻¹. The results suggest that neutral complexes 2a and 2b bind to DNA in an intercalative mode. On the other hand, cationic complexes 1a and 1b bind with DNA via weak electrostatic/covalent interaction.

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