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Metal directed self-assembly of Tetranuclear \(\hbox {Cu}^{\mathrm{II}}\) and \(\hbox {Ni}^{\mathrm{II}}\) clusters

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Abstract

The self-assembly of two pyridine hydrazone based tritopic ligands appended with terminal carboxylate groups with \(\hbox {Cu}^{\mathrm{II}}\) and \(\hbox {Ni}^{\mathrm{II}}\) have been investigated. These polytopic ligands with tridentate coordination pockets were designed to produce homoleptic [\(3\times 3\)] grid complexes on reaction with transition metals. Despite the formation of anticipated metallogrids as the final self-assembly outcome, metal ion geometric preferences and ligand flexibility lead to the formation of tetranuclear clusters in the self-assembly process with \(\hbox {Cu}^{\mathrm{II}}\) and \(\hbox {Ni}^{\mathrm{II}}\) metal ions. These results illustrate the dynamic nature of the metal–ligand interactions and flexible nature of the ligand backbone in coordination self-assembly. The synthesis, structure and magnetic properties of three tetraanuclear species {[\(\hbox {Cu}_{4}(\hbox {H}_{2}\hbox {L}^{\mathrm{1b}})_{2}(\hbox {OTf})_{4}(\hbox {OH})_{2}(\hbox {H}_{2}\hbox {O})_{2}\)]\(\cdot 6\hbox {H}_{2}\hbox {O}\}_{\mathrm{n}}\) (1), [\(\hbox {Ni}_{4}(\hbox {L}^{\mathrm{2a}})_{2}(\hbox {OCH}_{3})_{4}]{\cdot }4\hbox {H}_{2}\hbox {O}\) (2), [\(\hbox {Cu}_{4}(\hbox {L}^{\mathrm{2b}})_{2}(\hbox {OTf})_{4}(\hbox {H}_{2}\hbox {O})_{4}]{\cdot }6\hbox {H}_{2}\hbox {O}\) (3) involving two tritopic ligands with central pyridine framework are described.

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Synopsis: Metal Directed Self-Assembly of Tetra Nuclear \(\hbox {Cu}^{\mathrm{II}}\) and \(\hbox {Ni}^{\mathrm{II}}\) Clusters Avinash Lakma, Sayed Muktar Hossain, Rabindranath Pradhan and Akhilesh Kumar Singh ...................xxxx-xxxx Three tetranuclear non-grid complexes have been synthesized by reacting two pyridine hydrazone-based tritopic ligands with \(\hbox {Cu}^{\mathrm{II}}\) and \(\hbox {Ni}^{\mathrm{II}}\) salts. All complexes are spectroscopically and structurally characterized and their magnetic properties have been studied.

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Acknowledgements

AKS acknowledges IIT Bhubaneswar for infrastructure and SERB, India (SR/S1/IC-20/2011) and UGC-DAE CSR, India (CSR/Accts/2015-16/2017) for funding. AL and RNP thank UGC, Delhi for their fellowships. SMH acknowledges IIT Bhubaneswar for the fellowship.

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Authors and Affiliations

  1. School of Basic Sciences, Indian Institute of Technology Bhubaneswar, Bhubaneswar, Odisha, 752 050, India

    Avinash Lakma, Sayed Muktar Hossain, Rabindra Nath Pradhan & Akhilesh Kumar Singh

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  1. Avinash Lakma
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  2. Sayed Muktar Hossain
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  3. Rabindra Nath Pradhan
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  4. Akhilesh Kumar Singh
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Correspondence to Akhilesh Kumar Singh.

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Special Issue on Modern Trends in Inorganic Chemistry

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Lakma, A., Hossain, S.M., Pradhan, R.N. et al. Metal directed self-assembly of Tetranuclear \(\hbox {Cu}^{\mathrm{II}}\) and \(\hbox {Ni}^{\mathrm{II}}\) clusters. J Chem Sci 130, 80 (2018). https://doi.org/10.1007/s12039-018-1483-7

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  • DOI: https://doi.org/10.1007/s12039-018-1483-7

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