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Synthesis and ferroelectric behaviour of an axially symmetric octahedral [Cu6L8]12+ cage

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Abstract

Metal-organic hybrid supramolecular architectures based on lighter transition metal ions are an emerging class of ferroelectric materials due to their highly crystalline nature and less toxicity. However, synthesizing polar metal-ligand assemblies is still challenging as well-defined design strategies are unknown for obtaining these crystalline solids in non-centrosymmetric structures. Herein, we report a new discrete octahedral metal-organic cage [Cu6(TPPA)8(H2O)12]·(NO3)12·32H2O] (1) by employing a tripodal phosphoramide ligand, [PO(NH3Py)3] (TPPA). Ferroelectric measurements on 1 showed improved polarization vs. the electric field (P-E) hysteresis loop characteristics than those observed for similar cages, with a sizable remnant polarization (Pr) value of 39.2 µC/cm2. The non-centrosymmetric structure of 1 can be tracked to the uniform rotation of the octahedra around the metal centre. At the same time, the polarization in the framework stems from the toggling of the disordered nitrate anions. The temperature-dependent dielectric constant measurements on 1 showed a desolvation-assisted dielectric relaxation behaviour, indicating the involvement of solvate molecules in establishing the long-range polar order.

Graphical abstract

A new discrete octahedral metal-ligand cage was prepared by employing a flexible tripodal phosphoramide ligand. The polarization in this assembly originates from the toggling of the nitrate anions and its long-range order assisted by solvate molecules of water. The ferroelectric measurements of the cage gave a well-defined rectangular P-E hysteresis loop with a remnant polarization value.

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Acknowledgements

This work was funded by SERB, India, by grant no. CRG/2019/004615 (R.B.). R.B. thanks the SERB-STAR Award via Grant no. STR/2021/000016. N.P. thanks the CSIR, India, for the fellowship. RG thanks the UGC, India, for the fellowship.

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  1. Rani Gourkhede and Neetu Prajesh contributed equally.

Authors and Affiliations

  1. Department of Chemistry and Centre for Energy Science, Indian Institute of Science Education and Research (IISER), Pune, Dr. Homi Bhabha Road, Pune, 411008, India

    Rani Gourkhede, Neetu Prajesh, Rishabh Gupta & Ramamoorthy Boomishankar

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  1. Rani Gourkhede
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  2. Neetu Prajesh
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  3. Rishabh Gupta
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Correspondence to Ramamoorthy Boomishankar.

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Gourkhede, R., Prajesh, N., Gupta, R. et al. Synthesis and ferroelectric behaviour of an axially symmetric octahedral [Cu6L8]12+ cage. J Chem Sci 134, 115 (2022). https://doi.org/10.1007/s12039-022-02112-7

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  • DOI: https://doi.org/10.1007/s12039-022-02112-7

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