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Identification of a (H 2 O) 8 cluster in a supramolecular host of a charge transfer platinum(II) complex

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Abstract

The chemical reaction of PtII(L1)Cl2 [L1= 2-(phenylazo)pyridine] with a bidentate N,S-donor atom ligand, 2-phenylthioaniline, (HL2) in alkaline acetonitrile yielded a mixed ligand donor acceptor complex, [PtII(L1)(L2)−]Cl, [1]Cl. The complex has been characterized by using a host of physical methods: X-ray crystallography, nuclear magnetic resonance, cyclic voltammetry, absorption spectroscopy, electron paramagnetic resonance. The complex showed intense interligand charge transfer (ILCT) transition in the long wavelength region of UV-vis spectrum at 785 nm. The single-crystal X-ray structure of complex, [1]Cl⋅2.6H2O is reported. The cationic complex upon crystallization from aqueous methanol solvent produces an assembly of three dimensional (H2O)8 guest moiety within the host lattice of reference Pt-complex. The water assembly showed a unique type of aggregation of two trigonal pyramids hydrogen bonded with three chloride anions. The complex displayed two reversible responses at −0.34 and −1.05 V along with one irreversible anodic response at 0.91 V versus Ag/AgCl reference electrode. The redox processes are characterized by examination of EPR spectra of the electrogenerated complexes.

An unusual and three dimensional (H2O)8 cluster having aggregation of two trigonal pyramids is reported in the inorganic host lattice of cationic PtII-complex. The complex shows characteristic intramolecular interligand charge transfer transition in the long wavelength region of the visible spectrum at 785 nm.

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Acknowledgements

Financial support received from the Council of Scientific and Industrial Research, New Delhi (Project 01/2714/13/EMR-II) is gratefully acknowledged. S G thanks DST for a J C Bose fellowship. Crystallography was performed at the DST-funded National Single Crystal Diffractometer Facility at the Department of Inorganic Chemistry, IACS. I C thanks the Council of Scientific and Industrial Research for her fellowship.

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Authors and Affiliations

  1. Department of Inorganic Chemistry, Indian Association for the Cultivation of Science, Kolkata, 700 032, India

    SUTANUVA MANDAL, IPSITA CHATTERJEE & SREEBRATA GOSWAMI

  2. Departamento de Química Inorgánica, Universidade de Santiago de Compostela, Campus Universitario Sur, 15782, Santiago de Compostela, Spain

    ALFONSO CASTIÑEIRS

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  1. SUTANUVA MANDAL
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  2. IPSITA CHATTERJEE
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  3. ALFONSO CASTIÑEIRS
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Correspondence to ALFONSO CASTIÑEIRS or SREEBRATA GOSWAMI.

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MANDAL, S., CHATTERJEE, I., CASTIÑEIRS, A. et al. Identification of a (H 2 O) 8 cluster in a supramolecular host of a charge transfer platinum(II) complex. J Chem Sci 126, 1507–1513 (2014). https://doi.org/10.1007/s12039-014-0656-2

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  • DOI: https://doi.org/10.1007/s12039-014-0656-2

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