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Two-Dimensional Bicapped Supramolecular Hybrid Semiconductor Material Constructed from the Insulators α-Keggin Polyoxomolybdate and 4,4′-Bipyridine

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    Two-Dimensional Bicapped Supramolecular Hybrid Semiconductor Material Constructed from the Insulators α-Keggin Polyoxomolybdate and 4,4′-Bipyridine
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    New Chemistry Unit, Jawaharlal Nehru Centre for Advanced Scientific Research, Jakkur, Bangalore, 560064 India
    *E-mail: [email protected]. Phone: 080-22082998. Fax: 080-22082627.
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    Inorganic Chemistry

    Cite this: Inorg. Chem. 2014, 53, 1, 653–660
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    https://doi.org/10.1021/ic402858u
    Published December 23, 2013
    Copyright © 2013 American Chemical Society
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    Abstract

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    A new organic–inorganic hybrid material [SiMo14O44](H4,4′-bpy)2·xH2O (4,4′-bpy = 4,4′-bipyridine) was synthesized using a hydrothermal method. The compound was characterized using single crystal X-ray diffraction (XRD), infrared spectroscopy (IR), ultraviolet–visible spectroscopy (UV–vis), and X-ray photoelectron spectroscopy (XPS). XRD studies on selected single crystals suggested that the compound consists of supramolecular 2D layer structures composed of capped α-Keggin polyoxomolybdate anions and 4,4′-bpy organic ligands. Absorption measurements show a band gap of 2.99 eV in the hybrid which suggests a semiconducting nature compared to the insulating free α-Keggin and 4,4′-bpy. The magnetic susceptibility of the hybrid material was investigated in the temperature range 1.8–300 K obeying the Curie–Weiss law above 70 K. Experimentally measured magnetic moment of 2.71 μB/formula indicates possible mixed valent molybdenum in the compound. The XPS measurements confirm the presence of both MoV and MoVI in the ratio 15:85 resulting in the structural formula of the hybrid as [SiMoV2MoVI12O44](H4,4′-bpy)2·xH2O.

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    Supporting Information

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    Crystallographic information file (CIF) for SiMo14-bpy2, table of bond lengths, and the coordination sphere of each MoO6 octahedral unit of SiMo14-bpy2. Table of IR absorption frequencies for the compounds SiMo14-bpy2 and SiMoO12-bpy3, table of XPS binding energy of 3d orbitals for SiMo14-bpy2, EDAX spectrum, and temperature dependent magnetic susceptibility plots for SiMo14-bpy2 and SiMoO12-bpy3. This material is available free of charge via the Internet at http://pubs.acs.org.

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    Inorganic Chemistry

    Cite this: Inorg. Chem. 2014, 53, 1, 653–660
    Click to copy citationCitation copied!
    https://doi.org/10.1021/ic402858u
    Published December 23, 2013
    Copyright © 2013 American Chemical Society
    Request reuse permissions

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