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Issue 19, 2018
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Aromatic sulfonium polyoxomolybdates: tuning the photochromic properties through substitutions on the counter ion moiety

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Abstract

Development of new photoresponsive polyoxometalate hybrids is an active research area in recent years. Aromatic sulfonium counter ion based polyoxometalates are a relatively new class of materials having immense potential for structural and electronic fine-tuning. Continuing our studies on aromatic sulfonium polyoxometalates as tunable photochromic materials, herein we report four new aromatic sulfonium polyoxomolybdates, (DMTS)3[PMo12O40] (1), (MPDS)3[PMo12O40] (2), (HMPDS)3[PMo12O40] (3) and (BMPMS)3[PMo12O40] (4); where DMTS = dimethyl(p-tolyl)sulfonium, MPDS = (4-methoxyphenyl)dimethylsulfonium, HMPDS = (4-hydroxy-2-methylphenyl)dimethylsulfonium and BMPMS = butyl(4-methoxyphenyl)methylsulfonium. These hybrids were characterized by various analytical and spectroscopic techniques including ESI-MS and single crystal X-ray diffraction (hybrids 1, 2 and 4) analyses. Solid state studies revealed that these hybrids exhibit a color change from yellow to green or dark green under UV illumination and the photochromic properties exhibited by these hybrids can be fine-tuned by introducing various substituents on the counter ion moiety at multiple locations. The observed color change is due to the reduction of the Mo6+ centers of the cluster to Mo5+, as evidenced by EPR studies. The effects of various substitutions introduced on the counter ion moiety in determining the photocoloration speeds of the hybrids are discussed.

Graphical abstract: Aromatic sulfonium polyoxomolybdates: tuning the photochromic properties through substitutions on the counter ion moiety

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Publication details

The article was received on 04 Mar 2018, accepted on 31 Mar 2018 and first published on 02 Apr 2018


Article type: Paper
DOI: 10.1039/C8CE00345A
Citation: CrystEngComm, 2018,20, 2733-2740
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    Aromatic sulfonium polyoxomolybdates: tuning the photochromic properties through substitutions on the counter ion moiety

    A. Kumar and C. P. Pradeep, CrystEngComm, 2018, 20, 2733
    DOI: 10.1039/C8CE00345A

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