A Vanadium Porphyrin with Temperature-Dependent Phase Transformation: Synthesis, Crystal Structures, Supramolecular Motifs and Properties

Authors

  • Dr. Wentong Chen,

    1. Department of Material and Life Science, Graduate School of Engineering, Osaka University, Suita, SORST (Japan) Science Technology Agency, Osaka 565-0871 (Japan), Fax: (+81) 6-6879-7370
    2. School of Chemistry and Chemical Engineering, Jinggangshan University, Ji'an, Jiangxi 343009 (China)
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  • Dr. Tomoyoshi Suenobu,

    1. Department of Material and Life Science, Graduate School of Engineering, Osaka University, Suita, SORST (Japan) Science Technology Agency, Osaka 565-0871 (Japan), Fax: (+81) 6-6879-7370
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  • Prof. Shunichi Fukuzumi

    Corresponding author
    1. Department of Bioinspired Science, Ewha Womans University, Seoul 120-750 (Korea)
    • Department of Bioinspired Science, Ewha Womans University, Seoul 120-750 (Korea)

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Abstract

A vanadium porphyrin, V(O)TMeOPP (1; TMeOPP=5, 10, 15, 20-tetrakis(4-methoxyphenyl)-21 H, 23H-porphyrin), has been synthesized by solvothermal reactions and characterized by single-crystal X-ray diffractions at room temperature and low temperature to reveal two different structures and , respectively. Both and crystallized in the orthorhombic system, but their space groups were different: Pbca and Pca21 for and , respectively. The cell parameters of a, b, and c were different and the cell volume of was larger than that of by circa 200 Å3. and were characteristic of an isolated motif with a five-coordinate vanadium(IV) ion and a saddle-distorted nonplanar porphyrin macrocycle. Molecules of were interconnected through hydrogen-bonding interactions to yield a 3D framework; whilst for the low-temperature phase , there were more hydrogen-bonding interactions that link the molecules to construct a more-complex 3D supramolecular network. In a solution of acetone, the title compound exhibited purple and green colors at room temperature and low temperature, respectively, which is unprecedented for vanadium porphyrins. The spectral data of UV/Vis, FT-IR, and MALDI-TOF-MS of and are reported together with the electrochemical data.

Abstract

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