A Reversible Redox Reaction in a Keggin Polyoxometalate Crystal Driven by Visible Light: A Programmable Solid-State Photochromic Switch

作者：Tandekar Kesar; Garai Somenath; Supriya Sabbani^*

来源：Chemistry - A European Journal, 2018, 24(39): 9747-9753.

DOI：10.1002/chem.201801126

• photochromism
• polyoxometalate
• redox
• solid state
• visible light

The colourless crystals of (PPh4)(3)[PW12O40]center dot 3C(3)H(7)NO (1) are converted to the dark blue crystals of {(PPh4)(3)[PW12O40]center dot 3C(3)H(7)NO}(0.85){(PPh4)(3) (C3H7NO)(+center dot)[(PWW11O40)-W-V-O-VI](-)center dot 2C(3)H(7)NO)}(0.15) (2) upon irradiation with visible light in an interesting single crystal to single crystal transformation. This photochromic conversion is accompanied by the reduction of concerned Keggin anion from {PW12VI} to {(PWW11VI)-W-V}. This redox conversion is characterized by various spectroscopic techniques including single crystal X-ray diffraction studies. The photochromic properties of compound 1 can be controlled reversibly through the dimethylformamide (DMF) molecule as a function of temperature and proton exposure in a gas-solid reaction. The present work can be described as a new concept of programmable photochromism with the formation of photochromic pockets in crystalline 1 host (solid state), wherein a solvent can be plugged at a time to show light induced coloration.

• 出版日期2018-7-11