Thermal and Photoreductive Elimination from the Tellurium Center of 蟺-Conjugated Tellurophenes

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• 作者：Elisa I. Carrera ; Theresa M. McCormick ; Marius J. Kapp ; Alan J. Lough ; Dwight S. Seferos
• 刊名：Inorganic Chemistry
• 出版年：2013
• 出版时间：December 2, 2013
• 年：2013
• 卷：52
• 期：23
• 页码：13779-13790
• 全文大小：558K
• 年卷期：v.52,no.23(December 2, 2013)
• ISSN：1520-510X

文摘

This study introduces small molecule tellurophenes that can undergo photoreductive elimination. A tellurophene compound with strong light absorption properties and extended 蟺-conjugation, 2,5-bis[5-(N,N鈥?dihexylisoindigo)]tellurophene (1), has been synthesized. Halogen oxidative addition to the tellurium center from various halogen sources gives the dibromo- (1Br₂) and dichloro- (1Cl₂) adducts, leading to a red-shift in the optical absorption properties. In the presence of excess opposing halogen, 1Br₂ and 1Cl₂ can interconvert, with equilibrium favoring the dichlorotellurophene adduct. Reductive elimination reactions were studied using optical absorption spectroscopy, NMR spectroscopy, thermogravimetric analysis, and matrix-assisted laser desorption/ionization (MALDI) analysis. Thermal reductive elimination from 1Br₂ and 1Cl₂ occurs in the solid-state to restore 1. Photoreductive elimination occurs under irradiation with green (505 nm) light in solution in the presence of a halogen trap with some decomposition. This is the first example of photoreductive elimination from a mononuclear tellurophene complex.