Synthesis and O2 Reactivity of a Titanium(III) Metal鈥揙rganic Framework

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• 作者：Jarad A. Mason ; Lucy E. Darago ; Wayne W. Lukens ; Jr. ; Jeffrey R. Long
• 刊名：Inorganic Chemistry
• 出版年：2015
• 出版时间：October 19, 2015
• 年：2015
• 卷：54
• 期：20
• 页码：10096-10104
• 全文大小：522K
• ISSN：1520-510X

文摘

Metal鈥搊rganic frameworks featuring pores lined with exposed metal cations have received attention for a wide range of adsorption-related applications. While many frameworks with coordinatively unsaturated M^II centers have been reported, there are relatively few examples of porous materials with coordinatively unsaturated M^III centers. Here, we report the synthesis and characterization of Ti₃O(OEt)(bdc)₃(solv)₂ (Ti-MIL-101; bdc^{2鈥?/sup> = 1,4-benzenedicarboxylate; solv = N,N-dimethylformamide, tetrahydrofuran), the first metal鈥搊rganic framework containing exclusively TiIII centers. Through a combination of gas adsorption, X-ray diffraction, magnetic susceptibility, and electronic and vibrational spectroscopy measurements, this high-surface-area framework is shown to contain five-coordinate TiIII centers upon desolvation, which irreversibly bind O₂ to form titanium(IV) superoxo and peroxo species. Electronic absorption spectra suggest that the five-coordinate TiIII sites adopt a distorted trigonal-bipyramidal geometry that effectively shields nuclear charge and inhibits strong adsorption of nonredox-active gases.}