Photophysical Properties of cis-Mo2 Quadruply Bonded Complexes and Observation of Photoinduced Electron Transfer to Titanium Dioxide
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- 作者：Samantha E. Brown-Xu ; Malcolm H. Chisholm ; Christopher B. Durr ; Terry L. Gustafson ; Thomas F. Spilker
- 刊名：Journal of the American Chemical Society
- 出版年：2014
- 出版时间：August 13, 2014
- 年：2014
- 卷：136
- 期：32
- 页码：11428-11435
- 全文大小：460K
- ISSN：1520-5126
文摘
The compounds cis-Mo2(DAniF)2(L)2 have been prepared, where DAniF = (N,N鈥?-p-dianisyl formamidinate and L = thienyl-2-carboxylate (Th), 2,2鈥?bithienyl-5-carboxylate (BTh), and 2,2鈥?5鈥?5鈥?terthienyl-5-carboxylate (TTh). The compounds have been characterized by proton nuclear magnetic resonance (1H NMR), ultraviolet鈥搗isible (UV鈥搗is) absorption and emission, differential pulse voltammetry, and time-resolved transient absorption and infrared (IR) spectroscopy. An X-ray crystal structure was obtained for the thienyl complex. The related salt [nBu4N]2[Mo2(DAniF)2(TTh鈥揅O2)2], where TTh鈥揅O2 = 2,2鈥?5鈥?2鈥?terthienyl-5,5鈥?dicarboxylate, has also been prepared and employed in the attachment of the complex to TiO2 nanoparticles. The latter have been characterized by ground-state Fourier transform infrared spectroscopy (FTIR) and femtosecond time-resolved IR spectroscopy. The time-resolved data provide evidence for sub-picosecond charge injection from the Mo2 center to the semiconducting oxide particle.