Mo2 Paddlewheel Complexes Functionalized with a Single MLCT, S1 Infrared-Active Carboxylate Reporter Ligand: Preparation and Studies of Ground and Photoexcited States

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• 作者：Samantha E. Brown-Xu ; Malcolm H. Chisholm ; Christopher B. Durr ; Sharlene A. Lewis ; Thomas F. Spilker ; Philip J. Young
• 刊名：Inorganic Chemistry
• 出版年：2014
• 出版时间：January 6, 2014
• 年：2014
• 卷：53
• 期：1
• 页码：637-644
• 全文大小：451K
• ISSN：1520-510X

文摘

From the reactions between Mo₂(DAniF)₃pivalate (DAniF = N,N鈥?di(p-anisyl)formamidinate) and the carboxylic acids LH, the title compounds Mo₂(DAniF)₃L have been prepared and characterized: compounds I (L = O₂CC鈮Ph), II (L = O₂CC₄H₂SC鈮H), and III (L = O₂CC₆H₄-p-CN). The new compounds have been characterized in their ground states by spectroscopy (¹H NMR, ultraviolet鈥搗isible absorption, near-infrared absorption, and steady state emission), cyclic voltammetry, and density functional theory calculations. The compounds show strong metal Mo₂ to ligand L 未鈭捪€* transitions in their visible spectra. The nature of the S₁ ¹MLCT and T₁ states has been probed by time-resolved (femtosecond and nanosecond) transient absorption and infrared spectroscopy. The observed shifts of the C鈮 and C鈮 vibrational modes are found to be consistent with the negative charge being localized on the single L in the S₁ states, while the T₁ states are ³Mo₂ 未未*. The present results are compared to earlier studies of the photoexcited states of trans-Mo₂(2,4,6-triisopropylbenzoate)₂L₂ compounds that have been assigned as either localized or delocalized.