Femtosecond Study of Dimolybdenum Paddlewheel Compounds with Amide/Thioamide Ligands: Symmetry, Electronic Structure, and Charge Distribution in the 1MLCT S1 State

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• 作者：Changcheng JiangPhilip J. Young ; Samantha Brown-Xu ; Judith C. GallucciMalcolm H. Chisholm
• 刊名：Inorganic Chemistry
• 出版年：2017
• 出版时间：February 6, 2017
• 年：2017
• 卷：56
• 期：3
• 页码：1433-1445
• 全文大小：759K
• ISSN：1520-510X

文摘

Four photophysically interesting dimolybdenum paddlewheel compounds are synthesized and characterized: I and II contain amide ligand (N,3-diphenyl-2-propynamide), and III and IV contain thioamide ligand (N,3-diphenyl-2-propynethioamide). I and III are trans-Mo₂L₂(O₂C-TⁱPB)₂-type compounds, and II and IV are Mo₂L₄-type compounds, where O₂C-TⁱPB is 2,4,6-triisopropylbenzoate. I–IV display strong light absorption due to metal to ligand charge transfer (MLCT) transitions from molybdenum to the amide/thioamide ligands. Charge transfer dynamics in the MLCT excited states of I–IV have been examined using femtosecond transient absorption (fs-TA) spectroscopy and femtosecond time-resolved infrared (fs-TRIR) spectroscopy. The asymmetric amide/thioamide ligands show two forms of regioarrangements in the paddlewheel compounds. Analyses of the ν(C≡C) bands in the fs-TRIR spectra of I and II show similar electron density distribution over ligands in their ¹MLCT S₁ states where only two amide ligands are involved and the transferred electron is mainly localized on one of them. The fs-TRIR spectra of III and IV, however, show different charge distribution patterns where the transferred electron is fully delocalized over two thioamide ligands in III and partially delocalized in IV. Fast interligand electron transfer (ILET) was recognized as the explanation for the various charge distribution patterns, and ILET was shown to be influenced by both the ligands and the ligand arrangements.