Ultrafast Spectroscopy of the Uranium(IV) and Thorium(IV) Bis(ketimide) Complexes (C5Me5)2An[−NC(Ph)(CH2Ph)]2 (An = Th, U)

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• 作者：David J. Hilton ; Rohit P. Prasankumar ; Eric J. Schelter ; Verner K. Thorsmø ; lle ; Stuart A. Trugman ; Andrew P. Shreve ; Jaqueline L. Kiplinger ; David E. Morris ; Antoinette J. Taylor
• 刊名：Journal of Physical Chemistry A
• 出版年：2008
• 出版时间：August 28, 2008
• 年：2008
• 卷：112
• 期：34
• 页码：7840-7847
• 全文大小：266K
• 年卷期：v.112,no.34(August 28, 2008)
• ISSN：1520-5215

文摘

Ultrafast pump−probe spectroscopic studies have been performed on (C₅Me₅)₂U[−NC(Ph)(CH₂Ph)]₂ and (C₅Me₅)₂Th[−NC(Ph)(CH₂Ph)]₂ including, for the uranium complex, the first direct measurement of dynamics of electronic deactivation within a 5f-electron manifold. Evidence has been found for strong coupling between the electronic ground state and the f-electron manifold which dominates the dynamics of the excited states of the bis(ketimide) uranium complex. These also demonstrate strong singlet−f manifold coupling, which assists in the deactivation of the photoexcited state of the uranium complex, and provide information on intersystem crossing and internal conversion processes in both complexes.