文摘
Ultrafast pump−probe spectroscopic studies have been performed on (C5Me5)2U[−NC(Ph)(CH2Ph)]2 and (C5Me5)2Th[−NC(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.