1234796-61-2Relevant academic research and scientific papers
A molecular Ce2@ih-C80 switch-unprecedented oxidative pathway in photoinduced charge transfer reactivity
Guldi, Dirk M.,Feng, Lai,Radhakrishnan, Shankara Gayathri,Nikawa, Hidefumi,Yamada, Michio,Mizorogi, Naomi,Tsuchiya, Takahiro,Akasaka, Takeshi,Nagase, Shigeru,Angeles Herranz,Martin, Nazario
, p. 9078 - 9086 (2010)
We report for the first time the versatile Ce2@I h-C80 building block toward synthesizing a novel electron donor-acceptor conjugate, Ce2@Ih-C80-ZnP (1). A systematic investigation of the charge transfer chemistry documents a reductive charge transfer (i.e., formation of (Ce2@Ih-C 80)?--(ZnP)?+) in nonpolar media (i.e., toluene/THF), while an oxidative charge transfer (i.e., formation of (Ce2@Ih-C80)?+-(ZnP) ?-) dominates in polar media (i.e., benzonitrile/DMF). Reduction of the [Ce2]6+ cluster, which is highly localized and collinearly arranged with respect to the quaternary bridge carbon, is sufficiently exothermic in all solvents. Notably weak is the electronic coupling between the [Ce2]6+ cluster and the electron-donating ZnP. The oxidation of C806- and the simultaneous reduction of ZnP, on the other hand, necessitate solvent stabilization. In such a case, the strongly exothermic (Ce2@Ih-C80) ?--(ZnP)?+ radical ion pair state formation is compensated within the framework of a nonadiabatic charge transfer by a C 806-/ZnP electronic matrix element, as the sum of good overlap and short distance, that exceeds that for [Ce2] 6+/ZnP.
