期刊
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
卷 132, 期 26, 页码 9078-9086出版社
AMER CHEMICAL SOC
DOI: 10.1021/ja101856j
关键词
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资金
- Deutsche Forschungsgemeinschaft
- Cluster of Excellence Engineering of Advanced Materials
- FCI
- Office of Basic Energy Sciences of the U S.
- Ministry of Education, Culture, Sports, Science, and Technology of Japan [20108001, 20245006, 20036008, 20038007]
- Japan Society for the Promotion of Science (JSPS)
- National Natural Science Foundation of China [20702053]
- MICINN of Spain [CTQ2008-00795/BQU, Consolider-Ingenio 2010C-07-25200]
- CAM [P-PPQ-000225-0505]
- Grants-in-Aid for Scientific Research [22750030, 20108002, 20245006] Funding Source: KAKEN
We report for the first time the versatile Ce-2@I-h-C-80 building block toward synthesizing a novel electron donor-acceptor conjugate, Ce-2@I-h-C-80-ZnP (1) A systematic investigation of the charge transfer chemistry documents a reductive charge transfer (i e, formation of (Ce-2@I-h-C-80)(center dot-)-(ZnP)(center dot+)) in nonpolar media (i e, toluene/THF), while an oxidative charge transfer (i.e., formation of (Ce-2@I-h-C-80)(center dot+)(ZnP)(center dot-)) dominates in polar media (i.e, benzonitnle/DMF). Reduction of the [Ce-2](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 [Ce-2](6+) cluster and the electron-donating ZnP The oxidation of C-80(6-) and the simultaneous reduction of ZnP, on the other hand, necessitate solvent stabilization In such a case, the strongly exothermic (Ce-2@I-h-C-80)(center dot-)(ZnP)(center dot 4) radical ion pair state formation is compensated within the framework of a nonadiabatic charge transfer by a C-80(6-)/ZnP electronic matrix element, as the sum of good overlap and short distance, that exceeds that for [Ce-2](6+)/ZnP.
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