A Molecular Ce-2@I-h-C-80 Switch-Unprecedented Oxidative Pathway in Photoinduced Charge Transfer Reactivity

doi:10.1021/ja101856j

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	A Molecular Ce-2@I-h-C-80 Switch-Unprecedented Oxidative Pathway in Photoinduced Charge Transfer Reactivity
	Guldi, Dirk M.1,2; Feng, Lai 3,4; Radhakrishnan, Shankara Gayathri 1,2; Nikawa, Hidefumi 3; Yamada, Michio 3; Mizorogi, Naomi 3; Tsuchiya, Takahiro 3; Akasaka, Takeshi 3; Nagase, Shigeru 5; Angeles Herranz, M.6
刊名	JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
	2010-07-07
卷号	132 期号:26 页码:9078-9086
ISSN号	0002-7863
DOI	10.1021/ja101856j
英文摘要	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.
语种	英语
出版者	AMER CHEMICAL SOC
WOS记录号	WOS:000279561200065
内容类型	期刊论文
源URL	[http://ir.iccas.ac.cn/handle/121111/69669]
专题	中国科学院化学研究所
通讯作者	Guldi, Dirk M.
作者单位	1.Univ Erlangen Nurnberg, Dept Chem & Pharm, D-91058 Erlangen, Germany 2.Univ Erlangen Nurnberg, Interdisciplinary Ctr Mol Mat, D-91058 Erlangen, Germany 3.Univ Tsukuba, Ctr Tsukuba Adv Res Alliance, Tsukuba, Ibaraki 3058577, Japan 4.Chinese Acad Sci, Inst Chem, Beijing 100080, Peoples R China 5.Natl Inst Nat Sci, Inst Mol Sci, Dept Theoret & Computat Mol Sci, Okazaki, Aichi 4448585, Japan 6.Univ Complutense, Fac Quim, Dept Quim Organ, E-28040 Madrid, Spain
推荐引用方式 GB/T 7714	Guldi, Dirk M.,Feng, Lai,Radhakrishnan, Shankara Gayathri,et al. A Molecular Ce-2@I-h-C-80 Switch-Unprecedented Oxidative Pathway in Photoinduced Charge Transfer Reactivity[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY,2010,132(26):9078-9086.
APA	Guldi, Dirk M..,Feng, Lai.,Radhakrishnan, Shankara Gayathri.,Nikawa, Hidefumi.,Yamada, Michio.,...&Martin, Nazario.(2010).A Molecular Ce-2@I-h-C-80 Switch-Unprecedented Oxidative Pathway in Photoinduced Charge Transfer Reactivity.JOURNAL OF THE AMERICAN CHEMICAL SOCIETY,132(26),9078-9086.
MLA	Guldi, Dirk M.,et al."A Molecular Ce-2@I-h-C-80 Switch-Unprecedented Oxidative Pathway in Photoinduced Charge Transfer Reactivity".JOURNAL OF THE AMERICAN CHEMICAL SOCIETY 132.26(2010):9078-9086.