A molecular Ce2@ih-C80 switch-unprecedented oxidative pathway in photoinduced charge transfer reactivity

Guldi DM, Feng L, Radhakrishnan SG, Nikawa H, Yamada M, Mizorogi N, Tsuchiya T, Akasaka T, Nagase S, Angeles Herranz M, Martin N (2010)

Publication Type: Journal article, Original article

Publication year: 2010

Journal

Journal of the American Chemical Society American Chemical Society

Original Authors: Guldi D.M., Feng L., Radhakrishnan S.G., Nikawa H., Yamada M., Mizorogi N., Tsuchiya T., Akasaka T., Nagase S., Angeles Herranz M., Martin N.

Publisher: American Chemical Society

Book Volume: 132

Pages Range: 9078-9086

Journal Issue: 26

DOI: 10.1021/ja101856j

Abstract

We report for the first time the versatile Ce@I -C building block toward synthesizing a novel electron donor-acceptor conjugate, Ce@I-C-ZnP (1). A systematic investigation of the charge transfer chemistry documents a reductive charge transfer (i.e., formation of (Ce@I-C )-(ZnP)) in nonpolar media (i.e., toluene/THF), while an oxidative charge transfer (i.e., formation of (Ce@I-C)-(ZnP) ) dominates in polar media (i.e., benzonitrile/DMF). Reduction of the [Ce] 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] cluster and the electron-donating ZnP. The oxidation of C and the simultaneous reduction of ZnP, on the other hand, necessitate solvent stabilization. In such a case, the strongly exothermic (Ce@I-C) -(ZnP) radical ion pair state formation is compensated within the framework of a nonadiabatic charge transfer by a C /ZnP electronic matrix element, as the sum of good overlap and short distance, that exceeds that for [Ce] /ZnP. © 2010 American Chemical Society.

Authors with CRIS profile

Dirk Michael Guldi Lehrstuhl für Physikalische Chemie I

Additional Organisation(s)

Exzellenz-Cluster Engineering of Advanced Materials (EAM)

Involved external institutions

University of Tsukuba / 筑波大学 JP Japan (JP) National Institute for Basic Biology / 基礎生物学研究所 JP Japan (JP) Universidad Complutense de Madrid (UCM) ES Spain (ES)

How to cite

APA:

Guldi, D.M., Feng, L., Radhakrishnan, S.G., Nikawa, H., Yamada, M., Mizorogi, N.,... Martin, N. (2010). A molecular Ce2@ih-C80 switch-unprecedented oxidative pathway in photoinduced charge transfer reactivity. Journal of the American Chemical Society, 132(26), 9078-9086. https://doi.org/10.1021/ja101856j

MLA:

Guldi, Dirk Michael, et al. "A molecular Ce2@ih-C80 switch-unprecedented oxidative pathway in photoinduced charge transfer reactivity." Journal of the American Chemical Society 132.26 (2010): 9078-9086.

BibTeX: Download