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Probing charge separation in structurally different C-60/exTTF ensembles

Diaz, M.C.; Herranz, M.A.; Illescas, B.M.; Martin, N.; Godbert, N.; Bryce, M.R.; Luo, C.P.; Swartz, A.; Anderson, G.; Guldi, D.M.


M.C. Diaz

M.A. Herranz

B.M. Illescas

N. Martin

N. Godbert

C.P. Luo

A. Swartz

G. Anderson

D.M. Guldi


The scope of the present work is to highlight the effects stemming from different C-60/exTTF linkages (exTTF = 9,10-bis(1,3-dithiol-2-ylidene)-9,10-dihydroanthracene)-either via an anthracene unit or a dithiole ring. Particular emphasis is placed on photoinduced electron-transfer features. Therefore, we devised a new series Of C-60-exTTF ensembles, synthesized via 1,3-dipolar cycloaddition. and Diels-Alder cycloaddition reactions, in which exTTF units are separated from C-60 by two single bonds (3a-c, 4), one vinylene unit (5a), or two vinylene units (5b). The cyclic voltammetry reveals an amphoteric redox behavior with remarkably strong electron-donor ability of the trimethyl-substituted exTTF moiety in 4 and 5a,b. Steady-state and time-resolved photolytic techniques show that the fullerene singlet excited state in (3a-c, 4, and 5a,b) is subject to a rapid electron-transfer quenching. The resulting charge-separated states, that is C-60(.-)-exTTF(.+), were identified by transient absorption spectroscopy. We determined radical pair lifetimes of the order of 200 ns in benzonitrile. This suggests (i) that the positive charge of the exTTF(.+) is delocalized over the entire donor rather than localized on one of the 1,3-dithiole rings and (ii) that linking exTTF via the anthracene or 1,3-dithiole ring has no appreciable influence. Increasing the donor-acceptor separation via implementing one or two vinylene units as spacers led to improved radical pair lifetimes (5a: tau = 725 ns; 5b: tau = 1465 ns).


Diaz, M., Herranz, M., Illescas, B., Martin, N., Godbert, N., Bryce, M., …Guldi, D. (2003). Probing charge separation in structurally different C-60/exTTF ensembles. Journal of Organic Chemistry, 68(20), 7711-7721

Journal Article Type Article
Publication Date 2003-10
Journal Journal of Organic Chemistry
Print ISSN 0022-3263
Publisher American Chemical Society
Peer Reviewed Peer Reviewed
Volume 68
Issue 20
Pages 7711-7721