Kinetics and spectra of fullerene triplet states

R. Bruce Weisman; Kevin D. Ausman; Angelo F. Benedetto; David A. Samuels

doi:10.1117/12.279253

1 November 1997 Kinetics and spectra of fullerene triplet states

R. Bruce Weisman, Kevin D. Ausman, Angelo F. Benedetto, David A. Samuels

Proceedings Volume 3142, Fullerenes and Photonics IV; (1997) https://doi.org/10.1117/12.279253
Event: Optical Science, Engineering and Instrumentation '97, 1997, San Diego, CA, United States

Abstract

Optical kinetic spectroscopy is used to investigate the triplet state properties of solution phase fullerenes. These triplet states, which are the molecules' lowest-energy and longest-lived electronic excitations, show lifetimes and absorption spectra that vary from fullerene to fullerene. In room temperature toluene solution, the intrinsic triplet lifetime of C₇₀ exceeds that of C₆₀ by a factor at of least 80. The 'self-quenching' deactivation of triplet states through encounters with ground state molecules occurs with rate constants of 1.6 X 10⁷⁰ M^-1s^-1 for C₆₀ and 3 X 10⁷ M^-1s^-1 for C₇₀. In solutions containing mixtures of fullerenes, transfer of triplet excitation between species is efficient and reversible, with rate constants up to 2 X 10⁹ M^-1s^-1. When C₆₀ is aliphatically derivatized at two adjacent sites to form (6,6)-closed dihydrofullerene structure, intrinsic triplet lifetimes are shortened by more than a factor of 3 to approximately 45 microsecond(s) . The triplet spectra of these compounds, in which the derivitizing groups are not sterically strained, are very similar to each other but significantly different from the C₆₀ spectrum. The (6,6)-closed epoxide, C₆₀O, displays unusual triplet state behavior. Its initial triplet spectrum is distinct from that of the other derivatives studied and decays in approximately 6 microsecond(s) through nonexponential kinetics. Evolution of the induced spectrum suggest the possibility of epoxide ring opening form the triplet state of C₆₀O.

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R. Bruce Weisman, Kevin D. Ausman, Angelo F. Benedetto, and David A. Samuels "Kinetics and spectra of fullerene triplet states", Proc. SPIE 3142, Fullerenes and Photonics IV, (1 November 1997); https://doi.org/10.1117/12.279253

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