title: Small reorganization energies of photoinduced electron transfer between spherical fullerenes.
abstract: Rate constants of photoinduced electron transfer between spherical fullerenes were determined using triscandium nitride encapsulated C80 fullerene (Sc3N@C80) as an electron donor and the triplet excited state of lithium ion-encapsulated C60 fullerene (Li(+)@C60) as an electron acceptor in polar and less polar solvents by laser flash photolysis measurements. Upon nanosecond laser excitation at 355 nm of a benzonitrile (PhCN) solution of Li(+)@C60 and Sc3N@C80, electron transfer from Sc3N@C80 to the triplet excited state [(3)(Li(+)@C60)*] occurred to produce Sc3N@C80(•+) and Li(+)@C60(•-) (λ(max) = 1035 nm). The rates of the photoinduced electron transfer were monitored by the decay of absorption at λ(max) = 750 nm due to (3)(Li(+)@C60)*. The second-order rate constant of electron transfer from Sc3N@C80 to (3)(Li(+)@C60)* was determined to be k(et) = 1.5 × 10(9) M(-1) s(-1) from dependence of decay rate constant of (3)(Li(+)@C60)* on the Sc3N@C80 concentration. The rate constant of back electron transfer from Li(+)@C60(•-) to Sc3N@C80(•+) was also determined to be k(bet) = 1.9 × 10(9) M(-1) s(-1), which is close to be the diffusion limited value in PhCN. Similarly, the rate constants of photoinduced electron transfer from C60 to (3)(Li(+)@C60)* and from Sc3N@C80 to (3)C60* were determined together with the back electron-transfer reactions. The driving force dependence of log k(et) and log k(bet) was well fitted by using the Marcus theory of outer-sphere electron transfer, in which the internal (bond) reorganization energy (λi) was estimated by DFT calculations and the solvent reorganization energy (λs) was calculated by the Marcus equation. When PhCN was replaced by o-dichlorobenzene (o-DCB), the λ value was decreased because of the smaller solvation changes of highly spherical fullerenes upon electron transfer in a less polar solvent.
authors.affiliation: Department of Material and Life Science, Graduate School of Engineering, Osaka University, 2-1 Yamada-oka, Suita, Osaka 565-0871, Japan.
authors.forename: Yuki
authors.initials: Y
authors.lastname: Kawashima
authors.forename: Kei
authors.initials: K
authors.lastname: Ohkubo
authors.forename: Shunichi
authors.initials: S
authors.lastname: Fukuzumi
mesh_terms: D004579:Electron Transport; D037741:Fullerenes / Q000737:chemistry*; D008958:Models, Molecular; D010777:Photochemistry
chemical_list: D037741:Fullerenes