Sharing Orbitals: Ultrafast Excited State Deactivations with Different Outcomes in Bucky Ferrocenes and Ruthenocenes
journal contributionposted on 2006-07-26, 00:00 authored by Dirk M. Guldi, G. M. Aminur Rahman, Renata Marczak, Yutaka Matsuo, Masahiro Yamanaka, Eiichi Nakamura
We report on the singlet ground and singlet/triplet excited-state features of a series of bucky ferrocenes, bucky ruthenocenes, and respective reference compounds. In the bucky ferrocene conjugates, intimate contacts between the fullerenes and ferrocenes result in appreciable ground-state interactionssuggesting a substantial shift of charge density from the electron donor (i.e., ferrocene) to the electron acceptor (i.e., fullerene). In contrast, no prominent charge-transfer features were observed for the bucky ruthenocene conjugates. An arsenal of experimental techniques, ranging from fluorescence (i.e., steady state and time-resolved) and pump probe experiments (i.e., femtosecond and nanoseconds) to pulse radiolysis, were employed to examine excited-state interactions. In the excited states, bucky ferrocene conjugates are dominated by rapid charge separation reactions (0.8 ± 0.1 ps) to yield metastable radical ion pairs. The radical ion pair lifetimes vary between 27 and 39 ps. No charge separation was, however, found in the corresponding bucky ruthenocence. Instead, an intrinsically faster excited-state deactivation (∼ 200 ps) evolves from the heavier ruthenium centerrelative to iron. This effect is further augmented by the unfavorably shifted oxidation potential in ruthenocene of about 0.61 V, which in ruthenocene (−ΔGET = −0.26 eV), in contrast to ferrocene (−ΔGET = 0.35 eV), renders charge separation thermodynamically unfeasible.