%0 Journal Article
%A Guldi, Dirk
%A Swartz, Angela
%A Luo, Chuping
%A Gómez Aspe, Rafael
%A Segura Castedo, José Luis
%A Martín León, Nazario
%T Rigid dendritic donor-acceptor ensembles: Control over energy and electron transduction
%D 2002
%U https://hdl.handle.net/20.500.14352/105571
%X Several generations of phenylenevinylene dendrons, covalently attached to a C60 core, have been developed as synthetic model systems with hierarchical, fine-tuned architectures. End-capping of these dendritic spacers with dibutylaniline or dodecyloxynaphthalene, as antennas/electron donors, yielded new donor-bridge-acceptor ensembles in which one, two, or four donors are allocated at the peripheral positions of the well-defined dendrons, while the electron accepting fullerene is placed at the focal point of the dendron. On the basis of our cyclic voltammetry experiments, which disclose a single anodic oxidation and several cathodic reduction processes, we rule out significant, long-range couplings between the fullerene core and the end-standing donors in their ground-state configuration. Photophysical investigations, on the other hand, show that upon photoexcitation an efficient and rapid transfer of singlet excited-state energy (6 × 1010 to 2.5 × 1012 s-1) controls the reactivity of the initially excited antenna portion. Spectroscopic and kinetic evidence suggests that yet a second contribution, that is, an intramolecular electron-transfer, exists, affording C60.--dendron.+ with quantum yields (Φ) as high as 0.76 and lifetimes (τ) that are on the order of hundreds of nanoseconds (220-725 ns). Variation of the energy gap modulates the interplay of these two pathways (i.e., competition or sequence between energy and electron transfer).
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