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| - Heterogeneous Electron Transfer Processes in Self-AssembledMonolayers of Amine Terminated Conjugated Molecular Wires
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| Abstract
| - A versatile synthesis of triarylamine and phenothiazine end-capped oligo(phenyleneacetylene) molecular wireswhich are terminated by thiol functions is described. The repetitive synthesis allows the preparation of molecular wireswith different chain length and different substituents attached to the wire backbone. These molecular wires were usedto form dense self-assembled monolayers (SAM) on gold substrates as proved by cyclic voltammetry and quartz crystalmicrobalance measurements. The heterogeneous electron transfer rate constant of these SAMs was measured byimpedance spectroscopy between 1 MHz and 0.1 Hz. The rate constants are somewhat larger for the triarylamineterminated systems than for the phenothiazine compound, due to the higher reorganization energy in the latter. Whilethe molecular wires with electron withdrawing substituents display an electron transfer which is slow enough to bemeasurable with our impedance setup, we were unable to determine the rate of molecular wires with electron donatingsubstituents.
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