Heterogeneous electron transfer processes in self-assembled monolayers of amine terminated conjugated molecular wires.

A versatile synthesis of triarylamine and phenothiazine end-capped oligo(phenyleneacetylene) molecular wires which are terminated by thiol functions is described. The repetitive synthesis allows the preparation of molecular wires with different chain length and different substituents attached to the wire backbone. These molecular wires were used to form dense self-assembled monolayers (SAM) on gold substrates as proved by cyclic voltammetry and quartz crystal microbalance measurements. The heterogeneous electron transfer rate constant of these SAMs was measured by impedance spectroscopy between 1 MHz and 0.1 Hz. The rate constants are somewhat larger for the triarylamine terminated systems than for the phenothiazine compound, due to the higher reorganization energy in the latter. While the molecular wires with electron withdrawing substituents display an electron transfer which is slow enough to be measurable with our impedance setup, we were unable to determine the rate of molecular wires with electron donating substituents.

How delocalized is N,N,N',N'-tetraphenylphenylenediamine radical cation? An experimental and theoretical study on the electronic and molecular structure.

The electronic and molecular structure of N,N,N',N'-tetraphenylphenylenediamine radical cation 1(+) is in focus of this study. Resonance Raman experiments showed that at least eight vibrational modes are strongly coupled to the optical charge resonance band which is seen in the NIR. With the help of a DFT-based vibrational analysis, these eight modes were assigned to symmetric vibrations. The contribution of these symmetric modes to the total vibrational reorganization energy is dominant. These findings are in agreement with the conclusions from a simple two-state two-mode Marcus-Hush analysis which yields a tiny electron-transfer barrier. The excellent agreement of the X-ray crystal structure analysis and the DFT computed molecular structure of 1(+) on one hand as well as the solvent and solid-state IR spectra and the DFT-calculated IR active vibrations on the other hand prove 1(+) adopts a symmetrical delocalized Robin-Day class III structure both in the solid state and in solution.