Electronic states of radical cations of all- trans oligo[methyl(phenyl)silane

Abstract

The electronic states of radical cations of oligo[methyl(phenyl)silane] (OMPSi +) with all trans form ( n = 2–8, where n is number of monomer unit of OMPSi) have been investigated by means of density functional theory (DFT) calculation to shed light on the mechanism of hole-transport in oligosilanes with phenyl group in the side chain. For the shorter oligomers ( n < 3), the hole (unpaired electron) was widely distributed equivalently in both the Si main and side chains (55% for the Si main chain and 45% for the side chain). The distribution of hole on the chains was largely changed as a function of chain lengths ( n). Ratios of the hole distribution on the main and side chains became almost constant at n = 7–8: 70% of spin density was distributed on the Si-main chain and 30% on the side-chain, which is much different from that of oligo(dimethyl)silane (the spin density on the methyl side chain was less than 3% of spin density). From these results, it was concluded that the hole in OMPSi + can transfer by the mechanism for both intermolecular and the intrachain hole-transfer processes.