The evolution of doping-induced electronic states within the otherwise forbidden energy gap has been studied as a function of the polyene length in a series of diphenylpolyenes. The chemical and electronic structures have been studied using both X-ray and ultraviolet photoelectron spectroscopies. The results are interpreted with the help of quantum chemical calculations, performed using the semiempirical Austin Model 1 and valence effective Hamiltonian methods. The molecules studied are a series of diphenylpolyenes, DPx, with x = 1-7 C=C double bonds in the polyene part of the molecule. Since the frontier orbitals of the diphenylpolyenes are localized on the polyene chain portion of the molecule, there is a high degree of separation of the phenyl and polyene parts of the π-systems. Hence, many chemical and electronic properties of diphenylpolyenes are expected to be similar to those of short-chain trans-polyacetylene. For the longer molecules, n = 6 or 7, the present results indicate the presence of doubly charged, interacting soliton-antisoliton pairs, which appear as two new energy levels in the otherwise forbidden energy gap. In diphenyldecaheptaene to stilbene, i.e. 1 ≤ x ≤ 5, however, a singly charged state is formed at intermediate doping levels, after which the soliton-antisoliton pairs appear for the fully doubly charged systems. These results show that, remarkably, even for very short polyene segments, charges transferred are stored in the form of (confined) solitons.
ASJC Scopus subject areas
- General Engineering
- Physical and Theoretical Chemistry