Systematic investigation of absorption, fluorescence and laser properties of some p- and m-oligophenylenes.

Absorption, fluorescence and laser properties of ten selected aromatic compounds from the oligophenylene family are studied experimentally at room temperature (293 K). The first eight compounds are arranged in such way that odd numbered compounds reveal 1Lb --> 1A fluorescence, while even numbered compounds show 1La --> 1A fluorescence. All compounds are family related in pi-structure and are of the same degree of planarity and rigidity. The quantum yield of fluorescence, gamma, and the decay times, tau(f), of non-deaerated and deaerated cyclohexane solutions are measured. The oscillator strength, f(e), the fluorescence rate constant, Kf, natural lifetimes, tau(o)T, and intersystem crossing rate constant, K(ST), are calculated. The lowest 1Lb and 1La singlet and 3La, triplet (77 K) levels are determined. Investigations showed that transition from a polyphenyl molecule which shows 1La --> 1A fluorescence to a family related in the pi-structure molecule which reveals the 1Lb --> 1A fluorescence is accompanied by certain changes in all the fluorescence parameters. This indicates that gamma decreases, tau(f) increases, Kf and the FWRE of the fluorescence spectrum decrease. Moreover, K(ST) also decreases, sometimes very significantly. The decrease in the K(ST) value is explained by the fact that <psiS alpha/H(SO)/psiTi> matrix elements of the spin-orbit coupling of the S alpha and Ti states are much lower in value than analogous elements of the spin-orbit coupling of Sp and Ti states. It is shown that all p-polyphenyles exhibit excellent laser action, while m-polyphenyles do not produce laser oscillation under any conditions. The values of K(ST) and other fluorescence parameters measured can be used for various practical purposes and theoretical considerations.