Photoinduced Structural Changes in Poly(4-Vinyl Pyridine): A Luminescence Study

Abstract

In the present work we show a way of controlling photoluminescence (PL) properties through photoinduced quasi-crystal formation in a system based on poly(4-vinyl pyridine) (P4VPy). Under UV irradiation at 380 nm, concentrated solutions of P4VPy in pyridine turn into gel. This phase transition results in changes in the optical properties of this polymer. The position of the PL maximum can be changed continuously from 440 to 480 nm during irradiation. After several minutes of UV irradiation a new red-shifted PL at 492 nm appears upon excitation by light of a wavelength corresponding to that of the initial PL maximum, which is also red-shifted during irradiation. Solutions of P4VPy in pyrimidine show similar behavior, but those in pyridazine do not exhibit such behavior. We have found that the reason for the observed changes in the electronic properties is a photoinduced directional ordering of polymer molecules in a special quasi-crystal formation. The process originates from a structural change in the side chain of P4VPy, namely, protonation of the polymeric pyridine after solvation. During irradiation, the polymeric pyridinium ion interacts with neutral polymeric pyridine molecules. Interchain interaction through hydrogen bonds lead to an electronic property change. We observed that the process of photoinduced sol-gel transformation is reversible. Mechanical perturbation or heating can convert the gel back to a fluid solution. The red-shifted PL is not observed, and the initial PL is blue-shifted to 450 nm and stays there.