关键词: 乙烯基噻吩, 螺噁嗪, 密度泛函理论, 前线分子轨道, 电子吸收光谱

Abstract:

We carried out a theoretical study on the geometries, electronic structures, and frontier molecular orbitals of vinyl thiophene group conjugated spirooxazines (SO-SO3) using density functional theory (DFT) at the B3LYP/6-31G^* level. The calculated results show that the equalization of bond lengths at the left and right parts of the open-forms occurred during the ring-opening process. A large conjugated system was formed and this significantly narrowed the energy gap. The conjugated system became larger and its electrons flowed easily because of the introduction of different lengths of vinyl thiophene conjugation moieties into the spirooxazine molecule. The electrons and energy efficiently transferred from the vinyl thiophene to naphthoxazine. The orbital contribution rate of the vinyl thiophene group in the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) increased obviously. Time-dependent DFT (TD-DFT) calculations showed that as the conjugated vinyl thiophene unit reached 2-3 the first singlet excited state of SO2 and SO3 resulted from the electron transition from the HOMO to the LUMO, which were also assigned to the π-π^* transition. Meanwhile, λ_max was between 466 and 540 nm with an obvious red-shift while the λ_max of O-SO2 and O-SO3 reached 605 and 647 nm, respectively.

Key words: Vinyl thiophene, Spirooxazine, Density functional theory, Frontier molecular orbital, Electronic absorption spectrum