Citation: SUN Hai-Tao, TIAN Xiao-Hui, YUAN Yi-Zhong, SUN Jin-Yu, SUN Zhen-Rong, ZHUO Xiao-Ling. Density Functional Theory Study on Vinyl Thiophene Group Conjugated Spirooxazines[J]. Acta Physico-Chimica Sinica, ;2011, 27(08): 1847-1853. doi: 10.3866/PKU.WHXB20110840 shu

Density Functional Theory Study on Vinyl Thiophene Group Conjugated Spirooxazines

1.
1. Key Laboratory for Ultrafine Materials of Ministry of Education, School of Materials Science and Engineering, East China University of Science and Technology, Shanghai 200237, P. R. China;
2. State Key Laboratory of Precision Spectroscopy, East China Normal University, Shanghai 200062, P. R. China

Received Date: 21 April 2011
Available Online: 1 July 2011
Fund Project: 国家高技术研究发展计划(0099AA03500) (0099AA03500) 上海市重点学科(B502) (B502)重点实验室(08DZ2230500, 09JC1404300)资助项目 (08DZ2230500, 09JC1404300)

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.
- Vinyl thiophene,
- Spirooxazine,
- Density functional theory,
- Frontier molecular orbital,
- Electronic absorption spectrum
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