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
1. [1]
  
  (1) Fox, R. E. Research Reports and Test Items Pertaining to EyeProtection of Air Crew Personnel. USA Patent AD440226
2. [2]
  [P].1961 Final Report on Contract AF41 (657) 215, AD 440226,1961.
3. [3]
  (2) Fan, M. G. Basic Fundamentals of Photochemistry andMaterials Science of Photonics; Science Press: Beijing, 2001;p 226.
4. [4]
  [樊美公. 光化学基本原理与光子学材料科学. 北京:科学出版社, 2001: 226.]
5. [5]
  (3) Tamai, N.; Miyasaka, H. Chem. Rev. 2000, 100, 1875.
6. [6]
  (4) Chu, N. Y. C. Can. J. Chem. 1983, 61, 300.
7. [7]
  (5) Tang, Z.Y.; Hu, Y. C.; Zhao, Y.; Liu, S. B. Acta Phys. Chim. Sin.2009, 25, 701.
8. [8]
  [唐智勇, 胡云楚, 赵莹, 刘述斌. 物理化学学报, 2009, 25, 701.]
9. [9]
  (6) Xue, Y. S.; ng, X. D.; Xiao, H. M.; Tian, H. Acta Chim. Sin.2004, 62, 963.
10. [10]
  [薛运生, 贡雪东, 肖鹤鸣, 田禾. 化学学报,2004, 62, 963.]
11. [11]
  (7) Wang, J. Y.; Feng, C.G. Chinese Journal of Applied Chemistry2007, 24, 7.
12. [12]
  [王建营, 冯长根. 应用化学, 2007, 24, 7.]
13. [13]
  (8) Kanis, D. R.; Ratner, M. A.; Marks, T. J. Chem. Rev. 1994, 94,195.
14. [14]
  (9) Dehu, C.; Meyers, F.; Bredas, J. L. J. Am. Chem. Soc. 1993, 115,6198.
15. [15]
  (10) (a) Lee, C.; Yang,W.; Parr, R. G. Phys. Rev. B 1988, 37, 785. (b) Becke, A. D. J. Chem. Phys. 1993, 98, 5648. (c) Maurel, F.; Aubard, J.; Millie, P.; Dognon, J. P.; Rajzmann,M.; Guglielmetti, R.; Samat, A. J. Phys. Chem. A 2006, 110,4759. (d) Sheng, Y. H.; Leszczynski, J.; Garcia, A. A.; Rosario, R.;Gust, D.; Springer, J. J. Phys. Chem. B 2004, 108, 16233.
16. [16]
  (11) Frisch, M. J.; Trucks, G.W.; Schlegel, H. B.; et al. Gaussian 09,Revision B.01; Gaussian Inc.: Pittsburgh, PA, 2010
17. [17]
  (12) (a) Schneider, S. Z. Phys. Chem. Neue. Folge. 1987, 154, 91. (b) Maeda, S.; Mitsuhashi, K.; Osano, Y. T.; Nakamura, S.; Ito,M. Mol. Cryst. Liq. Cryst. 1994, 246, 223.
18. [18]
  (13) Millini, R.; Del Piero, G.; Allegrini, P.; Crisci, L.; Malatesta, V.Acta Crystallogr. C 1991, 47, 2567.
19. [19]
  (14) Ortiz, R. P.; Delgado, M. C. R.; Casado, J.; Hernández, V.; Kim,O.;Woo, H. Y.; Navarrete, J. T. L. J. Am. Chem. Soc. 2004, 126,13363.
20. [20]
  (15) Cufioni, A.; Andreoni,W. IBM J. Res. Dev. 2001, 45, 101.
21. [21]
  (16) Cufioni, A.; Mauro, B.; Andreoni,W. Chemical Physics Letters1998, 294, 263.
22. [22]
  (17) Bohne, C.; Fan, M. G.; Li, Z. J.; Lusztyk, J.; Scaiano, J. C.J. Chem. Soc. Chem. Commun. 1990, 571.
23. [23]
  (18) (a) Jr. Tyer, N.W.; Becker, R. S. J. Am. Chem. Soc. 1970, 92,1289. (b) Jr. Tyer, N.W.; Becker, R. S. J. Am. Chem. Soc. 1970, 92,1295.
24. [24]
  (19) Wang, X.W.; Jiang, G.; Du, J. G. Acta Phys. -Chim. Sin. 2011,27, 309.
25. [25]
  [王晓巍, 蒋刚, 杜际广. 物理化学学报, 2011,27, 309.]
26. [26]
  (20) Kumar, S.; Velasco, K.; McCurdy, A. J. Mol. Struct. 2010, 968,13.
27. [27]
  (21) Hudson, G. A.; Cheng, L.; Yu, J. M.; Yan, Y.; Dyer, D. J.;McCarroll, M. E.;Wang, L. C. J. Phys. Chem. B 2010, 114, 870.
1. [1]
  Jie ZHAO , Sen LIU , Qikang YIN , Xiaoqing LU , Zhaojie WANG . Theoretical calculation of selective adsorption and separation of CO₂ by alkali metal modified naphthalene/naphthalenediyne. Chinese Journal of Inorganic Chemistry, 2024, 40(3): 515-522. doi: 10.11862/CJIC.20230385
2. [2]
  Xiaochen Zhang , Fei Yu , Jie Ma . 多角度数理模拟在电容去离子中的前沿应用. Acta Physico-Chimica Sinica, 2024, 40(11): 2311026-. doi: 10.3866/PKU.WHXB202311026
3. [3]
  Jizhou Liu , Chenbin Ai , Chenrui Hu , Bei Cheng , Jianjun Zhang . 六氯锡酸铵促进钙钛矿太阳能电池界面电子转移及其飞秒瞬态吸收光谱研究. Acta Physico-Chimica Sinica, 2024, 40(11): 2402006-. doi: 10.3866/PKU.WHXB202402006
4. [4]
  Maitri Bhattacharjee , Rekha Boruah Smriti , R. N. Dutta Purkayastha , Waldemar Maniukiewicz , Shubhamoy Chowdhury , Debasish Maiti , Tamanna Akhtar . Synthesis, structural characterization, bio-activity, and density functional theory calculation on Cu(Ⅱ) complexes with hydrazone-based Schiff base ligands. Chinese Journal of Inorganic Chemistry, 2024, 40(7): 1409-1422. doi: 10.11862/CJIC.20240007
5. [5]
  Chengqian Mao , Yanghan Chen , Haotong Bai , Junru Huang , Junpeng Zhuang . Photodimerization of Styrylpyridinium Salt and Its Application in Silk Screen Printing. University Chemistry, 2024, 39(5): 354-362. doi: 10.3866/PKU.DXHX202312014
6. [6]
  Mengyao Shi , Kangle Su , Qingming Lu , Bin Zhang , Xiaowen Xu . Determination of Potassium Content in Tobacco Stem Ash by Flame Atomic Absorption Spectroscopy. University Chemistry, 2024, 39(10): 255-260. doi: 10.12461/PKU.DXHX202404105
7. [7]
  Caixia Lin , Zhaojiang Shi , Yi Yu , Jianfeng Yan , Keyin Ye , Yaofeng Yuan . Ideological and Political Design for the Electrochemical Synthesis of Benzoxathiazine Dioxide Experiment. University Chemistry, 2024, 39(2): 61-66. doi: 10.3866/PKU.DXHX202309005
8. [8]
  Tengjiao Wang , Tian Cheng , Rongjun Liu , Zeyi Wang , Yuxuan Qiao , An Wang , Peng Li . Conductive Hydrogel-based Flexible Electronic System: Innovative Experimental Design in Flexible Electronics. University Chemistry, 2024, 39(4): 286-295. doi: 10.3866/PKU.DXHX202309094
9. [9]
  Jia Yao , Xiaogang Peng . Theory of Macroscopic Molecular Systems: Theoretical Framework of the Physical Chemistry Course in the Chemistry “101 Plan”. University Chemistry, 2024, 39(10): 27-37. doi: 10.12461/PKU.DXHX202408117
10. [10]
  Yonghui ZHOU , Rujun HUANG , Dongchao YAO , Aiwei ZHANG , Yuhang SUN , Zhujun CHEN , Baisong ZHU , Youxuan ZHENG . Synthesis and photoelectric properties of fluorescence materials with electron donor-acceptor structures based on quinoxaline and pyridinopyrazine, carbazole, and diphenylamine derivatives. Chinese Journal of Inorganic Chemistry, 2024, 40(4): 701-712. doi: 10.11862/CJIC.20230373
11. [11]
  Yuhao SUN , Qingzhe DONG , Lei ZHAO , Xiaodan JIANG , Hailing GUO , Xianglong MENG , Yongmei GUO . Synthesis and antibacterial properties of silver-loaded sod-based zeolite. Chinese Journal of Inorganic Chemistry, 2024, 40(4): 761-770. doi: 10.11862/CJIC.20230169
12. [12]
  Qin Hu , Liuyun Chen , Xinling Xie , Zuzeng Qin , Hongbing Ji , Tongming Su . Ni掺杂构建电子桥及激活MoS₂惰性基面增强光催化分解水产氢. Acta Physico-Chimica Sinica, 2024, 40(11): 2406024-. doi: 10.3866/PKU.WHXB202406024
13. [13]
  Yanhui XUE , Shaofei CHAO , Man XU , Qiong WU , Fufa WU , Sufyan Javed Muhammad . Construction of high energy density hexagonal hole MXene aqueous supercapacitor by vacancy defect control strategy. Chinese Journal of Inorganic Chemistry, 2024, 40(9): 1640-1652. doi: 10.11862/CJIC.20240183
14. [14]
  Kaihui Huang , Dejun Chen , Xin Zhang , Rongchen Shen , Peng Zhang , Difa Xu , Xin Li . Constructing Covalent Triazine Frameworks/N-Doped Carbon-Coated Cu₂O S-Scheme Heterojunctions for Boosting Photocatalytic Hydrogen Production. Acta Physico-Chimica Sinica, 2024, 40(12): 2407020-. doi: 10.3866/PKU.WHXB202407020
15. [15]
  Jiaxin Su , Jiaqi Zhang , Shuming Chai , Yankun Wang , Sibo Wang , Yuanxing Fang . Optimizing Poly(heptazine imide) Photoanodes Using Binary Molten Salt Synthesis for Water Oxidation Reaction. Acta Physico-Chimica Sinica, 2024, 40(12): 2408012-. doi: 10.3866/PKU.WHXB202408012
16. [16]
  Hua Hou , Baoshan Wang . Course Ideology and Politics Education in Theoretical and Computational Chemistry. University Chemistry, 2024, 39(2): 307-313. doi: 10.3866/PKU.DXHX202309045
17. [17]
  Jin Tong , Shuyan Yu . Crystal Engineering for Supramolecular Chirality. University Chemistry, 2024, 39(3): 86-93. doi: 10.3866/PKU.DXHX202308113
18. [18]
  Yong Shu , Xing Chen , Sai Duan , Rongzhen Liao . How to Determine the Equilibrium Bond Distance of Homonuclear Diatomic Molecules: A Case Study of H₂. University Chemistry, 2024, 39(7): 386-393. doi: 10.3866/PKU.DXHX202310102
19. [19]
  Lu XU , Chengyu ZHANG , Wenjuan JI , Haiying YANG , Yunlong FU . Zinc metal-organic framework with high-density free carboxyl oxygen functionalized pore walls for targeted electrochemical sensing of paracetamol. Chinese Journal of Inorganic Chemistry, 2024, 40(5): 907-918. doi: 10.11862/CJIC.20230431
20. [20]
  Laiying Zhang , Yinghuan Wu , Yazi Yu , Yecheng Xu , Haojie Zhang , Weitai Wu . Innovation and Practice of Polymer Chemistry Experiment Teaching for Non-Polymer Major Students of Chemistry: Taking the Synthesis, Solution Property, Optical Performance and Application of Thermo-Sensitive Polymers as an Example. University Chemistry, 2024, 39(4): 213-220. doi: 10.3866/PKU.DXHX202310126

Get Citation

PDF

XML

Metrics

PDF Downloads(1027)
Abstract views(2777)
HTML views(17)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142