TTF+·-π 共轭桥-6-氧四联氮阳离子双自由基NLO性质的理论研究

doi:10.6023/A1109231

化学学报 ›› 2012, Vol. 70 ›› Issue (02): 107-113.DOI: 10.6023/A1109231 下一篇

研究论文

TTF^+·-π 共轭桥-6-氧四联氮阳离子双自由基NLO性质的理论研究

李灼, 杜晓凤, 麻娜娜, 孙世玲, 仇永清

东北师范大学化学学院功能材料化学研究所长春 130024

投稿日期:2011-09-23 修回日期:2011-11-29 发布日期:2012-02-25
通讯作者: 仇永清 E-mail:qiuyq466@nenu.edu.cn
基金资助:
国家自然科学基金(No.20873017);吉林省自然科学基金(No.20101154)资助项目

Theoretical Study on NLO Properties of TTF^+·-π Conjugated Bridge-verdazyl Cation Diradicals

Li Zhuo, Du Xiaofeng, Ma Nana, Sun Shiling, Qiu Yongqing

Institute of Functional Material Chemistry, Faculty of Chemistry, Northeast Normal University, Changchun 130024

Received:2011-09-23 Revised:2011-11-29 Published:2012-02-25
Supported by:
Project supported by the National Natural Science Foundation of China (No.20873017);and the Natural Science Foundation of Jilin Province (No.20101154).

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摘要/Abstract

采用量子化学UPBE1PBE 结合有限场(FF)方法, 对系列TTF^+·-π 共轭桥-6-氧四联氮阳离子双自由基体系的稳定性, 极化率α_s 和第一超极化率β_tot 进行研究. 结果表明, TTF^+·-6-氧四联氮阳离子双自由基引入共轭桥后, 随体系共轭性增强, α_s 和β_tot 值均增大(体系2S的β_tot值除外). 自旋多重度和构象对双自由基体系的极化率和第一超极化率都有影响, 双自由基体系由单重态转变为三重态时, 极化率减小, 而第一超极化率明显增大. 以体系2为例, 在单重态时α_s和β_tot值随构象变化较小, 而三重态时α_s和β_tot值随二面角θ₁ 和θ₂ 的增加而减小.

关键词: 双自由基体系, 自旋多重度, NLO 性质, UPBE1PBE 方法

The stabilities, polarizabilities α_s and the first hyperpolarizabilities β_tot for a series of TTF^+·-π conjugated bridge-verdazyl cation diradicals were investigated by using the UPBE1PBE method combined with the finite field (FF) approach. The results indicate that introducing conjugated bridges to TTF^+·- verdazyl cation diradicals results in the conjugation of systems increasing, and then the α_s and β_tot values increasing (except for the β_tot value of system 2S). The spin multiplicity and conformation both have influence on polarizability and the first hyperpolarizability. The polarizabilities of all systems decrease when the diradical systems change from singlet into triplet, while the first hyperpolarizabilities increase obviously. Taking the system 2 for example, the α_s and β_tot values change slightly with conformation in singlet, while the α_s and β_tot values decrease with increasing of the dihedral angle θ₁ and θ₂ in triplet.

Key words: diradical system, spin multiplicity, NLO property, UPBE1PBE method

引用此文

李灼, 杜晓凤, 麻娜娜, 孙世玲, 仇永清. TTF^+·-π 共轭桥-6-氧四联氮阳离子双自由基NLO性质的理论研究[J]. 化学学报, 2012, 70(02): 107-113.

Li Zhuo, Du Xiaofeng, Ma Nana, Sun Shiling, Qiu Yongqing. Theoretical Study on NLO Properties of TTF^+·-π Conjugated Bridge-verdazyl Cation Diradicals[J]. Acta Chimica Sinica, 2012, 70(02): 107-113.

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参考文献

1 Prasad, P. N.; Williams, D. J. Introduction to Nonlinear Optical Effects in Molecules and Polymers, John Wiley & Sons, Inc., New York, 1991.

2 Marder, S. R.; Perry, J. W. Science 1994, 263, 1706.

3 Kanis, D. R.; Ratner, M. A.; Marks, T. J. Chem. Rev. 1994, 94, 195.

4 Li, Q.-Q.; Qin, J.-G.; Li, Z. Chin. J. Org. Chem. 2011, 31, 1337 (in Chinese). (李倩倩, 秦金贵, 李振, 有机化学, 2011, 31, 1337.)

5 Kang, H.; Evmenenko, G.; Dutta, P.; Clays, K.; Song, K.; Marks, T. J. J. Am. Chem. Soc. 2006, 128, 6194.

6 Nalwa, H. S. Adv. Mater. 1993, 5, 341.

7 Kawata, S.; Sun, H. B.; Tanaka, T.; Takada, K. Nature2001, 412, 697.

8 Breitung, E. M.; Shu, C.-F.; McMahon, R. J. J. Am. Chem. Soc. 2000, 122, 1154.

9 Andreu, R.; Blesa, M. J.; Carrasquer, L.; Garín, J.; Orduna, J.; Villacampa, B.; Alcalá, R.; Casado, J.; Delgado, M. C. R.; Navarrete, J. T. L.; Allain, M. J. Am. Chem. Soc. 2005, 127, 8835.

10 Liu, H.-B.; Qiu, Y.-Q.; Sun, S.-L.; Liu, C.-G.; Sun, X.-N. Acta Chim. Sinica 2010, 68, 2509 (in Chinese). (刘海波, 仇永清, 孙世玲, 刘春光, 孙晓娜, 化学学报, 2010, 68, 2509.)

11 Nakano, M.; Yamada, S.; Yamaguchi, K. Chem. Phys. Lett. 1999, 311, 221.

12 Champagne, B.; Botek, E.; Nakano, M.; Nitta, T.; Yamaguchi, K. J. Chem. Phys. 2005, 122, 114315.

13 Nakano, M.; Kishi, R.; Ohta, S.; Takebe, A.; Takahashi, H.; Furukawa, S.; Kubo, T.; Morita, Y.; Nakasuji, K.; Yamaguchi, K.; Kamada, K.; Ohta, K.; Champagne, B.; Botek, E. J. Chem. Phys. 2006, 125, 74113.

14 Ohta, S.; Nakano, M.; Kubo, T.; Kamada, K.; Ohta, K.; Kishi, R.; Nakagawa, N.; Champagne, B.; Botek, E.; Takebe, A.; Umezaki, S.; Nate, M.; Takahashi, H.; Furukawa, S.; Morita, Y.; Nakasuji, K.; Yamaguchi, K. J. Phys. Chem. A 2007, 111, 3633.

15 Nakano, M.; Champagne, B.; Botek, E.; Ohta, K.; Kamada, K.; Kubo, T. J. Chem. Phys. 2010, 133, 154302.

16 Nakano, M.; Minami, T.; Yoneda, K.; Muhammad, S.; Kishi, R.; Shigeta, Y.; Kubo, T.; Rougier, L.; Champagne, B.; Kamada, K.; Ohta, K. J. Phys. Chem. Lett. 2011, 2, 1094.

17 Polo, V.; Alberola, A.; Andres, J.; Anthony, J.; Pilkington, M. Phys. Chem. Chem. Phys. 2008, 10, 857.

18 Segura, J. L.; Martín, N. Angew. Chem. Int. Ed. 2001, 40, 1372.

19 Liu, C. G.; Guan, W.; Song, P.; Yan, L. K.; Su, Z. M. Inorg. Chem. 2009, 48, 6548.

20 Liu, C. G.; Guan, X. H.; Su, Z. M. J. Phys. Chem. C 2011, 115, 6024.

21 Fico Jr., R. M.; Hay, M. F.; Reese, S.; Hammond, S.; Lambert, E.; Fox, M. A. J. Org. Chem. 1999, 64, 9386.

22 de Graaf, C.; Sousa, C.; de P. R. Moreira, I.; Illas, F. J. Phys. Chem. A 2001, 105, 11371.

23 Rota, J.-B.; Norel, L.; Train, C.; Amor, N. B.; Maynau, D.; Robert, V. J. Am. Chem. Soc. 2005, 130, 10380.

24 Rota, J.-B.; Le Guennic, B.; Robert, V. Inorg. Chem. 2010, 49, 1230.

25 Sun, X.-N.; Qiu, Y.-Q.; Sun, S.-L.; Du, Y.-Q.; Su, Z.-M. Acta Chim. Sinica 2009, 67, 1718 (in Chinese). (孙晓娜, 仇永清, 孙世玲, 杜艳青, 苏忠民, 化学学报, 2009, 67, 1718.)

26 Suponitsky, K. Y.; Liao, Y.; Masunov, A. E. J. Phys. Chem. A 2009, 113, 10994.

27 Adamo, C.; Barone, V. J. Chem. Phys. 1999, 110, 6158.

28 Champagne, B.; Perpète, E. A.; Jacquemin, D. J. Phys. Chem. A 2000, 104, 4755.

29 Machado, A. E. de A.; De Sousa, L. A.; Dos Santos, H. F.; De Almeida, W. B. J. Polym. Sci., Part B: Polym. Phys. 2011, 49, 1410.

30 Ma, N. N.; Yang, G. C.; Sun, S. L.; Liu, C. G.; Qiu, Y. Q. J. Organomet. Chem. 2011, 696, 2380.

31 Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Scalmani, G.; Barone, V.; Mennucci, B.; Petersson, G. A.; Nakatsuji, H.; Caricato, M.; Li, X.; Hratchian, H. P.; Izmaylov, A. F.; Bloino, J.; Zheng, G.; Sonnenberg, J. L.; Hada, M.; Ehara, M.; Toyota, K.; Fukuda, R.; Hasegawa, J.; Ishida, M.; Nakajima, T.; Honda, Y.; Kitao, O.; Nakai, H.; Vreven, T.; Montgomery, J. A.; Jr.; Peralta, J. E.; Ogliaro, F.; Bearpark, M.; Heyd, J. J.; Brothers, E.; Kudin, K. N.; Staroverov, V. N.; Kobayashi, R.; Normand, J.; Raghavachari, K.; Rendell, A.; Burant, J. C.; Iyengar, S. S.; Tomasi, J.; Cossi, M.; Rega, N.; Millam, J. M.; Klene, M.; Knox, J. E.; Cross, J. B.; Bakken, V.; Adamo, C.; Jaramillo, J.; Gomperts, R.; Stratmann, R. E.; Yazyev, O.; Austin, A. J.; Cammi, R.; Pomelli, C.; Ochterski, J. W.; Martin, R. L.; Morokuma, K.; Zakrzewski, V. G.; Voth, G. A.; Salvador, P.; Dannenberg, J. J.; Dapprich, S.; Daniels, A. D.; Farkas, O.; Foresman, J. B.; Ortiz, J. V.; Cioslowski, J.; Fox, D. J. Gaussian 09, Revision A. 1, Gaussian, Inc., Wallingford, CT, 2009.

32 Dehu, C.; Meyers, F.; Brédas, J. L. J. Am. Chem. Soc. 1993, 115, 6198.

33 Qiu, Y. Q.; Qin, C. S.; Su, Z. M.; Yang, G. C.; Pan, X. M.; Wang, R. S. Synth. Met. 2005, 152, 273.

34 Qiu, Y. Q.; Fan, H. L.; Sun, S. L.; Liu, C. G.; Su, Z. M. J. Phys. Chem. A 2008, 112, 83.

35 Du, X.-F.; Sun, S.-L.; Liu, H.-B.; Sun, X.-N.; Qiu, Y.-Q. Acta Chim. Sinica 2011, 69, 1387 (in Chinese). (杜晓凤, 孙世玲, 刘海波, 孙晓娜, 仇永清, 化学学报, 2011, 69, 1387.)

36 McLean, A. D.; Yoshimine, M. J. Chem. Phys. 1967, 47, 1927.

37 Champagne, B. Chem. Phys. Lett. 1996, 261, 57.

38 Prigogine, I.; Rice, S. A. In Advances in Chemical Physics, Vol. 104, Ed.: Bishop, D. M., John Wiley & Sons, Inc., New York, 1998, pp. 1～40.

39 Romaniello, P.; D'Andria, M. C.; Lelj, F. J. Phys. Chem. A 2010, 114, 5838.

40 Kanis, D. R.; Ratner, M. A.; Marks, T. J. Chem. Rev. 1994, 94, 195.

41 Chahma, M.; Macnamara, K.; van der Est, A.; Alberola, A.; Polo, V.; Pilkington, M. New J. Chem. 2007, 31, 1973.

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TTF^+·-π 共轭桥-6-氧四联氮阳离子双自由基NLO性质的理论研究

Theoretical Study on NLO Properties of TTF^+·-π Conjugated Bridge-verdazyl Cation Diradicals

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TTF+·-π 共轭桥-6-氧四联氮阳离子双自由基NLO性质的理论研究

Theoretical Study on NLO Properties of TTF+·-π Conjugated Bridge-verdazyl Cation Diradicals

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TTF^+·-π 共轭桥-6-氧四联氮阳离子双自由基NLO性质的理论研究

Theoretical Study on NLO Properties of TTF^+·-π Conjugated Bridge-verdazyl Cation Diradicals