Citation: GUO Xiao-Nan, DU Rui, ZHAO Yan-Ying, PEI Ke-Mei, WANG Hui-Gang, ZHENG Xu-Ming. Dynamic Structures of 2-Thiopyrimidone and 2-Thiopyridone in B-Band Absorptions[J]. Acta Physico-Chimica Sinica, ;2012, 28(07): 1570-1578. doi: 10.3866/PKU.WHXB201204173 shu

Dynamic Structures of 2-Thiopyrimidone and 2-Thiopyridone in B-Band Absorptions

1.
1. Department of Chemistry, Zhejiang Sci-Tech University, Hangzhou 310018, P. R. China;
2. Key Laboratory of Advanced Textiles Materials and Manufacturing Technology of the Ministry of Education, Zhejiang Sci-Tech University, Hangzhou 310018, P. R. China;
3. Engineering Research Center for Eco-dyeing and Finishing of Textiles of the Ministry of Education, Zhejiang Sci-Tech University, Hangzhou 310018, P. R. China

Received Date: 7 February 2012
Available Online: 17 April 2012
Fund Project: 国家自然科学基金(21033002) (21033002)国家重点基础研究发展规划项目(973) (2007CB815203)资助 (973) (2007CB815203)

The dynamic structures of 2-thiopyrimidone (2TPM) and 2-thiopyridone (2TP) in B-band absorptions were studied using the resonance Raman spectroscopy combined with quantum chemical calculations. In gas phase, 2-thiopyrimidine (2MPM, the thiol form) was more stable than 2TPM (the thione form) by ~15.1 kJ·mol^-1, whereas in water and acetonitrile 2TPM was more stable than 2MPM by 29.3 and 28.0 kJ·mol^-1, respectively. The transition barrier for the ground state proton transfer tautomerization reaction between 2TPM and 2MPM was ~130 kJ·mol^-1 in gas phase on the basis of the B3LYP/6-311++ G(d,p) level of theory calculations. The three absorption bands of 2-thiopyrimidone were respectively assigned as π_H→π_L^*, π_H→π_L+1^*, and π_H-1→π_L^* transitions. The vibrational assignments were carried out for the B-band resonance Raman spectra of 2TPM in water and acetonitrile solvents on the basis of the measurements from the Fourier transform (FT)-Raman and Fourier transform-infrared (FT-IR) spectra of 2TPM in solid and/or in solution phases and B3LYP/6-311++G(d,p) computations. The dynamic structures of 2TPM and 2TP were obtained by analysis of the resonance Raman intensity pattern. The differences in the dynamic structures of 2TPM and 2TP reflected differences in the structures of their ππ^*/πσ^* conical intersection points, and therefore could be used to provide insight into the photoinduced hydrogen-atom detachment-attachment mechanism.
- Thiol-thione phototautomeric reaction,
- Resonance Raman spectroscopy,
- Conical intersection,
- Excited-state structural dynamics,
- Vibrational spectrum,
- Density functional theory
1. [1]
  
  (1) Nimlos, M. R.; Kelley, D. F.; Bernstein, E. R. J. Phys. Chem.1989, 93, 643. doi: 10.1021/j100339a030
2. [2]
  (2) Held, A.; Pratt, D.W. J. Am. Chem. Soc. 1993, 115, 9708. doi: 10.1021/ja00074a042
3. [3]
  (3) Matsuda, Y.; Ebata, T.; Mikami, N. J. Chem. Phys. 1999, 110,8397. doi: 10.1063/1.478748
4. [4]
  (4) Matsuda, Y.; Ebata, T.; Mikami, N. J. Chem. Phys. 2000, 113,573. doi: 10.1063/1.481833
5. [5]
  (5) Matsuda, Y.; Ebata, T.; Mikami, N. J. Phys. Chem. A 2001, 105,3475. doi: 10.1021/jp003272x
6. [6]
  (6) Nowak, M. J.; Lapinski, L.; Fulara, J.; Les, A.; Adamowicz, L.J. Phys. Chem. 1992, 96, 1562. doi: 10.1021/j100183a015
7. [7]
  (7) Beak, P. Accounts Chem. Res. 1977, 10, 186. doi: 10.1021/ar50113a006
8. [8]
  (8) Hatherley, L. D.; Brown, R. D.; dfrey, P. D.; Pierlot, A. P.;Caminati,W.; Damiani, D.; Melandri, S.; Favero, L. B. J. Phys. Chem. 1993, 97, 46. doi: 10.1021/j100103a011
9. [9]
  (9) Sanchez, R.; Giuliano, B. M.; Melandri, S.; Favero, L. B.;Caminati,W. J. Am. Chem. Soc. 2007, 129, 6287. doi: 10.1021/ja070712q
10. [10]
  (10) Fujimoto, A.; Inuzuka, K.; Shiba, R. Bull. Chem. Soc. Jpn.1981, 54, 2802. doi: 10.1246/bcsj.54.2802
11. [11]
  (11) Sakota, K.; Tokuhara, S.; Sekiya, H. Chem. Phys. Lett. 2007,448, 159. doi: 10.1016/j.cplett.2007.09.085
12. [12]
  (12) Florio, G. M.; Gruenloh, C. J.; Quimpo, R. C.; Zwier, T. S.J. Chem. Phys. 2000, 113, 11143. doi: 10.1063/1.1324613
13. [13]
  (13) Moreno, M.; Miller,W. H. Chem. Phys. Lett. 1990, 171, 475.doi: 10.1016/0009-2614(90)85249-C
14. [14]
  (14) Sobolewski, A. L. Chem. Phys. Lett. 1993, 211, 82. doi: 10.1016/0009-2614(93)80055-T
15. [15]
  (15) Barone, V.; Adamo, C. Chem. Phys. Lett. 1994, 226, 399. doi: 10.1016/0009-2614(94)00744-6
16. [16]
  (16) Barone, V.; Adamo, C. J. Phys. Chem. 1995, 99, 15062. doi: 10.1021/j100041a022
17. [17]
  (17) Sobolewski, A. L.; Adamowicz, L. J. Phys. Chem. 1996, 100,3933. doi: 10.1021/jp950852z
18. [18]
  (18) Li, Q. S.; Fang,W. H.; Yu, J. G. J. Phys. Chem. A 2005, 109,3983. doi: 10.1021/jp044498t
19. [19]
  (19) Wang, J.; Boyd, R. J. J. Phys. Chem. 1996, 100, 16141. doi: 10.1021/jp961295z
20. [20]
  (20) Del Bene, J. E. J. Am. Chem. Soc. 1995, 117, 1607. doi: 10.1021/ja00110a016
21. [21]
  (21) Chou, P. T.;Wei, C. Y.; Hung, F. T. J. Phys. Chem. B 1997, 101,9119. doi: 10.1021/jp971824e
22. [22]
  (22) Dkhissi, A.; Adamowicz, L.; Maes, G. J. Phys. Chem. A 2000,104, 2112. doi: 10.1021/jp9938056
23. [23]
  (23) Esboui, M.; Nsan u, M.; Jaidane, N.; Ben Lakhdar, Z. Chem. Phys. 2005, 311, 277. doi: 10.1016/j.chemphys.2004.11.022
24. [24]
  (24) Krebs, C.; Forster,W.;Weiss, C.; Hofmann, H. J. J. Prakt. Chem. 1982, 324, 369. doi: 10.1002/prac.19823240304
25. [25]
  (25) Esboui, M.; Jaidane, N.; Ben Lakhdar, Z. Chem. Phys. Lett.2006, 430, 195. doi: 10.1016/j.cplett.2006.08.119
26. [26]
  (26) Lowdin, P. O. Rev. Mol. Phys. 1963, 35, 724. doi: 10.1103/RevModPhys.35.724
27. [27]
  (27) Pullman, B.; Pullman, A. Adv. Heterocycl. Chem. 1971, 13, 77.doi: 10.1016/S0065-2725(08)60349-9
28. [28]
  (28) Beak, P.; Covington, J. B.; Smith, S. G. J. Am. Chem. Soc. 1976,98, 8284. doi: 10.1021/ja00441a079
29. [29]
  (29) Beak, P.; Fry, F. S., Jr.; Lee, J.; Steele, F. J. Am. Chem. Soc.1976, 98, 171. doi: 10.1021/ja00417a027
30. [30]
  (30) Melandri, S.; Evangelisti, L.; Maris, A.; Caminati,W.; Giuliano,B. M.; Feyer, V.; Prince, K. C.; Coreno, M. J. Am. Chem. Soc.2010, 132, 10269. doi: 10.1021/ja104484b
31. [31]
  (31) Jones, P. A.; Katritzky, A. R. J. Chem. Soc. 1958, 3610.
32. [32]
  (32) Katritzky, A. R.; Jones, R. A. J. Chem. Soc. 1960, 2937.
33. [33]
  (33) Cook, M. J.; Katritzky, A. R.; Linda, P.; Tack, R. D. J. Chem. Soc. Perkin Trans. 1972, 2, 1295.
34. [34]
  (34) Albert, A.; Barlin, G. B. J. Chem. Soc. 1959, 2384.
35. [35]
  (35) Stoyanov, S.; Petkov, I.; Antonov, L.; Stoyanova, T.;Karagiannidis, P.; Aslanidis, P. Can. J. Chem. 1990, 68, 1482.doi: 10.1139/v90-227
36. [36]
  (36) Barlin, G. B.; Brown, D. J.; Fenn, M. D. Aust. J. Chem. 1984,37, 2391. doi: 10.1071/CH9842391
37. [37]
  (37) Spinner, E. J. Chem. Soc. 1960, 1237.
38. [38]
  (38) Lapinski, L.; Nowak, M. J.; Fulara, J.; Les, A.; Adamowicz, L.J. Phys. Chem. 1992, 96, 6250. doi: 10.1021/j100194a030
39. [39]
  (39) Contreras, J. G.; Alderete, J. B. J. Mol. Struct. -Theochem 1991,231, 257. doi: 10.1016/0166-1280(91)85224-U
40. [40]
  (40) Pang, Y. S.;Wang, H. J.; Kim, M. S. J. Mol. Struct. 1998, 441,63. doi: 10.1016/S0022-2860(97)00280-9
41. [41]
  (41) Colthup, N. B.; Daly, L. H.;Wiberley, S. E. Introduction to Infrared and Raman Spectroscopy, 3rd ed.; Academic Press:New York, 1990.
42. [42]
  (42) Santhayanarayana, D. N. Vibrational Spectroscopy: Theory and Applications; New Age International Publishers: New Delhi,2004; pp 452-453.
43. [43]
  (43) Krishnakumar, V.; Xavier, R. J. Spectrochimica Acta Part A2006, 63, 454. doi: 10.1016/j.saa.2005.05.031
44. [44]
  (44) Abdulla, H. I.; El-Bermani, M. F. Spectrochimica Acta Part A2001, 57, 2659. doi: 10.1016/S1386-1425(01)00455-3
45. [45]
  (45) Lima, M. C. P.; Coutinho, K.; Canuto, S.; Rocha,W. R. J. Phys. Chem. A 2006, 110, 7253. doi: 10.1021/jp060821b
46. [46]
  (46) Penfold, B. R. Acta Crystallogr. 1953, 6, 707. doi: 10.1107/S0365110X5300199X
47. [47]
  (47) Ohms, U.; Guth, H.; Kutoglu, A.; Scheringer, C. Acta Crystallogr. Section B 1982, 38, 831. doi: 10.1107/S0567740882004166
48. [48]
  (48) Aksnes, D.W.; Kryvi, H. Acta Chim. Scand. 1972, 26, 2255.doi: 10.3891/acta.chem.scand.26-2255
49. [49]
  (49) Nowak, M. J.; Rotkowska, H.; Lapinski, L.; Leszczynski, J.;Kwiatkowski, J. S. Spectrochimica Acta Part A 1991, 47, 339.doi: 10.1016/0584-8539(91)80112-V
50. [50]
  (50) Gronneberg, T.; Undheim, K. Org. Mass Spectrom. 1972, 6,823. doi: 10.1002/oms.1210060713
51. [51]
  (51) Maquestiau, A.; Haverbeke, Y. V.; Meyer, C. D.; Katritzky, A.R.; Cook, M. J.; Page, A. D. Can. J. Chem. 1975, 53, 490. doi: 10.1139/v75-068
52. [52]
  (52) Cook, M. J.; El-Abbady, S.; Katritzky, A. R.; Guimon, C.;Pfister-Guillouzo, G. J. Chem. Soc. Perkin Trans. 2 1977, 2,1652.
53. [53]
  (53) Zhu, X. M.; Zhang, S. Q.; Zheng, X. M.; Phillips, D. L. J. Phys. Chem. A 2005, 109, 3086. doi: 10.1021/jp0444114
54. [54]
  (54) Weng, K. F.; Shi, Y.; Zheng, X. M.; Phillips, D. L. J. Phys. Chem. A 2006, 110, 851. doi: 10.1021/jp055069d
55. [55]
  (55) Frisch, M. J.; Trucks, G.W.; Schlegel, H. B.; et al. Gaussian 03, Revision B.02; Gaussian Inc.: Pittsburgh, PA, 2003.
56. [56]
  (56) Du, R.; Liu, C.; Zhao, Y. Y.; Pei, K. M.;Wang, H. G.; Zheng, X.M.; Li, M. D.; Xue, J. D.; Phillips, D. L. J. Phys. Chem. B 2011,115, 8266. doi: 10.1021/jp203185a
57. [57]
  (57) Sobolewski, A. L.; Domcke,W.; Dedonder-Ladeux, C.; Jouvet,C. Phys. Chem. Chem. Phys. 2002, 4, 1093.
58. [58]
  (58) Nowak, M. J.; Lapinski, L.; Fulara, J.; Les, A.; Adamowicz, L.J. Phys. Chem. 1991, 95, 2404. doi: 10.1021/j100159a053
59. [59]
  (59) Nowak, M. J.; Lapinski, L.; Rostkowska, H.; Les, A.;Adamowicz, L. J. Phys. Chem. 1990, 94, 7406. doi: 10.1021/j100382a018
60. [60]
  (60) Rostkowska, H.; Lapinski, L.; Nowak, M. J. J. Phys. Org. Chem. 2010, 23, 56.
61. [61]
  (61) Chmura, B.; Rode, M. F.; Sobolewski, A. L.; Lapinski, L.;Nowak, M. J. J. Phys. Chem. A 2008, 112, 13655.
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