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Acta Chimica Sinica >

2012 , Vol. 70 >Issue 06: 699 - 706

DOI: https://doi.org/10.6023/A1108092

Special Topic

Theoretical Study on Excited-State Intramolecular Proton Transfer of 2-(2'-Aminophenyl)benzimidazole Derivatives: Substituent Effect

  • Yi Pinggui ,
  • Zhou Jiming ,
  • Yu Xianyong ,
  • Wang Zhaoxu ,
  • Li Xiaofang ,
  • Liu Zhengjun ,
  • Hou Bo
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  • Key Laboratory of Theoretical Chemistry and Molecular Simulation of Ministry of Education, Hunan Province College Key Laboratory of QSAR/QSPR, School of Chemistry and Chemical Engineering, Hunan University of Science and Technology, Xiangtan 411201

Received date: 2011-08-09

  Revised date: 2011-11-20

  Online published: 2011-12-06

Supported by

Project supported by the National Natural Science Foundation of China (Nos. 21172066, 20272077, 20803020), Scientific Research Fund of Hunan Provincial Education Department (No. 09K081), and Hunan Provincial Natural Science Foundation of China (No. 11JJ2007).

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Abstract

The effects of chemical substitution on the ground and excited state intramolecular proton transfer (ESIPT) of 2-(2'-aminophenyl)benzimidazole (APBI) have been theoretically studied when a hydrogen atom of the amino group was replaced by CH3 (E-C), SiH3 (E-OSi), NH2 (E-N), COH (E-CO), NO2 (E-NO2), CF3 (E-F), CN (E-CN3), OMe (E-OMe), COCH3 (E-CC), Ts (E-S), p-CH3C6H4CO (E-C＝O) and p-CH3C6H4NHCO (E-NH). The results show that in ground state the most stable configuration is the enolic form E; sub-stable configuration is the rotational isomer R. The keto form K only exists in the ground state when substituents is E-CN3, E-F, E-NO2, E-N or E-OMe. The results of nucleus independent chemical shifts (NICS) show that substituents affect electron delocalization of the APBI ring. Excited state proton transfer potential energy surface studies have shown that intramolecular proton transfer of all the derivatives could occur in excited state. The ESIPT of the APBI is barrierless process in S1 state when introducing the substituents E-CN3, E-N, or E-OMe. There is almost no effect on ESIPT when introducing the substituents E-C,E-C＝O or E-OSi. The K* configuration become more stable than E* in S1 state when substitutent is E-CC, E-NH, E-CO, E-F, E-NO2, or E-S.

Key words： 2-(2'-aminophenyl)benzimidazole derivatives; ESIPT; substituent effect; electron delocalization

Cite this article

Yi Pinggui , Zhou Jiming , Yu Xianyong , Wang Zhaoxu , Li Xiaofang , Liu Zhengjun , Hou Bo . Theoretical Study on Excited-State Intramolecular Proton Transfer of 2-(2'-Aminophenyl)benzimidazole Derivatives: Substituent Effect[J]. Acta Chimica Sinica, 2012 , 70(06) : 699 -706 . DOI: 10.6023/A1108092

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