物理化学学报 >> 2015, Vol. 31 >> Issue (9): 1647-1654.doi: 10.3866/PKU.WHXB201506182

热力学,动力学和结构化学 上一篇    下一篇

N, N'-二-[3-羟基-4-(2-苯并噻唑)苯基]脲的光谱实验与密度泛函理论研究

崔颖娜1,*(),尹静梅1,2,贾颖萍1,李慎敏1,2,*()   

  1. 1 大连大学环境与化学工程学院,辽宁大连116622
    2 大连大学生物有机省重点实验室,辽宁大连116622
  • 收稿日期:2015-05-11 发布日期:2015-09-06
  • 通讯作者: 崔颖娜,李慎敏 E-mail:cuiyn2008@163.com;lishenmin@dlu.edu.cn
  • 基金资助:
    国家自然科学基金(21133005);辽宁省自然科学基金(201205535);辽宁省教育厅2010年度高等学校科研项目(重点实验室项目)(LS2010005)

Experimental and Density Functional Theoretical Studies on the Spectra of N, N'-di[3-hydroxy-4-(2-benzothiazole)phenyl]urea

Ying-Na. CUI1,*(),Jing-Mei. YIN1,2,Ying-Ping. JIA1,Shen-Min. LI1,2,*()   

  1. 1 College of Environment and Chemical Engineering, Dalian University, Dalian 116622, Liaoning Province, P. R. China
    2 Liaoning Key Laboratory of Bio-organic Chemistry, Dalian University, Dalian 116622, Liaoning Province, P. R. China
  • Received:2015-05-11 Published:2015-09-06
  • Contact: Ying-Na. CUI,Shen-Min. LI E-mail:cuiyn2008@163.com;lishenmin@dlu.edu.cn
  • Supported by:
    the National Natural Science Foundation of China(21133005);National Natural Science Foundation of LiaoningProvince, China(201205535);Scientific Research Foundation of the Higher Education Institutions of Education Bureau of Liaoning Province(Key Laboratory Project 2010), China(LS2010005)

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摘要：

利用实验观测与密度泛函理论(DFT)计算方法考察了新化合物N, N'-二-[3-羟基-4-(2-苯并噻唑)苯基]脲(4-DHBTU)的红外、核磁与紫外吸收光谱性质.与单体2-(4-氨基-2-羟苯基)苯并噻唑(4-AHBT)相比, 4-DHBTU的实验紫外吸收强度显著增强,最大吸收峰发生了明显红移,并呈现出双吸收峰特征.结合实验光谱数据与密度泛函理论计算分析表明, 4-DHBTU分子最稳定的基态异构体为cis-C11和trans-C11,而导致上述紫外光谱差异的主要原因是4-DHBTU样品中cis-C11, trans-C11, cis-C22, trans-C22等多种异构体共存.此外, 4-DHBTU与溶剂二甲基亚砜(DMSO)间氢键作用使得核磁实验中4-DHBTU的15H、16H氢谱化学位移显著增大.

关键词: N, N'-二-[3-羟基-4-(2-苯并噻唑)苯基]脲, 紫外光谱, 激发态, 密度泛函理论

Abstract:

The experimental infrared (IR), nuclear magnetic resonance (NMR), and ultraviolet (UV) spectra, and density functional theory (DFT) calculations of the novel compound N, N'-di[3-hydroxy-4-(2-benzothiazole) phenyl]urea (4-DHBTU) are presented. Compared with the UV spectra of the 2-(4-amino-2-hydroxyphenyl) benzothiazole (4-AHBT) monomer, the experimental spectra of 4-DHBTU, a dimer of 4-AHBT, show dualwavelength absorption with significantly enhanced absorption intensity and an obvious red shift of the maximum absorption peak. Analysis of the experimental spectra and the DFT calculations shows that the structures of cis-C11 and trans-C11 are the two most stable conformers, and that the main reason for the different UV spectral properties of the dimer and monomer is the coexistence of cis-C11, trans-C11, cis-C22, and trans-C22 in the 4-DHBTU sample. In addition, the DFT calculations indicate that a hydrogen-bonding interaction between 4-DHBTU and the dimethyl sulfoxide (DMSO) solvent leads to a large 1H NMR chemical shift for atoms 15H and 16H in 4-DHBTU.

Key words: N, N'-di[3-hydroxy-4-(2-benzothiazole)phenyl]urea, Ultraviolet spectroscopy, Excited state, Density functional theory