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Triangular Halogen Bond and Hydrogen Bond Supramolecular Complex Consisting of Carbon Tetrabromide, Halide, and Solvent Molecule: A Theoretical and Spectroscopic Study
Yu-jie Wu,Xiao-ran Zhao,Hai-yue Gao,Wei-jun Jin*
Author NameAffiliationE-mail
Yu-jie Wu College of Chemistry, Beijing Normal University, Beijing 100875, China  
Xiao-ran Zhao College of Chemistry, Beijing Normal University, Beijing 100875, China  
Hai-yue Gao College of Chemistry, Beijing Normal University, Beijing 100875, China  
Wei-jun Jin* College of Chemistry, Beijing Normal University, Beijing 100875, China wjjin@bnu.edu.cn 
Abstract:
The theoretical calculation and spectroscopic experiments indicate a kind of triangu-lar three bonding supramolecular complexes CBr4…X-…H-C, which consist of carbon tetrabromide, halide, and protic solvent molecule (referring to dichloromethane, chloro-form and acetonitrile), can be formed in solution. The strength of halogen and hydro-gen bonds in the triangular complexes using halide as common acceptor obeys the order of iodide>bromide>chloride. The halogen and hydrogen bonds work weak-cooperatively. Charge transfer bands of halogen bonding complexes between CBr4 and halide are observed in UV-Vis absorption spectroscopy in three solvents, and then the stoichiometry of 1:1, for-mation constants K and molar extinction coefficients ? of the halogen bonding complexes are obtained by Benesi-Hildebrand method. The K and ? show a dependence on the solvent dielectric constant and, on the whole, obey an order of iodide>bromide>chloride in the same solvents. Furthermore, the C-H vibrational frequencies of solvent molecules vary obviously with the addition of halide, which indicates the C-H…X- interaction. The experimental data indicate that the halogen bond and hydrogen bond coexist by sharing a common halide acceptor as predicted by calculation.
Key words:  Halogen bond, Hydrogen bond, Halide, Carbon tetrabromide, Charge transfer
FundProject:
由四溴化碳、卤阴离子和溶剂分子组成的三角形卤键和氢键超分子复合物的理论与谱学研究
吴玉杰,赵晓冉,高海月,晋卫军*
摘要:
通过计算化学结合谱学实验揭示了四溴化碳与卤阴离子在质子溶剂中形成的CBr4…X-…H-C三角形的三键超分子复合物的作用模式. 卤键与氢键的强度均遵循:碘化物>溴化物>氯化物. 三键复合物中的卤键与氢键均呈现一定的协同效应. 紫外可见吸收光谱观察到四溴化碳与卤阴离子作用出现的新电荷转移峰,即卤键作用的吸收峰. 并利用Benesi-Hildebrand法确定了1:1的化学计量比、摩尔吸光系数及键合常数. 摩尔吸光系数及键合常数受溶剂的介电常数影响,在相同溶剂中遵循碘化物>溴化物>氯化物. 由键合常数表示的作用强度与理论计算的作用能相一致. 红外光谱测定的溶剂分子C-H振动频率随卤阴离子的加入有明显的红移,预示着C-H…X-氢键的形成. 实验与理论均证明这种通过共享卤阴离子的三键复合物的存在.
关键词:  卤键,氢键,卤阴离子,四溴化碳,电荷转移
DOI:10.1063/1674-0068/27/03/265-273
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