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本文采用DFT-B3LYP和MP2(full)方法对三聚体Cl–…苯氰…H2O中O/C–H…Cl–阴离子氢键与传统氢键O–H…N和C–H…O之间的协同效应、热力学性质以及芳香性进行了研究.结果表明阴离子氢键O/C–H…Cl–对O–H…N或C–H…O相互作用的影响更显著.在线性结构中发生正协同效应,熵变是促进热力学协同效应的主要因素,而在环状结构中发生反协同效应,焓变成为主要因素.在三聚体形成过程中,苯氰环的芳香性是减弱的,而苯氰中π→π*共轭效应是增强的.结果表明,协同效应能Ecoop.分别与Rc(NICS(1)ternary/NICS(1)binary),ΔΔδ(Δδternary-Δδbinary),Rc’((NICS(1)ternary-NICS(1)binary)/NICS(1)binary)和RBDE(C–CN)(BDE(C–CN)ternary/BDE(C–CN)binary)均具有良好的线性关系.同时,AIM的分析也佐证了协同效应的存在.
In this paper, the DFT-B3LYP and MP2 (full) methods were applied to the O / C-H ... Cl- anion hydrogen bond in the trimer Cl- ... benzene cyano ... H2O and the traditional hydrogen bonds O-H ... N and C-H ... O The synergistic effect, the thermodynamic properties and the aromaticity were studied.The results show that the anion hydrogen bond O / C-H ... Cl- has a more significant effect on the interaction of O-H ... N or C-H ... O In the linear structure Positive synergistic effect occurs, and entropy change is the main factor to promote the synergistic effect of thermodynamics. In the anti-synergistic effect in the ring structure, the enthalpy becomes the main factor. During the formation of trimer, the aromaticity of the benzene ring is weakened , While the π → π * conjugation effect was enhanced in benzene cyanogens.The results showed that the synergistic effect can be related to Rc (NICS (1) ternary / NICS (1) binary), ΔΔδ (Δδternary-Δδbinary) (NICS (1) ternary-NICS (1) binary) / NICS (1) binary and RBDE (C-CN) BDE (C-CN) ternary / BDE (C-CN) binary all have good Linear relationship at the same time, AIM analysis also corroborated the existence of synergies.