基于两种偶氮苯衍生物顺反构型的理论计算  

Theoretical Study on the Cis-Trans Configurations of Two Azobenzene Derivatives

作　　者：李珂庆 殷园园[1] 张祥 姜垒[1] 付阳[1] LI Keqing;YIN Yuanyuan;ZHANG Xiang;JIANG Lei;FU Yang(High&New Technology Research Center,Henan Academy of Sciences,Zhengzhou 450002,China)

机构地区：[1]河南省科学院高新技术研究中心,郑州450002

出　　处：《河南科学》2025年第4期512-517,共6页Henan Science

基　　金：河南省科学院高层次人才科研启动项目资助(241802039);河南省科技攻关计划项目(252102231011)。

摘　　要：偶氮苯衍生物作为典型的光异构分子,在光智能材料领域受到大家的青睐。其顺反构型可以通过可见光与紫外光的照射来相互转换,理论计算对光异构化过程的原理探索具有重要的作用,但目前鲜有报道对偶氮苯衍生物分子顺反构型的理论计算研究。通过DFT密度泛函理论对对二氨基偶氮苯衍生物的两种构型进行理论计算,利用B3LYP/6-31G(d)基组对两组顺反构型进行分子模拟优化。通过模拟分子前线轨道(LUMO轨道、HOMO轨道)、红外光谱(IR spectra)得出这两种构型在能量、分子前线轨道的分布以及红外光谱上有很大的差异,其中反式构型较为稳定。在红外光谱上,其1650~1500 cm^(-1)为仲胺的弯曲振动区域,可作为区分伯胺与仲胺的明显特征。同时利用福井函数(Fukui Function)和Mulliken电荷分布对偶氮苯衍生物G5进行计算模拟,预测了该化合物的反应位点,结果表明提供电子的区域主要集中在胺基上。以上结论为偶氮苯类化合物在反应位点的选择上提供了理论上的参考,也为更好地设计光智能材料提供了理论依据。Azobenzene derivatives,as typical photoisomers,are widely utilized in the field of optical intelligent materials.Its cis-trans configurations can interconvert under visible and ultraviolet light irradiation,and theoretical calculations play a crucial role in exploring the principles of the photoisomerization process.However,theoretical studies on the cis-trans configurations of diazo benzene derivatives remain limited.In this study,density functional theory(DFT)was employed to investigate the two configurations of diamino azobenzene derivatives.The B3LYP method was used with the 6-31G(d)basis set to optimize the molecular structures of the cis-trans configurations.Simulation of the molecular frontier orbitals(LUMO and HOMO)and infrared spectroscopy(IR spectra)revealed significant differences between the two configurations in terms of energy,molecular orbital distribution,and IR spectra,with the trans configuration exhibiting greater stability.In the infrared spectrum,the bending vibration region of secondary amines appears at 1650-1500 cm^(-1),serving as a distinct feature for differentiating primary and secondary amines.Additionally,the Fukui function and Mulliken charge distribution were employed to analyze the reactive sites of the diazo benzene derivative G5.Results indicated that electron-donating regions were primarily localized on the amino groups.These findings provide a theoretical basis for selecting reaction sites in azobenzene compounds and contribute to the improved design of optoelectronic materials.

关 键 词：偶氮苯衍生物 顺反构型 理论计算 密度泛函理论 

分 类 号：O641[理学—物理化学] O437[理学—化学]