间位基团激发态取代基常数的扩展及应用

doi:10.3866/PKU.WHXB201611291

物理化学学报 >> 2017, Vol. 33 >> Issue (4): 729-735.doi: 10.3866/PKU.WHXB201611291

间位基团激发态取代基常数的扩展及应用

朱倩,曹朝暾,曹晨忠*()

湖南科技大学化学化工学院,理论有机化学与功能分子教育部重点实验室,分子构效关系湖南省普通高校重点实验室,湖南湘潭411201

收稿日期:2016-10-13 发布日期:2017-03-23
通讯作者: 曹晨忠 E-mail:czcao@hnust.edu.cn
基金资助:
国家自然科学基金(21272063);国家自然科学基金(21672058);湖南省教育厅科研项目(14C0466);国家自然科学基金(湖南省自然科学基金)

Extension and Application of Excited-State Constants of meta-Substituents

Qian ZHU,Chao-Tun CAO,Chen-Zhong CAO*()

Key Laboratory of Theoretical Organic Chemistry and Function Molecule, Ministry of Education, Hunan Provincial University Key Laboratory of QSAR/QSPR, School of Chemistry and Chemical Engineering, Hunan University of Science and Technology, Xiangtan 411201, Hunan Province, P. R. China

Received:2016-10-13 Published:2017-03-23
Contact: Chen-Zhong CAO E-mail:czcao@hnust.edu.cn
Supported by:
The project was supported by the National Natural Science Foundation of China(21272063);The project was supported by the National Natural Science Foundation of China(21672058);Scientific Research Fund of Hunan Provincial Education Department, China(14C0466);Natural Science Foundation of Hunan Province, China(湖南省自然科学基金)

摘要/Abstract

摘要：

合成了七个系列含间位取代基X的二苯乙烯m-XArCH=CHArY-p（简称m-XSBY-p），其中X为NO₂、I、CHCH₂、Ph、Et、NMe₂和CCH。在无水乙醇中测定它们的紫外（UV）吸收光谱，得到紫外吸收最大波长λ_max（nm）。对λ_max的波数V_max（cm^-1）进行定量相关，采用曲线拟合方法，得到上述7个间位基团的激发态取代基常数σ_CC（m）^ex。将对位基团和间位基团的σ_CC^ex与Hammett常数σ进行对比，表明σ_CC^ex与σ分别表达取代基不同的电子效应。另外，合成了含上述间位基团的二芳基希夫碱（10个）和二苯乙烯（14个），用所得σ_CC（m）^ex预测它们的λ_max，并用实验测定它们的λ_max，结果表明预测值与实验值相吻合，验证了所得σ_CC（m）^ex常数的可靠性。收集了225个化合物（涉及二取代苯及二苯乙烯）的V_max，建立了一个统一的定量方程来表达这些化合物V_max的变化规律。

关键词: 激发态常数, 间位基团, 紫外吸收光谱, 二苯乙烯, 二芳基希夫碱

Abstract:

Seven series of 3, 4'-disubstituted stilbenes were synthesized, with meta-substituents X (m-XSBYp) including: NO₂, I, CHCH₂, Ph, Et, NMe₂, and CCH (m-XSBY-p). The longest wavelength maximum λ_max (nm) in ultraviolet absorption spectra of the compounds were measured. A quantitative correlation analysis was performed in terms of energy, the V_max (cm^-1) for 3, 4'-disubstituted stilbenes. The excited-state substituent constants σ_{CC (m)}^exof the seven meta-substituents were determined by curve-fitting. The constants σ_CC^exof the metaand para-substituents were compared with their Hammett constants σ. The results indicated that σ_CC^exand σ express the substituent electrostatic effects in the excited-and ground-states, respectively. In addition, 10 samples of aryl Schiff bases and 14 samples of 3, 3'-disubstituted stilbenes with meta-substituents X were synthesized, and their λ_max, pred. were predicated based on the obtained constants σ_{CC (m)}^ex. These results showed that the λ_max, pred. values agreed well with the experimental values, and confirmed the reliability of the obtained σ_{CC (m)}^exvalues. We also collected V_max values of 225 samples of disubstituted stilbenes and disubstituted benzenes and established a general quantitative equation to express the change regularity of their V_max.

Key words: Excited-state substituent constant, meta-Substituent, Ultraviolet absorption spectrum, Stilbene, Aryl Schiff base

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朱倩,曹朝暾,曹晨忠. 间位基团激发态取代基常数的扩展及应用[J]. 物理化学学报, 2017, 33(4): 729-735.

Qian ZHU,Chao-Tun CAO,Chen-Zhong CAO. Extension and Application of Excited-State Constants of meta-Substituents[J]. Acta Phys. -Chim. Sin., 2017, 33(4): 729-735.

链接本文: https://www.whxb.pku.edu.cn/CN/10.3866/PKU.WHXB201611291

https://www.whxb.pku.edu.cn/CN/Y2017/V33/I4/729

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间位基团激发态取代基常数的扩展及应用

Extension and Application of Excited-State Constants of meta-Substituents

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