间位基团激发态取代基常数的扩展及应用

引用本文: 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. doi: 10.3866/PKU.WHXB201611291 shu

Citation: ZHU Qian, CAO Chao-Tun, CAO Chen-Zhong. Extension and Application of Excited-State Constants of meta-Substituents[J]. Acta Physico-Chimica Sinica, 2017, 33(4): 729-735. doi: 10.3866/PKU.WHXB201611291 shu

间位基团激发态取代基常数的扩展及应用

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
基金项目:
国家自然科学基金（21272063，21672058），湖南省教育厅科研项目（14C0466）和湖南省自然科学基金（14JJ3112）资助

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:

English

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

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 Date: 13 October 2016
Revised Date: 29 November 2016
Available Online: 29 November 2016
Fund Project:
The project was supported by the National Natural Science Foundation of China (21272063, 21672058), Scientific Research Fund of Hunan Provincial Education Department, China (14C0466), and Natural Science Foundation of Hunan Province, China (14JJ3112).

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)^ex of the seven meta-substituents were determined by curve-fitting. The constants σ_CC^ex of the metaand para-substituents were compared with their Hammett constants σ. The results indicated that σ_CC^ex and 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)^ex values. 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.

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间位基团激发态取代基常数的扩展及应用

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

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间位基团激发态取代基常数的扩展及应用

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

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

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CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

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