高等学校化学学报

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三联吡啶化合物的溶剂致荧光变色及丁醇异构体鉴别

常慧1, 姚双全2, 韩文佳3, 康榭娜4, 张力4, 李新平4, 张召4,5()   

  1. 1.陕西科技大学机电工程学院, 西安 710021
    2.广西大学轻工与食品工程学院, 广西清洁化制浆造纸与污染控制重点实验室, 南宁 530004
    3.齐鲁工业大学(山东省科学院)生物基材料与绿色造纸国家重点实验室, 济南 250353
    4.陕西科技大学轻工科学与工程学院, 轻化工程国家级实验教学示范中心, 陕西省造纸技术及特种纸品开发重点实验室, 西安 710021
    5.华南理工大学制浆造纸工程国家重点实验室, 广州 510640
  • 收稿日期:2020-08-07
  • 通讯作者: 张召 E-mail:zhangzhaoqg@sust.edu.cn
  • 基金资助:
    国家自然科学基金(批准号(21703131);31370578)、 广西清洁化制浆造纸与污染控制重点实验室开放基金(批准号(2019KF18);2019KF33)、 生物基材料与绿色造纸国家重点实验室开放基金(KF201918);制浆造纸工程国家重点实验室开放基金(201821)

Highly Solvatochromic Terpyridine Compounds for Identification of Butanol Isomers

CHANG Hui1, YAO Shuangquan2, HAN Wenjia3, KANG Xiena4, ZHANG Li4, LI Xinping4, ZHANG Zhao4,5()   

  1. 1.College of Mechanical and Electrical Engineering,Sha’anxi University of Science and Technology,Xi’an 710021,China
    2.Guangxi Key Laboratory of Clean Pulp & Papermaking and Pollution Control,College of Light Industry and Food Engineering,Guangxi University,Nanning 530004,China
    3.State Key Laboratory of Biobased Material and Green Papermaking,Qilu University of Technology,Shandong Aca?demy of Sciences,Jinan 250353,China
    4.College of Bioresources Chemical and Materials Engineering,National Demonstration Center for Experimental Light Chemistry Engineering Education,Shaanxi Provincal Key Laboratory of Popermaking Technology and Specialty Paper Development,Shaanxi University of Science and Technology,Xi’an 710021,China
    5.State Key Laboratory of Pulp and Paper Engineering,South China University of Technology,Guangzhou 510640,China
  • Received:2020-08-07
  • Contact: ZHANG Zhao E-mail:zhangzhaoqg@sust.edu.cn

摘要:

在三联吡啶分子中引入N,N-二甲基官能团, 实现了三联吡啶分子的局部激发态发光. 研究发现, 溶剂的极性诱导三联吡啶的偶极矩发生变化, 实现了从深蓝光(λmax=384 nm)到黄光(λmax=558 nm)的溶剂致荧光变色. 由于三联吡啶的荧光易受醇溶剂中—OH基团振荡猝灭, 不同空间位阻的正丁醇、 异丁醇、 仲丁醇及叔丁醇溶剂使得三联吡啶发光光色相近, 但发光强度的差异较大. 三联吡啶进一步与ZnCl2配位得到了三联吡啶-Zn(Ⅱ)配合物, 金属离子Zn(Ⅱ)的配位作用促进了三联吡啶分子内电荷转移. 由于电子给体N,N-二甲基官能团可发生平面扭曲, 丁醇异构体可调节三联吡啶-Zn(Ⅱ)的局部激发态和扭曲分子内电荷转移发光, 进而实现其在丁醇异构体溶剂中发光光色的调节. 因此, 三联吡啶和三联吡啶-Zn(Ⅱ)具有良好的溶剂致荧光变色性能, 可应用于4种丁醇异构体的鉴别.

关键词: 溶剂致荧光变色, 三联吡啶, 丁醇异构体鉴别, 局部激发态, 扭曲分子内电荷转移

Abstract:

NN-Dimethyl functional group was introduced into the terpyridine molecule to realize the locally excited state luminescence of the terpyridine molecule. It was found that the polarity of the solvent induced a change in the dipole moment of terpyridine, achieving solvent-induced fluorescence discoloration from deep blue light(λmax=384 nm) to yellow light(λmax=558 nm). As the fluorescence of terpyridine is easily quenched by the oscillation of —OH group in alcohol solvent, the n-butanol, iso-butanol, sec-butanol and tert-butanol solvents with different steric hindrances make the light color of terpyridine close, while the luminous intensity difference is greater. The terpyridine is further coordinated with ZnCl2 to obtain the terpyridine-Zn(Ⅱ) complex. The coordination of the metal ion Zn(Ⅱ) promotes the charge transfer within the terpyridine molecule. Since the NN-dimethyl functional group, as the electron donor can undergo plane distortion, the butanol isomers can adjust the locally excited and twisted intramolecular charge transfer of terpyridine-Zn(Ⅱ), and then realize the adjustment of its light color in butanol isomer solvent. Terpyridine and terpyridine-Zn(Ⅱ) have good solvent-induced fluorescence discoloration properties, and can be used to identify four butanol isomers.

Key words: Solvatochromism, Terpyridine, Butanol isomers identification, Local excitation, Twisted intramolecular charge transfer

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