高等学校化学学报

高等学校化学学报

• 研究论文 • 上一篇    下一篇

苯甘氨酸修饰的聚(二苯基乙炔)：条件依赖的手性传递与聚集诱导发光增强效应

胡浩渊1，胡广泽1，刘雄1，陈曼玉1，张浩可1，2，孙景志1,2，唐本忠3   

  1. 1. 浙江大学高分子科学与工程学系，高分子合成与功能构造教育部重点实验室

    2. 浙江大学绍兴研究院，大健康材料中心 3. 香港中文大学（深圳）理工学院聚集体科学卓越基础研究中心

  • 收稿日期:2025-10-12 修回日期:2025-12-18 出版日期:2025-12-19 发布日期:2025-12-19
  • 通讯作者: 孙景志 E-mail:sunjz@zju.edu.cn
  • 基金资助:
    国家自然科学基金委员会；项目名称：双取代乙炔共聚合探索（批准号：22071215）

Phenylglycine modified poly(diphenylacetylene): Condition-dependent chiral transmission and aggregation-induced emission enhancement

Hu Haoyuan1, Hu Guangze1, Liu Xiong1, Chen Manyu1, Zhang Haoke1,2, Sun Jingzhi1,2,  Tang Benzhong3#br#   

  1. 1. MoE Key Laboratory of Macromolecular Synthesis and Functionalization, Department of Polymer Science and Engineering, Zhejiang University

    2. Centre of Healthcare Materials, Shaoxing Institute, Zhejiang University 3. Guangdong Basic Research Center of Excellence for Aggregate Science, School of Science and Engineering, The Chinese University of Hong Kong

  • Received:2025-10-12 Revised:2025-12-18 Online:2025-12-19 Published:2025-12-19
  • Supported by:
    Supported by the National Natural Science Foundation of China, (Exploration of Copolymerization of Di-substituted Acetylenes, Grant (No. 22071215)

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摘要： 采用聚合后修饰方法制备了D-/L--苯甘氨酸侧链修饰的聚二苯基乙炔衍生物（P-D和P-L），运用综合光谱技术对其结构进行了表征.通过精确地控制了聚合物中苯甘氨酸的种类和含量，使产物表现出独特的组成和溶剂依赖行为，均聚物P-L和P-D均未检测到圆二色性（CD）信号，而部分被苯甘氨酸取代的聚合物表现出依赖于共聚物组成和溶剂的诱导 CD 信号. 在四氢呋喃（THF）和二氯甲烷（DCM）溶液中的 P-L（1:19）、在 THF 和二甲基亚砜（DMSO）混合溶液中的 P-D（1:19）和 P-D（1:39）（括号中的数字表示被L-/D-苯甘氨酸取代的侧基与活化酯侧基的比例）. 除旋光活性外，这些聚二苯基乙炔衍生物还表现出典型的聚集增强发光（AEE）行为。在 THF/DMSO 混合溶剂中，P-L（1:19）的荧光强度的提高超过220%. 与侧链组成和溶剂相关的手性传递及AEE效应与苯甘氨酸侧链之间的强相互作用有关，导致聚二苯基乙炔主链的构象硬化，并且阻碍了手性从侧链向主链的传递. 同时，强的侧链相互作用限制了分子内运动对激发态能量的耗散，导致荧光增强，这些实验结果与密度泛函理论（DFT）和分子动力学（MD）模拟结果相一致.

关键词: 聚二苯基乙炔, 聚合后修饰, 圆二色性, 聚集诱导发光增强, 氢键

Abstract: Polydiphenylacetylenes (PDPAs) modified with D-/L-phenylglycine side chains have been prepared by post-polymerization modification strategy and their structures were well characterized using multiple spectroscopic technologies. Taking the advantage of the activated ester strategy, the species and content of the D-/L-phenylglycines in the polymers can be well-controlled. The chirality of these phenylglycine-modified PDPAs exhibits unique composition and solvent-dependent behaviors. No circular dichroism (CD) signals have been recorded for the homo-polymers P-L and P-D (with complete substitution by L- and D-phenylglycine) in different solvents. While some of the partially phenylglycine-substituted PDPAs exhibit induced CD signals, P-L (1:19) in tetrahydrofuran (THF) and dichloromethane (DCM) solutions, P-D (1:19) and P-D (1:39) in the mixtures of THF and dimethyl sulfone (DMSO) (the digitals in the brackets stand for the ratio between the L- or D-phenylglycine and activated ester groups). In addition to their chiral characteristics, these PDPAs show typical aggregation-enhanced emission (AEE) behavior. Over 220% enhancement in fluorescence intensity has been recorded for P-L (1:19) in THF/DMSO mixture solvent. Both of the substitution-/solvent-dependent chirality transmission and AEE behaviors can be associated with the strong interactions between the phenylglycine side chains, which are non-facile to the conformational change of the polydiphenylacetylene backbone and hinder the chirality transmission from side to main chains. Meanwhile, the strong interactions reduce the dissipation of the excited state energy by intramolecular motions and induce the fluorescence enhancement. These observations not only are experimentally consistent, but also theoretically compliant with the results of density function theory (DFT) and molecular dynamics (MD) simulations.

Key words: Polydiphenylacetylenes; post-polymerization modification, circular dichroism, aggregation-enhanced emission, hydrogen bond

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