配体对映选择性触发的热激活碳化聚合物点表面态手性异构化  

Thermally-activated chiral isomerization of surface state of carbonized polymer dots triggered by enantioselectivity of ligand

作　　者：周宾倩 郝俊杰 刘汝林 雷茜 敖秀琴 崔妍妍 张蕾[1] 李以文 贺廷超 朱熹 程佳吉 Binqian Zhou;Junjie Hao;Rulin Liu;Qian Lei;Xiuqin Ao;Yanyan Cui;Lei Zhang;Yiwen Li;Tingchao He;Xi Zhu;Jiaji Cheng(School of Materials Science and Engineering,Hubei University,Wuhan 430062,China;School of Science and Engineering,The Chinese University of Hong Kong,Shenzhen,Shenzhen 518172,China;College of Physics and Optoelectronic Engineering,Shenzhen University,Shenzhen 518060,China;College of Integrated Circuits and Optoelectronic Chips,Shenzhen Technology University,Shenzhen 518118,China)

机构地区：[1]湖北大学材料科学与工程学院,武汉430062 [2]香港中文大学(深圳)理工学院,深圳518172 [3]深圳大学物理与光电工程学院,深圳518060 [4]深圳技术大学集成电路与光电芯片学院,深圳518118

出　　处：《中国科学：化学》2024年第8期1369-1379,共11页SCIENTIA SINICA Chimica

基　　金：国家自然科学基金国际(地区)合作与交流项目(编号:62261136552);国家自然科学基金青年项目(编号:62204107);湖北省“楚天学者”以及“百人计划”项目;湖北省科学技术厅一般面上项目(编号:2023AFB635);湖北省科学技术厅青年项目(编号:2020CFB200,2021CFB018);深圳技术大学新引进高端人才科研启动经费(编号:GDRC202344);深圳高新区发展专项计划创新平台建设项目(编号:29853M-KCJ-2023-002-01)资助。

摘　　要：碳化聚合物点(CPDs)的选择性异构化与手性光学活性调控是多层次手性纳米材料的研究前沿问题.实现其表面态电子跃迁的可控手性效应是创制可见-近红外光区域内圆偏振光电器件与医用材料的重要基础.基于此,本文拟通过简单热激活的触发方式将N-乙酰-L/D-半胱氨酸的分子手性诱导至非手性CPDs上,通过有机配体与CPDs表面的界面手性诱导效应,实现表面态手性异构化与手性信号的调制与反转.研究表明,N-乙酰-L/D-半胱氨酸分子的用量以及热激活时间的长短等因素对CPDs中基于表面态的圆二色谱(g_(CD,max)~1.28×10^(-3))以及圆偏振发光光谱(g_(lum,max)~2.1×10^(-2))信号峰的位置与强弱都有着重要影响.相关密度泛函理论(DFT)数理模型分析指出手性配体在CPDs表面吸附的不对称性极有可能是产生该现象的原因。The selective isomerization of carbonized polymer dots(CPDs) and the modulation of chiroptical activities are the research frontiers of multilevel chiral nanomaterials. To realize controllable chiral effects via surface state electron transition is a significant basis for the creation and design of circularly polarized optoelectronic devices and medical materials in the visible-to-near infrared region. Herein, this article intends to induce molecular chirality from chiral N-AC-L/D-Cys to achiral CPDs through a simple thermal activation trigger, and achieve selective isomerization of surface states and the modulation and inversion of chiral signals through the interfacial chiral induction effect between organic ligands and CPDs surfaces with tunable and reversal circular dichroism(CD) and circularly polarized luminescence(CPL) properties. The results demonstrate that the position and strength of signal peaks in surface statesrelated CD(with g_(CD,max)~1.28×10^(-3)) and CPL spectrum(with g_(lum,max)~2.1×10^(-2)) in CPDs are greatly affected by the factors such as the amount of N-AC-L/D-Cys and the length of thermal treatment time. Related DFT simulations indicate that the asymmetry of enantioselective absorption of chiral ligands on the CPDs surface plays a crucial role in the chirality inversion phenomena.

关 键 词：碳化聚合物点 圆二色谱 热激活 手性反转 圆偏振发光 

分 类 号：O641.3[理学—物理化学] TB383.1[理学—化学]