摘要
The design and construction of highly effective circularly polarized luminescence(CPL)-active materials has aroused considerable attention due to their widespread applications in sensors,optical devices,and asymmetric synthesis.However,the exploration of novel CPL-active materials with high luminescence dissymmetry factor(glum)values is still a challenge.Herein,we describe a new approach for the preparation of supramolecular metallacycles with amplified CPL promoted by hierarchical self-assembly involving Pt···Pt interactions.Notably,the resultant metallacycles exhibited strong CPL signals with high glum values,while their corresponding precursors were CPL silent.The CPL amplification mechanism was comprehensively validated by ultravioletvisible absorption,emission spectroscopy,nuclear magnetic resonance spectroscopy,scanning electron microscopy,transmission electron microscopy,atomic force microscopy,coarse-grained molecular dynamics simulations,and timedependent density functional theory calculations.This work thus provides the first example of preparing highly effective CPL-active materials based on hierarchical self-assembly involving Pt···Pt interactions.
高效圆偏振发光材料在传感、光学器件、不对称合成等领域有着广泛的应用,设计和制备圆偏振发光材料引起了人们的广泛关注.然而,构筑具有高发光不对称因子的圆偏振发光材料仍然是一个挑战.这里,我们制备了一种手性超分子组装金属大环,该超分子组装金属大环可以通过分子间铂···铂相互作用诱导逐级自组装促进圆偏振光的放大.值得注意的是,超分子组装金属大环显示出高的发光不对称因子以及较强的圆偏振光信号,而其对应的组装配体没有显示出圆偏振光信号.通过紫外-可见吸收光谱和发射光谱、核磁共振氢谱、扫描电镜、透射电镜、原子力显微镜、粗粒化分子动力学模拟和含时密度泛函理论计算等手段对圆偏振光放大的机理进行了研究.该研究展示了第一例基于铂···铂相互作用驱动的逐级自组装策略制备的高效圆偏振发光材料.
作者
Gui-Fei Huo
Qian Tu
Yi-Xiong Hu
Bo Jiang
Qi-Feng Zhou
Yanfei Niu
Xiaoli Zhao
Hong-Ming Ding
Jin Wen
Guang-Qiang Yin
Xueliang Shi
Lin Xu
霍桂飞;涂倩;胡毅雄;江波;周启峰;牛艳霏;赵小莉;丁泓铭;闻瑾;尹光强;史学亮;徐林(Shanghai Key Laboratory of Green Chemistry and Chemical Processes,School of Chemistry and Molecular Engineering,East China Normal University,Shanghai 200062,China;Center for Soft Condensed Matter Physics and Interdisciplinary Research,School of Physical Science and Technology,Soochow University,Suzhou 215006,China;China State Key Laboratory for Modification of Chemical Fibers and Polymer Materials&College of Materials Science and Engineering,Donghua University,Shanghai 201620,China;Institute of Theoretical Chemistry,Faculty of Chemistry,University of Vienna,Währinger Str.17,1090 Vienna,Austria)
基金
supported by the National Natural Science Foundation of China(21922506,21871092,and 21603074)
Shanghai Pujiang Program(18PJD015)
the Fundamental Research Funds for the Central Universities
the Austrian Science Fund(M 2709-N28)for the financial support。
