新型环状d-f异金属配合物的设计、组装及荧光性能

Applications of the lanthanide luminescent materials developed currently are limited due to their typical disadvantagies, such as ultraviolet excitation, low energy transfer efficiency, low quantum yield and short luminescent lifetimes. This project will focus on design and synthesis of novel cyclic d-f heterometallic complexes from the molecular level, based on the fact that d metal complexes have efficient absorption in the visible region as sensitizers, and possess multiple delivery pathways of energy transfer in cyclic structure. In order to estabilish the new synthesis method and structure control method of of heterometallic complexes, we will further investigate a series of effects on the synthesis of heterometallic complexes, namely the bending angle and coordination selectivity of organic blocks, metal coordination environments, pH values and etc. Moreover, from the theoretical and practical perspective, we will build the relationship between the d-block metal chromophore, distance of metals, pathway of d→f energy transfer and f-block matel luminescent unit with excited wavelength, luminescent efficiency, quantum yield and lifetime. From this research, we seek to clarify the luminescent mechanism and enrich the the methods of sensitizing lanthanide's luminescence. Finally, we hope to provide theoretical basis in the application of low-energy excitation and high lumnescence efficiency based on cyclic d-f heterometallic materials.

本项目针对目前稀土金属配合物发光材料存在紫外区激发以及能量传递效率、量子产率、荧光寿命低等瓶颈问题，借助d区金属有机生色基团在可见光区域的良好吸收性以及环状结构的多能量传递途径，从分子水平出发，设计合成环状d-f异金属配合物发光材料；系统研究有机基块弯折角度及配位选择性、金属配位环境、pH变化等对构筑异金属配合物的影响规律，建立和发展异金属配合物的晶体工程学合成方法和结构控制的新方法；从理论和实验相结合的角度探究d区金属有机生色团、异金属间距、环形能量传递途径、f区金属发光单元等对异金属配合物的激发波长、发光效率、量子产率及荧光寿命的影响规律，探讨环形d→f能量传递规律及异金属结构-性能之间的构效关系，阐明发光机理，总结其中规律，丰富敏化稀土发光的思路和方法，为开发低能量光激发、高发光效率的d-f异金属发光材料提供理论和实验基础。

本项目借助 d 区金属有机生色基团在可见光区域的良好吸收性以及环状结构的多能量传递途径，从分子水平出发，设计合成了50余例基于三唑类杂环配体和杂环羧酸配体构筑的d区配合物砌块及d-f异核配合物；系统研究有机基块及d区配合物砌块弯折角度及配位选择性、金属配位环境、 pH 变化等对构筑异金属配合物的影响规律，建立和发展异金属配合物的晶体工程学合成方法和结构控制的新方法；从理论和实验相结合的角度总结了有机配体， d 区金属有机生色团、 f 区金属发光单元等对异金属配合物发光性能的影响规律，揭示了d→f 能量传递规律和发光机理，丰富敏化稀土发光的思路和方法，为开发低能量光激发、高发光效率的 d-f 异金属发光材料提供理论和实验基础。项目执行期间发表SCI文章17篇，获校自然科学奖一等奖1项，外出参加学术会议及与国外课题组交流3次，课题组牵头举办承办会议及论坛4次，邀请国内外专家交流7次，培养硕士研究生3人。