近红外金属有机材料的自组装与光电功能（二）

The integration and functionalization of new organometallic materials is a challenging topic. In this context, self-assembly on the basis of weak bond interaction has become a favorable choice for the construction of complex systems directed toward some special functions. We will design and develop novel organometallic building blocks and construct new integrated systems with near-infrared and photovoltaic functions in this project. The focus will also be placed on the studies of the relationship between the performance and architectures of self-assembled systems. Self-assembled multilayers containing mixed-valence dimetallic units will be constructed. These films are expected to exhibit efficient near-infrared electrochromism by manipulating the redox-controlled metal-to-metal charge-transfer transitions. New near-infrared emitting organometallic materials installing with ion-recognition site will be synthesized and used for switch-ON sensing of some important ions. The assembly between near-infrared organometallic dyes and inorganic semiconductor nanocrystals will be examined. These systems are suitable for applications in dye-sensitized solar cells and expected to boost the energy conversion efficiencies. The projects proposed herein will provide important materials for molecular electronics and new energy source conversions and are of great interest for the design and functionalization of new self-assembled systems.

目前功能金属有机材料面临的一个关键科学问题是金属配合物的集成与功能导向。基于弱键相互作用的自组装方法将在以某些特殊功能为导向的金属有机集成材料的制备中显示巨大优势。在本项目中，我们将以智能响应性近红外材料和光电转换为功能导向，设计和开发具有近红外功能的金属有机组装新基元，利用多层次、多组分的自组装方法，创造新型功能化可控自组装体系，并揭示组装结构和性能的关系。拟构建基于混合价双金属体系的多层组装膜，利用氧化还原控制的金属间电荷转移，实现高效近红外电致变色。制备含有离子识别基团的近红外发光金属有机材料，发展与生物相容的近红外离子识别与传感体系。制备近红外金属有机染料与无机半导体纳晶的新型复合组装体，优化染料敏化电池的光电转换效率。这些研究为分子电子学和新能源的转化与利用提供了物质基础，并对新型自组装体的设计和功能导向有重要的意义。

本项目以智能响应性近红外材料和光电转换为功能导向，设计金属有机组装新基元，利用多层次、多组分的自组装方法，创造新型功能化可控自组装体系。组装合成了三芳胺官能团化的线型金属钌配合物，具有多步氧化还原过程及近红外吸收功能。制备了一系列基于金属钌、锇和三芳胺共轭的近红外分子材料，通过羧基官能团化，在ITO电极表面制备了自组装单层膜，实现分子层次的近红外电致变色。利用电化学还原聚合，制备了金属有机共轭材料的配位聚合物薄膜，成功实现较高性能的多态近红外薄膜电致变色，在光纤通讯中有潜在应用。利用电化学氧化聚合，制备了双胺-双钌交替存在的高聚物薄膜，以该薄膜为活性层的三明治类型器件显示优秀的阻变存储效应。设计并合成了新型桥联钌-铂异核双金属近红外发光配合物，实现汞离子的选择性检测。制备了含有二吡啶胺离子识别基团的环金属钌配合物，实现二价铜离子的多渠道检测。合成了一系列环金属钌近红外染料，在敏化电池中取得初步结果。本项目研究成果在JACS，Chem. Sci.等期刊上发表IF>3.0论文18篇, 应邀在Coord. Chem. Rev.撰写综述，发表专著章节1篇。培养博士研究生3名。