基于主-客体配位聚合物的电子给-受体材料的构筑及性质研究

Donor-acceptor (D-A) materials constructed based on organic electron donor and acceptor molecules feature unique and highly tunable charge transport and optical properties. Therefore, the D-A materials have wide potential applications, which make them attract much attention and become a hot research field. However, with the supramolecular interactions as the only guiding force for the construction of organic D-A materials, the precise modulation of the components and the structure of the materials is limited. These has also limited the improvement of the properties of materials. Aiming at the development of D-A materials with enhanced properties, a host-guest coordination polymers (CPs) based strategy is raised in this proposal. By utilizing the inorganic-organic component features of CPs and taking the advantages of their readily tunable components and structures, the limitation in the construction of D-A materials could be broken through, and D-A materials showing more desirable properties could be expected. In this project, we will focus on the research and development of host-guest coordination polymers based D-A materials on the basis of the strategy for the exploration of new D-A material system. In addition to the exploration of new methods for targeted construction and modulation of the materials, much effort will be made on the systematic research of the optical and charge transport related properties of the resulted materials. The relationship between the structure and properties of the materials will also be illustrated. The achievements of the project will contribute to the performances targeted construction of D-A materials in both theoretical and experimental manners.

基于有机分子电子给体（Donor）和受体（Acceptor）构筑的分子基给-受（Donor-Acceptor, D-A）材料因其多样、可调的电荷传输、发光等性质成为材料研究的热点，具有广泛的应用前景。但单纯以组分间超分子相互作用为构筑导向力的有机D-A材料组装构筑机制限制了材料组成、组分空间排布方式等的精准调控及材料性能的进一步提升。针对该问题，我们提出了基于主-客体配位聚合物的D-A材料构筑新思路，利用配位聚合物无机-有机杂化的组成特性和组成、结构易于调控的优势，有望实现更为精准的D-A材料构筑，获得性能更为良好的材料。在本项目中，我们将基于该设计思想开展基于主-客体型配位聚合物的D-A材料构筑研究，开拓新的D-A材料体系，并在探索材料构筑及结构-性能调控方法的基础上，系统研究该类材料在光、电等方面的性质，总结结构-性能关系和调控规律，为D-A材料的功能导向构筑提供新的理论和实验依据。

基于有机分子电子给体（Donor）和受体（Acceptor）间的相互作用形成的分子基给-受（Donor-Acceptor, D-A）材料可基于对组成和结构的调控展现出多样、可调的电荷传输性和光学性能，因此成为光、电材料领域研究的重点之一。.本项目针对传统有机小分子D-A材料中以超分子作用为构筑导向力的情况下D和A组分堆积方式难以精准调控的问题，提出了利用配位聚合物（包括金属-有机框架，MOF）作为结构调控平台实现D-A材料精准构筑的研究方案，开展了系列主-客体结构配位聚合物D-A体系的构筑和性质研究，构筑了系列D-A体系配位聚合物新体系，研究了D-A体系与配位作用协同引导配位聚合物组装的规律，为D-A体系的精准构筑提供了有效方法。在此基础上，我们深入研究了D-A体系配位聚合物体系的微观-宏观多尺度组装特性及丰富的光物理性质，实现了基于D-A体系电荷转移（charge transfer）的宽范围发光调制及首个具有基于空间穿越电荷转移（TSCT）特性的热活化延迟荧光MOF的构筑等，并分别发展了利用分步组装和自由能驱动的自发有序配位组装进行宏观有序异质结构配位聚合物晶体构筑的方法，可实现光逻辑门、光晶体管等光逻辑器件功能。项目研究成果拓展了配位聚合物的应用研究领域，为后续相关工作的进一步深入开展奠定了良好基础。.项目相关研究成果已在Angew. Chem., Int. Ed.、Matter 、Natl. Sci. Rev.、Coord. Chem. Rev.、ACS Appl. Mater. Interfaces等期刊发表论文15篇，申请专利2项，1项已授权。项目执行期间培养了一批博士后、研究生等专业人才，促进了国内外学术交流与合作，实现了项目预期的研究目标。