高核铜(I)富勒烯配合物的组装

过渡金属富勒烯配合物具有广泛应用前景，但富勒烯的配位修饰存在巨大挑战。既没有充分发挥富勒烯球面高配位点的优势，也没有充分利用晶体工程学在配合物设计合成方面的研究成果，严重制约了富勒烯配位化学的发展。.本项目以前期成果为基础，拟充分利用C60分子球面高配位点的优势，以低配位数Cu(I)为中心金属，以含O羧酸/磺酸为辅助配体，用溶剂热方法合成高核铜(I)富勒烯配合物及配位聚合物/MOF材料。通过辅助配体分子结构和合成条件来调控配合物结构，丰富和完善C60配位模式的多样性。研究辅助配体、合成条件与配合物结构间的内在联系，探索Cu(I)配位单元与C60间的光物理/化学机制，运用量子化学方法探究其结构与功能性质间的联系，建立构效关系理论模型，揭示它们在功能材料方面的应用前景。.本项目紧扣富勒烯配合物材料的热点、难点和盲点，为促进富勒烯配位化学快速发展提供了独特的解决方案，有望取得开创性研究成果。

Great challenges exist in the field of exohedral coordination-modification for a fullerene molecule, though exohedral metallofullerene complexes have extensive application prospects. Neither the advantages of the spherical high coordination sites of a fullerene molecule nor the rich research fruits in the design and synthesis strategies of modern crystal engineering have been fully exerted, which seriously restricts the scope of fullerene-related coordination complexes. .On the base of our previous research fruits, this project intends to synthesize a series of high-nuclear copper(I)-fullerene (cuprofullerene) complexes, coordination polymers and metal-organic framework materials with cuprofullerenes as second building units, by making full use of the advantages of the spherical high coordination sites for a C60 molecule, the low coordination number of closed-shell Cu(I) as the metal center, and the bridging coordination ability of carboxylate/sulfonate anions as the auxiliary ligands. By regulating the molecular structures of auxiliary ligands and synthesis conditions, the intrinsic relationship between auxiliary ligands, synthesis conditions and the structures of the synthesized cuprofullerene complexes will be studied, the diversity of coordination modes for the C60 molecule will be investigated, and the photophysical/photochemical process between the Cu(I) coordination units and the C60 moieties will be explored. Their structure and functional properties will be simulated and explored by theoretical calculations to establish a theoretical model of structure-properties relationships, and to reveal their application prospects as functional materials..This project closely follows the hot spots, difficulties and blind spots of fullerene complex materials, and provides a unique solution to promote the rapid development of fullerene coordination chemistry, which is expected to achieve pioneering research results.