富勒烯环状配体及其金属配合物的合成与性能研究

Macrocyclic ligands such as porphirin and phthalocyanine have been widely used in catalysis, dyes and medicine. All the known aromatic macrocyclic ligands have the classical planar aromatic conjugation system. Curved-pi systems such as fullerene and nanotube have attracted much attention in recent years. The present proposal designed a series of macrocyclic ligands with curved-pi system. The strategy is based on our previous results on the synthesis of open-cage fullerene derivatives. Coordinating functional groups such as carboxylic and hydroxyl groups will be added on the rim of the orifice in the open-cage compounds. The synergetic interaction between the metal and the spherical-pi system on the ligand will be studied for their possible photocatalytic activity. In particular the present study will explore the interaction between the metal and small molecules such as H2O, NH3, CO trapped inside the cavity of the fullerene-based macrocyclic ligands. The present study will focus on the synthesis of novel metal complexes and explore their possible applications.

具有芳香骨架的大环配体如卟啉、酞菁等被广泛应用在催化、染料、医药等领域。目前已知的这类大环配体其芳香骨架均具有传统的平面结构。具有弯曲结构的非平面芳香体系如富勒烯、纳米管等是近年来的热门研究课题。本项目拟将非平面芳香性体系引入到大环配体，设计合成以非平面芳香性体系为基本骨架的大环配体。具体研究策略是通过拓展本课题组前期工作中在开孔富勒烯方面的一些结果，在开孔处引入可以与金属配位的官能团如羧基、羟基，探讨富勒烯芳香体系与配位金属的协同作用在光催化方面的可能应用，特别是研究富勒烯空腔内小分子配体如H2O, NH3, CO与金属的相互作用，开展新型配合物反应性能和功能特性的研究，总结有关反应规律，探讨新型配位化合物的合成和可能应用途径。

具有芳香骨架的大环配体如卟啉、酞菁等均具有传统的平面结构，具有弯曲结构的非平面芳香体系如富勒烯也有一定的配位能力，但由于其配位化合物稳定性较差应用有限，本项目以课题组前期工作为基础，利用富勒烯过氧化物为原料开展富勒烯开孔富勒烯的合成，在开孔周围引入配位基团，并将这类化合物用作大环配体与金属形成配位化合物，几年来合成了多个开孔富勒烯大环配体，并研究了这些配体与多种金属如钠、镁、铜、钛和钯的配位作用，合成了多个开孔富勒烯金属配合物，完成了主要预期目标。同时还在研究中还发现了一些原来没有设计但非常有意义的相关结果，如首次合成了空腔含卤素阴离子的富勒烯包合物，以及可以填充过氧化氢的开孔富勒烯衍生物，该化合物在递氧材料方面有一定应用前景。这些结果为深入开展开孔富勒烯化学的研究提供了重要基础。