金属富勒烯Gd@C82羟基加成的选择性合成设计研究

Due to their unique physical and chemical properties, Gd@C82 and its derivatives have attracted much attention in biological medicine field. However, the uncontrollable synthesis of its derivatives limits their application in this field and further research of the mechanism.. This proposal plans to selectively synthesize a series of different groups substituted endohedral fullerenol derivatives through distinguishing slight differences between double bonds in Gd@C82 together with expanding synthetic strategies. First, “selectivity induced by the catalyst” is introduced into the selectively addition of Gd@C82, to enhance the reaction selectivity, which may solve the problem of variable styles in addition reactions. Secondly, changing the traditional hydrolysis to "one-step reaction or functional group transformation" may supply new strategies to obtain different kinds of endohedral fullerenols and their derivatives, which will increase the possibility for selectively polyhydroxylation of Gd@C82.. This proposal plans to combine those two synthetic strategies to achieve selective synthesis of endohedral fullerenols and their derivatives, provides more sources of materials for the biomedical field, and further promotes the mechanism research.

金属富勒烯Gd@C82及其衍生物具有独特的理化性质，已成为生物医药领域研究的热点，但其衍生物的不可控合成限制了其在该领域中的应用和进一步机理的研究。本项目针对目前金属富勒烯Gd@C82羟基的选择性加成这一难题，从扩展反应思路和研究金属富勒烯Gd@C82双键之间的微小差异出发，探讨选择性合成多羟基富勒醇的可能性。1）将“催化剂诱导反应选择性”这一概念引入到金属富勒烯Gd@C82选择性加成反应，提高反应位点的选择性，从而解决金属富勒烯加成反应中数目不定和位点复杂的难题。2）改变传统水解得到羟基的思路，通过“一步反应引入或官能团转化”得到羟基，拓宽合成思路，增加羟基选择性加成的可能，实现羟基数目位置确定的金属富勒烯衍生物的合成。联合使用两种策略，本项目希望实现多羟基金属富勒醇及其衍生物的选择性合成，为其在生物医药领域的应用提供更多的原料来源，并进一步推动金属富勒烯生物效应作用机制的研究。

金属富勒烯Gd@C82及其衍生物具有独特的理化性质，已成为生物医药领域研究的热点，但其衍生物的不可控合成限制了其在该领域中的应用和进一步机理的研究。针对目前金属富勒烯Gd@C82选择性加成这一难题，本项目进行以下三方面的研究：1）利用富勒烯C60作为反应模板，选择性合成不同加成数目和LUMO能级的功能化富勒烯衍生物，并以该类富勒烯衍生物为电子传输层制备了一系列钙钛矿电池器件，其光电转化效率可以达到10.24%；2）共结晶单晶Gd@C2v(9)-C82·2.5(S8)·0.5(CS2)首次被培养出来，这一单晶结构从分子水平阐述了金属富勒烯Gd@C82的结构，为反应选择性提供了指导方向；3）在上面两个研究的基础上，实现了金属富勒烯Gd@C82与二级胺的多加成衍生物的选择性合成，并通过单晶培养确定了其最终结构，为其在生物医药领域的应用提供更多的原料来源，并进一步推动金属富勒烯生物效应作用机制的研究。.