金属-杯芳烃高核笼簇的模块化构筑及光催化CO2转化研究

High-nuclearity coordination cage clusters (HCCCs) have attracted increasing interest for their fascinating molecular structures and intriguing properties that are distinctly different from those of their lower-nuclearity cognates. Thiacalix[4]arene and its derivatives, due to their multi-coordination sites and modifiable properties, have been proved to be effective multidentate ligands for the formation of Mx(Thiacalix[4]arene) (M = Mn, Fe, Co, Ni, Cu, Zn; x=3/4) modular polynuclear second building units (PSBUs). The PSBUs can be further connected by functionalized ligands to build HCCCs materials. Aiming at the preparation of efficient CO2 reduction photocatalysts, PSBUs with functionalized calixarene are selected for the modular construction of HCCCs by the cooperation of bridging ligands with controllable light-harvesting and change transport favorable properties. The dispersible HCCCs with controlled inner spaces are designed to homogeneous materials for photocatalytic CO2 conversion in a confined space. Our proposed activities are expected to not only fabricate series of fascinating HCCCs, establish structure and photocatalytic activity relationship of HCCCs, but also offer the possibility of creating efficient functional HCCCs materials.

高核配位笼簇不仅结构新颖而且表现出与低核化合物相异的性能。硫杂杯[4]芳烃及其功能化衍生物作为多齿配体能与金属离子形成稳定的Mx(Thiacalix[4]arene) (M= Mn, Fe, Co, Ni, Cu, Zn; x= 3/4) 模块化多核金属构筑单元(PSBUs)，进而可被官能化有机配体桥连得到功能性高核笼簇化合物。本项目拟以PSBUs模块化单元作为节点，利用可调控光吸收和利于电子传输性能所需桥接配体（单元）为组装单元，定向构建具有不同空隙结构的杯芳烃基单分子高核笼簇化合物，用于限域空间内光催化CO2转化材料研究。本项目的顺利实施不仅能够定向构筑系列新颖的高核笼簇化合物，建立笼簇结构与光催化材料性能之间的关系，而且为构建其它新颖高核笼簇功能材料提供有价值的信息。

硫杂杯[4]芳烃（H4TC4A）及其功能化衍生物作为多齿配体能与金属离子形成稳定的Mx(Thiacalix[4]arene) (M= Mn, Fe, Co, Ni, Cu, Zn; x= 3/4) 模块化多核金属构筑单元(PSBUs)，被官能化配体桥连，制备了系列组分，结构形貌可控的分子基聚集体。这些配合物一般具有分子团簇结构，金属中心被杯芳烃包围。一方面实现了团簇的外围有机基团修饰，接受和调控可见光吸收。另外叔丁基的强疏水作用可以将金属团簇用于水体系实现各种催化反应，而保持化合物结构的稳定性。其中在气固反应中体系中，后修饰活性位点实现了光催化CO2到CO的选择性转化；在液固反应体系中，实现了CO2到HCOOH的选择性还原。金属-杯芳烃团簇具有明确的单晶结构，用于计算模型的搭建，从分子甚至原子层面理解了催化反应的机理。本项目的完成对开发新型光催化材料具有重要的学术研究价值。