钼氧簇-钛氧簇互为主客体的设计与合成

The supramolecular chemistry, possessing extensive applications in many areas ranging from biomaterial, smart material and self-healing material to catalyst, aims at developing complex systems generated by the intermolecular noncovalent interactions. This project devotes to the design and synthesis of host-guest molecules based on the combination of polyoxomolybdates and polyoxotitanates. The first issue is to explore the right experimental conditions for the coexistence of polyoxomolybdates and polyoxotitanates. On one hand, the polyoxomolybdate anions could play a key role as the template to direct the assembly process of titanium-oxo clusters with high nuclearity resulting in the formation of the {polyoxomolybdates @ polyoxotitanates} host-guest system. At the same time, the transformation induced effect of the polyoxomolybdate anions could work well together with the templated nucleation process in this system. On the other hand, the polyoxomolybdate anions, characteristic of huge cavity, act as the nanosized molecular container to recognize and stabilize the unprecedented polyoxotitanates leading to the isolation of the {polyoxotitanates @ polyoxomolybdates} host-guest species. The structural characterization and property investigation are essential to the desired species and do benefit to the conclusion of relationship between the structure and property.

超分子化学被广泛应用于生物材料、智能材料与结构、自修复材料以及催化等领域，本课题将通过超分子相互作用实现钼氧簇-钛氧簇互为主客体的设计与合成。此过程中首先探索钼氧簇与钛氧簇同时稳定存在的实验条件，进而将充分利用钼氧簇阴离子的模板效应以及模板效应与转换诱导效应的协同作用共同构筑{钼氧团簇@钛氧团簇}主客体化合物。与此同时，采用具有纳米级别空腔结构的钼氧簇阴离子作为微型反应容器稳定、保护、识别并捕获新颖钛氧簇形成从而构建{钛氧簇@钼氧簇}体系。并对获得的目标化合物进行结构表征以及性能表征，总结出钼氧簇-钛氧簇互为主客体化合物的结构与性能的构效关系的规律。

项目执行三年以来，按照研究计划和研究方案，我们首先利用配位延迟水解策略诱导钛氧簇-钼氧簇构筑。利用一步合成法实现了超分子钛氧簇{Ti8L12 +Ti(DMF)6} 以及 {Ti8L12+Ti12-oxo}的组装，利用不同碳链长度的二膦配体来稳定和诱导一系列Ti8Ag2氧簇的多级组装PTC-337 – PTC-339。通过异金属掺杂调节钛氧簇合物的禁带宽度以及可见光吸收行为。另外创新性的引入富电子Mo-Mo对构建钛氧簇TiIV4MoV4MoVI2O16(OCH3)16 和TiIV4MoV4O10(OC2H5)14(C6H5COO)2。在此基础上，进一步将研究领域扩展到铟主族金属并研究了其光刻性能，拓展了研究方向，为未来继续深入研究金属氧簇化学奠定了坚实基础。通过本项目的支持，三年内在国际学术刊物上发表学术论文5篇。较好实现了项目目标。