锆氧簇取代的钨氧簇的缺位导向合成、结构及性能

In the hydrothermal system containing inorganic or organic zirconium salt, the stable conditions of lacunary oxo tungsten clusters (such as Keggin-type tri-lacunary PW9, Dawson-type tri-lacunary P2W15 and hexa-lacunary P2W12, etc), and the coexistence conditions of mixed lacunary oxo tungsten clusters (such as PW9-P2W15, PW9- P2W12, and P2W15-P2W12, etc) will be explored in the crystallization process, and then the novel Zr-cluster substituted polyoxotungstates will be made via lacunary directing and synergistic lacunary directing roles. Their In the hydrothermal system containing inorganic or organic zirconium salt, the stable conditions of lacunary oxo tungsten clusters (such as Keggin-type tri-lacunary PW9, Dawson-type tri-lacunary P2W15 and hexa-lacunary P2W12, etc), and the coexistence conditions of mixed lacunary oxo tungsten clusters (such as PW9-P2W15, PW9- P2W12, and P2W15-P2W12, etc) will be explored in the crystallization process, and then the novel Zr-cluster substituted polyoxotungstates will be made via lacunary directing and synergistic lacunary directing roles. The crystal structures and catalytic oxidations of thioethers will be solved and investigated, respectively. In addition, the effects of the temperature, zirconium source, reaction time and acidity on the structures, and the influences of spatial effect, electron-donating/-withdrawing groups, and the substituted positions of the alkyl and aryl group on the catalytic oxidation of thioethers will also be studied. The structure-activity relationships between catalytic oxidation and structures will be summarized, in which the catalyst with good catalytic performance will be found. This project will not only extend the lacunary directing idea and hydrothermal method from divalent metal to tetravalent metal substituted polyoxotungstates but also push the development of cluster chemistry, synthetic chemistry, structural chemistry and material science.

在含有无机锆盐或有机锆盐的水热体系中，探索Keggin型三缺位PW9及Dawson型三缺位P2W15和六缺位P2W12等缺位钨氧簇分别稳定存在的条件，同时探索混合缺位钨氧簇(如PW9与P2W15、PW9与P2W12及P2W15与P2W12等)在晶化过程中共存的条件，进而通过缺位导向及缺位协同导向作用构建具有新颖结构的锆氧簇取代的钨氧簇，解析晶体结构并对其硫醚催化氧化性质进行研究。考察温度、锆源、反应时间及体系酸度等对产物结构的影响，同时考察硫醚中脂肪烷基和芳香烷基的空间效应、取代基的推拉电子属性及取代位置等对催化氧化反应的影响。总结产物结构与硫醚催化氧化间的构效关系，筛选具有良好催化性能的硫醚氧化催化剂。本研究不仅将缺位导向思想和水热技术由二价金属取代的钨氧簇拓展到四价金属取代的钨氧簇合成领域，而且必将推动原子簇化学、合成化学、结构化学及材料科学的发展。

本项目在“锆氧簇取代的钨氧簇的缺位导向合成、结构及性能”方面开展研究工作，将锆钨氧合团簇的合成方法由水溶液合成拓展到水热条件下的缺位导向合成。研究内容主要包括：在含有无机锆盐或有机锆盐的水热体系中，探索Keggin型三缺位XW9 (X=P/Ge/Si)及Dawson型三缺位P2W15等缺位钨氧簇分别稳定存在的条件，同时探索混合缺位钨氧簇(如PW9与P2W15等)在晶化过程中共存的条件，进而通过缺位导向及缺位协同导向作用构建具有新颖结构的锆氧簇取代的钨氧簇，解析晶体结构并对其硫醚催化氧化性质进行研究。考察温度、锆源、反应时间及体系酸度等对产物结构的影响，总结产物结构与硫醚催化氧化间的构效关系，筛选具有良好催化性能的硫醚氧化催化剂。本研究不仅将缺位导向思想和水热技术由二价金属取代的钨氧簇拓展到四价金属取代的钨氧簇合成领域，而且将推动原子簇化学、合成化学、结构化学及材料科学的发展。.项目负责人杨国昱教授为第一完成人的项目《氧基簇合物的设计合成与组装策略》获2016年国家自然科学奖二等奖；在徐如人院士主编的专著《Modern Inorganic Synthetic Chemistry》、在郑智平教授主编的专著《Structure and Bonding》及在卜显和教授主编的专著《配位聚合物化学》中各撰写专章一篇。本项目已取得重要进展，目前已在国外有影响的学术期刊上发表研究论文60篇(标注资助号)，包括Angew. Chem. Int. Ed. (1篇)、Chem. Comm. (4篇)、Acc. Chem. Res. (1篇)、Chem. Eur. J. (5篇)、Inorg. Chem. (7篇)、Catal. Sci. Tech. (1篇)、Dalton Trans. (6篇)、Cryst. Growth Des. (1篇)、CrystEngComm (5篇)、ChemPlusChem (1篇)、Eur. J. Inorg. Chem. (4篇)等。一些相关研究结果正在整理发表中。