多金属氧酸炔银簇合物的离子热合成及其性能研究

Polyoxometalates(POMs)-based silver alkynyl clusters are a class of material for promising applications in opto-electronic devices and catalysis,however, the related research is lack of progress due to their synthesis difficulties. In this project, we proposed a new ionothermal method for the synthesis of multifunctional POM-based silver alkynyl clusters. Firstly, the POM building blocks and silver alkynyl fragments will be carefully selected, followed by controlling assembly in ionic liquids via the combination of templating strategy and ionothermal technique, in purpose to afford POMs-based silver alkynyl clusters with unique structural features thus physical properities, which are inaccessibly by traditional methods. Secondly, at selecting suitable building blocks from the obtained clusters, which will be used to further connect with POMs, we aim to construct supramolecular intercluster compounds by self-assembly in ionic liquids. Besides, by investigation of the electrochemical behavior, catalytic activity, and opto-electronic properties of the obtained compounds, we are willing to understand the correlation of structures and properties, which will provide useful insight for their application in catalyst, opto-electronic and nanoscale devices.

鉴于多酸基炔银簇合物在光电、催化等领域的应用前景，以及目前常规合成方法存在的难点和局限，本项目首次提出发展新型的离子热法制备多功能化的多酸基炔银簇合物。拟通过全方位设计、筛选多酸结构单元和炔银片段，调控离子液体反应介质的微环境，以模板法和离子热法有效结合的策略，制备常规合成方法无法获得的结构多元化、性能优良的多酸基炔银簇合物；筛选部分产物为结构单元，进一步和多酸单元在离子液体环境中进行自组装，构筑超分子簇间化合物；研究产物的电化学、催化活性和光、磁学性能，并考察多酸与炔银以不同方式结合对性能产生的影响，为此类化合物在催化剂、光电及纳米器件等方面的应用提供依据。

本项目以多酸基炔银簇合物的可控合成和功能化为主体开展研究。取得的主要结果如下：（1）离子热法合成了含三缺位的多酸[PW9O34]9-为模板的Ag70团簇；（2）发现了多酸在炔银簇间化合物中既充当模板又充当抗衡离子的双重作用；（3）笼状的Ag64团簇促进和稳定了新颖的混价内消旋体多酸阴离子的生成；（4）将阴离子模板拓展到有机小分子，以方酸为模板合成了Ag24团簇；（5）综述总结了阴离子模板法应用于高核银簇的可控合成，认识了多酸阴离子的作用和团簇形成的规律，并探索了多酸阴离子协同金属中心展示出核壳电子转移、簇间电子转移等性质；（6）发现了迄今已报道的最大核数的含有110核的异金属金银纳米团簇Au80Ag30团簇；（7）引入新型有机配体来保护的银纳米团簇，获得了首例结构确定的由杯芳烃保护的金属纳米团簇。.作为通讯作者发表了Science Advances. (1 篇)、J. Am. Chem. Soc. (1 篇)、Chem.Commum.(3 篇)、Inorg. Chem. (1 篇)和 Dalton Trans.(1 篇)等学术论文。