高核稀土簇合物的合成、结构及性能研究

Due to the particular electronic configurations, poly-nuclear lanthanide clusters exhibit potential applications in single-molecule magnets, magnetic resonance imaging (MRI), and energy-efficient and environmentally friendly molecular refrigerants. Though much progress has been made in the investigation of poly-nuclear lanthanide clusters, the synthesis of high-nuclearity pure lanthanide clusters, especially over twenty nuclears, continues to be a big challenge. In this project we will introduce different anions as templates under high temperature and weak base condition to induce the slow hydrolysis of lanthanide anions, which will reslut in forming high-nuclearity lanthanide clusters. Then, we will explore the relationship between their structures and the physical capabilities. Through the control of the reaction conditions such as reaction time and temperature, we want to synthesize the nanoscale high-nuclearity lanthanide crystals and investigate the relationship between the scale and the physical capabilities. Additionally, we plan to synthesize the nano lanthanide oxide directly from high-nuclearity lanthanide clusters to find functional nano lanthanide materials. During the project implementation, 8-10 paper collected by SCI will be published, among which 5 research papers are with the IF > 3.0.The successful implementation of this proposed project can not only enrich the investigation of the lanthanide clusters, but also provide a new approach to the lanthanide-based functional materials.

由于具有独特的电子构型，多核稀土簇合物在单分子磁体、核磁成像以及节能且环境友好的分子制冷剂方面具有潜在的应用前景。虽然多核稀土簇合物的研究取得了较大的进展，但纯稀土高核簇尤其是稀土离子个数超过二十的高核簇的合成仍然面临着巨大的挑战。本项目拟在高温以及弱碱性条件下通过引入不同的阴离子作为模板剂诱导稀土离子进行缓慢水解从而晶化形成高核稀土簇合物，研究其物理性能，探讨结构与性能之间的关系；通过控制温度、时间等反应条件，合成高核稀土纳米晶，研究材料尺度对其性能的影响；以高核稀土簇合物为起始物合成纳米稀土氧化物，寻找性能优异的稀土纳米材料。预计发表SCI收录论文8－10篇，其中影响因子大于3.0的文章5篇。本课题的顺利实施不仅可以丰富稀土簇合物的研究，而且可为寻找稀土基功能材料开辟新的途径。

在项目执行期间，我们按照计划开展工作，主要围绕稀土簇合物的制备与功能开展了科研工作，探索了在高温以及弱碱性的条件下诱导稀土离子进行缓慢水解构筑高核稀土簇合物，研究各种反应条件如温度、浓度、pH值、配体、反应物的比例等对形成高核稀土簇的影响，着重考察不同阴离子的模板作用，合成一系列三核、四核、七核、十核、十一核、十九核、四十八核的稀土化合物，并对其荧光和磁性等性能进行了研究，探讨高核稀土簇合物的结构与性能之间的关系。在国际学术刊物上发表IF > 3.0共发表论文13篇，其中JCR分区一区（IF > 6.0）论文9篇，其中1篇Chem. Sci.，1篇Chem. Commun.和1篇CrystEngComm为封面文章。并为Springer出版社“Structure and Bonding”丛书中“Lanthanide Metal-Organic Frameworks”撰写专章。在国内重要学术会议上共做报告3次，并已培养了博士毕业生2名。