多功能金属纳米团簇的化学合成与组装

Due to their special physical and chemical properties, metal nanoclusters ('clusters'for short), especially transition metal clusters have great application potentials in the industries of optoelectronics, catalysis and biology. Much academic attention has been cast on its research in recent years. In the field of chemistry, the research of multifunctional materials with coupled properties is lagged compared to that in the physical field. Nowadays, chemical researchers have done a lot of synthesis work on the compounds with multi properties or functions, while the in-depth research on property-coupling such as magnetic-electronics or magnetic-optics coupling is overlooked to some extent. By chemical approaches, the metal clusters can be synthesized, which provides an ideal material basis for the research of the multi functional metal clusters with coupled properties. The program aims the research of multi functionalization of transition metal clusters, with the combination of the functional ligand and precursor molecular design, the coordination and bridge interactions of the metal and ligand, the chemical synthesis of metal clusters and nano-assembly techniques. Using organic-inorganic hybridization and property coupling as the guiding ideology, the program will focus on the synthesis of metal clusters with functional ligand modification, including: (1) The preparation, characterization, assembly of the metal clusters with controllable metal atom number, structure, doping, modification and bridge linking, (2) The relationship between the cluster structure and property, (3) The intra-cluster and inter-cluster property coupling such as magnetic-electronic-photonic coupling. It is an inter-disciplinary research that will provide the accumulation of technical and theoretical foundation for practical applications.

金属纳米团簇（简称金属团簇），尤其是过渡金属团簇由于其特殊的物理、化学性质，在光电子工业、催化、生物等方面极具应用潜力，近年来备受学界关注；在化学领域，具有多功能耦合性质的材料研究起步较晚，在如磁电、磁光耦合等方面的研究尚不深入。能够通过化学合成的金属团簇恰恰为开展这方面的研究提供了一个理想的物质基础。本项目针对过渡金属团簇多功能化的研究方向，拟通过功能配体分子与团簇前驱体分子的设计与合成技术，利用分子与金属的配位、桥联原理，将金属团簇的化学合成与纳米组装技术相结合，以有机-无机杂化与性质耦合为指导思想，化学合成多功能金属团簇，研究（1）金属原子数、结构、掺杂、配体修饰、化学桥联可控的金属团簇的化学制备、组装和表征，（2）金属团簇结构与性质之间的关系，（3）团簇内与组装团簇的磁、电、光学性质及其耦合。该项目在科学与技术上涉及多学科交叉，其探索研究将为实际应用积累理论与技术储备。

金属纳米团簇，尤其是过渡金属团簇由于其特殊的物理、化学性质，在光电子工业、催化、生物等方面极具应用潜力。本项目针对过渡金属团簇多功能化的研究方向，通过纳米合成与组装技术，研究了金属原子数、结构、掺杂、配体修饰可控的金属团簇的化学制备、组装和表征，对团簇的光、电、磁性质及其内在关系与其结构之间的关系进行了探索。取得的主要结果与创新点如下：1）通过变温还原方法，成功合成了过渡金属团簇Ni39(SC2H4Ph)24和Ni41(SC2H4Ph)25，Ni29(SC2H4Ph)20和Ni27(SC2H4Ph)19等，研究了Ni团簇的自组装特性、结构特征及其与光学性质和磁性的关系，揭示出其特殊的既有分子特性又有纳米颗粒特性的特征，特别地，Ni39和Ni41表现出室温铁磁性，为实现室温下工作的单分子磁体的合成提供了思路。该成果发表于Nanoscale，为该期的热点文章，并被ChemRev金属团簇综述文章所引用。2）通过金属团簇/纳米晶的表面配体设计与修饰策略，研究了金属团簇/纳米晶体的表面配位结构的多功能化，探索了团簇的表面光电特性的调控，实现了表面激子耦合对荧光性质的调控，拓宽了该类材料在发光器件、生物标记等领域的应用。研究成果发表于SciRep和ChemPhysChem。在该项目资助下共发表SCI论文10篇，培养研究生4人。