“柔性”大尺寸银簇的精准合成及其刺激诱导的转化反应和机理

Because of the wide applications in the fields of light-emitting materials, conductive materials and biological medicine, the synthesis, structure and physical properties of the large-sized silver clusters become an important research direction in cluster chemistry. In this project, the transformation syntheses of "flexible" large-sized silver clusters were set as the basic research objective, and the combination of "soft" and "hard" ligands constitute the dual-ligand system and will be used to achieve this target. Among them, some stimuli-responsive large-sized silver clusters will be selected and subjected to be simulated, which will induce rearrangement of ligands, increase or decrease of ligands on the surface, in turn, promote the re-arrangement of silver ions or anion templates, then realize the syntheses of new large-sized silver clusters through structural transformation. We will use X-ray single crystal diffraction technique and high resolution mass spectrometry characterization to elucidate the initial and final cluster structures, trap intermediates during structural transformation in the solution, seek the information of solution species evolution, and finally obtain transformation mechanism underpinning the solution assembly of such complex system, which will promote the precise synthesis of novel large-sized silver clusters and bring better understanding on the assembly mechanism of such cluster compounds. Based on the comparative research on the properties of products before and after the transformation, we will achieve the function regulation of large-sized silver clusters, which, in turn, promote the practical application of such materials.

因其在发光材料、导电材料和生物医药等领域表现出的广阔应用前景，大尺寸银簇的合成、结构和物性关系成为团簇化学的一个重要研究方向。本项目通过双配体体系的“软”和“硬”搭配和调节来实现“柔性”大尺寸银簇的精准合成。筛选具有应激响应活性的大尺寸银簇，利用外部刺激诱导其表面配体增减或重排，进而促进内部银核结构的调整，实现大尺寸银簇的整体结构转变，最终获得结构新颖的大尺寸银簇。利用X-射线单晶衍射技术和高分辨质谱表征，明确双配体在构建“柔性”大尺寸银簇中各自扮演的角色，捕捉溶液中结构转变中间体或溶液物种进化信息，获得“柔性”大尺寸银簇结构的转变机理，为进一步实现大尺寸银簇的精准转化合成，理解复杂体系组装机理奠定基础。通过对转变前后性质变化的研究，实现刺激诱导的大尺寸银簇功能调控，推动团簇材料的实际应用。

项目负责人利用软硬酸碱理论和双配体组合策略，实现“柔性”大尺寸银簇的精准合成，建立可控合成新方法和新技术，选择合适的外界刺激源并结合质谱研究团簇转化组装机理。此外，结合“软硬”双配体和“异阴离子”模板，构筑了多壳层嵌套多面体大尺寸银簇，为“开普勒宇宙”模型提供了实际研究模型。受超分子自组装策略启发，在多种非共价键作用的驱动下，制备了具有功能应用前景的银簇材料，并探究了构效关系，阐明了内在科学原理，优化了材料功能特性，推进了材料的实际应用。总的说来，项目负责人在金属团簇领域系统开展了从“柔性”大尺寸银簇的普适合成方法学、反应新范式的建立到功能实现的基础应用研究工作。以通讯作者身份在Nat. Commun. (4篇), J. Am. Chem. Soc. (3篇), Angew. Chem. Int. Ed. (7篇), Adv. Mater. (1篇), ACS Nano (5篇)等期刊发表SCI论文40余篇。研究工作被Chem. Rev., Chem. Soc. Rev., Angew. Chem. Int. Ed., J. Am. Chem. Soc.等许多国际著名学术期刊论文引用。同时也被Research Outreach等学术组织或网站撰写专文亮点评述，为推动团簇科学发展做出一定的贡献。