炔铜(I)纳米团簇的合成、结构规律与光电性质  

Synthesis, crystal structures and photoelectric properties of copper(I) alkynyl nanoclusters

作　　者：方俊杰 刘铮 谢云鹏 卢兴 Junjie Fang;Zheng Liu;Yun-Peng Xie;Xing Lu(State Key Laboratory of Materials Processing ami Die&Mould Technology,School of Materials Science and Engineering,Hitazhong University of Science and Technology,Wuhan 430074,China)

机构地区：[1]华中科技大学材料科学与工程学院,材料成形与模具技术国家重点实验室,武汉430074

出　　处：《科学通报》2022年第11期1119-1136,共18页Chinese Science Bulletin

基　　金：国家自然科学基金(21771071,22171094,21925104)资助。

摘　　要：金属纳米团簇是由几个到上千个金属原子通过化学键或弱相互作用力组成的相对稳定的聚集体,其尺寸一般小于3 nm.这种超小的尺寸使它们具有量子尺寸效应,进而展现出不同于块体金属材料的电子/几何结构和物理/化学性质.相比其他币族金属(如金和银),铜具有储量大等明显优势,并且炔基配体相比硫配体和膦配体等其他保护配体具有更丰富的配位模式.近年来,科学家一直探索着炔铜(I)纳米团簇的合成策略及规律.结合本课题组的研究工作,本文对原子精确的炔铜(I)纳米团簇的合成方法、晶体结构规律、光致发光等性质和应用进行了综述,有助于理解其结构-性质间的构效关系;并对炔铜(I)纳米团簇的研究和挑战进行了总结和展望.Metal nanoclusters(NCs) are composed of several to thousands of metal atoms with a diameter of < 3 nm. Such metal NCs exhibit dramatically unique electronic/geometric structures and physical/chemical properties which differ from those of bulk metal materials. Among metal NCs, coinage metal(Au, Ag, and Cu) NCs have received extensive attention because of their chirality, optical and catalytic properties. Cu is more abundant than Au and Ag, yet copper(0)/copper(I) is more reactive and easier to oxidize than silver or gold, which makes it more difficult to prepare Cu NCs and investigate their properties. By taking guidelines from Au and Ag NC research, thiolate, phosphine, and alkynyl ligand-protected Cu NCs have recently received increasing attention. Alkynyl ligands have more abundant coordination modes compared to thiolate and phosphine ligands. Some copper(I) alkynyl NCs with unique crystal structures, good stability and rich properties have been recently reported. Herein, firstly, this paper introduces recent advances in developing efficient synthetic methods for copper(I) alkynyl NCs, highlighting the underlying physical and chemical properties that make the delicate control of their sizes and surfaces possible. The synthesis of copper(I) alkynyl NCs can be roughly classified into four categories:Solvothermal, reduction, template, and ligand exchange. Generally, the steric effect of the introduced protective ligand breaks their polymeric structures and improves solubility. Some copper(I) alkynyl NCs can also be produced by adjusting the auxiliary ligands and anionic templating agents. In addition, the concentration of ligands and precursors, p H and temperature of the reaction system can be used to adjust the reaction kinetics, and this leads to the formation of the monodisperse copper(I) alkynyl NCs. Secondly, we discuss recent advances in the structural determination of copper(I)alkynyl NCs, of which the size and shape can be controlled to a certain extent by the judicious choice of templating anions and aux

关 键 词：金属纳米团簇 炔铜团簇 晶体结构 光致发光 

分 类 号：O641.4[理学—物理化学] TB383.1[理学—化学]