Pd和Hg共掺杂的金属纳米团簇HgPdAu_(23)(PET)_(18)  

Pd and Hg Atoms Co-doped HgPdAu_(23)(PET)_(18) Nanocluster

作　　者：张玉莹 蔡潇 胡维刚 李光俊 祝艳 Zhang Yuying;Cai Xiao;Hu Weigang;Li Guangjun;Zhu Yan(Department of Applied Chemistry,Yuncheng University,Yuncheng 044000;School of Chemistry and Chemical Engineering,Nanjing University,Nanjing 210023)

机构地区：[1]运城学院应用化学系,运城044000 [2]南京大学化学化工学院,南京210023

出　　处：《化学学报》2023年第7期703-708,共6页Acta Chimica Sinica

基　　金：运城学院优秀博士来晋科研项目(No.QZX-2023008);中国博士后基金(No.2022M721551)资助。

摘　　要：异金属原子引入原子精确的金属纳米团簇是调控团簇物理化学性质的有效手段,目前报道的异金属原子掺杂团簇大多数是单个金属原子掺入金属团簇中形成的二元金属纳米团簇,而两个异金属原子同时掺入同一个金属团簇中形成三元金属纳米团簇的报道较少.本工作中,我们报道了Pd和Hg双原子同时掺入Au_(25)(PET)_(18)(PET=苯乙硫醇)团簇中形成HgPdAu_(23)(PET)_(18)新团簇,推测了Pd和Hg在三元金属团簇中最可能的位置,即Pd位于三元金属团簇的内核中心,而Hg原子位于三元金属团簇内核的表面.不同金属种类以及不同的掺杂位置导致了三元金属团簇HgPdAu_(23)(PET)_(18)具有不同于原始团簇Au_(25)(PET)_(18)和二元金属团簇PdAu_(24)(PET)_(18)和HgAu_(24)(PET)_(18)的电子构型.本研究为双金属异原子掺入金属纳米团簇的精准制备提供了新的思路.The introduction of heteroatoms into metal nanoclusters is an effective strategy to regulate the physical and chemical properties of clusters.Most of the doped clusters reported are binary metal nanoclusters via one metal heteroatom doping into a metal nanocluster,while the preparation and properties of ternary metal nanoclusters via two heteroatoms doping into a metal nanocluster are rarely studied.In this work,we report the Pd and Hg co-doped ternary metal nanocluster HgPdAu_(23)(PET)_(18)(PET=2-phenylethanethiol)using the Au_(25)(PET)_(18) nanocluster as an ideal template that can be viewed as a Au13 icosahedral core protected by the exterior 12 Au atoms as a shell.The structural framework of the HgPdAu_(23)(PET)_(18) nanocluster is similar to that of its parent Au_(25)(PET)_(18) nanocluster,determined by single-crystal X-ray crystallography and electrospray ionization mass spectroscopy(ESI-MS),which shows a 13-atom icosahedral core and a 12-atom shell capped by 18 thiolate ligands.It indicated that the doping strategy might destroy the total structure(core plus surface)of the parent nanocluster,which will offer an excited opportunity for the correlation of the structure with properties of the doped nanoclusters.More notably,the possible doping location of the Pd and Hg atoms in the HgPdAu_(23)(PET)_(18) nanocluster can be determined by the combination of single-crystal X-ray crystallography and nuclear magnetic resonance(NMR)spectroscopy(i.e.,1H NMR and two-dimentional NMR).It is suggested that the Pd atom is possibly located on the center of the icosahedron of the HgPdAu_(23)(PET)_(18) nanocluster,while the Hg atom is possibly located on the surface of the icosahedron of the HgPdAu_(23)(PET)_(18) nanocluster.The electronic configuration of HgPdAu_(23)(PET)_(18) nanocluster is distinct from those of the parent Au_(25)(PET)_(18) and one-metal doped PdAu_(24)(PET)_(18) and HgAu_(24)(PET)_(18) nanoclusters,which can be implied by the X-ray photoelectron spectroscopy(XPS)and UV-Vis absorption spectroscopy.This st

关 键 词：金属团簇 异原子 掺杂 结构 

分 类 号：TB383.1[一般工业技术—材料科学与工程] O641.1[理学—物理化学]