摘要
我们在此报道了一种未曾发现的有趣现象:尽管[Au_(23)(SC_6H_(11))_(16)]-、Au_(24)(SC_2H_4Ph)_(20)(Ph:苯环)、Au_(36)(TBBT)_(28)(TBBTH:对叔丁基苯硫酚)、Au_(38)(SC_2H_4Ph)_(24)、混合Au_x(SC_2H_4Ph)_y团簇及3nm的金纳米粒子有不同的组成、结构、尺寸和保护性硫醇配体,但它们在三苯基膦(PPh_3)作用下,均能统一地经由亚稳的[Au_(11)(PPh_3)_8Cl_2]^(2+)最终转化为稳定的双二十面体[Au_(25)(PPh_3)_(10)(SR)_5Cl_2]^(2+)(SR:硫醇配体)。换句话说,三苯基膦是这些硫醇保护的纳米粒子的统一转化器。然而,聚乙稀吡咯烷酮(PVP)/柠檬酸盐(Citrate)保护的金纳米粒子和[Ag_(25)(SPhMe_2)_(18)]-(Me:甲基)在同样的条件下,却不能转化为[Au_(25)(PPh_3)_(10)(SR)_5Cl_2]^(2+)或[Ag_(25)(PPh_3)_(10)(SR)_5Cl_2]^(2+),暗示了硫醇保护的金纳米粒子具有与三苯基膦反应的独特性能。另外,我们考察了配体对双二十面体[Au_(25)(PPh_3)_(10)(SR)_5Cl_2]^(2+)团簇荧光性能的影响。
Abstract： Research on gold nanoclusters is at the frontier of nanoscience and nanotechnology. The introduction of the first phosphine- protected gold nanocluster, Au11（PPh3）7（SCN）3 （where PPh3 stands for triphenylphosphine and Ph stands for benzene）, can be dated back to 1969. As research in the field progressed, many structures of phosphine- protected nanoclusters such as Au5, Au8, Au13, and Au39 were reported. However, the stability of these phosphine-protected nanoclusters was not satisfactory, which handicapped their research and application. In an attempt to find alternatives for phosphine-protected nanoclusters, thiolated gold nanoclusters have attracted extensive attention in recent years. So far, there has been great progress primarily owing to the development of wet-chemical synthesis techniques, among which the utilization of ligand-exchange has been proved to be very effective to synthesize thiolated gold nanoclusters. It can be easily understood that phosphine in gold nanoclusters can be exchanged with thiolate because the latter has stronger affinity for gold. However, we recently found that the reverse ligand-exchange, i.e., the exchange of thiolate with phosphine, can also take place. Some questions have naturally arisen： Is the reverse ligand-exchange only applicable to superatomic [Au25（SR）18]- （SR： thiolate） nanoclusters？ Can it occur in other thiolated gold nanoclusters？ If so, is this reverse ligand-exchange also dependent on the starting nanoclusters？ These intriguing issues have inspired us to conduct this work. We investigated the reactions of PPh3 with some thiolated gold nanoparticles, including [Au23（SC6H11）16]-, Au24（SC2H4Ph）20, Au36（TBBT）28 （where TBBT stands for 4-（tert-butyl） benzene-l-thiolate）, Au38（SC2H4Ph）20, mixed nanoclusters, and 3 nm Au nanoparticles. Surprisingly, the experimental results showed that under the action of PPh3, thiolated gold nanoclusters （or nanoparticles） with different compositions, structures, si
作者
祝敏
李漫波
姚传好
夏楠
赵燕
闫楠
廖玲文
伍志鲲
ZHU Min;LI Manbo;YAO Chuanhao;XIA Nan;ZHAO Yan;YAN Nan;LIAO Lingwen;WU Zhikun(Key Laboratory of Materials Physics, Anhui Key Laboratory of Nanomaterials and Nanotechnology, CAS Center for Excellence in Nanoscience, Institute of Solid State Physics, Chinese Academy of Sciences, Hefiei 230031, P. R. China;University of Science and Technology of China, Hefei 230026, R R. China.)
出处
《物理化学学报》
SCIE
CAS
CSCD
北大核心
2018年第7期792-798,共7页
Acta Physico-Chimica Sinica
基金
supported by the National Natural Science Foundation of China(21222301,21528303,21603234,21771186,21171170,and 21601193)
the National Basic Research Program of China(2013CB934302)
the Innovative Program of Development Foundation of Hefei Center for Physical Science and Technology(2014FXCX002)
the CAS/SAFEA International Partnership Program for Creative Research Teams~~
