摘要
As an interdisciplinary product,water-soluble gold nanoclusters(AuNCs)stabilized by ligands containing carboxyl(-COOH)group have garnered significant attention from synthetic chemists and biologists due to their immense potential for biomedical applications.However,revealing the crystallographic structures of-COOH-functionalized AuNCs remains a bottleneck.Herein,we successfully applied the salting-out method to obtain a series of high-quality single crystals of-COOH-functionalized Au_(25)nanoclusters and revealed their crystallographic structures.Particularly,K_(3)Au_(25)(2-Hmna)_9(mna)_6]^(-)(Au25a)protected by 2-mercaptonicotinic acid features an unprecedented tetrameric Au_(4)(SR^(S))_(3)(SR^(S,N))_(2)staple motifs surrounding the icosahedral Au_(13)kernel,breaking the traditional perception on the structure of Au_(25)(SR)_(18).Au25a exhibits a distinct near-infrared emission at 970 nm with long lifetime of 8690 ns,which have been studied by transient absorption spectroscopy and time-dependent density functional theory.This work compensates for the research gap in the experimental structure of-COOHfunctionalized AuNCs and opens up a new avenue to explore their structure-property correlations.
作者
田伟东
司为丹
Shana Havenridge
张成凯
王芝
Christine M.Aikens
佟振合
孙頔
Wei-Dong Tian;Wei-Dan Si;Shana Havenridge;Chengkai Zhang;Zhi Wang;Christine M.Aikens;Chen-Ho Tung;Di Sun(School of Chemistry and Chemical Engineering,State Key Laboratory of Crystal Materials,Shandong University,Jinan 250100,China;Department of Chemistry,Kansas State University,Manhattan KS 66506,USA)
基金
the National Natural Science Foundation of China(22201159 to Z.W.,22171164,22325105,52261135637 to D.S.)
the Fok Ying Tong Education Foundation(171009)
the Natural Science Foundation of Shandong Province(ZR2019ZD45,ZR2020ZD35,JQ201803,and ZR2017MB061)
the Taishan Scholar Project of Shandong Province of China(tsqn201812003 and ts20190908)
the National Postdoctoral Innovative Talents Support Program(BX2021171)
China Postdoctoral Science Foundation(2021M700081)。
