The controllable transformation of metal nanoclusters remains highly desirable for the preparation of new clusters with novel structures and the elucidation of cluster conversion mechanisms.Here,we present the reversi...The controllable transformation of metal nanoclusters remains highly desirable for the preparation of new clusters with novel structures and the elucidation of cluster conversion mechanisms.Here,we present the reversible transformation between two high-nuclearity silver cluster homologs,Ag_(32)S_(3)(S^(t)Bu)_(16)(CF_(3)COO)_(9)(CH_(3)CN)_(4)(NO_(3))(abbreviated as monomer-Ag_(32))and[Ag_(32)S_(3)(S^(t)Bu)_(16)(CF_(3)COO)_(9)(CH_(3)CN)(NO_(3))]_(2)(abbreviated as dimer-(Ag_(32))_(2)).Triggered by the solvent effect,the reversible conversion between monomer-Ag_(32) and dimer-(Ag_(32))_(2) nanoclusters has been accomplished.For dimer-(Ag_(32))_(2),two CF_(3)COO-linkers were bound onto the symmetrical edges of adjacent Ag_(32) subunits,giving rise to the dimeric existence form of the final cluster.The optical properties,including optical absorptions and emissions,of the cluster monomer and dimer were then compared.This work offered an interesting case for constructing self-assembled cluster structures with the assistance of certain solvents and multidentate ligands.展开更多
Monolayer-protected nanoclusters are ideal models for understanding the correlations between structures and properties of inorganic nanoparticles,especially for those molecules with identical sizes but comparable stru...Monolayer-protected nanoclusters are ideal models for understanding the correlations between structures and properties of inorganic nanoparticles,especially for those molecules with identical sizes but comparable structures.Here,we controllably prepared and structurally determined a valence-neutral Au_(24+x)Ag_(20-x)(SPhtBu)_(26)(0<x<4)nanocluster with comparable structure features to a well-known Au_(12)Ag_(32)(SPhF_(2))_(30) cluster.The Au_(24+x)Ag_(20-x)(SPhtBu)_(26) cluster contained a hollow Au_(12)@M_(20) metallic kernel(M=Au/Ag),12 Au_(1)(SR)_(2) staples,and two bridging SR molecules,and its average molecular formula was determined to be Au_(26.3)Ag_(17.7)(SPhtBu)_(26),as evidenced by X-ray crystallography and electrospray ionization mass spectrometry.Because of the ligand effect and the asymmetrical arrangement of the Au dopants in the dodecahedral cage,the Au_(24+x)Ag_(20-x)(SPhtBu)_(26) nanocluster exhibited lower molecular symmetry relative to Au_(12)Ag_(32)(SPhF_(2))_(30) in terms of the dodecahedral kernel and motif shell structures.Besides,the strong π-π interaction in Au2_(4+x)Ag_(20-x)(SPhtBu)_(26) contributed to its enhanced photoluminescence intensity compared with Au_(12)Ag_(32)(SPhF_(2))_(30).The study,herein,extends the 44-metal-atom cluster family,thereby enabling us to better understand the correlations between their structures and properties at the atomic level.展开更多
基金the financial support of the National Natural Science Foundation of China(21631001,21871001,and 22101001)the Ministry of Education,the University Synergy Innovation Program of Anhui Province(GXXT-2020-053)the Scientific Research Program of Universities in Anhui Province(2022AH030009).
文摘The controllable transformation of metal nanoclusters remains highly desirable for the preparation of new clusters with novel structures and the elucidation of cluster conversion mechanisms.Here,we present the reversible transformation between two high-nuclearity silver cluster homologs,Ag_(32)S_(3)(S^(t)Bu)_(16)(CF_(3)COO)_(9)(CH_(3)CN)_(4)(NO_(3))(abbreviated as monomer-Ag_(32))and[Ag_(32)S_(3)(S^(t)Bu)_(16)(CF_(3)COO)_(9)(CH_(3)CN)(NO_(3))]_(2)(abbreviated as dimer-(Ag_(32))_(2)).Triggered by the solvent effect,the reversible conversion between monomer-Ag_(32) and dimer-(Ag_(32))_(2) nanoclusters has been accomplished.For dimer-(Ag_(32))_(2),two CF_(3)COO-linkers were bound onto the symmetrical edges of adjacent Ag_(32) subunits,giving rise to the dimeric existence form of the final cluster.The optical properties,including optical absorptions and emissions,of the cluster monomer and dimer were then compared.This work offered an interesting case for constructing self-assembled cluster structures with the assistance of certain solvents and multidentate ligands.
基金the financial support of the NSFC(21631001,21871001,and 22101001)the Ministry of Education,and the University Synergy Innovation Program of Anhui Province(GXXT-2020-053).
文摘Monolayer-protected nanoclusters are ideal models for understanding the correlations between structures and properties of inorganic nanoparticles,especially for those molecules with identical sizes but comparable structures.Here,we controllably prepared and structurally determined a valence-neutral Au_(24+x)Ag_(20-x)(SPhtBu)_(26)(0<x<4)nanocluster with comparable structure features to a well-known Au_(12)Ag_(32)(SPhF_(2))_(30) cluster.The Au_(24+x)Ag_(20-x)(SPhtBu)_(26) cluster contained a hollow Au_(12)@M_(20) metallic kernel(M=Au/Ag),12 Au_(1)(SR)_(2) staples,and two bridging SR molecules,and its average molecular formula was determined to be Au_(26.3)Ag_(17.7)(SPhtBu)_(26),as evidenced by X-ray crystallography and electrospray ionization mass spectrometry.Because of the ligand effect and the asymmetrical arrangement of the Au dopants in the dodecahedral cage,the Au_(24+x)Ag_(20-x)(SPhtBu)_(26) nanocluster exhibited lower molecular symmetry relative to Au_(12)Ag_(32)(SPhF_(2))_(30) in terms of the dodecahedral kernel and motif shell structures.Besides,the strong π-π interaction in Au2_(4+x)Ag_(20-x)(SPhtBu)_(26) contributed to its enhanced photoluminescence intensity compared with Au_(12)Ag_(32)(SPhF_(2))_(30).The study,herein,extends the 44-metal-atom cluster family,thereby enabling us to better understand the correlations between their structures and properties at the atomic level.
