Crystallization-induced emission enhancement: A novel fluorescent Au-Ag bimetallic nanocluster with precise atomic structure

Abstract

Crystallization-induced emission enhancement was achieved in metal nanoclusters for the first time.

Isomer Structural Transformation in Au–Cu Alloy Nanoclusters: Water Ripple‐Like Transfer of Thiol Ligands

“…The atomically precise nanocluster is amenable to characterization by single crystal X‐ray diffraction (SC‐XRD) techniques . The internal arrangement of cluster can be revealed, especially for the organic–inorganic (ligand–metal) interfaces, which are beneficial for studies in terms of the origin of isomerism at the atomic level …”

Heteroatom‐Doping Increases Cluster Nuclearity: From an [Ag20] to an [Au3Ag18] Core

“…While structurally precise thiolate‐ and selenolate‐protected gold nanoclusters with different metal nuclearities and compositions have been extensively studied, recent advances in nanoscale synthesis also led to the inventions of a few atom‐precise thiol‐ and dithiol‐capped homoleptic silver nanoclusters, for example, [Ag 44 (SR) 30 ] 4− (SR=SPhF 2 /SPhCOOH),, [Ag 25 (SPhMe 2 ) 18 ] − , [Ag 20 {S 2 P(OR) 2 } 12 ] (R=Pr, i Pr), [Ag 21 {S 2 P(O i Pr) 2 } 12 ] + , and heteroatom‐doped (Au, Pd, and Pt) Ag‐rich nanoclusters for example, [Ag 24 Au(SR) 18 ] − (R=PhMe 2 ), [MAg 24 (SR) 18 ] 2− (M=Pd/Pt; SR=2,4‐SPhCl 2 ), [Pt 1 Au 6.4 Ag 17.6 (SPhMe 2 ) 18 ] 2− , and [AuAg 19 {S 2 P(OPr) 2 } 12 ] . In addition, some mixed thiolate‐ and phosphine‐protected Ag‐rich nanoclusters, such as [Ag 29 (BDT) 12 (TPP) 4, Au 4 Ag 13 (dppm) 3 (SPhMe 2 ) 9 ], [PtAg 28 (BDT) 12 (PPh 3 ) 4 ] 4− , and [Au x Ag 50− x (dppm) 6 (SR) 30 ] , are also known (BDT=benzene‐1,3‐dithiol; TPP=Ph 3 P; dppm=bis(diphenylphosphino)methane); SR=4‐ tert ‐butylbenzyl mercaptan). In contrast, structurally‐precise selenolate‐passivated silver nanoclusters have rarely been studied.…”

The Origin of the Photoluminescence Enhancement of Gold‐Doped Silver Nanoclusters: The Importance of Relativistic Effects and Heteronuclear Gold–Silver Bonds

“…[1][2][3][4][5][6][7][8][9] Over the past decades,t heir spectroscopic properties,e xcited-state relaxation, and photoluminescence dynamics have been studied both experimentally and computationally. [10][11][12][13][14][15][16][17][18][19][20][21][22][23][24][25][26][27][28] Luminescent nanoclusters offer great promise for applications in optoelectronics and optical sensors.H owever, atomically precise Ag nanoclusters with well-defined coreshell structures usually have weak photoluminescence,which limits their utility as luminescent nanomaterials.R ecently, Bakr and co-workers [29,30] systematically explored the photoluminescence properties of [Ag 29 (BDT) 12 (TPP) 4 ] 3À (BDT = 1,3-benzenedithiol, TPP = triphenylphosphine;a bbreviated as Ag 29 hereinafter;F igure 1) and its Au-doped nanoclusters by single-crystal X-ray diffraction, mass spectrometry,aswell as optical and NMR spectroscopy.Byvarying the Au amount in the Ag and Au precursors,as eries of [Ag 29Àx Au x (BDT) 12 -(TPP) 4 ] 3À (x = 1-5;A g 29Àx Au x )n anoclusters have been produced. Interestingly,u pon increasing the amount of the Au precursor from 0t o4 0mmol %, significantly enhanced luminescence was observed.…”

“…[31][32][33] However,a lmost all available computational studies of Ag nanoclusters focus on low-lying geometric structures and absorption spectra. [17][18][19][20][21][22][23][34][35][36][37] Almost no work on the luminescence of Ag nanoclusters has been published in the past years. [38] Moreover, the reasons for the photoluminescence enhancement of Au-doped Ag 29 nanoclusters have not been explored computationally until now.…”