Switching a Nanocluster Core from Hollow to Nonhollow

Abstract

ABSTRACT:Modulating the structure-property relationship in atomically precise nanoclusters (NCs) is vital for developing novel NC materials and advancing their applications. While promising biphasic ligand-exchange (LE) strategies have been developed primarily to attain novel NCs, understanding the mechanistic aspects involved in tuning the core and the ligand-shell of NCs in such biphasic processes is challenging. Here, we design a single phase LE process that enabled us to elucidate the mechanism of how a hollow NC (e.g., [Ag 44 (SR) 4-. Remarkably, both the forward and the backward reactions proceed through similar size intermediates that seem to be governed by the boundary conditions set by the thermodynamic and electronic stability of the hollow and non-hollow metal cores. Furthermore, the resizing of NCs highlights the surprisingly long-range effect of the ligands which are felt by atoms far deep in the metal core, thus opening a new path for controlling the structural evolution of nanoparticles.

[Ag67(SPhMe2)32(PPh3)8]3+: Synthesis, Total Structure, and Optical Properties of a Large Box-Shaped Silver Nanocluster

“…Nevertheless, the number of stable atomically monodisperse thiolate-protected silver NCs is rising, having attracted much research attention with the hope of utilizing them as a viable and cheaper alternative to gold. [25][26][27][28][29][30][31][32][33][34] A key challenge remaining for silver NCs is obtaining highly anisotropic shapes. In gold, NCs of anisotropic shapes were reported through solely thiols 35,36 and co-ligands of phosphines and thiols 37,38 .…”

Ligand-Exchange-Induced Growth of an Atomically Precise Cu29 Nanocluster from a Smaller Cluster

“…8 Similarly, thiolate ligand exchange mediates the conversion of a Ag 44 cluster into a smaller Ag 25 cluster. 9 In both of these examples, the change in cluster size likely occurs via thermally-induced disproportionation of an unstable intermediate in the presence of a very large excess of the new ligand, a process which has been called ligand-exchange-induced size/structure transformation (LEIST). 1,10 Generally speaking, however, the mechanisms of ligand exchange and cluster rearrangement are still poorly understood, and researchers are only now beginning to probe these questions.…”

Smart Transformation of a Polyhedral Oligomeric Silsesquioxane Shell Controlled by Thiolate Silver(I) Nanocluster Core in Cluster@Clusters Dendrimers

“…TheS i···S distances are about 5.095 and angles in SÀCÀCÀCÀSi are about 1128 8,1 238 8,a nd 1148 8,r espectively, which is an abnormal distortion (Supporting Information, Figure S2). 2, 4101.9, 3102.8, and 2104.6 5 + H] + .T ot he best of our knowledge,t his is the first example of as tructurally characterized POSS protected silver(I) cluster at the atomic level by single-crystal X-ray diffraction analysis. [12b] Thep urity of 1a is confirmed by its unique MALDI MS spectrum (Supporting Information, Figure S3), showing four characteristic fragmentation products at m/z 5099.…”

“…[1][2][3][4][5][6] Structure-defined silver(I) nanoclusters can be synthesized by self-assembly of alkynyl, thiolate or organophosphorus ligands with silver(I) salts, [4] of which their structures and functions can be modulated by different choice of central template anions,a uxiliary ligands,o r reaction conditions. [1][2][3][4][5][6] Structure-defined silver(I) nanoclusters can be synthesized by self-assembly of alkynyl, thiolate or organophosphorus ligands with silver(I) salts, [4] of which their structures and functions can be modulated by different choice of central template anions,a uxiliary ligands,o r reaction conditions.…”

“…Silver(I) nanoclusters have attracted much attention in recent years owing to their intriguing structures and potential applications in luminescence,sensors,and even as anticancer materials. [1][2][3][4][5][6] Structure-defined silver(I) nanoclusters can be synthesized by self-assembly of alkynyl, thiolate or organophosphorus ligands with silver(I) salts, [4] of which their structures and functions can be modulated by different choice of central template anions,a uxiliary ligands,o r reaction conditions. [5] Thec urrent study on these silver(I) clusters mainly focus on their diverse supramolecular structures,s uperficial physicochemical functions,a nd even chirality,while it remains elusive for the design of smart silver(I) clusters that can undergo as tructural change upon outside stimuli.…”