Abstract
Atomically precise Au and Ag clusters protected by monolayers of organic ligands have attracted growing interests as promising building units of functional materials and ideal platforms to study size-dependent evolution of structures and physicochemical properties. The use of gas-phase methods including mass spectrometry, ion mobility mass spectrometry, collision-induced dissociation mass spectrometry, photoelectron spectroscopy, and photodissociation spectroscopy will reveal novel and complementary information on their intrinsic geometric and electronic structures that cannot be obtained by conventional characterization methods. This Perspective surveys the recent progress and outlook of gas-phase studies on chemically synthesized Au/Ag clusters.
Highlights
Metal clusters composed of fewer than a few hundred atoms are located in terms of size between the nanoparticles and atoms of the corresponding metal (Scheme 1) and have attracted the attention of scientists over the last four decades.1 The central issue since the early stage of research has been observing the finite-size effects on the physical properties of metal clusters and understanding their origins from a microscopic viewpoint
Chemical properties and binding strength have been studied by collision-induced dissociation/reaction mass spectrometry (CID/CIR-MASS SPECTROMETRY (MS))
It is widely recognized that various physicochemical properties of metal clusters deviate significantly from those of their bulk counterparts due to the unique geometric and electronic structures (Scheme 1) and evolve dramatically as a function of size, as exemplified by the metal–insulator transition
Summary
Metal clusters composed of fewer than a few hundred atoms are located in terms of size between the nanoparticles and atoms of the corresponding metal (Scheme 1) and have attracted the attention of scientists over the last four decades. The central issue since the early stage of research has been observing the finite-size effects on the physical properties of metal clusters and understanding their origins from a microscopic viewpoint. The first requirement for the chemical synthesis is to stabilize individual Au clusters against aggregation so that they can be treated as conventional chemical compounds This is achieved by passivation of the Au cluster surface with organic ligands L to yield monolayer-protected Au clusters (Au MPCs) with the formula of [AuxLy]z or by decorating with polymers. Mass spectrometry plays an essential role in studies on synthesizing [(Au/Ag)xLy]z: [1] determination of the chemical formula including net charge (x, y, z), which are the key descriptors of the clusters and [2] detection and identification of intermediate species transiently formed in solution during the formation or transformation reactions of the clusters. This section showcases typical examples of mass spectrometric characterization of Au/Ag MPCs and mass spectrometric detection of reaction intermediates
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