Rapid solution-state exchange dynamics in nanoscale pieces of matter is revealed, taking isotopically pure atomically precise clusters as examples. As two isotopically pure silver clusters made of 107 Ag and 109 Ag are mixed, an isotopically mixed cluster of the same entity results, similar to the formation of HDO, from H 2 O and D 2 O. This spontaneous process is driven by the entropy of mixing and involves events at multiple time scales. Copyright © 2019 The Authors.

Pradeep Thalappil

Department Of Chemistry

Papri Chakraborty

Abhijit Nag

Ganapati Natarajan

Ganesan Paramasivam

ENTROPY OF MIXING

EXCHANGE DYNAMICS

ISOTOPIC EXCHANGE

MIXED CLUSTERS

MULTIPLE TIME SCALE

Nano scale

SILVER CLUSTER

SPONTANEOUS PROCESS

Fulltext

IIT Madras is a public technical and research university located in Chennai, Tamil Nadu. Founded in 1959, it is recognised as an Institute of National Importance.

IIT Madras has been ranked as the top engineering institute in India for four years in a row by the National Institutional Ranking Framework of the MHRD

It currently offers undergraduate, postgraduate and research degrees across 16 disciplines in Engineering, Sciences, Humanities and Management. About 596 faculty belonging to science and engineering departments and centres of the Institute are engaged in teaching, research and industrial consultancy.

IIT Madras

Science Advances

Mass spectrometry (MS), a hundred-year-old subject, has been a technique of profound importance to molecular science. Its impact in solid-state materials science has not been evident, although many materials of modern science, such as fullerenes, have their origins in MS. Of late, mass spectrometric interface with materials is increasingly strengthened with advances in atomically precise clusters of noble metals. Advances in instrumentation along with recent developments in synthetic approaches have expanded the chemistry of clusters, and new insights into matter at the nanoscale are emerging. High-resolution MS coupled with soft ionization techniques enable efficient characterization of atomically precise clusters. Apart from that, techniques such as ion mobility, tandem MS, etc. reveal structural details of these systems. Growth, nucleation, and reactivity of clusters are also probed by MS. Some of the recent advancements in this field include the development of new hyphenated techniques. Finer structural details may be obtained by coupling MS with spectroscopic tools, such as photoelectron spectroscopy, vacuum ultraviolet spectroscopy, etc. With such advancements in instrumentation, MS can evolve into a universal tool for the characterization of materials. The present review captures highlights of this area. © 2019, The Author(s).

NPG Asia Materials

The emerging interface of mass spectrometry with materials

Rapid isotopic exchange in nanoparticles

We present the first example of polymorphism (cubic &amp; trigonal) in single crystals of an atomically precise monolayer protected cluster, Ag29(BDT)12(TPP)43-. We demonstrate that C-H⋯π interactions of the secondary ligands (TPP) are dominant in a cubic lattice compared to a trigonal lattice, resulting in a greater rigidity of the structure, which in turn, results in a higher luminescence efficiency in it. © 2018 The Royal Society of Chemistry.

Nanoscale

Polymorphism of Ag29(BDT)12(TPP)43- cluster: Interactions of secondary ligands and their effect on solid state luminescence

Atomically precise pieces of matter of nanometer dimensions composed of noble metals are new categories of materials with many unusual properties. Over 100 molecules of this kind with formulas such as Au25(SR)18, Au38(SR)24, and Au102(SR)44 as well as Ag25(SR)18, Ag29(S2R)12, and Ag44(SR)30 (often with a few counterions to compensate charges) are known now. They can be made reproducibly with robust synthetic protocols, resulting in colored solutions, yielding powders or diffractable crystals. They are distinctly different from nanoparticles in their spectroscopic properties such as optical absorption and emission, showing well-defined features, just like molecules. They show isotopically resolved molecular ion peaks in mass spectra and provide diverse information when examined through multiple instrumental methods. Most important of these properties is luminescence, often in the visible-near-infrared window, useful in biological applications. Luminescence in the visible region, especially by clusters protected with proteins, with a large Stokes shift, has been used for various sensing applications, down to a few tens of molecules/ions, in air and water. Catalytic properties of clusters, especially oxidation of organic substrates, have been examined. Materials science of these systems presents numerous possibilities and is fast evolving. Computational insights have given reasons for their stability and unusual properties. The molecular nature of these materials is unequivocally manifested in a few recent studies such as intercluster reactions forming precise clusters. These systems manifest properties of the core, of the ligand shell, as well as that of the integrated system. They are better described as protected molecules or aspicules, where aspis means shield and cules refers to molecules, implying that they are "shielded molecules". In order to understand their diverse properties, a nomenclature has been introduced with which it is possible to draw their structures with positional labels on paper, with some training. Research in this area is captured here, based on the publications available up to December 2016. © 2017 American Chemical Society.

Chemical Reviews

Atomically Precise Clusters of Noble Metals: Emerging Link between Atoms and Nanoparticles

Ambient, structure-and topology-preserving chemical reactions between two archetypal nanoparticles, Ag 25 (SR) 18 and Au 25 (SR) 18, are presented. Despite their geometric robustness and electronic stability, reactions between them in solution produce alloys, Agm Aun (SR)18 (m+n=25), keeping their M25 (SR)18 composition, structure and topology intact. We demonstrate that a mixture of Ag25 (SR)18 and Au25 (SR)18 can be transformed to any arbitrary alloy composition, Agm Aun (SR)18 (n=1-24), merely by controlling the reactant compositions. We capture one of the earliest events of the process, namely the formation of the dianionic adduct, (Ag25 Au25 (SR)36) 2-, by electrospray ionization mass spectrometry. Molecular docking simulations and density functional theory (DFT) calculations also suggest that metal atom exchanges occur through the formation of an adduct between the two clusters. DFT calculations further confirm that metal atom exchanges are thermodynamically feasible. Such isomorphous transformations between nanoparticles imply that microscopic pieces of matter can be transformed completely to chemically different entities, preserving their structures, at least in the nanometric regime. © 2016 The Author(s).

Nature Communications

Structure-conserving spontaneous transformations between nanoparticles

Atomically precise monolayer protected clusters are molecules comprising a few-atom cluster core of a noble metal, typically Au or Ag, surrounded by a protective layer of ligands, exhibiting many special optical, electrical, catalytic, and magnetic properties, and are emerging as important materials in biology, medicine, catalysis, energy conversion and storage, and sensing. The structural diversity of these clusters or aspicules, as we definitively term them, meaning shielded molecules, combining the Greek word aspis (shield) with molecule, is rapidly increasing due to new compositions and modification routes such as ligand-exchange, alloying, or supramolecular functionalization. We present a structural analysis of the most stable cluster of this kind, Au25(SR)18, and propose a Borromean rings diagram for the cluster, showing its topological configuration of three interlocked (Au8S6)-rings. This simplified two-dimensional diagram is used to represent its structure and modifications via ligand or metal atom substitution uniquely. We enumerate and name its isomers with two-ligand or metal atom substituents. Among the several structural insights obtained, the identification of the Borromean rings-interlocked configuration in Au25(SR)18 may explain its high geometric stability and indicate a possible general unified structural viewpoint for these clusters without the division between core and staple motifs. On the basis of our structural analysis, we developed a structure-based nomenclature system that can be applied to both describe and understand the structure and modifications of gold thiolate clusters, AuM(SR)N, and is adaptable to the general case of MM(X)N (M, metal and X, ligand). The application of structural analysis and diagrams to Au38(SR)24 and Au102(SR)44, revealing the possible formation of the cluster core by stacking or growth of rings of metal atoms, is also presented. © 2015 American Chemical Society.

Journal of Physical Chemistry C

A Unified Framework for Understanding the Structure and Modifications of Atomically Precise Monolayer Protected Gold Clusters

Journal	Data powered by TypesetScience Advances
Publisher	Data powered by TypesetAmerican Association for the Advancement of Science
ISSN	23752548
Open Access	No