An alloy cluster containing a 13-atom core, with a composition Ag 7Au 6(H 2MSA) 10 (H 2MSA= mercaptosuccinic acid) was synthesized from silver clusters by a galvanic exchange reaction. The clusters were characterized by several spectroscopic and microscopic methods. The alloy cluster shows luminescence with a quantum yield of 3.5 × 10 -2 at room temperature. Theoretical calculations for Ag 7Au 6(SCH 3) 10 suggest a distorted icosahedral core. Copyright © 2012 WILEY-VCH Verlag GmbH &amp; Co. KGaA, Weinheim.

Pradeep Thalappil

Department Of Chemistry

ALLOY CLUSTER

ESI-MS

GALVANIC EXCHANGE

MERCAPTOSUCCINIC ACIDS

MICROSCOPIC METHODS

QUANTUM CLUSTERS

Room temperature

SILVER CLUSTER

Theoretical calculations

Alloys

Cerium alloys

Luminescence

quantum yield

Silver

Silver alloys

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

Angewandte Chemie - International Edition

ConspectusNanoparticles exhibit a rich variety in terms of structure, composition, and properties. However, reactions between them remain largely unexplored. In this Account, we discuss an emerging aspect of nanomaterials chemistry, namely, interparticle reactions in solution phase, similar to reactions between molecules, involving atomically precise noble metal clusters. A brief historical account of the developments, starting from the bare, gas phase clusters, which led to the synthesis of atomically precise monolayer protected clusters in solution, is presented first. Then a reaction between two thiolate-protected, atomically precise noble metal clusters, [Au25(PET)18]- and [Ag44(FTP)30]4- (PET = 2-phenylethanethiol, FTP = 4-fluorothiophenol), is presented wherein these clusters spontaneously exchange metal atoms, ligands, and metal-ligand fragments between them under ambient conditions. The number of exchanged species could be controlled by varying the initial compositions of the reactant clusters. Next, a reaction of [Au25(PET)18]- with its structural analogue [Ag25(DMBT)18]- (DMBT = 2,4-dimethylbenzenethiol) is presented, which shows that atom-exchange reactions happen with structures conserved. We detected a transient dianionic adduct, [Ag25Au25(DMBT)18(PET)18]2-, formed between the two clusters indicating that this adduct could be a possible intermediate of the reaction. A reaction involving a dithiolate-protected cluster, [Ag29(BDT)12]3- (BDT = 1,3-benzenedithiol), is also presented wherein metal atom exchange alone occurs, but with no ligand and fragment exchanges. These examples demonstrate that the nature of the metal-thiolate interface, that is, its bonding network and dynamics, play crucial roles in dictating the type of exchange processes and overall rates. We also discuss a recently proposed structural model of these clusters, namely, the Borromean ring model, to understand the dynamics of the metal-ligand interfaces and to address the site specificity and selectivity in these reactions.In the subsequent sections, reactions involving atomically precise noble metal clusters and one- and two-dimensional nanosystems are presented. We show that highly protected, stable clusters such as [Au25(PET)18]- undergo chemical transformation on graphenic surfaces to form a bigger cluster, Au135(PET)57. Finally, we present the transformation of tellurium nanowires (Te NWs) to Ag-Te-Ag dumbbell nanostructures through a reaction with an atomically precise silver cluster, Ag32(SG)19 (SG = glutathione thiolate).The starting materials and the products were characterized using high resolution electrospray ionization mass spectrometry, matrix assisted laser desorption ionization mass spectrometry, UV/vis absorption, luminescence spectroscopies, etc. We have analyzed principally mass spectrometric data to understand these reactions.In summary, we present the emergence of a new branch of chemistry involving the reactions of atomically precise cluster systems, which are prototypical nanoparticles. We demonstrate that such interparticle chemistry is not limited to metal clusters; it occurs across zero-, one-, and two-dimensional nanosystems leading to specific transformations. We conclude this Account with a discussion of the limitations in understanding of these reactions and future directions in this area of nanomaterials chemistry. © 2017 American Chemical Society.

Accounts of Chemical Research

Interparticle Reactions: An Emerging Direction in Nanomaterials Chemistry

Reactivity of monolayer protected atomically precise clusters of noble metals is of significant research interest. To date very few experimental data are available on the reaction thermodynamics of such clusters. Here we report a calorimetric study of the reaction of glutathione (GSH) protected silver clusters in the presence of excess ligand, GSH, using isothermal titration calorimetry (ITC). We have studied Ag11(SG)7 and Ag32(SG)19 clusters and compared their reactivity with GSH protected silver nanoparticles (AgNPs) and silver ions. Clusters show intermediate reactivity toward excess ligand compared to nanoparticles and silver ions. Several control experiments were performed to understand the degradation mechanism of these silver clusters and nanoparticles. The effect of dissolved oxygen in the degradation process was studied in detail, and it was found that it did not have a significant role, although alternate pathways of degradation with the involvement of oxygen cannot be ruled out. Direct confirmation of the fact that functionalized metal clusters fall in-between NPs and atomic systems in their stability is obtained experimentally for the first time. Several other thermophysical parameters of these clusters were also determined, including density, speed of sound, isentropic compressibility, and coefficient of thermal expansion. © 2017 American Chemical Society.

Fulltext

Journal of Physical Chemistry C

Reactivity of Monolayer Protected Silver Clusters toward Excess Ligand: A Calorimetric Study

Reactivity of two different nanosystems of silver, namely nanoparticles and atomically precise clusters, toward 1D tellurium nanowires (NWs) was probed and compared with the reaction of silver ions. While the reaction of nanoparticles and ions led to silver telluride nanowires, a different reactivity was exhibited by clusters which resulted in silver islands at different positions on the Te NWs. These hybrid Ag nodule-decorated Te NWs are sensitive to temperature, and they transform to dumbbell-shaped silver-tipped Te NWs upon solution phase annealing. Differences in chemical reactivity of nanoparticles of two different size regimes with nanowires are demonstrated. Synthetic methods of this kind will be useful in creating complex nanostructures which are difficult to be made in the solution phase. © 2014 American Chemical Society.

Chemistry of Materials

Manifestation of the difference in reactivity of silver clusters in contrast to its ions and nanoparticles: The growth of metal tipped Te nanowires

A selenolate-protected Ag-Pd alloy cluster was synthesized using a one-pot solution-phase route. The crude product upon chromatographic analyses under optimized conditions gave three distinct clusters with unique optical features. One of these exhibits a molecular peak centered at m/z 2839, in its negative ion mass spectrum assigned to Ag5Pd4(SePh)12-, having an exact match with the corresponding calculated spectrum. Tandem mass spectrometry of the molecular ion peak up to MS9 was performed. Complex isotope distributions in each of the mass peaks confirmed the alloy composition. We find the Ag3Pd3- core to be highly stable. The composition was further supported by scanning electron microscopy, energy-dispersive spectroscopy, and X-ray photoelectron spectroscopy. (Graph Presented). © 2014 American Chemical Society.

Journal of Physical Chemistry Letters

Isolation and tandem mass spectrometric identification of a stable monolayer protected silver-palladium alloy cluster

A new strategy to synthesize a diverse array of organic-soluble, atomically precise silver clusters has been developed. The technique is based on the miscibility principle of solvents and uses no phase-transfer agents; various clusters of masses 8.0, 13.4, 22.8, 29.2, and 34.4 kDa were synthesized by changing the reactant composition. We have also synthesized the well-known Au<inf>25</inf>(SR)<inf>18</inf> cluster by the same method. Among the silver clusters formed, we have studied the new 13.4 kDa species, which has unique steplike features in its UV/Vis spectrum, in detail by mass spectrometry and other analytical techniques. The compound has been assigned as Ag<inf>68</inf>(SR)<inf>34</inf>, which is reported for the first time. By time-dependent studies, we have shown that the synthetic route follows the bottom-up approach. The material forms microcrystals. We hope that the proposed synthetic strategy will extend the area of atomically precise clusters. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

European Journal of Inorganic Chemistry

Synthesis of atomically precise silver clusters by using the miscibility principle

We report the chemical interactions of unsupported and alumina-supported Ag7 and Ag8 clusters protected with MSA (mercaptosuccinic acid) with heavy metal ions Hg(II), Cd(II), and Pb(II) in water at different concentrations. The investigation was carried out to determine the feasibility of this interesting new class of materials called quantum clusters for water purification. These systems were studied using various spectroscopic and microscopic techniques such as ultraviolet-visible spectroscopy, Fourier transform infrared spectroscopy, X-ray diffraction, dynamic light scattering, zeta potential measurements, scanning electron microscopy, transmission electron microscopy, Raman spectroscopy, and photoluminescence spectroscopy and in detail by X-ray photoelectron spectroscopy. We observed that the metal ions interact with both the silver atoms of the clusters and the functional groups of the capping agent (MSA). The mercuric ions were reduced to metallic mercury by both supported and unsupported clusters, due to the feasibility of the redox reaction, whereas no reduction was observed for Cd(II) and Pb(II). As a result of the interaction, the luminescence of the cluster is lost which can be used to sense Hg(II). At lower concentrations, the metal ions were chemically bonded to the carboxylate groups of MSA. Absence of reduction of Hg(II) at lower concentration is due to the chemical affinity of the ligands and the lower silver content per cluster compared to the number of carboxylate groups. © 2011 American Chemical Society.

Langmuir

Investigation into the reactivity of unsupported and supported Ag 7 and Ag8 clusters with toxic metal ions

We report the synthesis of highly luminescent, water soluble quantum clusters (QCs) of gold, which are stabilized by an iron binding transferrin family protein, lactoferrin (Lf). The synthesized AuQC@Lf clusters were characterized using UV-Visible spectroscopy, X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), photoluminescence (PL), matrix assisted laser desorption ionization mass spectrometry (MALDI-MS), FTIR spectroscopy and circular dichroism (CD) spectroscopy along with picosecond-resolved lifetime measurements. Detailed investigations with FTIR and CD spectroscopy have revealed changes in the secondary structure of the protein in the cluster. We have also studied Förster resonance energy transfer (FRET) occurring between the protein and the cluster. The ability of the clusters to sense cupric ions selectively at ppm concentrations was tested. The stability of clusters in widely varying pH conditions and their continued luminescence make it feasible for them to be used for intracellular imaging and molecular delivery, particularly in view of Lf protection. © 2010 The Royal Society of Chemistry.

Nanoscale

Luminescent quantum clusters of gold in transferrin family protein, lactoferrin exhibiting FRET

Ligand exchange offers an effective way to modify the properties of the recently prepared quantum clusters of gold. To tune optical and photoluminescence properties of one of the most stable quantum clusters of gold, AU25SG18 (SG-glutathione thiolate), we functionalized it by the exchange of - SG with functionalized -SG and with an altogether different ligand, namely, 3-mercapto-2-butanol (MB). The products were characterized by various techniques such as optical absorption (UV - vis), Fourier-transform infrared (FT - IR), nuclear magnetic resonance (NMR), X-ray photoelectron (XPS), and luminescence spectroscopies, mass spectrometry, and thermogravimetry (TG). Analyses of the TG data helped to establish the molecular composition of the products. Ligand exchange reaction was monitored by NMR spectroscopy, and it was found that the exchange reaction follows a first order kinetics. The XPS study showed that after the exchange reaction there was no change in the chemical nature of the metal core and binding energy values of Au 4f7/2 and 4f5/2, which are similar in both the parent and the exchanged products. Photoluminescence studies of these clusters, done in the aerated conditions, showed that the excitation spectrum of the MB-exchanged product is entirely different from the acetyl- and formyl-glutathione exchanged products. The inherent fluorescence and solid-state emission of these clusters were observed. This intense emission allows optical imaging of the material in the solid state. The emission is strongly temperature dependent. The synthesis of a diverse variety of clusters and their chemical stability and intense luminescence offer numerous applications in areas such as energy transfer, sensors, biolabeling, and drug delivery. © 2008 American Chemical Society.

Ligand exchange of Au25SG18 leading to functionalized gold clusters: Spectroscopy, kinetics, and luminescence

We report the instantaneous decomposition of the small molecular gold cluster, Au25SG18 (SG-glutathione thiolate) in the presence of externally added chloroaurate ions resulting in the instantaneous formation of the insoluble gold-glutathione polymer. The rate of decomposition, however, was much slower for the metal ions such as Ag+, Fe3+, Cu2+, Ni2+, Cd2+, Zn2+ and Sr2+. This chemical reactivity is shown to have no direct correlation with the electrochemical potential of the added ions. © 2007 Elsevier B.V. All rights reserved.

Journal	Angewandte Chemie - International Edition
ISSN	14337851
Open Access	No