A copper cluster protected with 2-phenylethanethiol (PET) exhibiting distinct optical features in UV/Vis spectroscopy is reported. Matrix-assisted laser desorption ionisation mass spectrometry of the cluster shows a well-defined molecular ion peak at m/z 5,800, assigned to ~Cu 38(PET)25. Fragmented ions from the cluster show the expected isotope patterns in electrospray ionisation mass spectrometry. The as-synthesized cluster was well-characterised using other tools as well. Clusters undergo decomposition in about 2 h after synthesis as a metallic few-atom core of copper is highly unstable. The products of decomposition were also characterised. © 2013 Springer Science+Business Media Dordrecht.

Pradeep Thalappil

Department Of Chemistry

2-PHENYLETHANETHIOL

ATOMICALLY PRECISE

ELECTROSPRAY IONISATION MASS SPECTROMETRIES

ESI MS

MALDI-MS

MATRIX ASSISTED LASER DESORPTION

MOLECULAR ION PEAKS

UV/ VIS SPECTROSCOPY

Isotopes

Mass spectrometry

ultraviolet visible spectroscopy

Copper

isotope

phenyl group

PHENYLETHANETHIOL

unclassified drug

article

controlled study

decomposition

electrospray mass spectrometry

matrix assisted laser desorption ionization time of flight mass spectrometry

optics

priority journal

synthesis

Ultraviolet spectroscopy

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

Journal of Nanoparticle Research

The first atomically precise and monolayer protected iridium cluster in solution, Ir9(PET)6 (PET-2-phenyethanethiol) was synthesized via a solid state method. The absence of a plasmonic band at ∼350 nm, expected in the UV/Vis spectra for spherical Ir particles of 10 nm size indicated that the synthesized cluster is smaller than this dimension. Small angle X-ray scattering (SAXS) showed that the cluster has a particle size of ∼2 nm in solution which was confirmed by transmission electron microscopy (TEM). The blue emission of the cluster is much weaker than many noble metal clusters investigated so far. X-ray photoelectron spectroscopy (XPS) measurements showed that all Ir atoms of the cluster are close to the zero oxidation state. The characteristic S-H vibrational peak of PET at 2560 cm-1 was absent in the FT-IR spectrum of the cluster indicating RS-Ir bond formation. The molecular formula of the cluster, Ir9(PET)6 was assigned based on the most significant peak at m/z 2553 in the matrix assisted laser desorption ionization mass spectrum (MALDI MS), measured at the threshold laser intensity. Density functional theory calculations on small Ir@SCH3 and Ir@PET clusters and comparison of the predictions with the IR and 1H-NMR spectra of Ir9(PET)6 suggested that the PET ligands have two distinct structural arrangements and are likely to be present as bridging thiolates -(Ir-SR-Ir)- and singly attached thiolates -(Ir-SR). © 2016 The Royal Society of Chemistry.

RSC Advances

Atomically precise and monolayer protected iridium clusters in solution

The cluster Ag44SePh30, originally prepared from silver selenolate, upon oxidative decomposition by H2O2 gives the same cluster back, in an apparently reversible synthesis. Such an unusual phenomenon was not seen for the corresponding thiolate analogues. From several characterization studies such as mass spectrometry, Raman spectroscopy, etc., it has been confirmed that the degraded and as-synthesized selenolates are the same in nature, which leads to the reversible process. The possibility of making clusters from the degraded material makes cluster synthesis economical. This observation makes one to consider cluster synthesis to be a reversible chemical process, at least for selenolates. © The Royal Society of Chemistry 2014.

Nanoscale

Reversible formation of Ag44 from selenolates

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.

Fulltext

Journal of Physical Chemistry Letters

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

There is an urgent need for accessible purification and separation strategies of atomically precise metal clusters in order to promote the study of their fundamental properties. Although the separation of mixtures of atomically precise gold clusters Au25L18, where L are thiolates, has been demonstrated by advanced separation techniques, we present here the first separation of metal clusters by thin-layer chromatography (TLC), which is simple yet surprisingly efficient. This method was successfully applied to a binary mixture of Au25L18 with different ligands, as well as to a binary mixture of different cluster cores, Au25 and Au144, protected with the same ligand. Importantly, TLC even enabled the challenging separation of a multicomponent mixture of mixed-monolayer-protected Au25 clusters with closely similar chemical ligand compositions. We anticipate that the realization of such simple yet efficient separation technique will progress the detailed investigation of cluster properties. (Figure Presented). © 2014 American Chemical Society.

Analytical Chemistry

Simple and efficient separation of atomically precise noble metal clusters

A cluster obtained in high yield from the reduction of a silver-thiolate precursor, Ag-SCH2CH2Ph, exhibited a single sharp peak near 25 kDa in the matrix-assisted laser desorption mass spectrum (MALDI MS) and a well-defined metal core of ∼2 nm measured with transmission electron microscopy (TEM). The cluster yields a single fraction in high-performance liquid chromatography (HPLC). Increased laser fluence fragments the cluster until a new peak near 19 kDa predominates, suggesting that the parent cluster-Ag152(SCH2CH2Ph)60-evolves into a stable inorganic core-Ag152S60. Exploiting combined insights from investigations of clusters and surface science, a core-shell structure model was developed, with a 92-atom silver core having icosahedral-dodecahedral symmetry and an encapsulating protective shell containing 60 Ag atoms and 60 thiolates arranged in a network of six-membered rings resembling the geometry found in self-assembled monolayers on Ag(111). The structure is in agreement with small-angle X-ray scattering (SAXS) data. The protective layer encapsulating this silver cluster may be the smallest known three-dimensional self-assembled monolayer. First-principles electronic structure calculations show, for the geometry-optimized structure, the development of a ∼0.4 eV energy gap between the highest-occupied and lowest-unoccupied states, originating from a superatom 90-electron shell-closure and conferring stability to the cluster. The optical absorption spectrum of the cluster resembles that of plasmonic silver nanoparticles with a broad single feature peaking at 460 nm, but the luminescence spectrum shows two maxima with one attributed to the ligated shell and the other to the core. © 2012 American Chemical Society.

Nano Letters

The superstable 25 kDa monolayer protected silver nanoparticle: Measurements and interpretation as an icosahedral Ag152(SCH 2CH2Ph)60 cluster

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.

Angewandte Chemie - International Edition

Ag 7Au 6: A 13-atom alloy quantum cluster

A red luminescent silver cluster was synthesized in milligram quantities by the direct core reduction of the most widely studied class of large silver nanoparticles, namely silver@citrate of tens of nanometres diameter. No byproducts such as thiolates were detected, unlike in the case of typical methods of making such clusters. The route provides nearly pure clusters. The possibility to make diverse clusters from large nanoparticles expands the scope of cluster research.

Chemical Communications

Conversion of double layer charge-stabilized Ag@citrate colloids to thiol passivated luminescent quantum clusters

We report the first high temperature solution state synthesis of glutathione (-SG) protected atomically precise silver clusters. Noble metal cluster synthesis from metal ions generally requires ice cold temperatures as they are extremely sensitive and high temperature routes are used only for core reduction methods, starting from nanoparticles. The clusters formed by the new route have distinct features in their absorption profile and they exhibit red luminescence. They are characterised by other spectroscopic and microscopic techniques and a tentative formula of Ag 75(SG) 40 has been assigned. © The Royal Society of Chemistry 2012.

High temperature nucleation and growth of glutathione protected ∼ag 75 clusters

How low can you go? The visual detection of 2,4,6-trinitrotoluene and Hg2+ at the sub-zeptomole level is demonstrated. This was achieved using a hybrid material that allowed for the development of a single-particle, single-molecule detection technique, which may be the ultimate in ultra-trace sensitivity with selectivity. Copyright © 2012 WILEY-VCH Verlag GmbH &amp; Co. KGaA, Weinheim.

Selective visual detection of TNT at the sub-zeptomole level

A copper cluster protected with phenylethanethiol

Journal	Journal of Nanoparticle Research
Publisher	Kluwer Academic Publishers
ISSN	13880764
Open Access	No