Highly organized crossed bilayer assemblies of nanowires (NWs) are made using directed hydrogen bonding between the protecting ligand shells of atomically precise cluster molecules anchored on NWs. Layers of quantum clusters remain sandwiched between two neighboring NWs at a defined distance, dictated by the core-size of the cluster, while the orientation of the ligands in space dictates the interlayer geometry. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA.

Pradeep Thalappil

Department Of Chemistry

Shridevi Bhat

Hydrogen bonds

Ligands

Nanowires

Precious metals

Tellurium compounds

GOLD CLUSTERS

Nanoscale assemblies

NOBLE METAL CLUSTERS

SILVER CLUSTER

TELLURIUM NANOWIRES

Gold compounds

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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

Advanced Materials

ConspectusSupramolecular chemistry is a major area of chemistry that utilizes weaker non-covalent interactions between molecules, including hydrogen bonding, van der Waals, electrostatic, π···π, and C-H···π interactions. Such forces have been the basis of several molecular self-assemblies and host-guest complexes in organic, inorganic, and biological systems. Atomically precise nanoclusters (NCs) are materials of growing interest that display interesting structure-property correlations. The evolving science of such systems reaffirms their molecular behavior. This gives a possibility of exploring their supramolecular chemistry, leading to assemblies with similar or dissimilar cluster molecules. Such assemblies with compositional, structural, and conformational precision may ultimately result in cluster-assembled hybrid materials. In this Account, we present recent advancements on different possibilities of supramolecular interactions in atomically precise cluster systems that can occur at different length scales. We first present a brief discussion of the aspicule model of clusters, considering Au 25 (SR) 18 as an example, that can explain various aspects of its atomic precision and distinguish the similar or dissimilar interacting sites in their structures. The supramolecular interaction of 4-tert-butylbenzyl mercaptan (BBSH)-protected [Au 25 (SBB) 18 ] - NCs with cyclodextrins (CD) to form Au 25 SBB 18 ∩CD n (n = 1-4) and that of [Ag 29 (BDT) 12 ] 3- with fullerenes to form [Ag 29 (BDT) 12 (C 60 ) n ] 3- (n = 1-9) (BDT = 1,3-benzenedithiolate) are discussed subsequently. The formation of these adducts was studied by electrospray ionization mass spectrometry (ESI MS), optical absorption and NMR spectroscopy. In the subsequent sections, we discuss how variation in intercluster interactions can lead to polymorphic crystals, which are observable in single-crystal X-ray diffraction. Taking [Ag 29 (BDT) 12 (TPP) 4 ] 3- (TPP = triphenylphosphine) clusters as an example, we discuss how the different patterns of C-H···π and π···π interactions between the secondary ligands can alter the packing of the NCs into cubic and trigonal lattices. Finally, we discuss how the supramolecular interactions of atomically precise clusters can result in their hybrid assemblies with plasmonic nanostructures. The interaction of p-mercaptobenzoic acid (p-MBA)-protected Ag 44 (p-MBA) 30 NCs with tellurium nanowires (Te NWs) can form crossed-bilayer precision assemblies with a woven-fabric-like structure with an angle of 81° between the layers. Similar crossed-bilayer assemblies show an angle of 77° when Au 102 (p-MBA) 44 clusters are used to form the structure. Such assemblies were studied by transmission electron microscopy (TEM). Precision in these hybrid assemblies of Te NWs was highly controlled by the geometry of the ligands on the NC surface. Moreover, we also present how Ag 44 (p-MBA) 30 clusters can encapsulate gold nanorods to form cage-like nanostructures. Such studies involved TEM, scanning transmission electron microscopy (STEM), and three-dimensional tomographic reconstructions of the nanostructures. The hydrogen bonding interactions of the -COOH groups of the p-MBA ligands were the major driving force in both of these cases. An important aspect that is central to the advancement of the area is the close interplay of molecular tools such as MS with structural tools such as TEM along with detailed computational modeling. We finally conclude this Account with a future perspective on the supramolecular chemistry of clusters. Advancements in this field will help in developing new materials with potential optical, electrical, and mechanical properties. © Copyright © 2018 American Chemical Society.

Accounts of Chemical Research

Approaching Materials with Atomic Precision Using Supramolecular Cluster Assemblies

The self-assembled structures of atomically precise, ligand-protected noble metal nanoclusters leading to encapsulation of plasmonic gold nanorods (GNRs) is presented. Unlike highly sophisticated DNA nanotechnology, this strategically simple hydrogen bonding-directed self-assembly of nanoclusters leads to octahedral nanocrystals encapsulating GNRs. Specifically, the p-mercaptobenzoic acid (pMBA)-protected atomically precise silver nanocluster, Na4[Ag44(pMBA)30], and pMBA-functionalized GNRs were used. High-resolution transmission and scanning transmission electron tomographic reconstructions suggest that the geometry of the GNR surface is responsible for directing the assembly of silver nanoclusters via H-bonding, leading to octahedral symmetry. The use of water-dispersible gold nanoclusters, Au≈250(pMBA)n and Au102(pMBA)44, also formed layered shells encapsulating GNRs. Such cluster assemblies on colloidal particles are a new category of precision hybrids with diverse possibilities. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Angewandte Chemie - International Edition

Atomically Precise Nanocluster Assemblies Encapsulating Plasmonic Gold Nanorods

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

Selenolate protected, stable and atomically precise, hollow silver cluster was synthesized using solid state as well as solution state routes. The optical absorption spectrum shows multiple and sharp features similar to the thiolated Ag44 cluster, Ag44(SR)30 whose experimental structure was reported recently. High-resolution electrospray ionization mass spectrometry (HRESI MS) shows well-defined molecular ion features with two, three, and four ions with isotopic resolution, due to Ag44(SePh) 30. Additional characterization with diverse tools confirmed the composition. The closed-shell 18 electron superatom electronic structure, analogous to Ag44(SR)30 stabilizes the dodecahedral cage with a large HOMO-LUMO gap of 0.71 eV. The time-dependent density functional theory (TDDFT) prediction of the optical absorption spectrum, assuming the Ag44(SR)30 structure, matches the experimental data, confirming the structure. © 2013 American Chemical Society.

Journal of Physical Chemistry Letters

Ag44(SeR)30: A hollow cage silver cluster with selenolate protection

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.

Fulltext

Nano Letters

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

A silver cluster having the composition Ag9(H 2MSA)7 (H2MSA = mercaptosuccinic acid) was synthesized in macroscopic quantities using a solid-state route. The clusters were purified by PAGE and characterized by UV-vis, FTIR, luminescence, and NMR spectroscopy, TEM, XPS, XRD, TG, SEM/EDAX, elemental analysis, and ESI MS. The solid-state route provides nearly pure Ag9 clusters, and nanoparticle contamination was insignificant for routine studies. Formation of various clusters was observed by modifying the conditions. The effect of ligands on the synthesis was checked. The cluster decomposed slowly in water, and the decomposition followed first-order kinetics. However, it could be stabilized in solvent mixtures and in the solid state. Such materials may be important in cluster research because of their characteristic absorption profiles, which are similar to those of Au25 and Au38. The cluster showed luminescence with a quantum yield of 8 × 10-3 at 5 °C. © 2010 American Chemical Society.

Journal of the American Chemical Society

Ag9 quantum cluster through a solid-state route

Nature Materials

Hydrogen-bonded structure and mechanical chiral response of a silver nanoparticle superlattice

Cluster-Mediated Crossed Bilayer Precision Assemblies of 1D Nanowires

Journal	Data powered by TypesetAdvanced Materials
Publisher	Data powered by TypesetWiley-VCH Verlag
ISSN	09359648
Open Access	No