We present an example of an interparticle reaction between atomically precise nanoclusters (NCs) of the same metal, resulting in entirely different clusters. In detail, the clusters [Ag12(TBT)8(TFA)5(CH3CN)]+ (TBT = tert-butylthiolate, TFA = trifluoroacetate, CH3CN = acetonitrile) and [Ag18(TPP)10H16]2+ (TPP = triphenylphosphine) abbreviated as Ag12 and Ag18, respectively, react leading to [Ag16(TBT)8(TFA)7(CH3CN)3Cl]+ and [Ag17(TBT)8(TFA)7(CH3CN)3Cl]+, abbreviated as Ag16 and Ag17, respectively. The two product NCs crystallize together as both possess the same metal chalcogenolate shell, composed of Ag16S8, making them indistinguishable. The occupancies of Ag16 and Ag17 are 66.66 and 33.33%, respectively, in a single crystal. Electrospray ionization mass spectrometry (ESI MS) of the reaction product and a dissolved crystal show the population of Ag16 and Ag17 NCs to be in a 1:1 and 2:1 ratio, respectively. This suggests selective crystallization in the cocrystal. Time-dependent ESI MS was employed to understand the formation of product clusters by monitoring the reaction intermediates formed in the course of the reaction. We present an unprecedented growth mechanism for the formation of silver NCs mediated by silver thiolate intermediates. © 2019 American Chemical Society.

Pradeep Thalappil

Department Of Chemistry

Wakeel Ahmed Dar

Mohammad Bodiuzzaman

Debasmita Ghosh

Ganesan Paramasivam

Esma Khatun

Korath Shivan Sugi

Electrodeposition

Electrospray ionization

Mass spectrometry

Nanoclusters

Reaction intermediates

Silver

Single crystals

AG16 AND AG17

Co-crystals

Electrospray ionization mass spectrometry

HOMOMETALLIC CLUSTERS

INTER CLUSTERS

Selective crystallization

SILVER NANOCLUSTERS

Triphenyl phosphines

Silver compounds

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IIT Madras

ACS Nano

We introduce a cluster coprotected by thiol and diphosphine ligands, [Ag22(dppe)4(2,5-DMBT)12Cl4]2+ (dppe = 1,2-bis(diphenylphosphino)ethane; 2,5-DMBT= 2,5-dimethylbenzenethiol), which has an Ag10 core encapsulated by an Ag12(dppe)4(2,5-DMBT)12Cl4 shell. The Ag10 core comprises two Ag5 distorted trigonal bipyramidal units and is uncommon in Au and Ag nanoclusters. The electrospray ionization mass spectrum reveals that the cluster is divalent and contains four free electrons. An uncommon crystallization-induced enhancement of emission is observed in the cluster. The emission is weak in the solution and amorphous states. However, it is enhanced 12 times in the crystalline state compared to the amorphous state. A detailed investigation of the crystal structure suggests that well-arranged C-H⋯πand π⋯πinteractions between the ligands are the major factors for this enhanced emission. Further, in-depth structural elucidation and density functional theory calculations suggest that the cluster is a superatom with four magic electrons. © 2019 American Chemical Society.

Confining an Ag10 Core in an Ag12 Shell: A Four-Electron Superatom with Enhanced Photoluminescence upon Crystallization

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

Two ligand-protected nanoscale silver moieties, [Ag46(SPhMe2)24(PPh3)8](NO3)2 and [Ag40(SPhMe2)24(PPh3)8](NO3)2 (abbreviated as Ag46 and Ag40, respectively) with almost the same shell but different cores were synthesized simultaneously. As their external structures are identical, the clusters were not distinguishable and become co-crystallized. The occupancy of each cluster was 50 %. The outer shell of both is composed of Ag32S24P8, which is reminiscent of fullerenes, and it encapsulates a well-studied core, Ag14 and a completely new core, Ag8, which correspond to a face-centered cube and a simple cube, respectively, resulting in the Ag46 and Ag40 clusters. The presence of two entities (Ag40 and Ag46 clusters) in a single crystal and their molecular formulae were confirmed by detailed electrospray ionization mass spectrometry. The optical spectrum of the mixture showed unique features which were in good agreement with the results from time-dependent density functional theory (TD-DFT). © 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Angewandte Chemie - International Edition

Camouflaging Structural Diversity: Co-crystallization of Two Different Nanoparticles Having Different Cores But the Same Shell

Monolayer protected clusters exhibit rich diversity in geometric and electronic structures. However, structure-reactivity relationships in these clusters are rarely explored. In this context, [Ag44(SR)30]4-, where -SR is an alkyl/aryl thiolate, is an interesting system due to its geometrically and electronically closed-shell structures and distinct charge states. We demonstrate that these structural features of [Ag44(SR)30]4- are distinctly manifested in its solution-state reaction with another cluster, [Au25(SR)18]-. Through this reaction, an alloy cluster anion, [Au12Ag32(SR)30]4-, evolves spontaneously as revealed by high-resolution electrospray ionization mass spectrometry. Ultraviolet-visible absorption spectroscopy and density functional theory calculations indicate that [Au12Ag32(SR)30]4- is formed by the substitution of all of the Ag atoms in the innermost icosahedral shell of [Ag44(SR)30]4- and the abundance is attributed to its higher stability due to closed geometric as well as electronic shell structure, similar to the reactant clusters. We further demonstrate that the substitution of metal atoms in the middle dodecahedral shell and the outermost mount sites are also possible, however such substitutions produce AuxAg44-x(SR)30 alloy clusters with geometrically and electronically open shells. Depending on specific sites of substitution, an unexpected superatom-nonsuperatom transition occurs in the distribution of AuxAg44-x(SR)30 alloy clusters formed in this reaction. Our results present a unique example of a structure-reactivity relationship in the metal atom substitution chemistry of monolayer protected clusters, wherein a systematic trend, reflecting the geometric and the electronic shell structures of the reactant as well as the product clusters, was observed. © 2017 American Chemical Society.

Manifestation of Geometric and Electronic Shell Structures of Metal Clusters in Intercluster Reactions

We report the formation of naked cluster ions of silver of specific nuclearities, uncontaminated by other cluster ions, derived from monolayer-protected clusters. The hydride and phosphine co-protected cluster, [Ag18(TPP)10H16]2+ (TPP, triphenylphosphine), upon activation produces the naked cluster ion, Ag17 +, exclusively. The number of metal atoms present in the naked cluster is almost the same as that in the parent material. Two more naked cluster ions, Ag21 + and Ag19 +, were also formed starting from two other protected clusters, [Ag25(DPPE)8H22]3+ and [Ag22(DPPE)8H19]3+, respectively (DPPE, 1,2-bis(diphenylphosphino)ethane). By systematic fragmentation, naked clusters of varying nuclei are produced from Ag17 + to Ag1 + selectively, with systematic absence of Ag10 +, Ag6 +, and Ag4 +. A seemingly odd number of cluster ions are preferred due to the stability of the closed electronic shells. Sequential desorption of dihydrogen occurs from the cluster ion, Ag17H14 +, during the formation of Agn +. A comparison of the pathways in the formation of similar naked cluster ions starting from two differently ligated clusters has been presented. This approach developed bridges the usually distinct fields of gas-phase metal cluster chemistry and solution-phase metal cluster chemistry. We hope that our findings will enrich nanoscience and nanotechnology beyond the field of clusters. © 2017 American Chemical Society.

Fulltext

Sequential Dihydrogen Desorption from Hydride-Protected Atomically Precise Silver Clusters and the Formation of Naked Clusters in the Gas Phase

Interparticle Reactions between Silver Nanoclusters Leading to Product Cocrystals by Selective Cocrystallization

Journal	Data powered by TypesetACS Nano
Publisher	Data powered by TypesetAmerican Chemical Society
ISSN	19360851
Open Access	No