Modulating Decarboxylative Oxidation Photocatalysis by Ligand Engineering of Atomically Precise Copper Nanoclusters.

Copper nanoclusters (Cu NCs) characterized by their well-defined electronic and optical properties are an ideal platform for organic photocatalysis and exploring atomic-level behaviors. However, their potential as greener, efficient catalysts for challenging reactions like decarboxylative oxygenation under mild conditions remains unexplored. Herein, we present Cu13(Nap)3(PPh3)7H10 (hereafter Cu13Nap), protected by 1-naphthalene thiolate (Nap), which performs well in decarboxylative oxidation (90% yield) under photochemical conditions. In comparison, the isostructural Cu13(DCBT)3(PPh3)7H10 (hereafter Cu13DCBT), stabilized by 2,4-dichlorobenzenethiolate (DCBT), yields only 28%, and other previously reported Cu NCs (Cu28, Cu29, Cu45, Cu57, and Cu61) yield in the range of 6-18%. The introduction of naphthalene thiolate to the surface of Cu13 NCs influences their electronic structure and charge transfer in the ligand shell, enhancing visible light absorption and catalytic performance. Density functional theory (DFT) and experimental evidence suggest that the reaction proceeds primarily through an energy transfer mechanism. The energy transfer pathway is uncommon in the context of previous reports for decarboxylative oxidation reactions. Our findings suggest that strategically manipulating ligands holds significant potential for creating composite active sites on atomically precise copper NCs, resulting in enhanced catalytic efficacy and selectivity across various challenging reactions.

Planar Core and Macrocyclic Shell Stabilized Atomically Precise Copper Nanocluster Catalyst for Efficient Hydroboration of C-C Multiple Bond.

Atomically precise metal nanoclusters (NCs) have become an important class of catalysts due to their catalytic activity, high surface area, and tailored active sites. However, the design and development of bond-forming reaction catalysts based on copper NCs are still in their early stages. Herein, we report the synthesis of an atomically precise copper nanocluster with a planar core and unique shell, [Cu45(TBBT)29(TPP)4(C4H11N)2H14]2+ (Cu45) (TBBT: 4-tert-butylbenzenethiol; TPP: triphenylphosphine), in high yield via a one-pot reduction method. The resulting structurally well-defined Cu45 is a highly efficient catalyst for the hydroboration reaction of alkynes and alkenes. Mechanistic studies show that a single-electron oxidation of the in situ-formed ate complex enables the hydroboration via the formation of boryl-centered radicals under mild conditions. This work demonstrates the promise of tailored copper nanoclusters as catalysts for C-B heteroatom bond-forming reactions. The catalysts are compatible with a wide range of alkynes and alkenes and functional groups for producing hydroborated products.

Cocrystals of Atomically Precise Noble Metal Nanoclusters.

Cocrystallization is a phenomenon involving the assembly of two or more different chemical entities in a lattice, occurring typically through supramolecular interactions. In this concept, recent advancements in the cocrystallization of atomically precise noble metal clusters and their potential future directions are presented. Different strategies to create coassemblies of thiolate-protected noble metal nanoclusters are presented first. An approach is the simultaneous synthesis, and cocrystallization of two clusters having similar structures. A unique pair of clusters found recently, namely Ag40 and Ag46 with same core but different shell are taken to illustrate this. In another category, the case of the same core is presented, namely Ag116 with different shells, as in a mixture of Ag210 and Ag211 . Next, an intercluster reaction is presented to create cocrystals through selective crystallization of the reaction products. The coexistence of competing effects, magic sizes, and magic electron shells in a coassembly of alloy nanoclusters is discussed next. Finally, an assembly strategy for nanoclusters using electrostatic interactions is described. This concept is concluded with a future perspective on the emerging possibilities of such solids. Advancements in this field will certainly help the development of novel materials with exciting properties.

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

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 Ag32 S24 P8 , 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).

Isomerism in Supramolecular Adducts of Atomically Precise Nanoparticles.

We present isomerism in a few supramolecular adducts of atomically precise nanoparticles, [Ag29(BDT)12∩(CD) n]3- ( n = 1-6), abbreviated as I where BDT and CD are 1,3-benzenedithiol and cyclodextrins (α, ß and γ), respectively; ∩ symbolizes an inclusion complex. The different host-guest complexes of I were characterized in the solution state as well as in the gas phase. The CDs (α, ß and γ) encapsulate a pair of BDT ligands protecting the Ag29 core. This unique geometry of the supramolecular adducts makes the system similar to octahedral complexes of transition metals, which manifest various isomers. These isomers of I ( n = 2-4) were separated by ion mobility mass spectrometry (IM MS). We proposed structures of all the inclusion complexes with the help of IM MS measurements and molecular docking, density functional theory (DFT), and collision cross section (CCS) calculations.

Multiple neighboring active sites of an atomically precise copper nanocluster catalyst for efficient bond-forming reactions.

Atomically precise copper nanoclusters (NCs) are an emerging class of nanomaterials for catalysis. Their versatile core-shell architecture opens the possibility of tailoring their catalytically active sites. Here, we introduce a core-shell copper nanocluster (CuNC), [Cu29(StBu)13Cl5(PPh3)4H10]tBuSO3 (StBu: tert-butylthiol; PPh3: triphenylphosphine), Cu29NC, with multiple accessible active sites on its shell. We show that this nanocluster is a versatile catalyst for C-heteroatom bond formation (C-O, C-N, and C-S) with several advantages over previous Cu systems. When supported, the cluster can also be reused as a heterogeneous catalyst without losing its efficiency, making it a hybrid homogeneous and heterogeneous catalyst. We elucidated the atomic-level mechanism of the catalysis using density functional theory (DFT) calculations based on the single crystal structure. We found that the cooperative action of multiple neighboring active sites is essential for the catalyst's efficiency. The calculations also revealed that oxidative addition is the rate-limiting step that is facilitated by the neighboring active sites of the Cu29NC, which highlights a unique advantage of nanoclusters over traditional copper catalysts. Our results demonstrate the potential of nanoclusters for enabling the rational atomically precise design and investigation of multi-site catalysts.

Tunable reactivity of silver nanoclusters: a facile route to synthesize a range of bimetallic nanostructures.

Quantized energy levels and unique optoelectronic properties of atomically precise noble metal nanoclusters (NCs) have made them important in materials science, catalysis, sensors, and biomedicine. Recent studies on the profound chemical interactions of such NCs within themselves and with ultrasmall plasmonic nanoparticles (NPs) indicate that depending on the size, shape, and composition of the second reactant, NCs can either take part in colloidal assembly without any chemical modifications or lead to products with atoms exchanged. Anisotropic NPs are a unique class of plasmonic nanomaterials as their sharp edges and protrusions show higher chemical reactivity compared to flat surfaces, often leading to site-specific growth of foreign metals and metal oxide shells. Here, using chemical interactions between gold nanotriangles (AuNTs) and Ag NCs of different compositions, we show for the first time that metal atom etching, alloying/atom exchange, and colloidal assembly can all happen at a particular length scale. Specifically, Ag25(DMBT)18 NCs (denoted as 1), upon reacting with AuNTs of ∼57 nm edge length, etch gold atoms from their sharp tips and edges. Simultaneously, the two nanosystems exchange metal atoms, resulting in Ag-doped AuNTs and AuxAg24-x(DMBT)18 (x = 1, 2). However, another Ag NC with the same metallic core, but a different ligand shell, namely, Ag25H22(DPPE)8 (denoted as 2), creates dendritic shells made of Ag, surrounding these AuNTs under the same reaction conditions. Furthermore, we show that in the case of a more reactive thiol-protected Ag NC, namely, Ag44(pMBA)30 (denoted as 3), gold etching is faster from the edges and tips, which drastically alters the identities of both the reactants. Interestingly, when the AuNTs are protected by pMBA, 3 systematically assembles on AuNTs through H-bonding, resulting in an AuNT core-Ag NC shell nanocomposite. Thus, while shedding light on various factors affecting the reactivity of Ag NCs towards AuNTs, the present study proposes a single strategy to obtain a number of bimetallic nanosystems of targeted morphology and functionality.

Reaction between Ag17+ and acetylene outside the mass spectrometer: dehydrogenation in the gas phase.

We present the first example of acetylide protected silver clusters by a reaction between Ag17+ and acetylene, conducted around atmospheric pressure. The products were obtained after dehydrogenation of acetylene in the gas phase. The observed reaction mechanism may be helpful to design new catalysts useful in organometallic chemistry.

Formation of an NIR-emitting Ag34S3SBB20(CF3COO)62+ cluster from a hydride-protected silver cluster.

Recent reports have shown that the intercluster reaction is a new synthetic strategy to prepare alloy clusters. In this work, we performed an intercluster reaction between silver clusters and produced highly ionizable Ag-S-type clusters; we examined their formation by mass spectrometry. [Ag18(TPP)10H16]2+ (Ag18), a highly reactive hydride and phosphine-protected silver cluster, was used as a sacrificial cluster in this synthesis. An intercluster reaction between Ag18 and smaller silver-chalcogenolate clusters (SCC) resulted in a new cluster, [Ag34S3SBB20(CF3COO)6]2+. The cluster showed an NIR emission at around 1100 nm. The cluster composition was confirmed by high-resolution electrospray ionization mass spectrometry (ESI-MS), thermogravimetry (TGA), and X-ray photoelectron spectroscopy (XPS).

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

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···π and π···π interactions 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.

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

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.

A covalently linked dimer of [Ag25(DMBT)18].

We report the first example of a covalently bound dimer of monolayer protected atomically precise silver nanocluster [Ag25(DMBT)18]- (DMBT stands for 2,4-dimethylbenzenethiol). Covalently linked dimers could be important to design new cluster assembled materials with composite properties.

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

We present the first example of polymorphism (cubic & trigonal) in single crystals of an atomically precise monolayer protected cluster, Ag29(BDT)12(TPP)43-. We demonstrate that C-Hπ 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.

Preparation of gas phase naked silver cluster cations outside a mass spectrometer from ligand protected clusters in solution.

Gas phase clusters of noble metals prepared by laser desorption from the bulk have been investigated extensively in a vacuum using mass spectrometry. However, such clusters have not been known to exist under ambient conditions to date. In our previous work, we have shown that in-source fragmentation of ligands can be achieved starting from hydride and phosphine co-protected silver clusters leading to naked silver clusters inside a mass spectrometer. In a recent series of experiments, we have found that systematic desorption of ligands of the monolayer protected atomically precise silver cluster can also occur in the atmospheric gas phase. Here, we present the results, wherein the [Ag18H16(TPP)10]2+ (TPP = triphenylphosphine) cluster results in the formation of the naked cluster, Ag17+ along with Ag18H+ without mass selection, outside the mass spectrometer, in air. These cationic naked metal clusters are prepared by passing electrosprayed ligand protected clusters through a heated tube, in the gas phase. Reactions with oxygen suggest Ag17+ to be more reactive than Ag18H+, in agreement with their electronic structures. The more common thiolate protected clusters produce fragments of metal thiolates under identical processing conditions and no naked clusters were observed.

A thirty-fold photoluminescence enhancement induced by secondary ligands in monolayer protected silver clusters.

In this paper, we demonstrate that systematic replacement of the secondary ligand PPh3 leads to an enhancement in the near-infrared (NIR) photoluminescence (PL) of [Ag29(BDT)12(PPh3)4]3-. While the replacement of PPh3 with other monophosphines enhances luminescence slightly, the replacement with diphosphines of increasing chain length leads to a drastic PL enhancement, as high as 30 times compared to the parent cluster, [Ag29(BDT)12(PPh3)4]3-. Computational modeling suggests that the emission is a ligand to metal charge transfer (LMCT) which is affected by the nature of the secondary ligand. Control experiments with systematic replacement of the secondary ligand confirm its influence on the emission. The excited state dynamics shows this emission to be phosphorescent in nature which arises from the triplet excited state. This enhanced luminescence has been used to develop a prototypical O2 sensor. Moreover, a similar enhancement was also found for [Ag51(BDT)19(PPh3)3]3-. The work presents an easy approach to the PL enhancement of Ag clusters for various applications.

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

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.