A <i>N</i>-Heterocyclic Carbene-Stabilized Coinage Metal-Chalcogenide Framework with Tunable Optical Properties

Polgar, Alexander M.; Weigend, Florian; Zhang, Angel; Stillman, Martin J.; Corrigan, John F.

doi:10.1021/jacs.7b09025

Cited by 70 publications

(44 citation statements)

References 57 publications

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“…343 Recent reports of gold clusters with NHC ligands include the Au 8 cluster bearing bridging sulfide ligands described by Corrigan and co-workers, in which a central Au 4 core is supported by bridging sulfide ligands, and surrounded by four additional Au atoms each bound to an N-heterocyclic carbene (Scheme 71). 344 Shionoya and co-workers described a dicationic carboncentered hexagold(I) cluster stabilized by N-heterocyclic carbene ligands (Scheme 72), 345 similar to those reported by Schmidbaur with phosphine ligands, which also showed luminescent properties.…”

Section: Gold Clusterssupporting

confidence: 54%

Main Avenues in Gold Coordination Chemistry

2021

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In this contribution, we provide an overview of the main avenues that have emerged in gold coordination chemistry during the last years. The unique properties of gold have motivated research in gold chemistry, and especially regarding the properties and applications of gold compounds in catalysis, medicine, and materials chemistry. The advances in the synthesis and knowledge of gold coordination compounds have been possible with the design of novel ligands becoming relevant motifs that have allowed the preparation of elusive complexes in this area of research. Strong donor ligands with easily modulable electronic and steric properties, such as stable singlet carbenes or cyclometalated ligands, have been decisive in the stabilization of gold(0) species, gold fluoride complexes, gold hydrides, unprecedented π complexes, or cluster derivatives. These new ligands have been important not only from the fundamental structure and bonding studies but also for the synthesis of sophisticated catalysts to improve activity and selectivity of organic transformations. Moreover, they have enabled the facile oxidative addition from gold(I) to gold(III) and the design of a plethora of complexes with specific properties.

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Section: Gold Clusterssupporting

confidence: 54%

Main Avenues in Gold Coordination Chemistry

2021

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“…Atom‐precise metal chalcogenolate nanoclusters are a new category of materials with many unusual properties, the most important of which is luminescence . Among them, low‐cost Ag chalcogenolate clusters (SCCs)–– remain largely unexplored in contrast to Au thiolate clusters, and currently their structure–luminescence correlations are poorly understood. Structural isomers and pseudoisomers are excellent species to investigate structure–property relationships, which are favorable for guiding the design and synthesis of unique functional materials.…”

Section: Figurementioning

confidence: 99%

Tandem Silver Cluster Isomerism and Mixed Linkers to Modulate the Photoluminescence of Cluster‐Assembled Materials

et al. 2018

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Silver chalcogenolate cluster assembled materials (SCAMs) are a category of promising light‐emitting materials the luminescence of which can be modulated by variation of their building blocks (cluster nodes and organic linkers). The transformation of a singly emissive [Ag12(SBut)8(CF3COO)4(bpy)4]n (Ag12bpy, bpy=4,4′‐bipyridine) into a dual‐emissive [(Ag12(SBut)6(CF3COO)6(bpy)3)]n (Ag12bpy‐2) via cluster‐node isomerization, the critical importance of which was highlighted in dictating the photoluminescence properties of SCAMs. Moreover, the newly obtained Ag12bpy‐2 served to construct visual thermochromic Ag12bpy‐2/NH2 by a mixed‐linker synthesis, together with dichromatic core–shell Ag12bpy‐2@Ag12bpy‐NH2‐2 via solvent‐assisted linker exchange. This work provides insight into the significance of metal arrangement on physical properties of nanoclusters.

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“…[37][38] Several coinage metal clusters stabilized by NHCs have been prepared as well. [39][40][41] Theoretical work also suggested that NHCs may function as new ligands for gold surface modification and NCs protection. 42 Given these reports, it occurs to us that NHCs may mimic tertiary phosphines as a new class of ligands in stabilizing metal clusters, and may be a game-changer in metal cluster chemistry.…”

Section: Introductionmentioning

confidence: 99%

Highly Robust but Surface-Active: N-Heterocyclic Carbene-Stabilized Au25 Nanocluster as a Homogeneous Catalyst

Shen¹,

Deng²,

Kaappa³

et al. 2019

Preprint

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<div> <div> <div> <p>Surface organic ligands play a critical role in stabilizing atomically precise metal nanoclusters in solutions. However, it is still challenging to prepare highly robust ligated metal nanoclusters that are surface-active for liquid-phase catalysis without any pre-treatment. Herein, we report a novel N-heterocyclic carbine-stabilized Au25 nanocluster with high thermal and air stabilities as a homogenous catalyst for cycloisomerization of alkynyl amines to indoles. The nanocluster, characterized as [Au25(iPr2-bimy)10Br7]2+ (iPr2-bimy=diisopropyl-benzilidazolium) (1), was synthesized by direct reduction of AuSMe2Cl and iPr2- bimyAuBr with NaBH4 in one pot. X-ray crystallization analysis revealed that the cluster comprises two centered Au13 icosahedra sharing a vertex. Cluster 1 is highly stable and can survive in solution at 80 oC for 12 h, which is superior to Au25 nanoclusters passivated with phosphines or thiols. DFT computations reveal the origins of both electronic and thermal stability of 1 and point to the probable catalytic sites. This work provides new insights into the bonding capability of N-heterocyclic carbene to gold in a cluster, and offers an opportunity to probe the catalytic mechanism at the atomic level. </p> </div> </div> </div>

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A N-Heterocyclic Carbene-Stabilized Coinage Metal-Chalcogenide Framework with Tunable Optical Properties

Cited by 70 publications

References 57 publications

Main Avenues in Gold Coordination Chemistry

Main Avenues in Gold Coordination Chemistry

Tandem Silver Cluster Isomerism and Mixed Linkers to Modulate the Photoluminescence of Cluster‐Assembled Materials

Highly Robust but Surface-Active: N-Heterocyclic Carbene-Stabilized Au25 Nanocluster as a Homogeneous Catalyst

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