Recent progress in dichalcophosphate coinage metal clusters and superatoms

Abstract

Atomically precise clusters of the Group 11 metals (Cu, Ag, Au) attract considerable attention owing to their remarkable structure and fascinating properties. One of the unique subclasses of these clusters...

Diselenophosphate Ligands as a Surface Engineering Tool in PdH-Doped Silver Superatomic Nanoclusters

“…For the sake of computational limits, the dsep ligands were replaced by Se 2 PH 2 , a simplification which has been proved to be reasonable in many past investigations. 10,11,[13][14][15][16][19][20][21][22]28 The optimized geometries of 1 and 2 are in good agreement with their experimental counterparts and fully confirm the hydride locations (compare Tables 2 and 3). Following our investigation on the related dithiolates 1dtp and 2dtp, 19 we also computed various possible isomers of 1 and 2, all differing from the topology of their protecting outer shell made of 12 dsep ligands and 7 and 8 capping Ag(I) atoms, respectively.…”

“…Coinage metals are of particular interest in the formation of ligand-protected NCs, notably because of their rich optical properties . Since our first report on silver superatomic icosahedral frameworks, our priority has been to develop synthetic protocols for the optimal and precise control of the NC architecture and composition. − Ligand exchange-induced structure transformation (LEIST) has been an efficient tool in fine-tuning NC morphology and has been the subject of a review . We have previously established the ability of diselenophosphate (dsep) to completely substitute dithiophosphonates (dtp) in silver and copper frameworks and have expanded the methodology to group 10-doped NCs .…”

Locating Interstitial Hydrides in MH2@Cu14 (M = Cu, Ag) Clusters by Single-Crystal X-ray Diffraction

“…In recent years, extensive research has been conducted on metal hydrides to explore their potential applications in diverse fields, including organic synthesis, , catalysis, − and hydrogen storage. , Our particular interest is ligand-protected copper hydride clusters, which have garnered significant attention due to their remarkable stability, structural diversity, and unique bonding features. − These copper hydride compounds have emerged as important catalysts for various organic reactions and have shown promise in electrocatalytic CO 2 reduction and electrochemical hydrogen evolution reaction (HER) activity . To gain a comprehensive understanding of the atomic-level structure-property relationship of metal hydrides, single-crystal X-ray diffraction (SC-XRD) is an indispensable and cost-effective technology in comparison to neutron experiments.…”

Assembly of One-, Two-, and Three-Dimensional Cu(I)-Based Coordination Frameworks for Tunable White Light Emission and Effective Fluorescence Sensing

“…Luminescent coordination polymers (CPs) have received huge attention by virtue of their diverse topologies and broad applications in optics, display, bioimaging, sensing, and detection. − Of particular interest is the family of d 8 /d 10 transition-metal compounds, which is regarded as an emerging class of excellent luminescent solids benefiting from the presence of noncovalent metal···metal interactions in such complexes. − In particular, the copper­(I) halide-based coordination compounds, owing to not only the diverse coordination styles of Cu + (linear, trigonal, and tetrahedral geometry) and halide anions (from μ 2 - to μ 8 -linking) but also their unique photophysical or photochemical properties, have attracted huge interest. − Consequently, great efforts are being made in the pursuit of Cu-X-based (X = I, Br, Cl) networks with diverse structural motifs varying from discrete CuX or CuX 2 , Cu 2 X 2 dimers, Cu 3 X 3 , Cu 4 X 4 , or Cu 6 X 6 clusters, to zigzag [CuX] n or double-stranded [Cu 2 X 2 ] n chains and even to 2D Cu-X-based layers or 3D intricate frameworks. − Thanks to these various building blocks in the self-assembly process, numerous copper­(I) halide-based coordination frameworks have been fabricated in recent years with the assistance of diverse bridging ligands, which have a large possibility to exhibit vivid luminescence rooted in cluster-centered interactions or intracluster metal-halide charge transfer. , For example, Zang and co-workers reported a copper iodide cluster-based metal–organic framework (MOF) scintillator, which presents a high X-ray excited luminescence efficiency and can be used for X-ray flexible imaging …”