An All‐Alkynyl Protected 74‐Nuclei Silver(I)–Copper(I)‐Oxo Nanocluster: Oxo‐Induced Hierarchical Bimetal Aggregation and Anisotropic Surface Ligand Orientation

Abstract

The hardness of oxoions (O 2À )means that coinagemetal (Cu, Ag, Au) clusters supported by oxoi ons (O 2À )a re rare.H erein, an ovel m 4 -oxo supported all-alkynyl-protected silver(I)-copper(I) nanocluster [Ag 74Àx Cu x O 12 (PhC C) 50 ] (NC-1,a vg.x = 37.9) is characterized. NC-1 is the highest nuclearity silver-copper heterometallic cluster and contains an unprecedented twelve interstitial m 4 -oxo ions.T he oxoi ons originate from the reduction of nitrate ions by NaBH 4 .The oxo ions induce the hierarchical aggregation of Cu I and Ag I ions in the cluster,f orming the unique regioselective distribution of two different metal ions.T he anisotropic ligand coverage on the surface is caused by the jigsaw-puzzle-like cluster packing incorporating rare intermolecular C À H···metal agostic interactions and solvent molecules.T his work not only reveals an ew category of high-nuclearity coinage-metal clusters but shows the special clustering effect of oxo ions in the assembly of coinage-metal clusters.Supportinginformation and the ORCID identification number(s) for the author(s) of this article can be found under: https://doi.

The Structure–Property Correlations in the Isomerism of Au21(SR)15 Nanoclusters by Density Functional Theory Study

“…The atomic precisiono fu ltrasmall noble metal nanoclusters( < 2nm) sheds light on the atomicp acking modes of metal atoms to organic ligands( such as phosphines, [1][2][3] thiolates, [4][5][6][7] alkynes [8][9][10][11] )a nd the structure-property correlationsi ns ubnanometer scale. [12][13][14] Specifically, the recent reports on the isomeric nanoclusters with the same types &n umber of metal atoms and ligandsd emonstrate the variety of the atomic packing mode within ag iven metal-ligand setting (note:t he isomeristic nanoclusters correspond to an extended defination of isomerism, because the formula of ligand do not need to be identical, vide infra).…”

Alkynyl and halogen co-protected (AuAg)44 nanoclusters: a comparative study on their optical absorbance, structure, and hydrogen evolution performance

“…[1][2][3][4][5][6] Compared with homometallic nanoclusters, bimetallic nanoclusters usually exhibit significantly different optical properties, improved stability, and enhanced catalytic performance due to the alloying induced geometric and electronic structural change. [7][8][9][10][11] Among all types of bimetallic nanoclusters, AuAg alloys are the most widely studied ones, where thiolate and/or phosphide molecules are the most often employed ligands for protection. For instance, the total struc-ture and optical properties of thiolate and/or phosphide ligand protected Au 15 Ag 3 (SC 6 H 11 ) 14 , 12 Au 15 Ag 3 (SPhMe 2 ) 14 , 13 [Au 1 Ag 22 (S-Adm) 12 ] 3+ , 14 [Ag x Au 25−x (PPh 3 ) 10 (RS) 5 Cl 2 ] 2+ (x = 1-13), 15 Au 25−x Ag x (SC 6 H 11 ) 18 (x = 1-9), 16 Au 36−x Ag x (SPh-t Bu) 24 (x = 1-s6), 17 Au 38−x Ag x (SCH 2 CH 2 Ph) 24 (x = 1-5), 18 [Au 3 Ag 38 (SCH 2 Ph) 24 X 5 ] 2− (X = Cl or Br), 19 Au 2 Ag 42 (SAdm) 27 (BPh 4 ), 20 [Au 2 Ag 48 (S-t Bu) 20 (Dppm) 6 Br 11 ]Br(BPh 4 ), 20 [Ag 46 Au 24 (SR) 32 ] 2+ , 21 Au 130−x Ag x (TBBT) 55 (average x = 98), 22 etc.…”

Double Trigonal Pyramidal {SeO3} Groups Bridged 2-Picolinic Acid Modified Cerium-Inlaid Polyoxometalate Including Mixed Selenotungstate Subunits for Electrochemically Sensing Ochratoxin A

“…Polyoxometalates (POMs), as a very crucial and structurally abundant group of metal-oxo clusters, can be used to construct molecule-based functional materials and have shown broad application prospects in catalysis, medication, photology, electron devices, and material science. − Diverse POM building blocks (PBBs) usually derived from classic polyoxoanions such as Keggin, Silverton, Dawson, Anderson, Waugh, Lindqvist, and so on can bind transition-metal, lanthanide (Ln), organometal, main-group metal, and organic components to give birth to a plentiful POM family. − The previously reported Ln-inlaid POMs (LnIPOMs) are largely based on one type of PBB, but those including two or more types of PBBs are comparatively few. − For example, in 1990, Yamase et al discovered a europium-inlaid tetrameric tungstoantimonate [Eu 3 (H 2 O)­(SbW 9 O 33 )­(W 5 O 18 ) 3 ] 18– comprising one trivacant [SbW 9 O 33 ] 9– and three monolacunary [W 5 O 18 ] 6– PBBs (Figure a) . In 1997, Pope and his collaborators synthesized a gigantic multi-Ce 3+ -inserted high-nuclear arsenotungstate (AT) [As 12 Ce 16 (H 2 O) 36 W 148 O 524 ] 76– , which simultaneously comprises 12 trivacant [SbW 9 O 33 ] 9– and four monolacunary [W 5 O 18 ] 6– PBBs (Figure b) .…”