Halide‐Directed Ligand Engineering Enables Expedient, Controlled and Divergent Syntheses of Diphosphine‐Protected Au Nanoclusters

Small, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 25, 2025

Despite substantial progress in ligand engineering, the efforts field of Au nanoclusters have been concentrated almost exclusively on organic ligands. Halides, most typical auxiliary inorganic ligands widely present clusters, remain virtually unexplored, particularly regarding their effects cluster construction. Herein, diphosphine Ph2P(CH2)nPPh2 (Ln, n = 1-6) is chosen as co-protecting and a comparative analysis influential roles halide ions (Cl-, Br-, I-) guiding synthesis conducted. A simple yet efficient halide-directed synthetic approach has developed series nanoclusters, including known [Au18(L1)6Br4]2+, [Au13(L2)5Cl2]3+ [Au8(L3)4Cl2]2+ that however crystallized new polymorphic forms, well reduction-active [Au18(L1)6Cl4]2+, luminescence-enhanced [Au14(L3)5Br4]2+ core-isomeric [Au11(Ln)4X2]+ (n 4-6; X Cl, Br, I), are obtained more expedient controllable manner. This work clearly demonstrates non-negligible directing synthesis, provides an easier access to diverse diphosphine-protected nanoclusters. approach, promising gram-scale expected further extend scope holds promise for advancing diversified syntheses broader range ligand-protected metal

Language: Английский

Copper nanoclusters: emerging photoredox catalysts for organic bond formations

Chemical Communications, Journal Year: 2024, Volume and Issue: 60(94), P. 13858 - 13866

Published: Jan. 1, 2024

Advancements in fine chemical synthesis and drug discovery continuously demand the development of new more efficient catalytic systems. In this regard, numerous transition metal-based catalysts have been developed successfully applied industrial processes. However, need for innovative catalyst systems to further enhance efficiency transformations applications persists. Metal nanoclusters (NCs) represent a distinct class ultra-small nanoparticles (<3 nm) characterized by precise number metal atoms coordinated with defined ligands. This structure confers abundant unsaturated active sites unique electronic optical properties, setting them apart from conventional or bulk metals. The well-defined monodisperse nature NCs make particularly attractive applications. Among these, copper-based emerged as versatile sustainable challenging organic bond-forming reactions. Their including natural abundance, accessible oxidation states, diverse ligand architectures, strong photophysical characteristics, contribute their growing prominence field. review, we discuss photocatalytic activities Cu-based nanoclusters, focusing on cross-coupling reactions (C-C C-N), click reactions, multicomponent couplings,

Language: Английский