Elucidating the coordination structures and assembling modes of atomically precise metal nanoclusters (NCs) remains a hot topic as it gives answers to underlying mechanism of nanomaterials and bulk materials in...
Copper nanostructures represent an important class of
materials
in CO2 electrocatalytic reduction (CO2ER) reactions,
but deciphering their molecular structures, especially those with
multiple and irregular organic–inorganic interfaces, remains
a grand challenge. Through comprehensive characterization of a 26-nuclei
copper nanocluster of [Cu26(DPPE)3(CF3CO2)8(CH3O)2(tBuCC)4H11]+ (DPPE is 1,2-bis(diphenylphosphino)ethane),
which is stabilized by quintuple ligand shells of phosphine, carboxylic
acid, alcohol, alkynyl, and hydride, we demonstrate in this work the
efficiency of hybrid ligands in controlling geometrical arrangements,
electronic structures, and catalytic performance of copper nanoclusters.
The diverse ligands in the cluster endow it with a peculiar geometric
structure and distinct electronic structure and, more importantly,
a delicate surface structure. As a result, the cluster displays high
performance in CO2ER to CO reaction.
An effective strategy is developed to synthesize a novel and stable layered Cu nanocluster in one pot reduction method. The cluster, with molecular formula of [Cu14(tBuS)3(PPh3)7H10]BF4 which has been unambiguously...
A novel alkynyl-stabilized silver-copper alloy nanocluster with the composition of [Ag13-xCu6+x(tBuC6H4C≡C)14(PPh3)6](SbF6)3 was prepared by (PPh3)2CuBH4-mediated reduction approach. The nanocluster featured a centred disordered-octahedral Ag7Cu6 kernel, which was protected by hybrid...
Intrinsically chiral metal nanoclusters with crystal structure are highly desirable to gain deep insights into chirality origin of chiral nanostructures and understand structure‐and‐property relationship of heterogeneous catalysts in asymmetric catalysis. Although several strategies including the use of chiral ligands and high‐performance liquid chromatography have been routinely employed to gain nanoclusters with inherent chirality, another simple methodology of spontaneous resolution remains largely unexplored. In this work, we report the isolation of homochiral Ag/Cu nanoclusters stabilized by alkynyl ligands from spontaneous self‐resolution, which represents a pioneering example in the realm of alkynyl‐protected metal nanoclusters. The cluster, with the formula of [Ag12Cu7(dppe)3(RC≡C)14]3+, has been prepared in one‐pot, with the high yield of 71%. Structural anatomy reveals that the metal architecture, metal‐ligand interface and ligand arrangement of the cluster all display chirality. The cluster features superatomic free electrons, implying its potential application in specific fields. This work not only offers strategic guidance for the simple synthesis of alkynyl‐protected metal nanoclusters with inherent chirality in an all‐achiral environment, but also displays the hierarchical chirality of cluster moieties at molecular level.
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