Journal of the American Chemical Society · 2023 · 64 citations · 71 references
Natural SciencesChemistryMaterials ScienceMaterials ChemistryPhysical ChemistrySolid-state ChemistryCluster ChemistryCluster CompoundsCoordination ChemistryMetal-ligand BondingMolecular SymmetryTransition Metal ComplexesHomometallic ClustersHydride FormationLigand-stabilized ClustersMolecular Metal ClustersPhotoluminescencePhotoluminescence Quantum YieldPhotoluminescence SpectroscopyTransition Metal Clusters
The manipulation of metal cluster enantiomers and their reconstruction remain challenging. Here, for the first time, we report an enantiomeric pair of hydride copper clusters [Cu 18 H( R/S -PEA) 12 ](BF 4 ) 5 ( R/S-Cu 18 H ) made using designed chiral ligands. By manipulation of R/S-Cu 18 H with Ag + ions, H – ions are released, leading to the reconstruction of 15 Cu atoms. Moreover, 4 Ag atoms replaced Cu atoms at the specific sites, resulting in the formation of homochiral [Cu 15 Ag 4 ( R/S -PEA) 12 ](BF 4 ) 5 ( R/S-Cu 15 Ag 4 ) with an isomorphic metal skeleton. This process was accompanied by a reduction reaction generating two free valence elections in the chiral alloying counterparts, which displayed orange emission. The solid-state R/S-Cu 15 Ag 4 exhibited a photoluminescence quantum yield of 7.02% and excellent circularly polarized luminescence. The chiral transformations were resolved by single-crystal X-ray diffraction. The development of chiral copper hydride precursor-based metal clusters with chiroptical activities holds tremendous promise for advancing the field of optoelectronics and enabling new applications in lighting, displays, and beyond.
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Atanu Ghosh, Omar F. Mohammed, Osman M. Bakr · Accounts of Chemical Research · 2018 · 446 citations · Full text