RESUMEN
Atomically precise copper nanoclusters (Cu NCs), an emerging class of nanomaterials, have garnered significant attention owing to their versatile core-shell architecture and their potential applications in catalytic reactions. In this study, we present a straightforward synthesis strategy for [Cu29(StBu)12(PPh3)4Cl6H10][BF4] (Cu29) NCs and explore their catalytic activity in the carbonylative C-N coupling reaction involving aromatic amines and N-heteroarenes with dialkyl azodicarboxylates. Through a combination of experimental investigations and density functional theory studies, we elucidate the radical mechanisms at play. The crucial step in the catalytic process is identified as the decomposition of diisopropyl azodicarboxylates on the surface of Cu29 NCs, leading to the generation of oxyacyl radicals and the liberation of nitrogen gas. Subsequently, an oxyacyl radical abstracts a hydrogen atom from aniline, initiating the formation of an aminyl radical. Finally, the aminyl radical reacts with another oxyacyl radical, culminating in the synthesis of the desired carbamate product. This detailed analysis provides insights into the intricate catalytic pathways of Cu29 NCs, shedding light on their potential for catalyzing carbonylative C-N coupling reactions.
RESUMEN
Owing to the quantized size and associated discrete energy levels, atomically precise silver nanoclusters (Ag NCs) hold great potential for designing functional luminescent materials. However, the thermally activated non-radiative transition of Ag(I)-based NCs has faded the opportunities. To acquire the structurally rigid architecture of cluster nodes for constraining such transitions, a new synthetic approach is unveiled here that utilizes a neutral template as a cluster-directing agent to assemble twenty Ag(I) atoms that ensure the maximum number of surface-protecting ligand attachment possibilities in a particular solvent medium. The solvent polarity triggers the precise structural design to circumvent the over-reliance of the templates, which results in the formation of [CO2@Ag20(SAdm)10(CF3COO)10(DMA)2] NC (where SAdm = 1-adamantanethiolate and DMA = N,N-dimethylacetamide) exhibiting an unprecedented room-temperature photoluminescence emission. The high quantum yield of the generated blue emission ensures its candidature as an ideal donor for artificial light-harvesting system design, and it is utilized with the two-step sequential energy transfer process, which finally results in the generation of ideal white light. For implementing perfect white light emission, the required chromophores in the green and red emission regions were chosen based on their effective spectral overlap with the donor components. Due to their favorable energy-level distribution, excited state energy transfers occurred from the NC to ß-carotene at the initial step, then from the conjugate of the NC and ß-carotene to another chromophore, Nile Blue, at the second step via a sequential Förster resonance energy transfer pathway.