Luminescent [CO

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 [CO