LAUSR

Unraveling the rules governing the size regulation of nanoclusters is of great importance not only in fundamental research, but also in practical applications because of the high structure-property correlation in nanoclusters. Diphosphine-mediated size tailoring is recognized as a powerful method for modulating the size, configuration, and properties of nanoclusters, but the role of diphosphines in these size-controlled processes is still poorly understood due to a lack of systematic studies. Herein, using Au23(SR)16- as the template for modification, the factors influencing the size-modulation of nanoclusters by diphosphines were systematically investigated. It is revealed that by controlling the length of the diphosphines (from shorter to longer), Au21(SR)12L2+ (L = diphosphine) and Au22(SR)14L can be produced. Moreover, introducing a rigid group into the diphosphines can twist the structural framework or lead to the formation of a new surface motif configuration in the nanoclusters, forming twisted Au22(SR)14L and Au25(SR)16L2+. The size regulation of these nanoclusters enables fine-tuning of the optical properties, including the absorption wavelengths and photoluminescence emission intensity, affording an avenue for precise control of the physicochemical properties of nanoclusters for practical applications.