Insights into mechanisms of diphosphine-mediated controlled surface construction on Au nanoclusters

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 Au 23 (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), Au 21 (SR) 12 L 2 + (L = diphosphine) and Au 22 (SR) 14 L 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 Au 22 (SR) 14 L and Au 25 (SR) 16 L 2 + . 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. Controlled diphosphine-mediated surface modification on Au 23 (SR) 16 − nanoclusters is realized. Mechanistic study shows that the size of the resulting nanoclusters can be controlled by tuning the length and configuration of diphosphines.