Dual External Field-Engineered Hyperhalogen.

Hyperhalogens, a superatom featuring the highest known electron affinity (EA), have promising applications in the synthesis of superoxidizers. Contributions regarding the identified numbers and corresponding design strategies of hyperhalogens, however, are scarce. Herein, a novel and noninvasive dual external field (DEF) strategy, including the ligand field and oriented external electric field (OEEF), is proposed to construct hyperhalogens. The DEF strategy was shown to possess the power to increase Au's EA, forming the hyperhalogen. Strikingly, the ligation process can increase the cluster's stability, while OEEF can realize the precise and continuous regulation of the cluster's EA. Moreover, besides the model Au system, an experimentally synthesized Ag nanocluster was also investigated, further demonstrating the reliability of the proposed strategy. Considering the crucial role of ligands in the liquid synthesis of clusters and the convenient source of OEEF, such a DEF strategy may greatly increase the synthesis and applications of hyperhalogens in the condensed phase.