Zhiyuan Hu, Shiyu Ji, Wenying Wang, Wanmiao Gu, Guowei Guan, Mingxing Chen, Qing You, Yue Zhou, Jian Cheng, Lingwen Liao, Nan Yan, Zhikun Wu
Abstract The stabilization and multifunctionalization of radicals constitute two major challenges. We introduce a “kill two birds with one stone” methodology and illustrate the production of Au 64 (CPT) 31 S· from the newly obtained precursor nanocluster Au 64 (CPT) 32 (CPT: cyclopentanethiolate). Despite the isolated Au 64 (CPT) 31 S· are ultrastable (maintain the majority under 100 °C for 2 h in an atmospheric solution environment), they can initiate the polymerization of pentaerythritol triacrylate in 3D printing. In addition, the superradicial(which means it is not a single (super)atom but a complex system with superstability) exhibited NIR‐II emission, as well as high photothermal conversion efficiencies of 82.9% and 65.1% under 532 and 980 nm laser irradiation, respectively. Therefore, this study can serve as a foundation for novel superradical studies and applications and the findings hold notable implications for radical stabilization, multifunctionalization, and structure–composition–property correlations.