Assembly of the Thiolated [Au1Ag22(S‐Adm)12]3+ Superatom Complex into a Framework Material through Direct Linkage by SbF6− Anions

: Building framework materials with desirable properties and enhanced functionalities with nanocluster/superatom complexes as building blocks remains a challenge in the field of nanomaterials. Herein, the chiral [Au 1 Ag 22 (S-Adm) 12 ] 3+ nanocluster/superatom complex (SC, where S-Adm = 1-adamantanethiol) is employed as a building block to construct the 3-dimensional (3D) superatom complex inorganic framework (SCIF) materials, SCIF-1 and SCIF-2, through inorganic SbF 6 - linkers. SCIF-1 is racemic due to the assembly of two SC enantiomers in single crystal. In SCIF-2, the SC enantiomers are packed in separate crystals, which produce larger channels and a circularly polarized luminescence (CPL) response. These two 3D SCIF materials exhibit unique sensitive photoluminescence (PL) in protic solvents. Our work provides a new path for creating novel open-framework materials with superatom complexes and a foundation for the further development of 3D framework materials for sensing and other applications.