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. In this study, the chiral [Au1 Ag22 (S-Adm)12 ]3+ nanocluster/superatom complex (SC, in which S-Adm=1-adamantanethiol) was employed as a building block to construct the three-dimensional (3D) superatom complex inorganic framework (SCIF) materials SCIF-1 and SCIF-2 through inorganic SbF6- linkers. SCIF-1 is racemic due to the assembly of two SC enantiomers in a single crystal. In SCIF-2, the SC enantiomers are packed in separate crystals, thus producing larger channels and a circularly polarized luminescence (CPL) response. These two 3D SCIF materials exhibit unique sensitive photoluminescence (PL) in protic solvents. Our study provides a new pathway 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.