Synthesis, Structural Characterization, and Electronic Structure Analysis of F-type Superatomic Molecules.

The investigation of bonding interactions between superatoms continues to be a largely unexplored area of study. In this study, we present the synthesis and characterization of two F-type superatomic molecules [AuAg(CHNOS)(DPPB)] and [AuAg(CHNS)(DPPM)] ( and for short, respectively). The overall structures were confirmed via X-ray crystallography, revealing the horizontal expansion of the biicosahedral AuAg yielding [AuAg(CHNOS)(DPPB)] and vertical expansion of the biicosahedral AuAg yielding [AuAg(CHNS)(DPPM)]. Furthermore, their electronic structures were elucidated through density functional theory (DFT) calculations. Spectroscopic analysis of electronic absorption characteristics, in conjunction with Tamm-Dancoff approximation DFT (TDA-DFT) calculations, revealed that the AuAg and AuAg cores were analogues of the F molecule in electronic configuration.