Synthesis, Structural Characterization, and Electronic Structure Analysis of F2-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 F2-type superatomic molecules [Au2Ag25(C7H4NOS)13(DPPB)3] and [Au9Ag18(C5H4NS)11(DPPM)5]2+(Au2Ag25and Au9Ag18for short, respectively). The overall structures were confirmed via X-ray crystallography, revealing the horizontal expansion of the biicosahedral Au2Ag21yielding [Au2Ag25(C7H4NOS)13(DPPB)3] and vertical expansion of the biicosahedral Au8Ag15yielding [Au9Ag18(C5H4NS)11(DPPM)5]2+. 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 Au2Ag21(+9)and Au8Ag15(+9)cores were analogues of the F2molecule in electronic configuration.