Triple 1D1D superatomic bonding. Au22(dppo)6 as a Π4- and Δ2-triply bonded cluster based on Au11 assembled units

Abstract

δ-Bonds have been intimately related to metal–metal bonds of d-elements since the archetypal d⁴–d⁴ [Re₂Cl₈]²⁻ ion with a σ²π⁴δ² bond. Currently, the notion of multiple superatom arrangements as initial steps toward molecular materials within the building-up approach is dominated by P-shell characteristics, as given in the well-described Au₂₅(SR)₁₈ ligand protected cluster. In this work we rationalize the Au₂₂(dppo)₆ cluster as a triple-bonded 22-valence electron (ve) supermolecule, featuring a bonding scheme based on 1D + 1D shell combinations, which largely contrasts with the 14-ve Au₃₈(SR)₂₄ with mainly 1P + 1P patterns mimicking a F₂ molecule. The resulting Π⁴Δ²-bonding pattern shows an unprecedented superatomic counterpart of a d-shell based bond inherently related to transition-metal dimers, adding useful key aspects to the understanding of species based on cluster-assembly.