Stabilizing hydrogen-mediated sextuple bonds by quintuple superatomic bonding and a bond

Abstract

Multiple bond orders of four and five are frequently obtained for d-block elements. However, compounds with sextuple bonding (2σ, 2π, 2δ), for instance, Cr2, Mo2 and W2, are less stable...

Ligand-free supermolecules: [Pd2@Ge18]4− and [Pd2@Sn18]4− as multiple-bonded Zintl-ion clusters based on Pd@Ge9 and Pd@Sn9 assembled units

“…Thus, the rationalization of cluster-cluster aggregates contributes to further design strategies for building materials from specific units. The resulting aggregates have been coined as supermolecules 26,27 involving single and multiple intercluster bonding features as rationalized for Pd 2 @Au 36 (SR) 24 , 28–30 Au 22 (dppo) 6 , 31 and Au 36 Ag 2 (SR) 18 , 32 where a super valence bond (SVB) model approach is useful to characterize such binding situation. 33–36…”

[Ba4@Sn56]36– as a Main-Group Second-Order Superatom. Interpenetrated Dodecahedrons as a Three-Dimensional Cluster-of-Clusters Structure

“…The superatom approach , enables the recognition of superatomic shells highlighting the Au 25 (SR) 18 – cluster (R = alkyl ligand), − which features eight cluster electrons (8- ce ) in a closed-shell 1S 2 1P 6 electronic configuration, denoting a set of tangential shells, i.e., lying at the cluster surface with no radial nodes. Further aggregation of two Au 25 (SR) 18 units after ligand removal and vertex sharing leads to the formation of supermolecules, , resembling 14-, 12-, and 10- ce species denoting single-, double-, and triple-intercluster bonds controlled electrochemically. − In addition, three-center bond species have been depicted . Moreover, the super valence bond (SVB) model approach has been proposed to rationalize such bonding characteristics. − …”

Second-order superatoms: Au52-PAP featuring a three-dimensional cluster-of-clusters core

“…4,14,18 The metal-centered icosahedral Au 13 5+ core is a relevant prototypical motif as denoted in the seminal Au 25 (SR) 18 − cluster 19–26 featuring eight cluster electrons (8- ce ) in a closed-shell 1S 2 1P 6 electronic configuration; 4,27 described as a superatom in analogy to isolated atoms. Noteworthy, such a motif can aggregate into dimers, trimers, and rings, leading to the formation of supermolecules, 28,29 highlighting M 2 Au 36 (SR) 24 , resembling 14-, 12-, and 10- ce species that retain single-, double-, and triple-intercluster bonds, in resemblance to Cl–Cl, OO, and NN molecules, which can be reversibly controlled electrochemically. 30–32 Moreover, three-center bonds have also been depicted recently.…”