Multiple d–d bonds between early transition metals in TM₂Li_n (TM = Sc, Ti) superatomic molecule clusters

Abstract

The synthesis and application of compounds with Cr-Cr and V-V d-d quintuple bonds (σ, 2π, 2δ) have led to a new thinking about whether d-d multiple bonds also exist between...

Superatomic Three-Center Bond in a Tri-Icosahedral Au36Ag2(SR)18 Cluster: Analogue of 3c-2e Bond in Molecules

“…Alternatively, it is proposed that this Au 23 9+ core is formed by two face-sharing Au 13 6+ (7e) superatoms through a single super valence bond (SVB) to reach the octet rule, and it is an electronic analogue of the F 2 molecule. Subsequently, a number of liganded gold clusters are proven to be superatomic analogues of Bi 2 2– , N 2 , Re 2 , V 2 molecules, and their two-superatom-center two-electron (2sc-2e) bonding patterns, including super single bond to quintuple bond, have been thoroughly investigated in bi-superatomic molecules and linear multi-superatomic molecules. − …”

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

“…Quintuple superatomic bonds have been verified in superatomic molecules of metallic clusters, 59–61 which could exist in bridging hydride compounds as well. However, to date, we have failed to find quintuple bridging hydride compounds either experimentally or theoretically.…”

Superatomic Aromaticity in Cyclic Superatomic Molecules: Ligand-Protected Penta-Icosahedral [M@Au11]5 (M = Au, Pt) Clusters

“…From electronic characters, if the individual icosahedral building blocks exhibit superatomic closed-shell, the superatom assemblies can be described by the superatom network (SAN) model . Open-shell superatoms could form superatomic molecules through supervalence bonds (SVBs), by sharing superatomic valence electrons. , From geometric characters, the most common pattern of superatom-assembling is dimerization, where various bisuperatomic molecules are predicted and synthesized, in which SVBs with different bond orders, from super-single bond to super-quintuple bond, are involved. − Superatomic dimers could extend to linear trimer, tetramer, or superatomic nanowire through SVBs . Besides, an intriguing triangle trisuperatomic assembly was reported recently, and a three-superatom-center two-electron (3sc-2e) bonding model is proposed to reveal the electronic stabilities of this superatomic triangle, which further develops the family of SVBs. , Therefore, superatomic assemblies mimic the electronic shells of atomic molecules, which are able to reproduce the superatomic versions of functional molecules, favoring material science .…”