A multicentre-bonded [ZnI]8 cluster with cubic aromaticity

Abstract

8 ] cluster fully occupy four bonding molecular orbitals and leave four antibonding ones entirely empty, leading to an extensive electron delocalization over the cube and significant stabilization. The bonding pattern of the cube represents a class of aromatic system that we refer to as cubic aromaticity, which follows a 6n þ 2 electron counting rule. Our finding extends the aromaticity concept to cubic metallic systems, and enriches Zn-Zn bonding chemistry.

A Discrete Nickel Cubane with [Ni4O4] Cluster: Synthesis, Structure, and Magnetic Property

“…All the Ni atoms are six coordinated with a distorted octahedral coordination polyhedron, in which three oxygen atoms act as bridges to connect the other remaining three Ni atoms. Up to now, many Ni II cluster-based compounds have been previously reported, such as {Ni 2 }clusters, [14] liner-shaped {Ni 3 }clusters, [15] triangle-shaped {Ni 3 }clusters linked by μ 3 -O atom, [16] rhombus-shaped {Ni 4 }clusters, [17] cubane-like {Ni 4 }clusters, [18] {Ni 5 }clusters with rectangular symmetry, [19] {Ni 6 } clusters constructed by two {Ni 3 }clusters and so on, [10,20] all of which exhibit various magnetic behaviors.…”

“…[2] Up to now, many different kinds of transition metallic clusters have been studied, such as {Co 3 }, [3] {Ni 4 }, [4] {Zn 8 }, [5] {Cu 10 }, [6] {Mn 12 }, [7] or {Fe 18 }, [8] of which some polynuclear clusters display interesting structure types and properties. Among the reported clusters, the tetranuclear cubane like {M 4 O 4 } clusters (M = Cu, Ni, Co, etc.)…”

The Planar CoB18− Cluster as a Motif for Metallo‐Borophenes

“…Therefore, CoB 18 À is ad 8 -complex with Co in arare oxidation state of + 1 and can be viewed approximately as Co + 2B 18 2À with additional ionic bonding.T his species thus adds to the family of unusual monovalent transition metal cluster compounds. [54,55] As the CoB 18 À anion is closed shell, the neutral CoB 18 is thus open-shell with an unpaired 3d electron and should be magnetic.…”

Metal–Organic Frameworks (MOFs) of a Cubic Metal Cluster with Multicentered MnIMnI Bonds

“…Theoretical studies with density functional theory (DFT) reveal extensive electron delocalization over the [Mn I 8 ]cube.The 48 electrons in the [Mn I 8 ]cube fully occupyh alf of the 3d-based and the lowest 4s-based bonding orbitals,with six electrons lying at the nonbonding 3dorbitals.T his bonding feature renders so-called cubic aromaticity.M agnetic properties measurements show that 1 is an antiferromagnet. [4] On the other hand, oxidation state as acentral concept in chemistry is associated with both the electronic structure and chemical properties of agiven atom. [1, 2] In construction and design of MOFs with characteristic properties and functions,m etal ions play ac rucial role.…”

“…[1, 2] In construction and design of MOFs with characteristic properties and functions,m etal ions play ac rucial role. [4] On the other hand, oxidation state as acentral concept in chemistry is associated with both the electronic structure and chemical properties of agiven atom. [3] In more than 25 000 MOF-related publications,c luster-based MOFs with low-oxidation-state (LOS) metals and multicentered metal-metal bonding were unknown until recently when aZ n 8 cluster was synthesized.…”