Affiliation:
1. Institute of Atomic and Molecular Physics Jilin University Changchun 130023 China
Abstract
AbstractThe achievement of the rule‐breaking planar hypercoordinate motifs (carbon and other elements) is mainly attributed to a practical electronic stabilization mechanism, where the bonding of the central atom pz π electrons is a crucial issue. We have demonstrated that strong multiple bonds between the central atom and partial ligands can be an effective approach to explore stable planar hypercoordinate species. A set of planar tetra‐, penta‐ and hexa‐coordinate silicon clusters were herein found to be the lowest‐energy structure, which can be viewed as decorating SiO3 by alkali metals in the MSiO3−, M2SiO3 and M3SiO3+ (M=Li, Na) clusters. The strong charge transfer from M atoms to SiO3 effectively results in [M]+SiO32−, [M2]2+SiO32− and [M3]3+SiO32− salt complexes, where the Si−O multiple bonding and structural integrity of the Benz‐like SiO3 framework is maintained better than the corresponding SiO32− motifs. The bonding between M atoms and SiO3 motif is best described as M+ forming a few dative interactions by employing its vacant s, p, and high‐lying d orbitals. These considerable M←SiO3 interactions and Si−O multiple bonding give rise to the highly stable planar hypercoordinate silicon clusters.
Funder
National Natural Science Foundation of China
Subject
Physical and Theoretical Chemistry,Atomic and Molecular Physics, and Optics