Global Planar Tetra-, Penta- and Hexa-coordinate Silicon Clusters Constructed by Decorating SiO3 with Alkali Metals

The 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 p_z 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.