Li₆E₅Li₆: Tetrel Sandwich Complexes with 10-π-Electrons

When (4n +2) π-electrons are located in single planar ring, it conventionally qualifies as aromatic. According Hückel's rule, systems possessing ten π-electrons should be aromatic. Herein we report a series of D_5h Li₆E₅Li₆ sandwich structures, representing the first global minima featuring ten π-electrons E₅¹⁰⁻ ring (E=Si−Pb). However, these π-electrons localize as five π-lone-pairs rather than delocalized orbitals. The high symmetry structure achieved is a direct consequence of σ-aromaticity, particularly favored in elements from Si to Pb, resulting in a pronounced diatropic ring current flow that contributes to the enhanced stability of these systems.