Linear Group 13 E≡E Triple Bonds in E2 Li6 2.

The triply bonded heavier main-group compounds have a textbook trans-bent geometry, in contrast to a familiar linear form found for the lightest analogues. Strikingly, the unexpected linear group 13 E≡E triple bonds were herein found in the D4h -symmetry E2 Li6 2+ clusters, and they possess a large barrier (>18.0 kcal/mol) towards the dissociation of Li+ . The perfectly surrounded Li4 motifs and two linear coordinated Li atoms strongly suppress the increasing nonbonded electron density of heavier E atoms, making two degenerate π bonds and one multi-center σ bond in linear heavier main-group triple bonds. The surrounding Li6 motifs not only creates an effective electronic structure to form a linear E≡E triple bond, but the resulting electrostatic interactions account for the highly stable global E2 Li6 2+ clusters.