New kind of electride sandwich complexes based on the cyclooctatetraene ligand M12(η8-C8H8)2M22 (M1 = Na, K and M2 = Ca, Mg): a theoretical study

Abstract

In the present study, the electronic structures of a series of binuclear sandwich complexes based on the cyclooctatetraene ligand M¹₂(η⁸-C₈H₈)₂M²₂ (M¹ = Na, K and M² = Ca, Mg) are studied theoretically. Each cyclooctatetraene ligand binds with the metal in the η⁸ binding mode. The M²–M² bond length agrees well with the reported bimetallic covalent Ca₂ and Mg₂ bond lengths. The Wiberg bond index (WBI) also indicates the presence of covalent M²–M² bonds, which gives additional stability to the complex. A non-nuclear attractor (NNA) is found in-between the M²–M² bond and the negative Laplacian of the electron density is found at the NNA. Noncovalent interaction (NCI) plot shows that electron density is localized at the M²–M² bond. Based on the performed analysis, we have concluded that the designed sandwich complexes are electrides. We herein report, for the first time, the electride sandwich complexes of the cyclooctatetraene ligand. Due to the presence of a diffuse electron system, the electride complexes exhibit higher values of the static second hyperpolarizability within the range of 2.6 × 10⁵ to 1.4 × 10⁶ a.u. Among the studied complexes, M¹₂(η⁸-C₈H₈)₂Ca₂ exhibit a higher value of static second hyperpolarizability.