Mixing Li and Cs in the reduction of corannulene for the assembly of a cesium-capped sandwich with a hexanuclear heterometallic core

Abstract

The use of two alkali metals having the greatest ion size mismatch, Li and Cs, in the reduction of bowl-shaped corannulene (C₂₀H₁₀, 1), results in the preparation of a heterobimetallic organometallic self-assembly, [Cs(diglyme)]₂//[Li₃Cs₃(C₂₀H₁₀)₂(diglyme)₂] (2). The X-ray crystallographic investigation of 2 revealed the formation of a triple-decker sandwich having a highly-charged hexanuclear core, (Li₃Cs₃)⁶⁺, held between two tetrareduced corannulene decks. The sandwich is capped by external cesium ions filling the concave cavities of corannulene bowls. The average depth of two C₂₀H₁₀⁴⁻ anions of 0.754(14) Å is significantly greater in 2 compared to the values of 0.241(2)–0.355(2) Å observed in the homometallic lithium sandwiches formed by tetrareduced corannulene, thus illustrating the unique flexibility of its carbon framework to adapt to different internal and external coordination environments.