Designable Aluminum Molecular Rings: Ring Expansion and Ligand Functionalization

Abstract

Presented herein are the Al^III molecular ring architectures from 8-ring to 16-ring. Although there are numerous reported cyclic coordination compounds based on transition metals, gallium, or lanthanides, the Al versions are less developed due to the fast hydrolysis nature of Al³⁺ ion. With the assistant of monohydric alcohols, a series of atomic precisely Al molecular rings based on benzoates are synthesized. The ring expansion of these Al-rings from 8-ring to 16-ring is related to the monohydric alcohol structure-directing agents. Moreover, the organic ligands on the Al-rings can be modified by using various benzoate derivatives, which lead to tunable surface properties of the Al-rings from hydrophilicity to ultra-hydrophobicity. Importantly, 4-aminobenzoic acid bridged 16-ring is soluble in organic solvents and exhibits high solution stability revealed by mass spectroscopy. Ligand substitution also can be performed between these Al-rings, which reveal controllable ligand functionalization of these Al-rings.

Keywords: aluminum; crystal structures; cyclic coordination compounds; ligand substitution; molecular rings.