One-pot Solvothermal Synthesis of Well-ordered Layered Sodium Aluminoalcoholate Complex: A Useful Precursor for the Preparation of Porous Al2O3 Particles.

One-pot solvothermal synthesis of a robust tetranuclear sodium hexakis(glycolato)tris(methanolato)aluminate complex Na3[Al4(OCH3)3(OCH2CH2O)6] via a modified yet rigorous base-catalyzed transesterification mechanism is presented here. Single crystal X-ray diffraction (SCXRD) studies indicate that this unique Al complex contains three penta-coordinate Al3+ ions, each bound to two bidentate ethylene glycolate chelators and one monodentate methanolate ligand. The remaining fourth Al3+ ion is octahedrally coordinated to one oxygen atom from each of the six surrounding glycolate chelators, effectively stitching the three penta-coordinate Al moieties together into a novel tetranuclear Al complex. This aluminate complex is periodically self-assembled into well-ordered layers normal to the [110] axis with the intra-/inter-layer bindings involving extensive ionic bonds from the three charge-counterbalancing Na+ cations rather than the more typical hydrogen bonding interactions as a result of the fewer free hydroxyl groups present in its structure. It can also serve as a valuable precursor toward the facile synthesis of high-surface-area alumina powders using a very efficient rapid pyrolysis technique.