The synthesis of all [TAlA][M(dca)3] materials was performed by solvent layering, and through equimolar replacement of precursor quantities in each case. Typically, 10 mL of an aqueous solution (2 mmol) of the metal salt was placed at the bottom of a thin crystallization tube, and layered with a mixture of a sodium dicyanamide solution in 10 mL of water (6 mmol) and the tetraalkylammonium bromide in 10 mmol of ethanol (2 mmol). Block-shaped single crystals were isolated from the mother liquor after one week of slow evaporation in an open atmosphere at 298 K.