The amino-derivatized cyclotriveratrylene analogue, triaminotrimethoxytribenzocyclononene [CTV(NH2)(3)(OMe)(3)], 1, is readily converted into triply substituted imine compounds [CTV(sal)(3)(OMe)(3)], 2, in high yield by treatment of the acid salt of 1 with a variety of substituted salicylaldehydes. Cleavage of the protecting methoxy group generates the tristridentate chelate CTV(sal)(3)(OH)(3), 3, which is readily converted into new rim-metalated species CTV(sal)(3)(ONiL)(3), 4a (a, L = pyrrolidine; b, L = 1-n-butyl-imidazole). Taken together, these results illustrate the remarkable synthetic flexibility that is possible for the CTV-based metal complexes by alteration of the metal, the salicylaldehyde component of the CTV ligand, or the ancillary ligands coordinated to the metal.