The parallel syntheses of two new cross-bridged tetraazamacrocyclic complexes whose ligands are derived from 1,4,8,1 1-tetraazacyclotetradecane (cyclam = 14N4) and rac-1,4,8,1 1-tetraaza-5,5,7,12,12,14-hexamethylcyclotetradecane (tetB = 14N4Me(6)) have been characterized through the crystal structure determination of every stepwise intermediate ligand in the multistep ligand syntheses. These structures show that although the final ligand skeletons are nearly identical, the immediate precursors differ greatly because of the six additional methyl groups of the 14N4Me(6) macrocycle. The inversion from one diastereomer to another of the tetracycle derived from mc-14N4Me(6) has been chemically induced through the successive addition of methyl groups to the reactive tertiary nitrogens, and the novel heterocycles produced have been crystallographically characterized with one showing a conformation not previously known for these systems. The structures of the two copper(rr) complexes have significant geometrical differences, and accordingly, their electrochemical and spectroscopic properties are compared. The complexes exhibit remarkable kinetic stability under harsh conditions.