Two new 1, 7-disubstituted-1, 4, 7, 10-tetraazacyclododecane ligands, DO2P and DO2PME, and their complexes with Mg2+, Ca2+, Sr2+, Mn2+, Zn2+ and Ln(3+) were prepared and characterized by pH potentiometry. The pH titration data showed that DO2P and DO2PME both form 1:1 M:L complexes with all divalent and trivalent metal ions. Protonated complexes did not appear to form with the bis(phosphonate ester) ligand, DO2PME, but were evident for all of the metal ion-DO2P complexes. The alkaline earth metal ion-DO2P complexes formed both ML and MHL complexes while the lanthanide ion (Ln(3+)), Zn2+, and Mn2+ complexes of DO2P formed ML, MHL, and MH2L species. Zn2+ formed the most stable complex with both ligands. The stability (beta(101)) of the LnDO2PME(+) complexes increased by about 2 orders of magnitude along the lanthanide series (La3+ to Lu3+) while the stability of the LnDO2P(-) complexes over this same series increased by over 3 orders of magnitude. The bis(phosphonate) ligand, DO2P, and some of its complexes formed with Ln(3+) ions were further examined by NMR spectroscopy. H-1 and P-31 spectra of DO2P collected as a function of pH provided evidence that the first two protonations on the ligand take place largely at the tertiary nitrogens. The similarity of the P-31 chemical shifts of EuDO2P(-) and EuDOTP5- indicate that DO2P forms an "in-cage" complex with Eu3+ using all four macrocyclic ring nitrogens and the two phosphonate sidearms as ligands. O-17 NMR shifts of the water signal indicated that the DyDO2P(-) complex has two inner-sphere coordinated water molecules. In the presence of excess of DO2P, a 1:2 metal:ligand, LnDO2P(HDO2P)(4-), complex forms with the second ligand interacting only weakly with the coordination sites left vacant by the first DO2P. Both water proton relaxivity data for GdDO2P(-) and P-31 NMR spectra of EuDO2P(-) provide evidence for formation of an "out-of-cage" LnH(2)DO2P(+) complex at low pH values (<6.5) in which the two phosphonate groups of DO2P are only involved in bonding with the lanthanide cation.