In previous reports, salicylhydroxamic acid (H(3)shi) was used as a stabilizing ligand for metallacrowns, metal complexes with a structural analogy to crown ethers. An important goal for generalizing the metallacrown analogy was to prepare organic ligands with a wide variety of functional groups that retain a high-yield synthesis for a predicted metallacrown structural motif. The organic ligands used in this study ((4-hydroxysalicyl)hydroxamic acid, (5-deuterio- and (3,5-dideuteriosalicyl)hydroxamic acid, and 3 -hydroxynaphthohydroxamic acid) demonstrate in principle this objective. Each of these ligands will form the generalized 9-MC((VO3+)N)-3 structure previously reported with 9-MC((VO3+)N(shi))-3 in high-yield syntheses. The deuterio analogs are used to assign the H-1 NMR spectrum of 9-MC((VO3+)N(shi))-3,1, the 3-hydroxynaphthohydroxamic acid (H(3)nha) dramatically increases the metallacrown bulk, and (4-hydroxysalicyl)hydroxamic acid adds an additional chelating atom that may allow further modification of the metallacrown to append functional groups capable of binding to clean metal surfaces or forming metallomesogens. The X-ray structure of 9.MC((VO3+)N(nha))-3, 4, shows that the fundamental structural parameters of 1 are maintained. A variety of analytical methods including molecular weight determinations using mass spectroscopy and vapor pressure osmometry and solution probes such as H-1 and V-51 NMR and UV-vis spectroscopy allow us to conclude that the generalized 9-MC((vo3+)N)-3 structure is retained in solution for the entire series of compounds. The concentration dependence of the visible spectra of the complexes changes linearly over a wide range of concentrations and in a variety of solvents demonstrating that the complexes do not dissociate even at relatively low concentrations (greater than or equal to 200 mu M). Ligand-exchange studies between metallacrowns show that the metallacrowns are dynamic in methanol (exchange is complete after 10 h with k = 0.31 +/- 0.02 h(-1)) but relatively inert in acetonitrile (no exchange after 48 h). Complex 1 has been used to prove the solution stability of the metallacryptate 7 in methanol.