TREN-Me-3,2-HOPO, TR322-Me-3,2-HOPO, TR332-Me-3,2-HOPO, and TRPN-Me-3,2-HOPO correspond to stepwise replacement of ethylene by propylene bridges. A series of tripodal, hexadentate hydroxypyridinone ligands are reported. These incorporate 1-methyl-3,2-hydroxypyridinone (Me-3,2-HOPO) bidentate chelating units for metal binding. They are varied by systematic enlargement of the capping scaffold which connects the binding units. The series of ligands and their iron complexes are reported. Single crystal X-ray structures are reported for the ferric complexes of all four tripodal ligands: FeTREN-Me-3,2-HOPO.0.375C(4)H(10)O.0.5CH(2)Cl(2) [P2(1)/n (No. 14), Z = 8, a = 20.478(3) Angstrom, b = 12.353(2) Angstrom, c = 27.360(3) Angstrom; beta = 91.60(1)degrees]; FeTR322-Me-3,2-HOPO.CHCl3.0.5C(6)H(14).CH3OH.0.5H(2)O [P2(1)/n (No. 14), Z = 4, a = 12.520(3) Angstrom, b = 22.577(5) Angstrom, c = 16.525(3) Angstrom; beta = 111.37(3)degrees]; FeTR332-Me-3,2-HOPO.3.5CH(3)OH [C2/c (No. 15), Z = 8, a = 13.5294(3) Angstrom, b = 19.7831(4) Angstrom, c = 27.2439(4) Angstrom; = 101.15(3)degrees]; FeTRPN-Me-3,2-HOPO.C3H7NO.2C(4)H(10)O [P (1) over bar (No. 2), Z = 2, a = 11.4891(2) Angstrom, b = 12.3583(2) Angstrom, c = 15.0473(2) Angstrom; alpha = 86.857(1)degrees, beta = 88.414(1)degrees, gamma = 70.124(1)degrees]. The structures show the importance of intermolecular hydrogen bonds and the effect of cap enlargement to the stability and geometry of the metal complexes throughout the series, All protonation and iron complex formation constants have been determined from solution thermodynamic studies. The TREN-capped derivative is the most acidic, with a cumulative protonation constant, log beta(014), of 25.95. Corresponding values of 26.35, 26.93, and 27.53 were obtained for the TR322, TR332, and TRPN derivatives, respectively. The protonation constants and NMR spectroscopic data are interpreted as being due to the influence of specific hydrogen-bond interactions. The incremental enlargement of ligand size results in a decrease in iron-chelate stability, as reflected in the log beta(110) values of 26.8, 26.2, 26,42, and 24.48 for the TREN, TR322, TR332, and TRPN derivatives, respectively. The metal complex formation constants are also affected by the acidity of a proximal (non-metal-binding) amine in the complexes, a trend consistent with the effects of internal hydrogen bonding. The ferric complexes display reversible reduction potentials (measured relative to the normal hydrogen electrode (NHE)) between -0.170 and -0.223 V.