Metal ion complexing properties of the ligand 2,9-bis(hydroxymethyl)-1,10-phenanthroline (PDALC) are reported. For PDALC, the rigid 1, 10-phenanthroline backbone leads to high levels of preorganization and enhanced selectivity for larger metal ions with an ionic radius of about 1.0 A that can fit well into the cleft of the ligand. Structures of PDALC complexes with two larger metal ions, Ca(II) and Pb(II), are reported. [Ca(PDALC)(2)](ClO4)(2) (1) is triclinic, P-1(-), a = 7,646(3), b = 13.927(4), c = 14.859(5) (angstrom), alpha = 72.976(6), beta = 89.731(6), mu = 78.895(6)degrees, V = 1482.5(8) angstrom(3), Z = 2, R = 0.0818. [Pb(PDALC)(ClO4)(2)] (2) is triclinic, P-1(-), a = 8.84380(10), b = 9.0751(15), c = 12.178(2) (angstrom), alpha = 74.427(3), beta = 78.403(13), mu = 80.053(11)degrees, V = 915.0(2)angstrom(3), Z = 2, R = 0.0665. In 1, the Ca(II) is eight-coordinate, with an average Ca-N of 2.501 angstrom and Ca-O of 2.422 angstrom. The structure of 1 suggests that Ca(II) is coordinated in a very low-strain manner in the two PDALC ligands. In 2, Pb(II) appears to be eight-coordinate, with coordination of PDALC and four O donors from perchlorates bridging between neighboring Pb atoms. The Pb has very short Pb-N bonds averaging 2.486 angstrom and Pb-O bonds to the alcoholic groups of PDALC of 2.617 angstrom. It is suggested that the Pb(II) has a stereochemically active lone pair situated on the Pb(II) opposite the two N donors of the PDALC, and in line with this, the Pb-L bonds become longer as one moves around the Pb from the sites of the two N donors to the proposed position of the lone pair. There are two oxygen donors from two perchlorates, nearer the N donors, with shorter Pb-O lengths averaging 2.623 angstrom. Two oxygens from perchlorates nearer the proposed site of the lone pair form very long Pb-O bond lengths averaging 3.01 A. The Pb(II) also appears to coordinate in the cleft of PDALC in a low-strain manner. Formation constants are reported for PDALC in 0.1 M NaClO4 at 25.0 degrees C. These show that, relative to 1,10-phenanthroline, the hydroxymethyl groups of PDALC produce a significant stabilization for large metal ions such as Cd(II) or Pb(II) that are able to fit in the cleft of PDALC but destabilize the complexes of metal ions such as Ni(II) or Cu(II) that are too small for the cleft.