Short and very efficient syntheses of a series of d(6) rhodium(III) complexes, [Rh(X(4))phi](3+) (Xq = (NH3)(4), (en)(2), tren, [12]aneN(4), [12]aneS(4)), containing the 9,10-phenanthrenequinone diimine (phi) ligand and mono-, bi-, and tetradentate amine- or sulfur-containing ligands have been carried out. The synthetic strategies include two-step reaction sequences, in which the coordinated chlorides of [Rh(X(4))Cl-2](+) are replaced by 9,10-diaminophenanthrene, and a single-step method, in which RhCl3 is first reacted with 9,10-diaminophenanthrene and then the ancillary ligands are added, followed by oxidation with dioxygen. The complexes have been investigated with respect to their solid-state structure, spectroscopy; and photochemical reactivity. This detailed characterization provides the basis to explore systematically the contributions of hydrogen bonding and van der Waals interaction to sequence-specific recognition of DNA. Crystal structures of [Rh[(NH3)(4)phi] Cl-3.3H(2)O (triclinic crystal system, space group P (l) over bar (No. 2), Z = 2, a = 7.605(2) Angstrom, b = 9.081(2) Angstrom, c = 16.729(4) Angstrom, alpha = 87.95(2)degrees, beta = 76.92(2)degrees, gamma = 84.42(2)degrees, V = 1119.9(4) Angstrom(3)), [Rh([12]aneN(4))phi] (SCN)(3).2H(2)O (triclinic crystal system, space group P (l) over bar (No. 2), Z = 2, a = 15.479(5) Angstrom, b = 12.312(2) Angstrom, c = 8.679(2) Angstrom, alpha = 72.10(2)degrees, beta 83.98(2)degrees, gamma = 71.52(2)degrees, V = 1492.7(7) Angstrom(3)), and Rh([12]aneS(4))phi] Br-3.3H(2)O (triclinic crystal system, space group P (l) over bar (No. 2), Z = 2, a = 8.921(2) Angstrom, b = 12.846(4) Angstrom, c = 13.325(4) Angstrom, alpha = 70.50(2)degrees, beta = 86.43(2)degrees, gamma = 86.68(2)degrees, V = 1435.5(7) Angstrom(3)) are reported. Two isomers, which are also seen in solution in a ratio of 60:40 (Delta G = 0.99 kJ/mol), of C-2v (14% population) and C-s (86% population) symmetry have been found in the same crystal of [Rh([12]aneN(4))phi] (SCN)(3).2H(2)O, but only one isomer (point group C-s) has been found for the sulfur analogue [Rh([12]aneS(4))phi] Br-3. The substantial distortion of the octahedral geometry in the complexes [Rh([12]aneN(4))phi](3+) and [Rh([12]aneS(4))phi](3+) is associated with the small hole size of the coordinating macrocycles. Angles N(4)-Rh-N(6) between axial nitrogen atoms are as small as 160 degrees in [Rh([12]aneN(4))phi](3+) or 168.5 degrees for the angle S(1)-Rh-S(3) between the axial sulfur atoms of [Rh([12]aneS(4))phi](3+).