The synthesis, structure, and physical and/or photophysical properties of Re(bpm)(CO)(3)L(n+), where bpm is 2,2’-bipyrimidine and L = CH3CN, py (pyridine), MeQ(+) (N-methyl-4,4’-bipyridinium ion), and py-PTZ (10-(4-picolyl)phenothiazine), are described. The structure of [Re(bpm)(CO)(3)(CH3CN)]PF6 . 1/2CH(3)CN was determined by single-crystal X-ray diffraction. It crystallized in the space group P ($) over bar 1 with cell dimensions a = 10.089(11) Angstrom, b = 11.855(6) Angstrom, c = 18.990(6) Angstrom, alpha = 89.71(3)degrees, beta = 77.65(6)degrees, gamma = 65.83(6)degrees, Z = 4, and D-calcd = 2.082 g/cm(3). Of the 5565 reflections (Mo K alpha, 3.5 degrees less than or equal to 2 theta less than or equal to 45 degrees), 4721 reflections with F-0 > 3.0 sigma(F-0) were used in full-matrix least-squares refinement. Final residuals were R(F) = 0.0692 and R(w)(F) = 0.1026. The asymmetric unit contained two independent cations. The Re-N(bpm) bond distances were 2.171(9) and 2.198(10) Angstrom for one cation and 2.161(12) and 2.187(12) Angstrom for the other; the two Re-N(CH3CN) bond distances were 2.094(14) and 2.177(13) Angstrom, and the Re-C(CO) bond distances were 1.908(15), 1.938(17), and 1.912(12) Angstrom for the first cation and 1.897(15), 96(19), and 1.919(15) W for the second. The complexes exhibited three CO infrared-active bands in the 1900-2100 cm(-1) region and underwent optical transitions in the 300-350 nm region assigned to d pi(Re) --> pi*(bpm) transitions and in the 200-300 nm region assigned to intraligand pi --> pi* transitions. The complexes underwent multiple reductions attributed to reduction of coordinated bpm and MeQ(+). The first reduction of Re(bpm)(CO)(3)-py(+) was located at E(1/2) = -0.84 v VS SSCE, whereas the first reduction of Re(bpm)(CO)(3)MeQ(2+) was observed at E(1/2) = -0.70 V vs SSCE and was attributed to reduction of the MeQ(+) ligand.