The Cr(CN)(5)(py)(2-) anion (py pyridine) has been prepared by acid-promoted methanolysis of Cr(CN)(6)(3-) followed by reaction with pyridine, isolated as the potassium salt, and characterized by absorption spectra (lambda(max) : 403 and 256 nm in H2O; 411 nm in Me2SO) and phosphorescence, observed in Me2SO (lambda(max), 774 nm; tau = 56 mu s at 20 degrees C) but not in H2O. In acid aqueous solution the complex decomposes stepwise to Cr(H2O)(5)(py)(3+); by contrast, the thermal reaction in Me2SO leads to Cr(CN)(5)(Me2SO)(2-) with first-order kinetics (k(25) = 9.8 x 10(-7) s(-1), Delta H-double dagger = 138 +/- 8 kJ mol(-1)). Ligand-field (LF) band irradiation results in substitution of py and CN-. The quantum yields, measured by ligand analysis, spectrophotometry, and HPLC, are as follows : Phi(py) = 0.08, Phi(CN) = 0.01 in H2O (pH 7.2, phosphate buffer) and Phi(py) = 0.04, Phi(CN) = 0.002 in Me2SO. The preference for py release obeys the prediction of the Vanquickenborne-Ceulemans, additive angular overlap model (AOM) A notable feature of this complex is that both types of ligands are pi accepters, and the pi effect of py on bond labializing is evidenced by comparison with the photolysis of Cr(CN)(5)(NH3)(2-). Irradiation of the intense UV absorption due to overlap of charge-transfer (CT) and pi --> pi*, py localized transitions causes the increase of both quantum yields, suggesting the involvement of higher-energy states besides the LF ones. Co(sep)3+ (sep = 1,3,6,8,10,13,16,19-octaazabicyclo[6.6.6]eicosane = sepulchrate) quenches the phosphorescence (k(q) = 1.6 x 10(9) M-1 s(-1)) but has no effect on the photoreaction efficiencies : the photochemistry is thus inferred to originate entirely from the lowest quartet excited state(s) in competition with intersystem crossing. The marked solvent effects on the absorption spectrum, on the emission behavior, on the thermal reactivity, on the photolysis quantum yields, and, in particular, on the Phi(py)/Phi(CN) ratio, are discussed in terms of the proneness of the cyanide ligand to either protonation or hydrogen bonding and of solvent orientation toward anionic complexes.