The cis- and trans-azobenzenes are known as photochromic isomers with the trans- converting into the cis-form and vice versa upon irradiation with specific wavelengths. We have quantum chemically investigated the cis- and transforms of substituted azobenzene diradicals, with two nitronyl nitroxides, imino nitoxides, or verdazyls at para positions and serving as monoradical centers, to determine whether they can exhibit a photoassisted magnetic crossover. Geometries of both substituted and unsubstituted molecules have been optimized by density functional (DF) method UB3LYP using the 6-311G(d,p) basis set. Optimization of the geometry of the cis isomers has required special care. Single point singlet, triplet, and broken symmetry calculations have been done using 6-311++G(3df, 3pd) basis set. The magnetic exchange coupling constants have been estimated from the broken symmetry calculations. Absorption wavelengths have been estimated for both substituted and unsubstituted species from time-dependent DF treatment using restricted spin-polarized methodology RB3LYP and 6-311++G(3df, 3pd) basis set. From the similarity in the calculated absorption wavelengths for the unsubstituted and substituted azobenzenes, and the increased oscillator strengths (f) for the substituted species, we predict that the diradical isomers would be strongly photochromic. From our triplet state and broken symmetry calculations, we predict that both the cis- and the trans-diradicals are antiferromagnetically coupled. This prediction is consistent with the spin alternation rule, and the possibility of a magnetic crossover is nonexistent for these species.