Geometry parameters, total energy of the system in different spin states, harmonic vibrational frequencies, and absorption spectra were computed for a range of mononuclear quaterpyridine Ru(II), Fe(III/II), and Co(III/II) complexes with two axial ambidentate CNS ligands by using density functional theory (DFT) and time-dependent DFT calculations. Both structural and electronic properties were found to be correlating with the type of the binding atom in the CNS ligand (isomerization differs by 4-13 kcal·mol-1). The N-bonding of CNS ligands is energetically favored. It was also found that the low spin (LS) state is the ground state for both Ru(II) and Co(III) complexes regardless of the CNS arrangement. The other complexes are the high-spin (HS) ground-state ones with the only exception of the S-bonded CNS isomer of the Fe(III) complex. The dependencies of energy differences between the HS and LS states versus C demonstrated stabilization of the HS state with an increasing amount of the exact exchange admixture (C) for iron and cobalt complexes. An opposite behavior was observed for ruthenium complexes. The best match in harmonic vibrational frequencies between the experimental and calculated values has been reached at C = 0.15 for all the complexes. The absorption profile of the Fe(II) complex with the alternatively bonded CNS ligands strongly depends on the angle between them. The light-harvesting efficiency of the Fe(II) complexes is very similar (∼0.4) and sufficiently close to that of the Ru(II) complexes. The iron-based coordination compounds are considered as a prospective dye for dye-sensitized solar cells. The results of calculations were completed with experimental reference data, thus providing a systematic compendium for practical use.