A comprehensive electronic structure description of a biscyanotetraazacobalt(III) macrocyclic complex.

Molecular modeling and a detailed spectroscopic characterization of the macrocyclic complex [Co(meso)(CN)(2)](+) meso = 5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane is herein presented. Structural, electronic and vibrational features are discussed and assignments were proposed on the basis of semi-empirical (molecular mechanics (MM+), ZINDO/S and PM3) quantum-mechanics calculations. The energy and the composition of the molecular orbitals of the complex were calculated and a quantitative diagram was constructed. The simulated UV-vis spectrum exhibited a reasonably good accordance with the experimental one and fully assignments of seven bands were made. An optimized configuration of the complex showed a strong cobalt-cyanide axial bond in agreement with the major contribution of the cyanide to the composition of the molecular orbitals in contrast to a discrete participation of the macrocyclic meso to the ground state of the complex.