A theoretical approach to the influence of the macrocycle conformation on the molecular electronic structure in Mg-porphyrins

Nonplanar saddled (sad) ruffled (ruf) and domed (dom) conformations of the Mg-porphyrin (MgP) macrocycle in several degrees of deformation have been c omputed. These symmetrical distortion modes were induced in unsubstituted m acrocycle using molecular definitions for calculations which permits us to achieve a systematical variation of the nonplanarity varying only a conveni ent geometrical parameter of the molecule. Series of nonplanar macrocycles like those synthesized in previous works employing peripheral substitutions are obtained. The procedure here used to induce deformations gives the pos sibility of investigating the modulator role of the out-of-plane distortion s on the geometry and electronic properties of the porphyrin avoiding addit ional influences due to the substituents or the surrounding protein scaffol ding.