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Formation, Photophysics, Photochemistry and Quantum Chemistry of the Out-of-Plane Metalloporphyrins

Abstract Among the complexes of porphyrins, special attention has been paid to those possessing out-of-plane (OOP) structures, for the formation of which the size, as well as the coordinative character of the metal center are responsible. In these coordination compounds, the central atom cannot fit coplanarly into the cavity of the ligand, hence, it is located above the porphyrin plane, distorting it. Equilibria and kinetics of the complex formation, spectrophotometric, photophysical and primary photochemical properties of post-transition and lanthanide OOP metalloporphyrins were investigated, in addition electronic structural calculations were performed; hence, the general OOP characteristics were determined.Meanwhile, few doubtful questions have attempted to be answered concerning the categorization of metalloporphyrins, the borderline case complexes and hyperporphyrins.