Structure and mixed spin state of the chloroiron(III) complex of 2,3,7,8,12,13,17,18-octaphenyl-5,10,15,20-tetraphenylporphyrin, Fe(dpp)Cl

Abstract The chloroiron(III) complex Fe(dpp)Cl (1) of the peripherally crowded 2,3,7,8,12,13,17,18-octaphenyl-5,10,15,20-tetraphenylporphyrin or dodecaphenylporphyrin (dpp), has been synthesized and characterized by X-ray crystallography, normal-coordinate structural decomposition analysis (NSD), EPR and Mossbauer spectroscopy and magnetic susceptibility measurements. The dpp ligand present in the crystal structure of this molecule is predominantly saddle-shaped. It is also ruffled and slightly domed according to an analysis of the out-of-plane distortions performed by using NSD. This saddle deformation is significantly smaller than those observed in the chloroiron(III) complexes of the β-p…

The 5/2,3/2 Spin Admixture in the Chloroiron(III) Derivative of the Sterically Crowded 2,3,7,8,12,13,17,18-Octaethyl-5,10,15,20-tetraphenylporphyrin

Despite similar ring deformations in solution and in the solid state, the chloroiron(III) derivative of 2,3,7,8,12,13,17,18-octaethyl-5,10,15,20-tetraphenylporphyrin ([FeCl(oetpp)], shown schematically) prepared in this study exhibits only a very weak quantum-mechanical admixture of spin S=3/2 (only 4-10 %) with spin S=5/2. In contrast, for the variety of [FeCl(oetpp)] studied earlier by other researchers a 40 % contribution of the S=3/2 state was found.

Die 5/2,3/2-Spin-Beiträge im Chloroeisen(III)-Derivat des sterisch überfrachteten 2,3,7,8,12,13,17,18-Octaethyl-5,10,15,20-tetraphenylporphyrins