Inter-ring interactions in [Fe(TalkylP)(Cl)] (alkyl = ethyl, n-propyl, n-hexyl) complexes: control by meso-substituted groups

Syntheses, molecular structures and magnetic susceptibilities of three meso-substituted high-spin iron(III) porphyrinate complexes ([Fe(TEtP)(Cl)], [Fe(TPrP)(Cl)], and [Fe(THexP)(Cl)]) are described. It was determined that the inter-ring interactions within each dimeric unit change upon alteration of the alkyl groups at the meso positions. Magnetic exchange couplings between iron centers of the dimers are in accord with the trends in structural inter-ring geometries. Crystal data for [Fe(TEtP)(Cl)]: a = 10.1710(5) angstrom, b = 11.309(3) angstrom, c = 12.170(3) angstrom, alpha = 91.774(9)degrees, beta = 113.170(14)degrees, gamma = 112.149(9)degrees, V = 1165.2(4) angstrom(3), triclinic, P (1) over bar, Z = 2, R-1 = 0.0844 and wR(2) = 0.2073 for observed data. Crystal data for [Fe(TPrP)(Cl)]: a = 13.040(2) angstrom, b = 15.221(2) angstrom, c = 14.6681(9) angstrom, beta = 109.997(11)degrees, V = 2735.9(7) angstrom(3), monoclinic, P2(1)/n, Z = 4, R-1 = 0.0477 and wR(2) = 0.1176 for observed data. Crystal data for [Fe(THexP)(Cl)]: a = 10.246(7) angstrom, b = 12.834(4) angstrom, c = 17.420(15) angstrom, alpha = 69.74(3)degrees, beta = 87.52(4)degrees, gamma = 84.89(3)degrees, V = 2140(2) angstrom(3), triclinic, P (1) over bar, Z = 2, R-1 = 0.1024 and wR(2) = 0.2659 for observed data.