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

Abstract

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) Å, b = 11.309(3) Å, c = 12.170(3) Å, α = 91.774(9)°, β = 113.170(14)°, γ = 112.149(9)°, V = 1165.2(4) Å3, triclinic, [Formula: see text], Z = 2, R1= 0.0844 and wR2= 0.2073 for observed data. Crystal data for [ Fe(TPrP)(Cl) ]: a = 13.040(2) Å, b = 15.221(2) Å, c = 14.6681(9) Å, β = 109.997(11)°, V = 2735.9(7) Å3, monoclinic, P21/ n , Z = 4, R1= 0.0477 and wR2= 0.1176 for observed data. Crystal data for [ Fe(THexP)(Cl) ]: a = 10.246(7) Å, b = 12.834(4) Å, c = 17.420(15) Å, α = 69.74(3)°, β = 87.52(4)°, γ = 84.89(3)°, V = 2140(2) Å3, triclinic, [Formula: see text], Z = 2, R1= 0.1024 and wR2= 0.2659 for observed data.