Molecular structures of cobalt complexes of 2-aza-2-[p-methylbenzyl]-5,10,15,20-tetraphenyl-21-carbaporphyrin: [Co(2-NCH2-p-C6H4CH3-21-m-CH2C6H4CH3NCTPP)L] (L = Cl−, N*CS−)

Add time:08/05/2019    Source:sciencedirect.com

Two experimentally well characterized four-coordinate complexes of the general formula [Co(2-NCH2-p-C6H4CH3-21-m-CH2C6H4CH3NCTPP)L] (with L = Cl− and N*CS− for 3 and 4) are considered for this study. The crystal structures of the paramagnetic chloro(2-aza-2-[p-methyl benzyl]-5,10,15,20-tetraphenyl-21-m-xylyl-21-carbaporphyrinato-N,N′,N″) cobalt(II) octane solvate [Co(2-NCH2-p-C6H4CH3-21-m-CH2C6H4CH3NCTPP)Cl]·0.5C8H18 (3·0.5 C8H18) and thiocyanato-N-(2-aza-2-[p-methylbenzyl]-5,10,15,20-tetraphenyl-21-m-xylyl-21-carbaporphyrinato-N,N′,N″) cobalt(II) [Co(2-NCH2-p-C6H4CH3-21-m-CH2C6H4CH3NCTPP)(NCS)] (4) were established. The geometry around the Co2+ ion in 3·0.5 C8H18 (or 4) is a distorted tetrahedron, with C2v symmetry. The magnitude of the zero-field splitting (ZFS) parameter (D) was reported to change from 44.5 cm−1 in 3 to 30.0 cm−1 in 4 through DC magnetic susceptibility determinations. The |D| value can be related to the magnitude of the ligand-field splitting parameter of the axial k-donating Cl− ligand of 3 and the axial π-accepting NCS− ligand of 4 at the cobalt sites.

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