Metal complexes of tetradentate and pentadentate N-o-hydroxybenzamido-meso-tetraphenylporphyrin ligand: M(N-NCO(o-OH)C6H4-tpp) (M=Zn2+, Ni2+, Cu2+) and M′(N-NCO(o-O) C6H4-tpp) (M′=Mn3+) (tpp=5, 10, 15, 20-tetraphenylporphyrinate)

The crystal structures of N-o-hydroxybenzimido-meso-tetraphenylporphyrinatozinc(II) toluene solvate [Zn(N-NCO(o-OH)C6H4-tpp)·C6H5CH3; 4·C6H5CH3], N-o-hydroxybenzimido-meso-tetraphenylporphyrinatonickel(II) chloroform solvate [Ni(N-NCO(o-OH)C6H4-tpp)·0.6CHCl3; 5·0.6 CHCl3], N-o-hydroxybenzimido-meso-tetraphenylporphyrinatocopper(II) toluene solvate [Cu(N-NCO(o-OH)C6H4-tpp)·C6H5CH3; 6·C6H5CH3] and N-o-oxido-benzimido-meso-tetraphenylporphyrinato(-κ4,N1,N2,N3,N5,κO2) manganese (III) methylene chloride·methanol solvate [Mn(N-NCO(o-O)C6H4-tpp)·CH2Cl2·MeOH; 8·CH2Cl2·MeOH] were established. The coordination sphere around Zn2+ ion in 4·C6H5CH3, (or Ni2+ ion in 5·0.6 CHCl3 or Cu2+ ion in 6·C6H5CH3) is a distorted square planar (DSP) whereas for Mn3+ in 8·CH2Cl2·MeOH, it is a distorted trigonal bipyramid (DTBP) with O(1), N(1) and N(3) lying in the equatorial plane for 8·CH2Cl2·MeOH. The g value of 8.27 measured from the parallel polarization of X-band EPR spectra at 293 K is consistent with the high-spin mononuclear manganese(III) (S = 2) in 8. The magnitude of axial (D) zero-field splitting (ZFS) for the mononuclear Mn(III) in 8 was determined approximately as 3.0 cm−1 by the paramagnetic susceptibility measurements and conventional EPR spectroscopy.