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A highly oxidized cobalt porphyrin dimer is reported. Each cobalt(II) ion and porphyrin ring underwent 1e oxidation with iodine as the oxidant to give a 4e-oxidized cobalt(III) porphyrin π-cation radical dimer The bridging ethylene group allows for substantial conjugation of the porphyrin macrocycles, thus leading to a strong antiferromagnetic coupling between the π-cation radicals and to stabilization of the singlet state. X-ray crystallography clearly showed that the complex may be considered as a real supramolecule rather than two cobalt(III) porphyrin p-cation radicals that interact through space. [ABSTRACT FROM AUTHOR]

The syn-anti conformational switching has been demonstrated in the ethane-bridged dicobalt(II)bisporphyrin which is present in the syn-form only. The addition of either perylene or axial ligands to CoII(bisporphyrin) completely transforms the syn form into the anti because of strong π-π interaction and axial coordination, respectively. The complex undergoes four 1e-oxidations in CH2Cl2 which are indicative of strong through space interactions between the two cofacial Co-porphyrins at 295 K. The first oxidation is a metal centered one and occurs at a potential much lower than that of the monomeric analog. However, the second oxidation, which is again metal centered, was at a significantly higher potential. The large difference between the first two oxidations, as observed here, is due to much stronger inter-porphyrin interactions. The step-wise oxidations have been performed both chemically and electro-chemically while the progress of the reactions was monitored by UV-visible and 1H NMR spectroscopy. After 1e-oxidation, a very broad 1H NMR signal results with increased difference between two meso resonances, which indicates that the two macrocycles are in the syn-form with lesser interplanar separation as also observed by DFT. However, 2e-oxidation results in the stabilization of the anti form. The addition of axial ligands to CoII(bisporphyrin) also completely transforms the syn form into the anti form. While additions of THF and I2/I- both result in the formation of five-coordinate complexes, Co(II) is oxidized to Co(III) in the case of the latter. However, additions of 1-methylimidazole, pyridine and pyrazine as axial ligands result in the formation of a six-coordinate complex in which Co(II) is spontaneously oxidized to Co(III) in air. [ABSTRACT FROM AUTHOR]

The single-crystal X-ray structure of solvent-free (tmtaa)Co II reveals three different π-π intermacrocyclic interactions between tmtaa units (tmtaa = dibenzotetramethyltetraaza[14]annulene). Pairs of inequivalent (tmtaa)Co II units in the unit cell link into a one-dimensional π-π stacked array in the solid state. Magnetic susceptibility (χ) studies from 300 to 2 K reveal the effects of intermolecular interactions between (tmtaa)Co II units in the solid state. The effective magnetic moment per Co II center is constant at 2.83 μ B from 300 to 100 K and begins to significantly decrease at lower temperatures. The magnetic data are fit to a singlet ( S = 0) ground state with a triplet ( S = 1) excited state that is 13 cm -1 higher in energy (-2 J = 13 cm -1 ). Toluene solutions of (tmtaa)Co II have 1 H nuclear magnetic resonance (NMR) paramagnetic shifts, a solution-phase magnetic moment μ eff (295 K) of 2.1 μ B , and toluene glass electron paramagnetic resonance spectra that are most consistent with a low-spin ( S = 1 / 2 ) Co II with the unpaired electron located in the d yz orbital. Pyridine interacts with (tmtaa)Co II to form a five-coordinate monopyridine complex in which the unpaired electron is in the d z 2 orbital. The five-coordinate complex has been structurally characterized by single-crystal X-ray diffraction, and the equilibrium constant for pyridine binding at 295 K has been evaluated by both electronic and 1 H NMR spectra. Density functional theory computation using the UB3LYP hybrid functional places the unpaired electron for (tmtaa)Co II in the d yz orbital and that for the monopyridine complex in the d z 2 orbital, consistent with spectroscopic observations.

The binding of a series of substituted phenols as axial ligands onto a diiron(III)bisporphyrin framework have been investigated. Spectroscopic characterization revealed high-spin states of the iron centers in all of the phenolate complexes, with one exception in the 2,4,6-trinitrophenolate complex of diiron(III)bisporphyrin, which only stabilized the pure intermediate-spin (S=3/2) state of the iron centers. The average FeN (porphyrin) and FeO (phenol) distances that were observed with the 2,4,6-trinitrophenolate complex were 1.972(3) Å and 2.000(2) Å, respectively, which are the shortest and longest distances reported so far for any Fe(III) porphyrin with phenoxide coordination. The alternating shift pattern, which shows opposite signs of the chemical shifts for the meta versus ortho/para protons, is attributed to negative and positive spin densities on the phenolate carbon atoms, respectively, and is indicative of π-spin delocalization onto the bound phenolate. Electrochemical data reveals that the E1/2 value for the Fe(III) /Fe(II) couple is positively shifted with increasing acidity of the phenol. However, a plot of the E1/2 values for the Fe(III) /Fe(II) couple versus the pKa values of the phenols shows a linear relationship for all of the complexes, except for the 2,4,6-trinitrophenolate complex. The large deviation from linearity is probably due to the change of spin for the complex. Although 2,4,6-trinitrophenol is the weakest axial ligand in the series, its similar binding with the corresponding Fe(III) monoporphyrin only results in stabilization of the high-spin state. The porphyrin macrocycle in the 2,4,6-trinitrophenolate complex of diiron(III)bisporphyrin is the most distorted, whilst the "ruffling" deformation affects the energy levels of the iron d orbitals. The larger size and weaker binding of 2,4,6-trinitrophenol, along with hemeheme interactions in the diiron(III)bisporphyrin, are responsible for the larger ring deformations and eventual stabilization of the pure intermediate-spin states of the iron centers in the complex., (Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)