Syn–anti conformational switching in an ethane-bridged Co(ii)bisporphyrin induced by external stimuli: effects of inter-macrocyclic interactions, axial ligation and chemical and electrochemical oxidations

Abstract

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.