Abstract
Some picket fence porphyrinatocobalt(II) complexes which contain a replaced polar or non-polar group in their fences were newly prepared and characterized, and their oxygen affinities were measured spectrophotometrically. The O 2 affinities of the complexes containing a replaced polar group other than amido linkages are appreciably reduced as compared with those of the complexes with a similar non-polar group, regardless of the charge sign of the polarity in the cavity. On the other hand, solvent polarity affects the O 2 affinity of the complex with a polar group which is accessible to the coordinated dioxygen molecule, while solvation effects of the corresponding complex without such a group are little. On the basis of these results the relationships between O 2 affinity and pocket polarity or solvent polarity are discussed.
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