A study of the redox potentials of a range of metal phthalocyanines in non-aqueous media compared with analogous data for some porphyrin complexes provides evidence for extensive back donation in metallophthalocyanines. The potentials for some couples are exceedingly sensitive to axial ligation. It is suggested that this sensitivity may be used to 'tune' a redox couple for a specific purpose such as designing a reversible oxygen breathing system.