Photoelectrochemical properties of zinc(II) and copper(II) complexes of (1) phthalocyanine, (2) tetrapyrido[2,3‐b;2′, 3′‐g;2″,3″‐l;2‴,3‴‐q]‐5,10,15,20‐tetra‐azaporphyrin, and (3) tetrapyrazino[b;g;l;q]‐5,10,15,20‐tetra‐azaporphyrin, were investigated in thin‐film electrodes prepared by vacuum deposition (VD), drop‐casting (DC) and in situ synthesis (IS). The opposing behavior, photoreduction at electrodes of 1 and photo‐oxidation at electrodes of 2 and 3, are discussed in terms of a band‐energy shift of tetra‐azaporphyrin macrocycles caused by substitution with heterocyclic pyrido and pyrazino groups. The photoelectrochemical efficiency of the electrodes is strongly affected by the film morphology which is dependent on the preparation methods, and increased in order of DC < VD < IS .
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Yanagi et al. (1993) studied this question.