Molecular complexes between octaethyltetrathiaporphyrin dication and electron donors: A spectroscopic and electrochemical study

Octaethyltetrathiaporphyrin dication, OTP²⁺, is electrochemically reduced by two successive electron‐transfer processes to OPT⁰. OPT²⁺ forms intermolecular complexes with a series of π‐donors. The association constants of the resulting complexes are controlled by the oxidation potentials of the π‐donors and solvent properties. OTP²⁺ was incorporated into a Nafion membrane cast on a Pt electrode. Formation of OTP²⁺–π‐donor complexes in the polymer membrane was followed by electrochemical and spectroscopic means. The association constants of the OTP²⁺–π‐donor complexes in the Nafion membrane exhibit lower values than a homogeneous phase owing to the high ionic strength in the polyelectrolyte.