A Diprotonated Porphyrin as an Electron Mediator in Photoinduced Electron Transfer in Hydrogen-Bonded Supramolecular Assemblies

We have successfully constructed hydrogen-bonded supramolecular assemblies based on a diprotonated saddle-distorted porphyrin (H 4 DPP 2+ ) and redox-active molecules bearing a carboxylate group, such as a RuII polypyridyl complex (Ru II COO – ) that can act as an electron donor and a benzyl viologen derivative (BV 2+ COO – ) that can act as an electron acceptor. Formation of supramolecular assemblies of H 4 DPP 2+ with Ru II COO – (H 4 DPP 2+ (Ru II COO – ) 2 and H 4 DPP 2+ (Ru II COO – )­(Cl – )) and BV 2+ COO – (H 4 DPP 2+ (BV 2+ COO – ) 2 ) was confirmed in acetone by 1H NMR measurements, CSI-TOF-MS, and X-ray crystallographic analysis. The photodynamics of H 4 DPP 2+ (Ru II COO – ) 2 and H 4 DPP 2+ (BV 2+ COO – ) 2 was elucidated by femto-, pico-, and nanosecond time-resolved transient absorption spectroscopy. In H 4 DPP 2+ (Ru II COO – ) 2 , intrasupramolecular photoinduced electron transfer (ET) occurred from the RuII center to the singlet excited state of H 4 DPP 2+ to afford an ET state involving one-electron-reduced H 4 DPP •+ and the corresponding one-electron-oxidized RuIII complex with the lifetime of 150 ps. On the other hand, in the presence of an external electron donor, intermolecular photoinduced ET occurred from an electron donor to the triplet excited state of H 4 DPP 2+ (BV 2+ COO – ) 2 to afford H 4 DPP •+ , following intrasupramolecular thermal ET proceeded from H 4 DPP •+ to BV 2+ COO – to form H 4 DPP 2+ (BV •+ COO – )­(BV 2+ COO – ) with the lifetime of 1.1 ms. Thus, H 4 DPP 2+ can act as an electron mediator in hydrogen-bonded supramolecular assemblies. This is the first example of porphyrins as a photosensitizer and an electron mediator in hydrogen-bonded ET systems.