Dinuclear 2,4-di(pyridin-2-yl)-pyrimidine based ruthenium photosensitizers for hydrogen photo-evolution under red light

In this study, we report two dinuclear Ru(II) complexes C1 and C2 and compare them to their mononuclear analogues Ref1 and Ref2. The dinuclear species exhibit a much stronger absorption, longer excited-state lifetimes and higher luminescence quantum yields than the mononuclear complexes. In addition, C1 and C2 are easier to reduce. An estimation of the driving forces for the electron transfer processes relevant to photocatalytic hydrogen evolution suggests that C1 and Ref2 possess similar activity as photosensitizer (PS). Yet, the improved photophysical properties of C1 make it a more promising candidate for hydrogen evolution. In hydrogen evolution experiments, C1 indeed exhibits increased activity as PS, however, the catalytic system loses its activity after only a few hours. C2 is less active than the mononuclear complexes despite its superior photophysical properties. This observation is attributed to a lack of driving force for the electron transfer towards the catalyst. Further studies of the dinuclear complex C1 show that it is indeed the PS, which decomposes under the catalytic conditions, presumably due to the electron transfer towards the catalyst being the rate-limiting step.