Photosensitized hydrogen evolution from water using conjugated polymers wrapped in dendrimeric electrolytes.

High-efficiency light-driven hydrogen evolution from water was demonstrated by using poly(phenyleneethynylene) bearing negatively charged, [G3] poly(benzyl ether) dendrimeric side groups 3L4 as photosensitizer. Three-dimensional wrapping of the conjugated backbone suppressed self-quenching of the photoexcited state, while methyl viologen (MV2+), a positively charged electron acceptor, was trapped on its negatively charged surface, to form a spatially separated donor−acceptor supramolecular complex. Studies with time-resolved fluorescence spectroscopy showed that the quenching rate constant (kq = 1.2 × 1015 M-1 s-1) is much greater than diffusion control rate constants. Upon excitation of 3L4 in the presence of a mixture of MV2+, triethanolamine (TEOA; sacrificial electron donor), and a colloidal PVA-Pt, hydrogen evolution took place with an overall efficiency of 13%, 1 order of magnitude better than precedent examples. Comparative studies with several reference sensitizers showed that spatial isolation of...