In the field of direct production of hydrogen from solar energy and water, photocatalytic methods hold great potential especially when metal-free molecular components are preferred. In this work, we have developed a new class of calixarene-based molecular photosensitizers to be used as antenna systems in the photocatalytic production of hydrogen. The structure of the dyes has a typical donor-π-acceptor molecular architecture where a calixarene scaffold is used as an embedded donor. The new materials have been fully characterized in their optical, electrochemical, and photocatalytic properties. The properties conferred by the calixarene donor afforded twice larger performances compared to the corresponding linear system though showing similar quantitative optical properties. The new molecular design paves the way to a new strategy for photocatalytic hydrogen production where the calixarene scaffold can afford more efficient systems and can offer the potential for host-guest supramolecular effects.
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