Self-assembled biomimetic [2Fe2S]-hydrogenase-based photocatalyst for molecular hydrogen evolution

• Published in: Proceedings of the National Academy of Sciences - PNAS Vol. 106; no. 26; pp. 10460 - 10465
• Main Authors: Kluwer, A.M, Kapre, R, Hartl, F, Lutz, M, Spek, A.L, Brouwer, A.M, van Leeuwen, P.W.N.M, Reek, J.N.H
• Format: Journal Article
• Language: English
• Published: Washington National Academy of Sciences 30.06.2009; National Acad Sciences
• Series: Molecular Recognition and Self-Assembly Special Feature
• Subjects: Catalysts; Chemical compounds; Hydrogen bonds; Molecules; Physical Sciences; Studies
• ISSN: 0027-8424; 1091-6490
• DOI: 10.1073/pnas.0809666106

The large-scale production of clean energy is one of the major challenges society is currently facing. Molecular hydrogen is envisaged as a key green fuel for the future, but it becomes a sustainable alternative for classical fuels only if it is also produced in a clean fashion. Here, we report a supramolecular biomimetic approach to form a catalyst that produces molecular hydrogen using light as the energy source. It is composed of an assembly of chromophores to a bis(thiolate)-bridged diiron ([2Fe2S]) based hydrogenase catalyst. The supramolecular building block approach introduced in this article enabled the easy formation of a series of complexes, which are all thoroughly characterized, revealing that the photoactivity of the catalyst assembly strongly depends on its nature. The active species, formed from different complexes, appears to be the [Fe₂(μ-pdt)(CO)₄{PPh₂(4-py)}₂] (3) with 2 different types of porphyrins (5a and 5b) coordinated to it. The modular supramolecular approach was important in this study as with a limited number of building blocks several different complexes were generated.