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
Van't Hoff Institute for Molecular Sciences, University of Amsterdam, Nieuwe Achtergracht 166, 1018 WV Amsterdam, The Netherlands.
Proc Natl Acad Sci U S A. 2009 Jun 30;106(26):10460-5. doi: 10.1073/pnas.0809666106. Epub 2009 Jan 21.
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 [Fe(2)(micro-pdt)(CO)(4){PPh(2)(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.
清洁能源的大规模生产是当今社会面临的主要挑战之一。分子氢被设想为未来的一种关键绿色燃料，但只有当它也以清洁的方式生产时，它才成为传统燃料的可持续替代品。在此，我们报告一种超分子仿生方法，以形成一种利用光作为能源生产分子氢的催化剂。它由发色团与基于双（硫醇盐）桥连二铁（[2Fe2S]）的氢化酶催化剂组装而成。本文介绍的超分子构建模块方法能够轻松形成一系列配合物，所有这些配合物都经过了全面表征，表明催化剂组装体的光活性强烈依赖于其性质。由不同配合物形成的活性物种似乎是[Fe(2)(μ-pdt)(CO)(4){PPh(2)(4-py)}(2)] (3)，有2种不同类型的卟啉（5a和5b）与其配位。模块化超分子方法在本研究中很重要，因为用有限数量的构建模块生成了几种不同的配合物。
