Photoinduced Hydrogen Evolution Catalyzed by a Synthetic
Diiron Dithiolate Complex Embedded within a Protein Matrix
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Abstract
The hydrogen-evolving diiron complex,
(μ-S)<sub>2</sub>Fe<sub>2</sub>(CO)<sub>6</sub> with a tethered
maleimide moiety was synthesized
and covalently embedded within the cavity of a rigid β-barrel
protein matrix by coupling a maleimide moiety to a cysteine residue
within the β-barrel. The (μ-S)<sub>2</sub>Fe<sub>2</sub>(CO)<sub>6</sub> core within the cavity was characterized by UV–vis
absorption and a characteristic CO vibration determined by IR measurements.
The diiron complex embedded within the cavity retains the necessary
catalytic activity (TON up to 130 for 6 h) to evolve H<sub>2</sub> via a photocatalytic cycle with a Ru photosensitizer in a solution
of 100 mM ascorbate and 50 mM Tris/HCl at pH 4.0 and 25 °C
