Engineered [FeFe]-hydrogenase mimics featuring heteroaryl linkers: molecular design and photocatalytic hydrogen evolution under visible light

Abstract

Inspired by the active site of [FeFe]-hydrogenase, we have developed synthetic mimics engineered from the reaction of heteroaryl thioketone derivatives ferrocenyl(5-(4-(diphenylamino)phenyl)thiophen-2-yl)methanethione (PS-Fc-1), ferrocenyl(5′-(4-(diphenylamino)phenyl)-[2,2′-bithiophen]-5-yl)methanethione (PS-Fc-2) and phenyl(5′-(4-(diphenylamino)phenyl)-[2,2′-bithiophen]-5-yl)methanethione (PS-Ph) as pro-ligands with Fe₃(CO)₁₂. The resulting complexes contain thiolato ligands, which enable a close linkage between heteroaryl chromophores and the catalytic center, thereby promoting efficient photocatalytic hydrogen evolution under visible light irradiation. These mimics incorporate a push–pull organic chromophore, consisting of triphenylamine and (bi)thiophene groups, designed to facilitate direct photoexcitation into a charge-separated state. Electrochemical properties were examined using cyclic voltammetry, and photophysical characteristics were determined by steady-state spectroscopy and nanosecond transient absorption supported by (TD-)DFT simulations. Whilst both catalytically active species revealed the formation of charge-separated states directly upon excitation, fast deactivation due to relaxation into low-lying ferrocene-located states prevents the formation of long-lived excited states in the ferrocene-linked dyad. This explains the reduced activity for hydrogen generation of the dyad containing the ferrocene moiety compared to the phenyl one.