Photochemical dihydrogen production using an analogue of the active site of [NiFe] hydrogenase

The photoproduction of dihydrogen (H2) by a low molecular weight analogue of the active site of [NiFe] hydrogenase has been investigated by the reduction of the [NiFe2] cluster, 1, by a photosensitier PS (PS = [ReCl(CO)3(bpy)] or [Ru(bpy)3][PF6]2). Reductive quenching of the 3MLCT excited state of the photosensitiser by NEt3 or N(CH2CH2OH)3 (TEOA) generates PS•−, and subsequent intermolecular electron transfer to 1 produces the reduced anionic form of 1. Time-resolved infrared spectroscopy (TRIR) has been used to probe the intermediates throughout the reduction of 1 and subsequent photocatalytic H2 production from [HTEOA][BF4], which was monitored by gas chromatography. Two structural isomers of the reduced form of 1 (1a•− and 1b•−) were detected by Fourier transform infrared spectroscopy (FTIR) in both CH3CN and DMF (dimethylformamide), while only 1a•− was detected in CH2Cl2. Structures for these intermediates are proposed from the results of density functional theory calculations and FTIR spectroscopy. 1a•− is assigned to a similar structure to 1 with six terminal carbonyl ligands, while calculations suggest that in 1b•− two of the carbonyl groups bridge the Fe centres, consistent with the peak observed at 1714 cm−1 in the FTIR spectrum for 1b•− in CH3CN, assigned to a ν(CO) stretching vibration. The formation of 1a•− and 1b•− and the production of H2 was studied in CH3CN, DMF and CH2Cl2. Although the more catalytically active species (1a•− or 1b•−) could not be determined, photocatalysis was observed only in CH3CN and DMF

Exploring photoreactions between polyazaaromatic Ru(II) complexes and biomolecules by chemically induced dynamic nuclear polarization measurements.

Steady-state (1)H photo-chemically induced dynamic nuclear polarization (CIDNP) experiments were conducted at 14.1 T on deoxygenated (buffered pH 7) aqueous solutions of [Ru(phen)(3)](2+), [Ru(tap)(2)(phen)](2+), and [Ru(tap)(3)](2+) (tap = 1,4,5,8-tetraazaphenanthrene; phen = 1,10-phenanthroline) in the presence of guanosine-5'-monophosphate or N-acetyltyrosine. For the first time, CIDNP arising from photo-oxidation by polyazaaromatic Ru(II) complexes is reported. In agreement with the occurrence of a photo-electron-transfer process, photo-CIDNP effects are observed with [Ru(tap)(3)](2+) and [Ru(tap)(2)(phen)](2+) but not with [Ru(phen)(3)](2+). With [Ru(tap)(2)(phen)](2+), no significant photo-CIDNP is observed for the (1)H nuclei of the phen ligand, consistent with the fact that the metal-to-ligand charge-transfer triplet excited states responsible for the photo-oxidation involve a tap ligand. Successive experiments with [Ru(tap)(3)](2+) highlight the accumulation of long-lived radical species in solution that cause (1)H NMR signal broadening and photo-CIDNP extinction. The (1)H photo-CIDNP observed for the biomolecules is rather weak, less than about 30% of the equilibrium magnetization. However, up to 60% polarization enhancement is observed for H-2 and H-7 of the tap ligands, which indicates high unpaired electron density in the vicinity of these atoms in the transient radical pair. This is consistent with the structure of known photoadducts formed, for instance, between the metallic compounds and the guanine base of mono- and polynucleotides. Indeed, in these adducts the covalent bond involves carbon C-2 or C-7 of a tap ligand. The occurrence of photo-CIDNP with polyazaaromatic Ru(II) complexes opens new perspectives for the study of this type of compound.Journal ArticleResearch Support, Non-U.S. Gov'tinfo:eu-repo/semantics/publishe