Synthesis and Photophysical Study of a [NiFe] Hydrogenase Biomimetic Compound Covalently Linked to a Re-diimine Photosensitizer

[Image: see text] The synthesis, photophysics, and photochemistry of a linked dyad ([Re]-[NiFe(2)]) containing an analogue ([NiFe(2)]) of the active site of [NiFe] hydrogenase, covalently bound to a Re-diimine photosensitizer ([Re]), are described. Following excitation, the mechanisms of electron transfer involving the [Re] and [NiFe(2)] centers and the resulting decomposition were investigated. Excitation of the [Re] center results in the population of a diimine-based metal-to-ligand charge transfer excited state. Reductive quenching by NEt(3) produces the radically reduced form of [Re], [Re](−) (k(q) = 1.4 ± 0.1 × 10(7) M(–1) s(–1)). Once formed, [Re](−) reduces the [NiFe(2)] center to [NiFe(2)](−), and this reduction was followed using time-resolved infrared spectroscopy. The concentration dependence of the electron transfer rate constants suggests that both inter- and intramolecular electron transfer pathways are involved, and the rate constants for these processes have been estimated (k(inter) = 5.9 ± 0.7 × 10(8) M(–1) s(–1), k(intra) = 1.5 ± 0.1 × 10(5) s(–1)). For the analogous bimolecular system, only intermolecular electron transfer could be observed (k(inter) = 3.8 ± 0.5 × 10(9) M(–1) s(–1)). Fourier transform infrared spectroscopic studies confirms that decomposition of the dyad occurs upon prolonged photolysis, and this appears to be a major factor for the low activity of the system toward H(2) production in acidic conditions.