Photocatalytic Hydrogen Evolution from Plastoquinol Analogues as a Potential Functional Model of Photosystem I

The recent development of a functional model of photosystem II (PSII) has paved a new way to connect the PSII model with a functional model of photosystem I (PSI). However, PSI functional models have yet to be reported. We report herein the first potential functional model of PSI, in which plastoquinol (PQH₂) analogues were oxidized to plastoquinone (PQ) analogues, accompanied by hydrogen (H₂) evolution. Photoirradiation of a deaerated acetonitrile (MeCN) solution containing hydroquinone derivatives (X-QH₂) as a hydrogen source, 9-mesityl-10-methylacridinium ion (Acr⁺-Mes) as a photoredox catalyst, and a cobalt(III) complex, Co^III(dmgH)₂pyCl (dmgH = dimethylglyoximate monoanion; py = pyridine) as a redox catalyst resulted in the evolution of H₂ and formation of the corresponding p-benzoquinone derivatives (X-Q) quantitatively. The maximum quantum yield for photocatalytic H₂ evolution from tetrachlorohydroquinone (Cl₄QH₂) with Acr⁺-Mes and Co^III(dmgH)₂pyCl and H₂O in deaerated MeCN was determined to be 10%. Photocatalytic H₂ evolution is started by electron transfer (ET) from Cl₄QH₂ to the triplet ET state of Acr⁺-Mes to produce Cl₄QH₂^•+ and Acr^•-Mes with a rate constant of 7.2 × 10⁷ M^-1 s^-1, followed by ET from Acr^•-Mes to Co^III(dmgH)₂pyCl to produce [Co^II(dmgH)₂pyCl]^-, accompanied by the regeneration of Acr⁺-Mes. On the other hand, Cl₄QH₂^•+ is deprotonated to produce Cl₄QH^•, which transfers either a hydrogen-atom transfer or a proton-coupled electron transfer to [Co^II(dmgH)₂pyCl]^- to produce a cobalt(III) hydride complex, [Co^III(H)(dmgH)₂pyCl]^-, which reacts with H⁺ to evolve H₂, accompanied by the regeneration of Co^III(dmgH)₂pyCl. The formation of [Co^II(dmgH)₂pyCl]^- was detected by electron paramagnetic resonance measurements.