02146nas a2200193   4500008004100000245015900041210006900200260000800269300001400277490000700291520141500298100001601713700001801729700001601747700001801763700001701781700002401798856013001822       2017                        eng d00aProton-coupled electron-transfer processes in ultrafast time domain: evidence for effects of hydrogen-bond stabilization on photoinduced electron transfer0 aProtoncoupled electrontransfer processes in ultrafast time domai  cMAR  a3455-34650 v233 aThe proton-coupled electron-transfer (PCET) reaction is investigated for a newly synthesized imidazoleanthraquinone biomimetic model with a photoactive RuIIpolypyridyl moiety that is covalently coupled to the imidazole fragment. Intramolecular H-bonding interactions between imidazole and anthraquinone moieties favor the PCET process; this can be correlated to an appreciable positive shift in the one-electron reduction potential of the coordinated anthraquinone moiety functionalized with the imidazole fragment. This can also be attributed to the low luminescence quantum yield of the RuII-polypyridyl complex used. The dynamics of the intramolecular electron-transfer (ET) and PCET processes are studied by using femtosecond transient absorption spectroscopy. The steady- state spectroscopic studies and the results of the time- resolved absorption studies confirm that H- bonded water molecules play a major role in both ET and PCET dynamics as a proton relay in the excited state. The electron- transfer process is followed by a change in the H- bonding equilibrium between AQ and imidazole in acetonitrile solvent, and protonation of AQ(-) water leads to PCET in the presence of water. A slower forward and backward electron- transfer rate is observed in the presence of D2O compared with that in H2O. These results provide further experimental support for a detailed understanding of the PCET process.1 aDey, Ananta1 aDana, Jayanta1 aAute, Sunil1 aMaity, Partha1 aDas, Amitava1 aGhosh, Hirendra, N.  uhttps://library.ncl.res.in/content/proton-coupled-electron-transfer-processes-ultrafast-time-domain-evidence-effects-hydrogen