title: Tuning of photocatalytic hydrogen production and photoinduced intramolecular electron transfer rates by regioselective bridging ligand substitution.
abstract: Artificial photosynthesis based on supramolecular photocatalysts offers the unique possibility to study the molecular processes underlying catalytic conversion of photons into chemical fuels in great detail and to tune the properties of the photocatalyst by alterations of the molecular framework. Herein we focus on both possibilities in studying the photocatalytic reduction of protons by derivatives of the well-known photocatalyst [(tbbpy)(2)Ru(tpphz)PdCl(2)](PF(6))(2) [4,4'-di-tert-butyl-2,2'-bipyridine (tbbpy), tetrapyrido[3,2-a:2',3'-c:3'',2''-h:2''',3'''-j]phenazine (tpphz)]. We report on a modified photocatalyst where the crucial bridging ligand tpphz is substituted by bromine and investigate the effect of the structural variation on the catalytic properties of the complex and its ultrafast intramolecular charge transfer behavior. It is found that structural modification stabilizes the phenanthroline-centered metal-to-ligand charge-transfer state on the tpphz moiety, thereby reducing the electron transfer gradient across the entire electron-relaying bridging ligand and at the same time accelerating nanosecond ground-state recovery. The same structural modifications cause an overall reduction of the catalytic activity of the complex. Thus, the results highlight the potential of small structural variations in the molecular framework of supramolecular catalysts in understanding the photoinduced charge-transfer processes and optimizing their catalytic performance.
authors.affiliation: Department of Photochemistry and Molecular Science, Uppsala University, Sweden.
authors.forename: Michael
authors.initials: M
authors.lastname: Karnahl
authors.forename: Christian
authors.initials: C
authors.lastname: Kuhnt
authors.forename: Fei
authors.initials: F
authors.lastname: Ma
authors.forename: Arkady
authors.initials: A
authors.lastname: Yartsev
authors.forename: Michael
authors.initials: M
authors.lastname: Schmitt
authors.forename: Benjamin
authors.initials: B
authors.lastname: Dietzek
authors.forename: Sven
authors.initials: S
authors.lastname: Rau
authors.forename: Jürgen
authors.initials: J
authors.lastname: Popp