title: Rhodium-coordinated poly(arylene-ethynylene)-alt-poly(arylene-vinylene) copolymer acting as photocatalyst for visible-light-powered NAD⁺/NADH reduction.
abstract: A 2,2'-bipyridyl-containing poly(arylene-ethynylene)-alt-poly(arylene-vinylene) polymer, acting as a light-harvesting ligand system, was synthesized and coupled to an organometallic rhodium complex designed for photocatalytic NAD(+)/NADH reduction. The material, which absorbs over a wide spectral range, was characterized by using various analytical techniques, confirming its chemical structure and properties. The dielectric function of the material was determined from spectroscopic ellipsometry measurements. Photocatalytic reduction of nucleotide redox cofactors under visible light irradiation (390-650 nm) was performed and is discussed in detail. The new metal-containing polymer can be used to cover large surface areas (e.g. glass beads) and, due to this immobilization step, can be easily separated from the reaction solution after photolysis. Because of its high stability, the polymer-based catalyst system can be repeatedly used under different reaction conditions for (photo)chemical reduction of NAD(+). With this concept, enzymatic, photo-biocatalytic systems for solar energy conversion can be facilitated, and the precious metal catalyst can be recycled.
authors.affiliation: Institute of Inorganic Chemistry, Johannes Kepler University Linz , Altenberger Strasse 69, 4040 Linz, Austria.
authors.forename: Kerstin T
authors.initials: KT
authors.lastname: Oppelt
authors.forename: Jacek
authors.initials: J
authors.lastname: Gasiorowski
authors.forename: Daniel Ayuk Mbi
authors.initials: DA
authors.lastname: Egbe
authors.forename: Jan Philipp
authors.initials: JP
authors.lastname: Kollender
authors.forename: Markus
authors.initials: M
authors.lastname: Himmelsbach
authors.forename: Achim Walter
authors.initials: AW
authors.lastname: Hassel
authors.forename: Niyazi Serdar
authors.initials: NS
authors.lastname: Sariciftci
authors.forename: Günther
authors.initials: G
authors.lastname: Knör
mesh_terms: D015082:2,2'-Dipyridyl / Q000737:chemistry*; D002384:Catalysis; D056831:Coordination Complexes / Q000737:chemistry*; D008027:Light; D015394:Molecular Structure; D009243:NAD / Q000737:chemistry*; D009249:NADP / Q000737:chemistry*; D009942:Organometallic Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D010084:Oxidation-Reduction; D055668:Photochemical Processes; D053279:Polyynes / Q000737:chemistry*; D012238:Rhodium / Q000737:chemistry*
chemical_list: D056831:Coordination Complexes; D009942:Organometallic Compounds; D009243:NAD; D053279:Polyynes; D009249:NADP; D015082:2,2'-Dipyridyl; D012238:Rhodium