One-Step Electropolymerization of a Dicyanobenzene-Carbazole-Imidazole Dye to Prepare Photoactive Redox Polymer Films.

To the best of our knowledge, this study reports the first direct electropolymerization of a dicyanobenzene-carbazole dye functionalized with an imidazole group to prepare redox- and photoactive porous organic polymer (POP) films in controlled amounts. The POP films were grown on indium-doped tin oxide (ITO) and carbon surfaces using a new monomer, 1-imidazole-2,4,6-tri(carbazol-9-yl)-3,5-dicyanobenzene (, 3CzImIPN), through a simple one-step process. The structure and activities of the POP films were investigated as photoelectrodes for electrooxidations, as heterogeneous photocatalysts for photosynthetic olefin isomerizations, and for solid-state photoluminescence behavior tunable by lithium-ion concentrations in solution.

Carbazole-Cyanobenzene Dyes Electrografted to Carbon or Indium-Doped Tin Oxide Supports for Visible Light-Driven Photoanodes and Olefin Isomerizations.

The organic carbazole-cyanobenzene push-pull dye 1,2,3,5-tetrakis(carbazol-9-yl)-4,6-dicyanobenzene was derivatized and attached to carbon or indium-doped tin oxide (ITO) electrodes by simple diazonium electrografting. The surface-bound dye is active and stable for the visible light photosynthetic isomerization of a wide range of functionalized stilbene and cinnamic acid derivatives. Up to 87,000 net turnovers were obtained for the isomerization of -stilbene.

Solid-phase synthesis and photoactivity of Ru-polypyridyl visible light chromophores bonded through carbon to semiconductor surfaces.

1,10-Phenanthroline (phen) was grafted to either indium tin oxide (ITO), fluorine-doped tin oxide (FTO), or titanium dioxide (TiO) semiconductors (SC's) by electrochemical reduction of 5-diazo-phen. The phen ligand is bonded to the semiconductor at C5, and it can be handled in air. The semiconductor-phen (SC-phen) complexes displace both CHCN ligands from either cis-[Ru(Mebipy)(CHCN)] (Mebipy = 4,4'-methyl-2,2'-bipyridine), cis-[Ru(Bubipy)(CHCN)] (Bubipy = 4,4'-tert-butyl-2,2'-bipyridine), or cis-[Ru(pheno)(bipy)(CHCN)] (bipy = 2,2'-bipyridine; pheno = 1,10-phenanthroline-5,6-dione) dissolved in DCM/THF (4 h, 70 °C) to form the corresponding surface-bound SC-[(phen)Ru(bipyridyl)] chromophores.

Preparation and Study of Reusable Polymerized Catalysts for Ester Hydrogenation.

A cross-linked catalyst organic framework was prepared by an alternating ring-opening olefin metathesis polymerization between dichloro{,'-bis({(2-diphenylphosphino)phenyl}methylidene)bicyclo[2.2.1]-hept-5-ene-2,3-diamine}ruthenium, 1,2--di(-5-norbornene-2,3--dicarboximido)-ethane, and cyclooctene catalyzed by RuCl(=CHPh)(PCy) in the presence of a BaSO support.

Modular Construction of Photoanodes with Covalently Bonded Ru- and Ir-Polypyridyl Visible Light Chromophores.

1,10-phenanthroline is grafted to indium tin oxide (ITO) and titanium dioxide nanoparticle (TiO) semiconductors by electroreduction of 5-diazo-1,10-phenanthroline in 0.1 M HSO. The lower and upper potential limits (-0.

Highly Enantioselective Hydrogenation of Amides via Dynamic Kinetic Resolution Under Low Pressure and Room Temperature.

High-throughput screening and lab-scale optimization were combined to develop the catalytic system trans-RuCl((S,S)-skewphos)((R,R)-dpen), 2-PrONa, and 2-PrOH. This system hydrogenates functionalized α-phenoxy and related amides at room temperature under 4 atm H pressure to give chiral alcohols with up to 99% yield and in greater than 99% enantiomeric excess via dynamic kinetic resolution.