We have developed the first example of a photoredox catalytic method for formation carbon-fluorine (C-F) bonds. The mechanism has been studied using transient absorption spectroscopy and involves key single-electron transfer from (3)MLCT (triplet metal-to-ligand charge transfer) state Ru(bpy)3(2+) to Selectfluor. Not only does this represent new reaction catalysis, but mild conditions use visible light also make it practical improvement over previously UV-mediated decarboxylative fluorinations.

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTLiving Cyclopolymerization of 1,6-Heptadiyne Derivatives Using Well-Defined Alkylidene Complexes: Polymerization Mechanism, Polymer Structure, and PropertiesHarold H. Fox, Michael O. Wolf, Richard O'Dell, Beatrice L. Lin, R. Schrock, Mark S. WrightonCite this: J. Am. Chem. Soc. 1994, 116, 7, 2827–2843Publication Date (Print):April 1, 1994Publication History Published online1 May 2002Published inissue 1 April...

Recent literature describing nanocomposites of metal nanoparticles and conjugated polymers oligomers are reviewed. Preparation these by chemical electrochemical methods described, the electronic optical properties materials discussed. Some initial applications that have been investigated for such covered.

Bithiophene-based flexible Lewis pairs with P(O)R2 (R = phenyl, isopropyl) and BMes2 (Mes 2,4,6-trimethylphenyl) functionalities are able to toggle between closed, adduct open, unbound pair structures. The open structure is favored in strong hydrogen bond donating solvents or at higher temperatures giving rise an intense charge-transfer (CT) luminescence, while the closed without this emission dominates non-hydrogen lower temperatures. Intermediate result equilibrium mixture of both...

Pendant organic chromophores have been used to improve the photocatalytic performance of many metal-based photosensitizers, particularly in first-row metals, by increasing π conjugation ligands and lowering energy photoactive absorption band. Using a combination spectroscopic studies computational modeling, we rationalize excited state dynamics Co(III) complex containing pendant pyrene moieties, CoL1, where L1 = 1,1′-(4-(pyren-1-yl)pyridine-2,6-diyl)bis(3-methyl-1H-imidazol-3-ium). CoL1...

A series of conjugated mono(ferrocenylethynyl)oligothiophene and bis(ferrocenylethynyl)oligothiophene complexes have been prepared. The cyclic voltammograms the all contain a reversible ferrocene oxidation wave an irreversible oligothiophene-based wave. potential difference between two waves (ΔE) varies from 0.38 to 1.12 V, depending on length substitution oligothiophene group. Several couple when oxidized, resulting in deposition redox-active film electrode surface. In solution,...

Coordinating two dithienylethenes to a platinum center results in the reversible ring closure of both photochromic units model for photoresponsive pi-conjugated polymer. This system demonstrates how metal-sensitized photochemistry, from triplet excited state, circumvents problems associated with other multicomponent systems, where significant electronic interactions ground state and singlet prevent full photoswitching. Changes charge-transfer behavior based upon conversion their ring-closed...

Nanostructured PdO/CeO2 supported on mesoporous SBA-15 silica was synthesized using a combination of incipient wetness impregnation and surface-assisted reduction. After calcination, the materials showed good activity as catalysts for low-temperature oxidation methane, with sample having 5 wt % Pd loading showing 50% conversion to CO2 at ∼290 °C complete below 360 °C. The stability in presence water studied. formation Pd(0) during methane reaction increases oxygen vacancies surface...

trans-Ru(dppm)2(C⋮CFc)2 (1, dppm = Ph2PCH2PPh2, Fc ferrocenyl) was prepared by the CuI-catalyzed coupling of FcC⋮CSn(n-Bu)3 with cis-RuCl2(dppm)2. We have demonstrated cyclic voltammetry that ruthenium(II) bis(acetylide) bridge, −C⋮C−Ru(dppm)2−C⋮C−, 1 enhances ground-state electronic communication between terminal ferrocenyl groups compared to all-carbon butadiynyl bridge 1,4-diferrocenylbutadiyne, Fc−C⋮C−C⋮C−Fc.

The synthesis and properties of [cis-Ru(dppm)2(C⋮CFc)2]CuI (dppm = Ph2PCH2PPh2, Fc ferrocenyl) (1) trans,trans,trans-Ru(PBu3)2(CO)(L)(C⋮CFc)2 (3, L CO; 4, pyridine; 5, P(OMe)3) are reported. ruthenium bisacetylide bridges in these complexes allow electronic interaction between the terminal ferrocenyl groups. is enhanced when ancillary ligands on center electron donors lessened acceptors. Complex 1 was prepared 70% yield by coupling FcC⋮CSn(n-Bu)3 cis- or trans-RuCl2(dppm)2 presence excess...

Intramolecular energy-transfer results in sensitized ring closing of a pendant dithienylethene from platinum terpyridyl complex only when the two components are connected with short π-conjugated linker.

The synthesis and characterization of a new PEDOT−carbon composite prepared using microporous carbon template are described. electrochemical behavior this composite, as well that three other colloidal materials—PEDOT−silica, PEDOT, particles—is investigated with respect to their suitability electrode materials in supercapacitors. This was accomplished by combination cyclic voltammetry galvanostatic charge/discharge cycles. It found the PEDOT−silica had lowest specific capacitance four (ca....

A series of pyridine- and lutidine-linked bis-N-heterocyclic carbene (NHC) palladium pincer complexes were electrochemically characterized screened for CO2 reduction capability with 2,2,2-trifluoroethanol, acetic acid, or 2,2,2-trifluoroacetic acid (TFA) as proton sources. The electrocatalytically reduce to CO at potentials low -1.6 V versus Ag/AgNO3 in the presence TFA. one-electron these is shown be chemically reversible, yielding a monometallic species, density functional theory studies...

A general approach to enhancing the emission quantum yield of several widely studied organic chromophores is presented. The luminescence properties a series symmetrical sulfur-bridged are reported as function oxidation state bridging sulfur atom. photoluminescence significantly enhanced by successively oxidizing bridge from sulfide (S), sulfoxide (SO), sulfone (SO2).

Abstract Bowtie‐shaped NiCo 2 O 4 nanostructures are prepared using a hydrothermal method. Variation of the synthesis parameters, including reaction time, additives, and calcination temperature, allows an understanding origin bowtie‐shaped structure to be developed. Methane oxidation experiments performed temperature‐programed (TPO) show that new materials, which do not contain precious metals, have excellent activity for low‐temperature methane combustion, with 100% conversion at ≈410 °C...

Copper(I) complexes (Cu-DPSO and Cu-Me-DPSO) utilizing sulfoxide-bridged dipyridyl ligands are reported. Cu-DPSO demonstrates photophysical properties typical with [Cu(disphosphine)(diimine)]+ complexes, however additional steric bulk in the 6- 6′-positions of diimine ligand to give complex Cu-Me-DPSO; photophysics greatly altered. This species is isolated as an amorphous powder (a-Cu-Me-DPSO) which emits yellow light; upon heating 180 °C, a crystalline formed (c-Cu-Me-DPSO) shows large...

A new concept for difficult-to-replicate security inks use in advanced anti-counterfeiting applications is presented. Inks fabricated from a mixture of photoactive dyes result unique fluorescent color upon irradiation that differs the starting fluorescence. The are substituted 9,9'-dianthryl sulfoxides undergo photochemical extrusion sulfoxide moiety (SO) to produce emissive red, blue, and green emitters. resulting feature has specific Commission international de l'éclairage (CIE)...

Sulfur lone pairs in bridged dimers enhance intersystem crossing and phosphorescence through orbital mixing electrostatic screening.

The development of low-cost, non-toxic, scalable antimicrobial textiles is needed to address the spread deadly pathogens. Here, we report a polysiloxane textile coating that possesses two modes inactivation, passive contact inactivation through amine/imine functionalities and active photodynamic generation reactive oxygen species (ROS). This material can be coated cross-linked onto natural synthetic simple soak procedure, followed by UV cure afford materials exhibiting no aqueous leaching...