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  • 1. Fryxelius, J.
    et al.
    Eilers, G.
    Feyziyev, Y.
    Magnuson, A.
    Sun, Licheng C.
    Lomoth, R.
    Synthesis and redox properties of a meso-tris(4-nitrophenyl) corrolato Mn(III) complex2005Ingår i: Journal of Porphyrins and Phthalocyanines, ISSN 1088-4246, E-ISSN 1099-1409, Vol. 9, nr 6, s. 379-386Artikel i tidskrift (Refereegranskat)
    Abstract [en]

    The Mn complexated corrole [T(4-NO2P)Corr]Mn(py) (3) has been prepared (py = pyridine) where [T(4-NO2P)Corr] is the trianion of the electron-poor 5,10,15-tris(4-nitrophenyl)-corrole (1). The preparation of 3 includes a new synthetic method to form the corrole ligand 1 in a two-step synthesis. The Mn(III) complex gives a parallel mode EPR signal centered around g = 8.2 with six distinct hyperfine lines (A(parallel to) = 139 x 10(-4) cm(-1)). Electrochemically 3 undergoes one reversible oxidation (E-1/2 = 0.12 V vs Fc) and two reversible reductions (E-1/2 = -1.45, -1.61 V). The oxidation is metal-centered and the product has been characterized by EPR spectroscopy as an S = 3/2 Mn(IV) species with no indication for oxidation of the macrocycle. The reductions of complex 3 are ligand based, and at the potential of the second reduction step a stable nitrogen centered radical with g = 2.0055 is generated. Chemical oxidation of 3 by iodosobenzene yields a Mn(IV) complex and epoxidation of cis-stilbene is not catalyzed by the Mn complex.

  • 2. Gao, Yan
    et al.
    Liu, Jianhui
    Jiang, Wenfeng
    Xia, Ming
    Zhang, Wei
    Li, Minna
    Akermark, Bjorn
    Sun, Licheng
    KTH, Skolan för kemivetenskap (CHE), Kemi, Organisk kemi.
    Synthesis and photophysical and electrochemical properties of a binuclear Ru(bpy)(3)-Cu(III) corrole complex2007Ingår i: Journal of Porphyrins and Phthalocyanines, ISSN 1088-4246, E-ISSN 1099-1409, Vol. 11, nr 06-maj, s. 463-469Artikel i tidskrift (Refereegranskat)
    Abstract [en]

    A novel binuclear Ru-Cu complex, composed of a copper(III)-corrole and a ruthenium(II) tris(bipyridine) moicty linked by an amide bond, has been synthesized and characterized by H-1 NMR, UV-vis and mass spectrometry. The steady-state emission and the electrochemical properties were investigated. Compared to the parent [Ru(bpy)(3)](2+), the emission-of the desired complex was substantially quenched when the MLCT of [Ru(bpy)(3)](2+) was selectively photoexcited.

  • 3. He, Qinggang
    et al.
    Cheng, Xiao
    Wang, Ying
    KTH, Skolan för bioteknologi (BIO), Teoretisk kemi och biologi.
    Qiao, Ruimin
    Yang, Wanli
    Guo, Jinghua
    Electrochemical and spectroscopic characterization of a dicobalt macrocyclic Pacman complex in the catalysis of the oxygen reduction reaction in acid media2013Ingår i: Journal of Porphyrins and Phthalocyanines, ISSN 1088-4246, E-ISSN 1099-1409, Vol. 17, nr 4, s. 252-258Artikel i tidskrift (Refereegranskat)
    Abstract [en]

    The dicobalt complex [Co-2(L-2)] of a Schiff-base pyrrole macrocycle adopts a Pacman structure in solution and the solid state and shows much greater catalytic activity and selectivity for the four-electron oxygen reduction reaction (ORR) than the mononuclear cobalt phthalocyanine (CoPc) counterpart. Soft X-ray absorption spectroscopy (XAS) shows that the Co center in Co-2(L-2) is of the same valence as mononuclear CoPc. However, the former complex shows higher unoccupied Co 3d density which is believed to be beneficial for electron transfers. Furthermore, the XAS data suggests that the crystal fields for Co-2(L-2) and CoPc are different, and that an interaction remains between two Co atoms in Co-2(L-2). DFT calculations imply that the sterically hindered, cofacial structure of the dicobalt complex is critical for the operation of the four-electron reaction pathway during the ORR.

  • 4. Yanagisawa, M.
    et al.
    Korodi, F.
    Bergquist, J.
    Holmberg, A.
    Hagfeldt, A.
    Akermark, B.
    Sun, Licheng C.
    Synthesis of phthalocyanines with two carboxylic acid groups and their utilization in solar cells based on nanostructured TiO22004Ingår i: Journal of Porphyrins and Phthalocyanines, ISSN 1088-4246, E-ISSN 1099-1409, Vol. 8, nr 10, s. 1228-1235Artikel i tidskrift (Refereegranskat)
    Abstract [en]

    A way of anchoring unsymmetrical phthalocyaninato-metal complexes (metal ion: zinc and ruthenium) is described. The synthesis and characterization of these complexes are presented. In case of the zinc complex, the obtained product is an aggregate, while only the monomer is obtained in the case of the ruthenium derivative. Both complexes could be attached onto the TiO2 surface by using the reported method. Both dyes are expected to form monolayers with dye molecules standing on the surface of nano-structured TiO2, forming higher-order aggregates with the zinc but not with the ruthenium complex. A highest monochromatic incident photo-to-current conversion efficiency (IPCE) of 1.6% at 690 nm was obtained for a solar cell based on the Pc-Zn sensitized nano-structured TiO2 electrode, while an IPCE of 23% at 630 nm was obtained for the Pc-Ru sensitized electrode. Overall conversion efficiencies (eta) at a simulated AM 1.5 (100 W.m(-2)) of 0.03% and 0.40% for the zinc and ruthenium complexes were achieved, respectively. The difference in efficiencies could be due to the formation of face-to-face aggregation in the former case. This work shows that the ruthenium complex, with two axial methylpyridine ligands, does not form aggregates in solution nor on the surface of TiO2, making it possible for further construction of supramolecular systems with such types of phthalocyanine.

  • 5. Yanagisawa, M.
    et al.
    Korodi, F.
    He, J. J.
    Sun, Licheng C.
    Sundstrom, V.
    Akermark, B.
    Ruthenium phthalocyanines with axial carboxylate ligands. Synthesis and function in solar cells based on nanocrystalline TiO22002Ingår i: Journal of Porphyrins and Phthalocyanines, ISSN 1088-4246, E-ISSN 1099-1409, Vol. 6, nr 3, s. 217-224Artikel i tidskrift (Refereegranskat)
    Abstract [en]

    The synthesis and characterization of phthalocyaninato-ruthenium (PcRu) complexes with potential functional axial ligands are described. The solubility of these PcRu complexes was much improved compared to their parent phthalocyanines without Ru, enabling purification by normal flash column chromatography and also NMR measurements in common solvents (e. g. DMSO-d(6) and CDCl3). Adsorption of these phthalocyanine dyes onto the surface of a semiconductor through the carboxyl group(s) in the axial ligands prevents to some extent formation of H-aggregates, which is typical for phthalocyanines. It also prevents stacking of the dye molecules on the surface. The photovoltaic behavior of sandwich solar cells based on nanostructured TiO2 films sensitized by these PcRu complexes was studied under irradiation with visible light. For a solar cell based on bis(4-carboxypyridine)-phthalocyaninato ruthenium(II) (1) sensitized nanoporous-nanocrystalline TiO2, a monochromatic incident photon-to-current conversion efficiency (IPCE) of 21% was obtained at 640 nm. The overall conversion efficiency (eta) was 0.61%, which is one of the best results for a solar cell based on a phthalocyanine dye. For a cell based on (4-carboxypyridine)-(4-(2-ethoxy)ethyloxycarbonylpyridine)-2,3,9,10,16,17,23,24-octa(n-pentyloxy)-phthalocyaninato ruthenium(II) (5) sensitized TiO2, a IPCE of 6.6% at 640 nm and eta of 0.58% were obtained.

  • 6. Yang, X. C.
    et al.
    Kritikos, M.
    Akermark, B.
    Sun, Licheng C.
    Axial ligand exchange reaction on ruthenium phthalocyanines2005Ingår i: Journal of Porphyrins and Phthalocyanines, ISSN 1088-4246, E-ISSN 1099-1409, Vol. 9, nr 4, s. 248-255Artikel i tidskrift (Refereegranskat)
    Abstract [en]

    Bis(4-methylpyridine)phthalocyaninato ruthenium(II) has been synthesized. It was proved by single-crystal X-ray diffraction that the central Ru(II) atom is bonded to six N atoms in an elongated octahedral configuration, and the axial ligands have a significantly longer Ru-N bond distance, 2.101(4) angstrom, than the independent pyrrol Ru-N bond, 1.99 angstrom. Therefore, the axial ligands can be exchanged by other ligands. The ligand exchange reactions with diethyl pyridyl-4-phosphonate and diethyl pyridylmethyl-4-phosphonate were studied in high boiling-point solvents at elevated temperatures, ca 160 degrees C. Mono-ligand as well as double-ligand replaced complexes were obtained. The complexes have been isolated by column chromatography. These complexes have potential applications, such as in dye sensitized solar cells.

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