Novel metal-template assembled highly-functionalized cyanoporphyrazine ytterbium and vanadium complexes for potential photonic and optoelectronic applications
| Autor: | Ilya S. Grigoryev, Sergey A. Lavrentiev, A. I. Korytin, William E. Douglas, Valeriy M. Treushnikov, Larisa G. Klapshina, Michael A. Lopatin, Vladimir V. Semenov, Andrey Yu. Luk'yanov, Philippe Gerbier |
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| Přispěvatelé: | G. A. Razuvaev Institute of Organometallic Chemistry, Russian Academy of Sciences [Moscow] (RAS), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), Institute of Applied Physics of RAS, Institute of Microstructure Physics, NPP Reper-NN, INTAS, Russian President |
| Jazyk: | angličtina |
| Rok vydání: | 2009 |
| Předmět: |
Ytterbium
Nitrile 010405 organic chemistry Coordination polymer Inorganic chemistry Infrared spectroscopy chemistry.chemical_element General Chemistry Porphyrazine [CHIM.MATE]Chemical Sciences/Material chemistry Tetracyanoethylene 010402 general chemistry Photochemistry 01 natural sciences 0104 chemical sciences chemistry.chemical_compound Template reaction chemistry Materials Chemistry Molecule |
| Zdroj: | Journal of Materials Chemistry Journal of Materials Chemistry, Royal Society of Chemistry, 2009, 19 (22), pp.3668-3676. ⟨10.1039/b821667c⟩ |
| ISSN: | 0959-9428 1364-5501 |
| DOI: | 10.1039/b821667c⟩ |
| Popis: | International audience; A novel facile synthetic route to the metal-template assembly of a tetrapyrrollic framework from tetracyanoethylene (TCNE) and tricyanovinylbenzene (TCNVB) structural units through reaction of TCNE and TCNVB with metal -sandwich complexes has been developed. The reactions occur under extremely mild conditions, the porphyrazine macrocycles being assembled in high yield from TCNE and TCNVB building-blocks by VO2+ or Yb3+-template synthesis. The redox behaviour of the novel complexes has been investigated. The vanadyl octacyanoporphyrazine complex was found to be a rare example of a highly-absorbing dye combining significant electron-acceptor properties with a band gap unusually narrow for an organic semiconductor (ca. 1.1 eV). The preparation is described of a novel highly emissive ytterbium complex with a proposed unusual structure obtained by reaction of TCNVB with bis(indenyl)ytterbium(II) in THF. The analytical, spectral and electrochemical investigations of the obtained ytterbium complex indicate it to be a binuclear adduct with Yb(TCNVB)3 species in which a single doubly-reduced TCNVB molecule bridges two Yb3+ cations. The formation of a disordered polynuclear coordination polymer network including a macrocyclic structure and metal cations bridged through the nitrile nitrogen atoms is proposed. The complex is readily soluble and is compatible with a variety of polymeric matrices giving doped polymeric glasses and films which are highly luminescent in the biologically relevant optical window covering the visible and near-infrared (NIR) range (640–1000 nm). In addition, doped polymeric glasses and films highly emissive at the telecommunication wavelength (1540 nm), including a composition consisting of the novel ytterbium complex and an equimolar ratio of the novel ytterbium complex and a per se non-luminescent erbium chelate, have been obtained. The complex is found to be an extraordinarily strong sensitizer of NIR Er3+ emission. |
| Databáze: | OpenAIRE |
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