http://www.cnr.it/ontology/cnr/individuo/prodotto/ID51050
Mononuclear and dinuclear complexes of dibenzoeilatin: Synthesis, structure, and electrochemical and photophysical properties (Articolo in rivista)
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- Label
- Mononuclear and dinuclear complexes of dibenzoeilatin: Synthesis, structure, and electrochemical and photophysical properties (Articolo in rivista) (literal)
- Anno
- 2004-01-01T00:00:00+01:00 (literal)
- Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#doi
- 10.1021/ic0354062 (literal)
- Alternative label
S. D. Bergman; I. Goldberg; A. Barbieri; F. Barigelletti; M. Kol (2004)
Mononuclear and dinuclear complexes of dibenzoeilatin: Synthesis, structure, and electrochemical and photophysical properties
in Inorganic chemistry
(literal)
- Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#autori
- S. D. Bergman; I. Goldberg; A. Barbieri; F. Barigelletti; M. Kol (literal)
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- Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#numeroFascicolo
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- ISI Web of Science (WOS) (literal)
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- 1. Tel Aviv Univ, Raymond & Beverly Sackler Fac Exact Sci, Sch Chem, IL-69978 Tel Aviv, Israel
2. Ist ISOF, CNR, I-40129 Bologna, Italy (literal)
- Titolo
- Mononuclear and dinuclear complexes of dibenzoeilatin: Synthesis, structure, and electrochemical and photophysical properties (literal)
- Abstract
- This work describes a study of Ru(II) and Os(II) polypyridyl complexes of the symmetrical, fused-aromatic bridging ligand dibenzoeilatin (1). The synthesis, purification, and structural characterization by NMR of the mononuclear complexes [Ru(bPY)(2)(dbneil)](2+) (2), [Ru(tmbpy)(2)(dbneil)](2+) (3), and [Os(bpy)(2)(dbneil)](2+) (4), the homodinuclear complexes [{Ru(bpy)(2)}(2){mu-dbneil}](4+) (5), [{Ru(tmbpy)(2)}(2){mu-dbneil}](4+) (6), and [{Os(bpy)(2)}(2){mu-dbneil}](4+) (7), and the heterodinuclear complex [{Ru(bpy)(2)}{mu-dbneil}{Os(bpy)(2)}](4+) (8) are described, along with the crystal structures of 4, 6, and 7. Absorption spectra of the mononuclear complexes feature a low-lying MLCT band around 600 nm. The coordination of a second metal fragment results in a dramatic red shift of the MLCT band to beyond 700 nm. Cyclic and square wave voltammograms of the mononuclear complexes exhibit one reversible metal-based oxidation, as well as several ligand-based reduction waves. The first two reductions, attributed to reduction of the dibenzoeilatin ligand, are substantially anodically shifted compared to [M(bpy)(3)](2+) (M = Ru, Os), consistent with the low-lying pi* orbital of dibenzoeilatin. The dinuclear complexes exhibit two reversible, well-resolved, metal-centered oxidation waves, despite the chemical equivalence of the two metal centers, indicating a significant metal-metal interaction mediated by the conjugated dibenzoeilatin ligand. Luminescence spectra, quantum yield, and lifetime measurements at room temperature in argon-purged acetonitrile have shown that the complexes exhibit 3 MLCT emission, which occurs in the IR-region between 950 and 1300 nm. The heterodinuclear complex 8 exhibits luminescence only from the Ru-based fragment, the intensity of which is less than 1% of that observed in the corresponding homodinuclear complex 5; no emission from the Os-based unit is observed, and an intramolecular quenching constant of k(q) greater than or equal to 3 x 10(9) s(-1) is evaluated. The nature of the quenching process is briefly discussed. (literal)
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