http://www.cnr.it/ontology/cnr/individuo/prodotto/ID50662
A New Heptanuclear Dendritic Ruthenium(ii) Complex Featuring Photoinduced Energy (Articolo in rivista)
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- Label
- A New Heptanuclear Dendritic Ruthenium(ii) Complex Featuring Photoinduced Energy (Articolo in rivista) (literal)
- Anno
- 2005-01-01T00:00:00+01:00 (literal)
- Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#doi
- 10.1002/cphc.200400240 (literal)
- Alternative label
F. Puntoriero, S. Serroni, M. Galletta, A. Juris, A. Licciardello, C. Chiorboli, S. Campagna, F. Scandola (2005)
A New Heptanuclear Dendritic Ruthenium(ii) Complex Featuring Photoinduced Energy
in ChemPhysChem (Print)
(literal)
- Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#autori
- F. Puntoriero, S. Serroni, M. Galletta, A. Juris, A. Licciardello, C. Chiorboli, S. Campagna, F. Scandola (literal)
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- ISI Web of Science (WOS) (literal)
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- Dipartimento di Chimica Inorganica, Chimica Analitica e Chimica Fisica Universit?à di Messina,
Dipartimento di Chimica \"G. Ciamician\", Università? di Bologna
Dipartimento di Scienze Chimiche, Universit?à di Catania
ISOF-CNR Sezione di Ferrara
Dipartimento di Chimica, Università? di Ferrara, (literal)
- Titolo
- A New Heptanuclear Dendritic Ruthenium(ii) Complex Featuring Photoinduced Energy (literal)
- Abstract
- The new heptanuclear ruthenium(ii) dendron, [Cl2Ru{(m-2,3-
dpp)Ru[(m-2,3-dpp)Ru(bpy)2]2}2](PF6)12 (1; 2,3-dpp=2,3-bis(2'-pyridyl)
pyrazine; bpy=2,2'-bipyridine), was prepared by means of
the \"complexes as ligands/complexes as metals\" synthetic strategy,
and its absorption spectrum, redox behavior, and luminescence
properties were investigated. Compound 1 is a multicomponent
species, which contains three different types of chromophores
(namely, the {Cl2Ru(m-2,3-dpp)2} core, the {Ru(m-2,3-
dpp)3}2+ intermediate, and the {(bpy)2Ru(m-2,3-dpp)}2+ peripheral
subunits) and several redox-active sites. The new species exhibits
very intense absorption bands in the UV region (e value in the
105-106 m?1cm?1 range) as a result of spin-allowed ligand-centered
(LC) transitions, and intense bands in the visible region
(e value in the 104-105 m?1cm?1 range) as a result of the various
spin-allowed metal-to-ligand charge-transfer (MLCT) transitions.
The redox investigation (accomplished by cyclic and differential
pulse voltammetry) indicates that 1 undergoes a series of reversible
metal-centered oxidation and ligand-centered reduction processes
within the potential window investigated (+1.90/?1.40 V
vs. the standard calomel electrode, SCE). The assignment of each
absorption band and redox process to specific subunits of 1 was
achieved by comparison with the properties of smaller multinuclear
species of the same family, namely [Cl2Ru{(m-2,3-dpp)Ru(bpy)
2}2]4+ (2), [(bpy)2Ru(m-2,3-dpp)Ru(bpy)2]4+ (4), and [Ru{(m-2,3-
dpp)Ru(bpy)2}3]4+ (5). The title compound exhibits luminescence
both at room temperature in acetonitrile fluid solution and at
77 K in butyronitrile rigid matrix. The emission is attributed to the
triplet MLCT (3MLCT) state involving the core {Cl2Ru(m-2,3-dpp)2}
subunit. Interestingly, the 3MLCT levels involving the peripheral
{(bpy)2Ru(m-2,3-dpp)}2+ subunits are deactivated by energy transfer
to the emitting level, in spite of the presence of interposed
high-energy {Ru(m-2,3-dpp)3}2+ components, which, in other dendrimers,
acted as \"isolating\" subunits toward energy-transfer
processes. Ultrafast experiments on 1 and on the parent species
2 and 5 allowed us to rationalize this behavior and highlight
that a sequential two-step electron-transfer process can be held
responsible for the efficient overall energy transfer, which offers a
way to overcome a limitation in antenna metal dendrimers. (literal)
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