http://www.cnr.it/ontology/cnr/individuo/prodotto/ID39916
Electronic communication in homobimetallic anthracene-bridged ·5-cyclopentadienyl derivatives of rhodium(I): generation and characterization of the cation-radicals species [L2Rh{C5H4CH2(9,10-anthrylene)CH2C5H4}RhL2]+. (Articolo in rivista)
- Type
- Label
- Electronic communication in homobimetallic anthracene-bridged ·5-cyclopentadienyl derivatives of rhodium(I): generation and characterization of the cation-radicals species [L2Rh{C5H4CH2(9,10-anthrylene)CH2C5H4}RhL2]+. (Articolo in rivista) (literal)
- Anno
- 2001-01-01T00:00:00+01:00 (literal)
- Alternative label
M. Carano, M. Careri, F. Cicogna, I. DAmbra, J. L. Houben, G. Ingrosso, M. Marcaccio, F. Paolucci, C. Pinzino, S. Roffia (2001)
Electronic communication in homobimetallic anthracene-bridged ·5-cyclopentadienyl derivatives of rhodium(I): generation and characterization of the cation-radicals species [L2Rh{C5H4CH2(9,10-anthrylene)CH2C5H4}RhL2]+.
in Organometallics
(literal)
- Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#autori
- M. Carano, M. Careri, F. Cicogna, I. DAmbra, J. L. Houben, G. Ingrosso, M. Marcaccio, F. Paolucci, C. Pinzino, S. Roffia (literal)
- Pagina inizio
- Pagina fine
- Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#numeroVolume
- Rivista
- Note
- ISI Web of Science (WOS) (literal)
- Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#affiliazioni
- Dipartimento di Chimica G. Ciamician, Universita` di Bologna, Via Selmi 2, 40126 Bologna, Italy, Dipartimento di Chimica Generale ed Inorganica, Chimica Analitica, Chimica Fisica, Parco Area delle Scienze 17/A, 43100 Parma, Italy, Dipartimento di Chimica e Chimica Industriale, Universita` di Pisa, Via Risorgimento 35, 56126 Pisa, Italy, and Istituto
di Chimica Quantistica ed Energetica Molecolare del CNR, Area della Ricerca di Pisa, Via G. Moruzzi 1, 56010 Ghezzano San Giuliano Terme (Pisa), Italy (literal)
- Titolo
- Electronic communication in homobimetallic anthracene-bridged ·5-cyclopentadienyl derivatives of rhodium(I): generation and characterization of the cation-radicals species [L2Rh{C5H4CH2(9,10-anthrylene)CH2C5H4}RhL2]+. (literal)
- Abstract
- 9,10-Bis(cyclopentadienylmethyl)anthracene (1) is obtained by reacting 9,10-bis(bromomethyl)
anthracene with cyclopentadienylsodium and transformed into its dithallium(I)
derivative 3 on reaction with thallium ethoxide. The reaction of 3 with the chloro derivatives
of rhodium(I) of formula [RhClL2]2 (L ) è2-C2H4 or CO; L2 ) è4-C7H8) leads to the
corresponding bimetallic complexes [L2Rh{C5H4CH2(9,10-anthrylene)CH2C5H4}RhL2], 4 (L
) è2-C2H4), 5 (L ) CO), and 6 (L2 ) è4-C7H8), in 13, 22, and 55% yields, respectively. All
complexes have been characterized by elemental analysis, particle beam mass spectrometry,
1H NMR, and FT-IR. The UV-vis spectra (280-800 nm) of 4-6 are indicative of the existence
of strong electronic interactions among the anthrylic chromophore and the two cyclopentadienylRhL2
moieties. When excited at ca. 370 nm, 1 becomes an efficient light-emitting
molecule, while 4-6 are poorly luminescent compounds. The fluorescence spectra of all the
complexes present the vibrational structure typical of the anthrylic fluorophore but have
low intensity: 6, 3, and 15% of the one observed for 9-methylanthracene, taken as the
reference compound, respectively for 4, 5, and 6. The study of the electrochemical behavior
of 4-6 in strictly aprotic conditions allows a satisfactory interpretation of the observed
electrode processes and furnishes information about the location of the redox sites along
with the thermodynamic characterization of the corresponding redox processes. These data
show that the occurrence of an intramolecular charge-transfer process between the
photoexcited 9,10-anthrylenic moiety and the cyclopentadienylRhL2 unit is a possible route
for the observed quenching of emission in the compounds 4-6. The one-electron oxidation
of compounds 4-6 by thallium(III) trifluoroacetate in a 1:1 dichloromethane/1,1,1,3,3,3-
hexafluoropropan-2-ol mixture leads to the formation of the corresponding radical cations
[L2Rh{C5H4CH2(9,10-anthrylene)CH2C5H4}RhL2]+. Two of them, i.e., 4+ (L ) è2-C2H4) and
5+ (L ) CO), give rise to highly resolved EPR spectra which allow one to describe such
species as average-valence [Rh+1/2, Rh+1/2] complexes. DFT calculations of spin density
distribution confirm the EPR results and allow a further insight into the structure of 4+
and 5+ complexes. (literal)
- Prodotto di
- Autore CNR
Incoming links:
- Prodotto
- Autore CNR di
- Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#rivistaDi