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Homobimetallic anthracene-bridged h5-cyclopentadienyl derivatives of rhodium(I) and iridium(I): large molecules or supramolecular species? (Articolo in rivista)
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- Homobimetallic anthracene-bridged h5-cyclopentadienyl derivatives of rhodium(I) and iridium(I): large molecules or supramolecular species? (Articolo in rivista) (literal)
- Anno
- 2004-01-01T00:00:00+01:00 (literal)
- Alternative label
Francesca Cicogna a, Benedetta Gaddi a, Giovanni Ingrosso a,*, Massimo Marcaccio b,
Fabio Marchetti a, Demis Paolucci b, Francesco Paolucci b, Calogero Pinzino c,
Riccardo Viglione a (2004)
Homobimetallic anthracene-bridged h5-cyclopentadienyl derivatives of rhodium(I) and iridium(I): large molecules or supramolecular species?
in Inorganica Chimica Acta (Testo stamp.)
(literal)
- Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#autori
- Francesca Cicogna a, Benedetta Gaddi a, Giovanni Ingrosso a,*, Massimo Marcaccio b,
Fabio Marchetti a, Demis Paolucci b, Francesco Paolucci b, Calogero Pinzino c,
Riccardo Viglione a (literal)
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- ISI Web of Science (WOS) (literal)
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- a Dipartimento di Chimica e Chimica Industriale, Università di Pisa, Via Risorgimento 35, 56126 Pisa, Italy
b Dipartimento di Chimica 'G. Ciamician', Università di Bologna, Via Selmi 2, 40126 Bologna, Italy
c Istituto per i Processi Chimico-Fisici del C.N.R., Area della Ricerca di Pisa, Via G. Moruzzi 1, 56124 Pisa, Italy (literal)
- Titolo
- Homobimetallic anthracene-bridged h5-cyclopentadienyl derivatives of rhodium(I) and iridium(I): large molecules or supramolecular species? (literal)
- Abstract
- The reaction of 9,10-bis[(cyclopentadienylmethyl)thallium(I)]anthracene (2), obtained from 9,10-bis(cyclopentadienylmethyl)
anthracene (1), with the chloro derivatives of rhodium(I) of formula [RhClL2]2 (L=g2-C8H14 or L2 =g4-C8H12) leads to the
corresponding bimetallic complexes [L2Rh{C5H4CH2(9,10-anthrylene)CH2C5H4}RhL2] 3 (L=g2-C8H14) and 4 (L2 =g4-C8H12),
in 22.8% and 15.0% yields, respectively. Analogously, by reacting 2 with [IrClL2]2 (L=g2-C8H14 or L2 =g4-C8H12), the corresponding
bimetallic iridium(I) complexes [L2Ir{C5H4CH2(9,10-anthrylene)CH2C5H4}IrL2] 5 (L=g2-C8H14) and 6 (L2 =g4-C8H12)
were obtained, in 24.5% and 43.0% yields, respectively. All complexes have been characterised by elemental analysis, mass spectrometry,
and 1H NMR. The structure of 4 was elucidated also by single crystal X-ray diffraction: it crystallises in the P21=c space
group with a = 19:932(11), b = 6:4417(4), c = 12:377(2) A; a = 90°, b = 100.90(4)°, c = 90°. V = 1560.5(9) A3. Z = 2,
Dcalc = 1.606 g cm-1, R1 = 0.0449 [I > r(I)], wR2 = 0.1121. The UVVis spectra (280530 nm) of 36 are indicative of the existence
of strong electronic interactions among the 9,10-anthrylene chromophore and the two cyclopentadienylML2 moieties. When excited
at ca. 370 nm, 1 results to be an efficient light-emitting molecule, while the fluorescence emission of the 9,10-anthrylene chromophore
is almost completely quenched in complexes 36. The study of the electrochemical behaviour of 36 in strictly aprotic conditions
allows a satisfactory interpretation of the observed electrode processes and gives information about the location of the redox sites
along with the thermodynamic characterisation of the corresponding redox processes. These data show that the occurrence of an
intramolecular charge-transfer process between the photo-excited 9,10-anthrylene group and the cyclopentadienylML2 moiety is a
possible route for the observed quenching of emission in the compounds 36. The one-electron oxidation of compounds 36 by
thallium(III) trifluoroacetate leads to the formation of the corresponding cation radicals. Three of them, i.e., 3+, 5+ and 6+, give rise
to good X-band EPR spectra that were fully interpreted by computer simulation as well as by semi-empirical calculations (PM3
level) of the spin density distribution. (literal)
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