Symmetry breaking effect in the ferrocene electronic structure by hydrocarbon-monosubstitution: An experimental and theoretical study (Articolo in rivista)

Type
Label
  • Symmetry breaking effect in the ferrocene electronic structure by hydrocarbon-monosubstitution: An experimental and theoretical study (Articolo in rivista) (literal)
Anno
  • 2008-01-01T00:00:00+01:00 (literal)
Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#doi
  • 10.1063/1.2898498 (literal)
Alternative label
  • Boccia, A (Boccia, A.)1; Marrani, AG (Marrani, A. G.)1; Stranges, S (Stranges, S.)1,2,3; Zanoni, R (Zanoni, R.)1,4; Alagia, M (Alagia, M.)2,3; Cossi, M (Cossi, M.)5; Iozzi, MF (Iozzi, M. F.)5 (2008)
    Symmetry breaking effect in the ferrocene electronic structure by hydrocarbon-monosubstitution: An experimental and theoretical study
    in The Journal of chemical physics
    (literal)
Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#autori
  • Boccia, A (Boccia, A.)1; Marrani, AG (Marrani, A. G.)1; Stranges, S (Stranges, S.)1,2,3; Zanoni, R (Zanoni, R.)1,4; Alagia, M (Alagia, M.)2,3; Cossi, M (Cossi, M.)5; Iozzi, MF (Iozzi, M. F.)5 (literal)
Pagina inizio
  • 154315 (literal)
Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#numeroVolume
  • 128 (literal)
Rivista
Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#numeroFascicolo
  • 15 (literal)
Note
  • ISI Web of Science (WOS) (literal)
Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#affiliazioni
  • 1. Univ Roma La Sapienza, Dipartimento Chim, I-00185 Rome, Italy 2. CNR, ISMN, I-00185 Rome, Italy 3. CNR, TASC, Lab Nazl, I-34012 Trieste, Italy 4. Univ Roma La Sapienza, INSTM, I-00185 Rome, Italy 5. Univ Piemonte Orientale, Dipartimento Sci & Tecnol Avanzate, I-15100 Alessandria, Italy (literal)
Titolo
  • Symmetry breaking effect in the ferrocene electronic structure by hydrocarbon-monosubstitution: An experimental and theoretical study (literal)
Abstract
  • We present here the results of a synchrotron radiation-excited UV-photoemission investigation and density functional theory calculations on a structurally related series of organometallic free molecules: ethylferrocene (EtFC), vinylferrocene (VFC), and ethynylferrocene (EFC). This series exemplifies the electronic interactions operating when the C-C substituent group of an aromatic ring is bound to the substrate surface atoms, from a single C-C bond to the double and triple C-C bond pi systems which are still able to preserve substrate-molecule conjugation. A detailed assignment of the gas phase valence photoelectron spectra is discussed, providing new data on the electronic structure of EtFC and EFC and offering a partial reinterpretation of previous assignments on VFC. The broken symmetry of ferrocene caused by the monosubstitution has notable effects on the removal of the molecular orbital (MO) degeneracy which is found to be especially remarkable for the ferrocenelike e(1)' MOs. This effect is ascribed to the interaction between the aromatic cyclopentadyenyl ring and the substituent through sigma/pi hyperconjugation and pi-conjugation mechanisms depending on the nature of the hydrocarbon moiety and its conformational geometry. The vertical ionization energy values of the highest occupied MO for the alkylferrocene and ferrocene free molecules linearly correlate with the redox potential in acetonitrile for ferrocene and the corresponding hybrids obtained by covalently anchoring the free molecule on silicon. (c) 2008 American Institute of Physics. (literal)
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