C–C bond unsaturation degree in monosubstituted ferrocenes formolecular electronics investigated by a combined near-edge x-rayabsorption fine structure, x-ray photoemission spectroscopy, and density functional theory approach
| Autor: | A. Boccia 1, V. Lanzilotto 1, A. G. Marrani 1, S. Stranges 1, 2, R. Zanoni 1, M. Alagia 2, G. Fronzoni 3, P. Decleva 3 |
|---|---|
| Přispěvatelé: | A., Boccia, 1 V., Lanzilotto, 1 A. G., Marrani, 1 S., Strange, R., Zanoni, M., Alagia, Fronzoni, Giovanna, Decleva, Pietro |
| Jazyk: | angličtina |
| Rok vydání: | 2012 |
| Předmět: |
Absorption spectroscopy
Substituent General Physics and Astronomy monosubstituted ethyl and ethynyl-ferrocene chemical shift xps synchrotron radiation nexafs ferrocenes organometallic compounds chemistry.chemical_compound C 1s photoabsorption (NEXAFS) and photoemission spectroscopies Computational chemistry vinyl density functional theory (DFT) calculations Molecule Physical and Theoretical Chemistry Extended X-ray absorption fine structure Molecular electronics XANES Crystallography Chemical bond chemistry Density functional theory C 1s photoabsorption (NEXAFS) and photoemission spectroscopie |
| Zdroj: | Journal of chemical physics online 136 (2012): 134308–134308-12. doi:10.1063/1.3698283 info:cnr-pdr/source/autori:A. Boccia 1, V. Lanzilotto 1, A. G. Marrani 1, S. Stranges 1,2, R. Zanoni 1, M. Alagia 2, G. Fronzoni 3, and P. Decleva 3/titolo:C-C bond unsaturation degree in monosubstituted ferrocenes for molecular electronics investigated by a combined near-edge x-ray absorption fine structure, x-ray photoemission spectroscopy, and density functional theory approach/doi:10.1063%2F1.3698283/rivista:Journal of chemical physics online/anno:2012/pagina_da:134308/pagina_a:134308-12/intervallo_pagine:134308–134308-12/volume:136 |
| DOI: | 10.1063/1.3698283 |
| Popis: | We present the results of an experimental and theoretical investigation of monosubstituted ethyl-, vinyl-, and ethynyl-ferrocene (EtFC, VFC, and EFC) free molecules, obtained by means of synchrotron-radiation based C 1s photoabsorption (NEXAFS) and photoemission (C 1s XPS) spectroscopies, and density functional theory (DFT) calculations. Such a combined study is aimed at elucidating the role played by the C-C bond unsaturation degree of the substituent on the electronic structure of the ferrocene derivatives. Such substituents are required for molecular chemical anchoring onto relevant surfaces when ferrocenes are used for molecular electronics hybrid devices. The high resolution C 1s NEXAFS spectra exhibit distinctive features that depend on the degree of unsaturation of the hydrocarbon substituent. The theoretical approach to consider the NEXAFS spectrum made of three parts allowed to disentangle the specific contribution of the substituent group to the experimental spectrum as a function of its unsaturation degree. C 1s IEs were derived from the experimental data analysis based on the DFT calculated IE values for the different carbon atoms of the substituent and cyclopentadienyl (Cp) rings. Distinctive trends of chemical shifts were observed for the substituent carbon atoms and the substituted atom of the Cp ring along the series of ferrocenes. The calculated IE pattern was rationalized in terms of initial and final state effects influencing the IE value, with special regard to the different mechanism of electron conjugation between the Cp ring and the substituent, namely the σ/π hyperconjugation in EtFC and the π-conjugation in VFC and EFC. |
| Databáze: | OpenAIRE |
| Externí odkaz: |
|