Donor- and/or acceptor-substituted pi-conjugated systems represent an important class of compounds in organic chemistry. However, up to now, a general method to quantitatively address the efficiency of a conjugated path is still missing. In this work, a novel computational approach based on deletion energies and on second-order orbital interaction energies in a natural bond orbital (NBO) scheme is employed to quantitatively assess ("measure") delocalization energies. Moreover, the purpose of this work is to assess the efficiency of distinct pi-conjugated paths, that is, geminal, cis, and trans, as well as to predict the impact of substituents on a given backbone. This study is focused on various mono-, di-, tri-, and tetrasubstituted tetraethynylethenes (TEEs). These model systems are suitable for our analysis, because they offer distinct conjugation paths within the same molecule, and can also be substituted in multiple ways. Differences between conjugation paths, the effect of neighbor paths, and the impact of donor and acceptor substituents on the various paths are discussed

Giuffreda, M., Bruschi, M., & Luthi, H. (2004). Electron delocalization in linearly pi-conjugated systems: A concept for quantitative analysis. CHEMISTRY-A EUROPEAN JOURNAL, 10(22), 5671-5680 [10.1002/chem.200400313].

Electron delocalization in linearly pi-conjugated systems: A concept for quantitative analysis

BRUSCHI, MAURIZIO;
2004-11

Abstract

Donor- and/or acceptor-substituted pi-conjugated systems represent an important class of compounds in organic chemistry. However, up to now, a general method to quantitatively address the efficiency of a conjugated path is still missing. In this work, a novel computational approach based on deletion energies and on second-order orbital interaction energies in a natural bond orbital (NBO) scheme is employed to quantitatively assess ("measure") delocalization energies. Moreover, the purpose of this work is to assess the efficiency of distinct pi-conjugated paths, that is, geminal, cis, and trans, as well as to predict the impact of substituents on a given backbone. This study is focused on various mono-, di-, tri-, and tetrasubstituted tetraethynylethenes (TEEs). These model systems are suitable for our analysis, because they offer distinct conjugation paths within the same molecule, and can also be substituted in multiple ways. Differences between conjugation paths, the effect of neighbor paths, and the impact of donor and acceptor substituents on the various paths are discussed
Articolo in rivista - Articolo scientifico
Scientifica
onjugation; delocalization energy; density functional calculations; donor-acceptor systems; local properties; STRUCTURE-PROPERTY RELATIONSHIPS; SUBSTITUTED TETRAETHYNYLETHENES; MOLECULAR LENGTH; NONLINEAR OPTICS; RAPID ROUTE; BASIS SETS; POLYMERS; OLIGOMERS; WIRES; POLYMERIZATION
English
Giuffreda, M., Bruschi, M., & Luthi, H. (2004). Electron delocalization in linearly pi-conjugated systems: A concept for quantitative analysis. CHEMISTRY-A EUROPEAN JOURNAL, 10(22), 5671-5680 [10.1002/chem.200400313].
Giuffreda, M; Bruschi, M; Luthi, H
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Utilizza questo identificativo per citare o creare un link a questo documento: http://hdl.handle.net/10281/13890
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