Hindered rotational barriers in conjugated donor–acceptor substituted systems: calculations vs. experiments
| Autor: | Nina Larina, Mark Sigalov, Vladimir Khodorkovsky, Vladimir Lokshin |
|---|---|
| Přispěvatelé: | Ben-Gurion University of the Negev (BGU), Centre Interdisciplinaire de Nanoscience de Marseille (CINaM), Aix Marseille Université (AMU)-Centre National de la Recherche Scientifique (CNRS) |
| Jazyk: | angličtina |
| Rok vydání: | 2020 |
| Předmět: |
Materials science
010405 organic chemistry Substituent General Physics and Astronomy Electron Conjugated system 010402 general chemistry 01 natural sciences Acceptor Transition state 0104 chemical sciences NMR spectra database [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry chemistry.chemical_compound chemistry Chemical physics Molecule Physical and Theoretical Chemistry Basis set |
| Zdroj: | Physical Chemistry Chemical Physics Physical Chemistry Chemical Physics, 2020, 22 (3), pp.1214-1221. ⟨10.1039/c9cp06234c⟩ Physical Chemistry Chemical Physics, Royal Society of Chemistry, 2020, 22 (3), pp.1214-1221. ⟨10.1039/c9cp06234c⟩ |
| ISSN: | 1463-9076 1463-9084 |
| DOI: | 10.1039/c9cp06234c⟩ |
| Popis: | International audience; Quantum mechanical calculations of barriers to rotation within push-pull p-conjugated molecules involving strong electron donors (D) and acceptors (A) using the generally accepted approach fail to reproduce the experimental barriers determined by temperature-dependent NMR spectra. On the examples of seven derivatives of this type with substituents of varying electron donating and accepting strength, we find that determination of one of the rotational barriers, for instance, that of the acceptor substituent, requires not only the energy calculation of the respective transition state of this substituent, but also the transition state of the donor and the transition state involving both donor and acceptor substituents. Calculations of the rotation barriers using B3LYP and APFD functionals considering three transition states produce the results with mean absolute deviations from experimental 10 barriers of 0.28-0.19 kcal/mol depending on the basis set. |
| Databáze: | OpenAIRE |
| Externí odkaz: |
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