Dual XH–π Interaction of Hexafluoroisopropanol with Arenes
The dual XH (OH and CH) hydrogen-bond-donating property of 1,1,1,3,3,3-hexafluoroisopropanol (HFIP) and the strong dual XH–π interaction with arenes were firstly disclosed by theoretical studies. Here, the high accuracy post-Hartree–Fock methods, CCSD(T)/CBS, reveal the interaction energy of HFIP/be...
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doaj-b6e1bd8882e04eadb150ff439596a4422021-08-06T15:29:10ZengMDPI AGMolecules1420-30492021-07-01264558455810.3390/molecules26154558Dual XH–π Interaction of Hexafluoroisopropanol with ArenesLe Lu0Ruimao Hua1Key Laboratory of Organic Optoelectronics & Molecular Engineering of Ministry of Education, Department of Chemistry, Tsinghua University, Beijing 100084, ChinaKey Laboratory of Organic Optoelectronics & Molecular Engineering of Ministry of Education, Department of Chemistry, Tsinghua University, Beijing 100084, ChinaThe dual XH (OH and CH) hydrogen-bond-donating property of 1,1,1,3,3,3-hexafluoroisopropanol (HFIP) and the strong dual XH–π interaction with arenes were firstly disclosed by theoretical studies. Here, the high accuracy post-Hartree–Fock methods, CCSD(T)/CBS, reveal the interaction energy of HFIP/benzene complex (−7.22 kcal/mol) and the contribution of the electronic correlation energy in the total interaction energy. Strong orbital interaction between HFIP and benzene was found by using the DFT method in this work to disclose the dual XH–π intermolecular orbital interaction of HFIP with benzene-forming bonding and antibonding orbitals resulting from the orbital symmetry of HFIP. The density of states and charge decomposition analyses were used to investigate the orbital interactions. Isopropanol (IP), an analogue of HFIP, and chloroform (CHCl<sub>3</sub>) were studied to compare them with the classical OH–π, and non-classical CH–π interactions. In addition, the influence of the aggregating effect of HFIP, and the numbers of substituted methyl groups in benzene rings were also studied. The interaction energies of HFIP with the selected 24 common organic compounds were calculated to understand the role of HFIP as solvent or additive in organic transformation in a more detailed manner. A single-crystal X-ray diffraction study of hexafluoroisopropyl benzoate further disclosed and confirmed that the CH of HFIP shows the non-classical hydrogen-bond-donating behavior.https://www.mdpi.com/1420-3049/26/15/4558HFIPhydrogen bond–πnon-classical hydrogen bondorbital interactionsarenes |
collection |
DOAJ |
language |
English |
format |
Article |
sources |
DOAJ |
author |
Le Lu Ruimao Hua |
spellingShingle |
Le Lu Ruimao Hua Dual XH–π Interaction of Hexafluoroisopropanol with Arenes Molecules HFIP hydrogen bond–π non-classical hydrogen bond orbital interactions arenes |
author_facet |
Le Lu Ruimao Hua |
author_sort |
Le Lu |
title |
Dual XH–π Interaction of Hexafluoroisopropanol with Arenes |
title_short |
Dual XH–π Interaction of Hexafluoroisopropanol with Arenes |
title_full |
Dual XH–π Interaction of Hexafluoroisopropanol with Arenes |
title_fullStr |
Dual XH–π Interaction of Hexafluoroisopropanol with Arenes |
title_full_unstemmed |
Dual XH–π Interaction of Hexafluoroisopropanol with Arenes |
title_sort |
dual xh–π interaction of hexafluoroisopropanol with arenes |
publisher |
MDPI AG |
series |
Molecules |
issn |
1420-3049 |
publishDate |
2021-07-01 |
description |
The dual XH (OH and CH) hydrogen-bond-donating property of 1,1,1,3,3,3-hexafluoroisopropanol (HFIP) and the strong dual XH–π interaction with arenes were firstly disclosed by theoretical studies. Here, the high accuracy post-Hartree–Fock methods, CCSD(T)/CBS, reveal the interaction energy of HFIP/benzene complex (−7.22 kcal/mol) and the contribution of the electronic correlation energy in the total interaction energy. Strong orbital interaction between HFIP and benzene was found by using the DFT method in this work to disclose the dual XH–π intermolecular orbital interaction of HFIP with benzene-forming bonding and antibonding orbitals resulting from the orbital symmetry of HFIP. The density of states and charge decomposition analyses were used to investigate the orbital interactions. Isopropanol (IP), an analogue of HFIP, and chloroform (CHCl<sub>3</sub>) were studied to compare them with the classical OH–π, and non-classical CH–π interactions. In addition, the influence of the aggregating effect of HFIP, and the numbers of substituted methyl groups in benzene rings were also studied. The interaction energies of HFIP with the selected 24 common organic compounds were calculated to understand the role of HFIP as solvent or additive in organic transformation in a more detailed manner. A single-crystal X-ray diffraction study of hexafluoroisopropyl benzoate further disclosed and confirmed that the CH of HFIP shows the non-classical hydrogen-bond-donating behavior. |
topic |
HFIP hydrogen bond–π non-classical hydrogen bond orbital interactions arenes |
url |
https://www.mdpi.com/1420-3049/26/15/4558 |
work_keys_str_mv |
AT lelu dualxhpinteractionofhexafluoroisopropanolwitharenes AT ruimaohua dualxhpinteractionofhexafluoroisopropanolwitharenes |
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