title: Phosphine Oxides as Spectroscopic Halogen Bond Descriptors: IR and NMR Correlations with Interatomic Distances and Complexation Energy
metadata.name: dc.contributor.author
metadata.value: Ostras', Alexei S
metadata.lang: -
metadata.name: dc.contributor.author
metadata.value: Ivanov, Daniil M
metadata.lang: -
metadata.name: dc.contributor.author
metadata.value: Novikov, Alexander S
metadata.lang: -
metadata.name: dc.contributor.author
metadata.value: Tolstoy, Peter M
metadata.lang: -
metadata.name: dc.date.accessioned
metadata.value: 2020-10-06T04:25:04Z
metadata.lang: -
metadata.name: dc.date.available
metadata.value: 2020-10-06T04:25:04Z
metadata.lang: -
metadata.name: dc.date.issued
metadata.value: 2020-03-19
metadata.lang: -
metadata.name: dc.identifier
metadata.value: 10.3390/molecules25061406
metadata.lang: -
metadata.name: dc.identifier.issn
metadata.value: 10.3390/molecules25061406
metadata.lang: -
metadata.name: dc.identifier.uri
metadata.value: http://hdl.handle.net/11701/19772
metadata.lang: -
metadata.name: dc.description.abstract
metadata.value: An extensive series of 128 halogen-bonded complexes formed by trimethylphosphine oxide and various F-, Cl-, Br-, I- and At-containing molecules, ranging in energy from 0 to 124 kJ/mol, is studied by DFT calculations in vacuum. The results reveal correlations between R-X⋅⋅⋅O=PMe3 halogen bond energy ΔE, X⋅⋅⋅O distance r, halogen's σ-hole size, QTAIM parameters at halogen bond critical point and changes of spectroscopic parameters of phosphine oxide upon complexation, such as 31P NMR chemical shift, ΔδP, and P=O stretching frequency, Δν. Some of the correlations are halogen-specific, i.e., different for F, Cl, Br, I and At, such as ΔE(r), while others are general, i.e., fulfilled for the whole set of complexes at once, such as ΔE(ΔδP). The proposed correlations could be used to estimate the halogen bond properties in disordered media (liquids, solutions, polymers, glasses) from the corresponding NMR and IR spectra.
metadata.lang: en_GB
metadata.name: dc.language.iso
metadata.value: en
metadata.lang: en_GB
metadata.name: dc.title
metadata.value: Phosphine Oxides as Spectroscopic Halogen Bond Descriptors: IR and NMR Correlations with Interatomic Distances and Complexation Energy
metadata.lang: en_GB
resources.filename: molecules-25-01406-v2.pdf
resources.url: https://dspace.spbu.ru/bitstream/11701/19772/1/molecules-25-01406-v2.pdf
resources.format: Adobe PDF
resources.size: 11,41 MB
resources.filename: Ostras' ESI Corrected.pdf
resources.url: https://dspace.spbu.ru/bitstream/11701/19772/2/Ostras%27%20ESI%20Corrected.pdf
resources.format: Adobe PDF
resources.size: 2,84 MB