How do electron donating substituents affect the electronic structure, molecular topology, vibrational properties and intra- and intermolecular interactions of polyhalogenated pyridines?
Benassi E. Vaganova T. Malykhin E. Fan H.
14 February 2022Royal Society of Chemistry
Physical Chemistry Chemical Physics
2022#24Issue 64002 - 4021 pp.
Seven polyhalogenated pyridine derivatives bearing an amino or a hydroxyl group, either at the ortho or para position, were studied using a combined experimental and computational approach. The presence of an electron donating substituent strongly impacted on the geometry, electronic structure, electrostatic properties, molecular topology and vibrational characteristics of these compounds compared to the corresponding polyhalogenated pyridines. In particular the attention was focused on changes in wavenumbers, force constants and intensity of the seven in-plane Ring Normal Modes (RNMs). Due to the nature and position of the substituents, intra- and intermolecular interactions also underwent dramatic modifications, as revealed using Natural Bond Orbital (NBO) analysis, Non-Covalent Interaction (NCI) analysis and Atom-In-Molecule (AIM) theory. Raman and FT-IR spectra of these seven compounds were also collected in solid phase and rationalised by the simulated spectra for hydrogen bonding and/or π-π stacking based homodimers. The present study provides a strategy not only for the vibrational characterisation for the individual compounds, but also for shedding light on the ways of molecular packing in the molecular crystals or cocrystals involving these compounds.
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Novosibirsk State University, Novosibirsk, 630090, Russian Federation
Vorozhtsov Novosibirsk Institute of Organic Chemistry SB RAS, Novosibirsk, 630090, Russian Federation
Department of Chemistry, School of Sciences and Humanities, Nazarbayev University, Nursultan, 010000, Kazakhstan
Novosibirsk State University
Vorozhtsov Novosibirsk Institute of Organic Chemistry SB RAS
Department of Chemistry
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