How do electron donating substituents affect the electronic structure, molecular topology, vibrational properties and intra- and intermolecular interactions of polyhalogenated pyridines?

Standard

How do electron donating substituents affect the electronic structure, molecular topology, vibrational properties and intra- and intermolecular interactions of polyhalogenated pyridines? / Benassi, Enrico; Vaganova, Tamara; Malykhin, Evgenij et al.

In: Physical Chemistry Chemical Physics, Vol. 24, No. 6, 14.02.2022, p. 4002-4021.

Research output: Contribution to journal › Article › peer-review

BibTeX

@article{72821634f93b4748b9e5ce78e42ccf82,

title = "How do electron donating substituents affect the electronic structure, molecular topology, vibrational properties and intra- and intermolecular interactions of polyhalogenated pyridines?",

abstract = "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.",

keywords = "Electronics, Electrons, Models, Molecular, Molecular Structure, Pyridines, Quantum Theory, Spectroscopy, Fourier Transform Infrared, Spectrum Analysis, Raman",

author = "Enrico Benassi and Tamara Vaganova and Evgenij Malykhin and Haiyan Fan",

note = "Funding Information: H. F. thanks Nazarbayev University small grant 110119FD4542. T. V. and E. M. acknowledge the support by the Ministry of Science and Higher Education of the Russian Federation (project 1021051403061-8-1.4.1). The Authors are grateful to the Siberian Supercomputer Centre of Institute of Computational Mathematics and Mathematical Geophysics (Russian Academy of Sciences, Novosibirsk, Russian Federation) for kindly providing the computational resources; the technical staff of the Institute is also thanked for the assistance. The core and computational facilities offered by Nazarbayev University are acknowledged. Publisher Copyright: {\textcopyright} 2022 the Owner Societies.",

year = "2022",

month = feb,

day = "14",

doi = "10.1039/d1cp05956d",

language = "English",

volume = "24",

pages = "4002--4021",

journal = "Physical Chemistry Chemical Physics",

issn = "1463-9076",

publisher = "Royal Society of Chemistry",

number = "6",