A1 Journal article (refereed)
N−X···O−N Halogen Bonds in Complexes of N‐Haloimides and Pyridine‐N‐oxides : A Large Data Set Study (2023)


Puttreddy, R., Rautiainen, M., Yu, S., & Rissanen, K. (2023). N−X···O−N Halogen Bonds in Complexes of N‐Haloimides and Pyridine‐N‐oxides : A Large Data Set Study. Angewandte Chemie, 62(34), Article e202307372. https://doi.org/10.1002/anie.202307372


JYU authors or editors


Publication details

All authors or editorsPuttreddy, Rakesh; Rautiainen, Mikko; Yu, Shilin; Rissanen, Kari

Journal or seriesAngewandte Chemie

ISSN1433-7851

eISSN1521-3773

Publication year2023

Publication date14/06/2023

Volume62

Issue number34

Article numbere202307372

PublisherWiley

Publication countryGermany

Publication languageEnglish

DOIhttps://doi.org/10.1002/anie.202307372

Publication open accessOpenly available

Publication channel open accessPartially open access channel

Publication is parallel published (JYX)https://jyx.jyu.fi/handle/123456789/88952


Abstract

N–X···−O–N+ halogen-bonded systems formed by 27 pyridine N-oxides (PyNOs) as halogen bond (XB) acceptors and two N-halosuccinimides, two N-halophthalimides, and two N-halosaccharins as XB donors are studied in silico, in solution, and in the solid state. This large set of data (132 DFT optimized structures, 75 crystal structures, and 168 1H NMR titrations) provides a unique view to structural and bonding properties. In the computational part, a simple electrostatic model (SiElMo) for predicting XB energies using only the properties of halogen donors and oxygen acceptors is developed. The SiElMo energies are in perfect accord with energies calculated from XB complexes optimized with two high-level DFT approaches. Data from in silico bond energies and single crystal X-ray structures correlate, however data from solution do not. The polydentate bonding characteristic of the PyNOs’ oxygen in solution, as revealed by solid-state structures, is attributed to the lack of correlation between DFT/solid-state and solution data. XB strength is only slightly affected by the PyNO oxygen properties [(atomic charge (Q), ionization energy (Is,min) and local negative minima (Vs,min)], as the 𝜎-hole (Vs,max) of the donor halogen is the key determinant leading to the sequence N-halosaccharin>N-halosuccinimide> N-halophthalimide on the XB strength.


Keywordschemical bondscoordination complexesdensity functional theory

Free keywordshalogen bond; N-oxide; N-Haloimide; DFT; X-ray structure


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Ministry reportingYes

Reporting Year2023

Preliminary JUFO rating3


Last updated on 2024-18-02 at 19:27