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, J. 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

Puttreddy, Rakesh
Rautiainen, Mikko
Yu, Shilin
Rissanen, Kari

Publication details

All authors or editors: Puttreddy, Rakesh; Rautiainen, J. Mikko; Yu, Shilin; Rissanen, Kari

Journal or series: Angewandte Chemie

ISSN: 1433-7851

eISSN: 1521-3773

Publication year: 2023

Publication date: 14/06/2023

Volume: 62

Issue number: 34

Article number: e202307372

Publisher: Wiley

Publication country: Germany

Publication language: English

DOI: https://doi.org/10.1002/anie.202307372

Publication open access: Openly available

Publication channel open access: Partially 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.

Keywords: chemical bonds; coordination complexes; density functional theory

Free keywords: halogen bond; N-oxide; N-Haloimide; DFT; X-ray structure

Fields of science: