Supramolecular covalency of halogen bonds revealed by NMR contact shifts in paramagnetic cocrystals

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61389013%3A_____%2F25%3A00641330" target="_blank" >RIV/61389013:_____/25:00641330 - isvavai.cz</a>

Nalezeny alternativní kódy

RIV/00216224:14740/25:00142286

Výsledek na webu

<a href="https://pubs.rsc.org/en/content/articlelanding/2025/sc/d5sc05769h" target="_blank" >https://pubs.rsc.org/en/content/articlelanding/2025/sc/d5sc05769h</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1039/D5SC05769H" target="_blank" >10.1039/D5SC05769H</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Supramolecular covalency of halogen bonds revealed by NMR contact shifts in paramagnetic cocrystals

Popis výsledku v původním jazyce

Although supramolecular interactions such as halogen bonding are often classified as “non-covalent” interactions, computational methods have predicted that they possess a significant covalent component. In this article, we adopt a unique strategy that combines experimental solid-state NMR and relativistic DFT approaches to explore the electronic nature of previously postulated supramolecular covalency [Bora et al., Chem.–Eur. J., 2017, 23, 7315]. Our approach involves the analysis of hyperfine interactions and hyperfine shifts in the NMR spectra of halogen-bonded cocrystals containing a paramagnetic transition-metal complex. We demonstrate that the hyperfine interaction pertaining to the paramagnetic transition-metal center and observed at the probed nucleus of the cocrystallized (halogen-bonded) molecule is governed by the Fermi-contact mechanism. This contact mechanism originates in “through-bond” spin transmission and, therefore, unequivocally reports on the electron sharing between the halogen-bonded molecules, i.e., halogen-bond covalency.

Název v anglickém jazyce

Supramolecular covalency of halogen bonds revealed by NMR contact shifts in paramagnetic cocrystals

Popis výsledku anglicky

Although supramolecular interactions such as halogen bonding are often classified as “non-covalent” interactions, computational methods have predicted that they possess a significant covalent component. In this article, we adopt a unique strategy that combines experimental solid-state NMR and relativistic DFT approaches to explore the electronic nature of previously postulated supramolecular covalency [Bora et al., Chem.–Eur. J., 2017, 23, 7315]. Our approach involves the analysis of hyperfine interactions and hyperfine shifts in the NMR spectra of halogen-bonded cocrystals containing a paramagnetic transition-metal complex. We demonstrate that the hyperfine interaction pertaining to the paramagnetic transition-metal center and observed at the probed nucleus of the cocrystallized (halogen-bonded) molecule is governed by the Fermi-contact mechanism. This contact mechanism originates in “through-bond” spin transmission and, therefore, unequivocally reports on the electron sharing between the halogen-bonded molecules, i.e., halogen-bond covalency.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10403 - Physical chemistry

Projekt

Výsledek vznikl pri realizaci vícero projektů. Více informací v záložce Projekty.

Návaznosti

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Rok uplatnění

2025

Kód důvěrnosti údajů

S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Název periodika

Chemical Science

ISSN

2041-6520

e-ISSN

2041-6539

Svazek periodika

16

Číslo periodika v rámci svazku

43

Stát vydavatele periodika

GB - Spojené království Velké Británie a Severního Irska

Počet stran výsledku

6

Strana od-do

20239-20244

Kód UT WoS článku

001591456500001

EID výsledku v databázi Scopus

2-s2.0-105025932578