Fluorination switches CO–arene binding to a π-hole regime, enabling nonclassical carbonyl behaviour

Imanol Usabiaga; Weixing Li; Camilla Calabrese; Ahmet Altun; Assimo Maris; Sonia Melandri; Giovanni Bistoni; Luca Evangelisti

doi:10.1039/D6CP01323F

You do not have JavaScript enabled. Please enable JavaScript to access the full features of the site or access our non-JavaScript page.

Fluorination switches CO–arene binding to a π-hole regime, enabling nonclassical carbonyl behaviour

Imanol Usabiaga,

†^a Weixing Li,

‡^a Camilla Calabrese,

§^a Ahmet Altun,

^b Assimo Maris,

^a Sonia Melandri,

^a Giovanni Bistoni

*^c and Luca Evangelisti

*^a

Author affiliations

* Corresponding authors

^a Department of Chemistry G. Ciamician, University of Bologna, Via Gobetti 85, Bologna, Italy
E-mail: luca.evangelisti6@unibo.it

^b Max-Planck-Institut für Kohlenforschung, Kaiser-Wilhelm-Platz 1, Mülheim an der Ruhr, Germany

^c Department of Chemistry, Biology, and Biotechnology, University of Perugia, Perugia, Italy
E-mail: giovanni.bistoni@unipg.it

Abstract

Rotational spectroscopy reveals that fluorination switches CO–arene interactions to a nonclassical lp⋯π-hole binding motif. CO binds perpendicularly to perfluorinated aromatics, with C ← O bond contraction analogous to metal carbonyls, highlighting how π-hole interactions control ligand behaviour in weakly bound systems.

Download options Please wait...

Supplementary files

Supplementary information PDF (582K)

Article information

DOI: https://doi.org/10.1039/D6CP01323F
Article type: Communication
Submitted: 09 Apr 2026
Accepted: 26 May 2026
First published: 04 Jun 2026
This article is Open Access

Download Citation

Phys. Chem. Chem. Phys., 2026, Advance Article

Permissions

Request permissions

Fluorination switches CO–arene binding to a π-hole regime, enabling nonclassical carbonyl behaviour

I. Usabiaga, W. Li, C. Calabrese, A. Altun, A. Maris, S. Melandri, G. Bistoni and L. Evangelisti, Phys. Chem. Chem. Phys., 2026, Advance Article , DOI: 10.1039/D6CP01323F

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.

Physical Chemistry Chemical Physics

Fluorination switches CO–arene binding to a π-hole regime, enabling nonclassical carbonyl behaviour

Abstract

Supplementary files

Article information

Download Citation

Permissions

Fluorination switches CO–arene binding to a π-hole regime, enabling nonclassical carbonyl behaviour

Social activity

Search articles by author

Spotlight

Advertisements