Interplay Between Hydrogen Bonding and Electron Transfer in Mixed Valence Assemblies of Triarylamine Trisamides - Institut Parisien de Chimie Moléculaire Accéder directement au contenu
Article Dans Une Revue Chemistry - A European Journal Année : 2023

Interplay Between Hydrogen Bonding and Electron Transfer in Mixed Valence Assemblies of Triarylamine Trisamides

Sébastien Blanchard
Laurent Bouteiller
Matthieu Raynal

Résumé

Hydrogen-bonding interactions are assumed to play a critical role in the long-range transport of light or charge recently observed in supramolecular assemblies of C3-symmetrical discotic molecules. Herein, the structure of mixed valence assemblies formed by irradiating triarylamine trisamide (TATA) molecules was determined by multifarious techniques under various conditions with the aim of probing the interplay between the hydrogen bonding network and the rate of electron transport in different states (solution, gel, film). Irradiation was performed under initial states that vary by the degree of association of TATA monomers through hydrogen bonds. Firstly, a significant shift of the N−H and C=O stretching frequencies was observed by FTIR upon irradiation thus revealing an overlooked signature of TATA⋅+ species and interacting mixed valence aggregates. Secondly, gels and films both mostly consist of hydrogen-bonded TATA polymers but their EPR spectra recorded at 293 K reveal very different behaviors: localized electrons in the gels versus fully delocalized electrons in the films. Hydrogen bonding thus appears as a necessary but not sufficient condition to get fast electron transfer rates and a packing of the TATA monomers particularly suitable for charge transport is assumed to exist in the solid state. Finally, defects in the hydrogen bonding network are detected upon increasing the number of radical species in the mixed valence assemblies present in the film state without impeding the delocalization of the unpaired electrons. A delicate balance between hydrogen bonds and packing is thus necessary to get supramolecular polarons in mixed valence TATA assemblies.

Domaines

Chimie
Fichier principal
Vignette du fichier
Chem.Eur.J. main text + abstract revised.pdf (1.77 Mo) Télécharger le fichier
Origine : Fichiers éditeurs autorisés sur une archive ouverte
licence : CC BY - Paternité

Dates et versions

hal-03989447 , version 1 (24-02-2023)

Identifiants

Citer

Quentin Sallembien, Paméla Aoun, Sébastien Blanchard, Laurent Bouteiller, Matthieu Raynal. Interplay Between Hydrogen Bonding and Electron Transfer in Mixed Valence Assemblies of Triarylamine Trisamides. Chemistry - A European Journal, 2023, 29 (9), ⟨10.1002/chem.202203199⟩. ⟨hal-03989447⟩
34 Consultations
19 Téléchargements

Altmetric

Partager

Gmail Facebook X LinkedIn More