Article Dans Une Revue Chemistry - A European Journal Année : 2024

Chiral Spiro‐Tetrathiafulvalenes: Synthesis, Chiroptical Properties, Conformational Issues and Charge Transfer Complexes

Alexandra Bogdan
Narcis Avarvari
Flavia Pop

Résumé

Abstract Within this work we have investigated spiro‐based tetrathiafulvalenes (TTFs) obtained as mixtures of stereoisomers from racemic spiro[5.5]undeca‐1,8‐dien‐3‐one. Compared to previously described spiro‐TTFs, enantiomeric and diastereoisomeric forms have been here separated by chiral HPLC and fully characterized both experimentally and theoretically. The two types of spiro‐based chiral derivatives contain either one ( 2 ) or three ( 1 ) chiral centres out of each one is spiro‐type. Experimental CD, supported by TD‐DFT calculations, shows differences in the optical activity between the 1 and 2 and their intermediates. The low optical activity of 2 and 3 (spiro alone chirality) was attributed to the presence of two conformers in the solution ( ax and eq ) of opposite Cotton effect whereas in the case of 1 and 5 (spiro and stereogenic centres) the spiro chirality seems to be responsible of the Cotton effect in the high energy region whereas the R and S chirality in the low energy region. Racemic and enantiopure forms have been successfully used for the synthesis of charge transfer complexes with tetracyanoquinodimethane (TCNQ) based acceptors.

Domaines

Chimie
Fichier principal
Vignette du fichier
MAnuscript clean.pdf (3.37 Mo) Télécharger le fichier
Origine Fichiers produits par l'(les) auteur(s)
Licence

Dates et versions

hal-04786254 , version 1 (15-11-2024)

Licence

Identifiants

Citer

Alexandra Bogdan, Ionut-Tudor Moraru, Nicolas Vanthuyne, Pascale Auban-Senzier, Ion Grosu, et al.. Chiral Spiro‐Tetrathiafulvalenes: Synthesis, Chiroptical Properties, Conformational Issues and Charge Transfer Complexes. Chemistry - A European Journal, 2024, 30 (29), ⟨10.1002/chem.202400564⟩. ⟨hal-04786254⟩
8 Consultations
16 Téléchargements

Altmetric

Partager

More