Mutual Monomer Orientation To Bias the Supramolecular Polymerization of [6]Helicenes and the Resulting Circularly Polarized Light and Spin Filtering Properties - Université de Rennes Accéder directement au contenu
Article Dans Une Revue Journal of the American Chemical Society Année : 2022

Mutual Monomer Orientation To Bias the Supramolecular Polymerization of [6]Helicenes and the Resulting Circularly Polarized Light and Spin Filtering Properties

Résumé

We report on the synthesis and self-assembly of 2,15- and 4,13-disubstituted carbo[6]helicenes 1 and 2 bearing 3,4,5-tridodecyloxybenzamide groups. The self-assembly of these [6]helicenes is strongly influenced by the substitution pattern in the helicene core that affects the mutual orientation of the monomeric units in the aggregated form. Thus, the 2,15-substituted derivative 1 undergoes an isodesmic supramolecular polymerization forming globular nanoparticles that maintain circularly polarized light (CPL) with glum values as high as 2 × 10–2. Unlike carbo[6]helicene 1, the 4,13-substituted derivative 2 follows a cooperative mechanism generating helical one-dimensional fibers. As a result of this helical organization, [6]helicene 2 exhibits a unique modification in its ECD spectral pattern showing sign inversion at low energy, accompanied by a sign change of the CPL with glum values of 1.2 × 10–3, thus unveiling an example of CPL inversion upon supramolecular polymerization. These helical supramolecular structures with high chiroptical activity, when deposited on conductive surfaces, revealed highly efficient electron-spin filtering abilities, with electron spin polarizations up to 80% for 1 and 60% for 2, as measured by magnetic conducting atomic force microscopy.

Domaines

Chimie
Fichier principal
Vignette du fichier
jacs.2c00556_Crassous_2022.pdf (6.12 Mo) Télécharger le fichier
Origine : Fichiers éditeurs autorisés sur une archive ouverte

Dates et versions

hal-03643151 , version 1 (29-04-2022)

Identifiants

Citer

Rafael Rodríguez, Cristina Naranjo, Anil Kumar, Paola Matozzo, Tapan Kumar Das, et al.. Mutual Monomer Orientation To Bias the Supramolecular Polymerization of [6]Helicenes and the Resulting Circularly Polarized Light and Spin Filtering Properties. Journal of the American Chemical Society, 2022, ⟨10.1021/jacs.2c00556⟩. ⟨hal-03643151⟩
67 Consultations
84 Téléchargements

Altmetric

Partager

Gmail Facebook X LinkedIn More