Parallel Chirality Inductions in Möbius Zn(II) Hexaphyrin Transformation Networks - Archive ouverte HAL Accéder directement au contenu
Article Dans Une Revue Journal of the American Chemical Society Année : 2023

Parallel Chirality Inductions in Möbius Zn(II) Hexaphyrin Transformation Networks

Résumé

Networked chemical transformations are key features of biological systems, in which complex multicomponent interactions enable the emergence of sophisticated functions. Being interested in chirality induction phenomena with dynamic Möbius π-systems, we have designed a pair of Möbius [28]hexaphyrin ligands in order to investigate mixtures rather than isolated molecules. Thus, a hexaphyrin bearing a chiral amino arm was first optimized and found to bind a ZnOAc moiety, triggering an impressive quasi-quantitative chirality induction over the Möbius π-system. Second, this amino-type hexaphyrin was mixed with a second hexaphyrin bearing a chiral carboxylate arm, affording at first ill-defined coordination assemblies in the presence of zinc. In contrast, a social self-sorting behavior occurred upon the addition of two exogenous achiral effectors (AcO– and BuNH2), leading to a well-defined 1:1 mixture of two Möbius complexes featuring a sole Möbius twist configuration (parallel chirality inductions). We next successfully achieved compartmentalized switching, i.e., a single-component transformation from such a complex mixture. The BuNH2 effector was selectively protected with Boc2O, owing to a lower reactivity of the arm’s NH2 function intramolecularly bound to zinc, and subsequent addition of BuNH2 restored the initial mixture, retaining parallel chirality inductions (five cycles). By changing the nature and twist configuration of only one of the two complexes, at initial state or by switching, this approach enables a “two-channel” tuning of the chiroptical properties of the ensemble. Such multiple dynamic chirality inductions, controlled by selective metal–ligand recognition and chemical reactivity, set down the basis for Möbius-type stereoselective transformation networks with new functions.
Fichier sous embargo
Fichier sous embargo
0 0 23
Année Mois Jours
Avant la publication
jeudi 30 mai 2024
Fichier sous embargo
jeudi 30 mai 2024
Connectez-vous pour demander l'accès au fichier

Dates et versions

hal-04327533 , version 1 (31-01-2024)

Identifiants

Citer

Thomas Nédellec, Bernard Boitrel, Stéphane Le Gac. Parallel Chirality Inductions in Möbius Zn(II) Hexaphyrin Transformation Networks. Journal of the American Chemical Society, 2023, 145 (49), pp.27067-27079. ⟨10.1021/jacs.3c10835⟩. ⟨hal-04327533⟩
38 Consultations
2 Téléchargements

Altmetric

Partager

Gmail Facebook X LinkedIn More