Möbius Zn(II)-Hexaphyrins Bearing a Chiral Coordinating Arm: A Chiroptical Switch Featuring P/M Twist Inversion Controlled by Achiral Effectors
| Autor: | Bernard Boitrel, Stéphane Le Gac, Arnaud Fihey, Hervé Ruffin |
|---|---|
| Přispěvatelé: | Institut des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), Ministère de l’Enseignement Supérieur et de la Recherche and Agence Nationale de la Recherche for financial support (ANR-16-CE07-0014), ANR-16-CE07-0014,PRALLOCAT,Vers des catalyseurs processifs allostériques pour l'encodage moléculaire(2016), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS) |
| Jazyk: | angličtina |
| Rok vydání: | 2021 |
| Předmět: |
Chemistry
Ligand 010405 organic chemistry chiroptical properties porphyrinoids General Chemistry General Medicine Ring (chemistry) 010402 general chemistry 01 natural sciences Catalysis Möbius aromaticity Stereocenter 0104 chemical sciences dynamic chirality Crystallography Molecular recognition [CHIM]Chemical Sciences Stereoselectivity molecular recognition Chirality (chemistry) Cotton effect |
| Zdroj: | Angewandte Chemie International Edition Angewandte Chemie International Edition, Wiley-VCH Verlag, 2021, ⟨10.1002/anie.202113844⟩ Angewandte Chemie International Edition, 2022, 61 (6), ⟨10.1002/anie.202113844⟩ |
| ISSN: | 1433-7851 1521-3773 |
| DOI: | 10.1002/anie.202113844⟩ |
| Popis: | International audience; By their conformational flexibility, Möbius aromatic hexaphyrins provide a dynamic chirality attractive to develop stimuli responsive systems such as chiroptical switches. A regular [28]hexaphyrin has been equipped with a chiral coordinating arm to achieve transfer of chirality from a fix stereogenic element to the dynamic Möbius one. The arm allows straightforward formation of labile monometallic Zn(II) complexes with an exogenous ligand, either a carboxylato or an amino with opposite inwards / outwards orientations relative to the Möbius ring. As a corollary, the chiral coordinating arm is constrained over the ring or laterally, inducing opposite P and M Möbius configurations with unprecedented high stereoselectivity (diast. excess greater than 95 %). By tuning the transfer of chirality, these achiral effectors generate electronic circular dichroism spectra with bisignate Cotton effect of opposite signs. Switching between distinct chiroptical states was ultimately achieved in mild conditions owing to ligand exchange, with high robustness (10 cycles). |
| Databáze: | OpenAIRE |
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