%0 Journal Article %T Hexaphyrin-Cyclodextrin Hybrids: A Nest for Switchable Aromaticity, Asymmetric Confinement, and Isomorphic Fluxionality %+ Institut Parisien de Chimie Moléculaire (IPCM) %+ Institut des Sciences Chimiques de Rennes (ISCR) %A Ménand, Mickaël %A Sollogoub, Matthieu %A Boitrel, Bernard %A Le Gac, Stephane %Z ANR-12-BS07-0006, Agence Nationale de la Recherche %< avec comité de lecture %@ 1433-7851 %J Angewandte Chemie International Edition %I Wiley-VCH Verlag %V 55 %N 1 %P 297–301 %8 2016 %D 2016 %R 10.1002/anie.201508009 %M 26514249 %K conformation analysis %K cyclodextrins %K aromaticity %K degenerate equilibria %K porphyrinoids %Z Chemical SciencesJournal articles %X Conformational control over the highly flexible π-conjugated system of expanded porphyrins is a key step toward the fundamental understanding of aromaticity and for the development of molecular electronics. We have synthesized unprecedented hexaphyrin-cyclodextrin (HCD) capped hybrids in which the hexaphyrin part is constrained in a planar rectangular conformation in either a 26 or a 28 π-electron oxidation state ([26]/[28]HCD). These structures display strong aromaticity and antiaromaticity, respectively, exhibit markedly different chiroptical properties, and are interconvertible upon the addition of DDQ or NaBH(OAc)3 , thus affording a rare switchable aromatic-antiaromatic system with a free-base expanded porphyrin. Conformational analysis revealed discrimination of the two coordination sites of the hexaphyrin, one of which was coupled to a confined asymmetric environment, and fluxional behavior consisting of apparent rotation of the hexaphyrin cap through a shape-shifting mechanism. %G English %L hal-01231166 %U https://univ-rennes.hal.science/hal-01231166 %~ UPMC %~ UNIV-RENNES1 %~ CNRS %~ INSA-RENNES %~ ENSC-RENNES %~ IPCM %~ ISCR %~ SCR_OMC2012 %~ ISCR-OMC %~ STATS-UR1 %~ UR1-SPM %~ INC-CNRS %~ UR1-UFR-SPM %~ UR1-HAL %~ UR1-SDLM %~ UR1-SDLMJONCH %~ UPMC_POLE_2 %~ IPCM-GOBS %~ TEST-UNIV-RENNES %~ TEST-UR-CSS %~ UNIV-RENNES %~ INSA-GROUPE %~ SORBONNE-UNIVERSITE %~ SU-SCIENCES %~ ANR %~ UR1-MMS %~ ALLIANCE-SU %~ TEST2-HALCNRS %~ CHIMIE-SU