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Oxidation triggers guest dissociation during reorganization of an FeII 4L6 twisted parallelogram.

Published version
Peer-reviewed

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Type

Article

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Authors

Plajer, Alex J 
von Krbek, Larissa KS  ORCID logo  https://orcid.org/0000-0002-4278-5235
Gisbert, Yohan 
Martínez-Agramunt, Víctor 

Abstract

A three-dimensional FeII 4L6 parallelogram was prepared from ferrocene-containing ditopic ligands. The steric preference of the bulky ferrocene cores towards meridional vertex coordination brought about this new structure type, in which the ferrocene units adopt three distinct conformations. The structure possesses two distinct, bowl-like cavities that host anionic guests. Oxidation of the ferrocene FeII to ferrocenium FeIII causes rotation of the ferrocene hinges, converting the structure to an FeII 1L1 + species with release of anionic guests, even though the average charge per iron increases in a way that would ordinarily increase guest binding strength. The degrees of freedom exhibited by these new structures - derived from the different configurations of the three ligands surrounding a meridional FeII center and the rotation of ferrocene cores - thus underpin their ability to reconfigure and eject guests upon oxidation.

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Keywords

3402 Inorganic Chemistry, 3403 Macromolecular and Materials Chemistry, 34 Chemical Sciences

Journal Title

Chem Sci

Conference Name

Journal ISSN

2041-6520
2041-6539

Volume Title

11

Publisher

Royal Society of Chemistry (RSC)
Sponsorship
European Research Council (695009)
Engineering and Physical Sciences Research Council (EP/P027067/1)