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Oxidation triggers guest dissociation during reorganization of an FeII4L 6 twisted parallelogram

DOI: 10.1039/D0SC04352D DOI Help

Authors: Alex J. Plajer (University of Cambridge) , Felix Rizzuto (University of Cambridge) , Larissa K. S. Von Krbek (University of Cambridge) , Yohan Gisbert (University of Cambridge) , Víctor Martínez-agramunt (University of Cambridge) , Jonathan R. Nitschke (University of Cambridge)
Co-authored by industrial partner: No

Type: Journal Paper
Journal: Chemical Science , VOL 11 , PAGES 10399 - 10404

State: Published (Approved)
Published: October 2020
Diamond Proposal Number(s): 15768

Open Access Open Access

Abstract: A three-dimensional FeII4L6 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 FeII1L1+ 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.

Subject Areas: Chemistry

Instruments: I19-Small Molecule Single Crystal Diffraction


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