Multivalent Crown Ether Receptors Enable Allosteric Regulation of Anion Exchange in an Fe4 L6 Tetrahedron.
Accepted version
Peer-reviewed
Repository URI
Repository DOI
Change log
Authors
von Krbek, Larissa KS https://orcid.org/0000-0002-4278-5235
Roberts, Derrick A https://orcid.org/0000-0002-4663-7475
Pilgrim, Ben S https://orcid.org/0000-0002-3353-3327
Schalley, Christoph A https://orcid.org/0000-0002-8634-3578
Nitschke, Jonathan R https://orcid.org/0000-0002-4060-5122
Abstract
We report a strategy for regulating the rate of internally bound anion exchange within an Fe4 L6 metal-organic tetrahedron through external coordination of tripodal tris(alkylammonium) cations. The cage features three flexible 18-crown-6 receptors at each of its FeII vertices, facilitating strong tritopic interactions with tris(ammonium) cations to "cap" the vertices of the tetrahedron. This capping mechanism restricts the flexibility of the cage framework, thereby reducing the rate of anion exchange within its central cavity by 20-fold. Thus, we demonstrate the first use of an externally bound multivalent effector to allosterically control internal guest binding in a molecular cage.
Description
Keywords
allostery, cage compounds, host-guest systems, multivalency, self-assembly
Journal Title
Angew Chem Int Ed Engl
Conference Name
Journal ISSN
1433-7851
1521-3773
1521-3773
Volume Title
57
Publisher
Wiley
Publisher DOI
Sponsorship
Royal Commission for the Exhibition of 1851 (RF478/2016)
Engineering and Physical Sciences Research Council (EP/P027067/1)
European Research Council (695009)
Engineering and Physical Sciences Research Council (EP/P027067/1)
European Research Council (695009)
UK Engineering and Physical Sciences Research Council (EPSRC EP/P027067/1), the European Research Council (695009), and the Deutsche Forschungsgemeinschaft (SFB 765)