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Anion Binding in Water Drives Structural Adaptation in an Azaphosphatrane-Functionalized Fe(II)4L4 Tetrahedron

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Ronson, TK 
Mosquera, J 
Martinez, A 
Guy, L 


Anion-templated aqueous self-assembly resulted in the formation of an endohedrally functionalized FeII4L4 tetrahedron from azaphosphatrane-based subcomponents. This new water-soluble cage is flexible and able to encapsulate anions with volumes ranging from 35 to 219 Å3 via hydrogen bonding and electrostatic interactions. It structurally adapts in response to the size and shape of the template anions, dynamically adopting a conformation either where all four azaphosphatrane +P-H vectors point inward, or else where one points outward and the other three inward. The two cage isomers can coexist in solution and interconvert. A shape memory phenomenon was observed during guest displacement because guest exchange occurs more rapidly than structural reconfiguration.



3403 Macromolecular and Materials Chemistry, 3405 Organic Chemistry, 34 Chemical Sciences

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Journal of the American Chemical Society

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American Chemical Society
Engineering and Physical Sciences Research Council (EP/M008258/1)
Engineering and Physical Sciences Research Council (EP/K039520/1)
This work was supported by the UK Engineering and Physical Sciences Research Council (EPSRC EP/M008258/1). The authors thank the Department of Chemistry NMR facility, University of Cambridge for performing some NMR experiments, and the EPSRC UK National Mass Spectrometry Facility at Swansea University for carrying out high-resolution mass spectrometry. D.Z. acknowledges a grant from the China Scholarship Council, Accueil Doc Bursary from France RhôneAlpes Region, and Enveloppe AttractivitéFellowship from ENSLyon for Ph.D. studies.
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