3 years ago

Anion Binding in Water Drives Structural Adaptation in an Azaphosphatrane-Functionalized FeII4L4 Tetrahedron

Anion Binding in Water Drives Structural Adaptation in an Azaphosphatrane-Functionalized FeII4L4 Tetrahedron
Jonathan R. Nitschke, Laure Guy, Dawei Zhang, Jesús Mosquera, Alexandre Martinez, Tanya K. Ronson
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.

Publisher URL: http://dx.doi.org/10.1021/jacs.7b02950

DOI: 10.1021/jacs.7b02950

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