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Covalent Post-assembly Modification Triggers Multiple Structural Transformations of a Tetrazine-Edged Fe4L6 Tetrahedron

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Roberts, Derrick A 
Pilgrim, Ben S 
Sirvinskaite, Giedre 
Ronson, Tanya K 
Nitschke, Jonathan R 


Covalent post-assembly modification (PAM) reactions are useful synthetic tools for functionalizing and stabilizing self-assembled metal-organic complexes. Recently, PAM reactions have also been explored as stimuli for triggering supramolecular structural transformations. Herein we demonstrate the use of inverse electron-demand Diels-Alder (IEDDA) PAM reactions to induce supramolecular structural transformations starting from a tetrazine-edged FeII4L6 tetrahedral precursor. Following PAM, this tetrahedron rearranged to form three different architectures depending on the addition of other stimuli: an electron-rich aniline or a templating anion. By tracing the stimulus-response relationships within the system, we deciphered a network of transformations that mapped different combinations of stimuli onto specific transformation products. Given the many functions being developed for self-assembled three-dimensional architectures, this newly established ability to control the interconversion between structures using combinations of different stimulus types may serve as the basis for switching the functions expressed within a system.



0303 Macromolecular and Materials Chemistry, 0305 Organic Chemistry, 0302 Inorganic Chemistry

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Journal of the American Chemical Society

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American Chemical Society (ACS)
Royal Commission for the Exhibition of 1851 (RF478/2016)
Engineering and Physical Sciences Research Council (EP/M01083X/1)
European Research Council (695009)
D.A.R. acknowledges the Gates Cambridge Trust. B.S.P. acknowledges the Royal Commission for the Exhibition of 1851 Fellowship and Corpus Christi College, Cambridge. This work was supported by the UK Engineering and Physical Sciences Research Council (EP/M01083X/1).