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

Roberts, Derrick A., Pilgrim, Ben S., Sirvinskaite, Giedre, Ronson, Tanya K., Nitschke, Jonathan R.
Journal of the American Chemical Society 2018 v.140 no.30 pp. 9616-9623
aniline, cycloaddition reactions
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.