Covalent post-assembly modification (PAM) provides a versatile means of functionalizing and stabilizing self-assembled metal-organic complexes. However, PAM can also alter the sterics and electronics of ligands to engender distinct structural changes in their parent complexes. Herein we demonstrate the use of covalent PAM to trigger diverse supramolecular structural transformations from a common precursor, a tetrazine-edged FeII4L6 tetrahedron. This tetrahedron rearranged following post-assembly inverse electron-demand Diels-Alder (IEDDA) reactions with cyclooctyne. The addition of one of two stimuli (an electron-rich aniline or a templating anion) alongside the cyclooctyne led to different product structures. By tracing the stimulus-response relationships within the system, we deciphered a network that maps 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 multiple different stimuli can serve the basis for switching the functions expressed within a system.

Covalent post-assembly modification triggers multiple structural transformations of a tetrazine-edged Fe4L6 tetrahedron

256th National Meeting (2018)

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