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.

Abstract

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.

Citation

Roberts, D. A., Pilgrim, B. S., Sirvinskaite, G., Ronson, T. K., & Nitschke, J. R. (2018). Covalent Post-assembly Modification Triggers Multiple Structural Transformations of a Tetrazine-Edged Fe4L6 Tetrahedron. Journal of the American Chemical Society, 140(30), 9616-9623. https://doi.org/10.1021/jacs.8b05082

• Journal Article Type: Article
• Acceptance Date: Jul 7, 2018
• Online Publication Date: Jul 8, 2018
• Publication Date: 2018-08
• Deposit Date: Feb 24, 2020
• Publicly Available Date: Apr 21, 2020
• Journal: Journal of the American Chemical Society
• Print ISSN: 0002-7863
• Electronic ISSN: 1520-5126
• Publisher: American Chemical Society
• Peer Reviewed: Peer Reviewed
• Volume: 140
• Issue: 30
• Pages: 9616-9623
• DOI: https://doi.org/10.1021/jacs.8b05082
• Keywords: Supramolecular Chemistry; Organic Chemistry; Self-Assembly; Metal-Organic Cages
• Public URL: https://nottingham-repository.worktribe.com/output/4026108
• Publisher URL: https://pubs.acs.org/doi/10.1021/jacs.8b05082
• Additional Information: This document is the Accepted Manuscript version of a Published Work that appeared in final form in Journal of the American Chemical Society, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://pubs.acs.org/doi/10.1021/jacs.8b05082.