Post-assembly Modification of Tetrazine-Edged FeII4L6 Tetrahedra

Roberts, Derrick A.; Pilgrim, Ben S.; Cooper, Jonathan D.; Ronson, Tanya K.; Zarra, Salvatore; Nitschke, Jonathan R.

Abstract

Post-assembly modification (PAM) is a powerful tool for the modular functionalization of self-assembled structures. We report a new family of tetrazine-edged FeII4L6 tetrahedral cages, prepared using different aniline subcomponents, which undergo rapid and efficient PAM by inverse electron-demand Diels–Alder (IEDDA) reactions. Remarkably, the electron-donating or -withdrawing ability of the para-substituent on the aniline moiety influences the IEDDA reactivity of the tetrazine ring 11 bonds away. This effect manifests as a linear free energy relationship, quantified using the Hammett equation, between σpara and the rate of the IEDDA reaction. The rate of PAM can thus be adjusted by varying the aniline subcomponent.

Citation

Roberts, D. A., Pilgrim, B. S., Cooper, J. D., Ronson, T. K., Zarra, S., & Nitschke, J. R. (2015). Post-assembly Modification of Tetrazine-Edged FeII4L6 Tetrahedra. Journal of the American Chemical Society, 137(32), 10068-10071. https://doi.org/10.1021/jacs.5b05080

• Journal Article Type: Article
• Acceptance Date: Jul 31, 2015
• Online Publication Date: Aug 11, 2015
• Publication Date: Aug 19, 2015
• Deposit Date: Feb 24, 2020
• Publicly Available Date: Apr 6, 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: 137
• Issue: 32
• Pages: 10068-10071
• DOI: https://doi.org/10.1021/jacs.5b05080
• Public URL: https://nottingham-repository.worktribe.com/output/4026188
• Publisher URL: https://pubs.acs.org/doi/10.1021/jacs.5b05080