Post-Assembly Modification of Tetrazine-Edged Fe(II)4L6 Tetrahedra
Journal of the American Chemical Society
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Roberts, D., Pilgrim, B., Cooper, J., Ronson, T., Zarra, S., & Nitschke, J. (2015). Post-Assembly Modification of Tetrazine-Edged Fe(II)4L6 Tetrahedra. Journal of the American Chemical Society, 137 10068-10071. https://doi.org/10.1021/jacs.5b05080
Post-assembly modification (PAM) is a powerful tool for the modular functionalization of self-assembled structures. We report a new family of tetrazine-edged Fe^II_4L_6 tetrahedral cages, prepared using different aniline subcomponents, which un-dergo 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.
This work was supported by the UK Engineering and Physical Sciences Research Council (EPSRC). The au-thors thank Diamond Light Source (UK) for synchro-tron beamtime on I19 (MT8464), the Department of Chemistry NMR facility, University of Cambridge, and the EPSRC UK National Mass Spectrometry Facility at Swansea University. D.A.R. acknowledges the Gates Cambridge Trust for Ph.D. funding. B.S.P. acknowledges the Herchel Smith Research Fellowship from the University of Cambridge and the Fellowship from Corpus Christi College, Cambridge.
External DOI: https://doi.org/10.1021/jacs.5b05080
This record's URL: https://www.repository.cam.ac.uk/handle/1810/249277
Attribution 2.0 UK: England & Wales
Licence URL: http://creativecommons.org/licenses/by/2.0/uk/