title: Post-assembly Modification of Tetrazine-Edged Fe(II)4L6 Tetrahedra.
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 Fe(II)4L6 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 σ(para) and the rate of the IEDDA reaction. The rate of PAM can thus be adjusted by varying the aniline subcomponent.
authors.affiliation: Department of Chemistry, The University of Cambridge, Lensfield Road, Cambridge CB2 1EW, United Kingdom.
authors.forename: Derrick A
authors.initials: DA
authors.lastname: Roberts
authors.affiliation: Department of Chemistry, The University of Cambridge, Lensfield Road, Cambridge CB2 1EW, United Kingdom.
authors.forename: Ben S
authors.initials: BS
authors.lastname: Pilgrim
authors.affiliation: Department of Chemistry, The University of Cambridge, Lensfield Road, Cambridge CB2 1EW, United Kingdom.
authors.forename: Jonathan D
authors.initials: JD
authors.lastname: Cooper
authors.affiliation: Department of Chemistry, The University of Cambridge, Lensfield Road, Cambridge CB2 1EW, United Kingdom.
authors.forename: Tanya K
authors.initials: TK
authors.lastname: Ronson
authors.affiliation: Department of Chemistry, The University of Cambridge, Lensfield Road, Cambridge CB2 1EW, United Kingdom.
authors.forename: Salvatore
authors.initials: S
authors.lastname: Zarra
authors.affiliation: Department of Chemistry, The University of Cambridge, Lensfield Road, Cambridge CB2 1EW, United Kingdom.
authors.forename: Jonathan R
authors.initials: JR
authors.lastname: Nitschke