Post-assembly Modification of Tetrazine-Edged FeII4L6 Tetrahedra
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- 作者：Derrick A. Roberts ; Ben S. Pilgrim ; Jonathan D. Cooper ; Tanya K. Ronson ; Salvatore Zarra ; Jonathan R. Nitschke
- 刊名：Journal of the American Chemical Society
- 出版年：2015
- 出版时间：August 19, 2015
- 年：2015
- 卷：137
- 期：32
- 页码：10068-10071
- 全文大小：391K
- ISSN：1520-5126
文摘
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鈥揂lder (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 蟽para and the rate of the IEDDA reaction. The rate of PAM can thus be adjusted by varying the aniline subcomponent.