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 Fe^II₄L₆ 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.