Dual Role for 1,2,4,5-Tetrazines in Polymer Networks: Combining Diels-Alder Reactions and Metal Coordination To Generate Functional Supramolecular Gels

TitleDual Role for 1,2,4,5-Tetrazines in Polymer Networks: Combining Diels-Alder Reactions and Metal Coordination To Generate Functional Supramolecular Gels
Publication TypeJournal Article
Year of Publication2015
AuthorsKawamoto, K, Grindy, SC, Liu, J, Holten-Andersen, N, Johnson, JA
JournalACS Macro Letters
Volume4
Issue4
Pagination458 - 461
Date Published2015/04//
Abstract

The inverse-electron demand Diels-Alder cycloaddition of tetrazines and olefins has emerged as a powerful coupling reaction for the formation of polymer gels with diverse applications. Tetrazines are also excellent ligands for metal atoms. For example, 3,6-bis(2-pyridy1)-1,2,4,5-tetrazines (bptz) have been used to generate discrete supramolecular M(x)bptz(y) metal clusters and extended 2D grid structures. We reasoned that both the Diels-Alder and the metal-coordination modes of reactivity of bptz derivatives could be leveraged in the context of hydrogel design to yield novel hybrid materials. Here we report on the formation of supramolecular hydrogels via substoichiometric Diels-Alder functionalization of bptz ligands bound to the ends of poly(ethylene glycol) (PEG) chains followed by metal-coordination-induced gelation in the presence of Ni2+ and Fe2+ salts. Our results show that simple bptz-based polymers are versatile precursors to a diverse range of novel functional materials.