Self-assembly using a retro Diels-Alder reaction

Jaeyoung Park,Jung-Moo Heo,Jong-Man Kim,Jaegeun Noh,Sicheon Seong

doi:10.1038/s41467-021-24492-z

Abstract

Despite their great utility in synthetic and materials chemistry, Diels-Alder (DA) and retro Diels-Alder (rDA) reactions have been vastly unexplored in promoting self-assembly processes. Herein we describe the first example of a retro Diels-Alder (rDA) reaction-triggered self-assembly method. Release of the steric bulkiness associated with the bridged bicyclic DA adduct by the rDA reaction allowed generation of two building blocks that spontaneously self-assembled to form a supramolecular polymer. By employing photopolymerizable lipid building blocks, we demonstrated the efficiency of the rDA-based self-assembly strategy. Generation of reactive functional groups (maleimide and furan) that can be used for further modification of the supramolecular polymer is an additional meritorious feature of the rDA-based approach. Advantage was taken of reactive functional groups to fabricate stimulus-responsive selective and tunable colorimetric sensors. The strategy developed in this study should be useful for the design of systems that participate in triggered molecular assembly.

Highlights

Despite their great utility in synthetic and materials chemistry, Diels-Alder (DA) and retro Diels-Alder reactions have been vastly unexplored in promoting self-assembly processes
One remarkable feature of the rDAbased self-assembly and one that is difficult to attain by using conventional triggering methods is that it enables the generation of reactive functional groups that can be used for further modification of the supramolecule
The strategy and design of the retro Diels-Alder (rDA)-based self-assembly process are based on the bis-diacetylene-linked DA adduct 1-endo, in which two diacetylenecontaining lipid groups are connected in the form of a DA adduct (Fig. 2a)

Summary

Introduction

Despite their great utility in synthetic and materials chemistry, Diels-Alder (DA) and retro Diels-Alder (rDA) reactions have been vastly unexplored in promoting self-assembly processes. Heat treatment of 1-endo was expected to generate diacetylene-containing furan F and maleimide M through rDA reaction (Fig. 2b).

Results

Conclusion