Solving fundamental concepts in supramolecular science with functionality-tolerant living polymerizations of self-assembling monomers and dendronized monomers

Abstract

The evolution and development of several examples of functionality-tolerant living polymerizations to the level of perfection that they could be employed to solve fundamental concepts in supramolecular science by living polymerization of self-assembling monomers and self-organizable dendronized monomers is briefly reviewed. The review focuses on the development of the living polymerization methodology with brief examples on how they impacted the field of self-assembly and self-organization. The first polymerization reaction discussed is the stereoselective polymerization of phenylacetylene and of other arylacetylenes to generate helical poly(arylacetylene) stereoisomers. The transition from functionality non-tolerant to functionality-tolerant stereoselective polymerizations and the evolution to functionality-tolerant living stereoselective polymerization of phenylacetylene is used as the main example of this brief review. This living polymerization methodology is followed by living polymerization of vinyl ethers, oxazolines, of group transfer polymerization, of cationic ring-opening polymerization of cyclic siloxanes combined with hydrosilylation, of ROMP of cylooxanorbornene. This brief review is concluded by a brief discussion of the capabilities of the above-mentioned living methodologies with living radical polymerizations. The numerous applications in the field of supramolecular science of these living methodologies are not reviewed. However, the reader is directed to numerous comprehensive review articles discussing these applications. The challenges that remain to be solved in all these functionality-tolerant living polymerizations are presented.