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Terminal coupling of the crystalline fibers, which would lead to a decrease in the total cross-sectional area for autocatalysis, barely took place in SF-ASP, likely due to their very sluggish diffusion in the hot melt of PNC4 under solvent-free conditions. When metal oleates are present, SF-ASP produces metallophthalocyanines as crystalline fibers again in exceptionally high yields, which grow in both directions without terminal coupling until the phthalonitrile precursors are completely consumed. Taking advantage of the living nature of this supramolecular polymerization, multistep SF-ASP without/with metal oleates results in the precision synthesis of ABA and ABCBA types of multi-block supramolecular copolymers. The finding of all of these qualities of SF-ASP that occur only under environmentally friendly solvent-free conditions was beyond our expectations. This demonstrates the significant potential of supramolecular polymerization to bring about change in chemical manufacturing processes and in the utilization of polymeric materials for the realization of a sustainable society. We hope that this report will encourage polymer chemists to focus much needed attention on the solid-state properties of supramolecular polymers. Certainly, to have a chance at finding widespread practical use and replacing traditional polymers, supramolecular polymer materials showing mechanical robustness under a range of usage conditions must be realized. Although dynamicity and mechanical robustness of polymeric materials have been considered mutually exclusive, by an advanced molecular design, one might sweep away this preconception, and make mechanically robust polymers that are recyclable or structurally reorganizable at the monomer level under particular conditions. We envision a world in which society overcomes its chronic dependency on traditional plastics, through the gradual adoption of supramolecular polymers and other green materials. The intrinsically reversible nature of noncovalent bonds affords supramolecular polymers the potential for self-healing, reconfigurability and complete recycling, enabling materials whose lifespan can be extended and whose properties can be enhanced in subsequent life cycles. ◆
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