Solvent-free chemical manufacturing is one of the awaited technologies for addressing an emergent issue of environmental pollution. Here, we report solvent-free autocatalytic supramolecular polymerization (SF-ASP), which provides an inhibition-free template-assisted catalytic organic transformation that takes great advantage of the fact that the product (template) undergoes a termination-free nucleation–elongation assembly (living supramolecular polymerization) under solvent-free conditions. SF-ASP allows for reductive cyclotetramerization of hydrogen-bonding phthalonitriles into the corresponding phthalocyanines in exceptionally high yields (>80%). SF-ASP requires the growing polymer to form hexagonally packed crystalline fibres, which possibly preorganize the phthalonitriles at their cross-sectional edges for their efficient transformation. With metal oleates, SF-ASP produces single-crystalline fibres of metallophthalocyanines again in exceptionally high yields, which grow in both directions without terminal coupling until the phthalonitrile precursors are completely consumed. By taking advantage of this living nature of polymerization, multistep SF-ASP without/with metal oleates allows for the precision synthesis of multi-block supramolecular copolymers.

无溶剂化学品制造是解决环境污染问题的一项备受期待的技术。在这里，我们报告了无溶剂自催化超分子聚合 (SF-ASP)，它提供了一种无抑制的模板辅助催化有机转化，它充分利用了产物（模板）经历无终止成核-伸长组装这一事实（活性超分子聚合）在无溶剂条件下。SF-ASP 允许以极高的产率 (>80%) 将氢键邻苯二甲腈还原成相应的酞菁。SF-ASP 需要生长的聚合物形成六边形堆积的结晶纤维，这可能会在其横截面边缘预先组织邻苯二甲腈以实现其有效转化。使用金属油酸盐，SF-ASP 再次以极高的产率生产金属酞菁的单晶纤维，在苯二甲腈前体完全消耗之前，它在没有末端耦合的情况下在两个方向上生长。通过利用聚合的这种活性性质，多步 SF-ASP（不含/含金属油酸盐）可以精确合成多嵌段超分子共聚物。