Single-Crystal-to-Single-Crystal Topochemical Polymerizations by Design

摘要: The polymerization of simple conjugated dienes has long been interest: polydienes occur throughout Nature, and polyisoprene its analogues form the basis entire industries. In contrast, polymers similar small compounds, diacetylenes, trienes, triacetylenes, are either unknown or laboratory curiosities. For 40 years, only viable synthetic method for 1,4-polymerization a diacetylene was topochemical in condensed phase. But such an approach is hit miss: if monomers have solid-state structure preorganized at distances matching repeat distance final polymer, then thermal photochemical energy can bring about polymerization. However, most lack proper structural parameters simply do not react. As discussed this Account, we developed supramolecular host−guest strategy that imposes necessary upon monomer otherwise does polymerize. We apply th...