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Folding Construction of Doubly Fused Tricyclic, β- and γ‑Graph Polymer Topologies with kyklo-Telechelic Precursors Obtained through an Orthogonal Click/ESA-CF Protocol

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journal contribution
posted on 24.09.2013, 00:00 by Masahito Igari, Hiroyuki Heguri, Takuya Yamamoto, Yasuyuki Tezuka
An alkyne–azide addition (click) reaction of a linear poly­(tetrahydrofuran), poly­(THF), precursor having an alkyne group at the center position and cyclic ammonium salt end groups has been applied with the complementary linear poly­(THF) precursors having an azide group at single or both chain ends to produce asymmetric star- and H-shaped poly­(THF) precursors having cyclic ammonium salt end groups. The subsequent electrostatic self-assembly and covalent fixation (ESA-CF) process after introducing dicarboxylate counteranions having an additional alkene or alkyne group could afford the designated kyklo-telechelic precursors, having either a tadpole form containing an alkyne group at the top-head and an alkene group at the tail-end positions or an isomeric manacle/theta form containing two alkene groups at the orthogonal positions. The further click coupling of the former with a linear telechelic precursor having azide groups followed by the metathesis folding (clip) process could produce effectively a doubly fused tricyclic polymer having β-graph topology. Moreover, the convergent folding by the clip reaction of the latter manacle/theta isomeric precursors could produce exclusively another doubly fused tricyclic polymer having γ-graph topology.