Fabrication of Supramolecular Fibers Having Hydrogen-bonded Main Chains and Development of Their Functions

近年来，具有非共价主链骨架的超分子聚合物的研究十分活跃。在这项研究中，我们采用了一种新颖的分子设计，使用可调节的软段来保护刚性氢键主链，这使得超分子纤维可以通过外加机械力来分层制造具有沿纤维轴宏观排列的聚合物链的超分子纤维。在初步研究中，我们通过熔融纺丝的方法成功地从含有柔性烷基硅基侧链的鸟苷衍生物中获得了稳定且柔性的超分子纤维。为了验证这种分层设计在制备超分子纤维方面的有效性和适用性，我们引入了柔性烷基硅链作为可调节软段的环己三胺衍生物的三氢键超分子聚合物。还通过纺丝获得了柔性的大尺度超分子纤维，并得到了具有…的氢键线性聚合物链更多的环己烷核心的柱状堆叠显示出沿纤维轴线排列。此外，我们发现氢键聚合物链上的单体序列可以很容易地被烷基硅基侧链的膨胀性所控制，两个单体单元简单地混合就可以得到交替的超分子共聚物。为了开发功能性超分子纤维，我们设计了由多个氢键和π基芳族核形成的苯三胺和联苯四胺衍生物的超分子聚合物，并通过纺丝成功地将其制备成纤维。这些结果证实了利用柔性烷基硅基侧链作为可调软链段的分级分子设计是在外力作用下诱导超分子聚合物高度排列的有效方法。我们通过成功地制备晶体和薄膜等超分子材料，进一步证明了这种分子设计在宏观超分子结构分级结构中的广泛适用性。较少

Recently, supramolecular polymers having non-covalent main-chain backbones have been actively studied. In this study, we adopted a novel molecular design to use adjustable soft segments for protection of the rigid hydrogen-bonded main chain, which allowed hierarchical fabrication of supramolecular fibers having macro-scale alignment of the polymer chains along the fiber axis by application of external mechanical force. In the preliminary study, we successfully obtained stable and flexible supramolecular fibers from a guanosine derivative having flexible alkylsilyl side chains by melt-spinning.To test the validity and applicability of this hierarchical design for fabrication of the supramolecular fiber, flexible alkylsilyl chains were introduced to triply hydrogen-bonded supramolecular polymers of cyclohexanetriamide derivatives as the adjustable soft segment. Flexible macro-scale supramolecular fibers were also obtained by spinning, and the hydrogen-bonded linear polymer chains having … More columnar stacks of the cyclohexane core were shown to be aligned along the fiber axis. Furthermore, we found that monomer sequence of the hydrogen-bonded polymer chain could be easily controlled by bulkiness of the alkylsilyl side chains, and alternating supramolecular copolymers were obtained by simple mixing of two monomer units.To develop functional supramolecular fibers, we designed supramolecular polymers of benzenetriamide and biphenyltetraamide derivatives formed by multiple hydrogen bonds and π-staked aromatic core, and successfully fabricated them into fibers by spinning. These results confirmed that the hierarchical molecular design to use flexible alkylsilyl side chains as adjustable soft segment is effective to induce high alignment of supramolecular polymers by external mechanical force.We further demonstrated wide applicability of this molecular design for hierarchical construction of macro-scale supramolecular structures through successful fabrication of supramolecular materials such as crystals and films. Less