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

最近，具有非共价主链的超分子聚合物已被积极地研究。在这项研究中，我们采用了一种新的分子设计，使用可调节的软段保护的刚性氢键的主链，这使得分层制造的超分子纤维具有宏观尺度的排列的聚合物链沿着纤维轴通过施加外部机械力。在前期研究中，我们利用熔融纺丝法成功地从具有柔性烷基硅侧链的鸟苷衍生物中获得了稳定、柔性的超分子纤维，并将柔性烷基硅侧链引入到环己烷三酰胺衍生物的三重氢键超分子聚合物中作为可调软段，以验证这种分层设计方法制备超分子纤维的有效性和适用性。柔性宏观尺度超分子纤维也通过纺丝获得，并且具有以下结构的氢键键合的线性聚合物链 关于我们 环己烷芯的柱状堆叠显示为沿着纤维轴排列。此外，我们发现氢键聚合物链的单体序列可以很容易地通过烷基硅烷基侧链的蓬松度来控制，通过两个单体单元的简单混合即可获得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-堆积芳香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它们制成纤维。这些结果证实了以柔性烷基硅基侧链为可调软段的分级分子设计能有效地诱导超分子聚合物在外力作用下的高度取向，并通过晶体和薄膜等超分子材料的成功制备进一步证明了这种分子设计在分级构筑宏观尺度超分子结构中的广泛适用性.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