The macrocyclic structure offers direction-control self-assembly to generate columnar supramolecular architectures with a guest molecule-accessible interior cavity. Owing to the π–π stacking characteristic and photopolymerizable feature of the diacetylenic template, macrocyclic diacetylenes (MCDAs) have emerged as an intriguing molecular design for constructing arrays of covalently connected nanochannels. The energy transfer mechanism by engineering host–guest cocrystals of self-assembling π-electron-rich motifs has been widely accepted for devising organic electronics. A highly fluorescent and polymerizable cocrystal of macrocyclic diacetylene-terthiophene (MCDA-3T) was constructed. Single-crystal X-ray diffraction analysis reveals well-ordered columnar assembly of MCDA with stacking geometry close-to-ideal packing parameters preferred for the topochemical polymerization. Inspection of the extended crystal packing pattern and by elemental analysis confirms the inclusion of the 3T guest in outer-space positioned along the parallel-packed MCDA columns, resulting in an array of nanochannels. UV-induced polymerization of MCDA-3T cocrystal transforms into covalently cross-linked PDAs and displays Förster resonance energy transfer behavior between fluorescent 3T and conjugated PDA polymer. The energy transfer phenomenon observed with the tubular PDA and oligothiophenes should be useful in the design of new energy harvesting functional supramolecules.

中文翻译：

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大环二乙炔-对噻吩共晶体：分子自组装，拓扑化学聚合和能量转移

大环结构提供方向控制自组装，以生成具有来宾分子可接近的内部空腔的柱状超分子结构。由于二乙炔模板的π-π堆积特性和可光聚合的特性，大环二乙炔（MCDAs）作为构建共价连接的纳米通道阵列的一种引人入胜的分子设计而出现。通过工程自组装富电子富集的主客体共晶体的能量转移机制已被广泛用于设计有机电子学。大环二乙炔-对噻吩（MCDA-3T）的高荧光和可聚合共晶体）的建筑。单晶X射线衍射分析揭示了MCDA的井然有序的柱状组装，其堆积几何形状接近理想的堆积参数，是拓扑化学聚合的首选参数。检查扩展的晶体堆积模式并通过元素分析确认3T客体包含在沿着平行堆积的MCDA柱定位的外部空间中，从而形成了纳米通道阵列。紫外线诱导的MCDA-3T共晶体聚合转变为共价交联的PDA，并显示荧光3T与共轭PDA聚合物之间的Förster共振能量转移行为。用管状PDA和低聚噻吩观察到的能量转移现象应在设计新的能量收集功能超分子中有用。