This work describes the search for reactive crystal packings of anthraphane, a D_3h-symmetric cyclophane with three vertically arranged anthracene units. Packings in which anthracene units of neighboring anthraphanes assume a face-to-face stacked geometry were selected from the available library of crystal structures of this compound. The corresponding single crystals were irradiated at 465 nm in the temperature range of −100 to 25 °C, and the dimerization between the anthracene units was followed and quantified by XRD. This was possible because all these reactions proceeded in a single-crystal-to-single-crystal (SCSC) fashion. While all findings comply with the critical distance between reactive units postulated by Schmidt, significant reactivity differences were observed among reactive anthracene pairs. Qualitative explanations for the different reactivities will be provided using as geometrical descriptors the Schmidt distance and the offsets between the anthracene pairs, and also considering the degree of structural rearrangement required during reaction. All reactive packings afforded dimers, and in a particular case, a two-step polymerization afforded the novel ladder polymer poly_1Danthraphane, the first case of a linear macromolecule synthesized in single crystals using anthracene dimerization as the growth reaction. An investigation into the temperature range required to induce retro-cycloaddition reactions in the dimers formed upon photoirradiation is also presented.

中文翻译：

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蒽与双硫蒽和聚_一维蒽的光化学单晶至单晶（SCSC）反应

这项工作描述了搜索anthraphane的反应性液晶的密封垫，一个d _{3 ħ}具有三个垂直排列的蒽单元的对称对称环烷。从该化合物的晶体结构库中选择了相邻蒽的蒽单元呈面对面堆叠的几何形状的填料。在-100至25℃的温度范围内在465nm下照射相应的单晶，并通过XRD对蒽单元之间的二聚化进行追踪和定量。这是可能的，因为所有这些反应都以单晶到单晶（SCSC）的方式进行。尽管所有发现均符合Schmidt假设的反应单元之间的临界距离，但在反应性蒽对之间观察到显着的反应性差异。将使用Schmidt距离和蒽对之间的偏移作为几何描述符来提供对不同反应性的定性解释，并考虑反应过程中所需的结构重排程度。所有反应性填料均提供二聚体，在特定情况下，两步聚合可提供新型梯形聚合物聚_1D蒽，这是使用蒽二聚化作为生长反应在单晶中合成线性大分子的第一种情况。还介绍了在光辐照下形成的二聚体中引起逆向加成反应所需温度范围的研究。