O−H···N Heterosynthon: A Robust Supramolecular Unit For Crystal Engineering

To explore the robust nature of template resorcinols in organic solid-state reactions, a series of mono- and dipyridines were cocrystallized with different substituted resorcinols. The organizational consequences of hydrogen-bonds in the hydroxyl···pyridine heterosynthon in the presence of competitive hydrogen-bonding functional groups are elucidated. C−O bond flexibility, steric hindrance, and formation of undesired intramolecular hydrogen bonds have strongly affected the ability of the template for a parallel alignment of olefins. Finally, structural changes that occurred at a molecular level during [2 + 2] photodimerization of the complex of 1,4-bis[(E)-2-(4-pyridyl)ethenyl]-2-fluorobenzene (bpef) with 2,4-dihydroxy-benzaldehyde were studied in detail by performing a rather rare single-crystal-to-single-crystal photoirradiation.

为探究模板间苯二酚类化合物在有机固态反应中的稳健特性，我们将一系列单吡啶与二吡啶类化合物与不同取代基取代的间苯二酚进行共结晶。本研究阐明了在竞争性氢键官能团存在的条件下，羟基···吡啶异合成子中氢键的组织调控效应。C-O键柔性、空间位阻以及非目标分子内氢键的形成，均显著影响了模板实现烯烃平行排布的能力。最后，通过开展极为罕见的单晶到单晶（single-crystal-to-single-crystal）光辐照实验，我们对1,4-双[(E)-2-(4-吡啶基)乙烯基]-2-氟苯（bpef）与2,4-二羟基苯甲醛形成的配合物的[2+2]光二聚反应过程中发生的分子级结构变化进行了详细研究。