Organisch-Chemisches Institut, Westfälische Wilhelms-Universität Münster, Corrensstraße 36, 48149, Münster, Germany.
Department of Chemistry and Biochemistry, University of South Carolina, Columbia, SC 29208, USA.
Angew Chem Int Ed Engl. 2022 Apr 19;61(17):e202200390. doi: 10.1002/anie.202200390. Epub 2022 Mar 2.
Herein, we present a strategy to enable a maintained emissive behavior in the self-assembled state by enforcing an anti-cooperative self-assembly involving weak intermolecular dye interactions. To achieve this goal, we designed a conformationally flexible monomer unit 1 with a central 1,3-substituted (diphenyl)urea hydrogen bonding synthon that is tethered to two BODIPY dyes featuring sterically bulky trialkoxybenzene substituents at the meso-position. The competition between attractive forces (H-bonding and aromatic interactions) and destabilizing effects (steric and competing conformational effects) limits the assembly, halting the supramolecular growth at the stage of small oligomers. Given the presence of weak dye-dye interactions, the emission properties of molecularly dissolved 1 are negligibly affected upon aggregation. Our findings contribute to broadening the scope of emissive supramolecular assemblies and controlled supramolecular polymerization.
在此，我们提出了一种策略，通过强制涉及弱分子间染料相互作用的反协同自组装，来实现自组装状态下保持发光行为。为了实现这一目标，我们设计了一个构象灵活的单体单元 1，其中央有一个 1,3-取代的（二苯基）脲氢键合成子，它与两个 BODIPY 染料连接，在中位带有空间位阻的三烷氧基苯取代基。吸引力（氢键和芳香相互作用）和失稳效应（空间位阻和竞争构象效应）之间的竞争限制了组装，使超分子生长在小寡聚物阶段停止。由于存在弱的染料-染料相互作用，分子溶解的 1 的发射性质在聚集时几乎不受影响。我们的发现有助于扩大发光超分子组装和可控超分子聚合的范围。
