Supramolecular polymers are often investigated for highly symmetric and planar molecules, such as typically explored BF₂-substituted BODIPY dyes. However, it is surprising that the possibility of desymmetrizing the sp³ hybridized boron centre of BODIPY dyes has remained unexplored in the context of supramolecular polymerization. Herein, we synthesized a new BODIPY derivative 2 with two different substituents at the boron (fluorine and phenyl), resulting in a system with two different π-surfaces, and analyzed its supramolecular polymerization in non-polar media. Notably, this symmetry reduction increases the complexity of the self-assembly by enabling the formation of an intermediate assembled state, which cannot be found in the symmetrical model BODIPY 1 with a BF₂ group. Different experimental and theoretical studies suggest that significant steric effects together with multiple potential intermolecular stacking modes of the BODIPY dyes lead to discrete nanoparticle intermediates that ultimately transform into more-ordered H-type supramolecular polymers at lower temperatures. Our results introduce a new design strategy for controlled supramolecular polymerization.

中文翻译：

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硼去对称化对 BODIPY 染料超分子聚合的影响


超分子聚合物通常用于高度对称和平面分子的研究，例如通常探索的 BF₂ 取代的 BODIPY 染料。然而，令人惊讶的是，在超分子聚合的背景下，BODIPY 染料的 sp³ 杂化硼中心去对称的可能性仍未得到探索。在此，我们在硼上合成了一种新的 BODIPY 衍生物 2，在硼上具有两个不同的取代基（氟和苯基），从而得到一个具有两个不同π表面的系统，并分析了其在非极性介质中的超分子聚合。值得注意的是，这种对称性的降低通过形成中间组装状态来增加自组装的复杂性，这在具有 BF₂ 组的对称模型 BODIPY 1 中是找不到的。不同的实验和理论研究表明，BODIPY 染料的显着空间效应以及多种潜在的分子间堆叠模式导致离散的纳米颗粒中间体，最终在较低温度下转化为更有序的 H 型超分子聚合物。我们的结果引入了一种受控超分子聚合的新设计策略。