Driving self-assembly through donor–acceptor interactions to create nanostructured materials is a key feature of supramolecular chemistry; however, the connection between molecular-level changes and larger-scale organization is still unknown. Here, we propose the concept of Lewis adduct binding-induced bond polarization, where the formation of the Lewis adduct leads to a large dipole (here estimated to be 12.5 D), significantly altering the intermolecular interactions between different species and inducing self-assembly. Specifically, a diblock copolymer, poly(2-(dimethylamino)ethyl methacrylate)-polystyrene (PDMAEMA-PS), self-assembles into nanostructured colloidal aggregates on the addition of the Lewis acid tris(pentafluorophenyl) borane (BCF) in toluene. The morphology of the nanostructured colloidal structures is controlled by tuning the block mole fraction of the poly(Lewis base) (polyLB, i.e., PDMAEMA) within the diblock copolymer, resulting in spherical micelles, vesicles, and large compound vesicles with an increasing PDMAEMA block mole fraction. The self-assembly is driven by binding-induced bond polarization during Lewis adduct formation, where the degree of bond polarization of the Lewis adducts is quantified by measuring the dielectric constant of adduct mixtures. We propose that the large dipole formed because of the Lewis adduct leads to substantial changes in the polymer–solvent interactions, driving the self-assembly. The reported findings regarding the Lewis adduct-induced self-assembly in polymer systems have far-ranging potential implications in supermolecular chemistry.

中文翻译：

---

聚合物溶液中结合诱导的键极化驱动胶束和囊泡的形成


通过供体-受体相互作用驱动自组装以产生纳米结构材料是超分子化学的一个关键特征;然而，分子水平变化与更大规模组织之间的联系仍然未知。在这里，我们提出了 Lewis 加合物结合诱导键极化的概念，其中 Lewis 加合物的形成导致一个大偶极子（这里估计为 12.5 D），显着改变了不同物种之间的分子间相互作用并诱导自组装。具体来说，二嵌段共聚物聚（2-（二甲氨基）甲基丙烯酸乙酯）-聚苯乙烯 （PDMAEMA-PS） 在甲苯中加入路易斯酸三（五氟苯基）硼烷 （BCF） 后自组装成纳米结构的胶体聚集体。纳米结构胶体结构的形态是通过调整二嵌段共聚物内聚（路易斯碱）（polyLB，即 PDMAEMA）的嵌段摩尔分数来控制的，从而产生球形胶束、囊泡和大化合物囊泡，PDMAEMA 嵌段摩尔分数增加。在 Lewis 加合物形成过程中，自组装由结合诱导的键极化驱动，其中 Lewis 加合物的键极化程度通过测量加合物混合物的介电常数来量化。我们提出，由于 Lewis 加合物形成的大偶极子导致聚合物-溶剂相互作用的实质性变化，从而驱动自组装。关于 Lewis 加合物诱导的聚合物系统中自组装的报道结果在超分子化学中具有深远的潜在影响。