Solute–solvent interactions are key for the assembly and proper functioning of biomacromolecules and play important roles in many fields of organic and polymer chemistry. Despite numerous reports describing the effects of (chiral) solvents on helical conformations of (supramolecular) polymers, the combination of chiral solvents and chiral monomers is unexplored. Here we report diastereomeric differences in the supramolecular polymerization of enantiomers of chiral triphenylene-2,6,10-tricarboxamides in chiral chlorinated solvents. Competition between the preferences induced by the stereocentres of the assembled monomers and those present in the solvent molecules results in unforeseen temperature-dependent solvation effects. By combining experiments and mathematical modelling, we show that the observed differences between enantiomers originate from the combined additive entropic effects of stereocentres present in the monomer and in the solvent. Remarkably, copolymerizations show that the chiral solvent can bias the copolymer helicity and thereby overrule the helical preference of the monomers. Our results highlight the importance of cumulative solvation effects in supramolecular polymerizations.

溶质-溶剂相互作用是生物大分子组装和正常运作的关键，并在有机和高分子化学的许多领域发挥重要作用。尽管有许多报告描述了（手性）溶剂对（超分子）聚合物螺旋构象的影响，但手性溶剂和手性单体的组合尚未得到探索。在这里，我们报告了手性三亚苯基-2,6,10-三甲酰胺在手性氯化溶剂中的对映体超分子聚合中的非对映体差异。由组装单体的立体中心引起的偏好与溶剂分子中存在的偏好之间的竞争导致不可预见的温度依赖性溶剂化效应。通过结合实验和数学建模，我们表明观察到的对映体之间的差异源于单体和溶剂中存在的立构中心的组合加性熵效应。值得注意的是，共聚表明手性溶剂可以偏向共聚物的螺旋度，从而否决单体的螺旋偏好。我们的结果强调了累积溶剂化效应在超分子聚合中的重要性。