J Am Chem Soc. 2013 Nov 6;135(44):16497-506. doi: 10.1021/ja4073645.
A detailed analysis of the conformational states of self-assembled, stereoselectively deuterated benzene-1,3,5-tricarboxamides ((S,S,S)-D-BTAs) reveals four different conformers for the supramolecular polymers. The relative amount of the conformers depends on the solvent structure and the temperature. With the help of a model, the thermodynamic parameters that characterize the different conformational states were quantified as well as the amount of the species that occur at different stages of the polymerization process. The results show that small changes in the stability between different types of conformers formed by (S,S,S)-D-BTAs—in the order of a few J mol(–1)—arise from the combination of interactions between the solvent/supramolecular aggregate, temperature, and solvent structure. While the introduction of a deuterium label allows to sensitively probe the solvophobic effects in the supramolecular aggregation, a rationalization of the observed effects on a molecular level is not yet straightforward but is proposed to result from subtle effects in the vibrational enthalpy and entropy terms of the isotope effect.
对自组装的、立体选择性氘代苯-1,3,5-三羧酸酰胺（(S,S,S)-D-BTAs）的构象状态进行详细分析，揭示了超分子聚合物的四种不同构象。构象的相对含量取决于溶剂结构和温度。借助模型，定量了表征不同构象态的热力学参数以及聚合过程不同阶段出现的物质的量。结果表明，(S,S,S)-D-BTAs 形成的不同构象类型之间的稳定性变化很小——在几个 J mol(–1) 的范围内——源于溶剂/超分子聚集体、温度和溶剂结构之间的相互作用。虽然引入氘标记可以灵敏地探测超分子聚集中的疏溶剂效应，但对观察到的效应在分子水平上的合理化并不简单，据推测，这是由于同位素效应的振动焓和熵项中的微妙效应所致。
