Department of Organic Chemistry, University of Complutense of Madrid, Ciudad Universitaria sn, Spain.
Spanish National Centre of Biotechnology (CNB), CSIC, E-28049, Madrid, Spain.
Chemistry. 2018 May 28;24(30):7755-7760. doi: 10.1002/chem.201801238. Epub 2018 May 3.
Supramolecular chemistry has evolved from the traditional focus on thermodynamic on-pathways to the complex study of kinetic off-pathways, which are strongly dependent on environmental conditions. Moreover, the control over pathway complexity allows nanostructures to be obtained that are inaccessible through spontaneous thermodynamic processes. Herein, we present a family of peptide-based π-extended tetrathiafulvalene (exTTF) molecules that show two self-assembly pathways leading to two distinct J-aggregates, namely metastable (M) and thermodynamic (T), with different spectroscopic, chiroptical, and electrochemical behavior. Moreover, cryo-transmission electron microscopy (cryo-TEM) reveals a different morphology for both aggregates and a direct observation of the morphological transformations from tapes to twisted ribbons.
超分子化学已经从传统的关注热力学途径演变为对动力学非途径的复杂研究，这强烈依赖于环境条件。此外，对途径复杂性的控制使得可以获得通过自发热力学过程无法获得的纳米结构。在此，我们提出了一类基于肽的π扩展四硫富瓦烯（exTTF）分子，它们显示出两种自组装途径，导致两种不同的 J 聚集体，即亚稳（M）和热力学（T），具有不同的光谱、手性光学和电化学行为。此外，低温透射电子显微镜（cryo-TEM）揭示了两种聚集体的不同形态，并且可以直接观察到从带材到扭曲带的形态转变。
