[Synthesis, Aggregation, Self-assembly, and Dynamic Properties of Helicene Oligomers]

Biological systems exhibit dynamic phenomena at the macroscopic level as a result of the hierarchical integration of phenomena at the molecular level. For example, a number of amino acids compose actin proteins, which form three-dimensional structures determined by the sequence of amino acids. They form fibers by self-assembly, which then form ordered structures such as meshes, lyotropic liquid crystals (LCs), and bundles. The dynamic and reversible polymorphism between these nano- to centimeter-sized ordered structures is essential for biological functions such as cell division, contraction, and locomotion. To understand biological systems and create new functional materials, it is essential to develop a methodology to integrate phenomena at the molecular level into those at the macroscopic level using synthetic molecules. In this research, synthetic oligomers containing helicenes, which exhibit reversible structural transitions between cylindrical double helices and random coils in response to thermal stimuli, were employed as building blocks for the development of such a methodology. The properties of homo- and hetero-double helices at the molecular level were first controlled by taking advantage of the diversity of their molecular structures. Then, nano- to micrometer-sized structures were constructed by the self-assembly of hetero-double helices, which include fibers/gels, vesicles, and lyotropic LCs, and their dynamic properties were controlled by molecular design.