2026-04-20 千葉大学
＜関連情報＞
- https://www.chiba-u.ac.jp/news/research-collab/post_659.html
- https://www.chiba-u.ac.jp/news/files/pdf/0420_stuff.pdf
- https://pubs.acs.org/doi/10.1021/jacs.6c00854
立体的にかさ高いπ発光体ダイアドの折り畳みを介した自己組織化による多方向励起子輸送を示すナノチューブの形成 Folding-Mediated Self-Assembly of Sterically Demanding π-Luminophore Dyads into Nanotubes Exhibiting Multidirectional Exciton Transport
Takumi Aizawa,Hironari Arima,Sota Mihara,Takahiro Ueno,Shotaroh Yoshii,Takuho Saito,Hiroki Itabashi,Sougata Datta,Hiroki Hanayama,Akira Sakamoto,Rintaro Shimada,Sarah E. Rogers,Martin J. Hollamby,Takashi Kajitani,Yoshiki Ishii,Go Watanabe,Koji Harano,Takuma Matsumoto,Nithin Pathoor,Martin Vacha,Hikaru Sotome,and Shiki Yagai
Journal of the American Chemical Society Published: April 1, 2026
DOI:https://doi.org/10.1021/jacs.6c00854
Abstract
The hierarchical self-assembly of folded proteins into functional nanostructures has long served as a conceptual foundation for designing synthetic polymer systems. However, the efficacy of folding-based strategies in small-molecule assemblies remains largely unproven. Here we show that sterically demanding, highly emissive diphenylanthracene derivatives, previously considered aggregation-incompetent, can be programmed to form highly ordered supramolecular nanotubes through conformational preorganization via scissor-shaped dimerization. Stepwise π-core expansion from terphenylene to diphenylnaphthalene to diphenylanthracene in the foldable supramolecular synthons induces a morphological progression from twisted ribbons to helical coils and, ultimately, to hollow nanotubes. This structural evolution is driven by folding-assisted directional π–π stacking and cooperative hydrogen bonding. Structural analyses and all-atom molecular dynamics simulations of nanotubes reveal a herringbone-like chromophore wall that reconciles dense π-stacking with curvature. Strikingly, time-resolved fluorescence anisotropy measurements demonstrate exciton migration along the tube axis (≈55 nm) and around the circumference (≈11 nm). These findings demonstrate that intramolecular folding preorganizes the spatial arrangement of intermolecular interaction sites, thereby directing curved supramolecular assembly and enabling the emergence of complex nanostructures with advanced optoelectronic function in π-systems.
