Hydrogen-bonded supermacrocycles (rosettes) composed of dinaphthylethene π-conjugated systems show unique supramolecular polymorphism affording nanorings and nanorods via kinetically controlled self-assembly.
Angewandte Chemie International Edition 2023年9月22日 査読有り
Insolubility of functional molecules caused by polymorphism sometimes poses limitations for their solution‐based processing. Such a situation can also occur in the preparation processes of supramolecular polymers formed in a solution. An effective strategy to address this issue is to prepare amorphous solid states by introducing a “coformer” molecule capable of inhibiting the formation of an insoluble polymorph through co‐aggregation. Herein, inspired by the coformer approach, we demonstrated a solubility enhancement of a barbiturate π‐conjugated compound that can supramolecularly polymerize through six‐membered hydrogen‐bonded rosettes. Our newly synthesized supramolecular coformer molecule features a sterically demanding methyl group in the π‐conjugated unit of the parent molecule. Although the parent molecule exhibits low solubility in nonpolar solvents due to the formation of a crystalline polymorph comprising a tape‐like hydrogen‐bonded array prior to the supramolecular polymerization, mixing with the coformer compound enhanced the solubility by inhibiting mesoscopic organization of the tapes. The two monomers were then co‐polymerized into desired helicoidal supramolecular polymers through the formation of heteromeric rosettes.
Hiroki Itabashi, Keigo Tashiro, Shumpei Koshikawa, Sougata Datta, Shiki Yagai
Chemical Communications 59 7375-7378 2023年5月 査読有り
Toroidal and helicoidal supramolecular polymers allow us to observe distinct kinetics of secondary nucleation on the aggregate surface and elongation from the facet of aggregate termini on seeded supramolecular polymerization.
Yamada, H., Yagai, S. (担当:共編者(共編著者), 範囲:Chapter4 Hydrogen-Bond-Directed Nanostructurization of Oligothiophene Semiconductors for Organic Photovoltaics)
T. Karatsu, S. Yagai, A. Kitamura (担当:共著, 範囲:Chapter6, Intramolecular Interactions of Aryloligosilanes: Functions in their Excimer/Exciplex Formation, Charge-transfer, and Energy Transfer Processes)
M. A. Cato, Ed., Nova Science Pub Inc 2006年2月28日 (ISBN: 1594544948)