Development of fluorescent supramolecular materials based on the fluorescent double-tweezer-shaped molecules

2021 Fiscal Year Final Research Report

• Project/Area Number: 20K15255
• Research Category: Grant-in-Aid for Early-Career Scientists
• Allocation Type: Multi-year Fund
• Review Section: Basic Section 33010:Structural organic chemistry and physical organic chemistry-related
• Research Institution: Tokyo Institute of Technology
• Principal Investigator: Yamashina Masahiro 東京工業大学, 理学院, 助教 (80847153)
• Project Period (FY): 2020-04-01 – 2022-03-31
• Keywords: 両親媒性分子 / 分子内包 / アザイリド / シュタウディンガー反応

Outline of Final Research Achievements

Amphiphilic molecules that can self-aggregate and encapsulate guest molecules in water have attracted attention in various fields. Herein, we report the development of new amphiphiles through the Staudinger reaction. Simple mixing of chlorinated aryl azide with a hydrophilic moiety and various triarylphosphines (PAr3) gave rise to azaylide-based amphiphiles NPAr3, rapidly and quantitatively. The obtained NPAr3 formed ca. 2 nm-sized spherical aggregates (NPAr3)n in water. The hydrolysis of NPAr3 was significantly suppressed as compared with those of non-chlorinated amphiphiles. Computational studies revealed that the stability is mainly governed by the decrease in LUMO around the phosphorus atom owing to the o-substituted halogen groups. Furthermore, hydrophobic dyes such as Nile red and BODIPY were encapsulated by the spherical aggregates (NPAr3)n in water.

Free Research Field

超分子化学

Academic Significance and Societal Importance of the Research Achievements

本研究では、シュタウディンガー反応を用い、親水性アジ化物と疎水性リン化合物をアザイリドで直接連結することで、前例のない両親媒性分子の簡便な合成法の開発に成功した。リン化合物は有機合成で幅広く使われており、その有用性・汎用性の高さから膨大な種類が販売・報告されている。即ち本成果は、アジ化物とリン化合物の組み合わせ次第で、両親媒性分子に留まらず、多種多様な機能性分子の創出手段の一つになることが期待される。今後は、アザイリドの特異的な反応性や化学的性質を通じて、アジ化物とリン化合物の性質を融合させた新材料を開発していく計画である。