Construction of dioxetane-type high-efficiency chemiluminescence system assisted by intermolecular hydrogen bonding in solid phase

2019 Fiscal Year Final Research Report

• Project/Area Number: 16K05707
• Research Category: Grant-in-Aid for Scientific Research (C)
• Allocation Type: Multi-year Fund
• Section: 一般
• Research Field: Organic chemistry
• Research Institution: Kanagawa University
• Principal Investigator: Watanabe Nobuko 神奈川大学, 理学部, 助教 (40291744)
• Co-Investigator(Kenkyū-buntansha): 松本 正勝 神奈川大学, 付置研究所, 名誉教授 (10260986)
• Project Period (FY): 2016-10-21 – 2020-03-31
• Keywords: 光有機化学 / ジオキセタン / 固体化学

Outline of Final Research Achievements

Deprotonation of a dioxetane bearing a hydroxyaryl group generates an unstable dioxetane having oxidoaryl anion, which undergoes intramolecular charge-transfer-induced decomposition (CTID) to produce a singlet-excited carbonyl fragment while effectively emitting light especially in an aprotic polar solvent.
To realize highly efficient chemiluminescence of dioxetane in the solid state, we attempted CTID-type decomposition of dioxetane by using of intermolecular hydrogen bonding between a phenolic OH of dioxetane and an additive such as organic super base. As a preliminary study, we found that organic super bases can be used for CTID of dioxetane bearing a hydroxyaryl group in an organic solvent. In addition, we investigated base-induced decomposition of dioxetanes bearing a 3-hydroxyphenyl substituted with 4-p-oligophenylene moiety. Thus, we found that base-induced decomposition of these dioxetanes rapidly proceeded to give bright light even in water as well as in acetonitrile or DMSO.

Free Research Field

有機光化学

Academic Significance and Societal Importance of the Research Achievements

3-ヒドロキシフェニル置換ジオキセタンに代表されるCTID型ジオキセタンは、蛍光性化合物からの発光と異なり光源を必要とせず、また感度も高く、医療衛生分野での生体内微量物質の検出に使用されているほか、分子イメージングへの応用も行なわれている。さらにポリマーへジオキセタンを導入し、ポリマーの機械的な応答をジオキセタンの分解発光で検出する検討も行なわれている。この様な背景のもと、固体状態でジオキセタンの発光効率の良いCTID型発光系を組み上げることはジオキセタンの応用に大きく貢献すると期待できる。