2021 Fiscal Year Final Research Report

Synthesis and Development of Chemiluminescent Soft Crystals for Spatiotemporal Control of the Stimulus-responsive Functions

Planned Research

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Project Area	Soft Crystals: Science and Photofunctions of Easy-Responsive Systems with Felxibility and Higher-Ordering
Project/Area Number	17H06371
Research Category	Grant-in-Aid for Scientific Research on Innovative Areas (Research in a proposed research area)
Allocation Type	Single-year Grants
Review Section	Science and Engineering
Research Institution	The University of Electro-Communications
Principal Investigator	Hirano Takashi 電気通信大学, 大学院情報理工学研究科, 教授 (20238380)
Co-Investigator(Kenkyū-buntansha)	石田尚行電気通信大学, 大学院情報理工学研究科, 教授 (00232306) 池田浩大阪府立大学, 工学(系)研究科(研究院), 教授 (30211717) 末延知義大阪大学, 工学研究科, 助教 (90271030)
Project Period (FY)	2017-06-30 – 2022-03-31
Keywords	ソフトクリスタル / 化学発光 / 分子結晶 / 有機過酸化物 / 光物性 / X線回折 / 反応速度論 / 熱物性
Outline of Final Research Achievements	We have constructed the soft crystal chemiluminescence (CL) systems, in which a crystalline-state CL reaction is able to progress by soft character of a molecular crystal. A crystalline-state CL reaction was initiated by heating a crystal sample of a 1,2-dioxetane derivative linked with a fluorophore and its progress has been tracked by detecting CL emission in real time together with XRD and thermophysical measurements. We gave the world’s first demonstration of the dynamic behaviors of the crystalline-state CL reactions including zero-order kinetics. The methodology to compare the crystals of the isomers of the 1,2-dioxetanes provided valuable evidences that the differences in the crystal structures are related to the luminescence property, reactivity, and phase-transition property associated with the reaction progress. These results are useful to construct the theory of kinetics and energetics for the crystalline-state reactions and to develop functional CL materials.
Free Research Field	光化学
Academic Significance and Societal Importance of the Research Achievements	結晶化学反応は、環境負荷を低減する固相有機合成、医薬品結晶の安定性の向上、動くソフトマテリアル開発において注目される。ソフトクリスタル化学発光系は結晶内で進行する化学反応を「発光」によってリアルタイム追跡できる特徴を持つため、発光性や反応性の結晶構造依存性、結晶化学反応の速度論的特徴、反応進行によって誘起される結晶相変化に関する情報を簡便かつ詳細に得ることができる。そのため、本発光系は結晶化学反応の理論的基盤の構築を進歩させると共に、上記の注目分野の発展に貢献できる。本発光系の材料化は未開拓であり、刺激応答性などの機能を有する発光性結晶材料の開発基盤も提供する。