Moriuchi-Kawakami Takayo, Hisada Youji, Higashikado Akihisa, Inoue Tsubasa, Fujimori Keiichi, Moriuchi Toshiyuki
Department of Applied Chemistry, Faculty of Engineering, Osaka Institute of Technology, 5-16-1 Omiya, Asahi, Osaka 535-8585, Japan.
Department of Applied Chemistry, Graduate School of Engineering, Osaka University, 2-1 Yamada-oka, Suita, Osaka 565-0871, Japan.
Molecules. 2017 Aug 25;22(9):1415. doi: 10.3390/molecules22091415.
A new malonate possessing two pyrene moieties was synthesized as a fluoroionophore, and its structure and fluorescence spectroscopic properties were investigated. When excited at 344 nm in acetonitrile/chloroform (9:1, /), the synthesized bispyrenyl malonate has the fluorescence of intramolecular excimer (λ = 467 nm) emissions and not a pyrene monomer emission (λ = 394 nm). A large absolute fluorescence quantum yield was obtained in the solid state (Φ = 0.65) rather than in solution (Φ = 0.13). X-ray crystallography analysis clarified the molecular structure and alignment of the bispyrenyl malonate in the crystal phase, elucidating its fluorescence spectroscopic properties. Such analysis also suggests there are intramolecular C-H···π interactions and intermolecular π···π interactions between the pyrenyl rings. Interestingly, the synthesized bispyrenyl malonate exhibits excellent fluorescence sensing for the Cu ion. Remarkable fluorescence intensity enhancement was only observed with the addition of the Cu ion.
合成了一种含有两个芘基团的新型丙二酸酯作为氟离子载体，并对其结构和荧光光谱性质进行了研究。在乙腈/氯仿（9:1，v/v）中于344 nm激发时，合成的双芘基丙二酸酯具有分子内激基缔合物的荧光（λ = 467 nm）发射，而非芘单体发射（λ = 394 nm）。在固态下获得了较大的绝对荧光量子产率（Φ = 0.65），而在溶液中则为（Φ = 0.13）。X射线晶体学分析阐明了双芘基丙二酸酯在晶相中的分子结构和排列，解释了其荧光光谱性质。这种分析还表明芘基环之间存在分子内C-H···π相互作用和分子间π···π相互作用。有趣的是，合成的双芘基丙二酸酯对铜离子表现出优异的荧光传感性能。仅在加入铜离子时观察到显著的荧光强度增强。
