Department of Applied Chemistry, Graduate School of Urban Environmental Sciences, Tokyo Metropolitan University, Minami-Osawa, Hachioji, Tokyo, 192-0397, Japan.
Department of Applied Chemistry, Graduate School of Engineering, Osaka Prefecture University, 1-1 Gakuen-cho, Naka-ku, Sakai, Osaka, 599-8531, Japan.
Chem Asian J. 2020 Mar 16;15(6):787-795. doi: 10.1002/asia.201901740. Epub 2020 Feb 18.
We found that boronate particles (BP), as a self-assembled system prepared by sequential dehydration of benzene-1,4-diboronic acid with pentaerythritol, showed greenish room-temperature phosphorescence (RTP). This emission was observed in both solid and dispersion state in water. To understand the RTP properties, X-ray crystallographic analysis, and density functional theory (DFT) and time-dependent DFT at M06-2X/6-31G(d,p) level were performed using 3,9-dibenzo-2,4,8,10-tetraoxa-3,9-diboraspiro[5.5]undecane (1) as a model compound. Our interest in functionalizing the RTP-active particles led us to graft Rhodamine B onto their surface. The resulting system emitted a dual afterglow via a Förster-type resonance energy transfer process from the BP in the excited triplet state to Rhodamine B acting as an acceptor fluorophore. This emission behavior was used for ratiometric afterglow sensing of water content in THF with a detection limit of 0.28 %, indicating that this study could pave the way for a new strategy for developing color-variable afterglow chemosensors for various analytes.
我们发现硼酸酯粒子（BP）作为苯-1,4-二硼酸与季戊四醇通过顺序脱水制备的自组装体系，在室温下显示出绿色磷光（RTP）。这种发射在水的固态和分散态中都可以观察到。为了理解 RTP 性质，使用 3,9-二苯并-2,4,8,10-四氧杂-3,9-二硼螺[5.5]十一烷（1）作为模型化合物进行了 X 射线晶体学分析和密度泛函理论（DFT）和 M06-2X/6-31G(d,p)水平的时间相关 DFT 计算。我们对功能化 RTP 活性粒子的兴趣促使我们将罗丹明 B 接枝到它们的表面上。所得系统通过从处于激发三重态的 BP 到作为受体荧光团的罗丹明 B 的Förster 型共振能量转移过程发出双重余晖。这种发射行为用于通过比率后发光法检测四氢呋喃中含水量，检测限为 0.28%，表明这项研究为开发用于各种分析物的可变颜色余晖化学传感器的新策略铺平了道路。
