Huang Hsin-Hua, Song Kyung Seob, Prescimone Alessandro, Aster Alexander, Cohen Gabriel, Mannancherry Rajesh, Vauthey Eric, Coskun Ali, Šolomek Tomáš
Department of Chemistry, University of Basel St. Johanns-Ring 19 CH-4056 Basel Switzerland
Department of Chemistry, University of Fribourg Chemin Du Musée 9 1700 Fribourg Switzerland
Chem Sci. 2021 Mar 9;12(14):5275-5285. doi: 10.1039/d1sc00347j.
A simultaneous combination of porosity and tunable optoelectronic properties, common in covalent organic frameworks, is rare in shape-persistent organic cages. Yet, organic cages offer important molecular advantages such as solubility and modularity. Herein, we report the synthesis of a series of chiral imine organic cages with three built-in rylene units by means of dynamic imine chemistry and we investigate their textural and optoelectronic properties. Thereby we demonstrate that the synthesized rylene cages can be reversibly reduced at accessible potentials, absorb from UV up to green light, are porous, and preferentially adsorb CO over N and CH with a good selectivity. In addition, we discovered that the cage incorporating three perylene-3,4:9,10-bis(dicarboximide) units displays an efficient delayed fluorescence. Time-correlated single photon counting and transient absorption spectroscopy measurements suggest that the delayed fluorescence is likely a consequence of a reversible intracage charge-separation event. Rylene cages thus offer a promising platform that allows combining the porosity of processable materials and photochemical phenomena useful in diverse applications such as photocatalysis or energy storage.
共价有机框架中常见的孔隙率和可调谐光电特性的同时结合，在形状持久的有机笼中很少见。然而，有机笼具有重要的分子优势，如溶解性和模块化。在此，我们报告了通过动态亚胺化学合成一系列具有三个内置苝单元的手性亚胺有机笼，并研究了它们的结构和光电特性。由此我们证明，合成的苝笼可以在可及电位下可逆还原，吸收从紫外光到绿光的光，具有多孔性，并且对CO的吸附优先于N和CH，具有良好的选择性。此外，我们发现包含三个苝-3,4:9,10-双（二甲酰亚胺）单元的笼显示出高效的延迟荧光。时间相关单光子计数和瞬态吸收光谱测量表明，延迟荧光可能是笼内可逆电荷分离事件的结果。因此苝笼提供了一个有前景的平台，能够将可加工材料的孔隙率与光催化或能量存储等多种应用中有用的光化学现象相结合。
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