Highly Emissive Covalent Organic Frameworks
Highly Emissive Covalent Organic Frameworks
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DOI：
10.1021/jacs.6b02700
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发表时间：
2016-05-11
影响因子：
15
通讯作者：
Jiang, Donglin
中科院分区：
文献类型：
--
作者：
Dalapati, Sasanka;Jin, Enquan;Jiang, Donglin
由于π-π堆叠层的聚集引起的淬灭（ACQ），很少实现高度发光的共价有机框架（COF）。在这里，我们报告了一个一般性的战略，设计高发射COFs通过引入聚集诱导发射（AIE）机制。将AIE活性单元整合到多边形顶点中产生具有周期性π堆叠的柱状AIE阵列的结晶多孔COF。这些柱状AIE π-阵列主导COF的发光，通过层内共价键合和层间非共价π-π相互作用的协同结构锁定效应实现优异的量子产率，并用作高度灵敏的传感器以报告低至亚ppm水平的氨。我们的策略突破了COF基于ACQ的机械限制，并开辟了一条探索高发射COF材料的道路。
Highly luminescent covalent organic frameworks (COFs) are rarely achieved because of the aggregation-caused quenching (ACQ) of pi-pi stacked layers. Here, we report a general strategy to design highly emissive COFs by introducing an aggregation-induced emission (AIE) mechanism. The integration of AIE-active units into the polygon vertices yields crystalline porous COFs with periodic pi-stacked columnar AIE arrays. These columnar AIE pi-arrays dominate the luminescence of the COFs, achieve exceptional quantum yield via a synergistic structural locking effect of intralayer covalent bonding and interlayer noncovalent pi-pi interactions and serve as a highly sensitive sensor to report ammonia down to sub ppm level. Our strategy breaks through the ACQ-based mechanistic limitations of COFs and opens a way to explore highly emissive COF materials.