Li Ya-Jie, Cui Wei-Rong, Jiang Qiao-Qiao, Liang Ru-Ping, Li Xue-Jing, Wu Qiong, Luo Qiu-Xia, Liu Juewen, Qiu Jian-Ding
College of Chemistry, Nanchang University, Nanchang 330031, China.
Department of Chemistry, Waterloo Institute for Nanotechnology, University of Waterloo, Waterloo, Ontario N2L 3G1, Canada.
ACS Appl Mater Interfaces. 2021 Oct 13;13(40):47921-47931. doi: 10.1021/acsami.1c12958. Epub 2021 Oct 3.
Covalent organic frameworks (COFs) with stable long-range ordered arrangements are promising materials for organic optoelectronics. However, their electrochemiluminescence (ECL) from non-ECL active monomers has not been realized. Here, we report a design strategy for ECL-emitting COF family. The donors and acceptors co-crystallized and stacked into the highly aligned array of olefin-linked COFs, so that electrons can be transported freely. By this means, a tunable ECL is activated from non-ECL molecules with the maximum efficiency of 32.1% in water with the dissolved oxygen as an inner coreactant, and no additional noxious co-reactant is needed any more. Quantum chemistry calculations further demonstrate that this design reduces the COFs' band gaps and the overlap of electrons and holes in the excited state for better photoelectric properties and stronger ECL signals. This work exploits a basis to envisage the broad application potential of ECL-COFs for various biosensors and light-emitting display.
具有稳定长程有序排列的共价有机框架(COF)是有机光电子学领域颇具前景的材料。然而,尚未实现由非电化学发光(ECL)活性单体产生的ECL。在此,我们报告了一种用于发光ECL的COF家族的设计策略。供体和受体共结晶并堆叠成高度排列的烯烃连接COF阵列,从而使电子能够自由传输。通过这种方式,可从非ECL分子激活可调谐的ECL,在以溶解氧作为内共反应剂的水中,最大效率可达32.1%,且不再需要额外的有害共反应剂。量子化学计算进一步表明,这种设计减小了COF的带隙以及激发态中电子与空穴的重叠,以实现更好的光电性能和更强的ECL信号。这项工作为设想ECL-COF在各种生物传感器和发光显示器中的广泛应用潜力奠定了基础。