文献类型：期刊文献

英文题名：Facile construction of AIE-active pyridinyl-diphenylacrylonitrile derivatives with optical properties finely modulated by D-A regulation

作者：Wang, Yipu[1];Zhong, Yanlang[1];Zhang, Xinyi[1];Qu, Da-Hui[1];Mei, Dong[2];Mei, Ju[1]

机构：[1]East China Univ Sci & Technol, Frontiers Sci Ctr Materiobiol & Dynam Chem, Inst Fine Chem,Sch Chem & Mol Engn,Joint Int Res, Feringa Nobel Prize Scientist Joint Res Ctr,Key L, 130 Meilong Rd, Shanghai 200237, Peoples R China;[2]Capital Med Univ, Natl Ctr Childrens Hlth, Beijing Childrens Hosp, Clin Res Ctr, Beijing 100045, Peoples R China

年份：2022

卷号：6

期号：15

起止页码：2103

外文期刊名：MATERIALS CHEMISTRY FRONTIERS

收录：;EI(收录号：20223312579648);WOS:【SCI-EXPANDED(收录号:WOS:000820617400001)】；

基金：We are grateful for the financial support from the NSFC/China (21788102, 21875064, 81903545, and 21790361), the Shanghai Science and Technology Commission Basic Project-Shanghai Natural Science Foundation (21ZR1417600), the Shanghai Municipal Science and Technology Major Project (2018SHZDZX03), the Programme of Introducing Talents of Discipline to Universities (B16017), the Shanghai Science and Technology Committee (17520750100), the Beijing New-Star Plan of Science and Technology (Z201100006820009), and the Fundamental Research Funds for the Central Universities.

语种：英文

外文关键词：Charge transfer - Chemical reactions - Density functional theory - Electrons - Functional materials - Gas generators - Light - Single crystals

摘要：A series of simply-structured adducts of pyridine and diphenylacrylonitrile, i.e. PyDPACNs, featuring aggregation-induced emission (AIE) characteristics have been designed according to the principle of restriction of intramolecular motion (RIM), and facilely constructed via simple Knoevenagel condensation and Suzuki-Miyaura cross-coupling. The optical properties of these AIEgens could be finely modulated by the regulation of the electron-donating (D)-electron-accepting (A) effect, with the substituent on the terminal of the PyDPACN framework ranging from a strong D to strong A group. Interestingly, the role of the pyridinyl group could be flipped from an electron acceptor to an electron donor. Emission maxima of these PyDPACNs vary from 439 to 635 nm, covering nearly the whole visible light region. Amongst them, PyDPACNs with the strongest D (i.e. PyDPACN-N) or A group (i.e. PyDPACN-TCF) show the most significant intramolecular charge transfer (ICT) effect. PyDPACN-TCF possesses a high singlet-oxygen generation ability under white-light irradiation as well as moderate cytotoxicity in dark. The AIE mechanism, i.e. the RIM principle, was clarified through X-ray single crystal diffraction analysis. Density functional theory (DFT) calculations uncovered the electron-cloud distribution of PyDPACN derivatives in the ground and excited states, which not only reveals the role reversal of the pyridinyl moiety and the mutual conversion of D and A groups, but also provides an explanation for their distinct photophysical behaviours. The present work could provide both a new avenue for spectral modulation and effective molecular platforms for the development of advanced functional materials.