Photoswitchable Photon Upconversion from Turn-on Mode Fluorescent Diarylethenes  

作　　者：Jianlei Han Jian Zhang Tonghan Zhao Minghua Liu Pengfei Duan 

机构地区：[1]CAS Center for Excellence in Nanoscience,CAS Key Laboratory of Nanosystem and Hierarchical Fabrication,National Center for Nanoscience and Technology(NCNST),Beijing 100190 [2]College of Chemistry,Chemical Engineering and Materials Science,Collaborative Innovation Center of Functionalized Probes for Chemical Imaging in Universities of Shandong,Key Laboratory of Molecular and Nano Probes,Ministry of Education,Institute of Molecular and Nano Science,Shandong Normal University,Jinan 250014 [3]Beijing National Laboratory for Molecular Science,CAS Key Laboratory of Colloid,Interface and Chemical Thermodynamics,Institute of Chemistry,Chinese Academy of Sciences,Beijing 100190 [4]University of Chinese Academy of Sciences,Beijing 100049

出　　处：《CCS Chemistry》2021年第1期665-674,共10页中国化学会会刊（英文）

基　　金：supported by National Natural Science Foundation of China(51673050,91856115,21905065,and 21907060);the Ministry of Science and Technology of the People’s Republic of China(2017YFA0206600 and 2016YFA0203400);support of China Postdoctoral Science Foundation(BX20180082 and 2019M650603).

摘　　要：Photon upconversion(UC)is one kind of anti-Stokes shift process,which generally requires a combination of two or more low-energy photons to produce one high-energy photon.However,another interesting anti-Stokes process,namely,single-photon-absorption-based upconversion(SPA-UC),can take place by exciting thermally excited vibrational-rotational energy levels of ground state to the first level of excited state.This phenomenon is less involved in organic systems due to the limitation of appropriate materials.Herein,for the first time,we have demonstrated a series of turn-on mode fluorescent diarylethenes,including Thiophene-and p-alkoxybromo-substituted phenyl-substituted derivatives(DAES and DAEC4),which exhibited SPA-UC phenomenon in the closed-ring state.An anti-Stokes shift of 0.36 eV was observed in these molecules,which was the highest value accessible in such UC systems.A relatively high quantum efficiency(13.5%)was evaluated through a relative method by using methylene blue as a standard.Phonon-assisted or hot band absorption was in charge of the achievement of SPA-UC.Besides,the upconverted emission could be switched on/off by cyclization and cycloreversion reaction,regulated by UV–visible light.Thus,this unique finding of the SPA-UC phenomena in photoswitchable diarylethenes might enrich the development of new molecular engineering strategies for designing photofunctional materials.

关 键 词：photon upconversion PHOTOCHROMISM DIARYLETHENE single-photon absorption fluorescence 

分 类 号：O62[理学—有机化学]