文献类型：期刊文献

英文题名：Photoswitchable Boronic Acid Derived Salicylidenehydrazone Enabled by Photochromic Spirooxazine and Fulgide Moieties: Multiple Responses of Optical Absorption, Fluorescence Emission, and Quadratic Nonlinear Optics

作者：Yuan, Jianyong[1,2];Yuan, Yizhong[1,2];Tian, Xiaohui[1,2];Wang, Hongshuai[3];Liu, Yidan[1,2];Feng, Ruishu[4]

机构：[1]East China Univ Sci & Technol, Minist Educ, Key Lab Ultrafine Mat, Shanghai, Peoples R China;[2]East China Univ Sci & Technol, Sch Mat Sci & Engn, Shanghai Key Lab Adv Polymer Mat, Shanghai, Peoples R China;[3]Soochow Univ, Inst Funct Nano & Soft Mat, Jiangsu Key Lab Carbon Based Funct Mat & Devices, Suzhou, Peoples R China;[4]Daqing Normal Univ, Sch Mechatron Engn, Daqing, Peoples R China

年份：2019

卷号：123

期号：49

起止页码：29838

外文期刊名：JOURNAL OF PHYSICAL CHEMISTRY C

收录：;EI(收录号：20195007827993);WOS:【SCI-EXPANDED(收录号:WOS:000503114100035)】；

基金：This research was supported by the Fundamental Research Funds for the Central Universities of China (22A201514002), Shanghai Leading Academic Discipline Project (No. B502), and Shanghai Key Laboratory Project (No. 08DZ2230500).

语种：英文

外文关键词：Photochromism - Nonlinear optics - Light absorption - Design for testability - Electron transitions - Fluorescence - Isomerization - Isomers

摘要：A novel protocol of the boronic acid derived salicylidenehydrazone (BASHY) core being sandwiched by photochromic spirooxazine and fulgide moieties was proposed here to design multistate fluorescent photoswitches with variable nonlinear optical (NLO) responses. Systematic investigations of their optical absorption, fluorescence emission, and static first hyperpolarizabilities (beta) were performed using density functional theory (DFT). It was found that the BASHY-based sandwiched series exhibited significant differences of absorption and emission properties among three photoisomers, which were essentially ascribed to the massive changes of corresponding electron transition characteristics quantified by hole-electron descriptors and visualized by electron density difference (EDD) plots. However, the isomerization of fulgide parts in the merocyanine (MC) form of spirooxazine failed to greatly shift maximum absorption/emission wavelengths, due to their high similarity of intrinsic transition features. Furthermore, large beta contrasts between three photoisomers were observed, which resulted from significant variations of contributions of spirooxazine and/or fulgide moieties to the total beta upon photoisomerization according to beta densities. Although the fulgide moiety contributes negatively and positively to spirooxazine (SO) isomers when fulgide switches from close (C-) to open (E-) forms, respectively, their dominant beta(xxx) values with opposite signs are still similar in magnitude, leading to quite close quadratic NLO responses. Therefore, the captivating ternary photoswitches with multiple responses of absorption, emission, and NLO were elaborately built in this context, promising to be applied as multifunctional optical materials in various scientific and technological fields.