10-甲基-10<i>H</i>-吩噻嗪-5,5-二氧化物衍生物的合成及其光物理和电化学性质

引用本文: 郑月游, 谢琼琳, 王炳喜. 10-甲基-10H-吩噻嗪-5,5-二氧化物衍生物的合成及其光物理和电化学性质[J]. 有机化学, 2016, 36(4): 803-811. doi: 10.6023/cjoc201510008 shu

Citation: Zheng Yueyou, Xie Qionglin, Wang Bingxi. Synthesis and Photophysical and Electrochemical Properties of 10-Methyl-10H-phenothiazine-5,5-dioxide Derivatives[J]. Chinese Journal of Organic Chemistry, 2016, 36(4): 803-811. doi: 10.6023/cjoc201510008 shu

10-甲基-10H-吩噻嗪-5,5-二氧化物衍生物的合成及其光物理和电化学性质

1.
福州大学材料科学与工程学院福州 350116

通讯作者: 王炳喜

基金项目:
福州大学科技发展基金(No.2010XQ02)资助项目. (No.2010XQ02)

摘要: 设计并合成了四种基于10-甲基-10H-吩噻嗪-5,5-二氧化物为受体(A),9,9-二甲基-9,10-二氢吖啶(DMAC)或吩噁嗪(PXZ)为给体(D)的分子内电荷转移荧光化合物1a、1b、2a和2b,并研究它们的光物理和电化学性质.结果表明:2a甲苯溶液的最大发射波长(λ_max)和除氧后的荧光量子效率(Φ_d)分别为422nm和0.367,而1a和1b分别为455nm、0.083和511nm、0.098.室温下1a和1b掺杂的PMMA薄膜的荧光寿命(τ_film)分别为5.78和20.00μs.根据77K时的时间分辨荧光和磷光光谱得到1a和1b的最低单重态(S₁)-最低三重态(T₁)的能级差ΔE_ST分别为0.203和0.177eV,表明它们都是潜在的热激活延迟荧光(TADF)材料.热重分析表明四种化合物热分解温度高于420℃.

关键词:

English

Synthesis and Photophysical and Electrochemical Properties of 10-Methyl-10H-phenothiazine-5,5-dioxide Derivatives

1.
College of Materials Science and Engineering, Fuzhou University, Fuzhou 350116

Corresponding author: 王炳喜

Received Date: 09 October 2015
Available Online: 15 December 2015
Fund Project:
福州大学科技发展基金(No.2010XQ02)资助项目.

Abstract: Based on 10-methyl-10H-phenothiazine-5,5-dioxide unit as an acceptor and 9,10-dihydro-9,9-dimethyl-acridine (DMAC) or phenoxazine (PXZ) as donors, four intramolecular charge transfer (ICT) compounds were designed and synthesized by Buchwald-Hartwig cross coupling reactions. Their ground-state geometries were optimized with density functional theory (DFT) at B3LYP level and vertical transition energies were calculated using the optimal Hartree-Fock (HF) exchange method. Resulting compounds were characterized by fourier transform infrared (FT-IR) spectroscopy, nuclear magnetic resonance (NMR) spectroscopy, liquid chromatography-mass (LC-MS) spectrometry and hybrid quadrupole time-of-flight mass spectrometry (QTOF). Their photophysical properties were systematically investigated. The results show that compound 2a has maximum emission wavelength (λ_max) of 422 nm in toluene and its oxygen-free one has photoluminescence quantum yield (PLQY) of 0.367. Theλ_max and PLQY for 1a and 1b are 455 nm, 0.083 and 511 nm, 0.098, respectively. Transient photoluminescence decay curves for 5 wt% 1a and 1b doped in PMMA films indicate that their delayed fluorescence lifetimes are 5.78 and 20.00 μs, respectively. According to the time-resolved fluorescence and phosphorescence spectra of 1a and 1b doped in PMMA films at 77 K, their energy gaps (ΔE_ST) between the lowest singlet state (S₁) and the lowest triplet excited state (T₁) are determined to be 0.203 and 0.177 eV, respectively, which are consistent with the theoretical values 0.232 and 0.295 eV calculated with time-dependent density functional theory (TD-DFT). As a result, 1a and 1b are expected to be potential thermally activated delayed fluorescence (TADF) materials. The electrochemical properties of the four compounds in dichloromethane solution were determined through cyclic voltammetry using TBAPF₆ as supporting electrolyte and ferrocene as internal standard. The HOMO energy levels of 1a, 1b, 2a and 2b are estimated to be -5.369, -5.111, -5.412 and -5.075 eV, respectively. The thermal properties of the four compounds were investigated by thermal gravimetric analysis under nitrogen atmosphere at a heating rate of 10 ℃·min^-1 and all compounds show good thermal stability with decomposition temperatures above 420 ℃.

Key words:

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1.
沈阳化工大学材料科学与工程学院沈阳 110142

10-甲基-10H-吩噻嗪-5,5-二氧化物衍生物的合成及其光物理和电化学性质

通讯作者: 王炳喜

English

Synthesis and Photophysical and Electrochemical Properties of 10-Methyl-10H-phenothiazine-5,5-dioxide Derivatives

Corresponding author: 王炳喜

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通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

10-甲基-10H-吩噻嗪-5,5-二氧化物衍生物的合成及其光物理和电化学性质

通讯作者: 王炳喜

English

Synthesis and Photophysical and Electrochemical Properties of 10-Methyl-10H-phenothiazine-5,5-dioxide Derivatives

Corresponding author: 王炳喜

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南： 你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

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