基于脱氢枞酸二芳胺的D-A-D型聚集诱导红光化合物的合成及其光谱性能OA北大核心CSTPCD
Synthesis and Spectral Properties of Dehydroabioic Acid Diarylamine-based D-A-D-type Aggregation-induced Red-light Compound
以12-脱氢枞酸二芳胺为供体(D),蒽醌基团为受体(A),通过C-N偶联的方法合成D-A-D型化合物6,6'-((9,10-二氧代-9,10-二氢蒽-2,6-二基)双((4-甲氧基苯基)氮二基))双(7-异丙基-1,4-二甲基-1,2,3,4,4a,9,10,10-八氢蒽-1-羧酸酯)(2DDPA-AQ),用核磁共振波谱和质谱表征其结构.测试2DDPA-AQ的紫外吸收光谱、荧光发射光谱、荧光量子产率及寿命、溶致变色效应、聚集诱导发光特性和抗光漂白特性;通过理论计算探讨其结构与性能间的关系.研究结果显示:2DDPA-AQ在甲苯中的最大紫外吸收波长为449 nm,在甲苯中和固体状态下的最大发射波长分别为630和653 nm,呈现红光发射;2DDPA-AQ在正己烷、环己烷、甲苯、二氧六环、四氢呋喃、乙酸乙酯中的最大荧光发射波长分别为578、584、630、638、645、650 nm.2DDPA-AQ的最大发射波长随溶剂极性的增大依次红移,表明其具有溶致变色效应和分子内的电荷转移行为.2DDPA-AQ的荧光发射强度随水/四氢呋喃(H2O/THF)中水体积分数的变化趋势表明其具有聚集诱导发光(AIE)特性;2DDPA-AQ在水体积分数为95％的H2O/THF中经连续30 min的紫外灯照射后,其荧光发射强度仅轻微减弱,表明其具有较强的抗光漂白特性.由实验所得数据计算2DDPA-AQ的HOMO/LUMO能级为-5.18 eV/-2.86 eV,带隙值为2.32 eV,按理论计算2DDPA-AQ的HOMO/LUMO能级为-4.91 eV/-2.14 eV,带隙值为2.77 eV,实验值与理论值略有偏差,由数据可知:2DDPA-AQ具有较窄带隙,符合红光分子的带隙特征.
A D-A-D-type compound named 6,6'-((9,10-dioxo-9,10-dihydroanth-racene-2,6-diyl)bis((4-methoxyphenyl)azanediyl))bis(7-isopropyl-1,4-dimethyl-1,2,3,4,4a,9,10,10a-octah-ydrophenanthr-ene-1-carboxylate)(2DDPA-AQ)was synthesized using 12-dehydroabietic acid diarylamine as the donor(D)and anthraquinone group as the acceptor(A),and its structure was characterized by the NMR and MS.The UV-Vis absorption and the fluorescence emission spectrum,the fluorescence quantum yield and lifetime,solvatochromic effect,aggregation-induced luminescence and photobleaching resistance characteristics were tested.The theoretical calculation was used to analyze the relationship between its structure and properties.The research results were as follows:the maximum ultraviolet absorption wavelength of 2DDPA-AQ in toluene was 449 nm,while the maximum emission wavelengths in toluene and solid state were 630 and 653 nm,showing red light emission.The maximum fluorescence emission wavelengths of 2DDPA-AQ in n-hexane,cyclohexane,toluene,dioxane,tetrahydrofuran,and ethyl acetate were 578,584,630,638,645,and 650 nm,respectively.The red shift of the maximum emission wavelength of 2DDPA-AQ along with the increase of the polarity of the solvent showed that it had solvatochromism effect and intramolecular charge transfer behaviour.The variation trend of fluorescence emission intensity of 2DDPA-AQ with water volume fraction in water/tetrahydrofuran(H2O/THF)indicated its aggregation induced emission(AIE)characteristics.After continuous 30 minutes of UV lamp irradiation in a H2O/THF mixed solution with water volume fraction of 95％,the fluorescence emission intensity of 2DDPA-AQ only slightly weakened,indicating its strong anti-photobleaching properties.Based on the experimental data,the HOMO/LUMO energy level of 2DDPA-AQ was-5.18 eV/-2.86 eV with a bandgap value of 2.32 eV.The theoretically calculated HOMO/LUMO energy level was-4.91 eV/2.14 eV with a bandgap value of 2.77 eV.The data showed that 2DDPA-AQ had a relatively narrow bandgap,which was consistent with the bandgap characteristics of red light molecules.
许立君;窦立薇;罗汉荣;高宏;商士斌;宋湛谦
中国林业科学研究院林产化学工业研究所||江苏省生物质能源与材料重点实验室||国家林业和草原局林产化学工程重点实验室||林木生物质低碳高效利用国家工程研究中心,江苏南京 210042||南京林业大学江苏省林业资源高效加工利用协同创新中心,江苏南京 210037杭州弘纶浆纸有限公司,浙江杭州 311407中国林业科学研究院林产化学工业研究所||江苏省生物质能源与材料重点实验室||国家林业和草原局林产化学工程重点实验室||林木生物质低碳高效利用国家工程研究中心,江苏南京 210042
化学工程
脱氢枞酸二芳胺蒽醌D-A-D型聚集诱导红光发射
ehydroabiotic acid diarylamineanthraquinoneD-A-D typeaggregation-induced red light emission
《林产化学与工业》 2024 (004)
1-8 / 8
国家自然科学基金资助项目(32171729)
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