以丙炔酸甲酯、丙炔酸乙酯和丙炔酸叔丁酯为原料,在常温条件下经三乙烯二胺催化的自偶联反应合成了3组含有烯炔二酯结构的有机荧光化合物。采用核磁共振波谱仪和傅里叶变换红外光谱仪验证了化合物的结构。采用荧光分光光度计和紫外-可见分光光度计探究了3组化合物的光学性能。结果表明:3组化合物除了具有非共轭荧光聚合物特有的浓度增强发射和激发波长依赖荧光现象以外,还表现出浓度和化合物结构诱导红移发射特性,即适宜的化合物内阻端基结构和相对高的化合物浓度,有助于诱导发射波长红移。该方法实现了以化合物结构和浓度对有机荧光化合物的发射波长和发光颜色调控,为红移发射和多彩有机荧光材料的设计合成提供了新的思路。
Using methyl propionate,ethyl propionate,and tert-butyl propionate as raw materials,three groups of organic fluorescent compounds containing alkenyl diester structures were synthesized via a triethylenediamine-catalyzed homocoupling reaction under ambient conditions.The structures of the compounds were confirmed by nuclear magnetic resonance (NMR) spectroscopy and Fourier-transform infrared (FT-IR) spectroscopy.The optical properties of the three groups of compounds were investigated using fluorescence spectrophotometry and ultraviolet-visible (UV-Vis) spectrophotometry.The results demonstrated that,in addition to exhibiting concentration-enhanced emission and excitation wavelength-dependent fluorescence characteristic of non-conjugated fluorescent polymers,these compounds also displayed concentration- and structure-induced red-shifted emission properties.Specifically,an appropriate internal steric hindrance from the terminal groups and a relatively high compound concentration facilitated the red-shifting of the emission wavelength.This approach achieved modulation of the emission wavelength and luminescence color of organic fluorescent compounds through structural design and concentration control,providing a new strategy for the design and synthesis of red-shifted and multicolor organic fluorescent materials.
[1] 杨冰,李瑛,徐创霞,等.有机荧光材料研究进展[J].化学研究与应用,2003,15(1):11-16.
[2] Bauri K,Saha B,Banerjee A,et al.Recent advances in the development and applications of nonconventional luminescent polymers[J].Polymer Chemistry,2020,11(46):7293-7315.
[3] 张红燕,蒋其民,史凌月,等.羟基-炔点击反应制备具有红移发射的非传统荧光化合物及性能[J].化工新型材料,2024,52(1):238-242.
[4] 黄田,汪昭旸,秦安军,等.含非典型性生色团的发光聚合物[J].化学学报,2013,71(7):979-990.
[5] Shang C,Wei N,Zhuo H,et al.Highly emissive poly(maleic anhydride-alt-vinyl pyrrolidone) with molecular weight-dependent and excitation-dependent fluorescence[J].Journal of Materials Chemistry C,2017,5(32):8082-8090.
[6] Barbara K,Kayla M,Donala T,et al.Non-traditional intrinsic luminescence:inexplicable blue fluorescence observed for dendrimers,macromolecules and small molecular structures lacking traditional/conventional luminophores[J].Progress in Polymer Science,2019,90:35-117.
[7] 唐金玉,江焕峰,邓国华,等.Glaser偶联反应研究进展[J].有机化学,2005,25(12):1503-1507.
[8] 陶李明,梁云,周芸,等.DABCO作为高效配体促进钯催化末端炔烃自偶联反应研究[J].化学研究与应用,2008,20(10):1292-1296.
[9] Han T,Chen S,Wang X,et al.Autonomous visualization of damage in polymers by metal-free polymerizations of microencapsulated activated alkynes[J].Advanced Science,2022,9(8):2105395.
[10] Jiang Q,Zhang H,Jiang Q,et al.Hydroxylyne click polymerization:a facile strategy toward poly(vinyl amino ether ester)s with color-tunable luminescence[J].Polymer Chemistry,2023,14(11):1232-1240.
[11] Chu B,Zhang H,Hu L,et al.Altering chain flexibility of aliphatic polyesters for yellow-green clusteroluminescence in 38% quantum yield[J].Angewandte Chemie International Edition,2022,61(6):202114117.
[12] Deng J,Jia H,Xie W,et al.Nontraditional organic/polymeric luminogens with red-shifted fluorescence emissions[J].Ma-cromolecular Chemistry and Physics,2022,223(5):2100425.
基金资助
江苏省高等学校基础科学(自然科学)研究重大项目(24KJA430004)
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