含萘酰亚胺基团的螺双芴类发光材料的制备及性能研究
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摘要
在光电显示领域,有机电致发光器件的研究和应用取得了重大进步和发展。有机电致发光器件由于直流电压驱动、主动发光、体积小、无视角限制、响应快、以及色彩全、制作工艺简单等优点,作为新型显示技术而备受瞩目。
螺双芴化合物在有机电致发光领域有重要的应用价值,这类化合物由于正交结构的存在,有利于提高材料的溶解性,热稳定性,同时可以降低激基缔合物和激基复合物的形成,提高荧光量子产率。萘酰亚胺衍生物是一类典型的荧光试剂,具有较高的荧光发射效率,但是平面刚性结构不利于溶解,作为电致发光材料,往往因为分子堆积或者是激基缔合物或激基复合物的形成而导致发光效率的降低,这些限制了萘酰亚胺化合物在电致发光领域的应用。
我们希望将萘酰亚胺引入到螺双芴分子中,使制备出的新化合物既具有良好的溶解性,热稳定性,又具有较高的电致发光效率,能够在电致发光领域发挥较大作用。
我们做了以下工作:
第一部分:合成出两种新型的螺双芴化合物SPF-NA-1和SPF-NA-2。以联苯为起始原料,通过傅克烷基化反应,溴化反应,格氏化反应,硝化反应,还原反应等六步反应制备了具有左-右不对称结构的化合物SPF-NA-1;以联苯为原料,通过傅克烷基化反应,溴化反应,盖布瑞尔合成,盖布瑞尔还原等六步反应,制备了具有上-下不对称结构的化合物SPF-NA-2。在合成过程中,我们对傅克烷基化反应,硝化反应等实验条件进行了优化。SPF-NA-1和SPF-NA-2经IR,1H NMR, 13C NMR,LC-MS等测试手段确认其结构。
第二部分:通过TG和DTA手段研究了SPF-NA-1和SPF-NA-2的热稳定性,测得它们的分解温度分别为451℃,448℃,都具有较高的热稳定性。通过紫外-可见吸收光谱,荧光光谱,测试了化合物的光学性能:随溶剂极性的增大,无论吸收光谱还是发射光谱都发生了红移。通过循环伏安法(CV),测得了化合物的起始氧化电位,通过边带吸收法及相关公式计算出起始还原电位,及前线轨道能级和能隙。
第三部分:将两种化合物分别作为发光层,制成相应的电致发光器件(器件SPF-NA-1和器件SPF-NA-2),测试了器件的相关性能,得到了器件SPF-NA-1和器件SPF-NA-2的最大发射波长分别为557 nm和551 nm,最大外量子效率分别为0.244%,0.175%,最大亮度分别为387.3 cd/m2 (26.1 V),298.5 cd/m2 (27.5 V)。比较发现,器件SPF-NA-1的电致发光性能优于器件SPF-NA-2。
In the field of photoelectric display,the research and applications of organic optoelectronic materials and devices have made signifieant progress and development. By virtue of the following properties: direct current driving,self-luminous,small volume, fast response, wide view, simple manufacture techniques and so on, Organic Ligh-Emitting Diodes (OLED) have received more and more attention .
Spirobifiuorene compounds paly an important role in the field of OLED. The existence of the orthogonal structure not only is useful for the solubility, thermal stability of materials, but also can reduce the formation of the excimer and excimer complex, so as to improve the fluorescence quantum yield. Naphthalimide derivatives with high emission efficiency are typical fluorescent reagents, but their plane rigid structure against dissolve and make for accumulation. As an electroluminescent material, the accumulation moleculars as well as the formation of the excimer and excimer complex can decrease fluorescence quantum yield, which limits the naphthalimide compounds application in the field of electroluminescence.
We hope that a new kind of fluorescent material with good solubility, thermal stability and high EL efficiency can be prepared by introducing these molecules above into a new molecule, which may play a role in the field of OLED.
The main achievements of this paper can be summarized as follows.
Part I: the synthesis of two new Spirobifiuorene compounds SPF-NA-1 and SPF-NA-2. Using biphenyl as the starting material, left-right asymmetry compound SPF-NA-1 was prepared, through the Friedel-Crafts reaction, bromination, Grignard reaction, nitration reaction, reduction reaction and so on. Top-down asymmetry compound SPF-NA-2 was prepared also using biphenyl as raw materials, by six-step reactions such as Friedel-Crafts reaction, bromination, Gabriel synthesis, Gabriel reduction and so on. During the synthesis process, the reaction conditions of Friedel-Crafts reaction, nitration and so on were optimized. Moreover, their structures of SPF-NA-1 and SPF-NA-2 were confirmed by IR, 1H NMR, 13C NMR, LC-MS, and other testing methods.
Part II: The thermal stability of SPF-NA-1 and SPF-NA-2 was characterised by TG and DTA. The results showed that their decomposition temperatures are 451℃, 448℃, separately, which indieated highly thermal stability. The optical properties of the compounds were examed by UV-vis and fluoreseence emission, both absorption and emission spectroscopy display a red shift with the increasing of solvent polarity. The onset oxidation potential of compounds were measured by CV. Onset reduction potential as well as the frontier orbital energy were evaluated by the relevant formulas.
Part III: The two compounds were made into OLEDs with SPF-NA-1 and SPF-NA-2 as luminous layer. Device performances showed that the maximum emission peaks of devices SPF-NA-1 and SPF-NA-2 were at 557 nm, 551 nm respectively; the maximum external quantum efficiency 0.244%, 0.175%; the maximum brightness 387.3 cd/m2 (26.1V), 298.5 cd/m2 (27.5V). By comparison, the performences of electroluminescent device SPF-NA-1 is superior to that of the electroluminescent device SPF-NA-2.
螺双芴化合物在有机电致发光领域有重要的应用价值,这类化合物由于正交结构的存在,有利于提高材料的溶解性,热稳定性,同时可以降低激基缔合物和激基复合物的形成,提高荧光量子产率。萘酰亚胺衍生物是一类典型的荧光试剂,具有较高的荧光发射效率,但是平面刚性结构不利于溶解,作为电致发光材料,往往因为分子堆积或者是激基缔合物或激基复合物的形成而导致发光效率的降低,这些限制了萘酰亚胺化合物在电致发光领域的应用。
我们希望将萘酰亚胺引入到螺双芴分子中,使制备出的新化合物既具有良好的溶解性,热稳定性,又具有较高的电致发光效率,能够在电致发光领域发挥较大作用。
我们做了以下工作:
第一部分:合成出两种新型的螺双芴化合物SPF-NA-1和SPF-NA-2。以联苯为起始原料,通过傅克烷基化反应,溴化反应,格氏化反应,硝化反应,还原反应等六步反应制备了具有左-右不对称结构的化合物SPF-NA-1;以联苯为原料,通过傅克烷基化反应,溴化反应,盖布瑞尔合成,盖布瑞尔还原等六步反应,制备了具有上-下不对称结构的化合物SPF-NA-2。在合成过程中,我们对傅克烷基化反应,硝化反应等实验条件进行了优化。SPF-NA-1和SPF-NA-2经IR,1H NMR, 13C NMR,LC-MS等测试手段确认其结构。
第二部分:通过TG和DTA手段研究了SPF-NA-1和SPF-NA-2的热稳定性,测得它们的分解温度分别为451℃,448℃,都具有较高的热稳定性。通过紫外-可见吸收光谱,荧光光谱,测试了化合物的光学性能:随溶剂极性的增大,无论吸收光谱还是发射光谱都发生了红移。通过循环伏安法(CV),测得了化合物的起始氧化电位,通过边带吸收法及相关公式计算出起始还原电位,及前线轨道能级和能隙。
第三部分:将两种化合物分别作为发光层,制成相应的电致发光器件(器件SPF-NA-1和器件SPF-NA-2),测试了器件的相关性能,得到了器件SPF-NA-1和器件SPF-NA-2的最大发射波长分别为557 nm和551 nm,最大外量子效率分别为0.244%,0.175%,最大亮度分别为387.3 cd/m2 (26.1 V),298.5 cd/m2 (27.5 V)。比较发现,器件SPF-NA-1的电致发光性能优于器件SPF-NA-2。
In the field of photoelectric display,the research and applications of organic optoelectronic materials and devices have made signifieant progress and development. By virtue of the following properties: direct current driving,self-luminous,small volume, fast response, wide view, simple manufacture techniques and so on, Organic Ligh-Emitting Diodes (OLED) have received more and more attention .
Spirobifiuorene compounds paly an important role in the field of OLED. The existence of the orthogonal structure not only is useful for the solubility, thermal stability of materials, but also can reduce the formation of the excimer and excimer complex, so as to improve the fluorescence quantum yield. Naphthalimide derivatives with high emission efficiency are typical fluorescent reagents, but their plane rigid structure against dissolve and make for accumulation. As an electroluminescent material, the accumulation moleculars as well as the formation of the excimer and excimer complex can decrease fluorescence quantum yield, which limits the naphthalimide compounds application in the field of electroluminescence.
We hope that a new kind of fluorescent material with good solubility, thermal stability and high EL efficiency can be prepared by introducing these molecules above into a new molecule, which may play a role in the field of OLED.
The main achievements of this paper can be summarized as follows.
Part I: the synthesis of two new Spirobifiuorene compounds SPF-NA-1 and SPF-NA-2. Using biphenyl as the starting material, left-right asymmetry compound SPF-NA-1 was prepared, through the Friedel-Crafts reaction, bromination, Grignard reaction, nitration reaction, reduction reaction and so on. Top-down asymmetry compound SPF-NA-2 was prepared also using biphenyl as raw materials, by six-step reactions such as Friedel-Crafts reaction, bromination, Gabriel synthesis, Gabriel reduction and so on. During the synthesis process, the reaction conditions of Friedel-Crafts reaction, nitration and so on were optimized. Moreover, their structures of SPF-NA-1 and SPF-NA-2 were confirmed by IR, 1H NMR, 13C NMR, LC-MS, and other testing methods.
Part II: The thermal stability of SPF-NA-1 and SPF-NA-2 was characterised by TG and DTA. The results showed that their decomposition temperatures are 451℃, 448℃, separately, which indieated highly thermal stability. The optical properties of the compounds were examed by UV-vis and fluoreseence emission, both absorption and emission spectroscopy display a red shift with the increasing of solvent polarity. The onset oxidation potential of compounds were measured by CV. Onset reduction potential as well as the frontier orbital energy were evaluated by the relevant formulas.
Part III: The two compounds were made into OLEDs with SPF-NA-1 and SPF-NA-2 as luminous layer. Device performances showed that the maximum emission peaks of devices SPF-NA-1 and SPF-NA-2 were at 557 nm, 551 nm respectively; the maximum external quantum efficiency 0.244%, 0.175%; the maximum brightness 387.3 cd/m2 (26.1V), 298.5 cd/m2 (27.5V). By comparison, the performences of electroluminescent device SPF-NA-1 is superior to that of the electroluminescent device SPF-NA-2.
引文
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