WO2022011863A1 - 一种氰基修饰吡啶并咪唑类衍生物及其制备方法和应用 - Google Patents

一种氰基修饰吡啶并咪唑类衍生物及其制备方法和应用 Download PDF

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WO2022011863A1
WO2022011863A1 PCT/CN2020/122079 CN2020122079W WO2022011863A1 WO 2022011863 A1 WO2022011863 A1 WO 2022011863A1 CN 2020122079 W CN2020122079 W CN 2020122079W WO 2022011863 A1 WO2022011863 A1 WO 2022011863A1
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cyano
pyridoimidazole
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霍延平
邱志鹏
黄酬
付裕
陈文铖
籍少敏
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Guangdong University of Technology
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    • C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
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  • the invention relates to the technical field of organic light-emitting materials, and more particularly, to a cyano group-modified pyridoimidazole derivative and a preparation method and application thereof.
  • OLEDs organic light-emitting diodes
  • the red light emitting materials in the current organic light emitting materials will greatly enhance the non-radiative transition rate of molecules, resulting in large energy loss, so there are low solid-state fluorescence quantum yield, thermal stability. and poor solubility.
  • Chinese patent CN102070632B discloses a pyridoimidazole derivative and its application in organic electroluminescent devices.
  • the pyridoimidazole derivative red-shifts its luminescent position to the visible light region by introducing a rigid structural substituent group , improve the luminous efficiency, destroy the coplanarity of the molecules, and improve the thermal stability of the compound, but the compound still has the problems of low fluorescence quantum yield and poor solubility.
  • the technical problem to be solved by the present invention is to overcome the defects and deficiencies of low fluorescence quantum yield and poor solubility of the existing pyridoimidazole derivative light-emitting materials, and provide a cyano group-modified pyridoimidazole derivative, which is It has high fluorescence quantum yield, can produce aggregation-induced emission (AIE) effect, can emit red light, and has good thermal stability and solubility.
  • AIE aggregation-induced emission
  • Another object of the present invention is to provide a preparation method of cyano group-modified pyridoimidazole derivatives.
  • Another object of the present invention is to provide an application of cyano group-modified pyridoimidazole derivatives.
  • a cyano group-modified pyridoimidazole derivative has the molecular structure shown in formula (I):
  • R1 is hydrogen or cyano
  • R2 is hydrogen or cyano
  • R1 and R2 are not both hydrogen
  • the cyano group-modified pyridoimidazole derivatives provided by the present invention due to the introduction of a bridged benzene ring between the N-aromatic anthracenyl group (or called hydrogenated phenoxazinyl group) and the carbonyl group in its structure, it forms a larger Conjugated planes; on the other hand, due to the existence of C...H... ⁇ stacking (provided by hydrogenated phenoxazine groups and N atoms on pyridoimidazole), the above structures are all conducive to molecular luminescence and obtain higher fluorescence quantum yields .
  • the cyano group also introduced into the molecule enhances the electron-donating ability of the molecule, resulting in a red shift of the spectrum, red light emission, and a significant reduction in the energy level difference between the singlet state and the triplet state, which makes the thermally activated delayed fluorescence (TADF) properties more excellent.
  • TADF thermally activated delayed fluorescence
  • the cyano group-modified pyridoimidazole derivatives also contain carbonyl groups, they can cause molecular vibrations, can produce aggregation-induced emission (AIE) effect, can effectively inhibit exciton annihilation, and make molecules in a high-concentration aggregation state than in a low-concentration state. It has stronger fluorescence emission, thus has higher luminescence intensity and better AIE performance.
  • the N-containing heterocyclic structure (pyridimidazole group) and the N-containing aromatic anthracenyl structure are conjugated, so that the prepared cyano group-modified Pyridimidazole derivatives have the advantage of good thermal stability.
  • the aromatic ring on the structure of the above-mentioned cyano-modified pyridoimidazole derivatives has a smaller volume and better solubility.
  • R1 is hydrogen
  • R2 is cyano
  • the present invention protects the preparation method of the above-mentioned cyano group-modified pyridoimidazole derivatives, wherein the compound of formula (I) is prepared by Buchwald-Hartwig cross-coupling reaction between the pyridoimidazole derivatives and 10-hydro-phenoxazine;
  • the pyridoimidazole derivatives are 4-(2-(4-bromophenyl)imidazo[1,a])pyridin-3-yl)benzonitrile, 4-(2-(4-bromophenyl)imidazo[1] ,a]) One of pyridin-3-yl)pyridinenitrile and 4-(2-(4-bromophenyl)imidazo[1,a])pyridin-3-yl)benzyl-pyridinenitrile.
  • the molar ratio of the pyridoimidazole derivatives to 10-hydro-phenoxazine is 1:1-1.2.
  • the molar ratio of the pyridoimidazole derivatives to 10-hydro-phenoxazine is 1:1.1.
  • the Buchwald-Hartwig cross-coupling reaction is carried out at 120-130° C. for 12-15 hours.
  • the Buchwald-Hartwig cross-coupling reaction is carried out at 128-130° C. for 13-15 hours.
  • the Buchwald-Hartwig cross-coupling reaction is carried out at 130° C. for 15 hours.
  • the Buchwald-Hartwig cross-coupling reaction is carried out at a pH of 10-14.
  • the catalyst for the Buchwald-Hartwig cross-coupling reaction is a palladium catalyst.
  • the palladium catalyst is palladium acetate.
  • the Buchwald-Hartwig cross-coupling reaction is carried out in an inert atmosphere.
  • the inert atmosphere is one of nitrogen, argon and helium.
  • the (4-(2-(4-bromophenyl)imidazo[1,a])pyridin-3-yl)benzonitrile is derived from (E)-4-(3-(4-bromophenylhydrazine) Benzonitrile and 2-aminopyridine are obtained by Michael cyclization reaction in the presence of iodine element.
  • the molar ratio of (E)-4-(3-(4-bromophenylhydrazine))benzonitrile, 2-aminopyridine and iodine is 1-1.1:2-2.2:0.23-0.25.
  • the molar ratio of ((E)-4-(3-(4-bromophenylhydrazine))benzonitrile, 2-aminopyridine and iodine is 1:2:0.23.
  • the (4-(2-(4-bromophenyl)imidazo[1,a])pyridin-3-yl)pyridinecarbonitrile is derived from (E)-4-(3-(4-bromophenylhydrazine) ) benzyl and 2-amino 4-cyanopyridine are obtained by Michael cyclization reaction in the presence of iodine element.
  • the molar ratio of ((E)-4-(3-(4-bromophenylhydrazine))benzyl, 2-amino-4-cyanopyridine and iodine element is 1 ⁇ 1.1:2 ⁇ 2.2:0.23 ⁇ 0.25.
  • the molar ratio of ((E)-4-(3-(4-bromophenylhydrazine))benzyl, 2-amino-4-cyanopyridine and iodine is 1:2:0.23.
  • the solvent for the Michael cyclization reaction is dichloroethane.
  • the Michael cyclization reaction is performed in air at 115-120° C. for 10-13 hours.
  • the Michael cyclization reaction is performed in air at 118-120° C. for 10-12 hours.
  • the Michael cyclization reaction is performed in air at 120° C. for 12 hours.
  • the preparation method further includes post-processing steps of cooling, distillation, extraction, drying, concentration and separation.
  • the post-processing step is cooling and collecting to obtain a yellow turbid liquid
  • the turbid liquid is distilled under reduced pressure to remove toluene
  • the remaining solid is extracted three times with dichloromethane, combined three times to obtain an organic phase, dried with anhydrous magnesium sulfate, and then reduced
  • the organic phase is distilled under pressure to obtain a crude product
  • the compound of formula (I) is isolated by silica gel column chromatography using ethyl acetate and petroleum ether as eluents.
  • the method also includes dissolving the cyano-modified pyridoimidazole derivative in an organic solvent to obtain a saturated solution, and then adding n-hexane to precipitate a crystal sample of the cyano-modified pyridoimidazole derivative at 20-30°C.
  • cyano-modified pyridoimidazole derivatives have low solubility in n-hexane, slow addition of n-hexane is beneficial to the precipitation of crystals.
  • the temperature of the crystallization is 25°C. If the crystallization temperature is too low, it is not conducive to the volatilization of the organic solvent and the n-hexane solvent, and is not conducive to the precipitation of crystals. If the temperature is too high, the organic solvent volatilizes too quickly, and needle-like polycrystals are easy to grow, and the crystal form is not good.
  • the organic solvent is one of tetrahydrofuran, dichloromethane and toluene.
  • the volume ratio of the organic solvent to n-hexane is 1:1-2.
  • the rate of adding n-hexane is 0.5-1.0 mL/min.
  • cyano group-modified pyridoimidazole derivative crystal sample is precipitated, post-processing steps of filtration, washing and drying are further included.
  • the washing uses n-hexane as a detergent.
  • the present invention also protects the application of the above-mentioned cyano group-modified pyridoimidazole derivatives in organic light-emitting materials.
  • the cyano group-modified pyridoimidazole derivatives prepared by the invention can be assembled into a single-layer light-emitting device, have good light-emitting performance, simplify the process and reduce the cost.
  • the cyano group-modified pyridoimidazole derivatives provided by the present invention contain N aromatic anthracenyl groups, and a bridged benzene ring is introduced between the cyano group and the carbonyl group to form a larger conjugated plane.
  • Fluorescence quantum yield, and the introduction of a cyano group enhances the electron-withdrawing ability of the acceptor group, the intramolecular charge transfer phenomenon is more prominent, the spectrum is red-shifted, and red light can be emitted, and the cyano group-modified pyridoimidazole derivatives of the present invention It also has good AIE effect, excellent TADF properties, good thermal stability and solubility, and can be used as a new type of soluble light-emitting molecule with good performance and low cost, which can be used as red light-emitting materials, light-emitting devices or Light-emitting smart materials, etc., can be applied to fields such as full-color display and solid-state lighting.
  • Fig. 1 is the hydrogen spectrum of the cyano group-modified pyridoimidazole derivative Ben-CN prepared in Example 1.
  • FIG. 2 is the mass spectrum of the cyano group-modified pyridoimidazole derivative Ben-CN prepared in Example 1.
  • FIG. 2 is the mass spectrum of the cyano group-modified pyridoimidazole derivative Ben-CN prepared in Example 1.
  • FIG. 3 is the hydrogen spectrum of the cyano group-modified pyridoimidazole derivative Bd-CN prepared in Example 2.
  • FIG. 4 is the mass spectrum of the cyano group-modified pyridoimidazole derivative Bd-CN prepared in Example 2.
  • FIG. 4 is the mass spectrum of the cyano group-modified pyridoimidazole derivative Bd-CN prepared in Example 2.
  • FIG. 5 is the UV-Vis absorption spectrum of the cyano group-modified pyridoimidazole derivative Ben-CN prepared in Example 1.
  • FIG. 5 is the UV-Vis absorption spectrum of the cyano group-modified pyridoimidazole derivative Ben-CN prepared in Example 1.
  • FIG. 6 is the ultraviolet-visible absorption spectrum and fluorescence emission of the cyano group-modified pyridoimidazole derivative Bd-CN prepared in Example 2.
  • FIG. 6 is the ultraviolet-visible absorption spectrum and fluorescence emission of the cyano group-modified pyridoimidazole derivative Bd-CN prepared in Example 2.
  • Example 7 is the AIE spectrum of the cyano-modified pyridoimidazole derivative Ben-CN prepared in Example 1 in solutions with different water contents.
  • FIG. 9 is a diagram showing the solvation effect of the cyano-modified pyridoimidazole derivative Ben-CN prepared in Example 1.
  • FIG. 9 is a diagram showing the solvation effect of the cyano-modified pyridoimidazole derivative Ben-CN prepared in Example 1.
  • Example 10 is a cyclic voltammogram of the cyano group-modified pyridoimidazole derivative Ben-CN prepared in Example 1.
  • FIG. 11 is the cyclic voltammogram of the cyano group-modified pyridoimidazole derivative Bd-CN prepared in Example 2.
  • FIG. 11 is the cyclic voltammogram of the cyano group-modified pyridoimidazole derivative Bd-CN prepared in Example 2.
  • FIG. 12 is a graph showing the single crystal result of the cyano group-modified pyridoimidazole derivative Ben-CN prepared in Example 1.
  • FIG. 12 is a graph showing the single crystal result of the cyano group-modified pyridoimidazole derivative Ben-CN prepared in Example 1.
  • FIG. 13 is a graph showing the single crystal result of the cyano group-modified pyridoimidazole derivative Bd-CN prepared in Example 2.
  • FIG. 14 is the single crystal and pure film fluorescence emission diagrams of the cyano group-modified pyridoimidazole derivative Ben-CN prepared in Example 1.
  • FIG. 14 is the single crystal and pure film fluorescence emission diagrams of the cyano group-modified pyridoimidazole derivative Ben-CN prepared in Example 1.
  • Figure 15 shows the fluorescence emission diagrams of the single crystal and pure film of the cyano-modified pyridoimidazole derivative Bd-CN prepared in Example 2.
  • FIG. 16 is a thermal stability diagram of the cyano group-modified pyridoimidazole derivatives Ben-CN and Bd-CN prepared in Example 1 and Example 2.
  • FIG. 16 is a thermal stability diagram of the cyano group-modified pyridoimidazole derivatives Ben-CN and Bd-CN prepared in Example 1 and Example 2.
  • 17 is the test spectrum of room temperature fluorescence and low temperature phosphorescence of the cyano-modified pyridoimidazole derivative Ben-CN prepared in Example 1.
  • the raw material reagents used in the examples of the present invention are conventionally purchased raw material reagents.
  • a cyano group-modified pyridoimidazole derivative named Ben-CN, has the following molecular structure:
  • the preparation method of above-mentioned Ben-CN comprises the steps:
  • the product is cooled, distilled, extracted, dried, concentrated, and separated; a yellow turbid liquid is obtained by cooling and collection, the turbid liquid is distilled under reduced pressure to remove toluene, the remaining solid is extracted three times with dichloromethane, and the organic phases obtained three times are combined, and anhydrous sulfuric acid is used.
  • a cyano group-modified pyridoimidazole derivative, named Bd-CN, has the following molecular structure:
  • the preparation method of the above-mentioned Bd-CN is the same as that in Example 1, except that (E)-4-(3-(4-bromophenylhydrazine))benzonitrile is replaced by (E)-4-(3-(4- Bromophenylhydrazine)) nitrile, 2-aminopyridine was replaced by 2-amino-4-cyano-pyridine to obtain (4-(2-(4-bromophenyl)imidazo[1,a])pyridin-3-yl ) pyridine nitrile;
  • a cyano group-modified pyridoimidazole derivative has the following molecular structure:
  • the preparation method of the above cyano group-modified pyridoimidazole derivatives is the same as that in Example 1, the difference is that (4-(2-(4-bromophenyl)imidazo[1,a])pyridin-3-yl)benzyl
  • the nitrile was replaced with (4-(2-(4-bromophenyl)imidazo[1,a])pyridin-3-yl)benzyl-pyridinecarbonitrile.
  • the cyano group-modified pyridoimidazole derivatives of this comparative example have the following molecular structures:
  • the hydrogen signal of Ben-CN prepared in Example 1 was scanned by nuclear magnetic resonance; the cyano-modified pyridoimidazole derivatives prepared in Examples 1 and 2 were dissolved in acetonitrile to prepare a solution with a concentration of 1 mg/mL , using a liquid mass spectrometer LCMS-2020 for mass spectrometry.
  • the main absorption peak position of Ben-CN is 334 nm, and the emission wavelength is 601 nm, which is red light emission.
  • the main absorption peak position of Bd-CN is 334 nm, and the emission wavelength is 610 nm, which is red light emission.
  • the molecule of Comparative Example 1 has an emission wavelength of 574 nm and cannot generate red light.
  • the AIE spectra of cyano-modified pyridoimidazole derivatives were measured by FLS980 fluorometer.
  • the fluorescence spectra of Bd-CN in tetrahydrofuran-water solution with water content of 0% to 99% were tested respectively; as shown in Figure 8, the direction indicated by the arrows is the direction in which the water content of the solution corresponding to the four fluorescence graph lines increases in turn,
  • the emission wavelength of Bd-CN is 610 nm; when the water content is less than 95%, the fluorescence emission wavelength of Bd-CN in solution has a significant red shift; when the water content exceeds 95%, the spectrum is blue-shifted, and the molecule is in the solution.
  • the precipitation and aggregation in Bd-CN were greatly enhanced, and the corresponding fluorescence intensity was greatly enhanced, indicating that Bd-CN had obvious AIE phenomenon.
  • the cyano-modified pyridoimidazole derivatives were dissolved in acetonitrile to make a solution of 1 mg/mL.
  • the Ben-CN prepared in Example 1 was dissolved in acetone, ethyl acetate, tetrahydrofuran, and dichloromethane solvent, specifically, 10 mg of the sample was dissolved in 1 ml of solvent.
  • Table 1 The results are shown in Table 1, where "+” indicates that it can be dissolved in the corresponding solvent, and the more "+”, the greater the solubility in the corresponding solvent.
  • the crystal structure was determined by Bruker X single crystal diffractometer in Germany. Test method: Select a single crystal with a moderate size and good crystal quality as a sample. When X-rays are irradiated on a single crystal, diffraction will occur. By analyzing the diffraction lines, the arrangement law of atoms in the crystal can be analyzed, and the diffraction data can be collected. Index the diffractogram, obtain the unit cell constant, sum up the extinction law according to the diffraction index of all diffraction lines, and infer the space group to which the crystal belongs. The measured diffraction intensity is subjected to absorption correction, LP correction and other processing to obtain the structural amplitude
  • Fluorescence spectrum use Edinburgh FL980 transient steady-state fluorescence phosphorescence spectrometer for solid fluorescence spectrum test; set the excitation wavelength to 370nm, set the slit width so that the ordinate value is close to one million, and then perform the spectrum test to obtain the spectrum.
  • Example 1 and Example 2 had better thermal stability.
  • the Ben-CN and Bd-CN prepared in Example 1 and Example 2 were tested for room temperature fluorescence and low temperature phosphorescence with FLS980 instrument.
  • the energy level difference of the singlet state S 1 and the lowest triplet state T 1 is as low as 0.03 and 0.02 electron volts, respectively, compared with the 0.05 eV energy level difference of the comparative example 1, indicating that the two molecules of the present invention have more efficient TADF performance.

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Abstract

本发明公开了一种氰基修饰吡啶并咪唑类衍生物及其制备方法和应用，具有如式(Ⅰ)所示的分子结构，其中R1为氢或氰基，R2为氢或氰基，R1和R2不同时为氢。本发明通过在吡啶并咪唑类衍生物中引入C…H…π堆积结构和氰基，以获得较高的荧光量子产率，受体基团吸电子能力增强，光谱红移，该类衍生物还具有较好的AIE效应、高效的热激活延迟荧光(TADF)性质、良好的热稳定性和溶解性，可用作红光发光材料、发光器件或发光智能材料等，可应用于全彩显示和固态照明等领域。

Description

一种氰基修饰吡啶并咪唑类衍生物及其制备方法和应用 技术领域
本发明涉及有机发光材料技术领域，更具体地，涉及一种氰基修饰吡啶并咪唑类衍生物及其制备方法和应用。
背景技术
有机发光材料用作有机发光二极管(OLED)的技术在平板显示、智能手机以及固体发光等领域有广泛的应用，归功于有机发光材料具有大面积和高质量显示与照明、超高分辨率、超快响应速度和柔性等显著优势。
但是，目前有机发光材料中的红光发光材料由于其固有的窄带隙会极大增强分子的非辐射跃迁速率，从而导致较大的能量损失，因此存在固态荧光量子产率不高、热稳定性和溶解性不好的问题。
如中国专利CN102070632B公开了一种吡啶并咪唑衍生物及其在有机电致发光器件中的应用，所述的吡啶并咪唑衍生物通过引入刚性结构的取代基团使其发光位置红移到可见光区域，提高发光效率，同时破坏分子共平面性，提高化合物的热稳定性，但是该化合物还存在荧光量子产率较低、溶解性不好的问题。
发明内容
本发明要解决的技术问题是克服现有吡啶并咪唑类衍生物发光材料的荧光量子产率较低、溶解性不好的缺陷和不足，提供一种氰基修饰吡啶并咪唑类衍生物，其荧光量子产率高，能产生聚集诱导发光(AIE)效应，可以发出红光，同时具有较好的热稳定性和溶解性。
本发明的又一目的是提供一种氰基修饰吡啶并咪唑类衍生物的制备方法。
本发明的另一目的是提供一种氰基修饰吡啶并咪唑类衍生物的应用。
本发明上述目的通过以下技术方案实现：
一种氰基修饰吡啶并咪唑类衍生物，具有如式(Ⅰ)所示的分子结构：
Figure PCTCN2020122079-appb-000001
其中R1为氢或氰基，R2为氢或氰基，R1和R2不同时为氢。
本发明提供的氰基修饰吡啶并咪唑类衍生物，一方面由于其结构中含N芳香蒽基(或称为氢化吩噁嗪基)与羰基之间引入桥联的苯环，形成较大的共轭平面；另一方面，由于存在C…H…π堆积(由氢化吩噁嗪基与吡啶并咪唑上的N原子提供)，以上结构均有利于分子发光，获得较高的荧光量子产率。此外，分子中还引入的氰基，使分子给电子能力增强，导致光谱红移，发出红光，单线态和三线态能级差显著减小，使得热激活延迟荧光(TADF)性质更加卓越。由于该氰基修饰吡啶并咪唑类衍生物还含有羰基，可以造成分子振动，能产生聚集诱导发光(AIE)效应，可以有效地抑制激子湮灭，使分子在高浓度聚集态下比低浓度下有更强的荧光发射，从而具有较高的发光强度，具有较好的AIE性能。并且，由于该氰基修饰吡啶并咪唑类衍生物的相对分子量较大，含N杂环结构(吡啶并咪唑基团)和含N芳香蒽基结构存在共轭情况，使得制备的该氰基修饰吡啶并咪唑类衍生物具有热稳定性良好的优点。另外，上述氰基修饰吡啶并咪唑类衍生物结构上的芳环体积较小，溶解性较好。
优选地，所述R1为氰基时，R2为氢时，氰基修饰吡啶并咪唑类衍生物结晶于正交晶系，空间群为P21/n，晶胞参数为
Figure PCTCN2020122079-appb-000002
Figure PCTCN2020122079-appb-000003
β＝95.651(2)°；
或者所述R1为氢时，R2为氰基时，氰基修饰吡啶并咪唑类衍生物结晶于正交晶系，空间群为P21/c，
Figure PCTCN2020122079-appb-000004
β＝102.328(2)°。
本发明保护上述氰基修饰吡啶并咪唑类衍生物的制备方法，将吡啶并咪唑类 衍生物与10-氢-吩噁嗪通过Buchwald-Hartwig交叉偶联反应制得式(Ⅰ)化合物；所述吡啶并咪唑类衍生物为4-(2-(4-溴苯)咪唑并[1,a])吡啶-3-基)苄腈、4-(2-(4-溴苯)咪唑并[1,a])吡啶-3-基)吡啶腈、4-(2-(4-溴苯)咪唑并[1,a])吡啶-3-基)苄-吡啶腈中的一种。
优选地，所述吡啶并咪唑类衍生物与10-氢-吩噁嗪的摩尔比为1∶1～2。
更优选地，所述吡啶并咪唑类衍生物与10-氢-吩噁嗪的摩尔比为1∶1～1.2。
进一步优选地，所述吡啶并咪唑类衍生物与10-氢-吩噁嗪的摩尔比为1∶1.1。
优选地，所述Buchwald-Hartwig交叉偶联反应在120～130℃下，反应12～15h。
更优选地，所述Buchwald-Hartwig交叉偶联反应在128～130℃下，反应13～15h。
进一步优选地，所述Buchwald-Hartwig交叉偶联反应在130℃下，反应15h。
优选地，所述Buchwald-Hartwig交叉偶联反应在pH值为10～14下进行。
优选地，所述Buchwald-Hartwig交叉偶联反应的催化剂为钯催化剂。
优选地，所述的钯催化剂为醋酸钯。
优选地，所述Buchwald-Hartwig交叉偶联反应在惰性氛围中进行。
优选地，所述惰性氛围为氮气、氩气、氦气中的一种。
优选地，所述(4-(2-(4-溴苯)咪唑并[1,a])吡啶-3-基)苄腈由(E)-4-(3-(4-溴苯肼)苄腈和2-氨基吡啶在碘单质存在下进行Michael环合反应得到。
优选地，所述(E)-4-(3-(4-溴苯肼))苄腈、2-氨基吡啶与碘单质的摩尔比为1～1.1∶2～2.2∶0.23～0.25。
更优选地，所述((E)-4-(3-(4-溴苯肼))苄腈、2-氨基吡啶与碘单质的摩尔比为1∶2∶0.23。
优选地，所述(4-(2-(4-溴苯)咪唑并[1,a])吡啶-3-基)吡啶腈由(E)-4-(3-(4-溴苯肼))苄和2-氨基4-氰基吡啶在碘单质存在下进行Michael环合反应得到。
优选地，所述((E)-4-(3-(4-溴苯肼))苄、2-氨基-4-氰基吡啶与碘单质的摩尔比为1～1.1∶2～2.2∶0.23～0.25。
更优选地，所述((E)-4-(3-(4-溴苯肼))苄、2-氨基-4-氰基吡啶与碘单质的摩尔比为1∶2∶0.23。
优选地，所述Michael环合反应的溶剂为二氯乙烷。
优选地，所述Michael环合反应是在空气中，115～120℃反应10～13h。
更优选地，所述Michael环合反应是在空气中，118～120℃反应10～12h。
进一步优选地，所述Michael环合反应是在空气中，120℃反应12h。
优选地，所述制备方法还包括冷却、蒸馏、萃取、干燥、浓缩、分离的后处理步骤。
具体地，所述后处理步骤为冷却收集得到黄色浑浊液，将浑浊液减压蒸馏除去甲苯，所剩固体用二氯甲烷萃取三次，合并三次得有机相，用无水硫酸镁干燥，再减压蒸馏有机相得到粗产品，最后用乙酸乙酯与石油醚作为洗脱剂进行硅胶柱层析分离出式(Ⅰ)化合物。
优选地，还包括将氰基修饰吡啶并咪唑类衍生物溶解于有机溶剂中，得饱和溶液，再加入正己烷，于20～30℃中析出氰基修饰吡啶并咪唑类衍生物晶体样品。
由于氰基修饰吡啶并咪唑类衍生物在正己烷中溶解度较小，缓慢加入正己烷有利于晶体的析出。
更优选地，所述结晶的温度为25℃。结晶温度如果过低，不利于有机溶剂与正己烷溶剂的挥发，不利于晶体的析出，而温度过高，有机溶剂挥发过快，容易长出针状的多晶，晶型不好。
优选地，所述有机溶剂为四氢呋喃、二氯甲烷，甲苯中的一种。
优选地，所述有机溶剂与正己烷的体积比为1∶1～2。
优选地，加入正己烷的速度为0.5～1.0mL/min。
优选地，所述析出氰基修饰吡啶并咪唑类衍生物晶体样品后，还包括过滤、洗涤、烘干的后处理步骤。
优选地，所述洗涤使用正己烷为洗涤剂。
本发明还保护上述氰基修饰吡啶并咪唑类衍生物在有机发光材料中的应用。
具体地，氰基修饰吡啶并咪唑类衍生物在有机红光发光材料中的应用。
本发明所制得的氰基修饰吡啶并咪唑类衍生物在实际应用中，能够组装成单层的发光器件，具有较好的发光性能，并简化工艺，降低成本。
与现有技术相比，本发明的有益效果是：
本发明提供的氰基修饰吡啶并咪唑类衍生物含N芳香蒽基，与羰基之间引入桥联的苯环，形成较大的共轭平面，存在C…H…π堆积，具有较高的荧光量 子产率，并且引入氰基，使得受体基团吸电子能力增强，分子内的电荷转移现象更加突出，光谱红移，可发出红光，并且本发明的氰基修饰吡啶并咪唑类衍生物还具有较好的AIE效应、卓越的TADF性质、良好的热稳定性和溶解性，可作为一种性能好、成本较低的新型可溶性发光分子，可用作红光发光材料、发光器件或发光智能材料等，可应用于全彩显示和固态照明等领域。
附图说明
图1为实施例1制得的氰基修饰吡啶并咪唑类衍生物Ben-CN的氢谱图。
图2为实施例1制得的氰基修饰吡啶并咪唑类衍生物Ben-CN的质谱图。
图3为实施例2制得的氰基修饰吡啶并咪唑类衍生物Bd-CN的氢谱图。
图4为实施例2制得的氰基修饰吡啶并咪唑类衍生物Bd-CN的质谱图。
图5为实施例1制得的氰基修饰吡啶并咪唑类衍生物Ben-CN的紫外可见吸收光谱图。
图6为实施例2制得的氰基修饰吡啶并咪唑类衍生物Bd-CN的紫外可见吸收光谱图及荧光发射图。
图7为实施例1制得的氰基修饰吡啶并咪唑类衍生物Ben-CN的在不同含水量的溶液中的AIE光谱图。
图8为实施例2制得的氰基修饰吡啶并咪唑类衍生物Bd-CN的在不同含水量的溶液中的AIE光谱图。
图9为实施例1制得的氰基修饰吡啶并咪唑类衍生物Ben-CN的溶剂化效应图。
图10为实施例1制得的氰基修饰吡啶并咪唑类衍生物Ben-CN的循环伏安图。
图11为实施例2制得的氰基修饰吡啶并咪唑类衍生物Bd-CN的循环伏安图。
图12为实施例1制得的氰基修饰吡啶并咪唑类衍生物Ben-CN的单晶结果图。
图13为实施例2制得的氰基修饰吡啶并咪唑类衍生物Bd-CN的单晶结果图。
图14为实施例1制得的氰基修饰吡啶并咪唑类衍生物Ben-CN的单晶与纯膜荧光发射图。
图15为实施例2制得的氰基修饰吡啶并咪唑类衍生物Bd-CN的单晶与纯膜 荧光发射图。
图16为实施例1及实施例2制得的氰基修饰吡啶并咪唑类衍生物Ben-CN及Bd-CN的热稳定性图。
图17为实施例1制得的氰基修饰吡啶并咪唑类衍生物Ben-CN的常温荧光及低温磷光的测试光谱。
图18为实施例2制得的氰基修饰吡啶并咪唑类衍生物Bd-CN的常温荧光及低温磷光的测试光谱。
具体实施方式
下面结合具体实施方式对本发明作进一步的说明，但实施例并不对本发明做任何形式的限定。除非另有说明，本发明实施例采用的原料试剂为常规购买的原料试剂。
实施例1
一种氰基修饰吡啶并咪唑类衍生物，命名为Ben-CN，具有如下所示的分子结构：
Figure PCTCN2020122079-appb-000005
上述Ben-CN的制备方法，包括如下步骤：
称取(E)-4-(3-(4-溴苯肼))苄腈150mg，2-氨基吡啶80mg碘单质60mg与3mL二氯乙烷于10mL封管内，温度120℃条件下进行Michael环合反应，处理后得到(4-(2-(4-溴苯)咪唑并[1,a])吡啶-3-基)苄腈；DCE为二氯乙烷；
其反应方程式为：
Figure PCTCN2020122079-appb-000006
称取上述制得的(4-(2-(4-溴苯)咪唑并[1,a])吡啶-3-基)苄腈180mg，10-氢- 吩噁嗪115mg，叔丁醇钾80mg，三叔丁基膦4mg，醋酸钯5.5mg和5mL的甲苯于封管内，搅拌抽掉装置中空气并充以氮气保护，在130℃氮气保护下加热搅拌回流反应15h，反应完后，将粗产物经过冷却、蒸馏、萃取、干燥、浓缩、分离；冷却收集得到黄色浑浊液，将浑浊液减压蒸馏除去甲苯，所剩固体用二氯甲烷萃取三次，合并三次所得有机相，用无水硫酸镁干燥，再减压蒸馏有机相得到粗产品；最后用乙酸乙酯与石油醚作为洗脱剂进行硅胶柱层析分离；得到的纯产物溶液减压蒸馏并真空干燥后得到90mg黄色固体，即为Ben-CN，纯度99％，产率50％；进一步将产物加入到四氢呋喃与正己烷1：1混合溶液中，在室温下缓慢挥发溶剂后得到晶体；
其反应方程式如下：
Figure PCTCN2020122079-appb-000007
实施例2
一种氰基修饰吡啶并咪唑类衍生物，命名为Bd-CN，具有如下所示的分子结构：
Figure PCTCN2020122079-appb-000008
上述Bd-CN的制备方法与实施例1相同，区别在于，将(E)-4-(3-(4-溴苯肼))苄腈替换为(E)-4-(3-(4-溴苯肼))腈，2-氨基吡啶替换为2-氨基-4-氰基-吡啶制得(4-(2-(4-溴苯)咪唑并[1,a])吡啶-3-基)吡啶腈；
其反应方程式如下：
Figure PCTCN2020122079-appb-000009
实施例3
一种氰基修饰吡啶并咪唑类衍生物，具有如下所示的分子结构：
Figure PCTCN2020122079-appb-000010
上述氰基修饰吡啶并咪唑类衍生物的制备方法与实施例1相同，区别在于，将(4-(2-(4-溴苯)咪唑并[1,a])吡啶-3-基)苄腈替换为(4-(2-(4-溴苯)咪唑并[1,a])吡啶-3-基)苄-吡啶腈。
其反应方程式如下：
Figure PCTCN2020122079-appb-000011
Figure PCTCN2020122079-appb-000012
对比例1
本对比例的氰基修饰吡啶并咪唑类衍生物，具有如下所示的分子结构：
Figure PCTCN2020122079-appb-000013
上述氰基修饰吡啶并咪唑类衍生物的制备方法与实施例1相同，区别在于，将(E)-4-(3-(4-溴苯肼))苯酮替换为(E)-4-(3-(4-溴苯肼))苄腈。
其反应方程式如下：
Figure PCTCN2020122079-appb-000014
结构表征及性能测试
1、核磁共振和质谱
采用核磁共振扫描了该实施例1制得的Ben-CN的氢信号；将实施例1及2制得的氰基修饰吡啶并咪唑类衍生物溶于乙腈，配成浓度为1mg/mL的溶液，采用液质联用仪LCMS-2020，进行质谱测试。
实施例1制得的Ben-CN的核磁图谱(图1)δ(ppm)为 1H NMR(400MHz,Chloroform-d)δ8.55–8.46(m,2H),8.07(d,J＝7.0Hz,1H),7.84(dd,J＝19.1,8.6Hz,3H),7.75(d,J＝8.1Hz,2H),7.51–7.45(m,2H),7.39(ddd,J＝9.1,6.6,1.1Hz,1H),6.96(td,J＝6.9,1.1Hz,1H),6.75–6.64(m,4H),6.61(td,J＝7.5,1.9Hz,2H),6.01(dd,J＝7.8,1.5Hz,2H).从Ben-CN质谱图(图3)中可以看到，图中相对分子质量为505.17，减去一个H，与所合成的Ben-CN的相对分子质量一致。结合以上核磁和质谱的结果可知，实施例1制得的产物为Ben-CN。
实施例2制得的Bd-CN的核磁图谱(图2)δ(ppm)为 1H NMR(400MHz,Chloroform-d)δ8.40(d,J＝8.4Hz,2H),8.19(d,J＝7.6Hz,1H),7.74(d,J＝8.3Hz,1H),7.61–7.51(m,4H),7.44(t,J＝7.9Hz,2H),7.15(t,J＝7.8Hz,1H),7.01(dd,J＝7.1,1.7Hz,1H),6.73–6.58(m,6H),5.97(dd,J＝7.9,1.4Hz,2H).从Bd-CN质谱图(图4)中可以看到，图中相对分子质量为505.17，减去一个H，与所合成的Bd-CN的相对分子质量一致。结合以上核磁和质谱的结果可知，实施例2制得的产物为Bd-CN。
2、紫外可见吸收光谱
采用岛津紫外可见光分光光度计UV-2700，将实施例1和2制得的氰基修饰吡啶并咪唑类衍生物溶于THF中配成1×10 -3mol/L的母液，稀释成1×10 -5mol/L进行测试。
从图5中看出，Ben-CN的主要吸收峰位置为334nm，发射波长为601nm，为红光发射。
从图6中看出，Bd-CN的主要吸收峰位置为334nm，发射波长为610nm，为红光发射。而对比例1的分子发射波长为574nm，不能产生红光。
3、AIE性能
将氰基修饰吡啶并咪唑类衍生物溶于四氢呋喃中配成1×10 -3mol/L的母液，维持测试溶液总体积为3mL。保持测试溶液中氰基修饰吡啶并咪唑类衍生物的浓度为1×10 -5mol/L，调节测试溶液中四氢呋喃和水的比例。例如：水含量为90％时，各成分加入量为母液∶水∶四氢呋喃＝30uL∶2700uL∶270uL。采用FLS980荧光仪测试氰基修饰吡啶并咪唑类衍生物的AIE光谱图。
分别测试了氰基修饰吡啶并咪唑类衍生物Ben-CN在水含量为0％～99％的四氢呋喃-水溶液中的荧光光谱，如图7所示，箭头指示方向为6条荧光图线所对 应的溶液的水含量依次增加方向，Ben-CN的发射波长为600nm；当水含量低于95％时，Ben-CN在溶液中的荧光发射波长出现明显的红移；而当水含量超过95％后，光谱蓝移，分子在溶液中析出聚集，对应荧光强度均发生大幅度增强，可知Ben-CN存在明显的AIE现象。
分别测试了Bd-CN在水含量为0％～99％的四氢呋喃-水溶液中的荧光光谱；如图8所示，箭头指示方向为4条荧光图线所对应的溶液的水含量依次增加方向，Bd-CN的发射波长为610nm；当水含量低于95％时，Bd-CN在溶液中的荧光发射波长出现明显的红移；而当水含量超过95％后，光谱蓝移，分子在溶液中析出聚集，对应荧光强度均发生大幅度增强，可知Bd-CN存在明显的AIE现象。
4、溶剂化效应
采用FLS980荧光仪测试氰基修饰吡啶并咪唑类衍生物在不同溶剂里归一化的光谱图。
从图9可以看出，氰基修饰吡啶并咪唑类衍生物Ben-CN在不同溶剂(按照溶剂极性由大到小排列：正己烷n-hex、甲苯Tol、二氯甲烷DCM、四氢呋喃THF、乙酸乙酯EtaOH)里，随着溶剂极性的增强，其光谱表现出明显的溶剂化变色效应，这是由于分子内的电荷转移效应(ICT)，即电荷转移激发态所引起的。
5、循环伏安图
采用电化学工作站PGSTAT302测试实施例1和实施例2制备得到的氰基修饰吡啶并咪唑类衍生物Ben-CN和Bd-CN的循环伏安图。
将氰基修饰吡啶并咪唑类衍生物溶于乙腈中配成1mg/mL的溶液，在电化学工作站下通过循环伏安法测得Ben-CN和Bd-CN的氧化电位为E＝0.74eV及E＝0.75eV(如图10,图11所示)。与对比例1的E＝0.67V相比，Ben-CN和Bd-CN具有氧化电位值更强，更有利于红光的生成。
6、溶解性
实施例1制得的Ben-CN溶于丙酮、乙酸乙酯、四氢呋喃、二氯甲烷溶剂中，具体以10毫克样品溶于1毫升溶剂中。结果如表1所示，其中“+”表示能够溶于对应的溶剂中，“+”个数越多表示在对应的溶剂中溶解度越大。
表1实施例1及实施例2制得的Ben-CN和Bd-CN的溶解性
溶剂 丙酮 乙酸乙酯 四氢呋喃 二氯甲烷
溶解性 +++ +++ ++ ++
以上表1结果表明，Ben-CN和Bd-CN的溶解性较好。
7、单晶X-射线衍射
晶体结构采用德国布鲁克X单晶衍射仪测定。测试方法：选择大小适度，晶质良好的单晶体作试样，利用X射线射到一粒单晶体上会发生衍射，由对衍射线的分析可以解析出原子在晶体中的排列规律，收集衍射数据，指标化衍射图，求出晶胞常数，依据全部衍射线的衍射指标，总结出消光规律，推断晶体所属的空间群。将测得的衍射强度作吸收校正，LP校正等各种处理以得出结构振幅|F|。利用派特逊函数法，推测相角和初结构。
如图12所示，单晶X-射线衍射数据表明，实施例1的Ben-CN属于正交晶系，空间群为P21/n,
Figure PCTCN2020122079-appb-000015
β＝95.651(2)°,
Figure PCTCN2020122079-appb-000016
Z＝4。从晶体的作用力图可以看到，分子之间存在C…H…O/N及C…H…π堆积，这有利于分子的发光，并且，采用FLS980的积分球测试其绝对量子产率，结果显示Ben-CN获得大于50％的高荧光量子产率。
如图13所示，单晶X-射线衍射数据表明，实施例2的Bd-CN属于正交晶系，空间群为P2 1/c,
Figure PCTCN2020122079-appb-000017
β＝102.328(2)°,
Figure PCTCN2020122079-appb-000018
Z＝4。从晶体的作用力图可以看到，分子之间存在C…H…O/N及C…H…π堆积，这有利于分子的发光，并且，采用FLS980的积分球测试其绝对量子产率，结果显示Bd-CN获得大于50％的高荧光量子产率。
8、单晶荧光发射测试
荧光光谱：采用爱丁堡FL980瞬态稳态荧光磷光光谱仪进行固体荧光光谱测试；设置激发波长370nm，设置狭缝宽度，使其纵坐标数值接近一百万，然后进行光谱测试获得谱图。
如图14及图15所示，在370nm的光激发下，实施例1及实施例2制得的Ben-CN和Bd-CN晶体和纯膜(将Ben-CN和Bd-CN分别真空蒸镀在石英片上制得薄膜)在600nm出现最大发射峰。通过比较，可以发现晶体发射波峰较宽，这可能归因于：与无定型的纯膜相比，在晶体结构中，分子之间存在比较明显的C…H…π堆积。纯膜中实施例1及实施例2制得的Ben-CN和Bd-CN都获得了大于600nm的荧光发射，与对比例1的574nm的荧光发射相比，体现出本发明制得的分子在红光发射上的优越性。并且，在纯膜中实施例1及实施例2制得的 Ben-CN和Bd-CN都获得了接近40％的荧光量子产率，而对比例1的薄膜的荧光量子产率为30.2％，说明在薄膜状态下Ben-CN和Bd-CN相对于对比例1的分子具有更好的发光性能。
如图16所示，在氮气氛围下以20℃的温度梯度升温，可知实施例1及实施例2制得的Ben-CN和Bd-CN的热分解温度都超过400℃，与对比例1的热分解温度为369.1℃，证明该实施例1及实施例2更优秀的热稳定性。
如图17及图18所示，在氮气氛围下，用FLS980仪器对实施例1及实施例2制得的Ben-CN和Bd-CN进行常温荧光及低温磷光的测试，根据光谱计算出来的最低单线态S 1及最低三线态T 1能级差分别低至0.03和0.02个电子伏特，与对比例1的0.05eV能级差相比，说明本发明的两种分子均具有更高效的TADF性能。
显然，本发明的上述实施例仅仅是为清楚地说明本发明所作的举例，而并非是对本发明的实施方式的限定。对于所属领域的普通技术人员来说，在上述说明的基础上还可以做出其它不同形式的变化或变动。这里无需也无法对所有的实施方式予以穷举。凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等，均应包含在本发明权利要求的保护范围之内。

Claims (10)

  1. 一种氰基修饰吡啶并咪唑类衍生物，其特征在于，具有如式(Ⅰ)所示的分子结构：
    Figure PCTCN2020122079-appb-100001
    其中R1为氢或氰基，R2为氢或氰基，R1和R2不同时为氢。
  2. 根据权利要求1所述的氰基修饰吡啶并咪唑类衍生物，其特征在于，所述R1为氰基时，R2为氢时，氰基修饰吡啶并咪唑类衍生物结晶于正交晶系，空间群为P21/n，晶胞参数为
    Figure PCTCN2020122079-appb-100002
    β＝95.651(2)°；
    或者所述R1为氢时，R2为氰基时，氰基修饰吡啶并咪唑类衍生物结晶于正交晶系，空间群为P21/c，晶胞参数为
    Figure PCTCN2020122079-appb-100003
    Figure PCTCN2020122079-appb-100004
    β＝102.328(2)°。
  3. 权利要求1或2所述的氰基修饰吡啶并咪唑类衍生物的制备方法，其特征在于，将吡啶并咪唑类衍生物与10-氢-吩噁嗪通过Buchwald-Hartwig交叉偶联反应制得式(Ⅰ)化合物；所述吡啶并咪唑类衍生物为4-(2-(4-溴苯)咪唑并[1,a])吡啶-3-基)苄腈、4-(2-(4-溴苯)咪唑并[1,a])吡啶-3-基)吡啶腈、4-(2-(4-溴苯)咪唑并[1,a])吡啶-3-基)苄-吡啶腈中的一种。
  4. 根据权利要求3所述的制备方法，其特征在于，所述吡啶并咪唑类衍生物与10-氢-吩噁嗪的摩尔比为1∶1～2。
  5. 根据权利要求3所述的制备方法，其特征在于，所述Buchwald-Hartwig交叉偶联反应在120～130℃下，反应12～15h。
  6. 根据权利要求3所述的制备方法，其特征在于，所述Buchwald-Hartwig 交叉偶联反应在pH值为10～14下进行。
  7. 根据权利要求3所述的制备方法，其特征在于，所述Buchwald-Hartwig交叉偶联反应的催化剂为钯催化剂。
  8. 根据权利要求3所述的制备方法，其特征在于，所述Buchwald-Hartwig交叉偶联反应在惰性氛围中进行。
  9. 根据权利要求3所述的制备方法，其特征在于，还包括将氰基修饰吡啶并咪唑类衍生物溶解于有机溶剂中，得饱和溶液，再加入正己烷，于20～30℃中析出氰基修饰吡啶并咪唑类衍生物晶体样品。
  10. 权利要求1或2所述的氰基修饰吡啶并咪唑类衍生物在有机发光材料中的应用。
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114716416A (zh) * 2022-04-11 2022-07-08 湖北大学 3,4-二氢吡咯衍生物及其一锅法合成
CN116768940A (zh) * 2023-06-14 2023-09-19 大连理工大学 一种氰基桥联三核自旋转变配合物及其制备方法和应用
NL2036209A (en) * 2023-11-08 2024-02-16 Univ Guangdong Technology Use of cyano-modified pyridino imidazole derivative in preparing organic photoelectric devices
CN117568022A (zh) * 2023-11-12 2024-02-20 桂林理工大学 3,5-二氰基吡啶小分子在晶态和掺杂体系中的动态和蓝色室温磷光及防伪性能

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112645949B (zh) * 2020-12-25 2022-04-19 广东工业大学 一种含有苯甲酮基团的芳香胺类衍生物及其制备方法和应用
CN112979649A (zh) * 2021-03-16 2021-06-18 广东工业大学 一种吡啶并咪唑衍生物及其制备方法和应用
CN113620947B (zh) * 2021-09-08 2022-05-31 广东工业大学 一种蒽衍生物及其制备方法和应用

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102070632A (zh) * 2009-11-20 2011-05-25 中国科学院理化技术研究所 吡啶并咪唑衍生物及其在有机电致发光器件中的应用

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109320459B (zh) * 2018-10-09 2020-05-05 广东工业大学 一种含芴的菲并咪唑类衍生物、晶体及其制备方法与应用
CN109705041B (zh) * 2019-01-29 2022-06-14 广东工业大学 一种三苯胺取代-乙烯基修饰的菲并咪唑类化合物及其制备方法和作为电致发光器件的应用
CN109942577A (zh) * 2019-03-22 2019-06-28 广东工业大学 一种含有取代氢化吖啶基团的n杂环苯甲酮类衍生物及其制备方法和应用
CN109851618A (zh) * 2019-03-22 2019-06-07 广东工业大学 一种含有氢化吩噻嗪基团的n杂环苯甲酮类衍生物及其制备方法和应用

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102070632A (zh) * 2009-11-20 2011-05-25 中国科学院理化技术研究所 吡啶并咪唑衍生物及其在有机电致发光器件中的应用

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
YANG ZHIWEN, ZHAN YINGYING, QIU ZHIPENG, ZENG JIAJIE, GUO JINGJING, HU SHENG, ZHAO ZUJIN, LI XIANWEI, JI SHAOMIN, HUO YANPING, SU : "Stimuli-Responsive Aggregation-Induced Delayed Fluorescence Emitters Featuring the Asymmetric D–A Structure with a Novel Diarylketone Acceptor Toward Efficient OLEDs with Negligible Efficiency Roll-Off", APPLIED MATERIALS & INTERFACES, vol. 12, no. 26, 6 August 2020 (2020-08-06), US , pages 29528 - 29539, XP055886985, ISSN: 1944-8244, DOI: 10.1021/acsami.0c07612 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114716416A (zh) * 2022-04-11 2022-07-08 湖北大学 3,4-二氢吡咯衍生物及其一锅法合成
CN114716416B (zh) * 2022-04-11 2023-06-16 湖北大学 3,4-二氢吡咯衍生物及其一锅法合成
CN116768940A (zh) * 2023-06-14 2023-09-19 大连理工大学 一种氰基桥联三核自旋转变配合物及其制备方法和应用
NL2036209A (en) * 2023-11-08 2024-02-16 Univ Guangdong Technology Use of cyano-modified pyridino imidazole derivative in preparing organic photoelectric devices
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