CN111875602B - Cyano-modified pyridino-imidazole derivative and preparation method and application thereof - Google Patents

Cyano-modified pyridino-imidazole derivative and preparation method and application thereof Download PDF

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CN111875602B
CN111875602B CN202010681777.4A CN202010681777A CN111875602B CN 111875602 B CN111875602 B CN 111875602B CN 202010681777 A CN202010681777 A CN 202010681777A CN 111875602 B CN111875602 B CN 111875602B
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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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Abstract

The invention discloses a cyano-modified pyridoimidazole derivative, a preparation method and application thereof, wherein the cyano-modified pyridoimidazole derivative has a molecular structure shown as a formula (I):
Figure DDA0002586116600000011
wherein R1 is hydrogen or cyano, R2 is hydrogen or cyano, and R1 and R2 are not simultaneously hydrogen. The invention introduces C \8230, H \8230, pi stacking structure and cyano group into the pyridine imidazole derivatives to obtain higher fluorescence quantum yield, enhanced electron-withdrawing capability of acceptor groups and red shift of spectra, and the derivatives also have better AIE effect, high-efficiency Thermally Activated Delayed Fluorescence (TADF) property, good thermal stability and solubility, can be used as red light emitting materials, light emitting devices or light emitting intelligent materials and the like, and can be applied to the fields of full-color display, solid state lighting and the like.

Description

Cyano-modified pyridino-imidazole derivative and preparation method and application thereof
Technical Field
The invention relates to the technical field of organic luminescent materials, in particular to a cyano-modified pyridoimidazole derivative and a preparation method and application thereof.
Background
The technology of using organic light emitting materials as Organic Light Emitting Diodes (OLEDs) has wide applications in the fields of flat panel displays, smart phones, solid state lighting, and the like, owing to the significant advantages of large area and high quality display and lighting, ultrahigh resolution, ultra-fast response speed, flexibility, and the like.
However, the red light emitting material in the current organic light emitting material has the problems of low solid state fluorescence quantum yield, poor thermal stability and poor solubility because the inherent narrow band gap can greatly enhance the non-radiative transition rate of molecules, thereby causing large energy loss.
For example, chinese patent CN102070632B discloses a pyridoimidazole derivative and its application in an organic electroluminescent device, wherein the pyridoimidazole derivative has a structure with a rigid substituent group introduced to red-shift the light-emitting position to the visible light region, thereby improving the light-emitting efficiency, and simultaneously destroying the molecular coplanarity and improving the thermal stability of the compound.
Disclosure of Invention
The invention aims to solve the technical problems of low fluorescence quantum yield and poor solubility of the existing pyridine imidazole derivative luminescent material, and provides a cyano-modified pyridine imidazole derivative which has high fluorescence quantum yield, can generate Aggregation Induced Emission (AIE) effect, can emit red light, and has good thermal stability and solubility.
The invention also aims to provide a preparation method of the cyano-modified pyridoimidazole derivative.
The invention also aims to provide application of the cyano-modified pyridoimidazole derivative.
The above purpose of the invention is realized by the following technical scheme:
a cyano-modified pyridoimidazole derivative has a molecular structure shown as a formula (I):
Figure BDA0002586116580000021
wherein R1 is hydrogen or cyano, R2 is hydrogen or cyano, and R1 and R2 are not simultaneously hydrogen.
On one hand, the cyano-modified pyridoimidazole derivative provided by the invention has a structure containing N aromatic anthracenyl (or hydrogenated phenoxazinyl) and a bridged benzene ring introduced between carbonyl groups, so that a larger conjugated plane is formed; on the other hand, the structure is favorable for molecular luminescence due to the existence of C (8230); H (8230); pi accumulation (provided by N atoms on hydrogenated phenoxazine and pyridoimidazole), and higher fluorescence quantum yield is obtained. In addition, a cyano group is also introduced into the molecule, so that the electron donating capability of the molecule is enhanced, the spectrum is red-shifted, the red light is emitted, and the difference between singlet state and triplet state energy levels is obviously reduced, so that the Thermal Activation Delayed Fluorescence (TADF) property is more excellent. The cyano-modified pyridoimidazole derivative also contains carbonyl, so that molecular vibration can be caused, an Aggregation Induced Emission (AIE) effect can be generated, exciton annihilation can be effectively inhibited, and molecules have stronger fluorescence emission in a high-concentration aggregation state than in a low-concentration state, so that the cyano-modified pyridoimidazole derivative has higher luminous intensity and better AIE performance. In addition, the cyano-modified pyridoimidazole derivative has the advantage of good thermal stability due to the fact that the relative molecular weight of the cyano-modified pyridoimidazole derivative is large and the N-containing heterocyclic structure (pyridoimidazole group) and the N-containing aromatic anthracenyl structure are conjugated. In addition, the aromatic ring on the structure of the cyano-modified pyridoimidazole derivative is small in volume and good in solubility.
Preferably, when R1 is cyano and R2 is hydrogen, the cyano-modified pyridoimidazole derivative is crystallized in an orthorhombic system, the space group is P21/n, and the unit cell parameters are
Figure BDA0002586116580000022
Figure BDA0002586116580000023
β＝95.651(2)°；
Or when R1 is hydrogen and R2 is cyano, the cyano-modified pyridoimidazole derivative is crystallized in an orthorhombic system, the space group is P21/c,
Figure BDA0002586116580000024
β＝102.328(2)°。
the invention protects the preparation method of the cyano-modified pyridoimidazole derivative, which comprises the steps of carrying out Buchwald-Hartwig cross coupling reaction on the pyridoimidazole derivative and 10-hydrogen-phenoxazine to prepare a compound shown in a formula (I); the pyridylimidazole derivative is one of 4- (2- (4-bromobenzene) imidazo [1, a ]) pyridine-3-yl) benzonitrile, 4- (2- (4-bromobenzene) imidazo [1, a ]) pyridine-3-yl) pyridine nitrile and 4- (2- (4-bromobenzene) imidazo [1, a ]) pyridine-3-yl) benzyl-pyridine nitrile.
Preferably, the molar ratio of the pyridoimidazole derivative to the 10-hydro-phenoxazine is 1: 1-2.
More preferably, the molar ratio of the pyridoimidazole derivative to the 10-hydro-phenoxazine is 1:1 to 1.2.
Further preferably, the molar ratio of the pyridimidazoles derivative to the 10-hydro-phenoxazine is 1: 1.1.
Preferably, the Buchwald-Hartwig cross-coupling reaction is carried out at 120-130 ℃ for 12-15 h.
More preferably, the Buchwald-Hartwig cross-coupling reaction is carried out at the temperature of between 128 and 130 ℃ for 13 to 15 hours.
Further preferably, the Buchwald-Hartwig cross-coupling reaction is carried out at 130 ℃ for 15h.
Preferably, the Buchwald-Hartwig cross-coupling reaction is carried out at a pH of 10 to 14.
Preferably, the catalyst for the Buchwald-Hartwig cross-coupling reaction is a palladium catalyst.
Preferably, the palladium catalyst is palladium acetate.
Preferably, the Buchwald-Hartwig cross-coupling reaction is carried out in an inert atmosphere.
Preferably, the inert atmosphere is one of nitrogen, argon, helium.
Preferably, the (4- (2- (4-bromobenzene) imidazo [1, a ]) pyridine-3-yl) benzonitrile is obtained by performing Michael cyclization reaction of (E) -4- (3- (4-bromophenylhydrazine) benzonitrile and 2-aminopyridine in the presence of iodine.
Preferably, the molar ratio of the (E) -4- (3- (4-bromophenylhydrazine)) benzonitrile, 2-aminopyridine and iodine is 1-1.1: 2-2.2: 0.23-0.25.
More preferably, the molar ratio of ((E) -4- (3- (4-bromophenylhydrazine)) benzonitrile, 2-aminopyridine to elemental iodine is 1: 2: 0.23.
Preferably, the (4- (2- (4-bromobenzene) imidazo [1, a ]) pyridine-3-yl) pyridine nitrile is obtained by Michael cyclization reaction of (E) -4- (3- (4-bromophenylhydrazine)) benzyl and 2-amino-4-cyanopyridine in the presence of iodine.
Preferably, the molar ratio of ((E) -4- (3- (4-bromophenylhydrazine)) benzyl, 2-amino-4-cyanopyridine and iodine is 1-1.1: 2-2.2: 0.23-0.25.
More preferably, the molar ratio of ((E) -4- (3- (4-bromophenylhydrazine)) benzyl, 2-amino-4-cyanopyridine to iodine is 1: 2: 0.23.
Preferably, the solvent for the Michael cyclization reaction is dichloroethane.
Preferably, the Michael cyclization reaction is carried out in air at 115-120 ℃ for 10-13 h.
More preferably, the Michael cyclization reaction is carried out in air at 118-120 ℃ for 10-12 h.
Further preferably, the Michael cyclization reaction is carried out in air at 120 ℃ for 12h.
Preferably, the preparation method further comprises the post-treatment steps of cooling, distilling, extracting, drying, concentrating and separating.
Specifically, the post-treatment step comprises the steps of cooling and collecting to obtain yellow turbid liquid, distilling the turbid liquid under reduced pressure to remove toluene, extracting the residual solid with dichloromethane for three times, combining the three times to obtain an organic phase, drying with anhydrous magnesium sulfate, distilling the organic phase under reduced pressure to obtain a crude product, and finally performing silica gel column chromatography by using ethyl acetate and petroleum ether as eluents to separate the compound shown in the formula (I).
Preferably, the method further comprises the steps of dissolving the cyano-modified pyridoimidazole derivative in an organic solvent to obtain a saturated solution, adding n-hexane, and separating out a cyano-modified pyridoimidazole derivative crystal sample at the temperature of 20-30 ℃.
Because the cyano-modified pyridoimidazole derivative has low solubility in n-hexane, the slow addition of n-hexane is beneficial to the precipitation of crystals.
More preferably, the temperature of the crystallization is 25 ℃. If the crystallization temperature is too low, the volatilization of the organic solvent and the normal hexane solvent is not facilitated, the precipitation of crystals is not facilitated, and if the temperature is too high, the volatilization of the organic solvent is too fast, needle-shaped polycrystal is easy to grow, and the crystal form is not good.
Preferably, the organic solvent is one of tetrahydrofuran, dichloromethane and toluene.
Preferably, the volume ratio of the organic solvent to the n-hexane is 1: 1-2.
Preferably, the rate of addition of n-hexane is 0.5 to 1.0mL/min.
Preferably, after the cyano-modified pyridoimidazole derivative crystal sample is precipitated, the method further comprises the post-treatment steps of filtering, washing and drying.
Preferably, the washing uses n-hexane as a detergent.
The invention also protects the application of the cyano-modified pyridoimidazole derivative in organic luminescent materials.
In particular to application of cyano-modified pyridoimidazole derivatives in organic red light emitting materials.
The cyano-modified pyridoimidazole derivative prepared by the invention can be assembled into a single-layer luminescent device in practical application, has better luminescent property, simplifies the process and reduces the cost.
Compared with the prior art, the invention has the beneficial effects that:
the cyano-modified pyrido imidazole derivative contains N aromatic anthracenyl, introduces a bridged benzene ring between the N aromatic anthracenyl and carbonyl to form a larger conjugated plane, has C8230H 8230Ph pi stacking, has higher fluorescence quantum yield, introduces cyano groups, enhances the electron-withdrawing capability of acceptor groups, has more prominent intramolecular charge transfer phenomenon and spectral red shift, and can emit red light.
Drawings
FIG. 1 is a hydrogen spectrum of a cyano-modified pyridoimidazole derivative Ben-CN prepared in example 1.
FIG. 2 is a mass spectrum of a cyano-modified pyridoimidazole derivative Ben-CN prepared in example 1.
FIG. 3 is a hydrogen spectrum of cyano-modified pyridoimidazole derivative Bd-CN prepared in example 2.
FIG. 4 is a mass spectrum of cyano-modified pyridoimidazole derivative Bd-CN obtained in example 2.
FIG. 5 is a diagram showing the UV-VIS absorption spectrum of the cyano-modified pyridoimidazole derivative Ben-CN prepared in example 1.
FIG. 6 is a UV-VIS absorption spectrum and a fluorescence emission spectrum of cyano-modified pyridoimidazole derivatives Bd-CN prepared in example 2.
FIG. 7 is a diagram showing AIE spectra of cyano-modified pyridoimidazole derivatives Ben-CN prepared in example 1 in solutions with different water contents.
FIG. 8 is a chart of AIE spectra of cyano-modified pyridoimidazole derivatives Bd-CN prepared in example 2 in solutions with different water contents.
FIG. 9 is a solvation effect diagram of a cyano-modified pyridoimidazole derivative Ben-CN prepared in example 1.
FIG. 10 is a cyclic voltammogram of a cyano-modified pyridoimidazole derivative Ben-CN prepared in example 1.
FIG. 11 is a cyclic voltammogram of cyano-modified pyridoimidazole derivative Bd-CN prepared in example 2.
FIG. 12 is a single crystal result chart of a cyano-modified pyridoimidazole derivative Ben-CN obtained in example 1.
FIG. 13 is a single crystal result chart of cyano-modified pyridoimidazole derivative Bd-CN obtained in example 2.
FIG. 14 is a single crystal and pure film fluorescence emission diagram of the cyano-modified pyridoimidazole derivative Ben-CN prepared in example 1.
FIG. 15 is a single crystal and pure film fluorescence emission diagram of cyano-modified pyridoimidazole derivative Bd-CN prepared in example 2.
FIG. 16 is a graph showing the thermal stability of the cyano-modified pyridoimidazole derivatives Ben-CN and Bd-CN obtained in examples 1 and 2.
FIG. 17 shows the test spectra of normal temperature fluorescence and low temperature phosphorescence of cyano-modified pyridoimidazole derivative Ben-CN prepared in example 1.
FIG. 18 shows the test spectra of normal temperature fluorescence and low temperature phosphorescence of cyano-modified pyridoimidazole derivative Bd-CN prepared in example 2.
Detailed Description
The present invention will be further described with reference to specific embodiments, but the present invention is not limited to the embodiments in any way. The starting reagents employed in the examples of the present invention are, unless otherwise specified, those that are conventionally purchased.
Example 1
A cyano-modified pyridoimidazole derivative is named as Ben-CN and has a molecular structure shown as follows:
Figure BDA0002586116580000061
the preparation method of the Ben-CN comprises the following steps:
weighing (E) -4- (3- (4-bromophenylhydrazine)) benzonitrile 150mg, 80mg of iodine simple substance 60mg of 2-aminopyridine and 3mL of dichloroethane, performing Michael cyclization reaction in a 10mL sealed tube at the temperature of 120 ℃, and treating to obtain (4- (2- (4-bromobenzene) imidazo [1, a ]) pyridin-3-yl) benzonitrile; DCE is dichloroethane;
the reaction equation is as follows:
Figure BDA0002586116580000062
weighing 180mg of the prepared (4- (2- (4-bromobenzene) imidazo [1, a ]) pyridine-3-yl) benzonitrile, 115mg of 10-hydrogen-phenoxazine, 80mg of potassium tert-butoxide, 4mg of tri-tert-butylphosphine, 5.5mg of palladium acetate and 5mL of toluene in a sealed tube, stirring, pumping out air in the device, filling nitrogen for protection, heating, stirring, refluxing and reacting for 15 hours at 130 ℃ under the protection of nitrogen, and after the reaction is finished, cooling, distilling, extracting, drying, concentrating and separating a crude product; cooling and collecting to obtain yellow turbid liquid, distilling the turbid liquid under reduced pressure to remove toluene, extracting the residual solid with dichloromethane for three times, combining organic phases obtained by the three times, drying with anhydrous magnesium sulfate, and distilling the organic phase under reduced pressure to obtain a crude product; finally, using ethyl acetate and petroleum ether as eluent to carry out silica gel column chromatography separation; distilling the obtained pure product solution under reduced pressure and drying in vacuum to obtain 90mg of yellow solid, namely Ben-CN, with the purity of 99 percent and the yield of 50 percent; the product was further added to tetrahydrofuran and n-hexane 1:1, slowly volatilizing the solvent at room temperature in the mixed solution to obtain crystals;
the reaction equation is as follows:
Figure BDA0002586116580000071
example 2
A cyano-modified pyridoimidazole derivative is named as Bd-CN and has a molecular structure shown as follows:
Figure BDA0002586116580000072
the above Bd-CN is prepared in the same manner as in example 1 except that (E) -4- (3- (4-bromophenylhydrazine)) benzonitrile is replaced with (E) -4- (3- (4-bromophenylhydrazine)) nitrile and 2-aminopyridine is replaced with 2-amino-4-cyano-pyridine to give (4- (2- (4-bromophenyl) imidazo [1, a ]) pyridin-3-yl) pyridinecarbonitrile;
the reaction equation is as follows:
Figure BDA0002586116580000081
example 3
A cyano-modified pyridoimidazole derivative has a molecular structure shown as follows:
Figure BDA0002586116580000082
the cyano-modified pyridoimidazole derivative was prepared in the same manner as in example 1, except that (4- (2- (4-bromobenzene) imidazo [1, a ]) pyridin-3-yl) benzonitrile was replaced with (4- (2- (4-bromobenzene) imidazo [1, a ]) pyridin-3-yl) benzyl-pyridinecarbonitrile.
The reaction equation is as follows:
Figure BDA0002586116580000083
Figure BDA0002586116580000091
comparative example 1
The cyano-modified pyridoimidazole derivative of the present comparative example has a molecular structure shown below:
Figure BDA0002586116580000092
the cyano-modified pyridoimidazole derivative was prepared in the same manner as in example 1, except that (E) -4- (3- (4-bromophenylhydrazine)) phenone was replaced with (E) -4- (3- (4-bromophenylhydrazine)) benzonitrile.
The reaction equation is as follows:
Figure BDA0002586116580000093
structural characterization and Performance testing
1. Nuclear magnetic resonance and mass spectrometry
The hydrogen signal of Ben-CN prepared in this example 1 was scanned by nmr; the cyano-modified pyridoimidazole derivatives prepared in examples 1 and 2 were dissolved in acetonitrile to prepare a solution with a concentration of 1mg/mL, and mass spectrometry was performed using a liquid chromatograph-mass spectrometer LCMS-2020.
Nuclear magnetic spectrum of Ben-CN obtained in example 1(FIG. 1) δ (ppm) is 1 H NMR (400mhz, chloroform-d) δ 8.55-8.46 (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, 1.1hz, 2h), 6.01 (dd, J =7.8,1.5hz, 2h), a mass spectrum from Ben-CN (fig. 3) can be seen, where the relative molecular mass is 505.17 minus the relative molecular mass of Ben-CN. The results of the above nuclear and mass spectra were combined to show that the product obtained in example 1 was Ben-CN.
The nuclear magnetic spectrum of Bd-CN obtained in example 2 (FIG. 2) delta (ppm) is 1 H NMR (400mhz, chloroform-d) δ 8.40 (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), as can be seen from Bd-CN mass spectrum (fig. 4), where the relative molecular mass is 505.17, minus one H, consistent with the relative molecular mass of the as-synthesized Bd-CN. The results of the above nuclear magnetic and mass spectra were combined to show that the product obtained in example 2 was Bd-CN.
2. Ultraviolet visible absorption spectrum
The cyano-modified pyridoimidazole derivatives obtained in examples 1 and 2 were dissolved in THF using Shimadzu UV-visible spectrophotometer UV-2700 to prepare 1X 10 -3 mol/L mother liquor, diluting to 1 × 10 -5 The mol/L is tested.
As seen from FIG. 5, ben-CN has a main absorption peak position of 334nm, an emission wavelength of 601nm, and red light emission.
As seen from FIG. 6, the main absorption peak position of Bd-CN is 334nm, the emission wavelength is 610nm, and the emission is red light. Whereas the molecule of comparative example 1 emitted at 574nm and was unable to produce red light.
3. AIE Performance
Dissolving cyano-modified pyridoimidazole derivative in tetrahydrofuran to prepare 1 × 10 -3 mol/L of mother liquor, and maintaining the total volume of the test solution to be 3mL. Maintaining the concentration of cyano-modified pyridoimidazole derivatives in the test solution at 1X 10 - 5 molL, the ratio of tetrahydrofuran to water in the test solution was adjusted. For example: when the water content is 90%, the addition amount of the components is mother liquor, water, tetrahydrofuran =30uL, 2700uL and 270uL. AIE spectra of cyano-modified pyridoimidazole derivatives were measured using FLS980 fluorometer.
Fluorescence spectra of cyano-modified pyridoimidazole derivatives Ben-CN in tetrahydrofuran-water solution with water content of 0% -99% are respectively tested, as shown in FIG. 7, the direction indicated by an arrow is the direction in which the water content of the solution corresponding to 6 fluorescence graphs is increased in sequence, and the emission wavelength of Ben-CN is 600nm; when the water content is lower than 95%, the fluorescence emission wavelength of Ben-CN in the solution shows obvious red shift; and when the water content exceeds 95%, the spectrum is blue-shifted, molecules are separated out and aggregated in the solution, and the corresponding fluorescence intensity is greatly enhanced, so that the Ben-CN has an obvious AIE phenomenon.
Respectively testing the fluorescence spectra of Bd-CN in tetrahydrofuran-water solution with water content of 0-99%; as shown in FIG. 8, the direction indicated by the arrow is the direction in which the water content of the solution increases in sequence corresponding to 4 fluorescence plots, and the emission wavelength of Bd-CN is 610nm; when the water content is lower than 95%, the fluorescence emission wavelength of Bd-CN in the solution shows obvious red shift; when the water content exceeds 95%, the spectrum is blue-shifted, molecules are separated out and aggregated in the solution, and the corresponding fluorescence intensity is greatly enhanced, so that the Bd-CN is known to have an obvious AIE phenomenon.
4. Solvation effect
The normalized spectra of cyano-modified pyridoimidazole derivatives in different solvents were tested using an FLS980 fluorometer.
As can be seen from FIG. 9, the spectrum of the cyano-modified pyridoimidazole derivative Ben-CN in different solvents (arranged according to the polarity of the solvents from large to small: n-hex, toluene Tol, dichloromethane DCM, tetrahydrofuran THF, ethyl acetate EtaOH) shows obvious solvatochromic effect along with the increase of the polarity of the solvents, which is caused by intramolecular charge transfer effect (ICT), namely, a charge transfer excited state.
5. Cyclic voltammogram
The cyclic voltammograms of the cyano-modified pyridoimidazole derivatives Ben-CN and Bd-CN prepared in example 1 and example 2 were tested by using a PGSTAT302 electrochemical workstation.
Cyano-modified pyridoimidazole derivatives were dissolved in acetonitrile to prepare a 1mg/mL solution, and oxidation potentials of Ben-CN and Bd-CN were measured by cyclic voltammetry under an electrochemical workstation as E =0.74eV and E =0.75eV (see fig. 10 and 11). Ben-CN and Bd-CN have stronger oxidation potential values than E =0.67V of comparative example 1, and are more favorable for the generation of red light.
6. Solubility in water
Ben-CN from example 1 was dissolved in acetone, ethyl acetate, tetrahydrofuran, dichloromethane solvent, specifically 10 mg of the sample was dissolved in 1 ml of the solvent. The results are shown in table 1, wherein "+" indicates solubility in the corresponding solvent, and a larger number of "+" indicates solubility in the corresponding solvent.
TABLE 1 solubility of Ben-CN and Bd-CN obtained in example 1 and example 2
Figure BDA0002586116580000111
Figure BDA0002586116580000121
The results in Table 1 above show that Ben-CN and Bd-CN have better solubility.
7. Single crystal X-ray diffraction
The crystal structure was determined using a german bruker X single crystal diffractometer. The test method comprises the following steps: selecting single crystals with proper size and good crystal quality as samples, utilizing X-rays to irradiate one single crystal to diffract, analyzing the arrangement rule of atoms in the crystal by analyzing diffraction lines, collecting diffraction data, indexing a diffraction pattern, solving a unit cell constant, summarizing an extinction rule according to diffraction indexes of all diffraction lines, and deducing a space group to which the crystal belongs. The measured diffraction intensity is subjected to various treatments such as absorption correction and LP correction to obtain the structure amplitude | F |. And (4) estimating a phase angle and a primary structure by using a Peterson function method.
As shown in FIG. 12, single crystal X-ray diffraction data indicate that Ben-CN of example 1 belongs to the orthorhombic system with a space group of P21/n,
Figure BDA0002586116580000122
β＝95.651(2)°,
Figure BDA0002586116580000123
z =4. As can be seen from the crystal force diagram, C \8230H/N and C \8230H \8230piaccumulation exists among molecules, which is beneficial to the luminescence of the molecules, and the absolute quantum yield of the molecules is tested by an integrating sphere of FLS980, and the result shows that the Ben-CN obtains a high fluorescence quantum yield of more than 50%.
As shown in FIG. 13, the single crystal X-ray diffraction data indicate that Bd-CN in example 2 belongs to the orthorhombic system with the space group P2 1 /c,
Figure BDA0002586116580000124
β＝102.328(2)°,
Figure BDA0002586116580000125
Z =4. As can be seen from the crystal force diagram, C \8230H/N and C \8230H \8230piaccumulation exists among molecules, which is beneficial to the luminescence of the molecules, and the absolute quantum yield of the molecules is tested by an integrating sphere of FLS980, and the result shows that Bd-CN obtains a high fluorescence quantum yield of more than 50%.
8. Single crystal fluorescence emission test
Fluorescence spectrum: performing solid fluorescence spectrum test by adopting an Edinburgh FL980 transient stable state fluorescence phosphorescence spectrometer; the excitation wavelength is set to be 370nm, the width of the slit is set to enable the longitudinal coordinate value to be close to one million, and then spectrum testing is carried out to obtain a spectrogram.
As shown in FIGS. 14 and 15, the Ben-CN and Bd-CN crystals and the pure films (thin films prepared by vacuum-evaporating Ben-CN and Bd-CN on a quartz plate, respectively) obtained in examples 1 and 2 exhibited maximum emission peaks at 600nm under 370nm excitation. By comparison, it can be found that the crystal emission peak is broad, which may be attributed to: compared with an amorphous pure film, the amorphous pure film has obvious C8230, H8230and pi accumulation among molecules in a crystal structure. The Ben-CN and Bd-CN prepared in the pure films in the examples 1 and 2 both obtain the fluorescence emission of more than 600nm, and show the superiority of the molecules prepared by the invention on the red light emission compared with the fluorescence emission of 574nm in the comparative example 1. Also, both Ben-CN and Bd-CN obtained in example 1 and example 2 obtained fluorescence quantum yields close to 40% in the pure films, while the fluorescence quantum yield of the thin film of comparative example 1 was 30.2%, indicating that Ben-CN and Bd-CN have better luminescence properties in the thin film state relative to the molecules of comparative example 1.
As shown in FIG. 16, when the temperature was increased in a nitrogen atmosphere with a temperature gradient of 20 ℃ it was found that the thermal decomposition temperatures of Ben-CN and Bd-CN obtained in examples 1 and 2 both exceeded 400 ℃ and were 369.1 ℃ as compared with those of comparative example 1, demonstrating the more excellent thermal stability of examples 1 and 2.
As shown in FIGS. 17 and 18, the Ben-CN and Bd-CN obtained in examples 1 and 2 were subjected to the fluorescence and phosphorescence measurements at room temperature and low temperature using FLS980 as a sample, and the lowest singlet S calculated from the spectra 1 And lowest triplet state T 1 The energy level differences were as low as 0.03 and 0.02 electron volts, respectively, indicating that both molecules of the invention have more efficient TADF performance compared to the 0.05eV energy level difference of comparative example 1.
It should be understood that the above-described embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. This need not be, nor should it be exhaustive of all embodiments. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the claims of the present invention.

Claims (10)

1. A cyano-modified pyridoimidazole derivative is characterized by having a molecular structure shown as a formula (I):
Figure FDA0003775992020000011
wherein R1 is hydrogen and R2 is cyano; or R1 is cyano and R2 is hydrogen.
2. The cyano-modified pyridoimidazole derivative according to claim 1, wherein R is 1 When it is cyano, R 2 When the crystal is hydrogen, the cyano-modified pyridoimidazole derivative is crystallized in an orthorhombic system, the space group is P21/n, and the unit cell parameter is
Figure FDA0003775992020000013
β＝95.651(2)°；
Or when R1 is hydrogen and R2 is cyano, the cyano-modified pyridoimidazole derivative is crystallized in an orthorhombic system, the space group is P21/c, and the unit cell parameter is
Figure FDA0003775992020000014
Figure FDA0003775992020000015
β＝102.328(2)°。
3. The method for preparing cyano-modified pyridoimidazole derivatives according to claim 1 or 2, characterized in that the compound of formula (i) is prepared by Buchwald-Hartwig cross-coupling reaction of the pyridoimidazole derivatives with 10-hydro-phenoxazine; the structural formula of the pyridoimidazole derivatives is shown in the specification
Figure FDA0003775992020000012
4. The preparation method according to claim 3, characterized in that the molar ratio of the pyridoimidazole derivative to the 10-hydro-phenoxazine is 1: 1-2.
5. The preparation method of claim 3, wherein the Buchwald-Hartwig cross-coupling reaction is carried out at 120-130 ℃ for 12-15 h.
6. The method of claim 3, wherein the Buchwald-Hartwig cross-coupling reaction is carried out at a pH of 10 to 14.
7. The method of claim 3, wherein the catalyst for the Buchwald-Hartwig cross-coupling reaction is a palladium catalyst.
8. The method of claim 3, wherein the Buchwald-Hartwig cross-coupling reaction is performed in an inert atmosphere.
9. The preparation method according to claim 3, characterized by further comprising dissolving the cyano-modified pyridoimidazole derivative in an organic solvent to obtain a saturated solution, adding n-hexane, and precipitating a cyano-modified pyridoimidazole derivative crystal sample at 20-30 ℃.
10. The application of the cyano-modified pyridoimidazole derivatives in organic luminescent materials according to claim 1 or 2.
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CN112645949B (en) * 2020-12-25 2022-04-19 广东工业大学 Aromatic amine derivative containing benzophenone group and preparation method and application thereof
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102070632A (en) * 2009-11-20 2011-05-25 中国科学院理化技术研究所 Pyridoimidazole derivative and application thereof in organic electroluminescent device
CN109320459A (en) * 2018-10-09 2019-02-12 广东工业大学 A kind of phenanthro- imidazole derivative containing fluorenes, crystal and the preparation method and application thereof
CN109705041A (en) * 2019-01-29 2019-05-03 广东工业大学 A kind of phenanthro- glyoxaline compound of triphenylamine substitution-modified by vinyl and preparation method thereof and application as electroluminescent device
CN110117283A (en) * 2019-03-22 2019-08-13 广东工业大学 A kind of N heterocycle Benzophenone analog derivative and preparation method thereof containing hydrogenation phenthazine group
CN110283169A (en) * 2019-03-22 2019-09-27 广东工业大学 A kind of N heterocycle Benzophenone analog derivative and preparation method thereof containing substituted hydrogenated acridine group

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102070632A (en) * 2009-11-20 2011-05-25 中国科学院理化技术研究所 Pyridoimidazole derivative and application thereof in organic electroluminescent device
CN109320459A (en) * 2018-10-09 2019-02-12 广东工业大学 A kind of phenanthro- imidazole derivative containing fluorenes, crystal and the preparation method and application thereof
CN109705041A (en) * 2019-01-29 2019-05-03 广东工业大学 A kind of phenanthro- glyoxaline compound of triphenylamine substitution-modified by vinyl and preparation method thereof and application as electroluminescent device
CN110117283A (en) * 2019-03-22 2019-08-13 广东工业大学 A kind of N heterocycle Benzophenone analog derivative and preparation method thereof containing hydrogenation phenthazine group
CN110283169A (en) * 2019-03-22 2019-09-27 广东工业大学 A kind of N heterocycle Benzophenone analog derivative and preparation method thereof containing substituted hydrogenated acridine group

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
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;Zhiwen Yang et al.;《ACS Applied Materials & Interfaces》;20200608;第12卷(第26期);29528-29539 *

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