CN118271295A - A dibenzophenazine derivative luminescent material and its preparation method and application - Google Patents
A dibenzophenazine derivative luminescent material and its preparation method and application Download PDFInfo
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Abstract
本发明公开了一种二苯并吩嗪衍生物发光材料及其制备方法与应用，属于电致发光材料技术领域。所述的二苯并吩嗪衍生物发光材料以平面刚性的二苯并吩嗪作为核心的受体部分，以3,9'‑联咔唑为给体基团，制备了系列给体‑受体和给体‑受体‑给体型的有机发光分子，具有极小的单重态三重态能隙差，可进行快速的反向系间窜越过程，具有热激活延迟荧光特性，可用于照明及显示等领域，所述的二苯并吩嗪衍生物发光材料的制备方法具有合成简单，反应步骤少的优点。The present invention discloses a dibenzophenazine derivative luminescent material and its preparation method and application, belonging to the technical field of electroluminescent materials. The dibenzophenazine derivative luminescent material uses planar rigid dibenzophenazine as the core acceptor part and 3,9'-bicarbazole as the donor group to prepare a series of donor-acceptor and donor-acceptor-donor organic luminescent molecules, which have a very small singlet-triplet energy gap difference, can undergo a rapid reverse intersystem crossing process, have thermally activated delayed fluorescence characteristics, and can be used in lighting and display fields. The preparation method of the dibenzophenazine derivative luminescent material has the advantages of simple synthesis and few reaction steps.
Description
Technical Field
The invention relates to the technical field of electroluminescent materials, in particular to a dibenzophenazine derivative luminescent material, a preparation method and application thereof.
Background
In the sixties of the last century, people observed the phenomenon of electroluminescence when anthracene single crystals applied four hundred volts high voltage for the first time, but because the driving voltage is too high, the anthracene single crystals are difficult to apply to actual production and life, and do not draw attention. By Deng Qingyun in the united states of america in 1987, it was taught that electroluminescent devices were successfully prepared for the first time, with a luminance of 1000cd/m 2 at a drive voltage of 10V. Since then, extensive research into electroluminescent materials has been initiated, and a certain market share is currently being occupied in the fields of display and lighting. The first generation of fluorescent OLEDs fluoresced with 25% singlet exciton radiative transitions, with an off-theoretical quantum efficiency EQE of only 5%, which has been rarely studied now due to inefficiency. The second generation phosphorescence OLED introduces noble metals such as iridium, platinum and the like in molecules, and the heavy atomic effect enables the original spin forbidden process to occur, and intersystem channeling crossing process can occur during transition so as to achieve 100% exciton utilization rate, thereby greatly improving EQE (equivalent emission) from mechanism and greatly improving the luminous efficiency of the device. However, the use of heavy atoms increases the manufacturing cost of the device and also creates a non-negligible environmental pollution problem. The most widely studied at present is the third generation of thermally activated delayed fluorescence TADF OLED materials, which require a very small energy gap difference (Δe ST) between the singlet and triplet states of the molecule, which allows the reverse intersystem crossing process (RISC) of the molecule to convert triplet excitons to singlet excitons, and finally to achieve 100% exciton utilization as well. The TADF material is generally a pure organic micromolecule, avoids the use of noble metals, can achieve higher efficiency, has simple structure, is easy to modify and modify, and has become a current research hot spot.
TADF molecules are commonly doped as guest materials with host materials for use in OLED devices as light emitting layers. The red light TADF molecules have a greatly increased non-radiative transition rate, which results in a generally lower luminous efficiency of the red light TADF molecules.
Disclosure of Invention
The invention aims at solving the problems, and researches and designs a dibenzophenazine derivative luminescent material, and a preparation method and application thereof. The invention adopts the following technical means:
a dibenzophenazine derivative luminescent material having the following structural formula:
Wherein R 1、R2 is independently selected from a hydrogen atom or 3,9' -dicarbazole, and R 3、R4 is independently selected from a hydrogen atom or cyano.
Further, the dibenzophenazine derivative luminescent material has a structural formula of one of the following:
In the molecule provided by the invention, 3,9' -bicarbazole is taken as a donor group, cyano-substituted dibenzophenazine with plane rigidity is taken as an acceptor part, and prepared donor-acceptor (D-A type) and donor-acceptor-donor (D-A-D type) organic luminescent molecules, namely D-A type molecules or D-A-D type molecules, and the molecular delta E ST gradually decreases along with the increase of the number of cyano groups. Through the design and modification of the molecular structure, the invention selects the acceptor with strong electron withdrawing capability and the acceptor with strong electron donating capability, and the acceptors are directly connected through covalent bonds, so that the overlapping degree between HOMO and LUMO is reduced as much as possible, and the extremely small triplet state energy gap difference is realized, thereby enabling molecules to quickly cross between reverse systems. The dibenzophenazine receptor has a large and rigid conjugated plane, widens the molecular plane and increases the molecular rigidity, is favorable for inhibiting non-radiative transition of molecules, and reduces energy loss, thereby improving the efficiency of a final device and improving the problem that the luminous efficiency of red light TADF molecules is generally low to a certain extent.
The preparation method of the dibenzophenazine derivative luminescent material comprises the following steps:
S1: taking bromophenanthrone and R 3、R4 substituted o-phenylenediamine derivative as raw materials, and obtaining an intermediate product through intermolecular cyclization reaction in acetic acid;
S2: the intermediate product prepared in the step S1 and 3,9' -bicarbazole are used as raw materials, palladium acetate, cesium carbonate and tri-tert-butylphosphine are added, and the dibenzophenazine derivative luminescent material is obtained through Buchwald-Hartwig coupling reaction, so that a donor and a receptor can be connected with each other in a high yield to obtain a final product.
In the step S1, the reaction is refluxed for 8 hours under the protection of nitrogen, and after the reaction is stopped, washing and filtering are carried out, and vacuum drying is carried out to obtain an intermediate product; in the step S2, the reaction solvent is anhydrous toluene, reflux is carried out for 24 hours under the protection of nitrogen, the reaction is stopped, the mixture is cooled to room temperature, the mixture is poured into water, dichloromethane is used for extraction, the organic phase is collected and dried by anhydrous sodium sulfate, silica gel powder is added for concentration, and the dibenzophenazine derivative luminescent material is obtained by separation through a column chromatography method.
Further, the bromophenanthrone is 3, 6-dibromophenanthrene-9, 10-dione or 3-bromophenanthrone-9, 10-dione, and the R 3、R4 -substituted o-phenylenediamine derivative is 1, 2-phenylenediamine, 3, 4-diaminobenzonitrile or 4, 5-diaminophthalonitrile.
The compound synthesis route of the invention is as follows:
The invention relates to an application of a dibenzophenazine derivative luminescent material in an electroluminescent device.
The dibenzophenazine derivative luminescent material is applied to an illumination device or a display device.
Compared with the prior art, the dibenzophenazine derivative luminescent material has the advantages of extremely small singlet state triplet state energy gap difference, capability of performing rapid reverse intersystem crossing process, thermal activation delay fluorescence characteristic, capability of being used as an organic luminescent material for preparing electroluminescent devices, capability of being used in the fields of illumination, display and the like, simple synthesis and few reaction steps.
Drawings
FIG. 1 is a graph of the ultraviolet-visible absorption spectra of dibenzophenazine derivatives in solvents of different polarity as disclosed in the examples of the present invention.
FIG. 2 is a graph showing the steady-state fluorescence spectra of dibenzophenazine derivatives in solvents of different polarities as disclosed in the examples of the present invention.
FIG. 3 is a graph showing steady state fluorescence and phosphorescence spectra of dibenzophenazine derivatives of the present invention at 77K in toluene solution.
FIG. 4 is an ultraviolet-visible absorption spectrum of a dibenzophenazine derivative doped in a PMMA film according to the embodiment of the present invention, wherein the mass ratio of the target molecule to PMMA is 1:10.
FIG. 5 is a steady-state fluorescence spectrum of a dibenzophenazine derivative doped in a PMMA film according to the embodiment of the invention, wherein the mass ratio of target molecules to PMMA is 1:10.
FIG. 6 is a graph of transient fluorescence of a dibenzophenazine derivative doped in a PMMA film according to an embodiment of the present invention, wherein the mass ratio of the target molecule to PMMA is 1:10.
FIG. 7 shows a temperature-changing transient fluorescence spectrum (a) and a normal-temperature transient fluorescence spectrum (b) of a molecule 3,6-DCz-DBPZDCN doped in PMMA and CBP films, wherein the mass ratio of 3,6-DBrDBPZDCN, PMMA to CBP is 1:10:10.
Detailed Description
Example 1: synthesis of Compounds 3, 6-DBrDBPZ:
3, 6-Dibromophenanthrene-9, 10-dione (2 mmol), 1, 2-phenylenediamine (2 mmol), and glacial acetic acid (20 ml) were added to a 50ml two-necked flask, and the mixture was refluxed under nitrogen atmosphere for 8 hours, and the progress of the reaction was monitored by a TLC plate. After the reaction is stopped, the mixture is washed and filtered by glacial acetic acid, water, methanol and chloroform in sequence to obtain a pale yellow filter cake, and the pale yellow filter cake is dried overnight in a vacuum drying oven to obtain pale yellow powder.
Example 2: synthesis of Compounds 3, 6-DBrDBPZCN:
3, 6-Dibromophenanthrene-9, 10-dione (2 mmol), 3, 4-diaminobenzonitrile (2 mmol), glacial acetic acid (20 ml) were added to a 50ml two-neck flask and refluxed under nitrogen for 8h, and the TLC plate monitored the progress of the reaction. After the reaction is stopped, the mixture is washed and filtered by glacial acetic acid, water, methanol and chloroform in sequence to obtain a pale yellow filter cake, and the pale yellow filter cake is dried overnight in a vacuum drying oven to obtain pale yellow powder.
Example 3: synthesis of Compounds 3, 6-DBrDBPZDCN:
3, 6-Dibromophenanthrene-9, 10-dione (2 mmol), 4, 5-diaminophthalonitrile (2 mmol), glacial acetic acid (20 ml) was added to a 50ml two-necked flask and refluxed for 8h under nitrogen atmosphere, and the progress of the reaction was monitored by TLC plate. After the reaction is stopped, the mixture is washed and filtered by glacial acetic acid, water, methanol and chloroform in sequence to obtain a pale yellow filter cake, and the pale yellow filter cake is dried overnight in a vacuum drying oven to obtain pale yellow powder.
Example 4: synthesis of Compounds 3-BrDBPZ:
3-bromophenanthrene-9, 10-dione (2 mmol), 1, 2-phenylenediamine (2 mmol), glacial acetic acid (20 ml) was added to a 50ml two-necked flask and refluxed under nitrogen atmosphere for 8h, and the progress of the reaction was monitored by TLC plate. After the reaction is stopped, the mixture is washed and filtered by glacial acetic acid, water, methanol and chloroform in sequence to obtain a pale yellow filter cake, and the pale yellow filter cake is dried overnight in a vacuum drying oven to obtain pale yellow powder.
Example 5: synthesis of Compounds 3-BrDBPZCN:
3-bromophenanthrene-9, 10-dione (2 mmol), 3, 4-diaminobenzonitrile (2 mmol), glacial acetic acid (20 ml) was added to a 50ml two-neck flask and refluxed under nitrogen for 8h, and the progress of the reaction was monitored by TLC plates. After the reaction is stopped, the mixture is washed and filtered by glacial acetic acid, water, methanol and chloroform in sequence to obtain a pale yellow filter cake, and the pale yellow filter cake is dried overnight in a vacuum drying oven to obtain pale yellow powder.
Example 6: synthesis of Compounds 3-BrDBPZDCN:
3-bromophenanthrene-9, 10-dione (2 mmol), 4, 5-diaminophthalonitrile (2 mmol), glacial acetic acid (20 ml) was added to a 50ml two-neck flask and refluxed under nitrogen for 8h, and the progress of the reaction was monitored by TLC plates. After the reaction is stopped, the mixture is washed and filtered by glacial acetic acid, water, methanol and chloroform in sequence to obtain a pale yellow filter cake, and the pale yellow filter cake is dried overnight in a vacuum drying oven to obtain pale yellow powder.
Example 7: synthesis of Compound 3, 6-DCz-DBPZ:
3,6-DBrDBPZ (1 mmol, 0.433 g), 3,9' -dicarbazole (2.2 mmol,0.73 g), toluene (10 ml), cesium carbonate (2 mmol,0.65 g) and palladium acetate (0.05 mmol, 0.0111 g) were added to a 50ml two-necked flask, tri-tert-butylphosphine (0.75 mmol,0.151 g) was added under nitrogen atmosphere, reflux was performed for 24h under nitrogen protection, and the TLC plate monitored for reaction progress. After the reaction was stopped and cooled to room temperature, the mixture was poured into water, extracted with dichloromethane, the organic phase was collected and dried overnight with anhydrous sodium sulfate, then silica gel powder was added for concentration, and the yellow powdery target product was obtained by separation by column chromatography, with a yield of 48.9%. The nuclear magnetic resonance hydrogen spectrum of the product is 1H NMR(400MHz,Methylene Chloride-d2)δ9.70(d,J＝8.5Hz,1H),8.87(d,J＝2.0Hz,1H),8.39(dd,J＝6.5,3.5Hz,1H),8.34(d,J＝2.1Hz,1H),8.19(d,J＝7.7Hz,2H),8.14(d,J＝7.8Hz,1H),8.10(d,J＝8.6Hz,1H),7.93(dt,J＝6.6,3.4Hz,1H),7.82(d,J＝8.6Hz,1H),7.69(d,J＝8.3Hz,1H),7.58(dd,J＝8.6,2.1Hz,1H),7.49(t,J＝7.7Hz,1H),7.45-7.34(m,4H),7.32(dt,J＝14.7,7.3Hz,3H).(, which indicates that: 13 C NMR cannot be obtained due to poor solubility of the product in organic solvents). The mass spectrum of the product was MALDI-TOF-HRMS: M/z Calcd for C 68H40N6: [ M ]940.3309, found:940.3323.
Example 8: synthesis of Compound 3, 6-DCz-DBPZCN:
3,6-DBrDBPZCN (1 mmol, 0.4635 g), 3,9' -dicarbazole (2.2 mmol,0.73 g), toluene (10 ml), cesium carbonate (2 mmol,0.65 g) and palladium acetate (0.05 mmol, 0.0111 g) were added to a 50ml two-necked flask, tri-tert-butylphosphine (0.75 mmol,0.151 g) was added under nitrogen atmosphere, reflux was performed for 24h under nitrogen protection, and the TLC plate monitored for reaction progress. After the reaction was stopped and cooled to room temperature, the mixture was poured into water, extracted with dichloromethane, the organic phase was collected and dried overnight with anhydrous sodium sulfate, then silica gel powder was added for concentration, and the orange-red powdery target product was obtained by separation by column chromatography in a yield of 28.7%. The nuclear magnetic resonance hydrogen spectrum of the product is 1H NMR(400MHz,Methylene Chloride-d2)δ9.81(dd,J＝8.6,6.1Hz,2H),8.94(d,J＝2.0Hz,2H),8.87(d,J＝1.8Hz,1H),8.57(d,J＝8.7Hz,1H),8.37(d,J＝2.0Hz,2H),8.24-8.19(m,8H),8.12(dd,J＝8.8,1.8Hz,1H),7.86(d,J＝8.6Hz,2H),7.73(d,J＝8.3Hz,2H),7.64(d,J＝2.0Hz,1H),7.62(d,J＝2.0Hz,1H),7.57-7.52(m,2H),7.45-7.37(m,10H),7.31(ddd,J＝8.0,6.1,2.0Hz,4H).(, which indicates that: 13 C NMR cannot be obtained due to poor solubility of the product in organic solvents). The mass spectrum of the product was MALDI-TOF-HRMS: M/z Calcd for C 69H39N7: [ M ]965.3267, found:965.3227.
Example 9: synthesis of Compound 3, 6-DCz-DBPZDCN:
3,6-DBrDBPZDCN (1 mmol, 0.4818 g), 3,9' -dicarbazole (2.2 mmol,0.73 g), toluene (10 ml), cesium carbonate (2 mmol,0.65 g) and palladium acetate (0.05 mmol, 0.0111 g) were added to a 50ml two-necked flask, tri-tert-butylphosphine (0.75 mmol,0.151 g) was added under nitrogen atmosphere, reflux was performed for 24h under nitrogen protection, and the TLC plate monitored for reaction progress. After the reaction was stopped and cooled to room temperature, the mixture was poured into water, extracted with dichloromethane, the organic phase was collected and dried overnight with anhydrous sodium sulfate, then silica gel powder was added for concentration, and the product was isolated by column chromatography to give 0.28g of the target product as a dark red powder with a yield of 28.3%. The nuclear magnetic resonance hydrogen spectrum of the product is 1H NMR(600MHz,DMSO-d6)δ9.59(d,J＝8.5Hz,2H),9.52(s,2H),9.31(s,2H),8.58(d,J＝2.2Hz,2H),8.39(d,J＝7.9Hz,2H),8.31(d,J＝8.6Hz,2H),8.25(d,J＝7.8Hz,4H),7.91(d,J＝8.6Hz,2H),7.73(d,J＝8.4Hz,2H),7.68–7.61(m,2H),7.54(t,J＝7.6Hz,2H),7.35(q,J＝8.2,7.7Hz,11H),7.26(t,J＝7.4Hz,4H).(, which indicates that: 13 C NMR cannot be obtained due to poor solubility of the product in organic solvents). The mass spectrum of the product was MALDI-TOF-HRMS: M/z Calcd for C 70H38N8: [ M ]990.3219, found:990.3230.
Example 10: synthesis of Compound 3-DCz-DBPZ:
3-BrDBPZ (1 mmol, 0.399 g), 3,9' -dicarbazole (1.1 mmol,0.365 g), toluene (10 ml), cesium carbonate (2 mmol,0.65 g) and palladium acetate (0.05 mmol, 0.0111 g) were added to a 50ml two-necked flask, tri-tert-butylphosphine (0.75 mmol,0.151 g) was added under nitrogen atmosphere, refluxed for 24h under nitrogen protection, and the TLC plate monitored the progress of the reaction. After the reaction was stopped and cooled to room temperature, the mixture was poured into water, extracted with dichloromethane, the organic phase was collected and dried overnight with anhydrous sodium sulfate, then silica gel powder was added for concentration, and the yellow powdery target product was isolated by column chromatography, the yield was 38.9％.1H NMR(400MHz,Methylene Chloride-d2)δ9.81(d,J＝8.6Hz,1H),9.64–9.52(m,1H),8.96(s,1H),8.64(d,J＝5.9Hz,1H),8.48(d,J＝8.9Hz,2H),8.43(s,1H),8.25(t,J＝6.5Hz,3H),8.14(d,J＝8.6Hz,1H),8.03–7.97(m,2H),7.94–7.86(m,3H),7.74(d,J＝8.4Hz,1H),7.67(d,J＝8.5Hz,1H),7.59(t,J＝7.8Hz,1H),7.53–7.41(m,5H),7.35(t,J＝7.0Hz,2H).(, thus indicating: 13 C NMR cannot be obtained due to poor solubility of the product in organic solvents). The mass spectrum of the product was MALDI-TOF-HRMS: M/z Calcd for C 44H16N4: [ M ]610.2157, found:610.2169.
Example 11: synthesis of Compounds 3-DCzDBPZCN:
3-BrDBPZCN (1 mmol, 0.3834 g), 3,9' -dicarbazole (1.1 mmol,0.365 g), toluene (10 ml), cesium carbonate (2 mmol,0.65 g) and palladium acetate (0.05 mmol, 0.0111 g) were added to a 50ml two-necked flask, tri-tert-butylphosphine (0.75 mmol,0.151 g) was added under nitrogen atmosphere, refluxed for 24h under nitrogen protection, and the TLC plate monitored the progress of the reaction. After the reaction was stopped and cooled to room temperature, the mixture was poured into water, extracted with dichloromethane, the organic phase was collected and dried overnight with anhydrous sodium sulfate, then silica gel powder was added for concentration, and the orange-yellow powdery target product was obtained by separation by column chromatography, with a yield of 28.7%. The nuclear magnetic resonance hydrogen spectrum of the product is 1H NMR(600MHz,Methylene Chloride-d2)δ9.64(dd,J＝10.0,8.5Hz,1H),9.41(ddd,J＝11.4,7.8,1.6Hz,1H),8.89(t,J＝2.3Hz,1H),8.74(dd,J＝5.4,1.8Hz,1H),8.59-8.53(m,1H),8.43(dd,J＝8.7,4.6Hz,1H),8.38(d,J＝2.1Hz,1H),8.20(t,J＝7.3Hz,3H),8.09(dt,J＝8.5,1.7Hz,1H),8.01(dd,J＝8.7,1.8Hz,1H),7.90-7.80(m,3H),7.70(dd,J＝8.4,2.5Hz,1H),7.63(dd,J＝8.6,2.1Hz,1H),7.55(ddd,J＝8.3,6.9,1.2Hz,1H),7.48-7.37(m,5H),7.30(ddd,J＝8.0,6.5,1.5Hz,2H).(, which indicates that: 13 C NMR cannot be obtained due to poor solubility of the product in organic solvents). The mass spectrum of the product was MALDI-TOF-HRMS: M/z Calcd for C 45H25N5: [ M ]635.2104, found:635.2112.
Example 12: synthesis of Compounds 3-DCzDBPZDCN:
3-BrDBPZDCN (1 mmol,0.408 g), 3,9' -dicarbazole (1.1 mmol,0.365 g), toluene (10 ml), cesium carbonate (2 mmol,0.65 g) and palladium acetate (0.05 mmol, 0.0111 g) were added to a 50ml two-necked flask, tri-tert-butylphosphine (0.75 mmol,0.151 g) was added under nitrogen atmosphere, refluxed for 24h under nitrogen protection, and the TLC plate monitored the progress of the reaction. After the reaction was stopped and cooled to room temperature, the mixture was poured into water, extracted with dichloromethane, the organic phase was collected and dried overnight with anhydrous sodium sulfate, then silica gel powder was added for concentration, and the red powdery target product was isolated by column chromatography to give 0.199g with a yield of 30.1%. The nuclear magnetic resonance hydrogen spectrum of the product is 1H NMR(600MHz,Methylene Chloride-d2)δ9.68(d,J＝8.5Hz,1H),9.46(d,J＝8.0Hz,1H),8.94(s,1H),8.89(d,J＝4.4Hz,2H),8.62(d,J＝8.1Hz,1H),8.39(s,1H),8.21(t,J＝8.5Hz,3H),8.15(d,J＝8.6Hz,1H),7.95(t,J＝7.6Hz,1H),7.88(dd,J＝26.0,8.2Hz,2H),7.72(d,J＝8.4Hz,1H),7.65(d,J＝8.6Hz,1H),7.56(t,J＝7.6Hz,1H),7.48-7.38(m,5H),7.31(t,J＝7.1Hz,2H).(, which indicates that: 13 C NMR cannot be obtained due to poor solubility of the product in organic solvents). The mass spectrum of the product was MALDI-TOF-HRMS: M/z Calcd for C 46H24N6: [ M ]662.2, found:662.2.
Test example 1: absorption emission spectra of the compounds prepared in examples 7 to 12 in solution and in the form of films.
A certain mass of sample is weighed into a 1ml volumetric flask by a ten-thousandth balance, and a solvent methylene dichloride is added to prepare a mother solution with the mol/L of 1 multiplied by 10 -3. N-hexane, toluene, tetrahydrofuran, chloroform, methylene dichloride and acetonitrile are respectively used as solvents (the polarity of the solvents is increased), a solution with the concentration of 1 multiplied by 10 -5 mol/L is prepared for testing, an ultraviolet-visible spectrophotometer is used for measuring the absorption spectrum, and the testing range is 280-600nm. As shown in FIG. 1, it can be seen that 6 molecules have LE state absorption peaks at 290nm and 340nm, pi-pi transition and n-pi transition of aromatic ring, and a weak and wide CT state absorption peak between 400 nm and 500 nm. FIG. 4 is a graph showing the ultraviolet-visible absorption spectrum of a sample in a film state, wherein 6 molecules have LE state absorption peaks at 290nm and 340nm, and a weak and wide CT state absorption peak between 400 nm and 500nm, which is basically consistent with the test result in a solution environment.
Test example 2: photoluminescence spectra of the compounds prepared in examples 7 to 12 were tested in solution and in the form of a film. The test conditions were the same as in test example 1.
The Edinburgh FLS1000 is used for testing the emission spectrum of the sample, and the maximum absorption wavelength in the ultraviolet-visible absorption spectrum is selected as the excitation wavelength for testing the steady-state fluorescence spectrum of the sample. The test results are shown in fig. 2 and 5. It can be seen that the emission spectra of all molecules changed significantly with increasing polarity of the solvent. Of these, 3,6-DCz-DBPZDCN,3,6-DCz-DBPZCN,3-DCz-DBPZDCN had only one broad emission peak in n-hexane and toluene, while fluorescence was quenched in more polar solvents. It can be seen in the spectra of the other 3 molecules that as the polarity of the solvent increases, the emission peak position is red shifted, the peak shape becomes broader and there is no fine structure. In addition, the emission peak in the toluene solvent was compared, and a significant red shift occurred with an increase in the number of cyano groups in the molecule, indicating that the regulation of the fluorescence color of the molecule was easily achieved by a slight change in the structure of the molecule. In toluene solvent, two molecules c and f substituted with dicyano groups, with emission peak positions of 641nm and 625nm, respectively, showed red emission. In the film, after the excitation of the CT absorption peak corresponding to the wavelength, the spectrogram shows a wide and strong emission peak, and the emission peak is subjected to red shift to different degrees relative to the normal hexane solution, and is subjected to blue shift relative to other solvents with higher polarities. Because in solid thin films, rotational vibration of molecules and the like are limited such that the energy dissipated by the molecules through non-radiative transitions is reduced, there are some differences in fluorescence spectrum test results from in solution.
Test example 3: transient fluorescence spectrum test of the compounds prepared in examples 7 to 12 in a thin film state. The test conditions were the same as in test example 1.
The transient fluorescence spectrum of the sample is tested by using Edinburgh FLS1000, and the maximum absorption wavelength in the ultraviolet-visible absorption spectrum is selected as the excitation wavelength. The test results are shown in fig. 6. The test results all exhibited nanosecond-scale short lifetimes, indicating that the samples failed to exhibit TADF properties in PMMA films.
Test example 4: the compounds prepared in examples 7-12 were tested for steady state fluorescence, phosphorescence spectra at 77K low temperature in toluene solution.
The low temperature fluorescence and phosphorescence spectra were measured using an Edinburgh FLS1000, and the test results are shown in FIG. 3. Samples c and f exhibited very small Δe ST, 0.065 and 0.058eV, respectively. Indicating that these two molecules are likely to have TADF properties.
Test example 5: the compound prepared in example 9 doped PMMA and CBP films were tested at a temperature transition transient fluorescence spectrum of 77K-300K. The ratio of 3,6-DBrDBPZDCN, PMMA, CBP in the film was 1:10:10.
The temperature-changing transient fluorescence spectrum and the constant temperature transient fluorescence spectrum of the 3,6-DBrDBPZDCN doped film are tested by using an Edinburgh FLS1000, and the test results are shown in figure 7. The samples showed a short lifetime of 29.80ns on the nanosecond scale and a long lifetime of 34.26 μs on the microsecond scale, and the specific gravity of the long lifetime increased with increasing test temperature, demonstrating the TADF properties of the compound when doped with PMMA and CBP.
The above examples are only illustrative of the preferred embodiments of the present invention and are not intended to limit the scope of the present invention, and various modifications and improvements made by those skilled in the art to the technical solution of the present invention should fall within the scope of protection defined by the claims of the present invention without departing from the spirit of the design of the present invention.
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