CN113087707A - 6/6/6-fused tetracyclic cyclometalated platinum (II) complex phosphorescent material based on aza-pyrazole-carbazole and application thereof - Google Patents

6/6/6-fused tetracyclic cyclometalated platinum (II) complex phosphorescent material based on aza-pyrazole-carbazole and application thereof Download PDF

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CN113087707A
CN113087707A CN202110383927.8A CN202110383927A CN113087707A CN 113087707 A CN113087707 A CN 113087707A CN 202110383927 A CN202110383927 A CN 202110383927A CN 113087707 A CN113087707 A CN 113087707A
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carbazole
azapyrazole
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李贵杰
佘远斌
许克伟
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Zhejiang University of Technology ZJUT
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Abstract

The invention provides an 6/6/6 fused tetracyclic cyclometalated platinum (II) complex phosphorescent material based on azapyrazole-carbazole and application thereof. Platinum (II) complex phosphorescent materials based on azapyrazole-carbazoles with very small energy level differences Delta ES1‑T1And Δ ES1‑T2And the lowest excited triplet state T1And a second excited triplet state T2Charge transfer type and lowest excited singlet state S of1And matching can increase the way of intersystem crossing, and is beneficial to improving the rate of the intersystem crossing. The doped OLED device can realize high maximum luminous brightness.

Description

6/6/6-fused tetracyclic cyclometalated platinum (II) complex phosphorescent material based on aza-pyrazole-carbazole and application thereof
Technical Field
The invention relates to a phosphorescent material and application thereof, in particular to an 6/6/6 tetradentate ring metal platinum (II) complex phosphorescent material based on azapyrazole-carbazole and application thereof in an organic light-emitting element.
Background
Compared with liquid crystal display, organic phosphorescent diodes (OLEDs) are self-luminous systems, and have the advantages of high luminous efficiency (up to 100%), low manufacturing cost and energy consumption, wide viewing angle, fast response, wide application temperature range and the like, so that OLEDs have been developed into a new generation of full-color display and solid-state lighting technology, have wide application prospects in the fields of display and lighting, and are widely concerned by academia and industry in China and abroad.
The design and development of light emitting materials is central to the OLED field. The fluorescent material can only use singlet excitons generated by electric excitation, so that the theoretical maximum internal quantum efficiency is only 25 percent; the ring metal complex phosphorescent material can fully utilize all singlet-state and triplet-state excitons generated by electric excitation due to the heavy atom effect thereof, so that the maximum theoretical quantum efficiency can reach 100 percent. However, the phosphorescent materials which are stable and efficient and can meet the commercial application are still quite rare, and are mainly cyclometalated iridium (III) complex phosphorescent materials. Therefore, the design and development of new luminescent materials are still the urgent problems to be solved to promote the development of the OLED field. Low driving voltage and high brightness OLED devices are still needed for the development of this field.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides an 6/6/6 fused tetracyclic cyclometalated platinum (II) complex phosphorescent material based on azapyrazole-carbazole and application thereof.
To achieve the above object of the invention: the invention provides an 6/6/6 fused tetracyclic cyclometalated platinum (II) complex phosphorescent material based on azapyrazole-carbazole, which has a chemical formula shown as a general formula (1):
Figure BDA0003014093170000021
wherein, Y1、Y2、Y3、Y4、Y5、Y6、Y7、Y8、Y9And Y10Each independently is C or N;
a is selected from B, CH, CD, CRa、SiH、SiD、SiRa、GeH、GeD、GeRdP, P ═ O, As ═ O, Bi, or Bi ═ O;
Ra、Rb、Rcand RdEach independently is hydrogen, deuterium, aryl, cycloalkyl, cycloalkenyl, heterocyclyl, heteroaryl, alkyl, alkenyl, alkynyl, halogen, hydroxy, mercapto, nitro, cyano, amino, mono-or dialkylamino, mono-or diarylamino, alkoxy, aryloxy, haloalkyl, ester, nitrile, isonitrile, heteroaryl, alkoxycarbonyl, amido, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, sulfamoyl, carbamoyl, alkylthio, sulfinyl, ureido, phosphoramido, imine, sulfo, carboxyl, hydrazine, substituted silyl, a polymeric group, or a combination thereof;
R1、R2、R3、R4、R5、R6and R7Each independently is hydrogen, deuterium, alkyl, alkoxy, cycloalkyl, heterocyclyl, alkenyl, substituted or unsubstituted aryl, substituted or unsubstituted aryloxy, substituted or unsubstituted heteroaryl, haloalkyl, halogen, hydroxy, mercapto, nitro, cyano, amino, carboxy, sulfo, hydrazino, ureido, alkynyloxy, ester, amide, sulfonyl, sulfinyl, sulfonylamino, phosphorylamino, alkoxycarbonylamino, aryloxycarbonylamino, silyl, alkylamino, dialkylamino, monoarylamino, diarylamino, ureylene, imino, or a combination thereof, R is hydrogen, deuterium, alkyl, alkoxy, cycloalkyl, heterocyclyl, alkenyl, substituted or unsubstituted aryl, substituted or unsubstituted aryloxy, substituted or unsubstituted heteroaryl, haloalkyl, hydroxyl, mercapto, nitro, cyano, amino, carboxyl, sulfo, hydrazino, ureido, alkynyloxy, ester, amido, sulfonyl1、R2、R3、 R4、R5、R6And R7Two or more of which may be joined to form a fused ring, which may also be fused with other rings.
Further, the structural formula of the general formula (1) includes, but is not limited to:
Figure BDA0003014093170000022
Figure BDA0003014093170000031
further, an 6/6/6 pentacyclic tetradentate ring metal platinum (II) complex phosphorescent material based on azapyrazole-carbazole is shown as a general formula (2):
Figure BDA0003014093170000041
wherein, Y1、Y2、Y3、Y4、Y5、Y6And Y7Each independently is C or N;
a is O, S, S ═ O or O ═ S ═ O;
R1、R2、R3、R4、R5and R6Each independently is hydrogen, deuterium, alkyl, alkoxy, cycloalkyl, heterocyclyl, alkenyl, substituted or unsubstituted aryl, substituted or unsubstituted aryloxy, substituted or unsubstituted heteroaryl, haloalkyl, halogen, hydroxy, mercapto, nitro, cyano, amino, carboxyl, sulfo, hydrazino, ureido, alkynyloxy, ester, amide, sulfonyl, sulfinyl, sulfonylamino, phosphorylamino, alkoxycarbonylamino, aryloxycarbonylamino, silyl, alkylamino, dialkylamido, monoarylamino, diarylamino, ureylene, imino, or a combination thereof, R is independently hydrogen, deuterium, alkyl, alkoxy, cycloalkyl, heterocyclyl, alkenyl, substituted or unsubstituted aryl, substituted or unsubstituted aryloxy, substituted or unsubstituted heteroaryl, haloalkyl, halogen, hydroxy, mercapto, nitro, cyano, amino, carboxyl, sulfo, hydrazino, ureido, alkynyloxy1、R2、R3、R4、 R5、R6And R7Two or more of which may be joined to form a fused ring, which may also be fused with other rings.
Further, the structural formula of the general formula (2) includes, but is not limited to:
Figure BDA0003014093170000042
Figure BDA0003014093170000051
further, an 6/6/6 pentacyclic tetradentate ring metal platinum (II) complex phosphorescent material based on azapyrazole-carbazole is applied to an organic light-emitting element. The organic light emitting element is an organic light emitting diode, a light emitting diode or a light emitting electrochemical cell.
Further, the organic light emitting element includes a first electrode, a second electrode, and at least one organic layer disposed between the first electrode and the second electrode; the organic layer comprises an 6/6/6 pentacyclic tetradentate ring metal platinum (II) complex based on azapyrazole-carbazole.
The invention has the beneficial effects that: 6/6/6 pentacyclic tetradentate ring metal platinum (II) complex phosphorescent material based on azapyrazole-carbazole, and energy level difference delta E of lowest excited singlet state and lowest excited triplet stateS1-T1And the energy level difference Δ E between the lowest excited singlet state and the second excited triplet stateS1-T1Is easy to regulate and control. Both Pt (ACzCz-1) and Pt (ACzCz-2) have very small Δ ES1-T1And Δ ES1-T2Especially Pt (ACzCz-1) of 0.048eV and 0.018eV, respectively, and T1And T2Charge transfer type of state and S1And matching can increase the way of intersystem crossing, and is beneficial to improving the speed of intersystem crossing.
Drawings
FIG. 1 is a graph showing emission spectra of Pt (ACzCz-1) and Pt (ACzCz-2) at 77K in 2-methyltetrahydrofuran;
FIG. 2 is a graph showing the emission spectra of Pt (ACzCz-1) and Pt (ACzCz-2) in a dichloromethane solution at room temperature;
FIG. 3 is a graph showing the emission spectra of Pt (ACzCz-1) and Pt (ACzCz-2) in polymethyl methacrylate (PMMA) at room temperature;
FIG. 4 is a graph showing the Spin Density distribution of the lowest triplet state, the optimized molecular structures of Pt (ACzCz-1) and Pt (ACzCz-2), the front linear orbital levels and their distributions, which are calculated by Density Functional Theory (DFT) and time-dependent Density functional theory (DT-DFT), wherein HOMO or H is the highest occupied molecular orbital, LUMO or L is the highest occupied molecular orbital, Spin Density is the Spin Density, and T is the Spin Density1Is the lowest triplet state;
FIG. 5 is a schematic structural diagram of an organic light emitting device;
FIG. 6 is a graph of the electroluminescence spectrum of an OLED device using Pt (ACzCz-2) as a doped luminescent material;
FIG. 7 is a graph of current-voltage-luminance for Pt (ACzCz-2) as a doped light emitting material OLED device;
Detailed Description
The present invention will be described in detail below. The following description of the constituent elements may be based on representative embodiments or specific examples of the present invention, but the present invention is not limited to such embodiments or specific examples.
The 6/6/6-fused tetracyclic cyclometalated platinum (II) complex phosphorescent material based on azapyrazole-carbazole comprises compounds with the structure of the following general formula (1) or (2).
Figure BDA0003014093170000061
The synthetic route of the complex in the general formulas (1) and (2) is shown as follows:
Figure BDA0003014093170000062
Figure BDA0003014093170000071
example 1: the synthetic route of the quadridentate ring metal platinum (II) complex phosphorescent material Pt (ACzCz-1) is as follows:
Figure BDA0003014093170000081
(1) intermediate ACzbPhNO2The synthesis of (2): to a dry sealed tube with a magnetic rotor was added 4 '-iodo-2-nitro-1, 1' -biphenyl (500mg,4.46mmol,1.5 equiv.), azacarbazole (1.45g,2.97mmol,1.0 equiv.), cuprous iodide (566 mg,2.97mmol,10 mol%), trans-1, 2-cyclohexanediamine (339mg,2.97mmol,10 mol%) and sodium tert-butoxide (600 mg,6.24mmol,2.1 equiv.) in that order, then nitrogen was purged three times and dimethyl sulfoxide (13mL) was added under nitrogen protection. The above operation was repeated three times. Four seal pipes are respectively arranged atStirring and reacting for 1 day in an oil bath kettle at 110 ℃, cooling to room temperature, mixing the four reaction solutions, adding ethyl acetate for extraction, washing an organic layer twice by using water, and extracting a water layer three times by using ethyl acetate. The organic phases were combined, dried over anhydrous sodium sulfate, filtered and the solvent was distilled off under reduced pressure. Separating and purifying the obtained crude product by using a silica gel chromatographic column, eluting a eluent: petroleum ether/dichloromethane/ethyl acetate 8:2:1 to give the product aczbph no22.07g of yellow solid, yield 48%.1H NMR(500 MHz,CDCl3):δ7.29(dd,J＝8.0Hz,1H),7.38(t,J＝7.5Hz,1H),7.51-7.61(m,6H),7.67-7.70(m, 1H),7.75(d,J＝8.5Hz,2H),7.92-7.94(m,1H),8.15(d,J＝7.5Hz,1H),8.45(d,J＝7.5Hz,1H), 8.52-8.53(m,1H)。
(2) Synthesis of intermediate ACzCzH: adding ACzbPhNO into a dry three-neck flask with a magnetic rotor and a thermometer in sequence2(603mg,1.64mmol,1.0 equiv.), triphenylphosphine (1.29g,4.92mmol,3.0 equiv.), then nitrogen was purged three times and ortho-dichlorobenzene (15mL) was added under nitrogen blanket. The mixture was reacted in an electric heating mantle at 180 ℃ for 1 day with stirring, cooled to room temperature, and the solvent was distilled off under reduced pressure. Separating and purifying the obtained crude product by using a silica gel chromatographic column, eluting a eluent: petroleum ether/dichloromethane/ethyl acetate 8:2:1 gave the product ACzCzH as a tan solid 475mg, 85% yield.1H NMR(500 MHz,DMSO-d6):δ7.22-7.25(m,1H),7.35-7.41(m,3H),7.40-7.46(m,1H),7.52-7.53(m,2H), 7.56(d,J＝8.5Hz,1H),7.74(d,J＝1.5Hz,1H),8.22(d,J＝7.5Hz,1H),8.34(t,J＝8.0Hz,2H), 8.45(dd,J＝5.0,1.5Hz,1H),8.67(dd,J＝8.0,1.5Hz,1H),11.46(s,1H)。13C NMR(125MHz, CDCl3):δ110.31,110.68,110.97,115.76,116.71,118.15,118.91,120.11,120.34,120.64,120.76, 120.83,122.47,122.90,125.56,127.13,128.84,132.92,140.43,140.79,141.04,145.54,152.27。
(3) Synthesis of ligand L (ACzCz-1): to a dry sealed tube with a magnetic rotor was added ACzCzH (200mg,0.6 mmol,1.0 equiv.), 1-Br (300mg,1.2mmol,2 equiv.), tris (dibenzylideneacetone) dipalladium (46mg,0.05mmol, 8 mol%), 2- (di-tert-butylphosphino) biphenyl (30mg,0.1mmol,16 mol%), and sodium tert-butoxide (115mg,1.2mmol,2.0 equiv.) followed by purging nitrogen three times, after which nitrogen was purgedToluene (12mL) was added under nitrogen. The mixture was stirred in an oil bath at 110 ℃ for 2 days, cooled to room temperature, and the solvent was distilled off under reduced pressure. Separating and purifying the obtained crude product by using a silica gel chromatographic column, eluting a eluent: petroleum ether/ethyl acetate 10:1-5:1 gave product L (ACzCz-1) as a white solid, 290mg, 96% yield.1H NMR(500 MHz,DMSO-d6):δ6.94-6.96(m,1H),7.07(d,J＝7.5Hz,1H),7.24-7.26(m,1H),7.34-7.40(m, 3H),7.45-7.50(m,3H),7.51-7.60(m,4H),7.67(t,J＝8.0Hz,1H),7.70-7.72(m,1H),7.73(d,J＝ 1.5Hz,1H),7.76-7.80(m,1H),8.33(d,J＝8.0Hz,1H),8.36-8.38(m,2H),8.50(d,J＝8.0Hz, 1H),8.67(dd,J＝7.5,1.5Hz,1H)。13C NMR(125MHz,CDCl3):δ109.54,110.13,110.48,111.86, 115.85,116.21,118.90,119.72,119.92,120.43,120.47,120.56,120.63,120.81,121.21,122.45, 123.17,126.29,128.20,130.70,134.09,138.34,139.46,140.74,141.18,141.28,146.50,147.51, 152.36,155.32,163.01。
(4) Synthesis of Pt (ACzCz-1): to a dry three-necked flask with a magnetic rotor was added the ligand ACzCzH (100 mg,0.2mmol,1.0 equiv.), platinum dichloride (54mg,0.21mmol,1.05 equiv.) in that order. Then, the nitrogen was purged three times, and benzonitrile (10mL) was added under nitrogen blanket. The mixture was stirred in an electric heating mantle at 180 ℃ for 3 days, cooled to room temperature, added with potassium tert-butoxide (45mg,0.4mmol,20 equivalents) and tetrahydrofuran (8mL) under nitrogen, stirred in an electric heating mantle at 78 ℃ for 5 hours, cooled to room temperature, and the solvent was distilled off under reduced pressure. Separating and purifying the obtained crude product by using a silica gel chromatographic column, eluting a eluent: petroleum ether/dichloromethane ═ 3:1-2:1, giving the product Pt (ACzCz-1) as a yellow solid 77mg, yield 55%.1H NMR(500MHz,DMSO-d6):δ7.00(dd,J＝7.5,1.5Hz,1H),7.17(t,J＝8.0Hz,1H),7.32 (t,J＝7.0Hz,1H),7.46-7.53(m,3H),7.60-7.63(m,1H),7.68-7.73(m,3H),7.78(d,J＝8.0Hz, 1H),8.07(d,J＝8.0Hz,1H),8.10(d,J＝8.0Hz,1H),8.24-8.30(m,3H),8.45(d,J＝8.0Hz, 1H),8.64(d,J＝5.0Hz,1H),9.01(dd,J＝5.5,6.5Hz,1H),9.04(dd,J＝7.5,1Hz,1H)。
Example 2: the synthetic route of the quadridentate ring metal platinum (II) complex phosphorescent material Pt (ACzCz-2) is as follows:
Figure BDA0003014093170000101
(1) synthesis of ligand L (ACzCz-2): to a dry lock tube with a magnetic rotor was added ACzCzH (400mg,1.2 mmol,1.0 equiv.), 2-Br (580mg,1.8mmol,1.5 equiv.), tris (dibenzylideneacetone) dipalladium (44mg,0.048mmol, 4 mol%), 2- (di-tert-butylphosphine) bis (29mg,0.096mmol,8 mol%), and sodium tert-butoxide (231mg,2.4mmol,2.0 equiv.) followed by purging with nitrogen three times and toluene (12mL) was added under nitrogen. The mixture was stirred in an oil bath at 110 ℃ for 2 days, cooled to room temperature, and the solvent was distilled off under reduced pressure. Separating and purifying the obtained crude product by using a silica gel chromatographic column, eluting a eluent: petroleum ether/ethyl acetate 10:1-5:1 gave product L (ACzCz-2) as a white solid, 400mg, 58% yield.1H NMR(500 MHz,DMSO-d6):δ7.28-7.34(m,2H),7.38(t,J＝8.0Hz,2H),7.42-7.39(m,2H),7.50-7.53(m, 4H),7.57(d,J＝8.5Hz,1H),7.63(d,J＝8.5Hz,1H),7.66(d,J＝8.5Hz,1H)7.83-7.86(m,2H), 8.05-8.08(m,1H),8.11(d,J＝2.0Hz,1H),8.27(d,J＝7.5Hz,1H),8.30-8.33(m,2H),8.38(d,J ＝8.0Hz,1H),8.48-8.52(m,2H),8.60-8.62(m,2H)。13C NMR(125MHz,CDCl3):δ109.33,110.13, 110.42,111.15,115.81,116.21,118.88,119.53,120.12,120.15,120.30,120.39,120.49,120.65, 120.79,121.16,121.26,121.31,121.47,122.89,122.96,123.74,126.20,126.55,126.85,128.16, 134.04,135.25,138.59,140.20,140.22,140.63,140.63,141.96,142.12,146.41,149.71,151.33, 152.28。
(2) Synthesis of Pt (ACzCz-2): to a dry three-necked flask with a magnetic rotor was added ligand L (ACzCz-2) (150mg,0.26mmol,1.0 equiv.), platinum dichloride (72mg,0.27mmol,1.05 equiv.) in that order. Then, nitrogen was purged three times, and benzonitrile (13mL) was added under nitrogen blanket. The mixture was stirred in an electric heating mantle at 180 ℃ for 3 days, cooled to room temperature, added with potassium tert-butoxide (58mg,0.52mmol,20 eq.) and tetrahydrofuran (12mL) under nitrogen, stirred in an electric heating mantle at 78 ℃ for 5 hours, cooled to room temperature and the solvent was distilled off under reduced pressure. Separating the crude product with silica gel chromatographic columnPurification and eluting agent: petroleum ether/dichloromethane ═ 3:1-2:1, giving the product Pt (ACzCz-2) as a yellow solid, 140mg, yield 70%.1H NMR(500MHz,DMSO-d6):δ7.34(t,J＝7.5Hz,1H),7.42(t,J＝7.5Hz,1H), 7.45-7.47(m,1H),7.49-7.56(m,4H),7.65-7.69(m,1H),7.86-7.88(m,3H),8.08(d,J＝8.0Hz, 1H),8.11-8.19(m,5H),8.30(dd,J＝8.5,3.5Hz,2H),8.45(d,J＝7.5Hz,1H),8.80-8.82(m,1H), 9.05-9.07(m,1H),9.20-9.21(m,1H)。
Specific examples of the phosphorescent phosphor material of the present invention represented by the following general formula (1) are illustrated below, however, not to be construed as limiting the present invention.
Unless otherwise indicated, all commercial reagents involved in the following experiments were purchased and used directly without further purification. The hydrogen spectrum and the carbon spectrum of the nuclear magnetic resonance are both in deuterated chloroform (CDCl)3) Or deuterated dimethyl sulfoxide (DMSO-d)6) The hydrogen spectrum is measured by a nuclear magnetic resonance spectrometer with 400 or 500 MHz, the carbon spectrum is measured by a nuclear magnetic resonance spectrometer with 100 or 126 MHz, and the chemical shifts are based on Tetramethylsilane (TMS) or residual solvent. If CDCl is used3As solvents, the hydrogen spectrum and the carbon spectrum are respectively expressed in TMS (delta-0.00 ppm) and CDCl3(δ 77.00ppm) as an internal standard. If DMSO-d is used6As solvents, the hydrogen spectrum and the carbon spectrum are respectively expressed in TMS (delta 0.00ppm) and DMSO-d6(δ 39.52ppm) as an internal standard. The following abbreviations (or combinations) are used to interpret the hydrogen peaks: s is singlet, d is doublet, t is triplet, q is quartet, p is quintet, m is multiplet, br is broad. High resolution mass spectra were measured on an ESI-QTOF mass spectrometer from Applied Biosystems, the sample ionization mode being electrospray ionization.
Electrochemical, photophysical tests and theoretical calculations show that:
absorption spectra were measured on an Agilent 8453 uv-vis spectrometer, steady state emission experiments and lifetime measurements were performed using a Horiba Jobin Yvon fluolog-3 spectrometer. Low temperature (77K) emission spectra and lifetimes were measured in 2-methyltetrahydrofuran (2-MeTHF) solution cooled with liquid nitrogen. The Pt (II) complex is theoretically calculated by using a Gaussian 09 software package, and the Density Functional Theory (DFT) is used for optimizing the ground state (S)0) The geometry of the molecule was calculated by DFT using the B3LYP functional, with C, H, O and N atoms using the 6-31G (d) basis set and Pt atoms using the LANL2DZ basis set.
Experimental data and analysis:
as can be seen from the photoluminescence emission spectra and photophysical data of Pt (ACzCz-1) and Pt (ACzCz-2) in the attached figures 1,2 and 3 and the table I under different conditions, Pt (ACzCz-1) and Pt (ACzCz-2) can be used as blue light to green light phosphorescent materials, and the derivatives thereof can have wider light emission colors from blue light to yellow light and even red light by regulating and controlling substituents in ligands. As shown in the attached figures 2 and 3, the emission spectra of Pt (ACzCz-1) and Pt (ACzCz-2) in methylene chloride solution and polymethyl methacrylate film at room temperature are both smooth and non-fine vibration structure spectra (i.e. Gaussian type spectra), which shows that the material has more metal-to-ligand charge transfer state (MLCT) components in the molecular excited state, shortens the excited state lifetime, and facilitates the cross-over rate between molecular systems of the phosphorescent material and the radiation luminescence rate (k)r obs) And further improve the quantum efficiency of the material. As can be seen from the table I, the radiative luminescence rates of Pt (ACzCz-1) and Pt (ACzCz-2) can reach 105s-1The above.
Table one: list of photophysical property data of quadridentate ring metal platinum (II) complex phosphorescent material
Figure BDA0003014093170000121
Note: λ is the emission wavelength; tau isobsIs the excited state lifetime of the material; phiPLFor phosphorescence quantum efficiency, the data will be lower due to the quenching effect of oxygen, tested in air atmosphere; k is a radical ofr obsIs the rate of irradiation; wherein k isr obs＝ΦPL/τobs. PMMA is polymethyl methacrylate.
Table 2: excited state energy level of quadridentate ring metal platinum (II) complex phosphorescent material
T1[eV] T2[eV] S1[eV] ΔES1-T1[eV] ΔES1-T2[eV]
Pt(ACzCz-1) 2.547 2.577 2.595 0.048 0.018
Pt(ACzCz-2) 2.244 2.494 2.524 0.280 0.030
Note: t is1Is the lowest excited triplet state; t is2Is a second excited triplet state; s1Is the lowest excited singlet state; delta ES1-T1Is S1And T1The difference in energy levels between; delta ES1-T2Is S1And T2The difference in energy levels between.
As can be seen from FIG. 4 and Table 2, 6/6/6 fused tetracyclic cyclometalated platinum (II) complex phosphorescent materials Pt (ACzCz-1) and Pt (ACzCz-2) based on azapyrazole-carbazole have very small Delta ES1-T1And Δ ES1-T2Especially Pt (ACzCz-1) of 0.048eV and 0.018eV, respectively, and T1And T2Charge transfer type of state and S1And matching can increase the way of intersystem crossing, is favorable for improving the speed of intersystem crossing, and is matched with the experimental data.
In an organic light-emitting element, carriers are injected into a light-emitting material from both positive and negative electrodes, and the light-emitting material in an excited state is generated and emits light. The complex of the present invention represented by the general formula (1) can be used as a phosphorescent material for an excellent organic light-emitting element such as an organic photoluminescent element or an organic electroluminescent element. The organic photoluminescent element has a structure in which at least a light-emitting layer is formed over a substrate. The organic electroluminescent element has a structure in which at least an anode, a cathode, and an organic layer between the anode and the cathode are formed. The organic layer may be composed of only the light-emitting layer, or may have 1 or more organic layers other than the light-emitting layer. Examples of such other organic layers include a hole transport layer, a hole injection layer, an electron blocking layer, a hole blocking layer, an electron injection layer, an electron transport layer, and an exciton blocking layer. The hole transport layer may be a hole injection transport layer having a hole injection function, and the electron transport layer may be an electron injection transport layer having an electron injection function. Fig. 5 shows a schematic structure of a specific organic light-emitting device. In fig. 5, 7 layers are shown from bottom to top, and the substrate, the anode, the hole injection layer, the hole transport layer, the light-emitting layer, the electron transport layer, and the cathode are sequentially shown, where the light-emitting layer is a mixed layer in which a guest material is doped into a host material.
The phosphorescent light-emitting material is doped into a host material as a guest material to prepare a light-emitting layer which can be applied to OLED devices, and the structure is shown as follows:
ITO/HATCN (10nm)/TAPC (65 nm)/host material Pt (ACzCz-2) (10 wt.%, 20nm)/TmPyPB (55 nm)/LiF/Al (device structure not optimized).
Wherein, the ITO is a transparent anode; HATCN is a hole injection layer, TAPC is a hole transport layer, the host materials are mCBP and 26mCPy, respectively, TmPyPB is an electron transport layer, LiF is an electron injection layer, and Al is a cathode. The number in parentheses in nanometers (nm) is the thickness of the film.
The molecular formula of the applied material in the device is as follows:
Figure BDA0003014093170000131
as can be seen from the attached FIGS. 6 and 7, the azapyrazole-carbazole based 6/6/6 pentacyclic tetradentate ring metal platinum (II) complex phosphorescent material Pt (ACzCz-2) doped OLED device is green light, has a lower turn-on voltage, and has maximum brightness of 19212cd/m for devices with mCBP and 26mCPy as host materials2And 24065cd/m2。
It should be noted that the structure is an example of an application of the phosphorescent material of the present invention, and does not constitute a limitation to the structure of a specific OLED device of the phosphorescent material of the present invention, nor is the phosphorescent material limited to the compounds shown in the examples.
It will be understood by those of ordinary skill in the art that the foregoing embodiments are specific examples for carrying out the invention, and that various changes in form and details may be made therein without departing from the spirit and scope of the invention in practice. For example, many of the substituent structures described herein may be substituted with other structures without departing from the spirit of the invention.

Claims (7)

1. An 6/6/6 pentacyclic tetradentate ring metal platinum (II) complex phosphorescent material based on azapyrazole-carbazole, which is characterized in that the chemical formula is shown as the general formula (1):
Figure FDA0003014093160000011
wherein, Y1、Y2、Y3、Y4、Y5、Y6、Y7、Y8、Y9And Y10Each independently is C or N;
a is selected from B, CH, CD, CRa、SiH、SiD、SiRa、GeH、GeD、GeRdP, P ═ O, As ═ O, Bi, or Bi ═ O;
Ra、Rb、Rcand RdEach independently is hydrogen, deuterium, aryl, cycloalkyl, cycloalkenyl, heterocyclyl, heteroaryl, alkyl, alkenyl, alkynyl, halogen, hydroxy, mercapto, nitro, cyano, amino, mono-or dialkylamino, mono-or diarylamino, alkoxy, aryloxy, haloalkyl, ester, nitrile, isonitrile, heteroaryl, alkoxycarbonyl, amido, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, sulfamoyl, carbamoyl, alkylthio, sulfinyl, ureido, phosphoramido, imine, sulfo, carboxyl, hydrazine, substituted silyl, a polymeric group, or a combination thereof;
R1、R2、R3、R4、R5、R6and R7Each independently is hydrogen, deuterium, alkyl, alkoxy, cycloalkyl, heterocyclyl, alkenyl, substituted or unsubstituted aryl, substituted or unsubstituted aryloxy, substituted or unsubstituted heteroaryl, haloalkyl, halogen, hydroxy, mercapto, nitro, cyano, amino, carboxyl, sulfo, hydrazino, ureido, alkynyloxy, ester, amide, sulfonyl, sulfinyl, sulfonylamino, phosphorylamino, alkoxycarbonylamino, aryloxycarbonylamino, silyl, alkylamino, dialkylamino, monoarylamino, diarylamino, ureylene, imino, or a combination thereof.
2. The azapyrazole-carbazole based 6/6/6-fused tetracyclic cyclometalated platinum (II) complex phosphorescent material according to claim 1, having a structural formula selected from the group consisting of:
Figure FDA0003014093160000021
3. an 6/6/6 pentacyclic tetradentate ring metal platinum (II) complex phosphorescent material based on azapyrazole-carbazole, which is characterized in that the chemical formula is shown as a general formula (2):
Figure FDA0003014093160000031
wherein, Y1、Y2、Y3、Y4、Y5、Y6And Y7Each independently is C or N;
a is O, S, S ═ O or O ═ S ═ O;
R1、R2、R3、R4、R5and R6Each independently is hydrogen, deuterium, alkyl, alkoxy, cycloalkyl, heterocyclyl, alkenyl, substituted or unsubstituted aryl, substituted or unsubstituted aryloxy, substituted or unsubstituted heteroaryl, haloalkyl, halogen, hydroxy, mercapto, nitro, cyano, amino, carboxyl, sulfo, hydrazino, ureido, alkynyloxy, ester, amide, sulfonyl, sulfinyl, sulfonylamino, phosphorylamino, alkoxycarbonylamino, aryloxycarbonylamino, silyl, alkylamino, dialkylamino, monoarylamino, diarylamino, ureylene, imino, or a combination thereof.
4. The azapyrazole-carbazole based 6/6/6 tetradentate cyclometalated platinum (II) complex phosphorescent material of claim 3, having a structural formula selected from the group consisting of:
Figure FDA0003014093160000032
Figure FDA0003014093160000041
5. use of the 6/6/6 pentacyclic tetradentate ring metal platinum (II) complex phosphorescent material based on azapyrazole-carbazole in organic light-emitting elements, according to any one of claims 1 to 4.
6. Use according to claim 5, wherein the organic light emitting element is an organic light emitting diode, a light emitting diode or a light emitting electrochemical cell.
7. The use according to claim 5, wherein the organic light emitting element comprises a first electrode, a second electrode, and at least one organic layer disposed between the first electrode and the second electrode; the organic layer comprises an 6/6/6 pentacyclic tetradentate ring metal platinum (II) complex based on azapyrazole-carbazole.
CN202110383927.8A 2021-04-09 2021-04-09 6/6/6-fused tetracyclic cyclometalated platinum (II) complex phosphorescent material based on aza-pyrazole-carbazole and application thereof Pending CN113087707A (en)

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