Blue light-emitting composition and organic light-emitting device comprising same

Abstract

The invention discloses a blue light-emitting composition and an organic electroluminescent device comprising the same. The blue light-emitting composition comprises a compound with a structural general formula as shown in a formula I and a compound with a structural general formula as shown in a formula II. Through analog calculation, the distance between host and guest molecules in the blue light-emitting composition provided by the invention is relatively large, so that guest molecule aggregation can be prevented, triplet state Dexter energy transfer can be inhibited, energy loss of non-radiative transition can be reduced, energy can be transferred from S1 of a host material to S1 of a guest material, Forster energy transfer efficiency can be improved, and the blue light-emitting composition can be applied to the field of organic light-emitting devices. The light-emitting performance of the organic light-emitting device is obviously improved, specifically, the external quantum efficiency of the device is effectively improved, the working voltage of the device is reduced, and the service life of the device is prolonged. # imgabs0 #

Description

Technical Field

[0001] The invention belongs to the technical field of OLED, and specifically comprises a blue light-emitting composition and an organic electroluminescent device comprising the same. Background Art

[0002] In recent years, under the premise that organic electroluminescent materials with excellent performance have been continuously developed and applied, OLED devices have shown excellent saturation, brilliant colors, short response time, wide color gamut, high contrast and other advantages. The field has developed rapidly and has achieved commercial success in the field of information display.

[0003] OLED blue light devices are composed of substrate, cathode, anode, hole injection layer, electron injection layer, hole transport layer, electron transport layer, electron blocking layer, hole blocking layer, light-emitting layer, etc. Among the currently used OLED products, most of the blue light devices are fluorescent emission. After the electrons and holes recombine, 25% of singlet excitons and 75% of triplet excitons will be generated. Fluorescence emission is to use 25% of singlet excitons to emit light, and the energy of singlet excitons is transferred from the host to the blue light dye, which belongs to fluorescence resonance energy transfer. This involves the interaction between the host and the guest. Selecting the host and guest combination that is conducive to energy transfer has become the focus of research in the industry.

[0004] At present, the performance of blue light devices is limited by the large conjugated planarity of the guest molecules, which makes them easily aggregated in the form of π-π stacking, resulting in aggregation-induced quenching, thereby reducing the exciton utilization efficiency, resulting in reduced device efficiency and shortened life. In general, there are two main methods to improve π-π stacking: the first is to introduce steric groups into aromatic molecules to balance the π-π interaction and repulsion, thereby achieving precise control of π-π stacking; the second is to increase the charge transfer integral between adjacent molecules by increasing the π-π stacking distance between molecules, thereby improving the Forester energy transfer of the material. However, the increase in the π-π stacking distance between molecules needs to be controlled within a reasonable range. If the π-π stacking distance is too large, it will also affect the Forester energy transfer between the host and the guest, thereby affecting the device performance.

[0005] Therefore, it is urgent to develop more suitable host-guest materials to reduce the π-π stacking phenomenon of molecules and further improve the performance of blue light fluorescent devices. Summary of the invention

[0006] In view of the above problems existing in the prior art, the present invention provides a blue light-emitting composition and an organic electroluminescent device comprising the same.

[0007] To achieve the above objectives, the technical solutions adopted by the present invention include:

[0008] The first aspect of the present invention provides a blue light-emitting composition, wherein the blue light-emitting composition comprises a compound having a general structural formula as shown in Formula I, and a compound having a general structural formula as shown in Formula II:

[0009]

[0010] In Formula I,

[0011] Ar1 represents a substituted or unsubstituted phenyl group, naphthyl group, phenanthryl group or pyrenyl group; L1 represents a single bond, a substituted or unsubstituted phenylene group or naphthyl group;

[0012] Ar2 represents the structure shown in formula A-1:

[0013]

[0014] R a1 To R a4 , R b1 To R b4 are each independently selected from hydrogen or deuterium;

[0015] When the R a1 To R a4 When any one of the above is selected from deuterium, the R b1 To R b4 are all hydrogen; when the R a1 To R a4 When neither is selected from deuterium, the R b1 To R b4 At least one of them is selected from deuterium; and when the R a1 To R a4 , R b1 To R b4 When any one of is selected from deuterium, all hydrogen atoms in the same benzene ring are replaced by deuterium;

[0016] R represents hydrogen or deuterium, and s represents an integer from 0 to 8;

[0017] R a1 To R a4 Any one of which is bonded to the formula I;

[0018] In formula II,

[0019] R1 and R2 each independently represent one of hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 30 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 30 carbon atoms, substituted or unsubstituted aryl having 6 to 60 carbon atoms, and substituted or unsubstituted heteroaryl having 5 to 60 carbon atoms;

[0020] R3 represents a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 60 carbon atoms, or a substituted or unsubstituted heteroaryl group having 5 to 60 carbon atoms;

[0021] R4 represents one of a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, and a substituted or unsubstituted aryl group having 6 to 60 carbon atoms;

[0022] R5 and R6 each independently represent one of hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 30 carbon atoms, substituted or unsubstituted alkoxy having 1 to 30 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 30 carbon atoms, substituted or unsubstituted aryl having 6 to 60 carbon atoms, substituted or unsubstituted heteroaryl having 5 to 60 carbon atoms, substituted or unsubstituted condensed ring aryl having 5 to 60 carbon atoms, substituted or unsubstituted heterocondensed ring aryl having 5 to 60 carbon atoms, and substituted or unsubstituted amine; two or more R5 and R6 may each be connected to form a ring structure;

[0023] m and n each independently represent 0, 1, 2, 3 or 4; when m is 2, 3 or 4, R5 may be the same or different; when n is 2, 3 or 4, R6 may be the same or different;

[0024] Ar3 represents one of the structures shown in formula B-1 to formula B-4:

[0025]

[0026] In formula B-1,

[0027] X1 and X2 each independently represent O, NR 30 , S or Se, p represents 1, 2, 3, 4 or 5;

[0028] R7 to R 11 Any one of which is bonded to the formula II;

[0029] R7 to R 11 , R 30 Each independently represents one of hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 60 carbon atoms, and a substituted or unsubstituted heteroaryl group having 5 to 60 carbon atoms;

[0030] In formula B-2,

[0031] X3 and X4 each independently represent O, NR 31 , S or Se;

[0032] R 12 To R 19 Any one of which is bonded to the formula II;

[0033] R 12 To R 19 , R 31 Each independently represents hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 60 carbon atoms, or a substituted or unsubstituted heteroaryl group having 5 to 60 carbon atoms; R at adjacent positions 12 To R 19 can be connected to each other to form a ring structure;

[0034] In formula B-3,

[0035] X5 means O, NR 32 , S or Se; q represents 0, 1, 2, 3, 4 or 5;

[0036] R 20 To R 24 Any one of which is bonded to the formula II;

[0037] R 20 To R 24 , R 32 Each independently represents one of hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 60 carbon atoms, and a substituted or unsubstituted heteroaryl group having 5 to 60 carbon atoms;

[0038] In formula B-4,

[0039] R 25 To R 29 Any one of which is bonded to the formula II;

[0040] R 25 To R 28 Each independently represents one of hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 60 carbon atoms, and a substituted or unsubstituted heteroaryl group having 5 to 60 carbon atoms;

[0041] R 29 represents one of hydrogen, deuterium, and a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms;

[0042] In formula I and formula II, any hydrogen can be replaced by deuterium, any nitrogen can be replaced by nitrogen-15, any sulfur can be replaced by sulfur-33, sulfur-34 or sulfur-36, any oxygen can be replaced by oxygen-17 or oxygen-18, and any carbon can be replaced by carbon-13.

[0043] Furthermore, at least one of R1 and R2 is selected from a substituted or unsubstituted phenyl or biphenyl group having 6 to 60 carbon atoms;

[0044] R3 represents a substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms;

[0045] The R4 represents one of a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms, and a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, and is preferably a tert-butyl group;

[0046] The R5 and R6 represent an alkyl group having 1 to 10 carbon atoms, preferably a tert-butyl group.

[0047] Further, the formula B-1 is selected from one of the structures shown below:

[0048]

[0049] Further, the formula B-2 is selected from one of the structures shown below:

[0050]

[0051] Further, the formula B-3 is selected from one of the structures shown below:

[0052]

[0053] Further, the formula B-4 is selected from one of the structures shown below:

[0054]

[0055] Further, the Ar3 is selected from one of the following structures:

[0056]

[0057] Further, Ar1 is selected from one of phenyl, biphenyl, naphthyl, phenyl-substituted naphthyl, phenanthrenyl, and pyrene; Ar2 is selected from one of the structures shown below:

[0058]

[0059] Furthermore, the compound represented by formula I is selected from any one of the following structures:

[0060]

[0061]

[0062]

[0063]

[0064]

[0065]

[0066] Furthermore, the compound represented by formula II is selected from any one of the following structures:

[0067]

[0068]

[0069]

[0070]

[0071]

[0072]

[0073]

[0074]

[0075]

[0076]

[0077]

[0078]

[0079] The second aspect of the present invention provides an organic electroluminescent device, which includes an anode, a hole transport region, a light-emitting layer, an electron transport region, and a cathode arranged in sequence on a substrate; wherein the light-emitting layer includes one or more blue light-emitting compositions as described above.

[0080] Furthermore, the light-emitting layer includes a host material and a guest material, wherein the host material includes one or more compounds with a general structural formula as shown in Formula I, and the guest material includes one or more compounds with a general structural formula as shown in Formula II.

[0081] Beneficial effects of the present invention:

[0082] The present invention provides a blue light-emitting composition composed of a host material (BH) shown in structural formula I and a guest material (BD) shown in structural formula II. By designing the structure of the guest material (especially the substituent selection at the Ar3 position) and using software simulation calculation, the distance between the host and guest molecules in the blue light-emitting composition is significantly enlarged, which is beneficial to preventing the guest molecules from aggregating, inhibiting triplet Dexter energy transfer, reducing the energy loss of non-radiative transitions, and facilitating the energy transfer from S1 of the host material to S1 of the guest material, thereby improving the Forster energy transfer efficiency. Therefore, the composition provided by the present invention is applied as a light-emitting layer in an organic electroluminescent device, which can significantly improve the performance of the organic electroluminescent device in terms of driving voltage, external quantum efficiency and lifespan. BRIEF DESCRIPTION OF THE DRAWINGS

[0083] Figure 1 It is a schematic structural diagram of the organic electroluminescent device of the present invention.

[0084] Description of the drawings: 1-substrate, 2-anode, 3-hole injection layer, 4-hole transport layer, 5-luminescence auxiliary layer, 6-luminescent layer, 7-hole blocking layer, 8-electron transport layer, 9-electron injection layer, 10-cathode. DETAILED DESCRIPTION

[0085] In order to more clearly understand the content of the present invention, it will be described in detail with reference to the drawings and embodiments.

[0086] The compounds of the present invention are suitable for use in light-emitting elements, display panels and electronic devices, and are particularly suitable for use in organic electroluminescent devices. The electronic device described in the present invention is a device comprising a layer of at least one organic compound, and the device may also comprise an inorganic material or a layer formed entirely of an inorganic material. The electronic device is preferably an organic electroluminescent device (OLED), an organic integrated circuit (O-IC), an organic field effect transistor (O-FET), an organic thin film transistor (O-TFT), an organic light-emitting transistor (O-LET), an organic solar cell (O-SC), an organic dye-sensitized solar cell (O-DSSC), an organic optical detector, an organic photoreceptor, an organic field quenching device (O-FQD), a light-emitting electrochemical cell (LEC), an organic laser diode (O-laser) and an organic plasma emission device. The electronic device is preferably an organic electroluminescent device (OLED). The structural schematic diagram of an exemplary organic electroluminescent device is shown in FIG. Figure 1 shown.

[0087] Experimental Section

[0088] In order to understand the content of the present invention more clearly, the polycyclic compound, the preparation method of the compound and the luminescent characteristics of the device will be explained in detail in conjunction with the examples. Various chemical reactions can be applied to the synthetic method of the compound of an embodiment of the present invention. However, it should be noted that the synthetic method of the compound of an embodiment of the present invention is not limited to the synthetic method described below. Unless otherwise indicated, the subsequent synthesis is carried out in anhydrous solvent under a protective gas atmosphere. Solvents and reagents can be purchased from conventional reagent suppliers.

[0089] Compound synthesis

[0090] BD Synthesis

[0091] Synthesis Example 1: Synthesis of S3

[0092]

[0093] S3-a (400 g, 1.75 mol), S3-b (443.24 g, 1.76 mol), tris(dibenzylideneacetone)dipalladium (15.99 g, 17.46 mmol), 4,5-bis(diphenylphosphine)-9,9-dimethylxanthene (20.20 g, 34.92 mmol) and sodium tert-butoxide (256.67 g, 2.62 mmol) were added to a 5L three-necked flask under nitrogen protection, and toluene (4000 ml) was used as solvent. The nitrogen was replaced three times, and the temperature was raised to 100°C for 4 hours. After the reaction was completed, the temperature was cooled to room temperature, deionized water (3000 ml) was added to quench, and the organic phase was concentrated under reduced pressure. S3-c (684.52 g, yield: 98.13%) was obtained by column chromatography (dichloromethane / heptane). MS: m / z 399.27 [M+].

[0094] Under nitrogen protection, S3-c (684.52 g, 1.71 mol), S3-d (470.39 g, 1.75 mol), di(tri-tert-butylphosphine)palladium (17.51 ​​g, 34.26 mmol) and sodium tert-butoxide (246.96 g, 2.57 mmol) were added to a 10 L three-necked flask, and toluene (7000 ml) was used as solvent. The nitrogen was replaced three times, and the temperature was raised to 100 ° C. for 4 h. After the reaction was completed, the temperature was lowered to room temperature, deionized water (5000 ml) was added, and the mixture was stirred for 10 minutes. The mixture was allowed to stand for separation, and the organic phase was concentrated under reduced pressure. S3-e (879.32 g, yield: 87.31%) was obtained by column chromatography (with dichloromethane / heptane as eluent), MS: m / z 587.32 [M+].

[0095] S3-e (879.32 g, 1.50 mol), triethylamine (227.04 g, 2.24 mol) and dichloromethane (5000 L) as solvent were added to a 10 L reaction bottle. Trifluoromethanesulfonic anhydride (506.40 g, 1.79 mol) was added dropwise under ice bath. After the addition was completed, the mixture was reacted at room temperature for 10 h. Deionized water (3000 ml) was added and stirred for 10 minutes. The mixture was allowed to stand for separation. The organic phase was concentrated under reduced pressure and column chromatography (dichloromethane / heptane as eluent) was used to obtain S3-f (886.13 g, yield: 82.29%). MS: m / z 719.28 [M+].

[0096] To a 10 L reaction bottle, S3-f (886.13 g, 1.23 mol), S3-g (172.73 g, 1.35 mol), cesium carbonate (601.56 g, 1.85 mol), 4,5-bis(diphenylphosphine)-9,9-dimethyloxanthene (14.24 g, 24.62 mmol), tris(dibenzylideneacetone)dipalladium (11.27 g, 12.31 mmol), and toluene (7000 ml) were added, and the nitrogen was replaced three times. The temperature was raised to 110°C and the reaction was carried out for 5 hours. After the reaction was completed, the temperature was lowered to room temperature, deionized water (5000 ml) was added, and the mixture was stirred for 10 minutes. The mixture was allowed to stand for separation, and the organic phase was concentrated under reduced pressure. S3-h (752.12 g, yield: 87.62%) was obtained by column chromatography (using dichloromethane / heptane as eluent), MS: m / z 696.34 [M+].

[0097] S3-h (752.12 g, 1.08 mmol), S3-i (559.88 g, 1.62 mol), sodium tert-butoxide (155.46 g, 1.62 mol), 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene (12.48 g, 21.57 mmol), tris(dibenzylideneacetone)dipalladium (9.88 g, 10.78 mmol) and toluene (7000 ml) were added to a 10 L reaction bottle, and the temperature was raised to 110°C for reaction for 8 h. After the reaction was completed, heating was stopped and the temperature was lowered to room temperature. Deionized water (4000 ml) was added, stirred for 10 minutes, allowed to stand for separation, the organic phase was concentrated under reduced pressure, and column chromatography (with dichloromethane / heptane as eluent) was performed to obtain S3-j (746.25 g, yield: 71.89%), MS: m / z 960.39 [M+].

[0098] Add S3-j (746.25 g, 775.23 mmol) to a 10L three-necked reaction bottle, and use tert-butylbenzene (4000 ml) as solvent. Replace nitrogen three times, cool to -60°C, and drop n-butyl lithium (620.18 ml, 1.55 mol, 2.5 M). After the addition is complete, gradually heat up to 60°C and react for 4 hours. After cooling the system to -40°C, add boron tribromide (115.95 ml, 1.55 mol, 2.5 g / ml), slowly heat up to room temperature, and react at room temperature for 2 hours. After cooling to -40°C, add N,N-diisopropylethylamine (406.20 ml, 2.33 mol, 0.74 g / ml), and heat to 120°C for 4 hours. The reaction solution was poured into 3000 ml of deionized water, stirred for 10 minutes, separated, the organic phase was collected, the aqueous phase was extracted with 2000 ml of dichloromethane, the organic phases were separated and combined, the organic phase was concentrated under reduced pressure, and column chromatography (with dichloromethane / heptane as eluent) was performed to obtain a yellow-green solid crude product; recrystallization was performed twice from dichloromethane / acetone to obtain a yellow solid S3-k (89.37 g, yield: 12.93%), MS: m / z 890.48 [M+].

[0099] Add S3-k (7.00 g, 7.85 mmol), S3-1 (2.83 g, 15.70 mol), bis(di-tert-butyl-4-dimethylaminophenylphosphine)palladium chloride (0.11 g, 0.16 mmol), potassium carbonate (2.17 g, 15.70 mmol) to a 250 ml reaction bottle, use toluene (70 ml), ethanol (25 ml) and water (10 ml) as solvents, replace nitrogen three times. Heat to 110 ° C for 8 hours, stop heating after the reaction is completed, and cool to room temperature. Add deionized water (100 ml), stir for 10 minutes, stand for separation, take the organic phase, extract the aqueous phase with dichloromethane (100 ml), and combine the organic phases. The organic phase was concentrated under reduced pressure and purified by column chromatography (using dichloromethane / heptane as the eluent) to give a yellow-green solid crude product. The product was recrystallized twice from dichloromethane / acetone to give a yellow solid S3 (4.32 g, yield: 55.51%), MS: m / z 990.54 [M+].

[0100] Synthesis Example 2: Synthesis of S4

[0101]

[0102] Referring to the synthesis method of compound S3, only S3-1 was replaced by S4-a (2.83 g, 15.70 mmol) to obtain the final product S4 (3.86 g, yield: 49.60%), MS: m / z 990.54 [M+].

[0103] Synthesis Example 3: Synthesis of S9

[0104]

[0105] Referring to the synthesis method of compound S3, only S3-1 was replaced by S9-a (2.61 g, 15.70 mmol) to obtain the final product S9 (3.86 g, yield: 50.31%), MS: m / z 976.53 [M+].

[0106] Synthesis Example 4: Synthesis of S20

[0107]

[0108] Referring to the synthesis method of compound S3, only S3-1 was replaced by S20-a (2.61 g, 15.70 mmol) to obtain the final product S20 (3.91 g, yield: 50.96%), MS: m / z 976.54 [M+].

[0109] Synthesis Example 5: Synthesis of S27

[0110]

[0111] Referring to the synthesis method of compound S3, only S3-1 was replaced with S27-a (3.05 g, 15.70 mmol) to obtain the final product S27 (4.12 g, yield: 52.20%), MS: m / z 1004.56 [M+].

[0112] Synthesis Example 6: Synthesis of S37

[0113]

[0114] Referring to the synthesis method of compound S3, only S3-1 was replaced by S37-a (2.56 g, 15.70 mmol) to obtain the final product S37 (4.36 g, yield: 55.24%), MS: m / z 973.54 [M+].

[0115] Synthesis Example 7: Synthesis of S43

[0116]

[0117] Referring to the synthesis method of compound S3-c, S3-a (200.00 g, 872.92 mmol) remained unchanged, and S3-b was replaced by 43-a (292.27 g, 881.65 mmol) to obtain intermediate S43-b (382.54 g, yield: 91.35%), MS: m / z 479.32 [M+].

[0118] Referring to the synthesis method of compound S3-e, S3-c was replaced with S43-b (382.54 g, 797.44 mmol), and S3-d (218.97 g, 813.39 mmol) remained unchanged to obtain intermediate S43-c (465.32 g, yield: 87.35%), MS: m / z 667.39 [M+].

[0119] Referring to the synthesis method of compound S3-f, S3-e was replaced by S43-c (465.32 g, 696.59 mmol) to obtain intermediate S43-d (506.35 g, yield: 90.86%), MS: m / z 799.34 [M+].

[0120] Referring to the synthesis method of compound S3-h, S3-f was replaced by S43-d (506.35 g, 532.90 mmol), and S3-g (88.81 g, 696.19 mmol) remained unchanged to obtain intermediate S43-e (455.35 g, yield: 92.53%), MS: m / z 776.40 [M+].

[0121] Referring to the synthesis method of compound S3-j, S3-h was replaced by S43-e (455.35 g, 585.62 mmol), and S3-i (304.03 g, 878.43 mmol) remained unchanged to obtain intermediate S43-f (436.21 g, yield: 71.43%), MS: m / z 1040.45 [M+].

[0122] Referring to the synthesis method of compound S3-k, S3-j was replaced by S43-f (436.21 g, 418.33 mmol) to obtain intermediate S43-g (52.42 g, yield: 12.90%), MS: m / z 970.53 [M+].

[0123] Referring to the synthesis method of compound S3, S3-k was replaced by S43-g (7.00 g, 7.20 mmol), and S3-1 was replaced by S43-h (2.51 g, 14.41 mmol) to obtain the final product S43 (5.13 g, yield: 66.84%), MS: m / z 1064.61 [M+].

[0124] Synthesis Example 8: Synthesis of S73

[0125]

[0126] Referring to the synthesis method of compound S43, S43-g (7.00 g, 7.20 mmol) remained unchanged, and S43-h was replaced by S73-a (3.75 g, 14.41 mmol) to obtain the final product S73 (5.23 g, yield: 63.04%), MS: m / z 1150.56 [M+].

[0127] Synthesis Example 9: Synthesis of S81

[0128]

[0129] Referring to the synthesis method of compound S43, S43-g (7.00 g, 7.20 mmol) remained unchanged, and S43-h was replaced by S3-1 (2.59 g, 14.41 mmol) to obtain the final product S81 (5.33 g, yield: 69.06%), MS: m / z 1070.61 [M+].

[0130] Synthesis Example 10: Synthesis of S169

[0131]

[0132] Referring to the synthesis method of compound S43, S43-g (7.00 g, 7.20 mmol) remained unchanged, and S43-h was replaced by S4-a (2.59 g, 14.41 mmol) to obtain the final product S169 (4.98 g, yield: 64.52%), MS: m / z 1070.62 [M+].

[0133] Synthesis Example 11: Synthesis of S171

[0134]

[0135] Referring to the synthesis method of compound S3-c, S3-a (200.00 g, 872.92 mmol) remained unchanged, and S3-b was replaced by S171-a (366.47 g, 881.65 mmol) to obtain the final product S171-b (442.23 g, yield: 89.85%), MS: m / z 563.42 [M+].

[0136] Referring to the synthesis method of compound S3-e, S3-c was replaced with S171-b (442.23 g, 784.28 mmol), and S3-d (215.35 g, 799.36 mmol) remained unchanged to obtain intermediate S171-c (503.25 g, yield: 85.31%), MS: m / z 751.49 [M+].

[0137] Referring to the synthesis method of compound S3-f, S3-e was replaced with S171-c (503.25 g, 669.07 mmol) to obtain the final product S171-d (565.43 g, yield: 95.58%), MS: m / z 883.44 [M+].

[0138] Referring to the synthesis method of compound S3-h, S3-f was replaced by S171-d (565.43 g, 639.47 mmol), and S3-g (89.74 g, 703.42 mmol) remained unchanged to obtain the final product S171-e (479.86 g, yield: 87.08%), MS: m / z 860.51 [M+].

[0139] Referring to the synthesis method of compound S3-j, S3-h was replaced by S171-e (479.86 g, 556.87 mmol), and S3-i (289.10 g, 835.30 mmol) remained unchanged to obtain the final product S171-f (487.53 g, yield: 77.69%), MS: m / z1124.55 [M+].

[0140] Referring to the synthesis method of compound S3-k, S3-j was replaced by S171-f (487.53 g, 432.63 mmol) to obtain the final product S171-g (456.77 g, yield: 12.55%), MS: m / z 1054.62 [M+].

[0141] Referring to the synthesis method of compound S43, S43-g was replaced by S171-g (7.00 g, 6.63 mmol), and S43-h was replaced by S4-a (2.39 g, 13.26 mmol) to obtain the final product S171 (5.23 g, yield: 68.27%), MS: m / z 1154.70 [M+].

[0142] Synthesis Example 12: Synthesis of S181

[0143]

[0144] Referring to the synthesis method of compound S171, S171-g (7.00 g, 6.63 mmol) remained unchanged, and S4-a was replaced by S9-a (2.20 g, 13.26 mmol) to obtain the final product S181 (5.12 g, yield: 67.65%), MS: m / z 1140.68 [M+].

[0145] Synthesis Example 13: Synthesis of S182

[0146]

[0147] Referring to the synthesis method of compound S171, S171-g (7.00 g, 6.63 mmol) remained unchanged, and S4-a was replaced by S20-a (2.20 g, 13.26 mmol) to obtain the final product S182 (4.53 g, yield: 59.86%), MS: m / z 1140.69 [M+].

[0148] Synthesis Example 14: Synthesis of S187

[0149]

[0150] Referring to the synthesis method of compound S171, S171-g (7.00 g, 6.63 mmol) remained unchanged, and S4-a was replaced by S27-a (2.57 g, 13.26 mmol) to obtain the final product S187 (4.79 g, yield: 61.77%), MS: m / z 1168.72 [M+].

[0151] Synthesis Example 15: Synthesis of S189

[0152]

[0153] Referring to the synthesis method of compound S3-c, S3-a (100.00 g, 436.46 mmol) remained unchanged, and S3-b was replaced by S171-a (183.23 g, 440.82 mmol) to obtain the final product S171-b (226.32 g, yield: 91.096%), MS: m / z 563.42 [M+].

[0154] Referring to the synthesis method of compound S3-e, S3-c was replaced by S171-b (226.32 g, 401.37 mmol), and S3-d was replaced by S189-a (132.35 g, 409.40 mmol) to obtain intermediate S189-b (323.60 g, yield: 88.18%), MS: m / z 805.54 [M+].

[0155] Referring to the synthesis method of compound S3-f, S3-e was replaced by S189-b (285.34 g, 353.91 mmol) to obtain the final product S189-c (286.35 g, yield: 86.23%), MS: m / z 937.48 [M+].

[0156] Referring to the synthesis method of compound S3-h, S3-f was replaced by S189-c (286.35 g, 305.18 mmol), and S3-g (42.82 g, 335.70 mmol) remained unchanged to obtain the final product S189-d (265.33 g, yield: 94.094%), MS: m / z 914.53 [M+].

[0157] Referring to the synthesis method of compound S3-j, S3-h was replaced by S189-d (265.33 g, 289.72 mmol), and S3-i (150.41 g, 434.58 mmol) remained unchanged to obtain the final product S189-e (302.16 g, yield: 88.31%), MS: m / z 1178.60 [M+].

[0158] Referring to the synthesis method of compound S3-k, S3-j was replaced by S189-e (302.16 g, 255.85 mmol) to obtain intermediate S189-f (35.16 g, yield: 12.38%), MS: m / z 1108.067 [M+].

[0159] Referring to the synthesis method of compound S43, S43-g was replaced by S189-f (10.00 g, 9.01 mmol), and S43-h was replaced by S3-1 (3.24 g, 18.02 mmol) to obtain the final product S189 (6.89 g, yield: 63.22%), MS: m / z 1208.75 [M+].

[0160] Synthesis Example 16: Synthesis of S192

[0161]

[0162] Referring to the synthesis method of compound S43, S43-g was replaced by S189-f (10.00 g, 9.01 mmol), and S43-g was replaced by S4-a (3.24 g, 18.02 mmol) to obtain the final product S192 (6.13 g, yield: 56.25%), MS: m / z 1208.76 [M+].

[0163] BH Synthesis

[0164] Synthesis Example 17: Synthesis of H-1

[0165]

[0166] In a 100mL reaction bottle, add compound 1-g (1.29 g, 10 mmol), 10mL D2O, 2mL isopropanol, and 2mL n-hexane. In an argon atmosphere, add Pt / C (1.0 g, 0.5 mmol). Raise the temperature to 90°C, react for 24 hours, cool to room temperature, filter out Pt / C, add 20mL dichloromethane, stir, let stand, separate the phases, dry the lower layer with anhydrous sodium sulfate, filter, and distill under reduced pressure to obtain compound 1-f (0.96 g, yield: 72%).

[0167] In a 250mL reaction bottle, 1-f (1.33g, 10mmol), diisopropylamine (0.10g, 1mmol), 20mL of dichloromethane were added, and N-bromosuccinimide (3.92g, 22mmol) was slowly added. The temperature was raised to 30°C, and the reaction was carried out for 12h. The temperature was lowered to room temperature, and the pH of the system was adjusted to 5 with 1mol / L hydrochloric acid solution. 20mL of water was added, and the mixture was stirred and allowed to stand for separation. The organic phase was taken, and the aqueous phase was extracted with 20mL of dichloromethane. The organic phases were combined, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and passed through a silica gel column to obtain compound 1-e (1.30g, yield: 62%).

[0168] In a 250mL three-necked flask, 30mL toluene, 15mL ethanol, and 15mL water were added under nitrogen protection, and then compound 1-e (2.10g, 10mmol), compound 1-d (1.40g, 10mmol), potassium carbonate (4.15g, 30mmol), and tetrakistriphenylphosphine palladium (0.35g, 0.3mmol) were added, heated to 80°C for 12h, cooled to room temperature, 15mL of water was added, stirred, and allowed to stand for stratification. The organic phase was evaporated to dryness under reduced pressure and passed through a silica gel column to obtain compound 1-c (1.67g, yield: 74%).

[0169] In a 250mL three-necked flask, compound 1-c (2.26g, 10mmol), potassium carbonate (4.15g, 30mmol), and NMP 30mL were added under nitrogen protection, and the mixture was heated to 120°C for 16h. After the reaction, the mixture was cooled to room temperature, 40mL of water was added, stirred, and allowed to stand for stratification. The aqueous phase was extracted with 30mL of ethyl acetate, and the organic phase was dried over anhydrous sodium sulfate, filtered, evaporated to dryness under reduced pressure, and passed through a silica gel column to obtain compound 1-b (1.46g, yield: 71%).

[0170] In a 250mL three-necked flask, 40mL of 1,4-dioxane and 10mL of water were added under nitrogen protection, and then compound 1-b (2.06g, 10mmol), compound 1-a (3.56g, 10mmol), potassium phosphate (6.37g, 30mmol), tetrakistriphenylphosphine palladium (0.35g, 0.3mmol) were added, and the mixture was heated to 90°C for 8h. After the reaction, the mixture was cooled to room temperature, 40mL of water and 30mL of dichloromethane were added, stirred, and allowed to stand for stratification. The aqueous phase was extracted with 30mL of dichloromethane, and the organic phases were combined. The organic phases were dried over anhydrous sodium sulfate, filtered, and then distilled under reduced pressure. The mixture was passed through a silica gel column and then recrystallized to obtain compound H-1 (3.18g, yield: 66%), MS: m / z 481.24 [M+].

[0171] Synthesis Example 18: Synthesis of H-2

[0172]

[0173] Referring to the synthesis method of compound 1-f, compound 1-g was replaced with compound 2-g (1.29 g, 10 mmol) to obtain compound 2-f (0.92 g, yield: 69%).

[0174] In a 100mL reaction bottle, add compound 2-f (1.33g, 10mmol), 20mL dichloromethane, and 1mL glacial acetic acid, cool to 0℃, slowly add bromine (1.60g, 10mmol), stir at 0℃ for 30min after the addition is complete, then warm to room temperature and react for 16h, add 30mL sodium thiosulfate solution, stir, stand for phase separation, extract the aqueous phase with 20mL dichloromethane, combine the organic phases, dry over anhydrous sodium sulfate, filter and evaporate under reduced pressure, pass through a silica gel column to obtain compound 2-e (0.51g, yield: 24%).

[0175] Referring to the synthesis method of compound 1-c, compound 1-e was replaced by compound 2-e (2.10 g, 10 mmol), and compound 1-d was replaced by compound 2-d (1.40 g, 10 mmol) to obtain compound 2-c (1.60 g, yield: 71%).

[0176] Referring to the synthesis method of compound 1-b, compound 1-c was replaced with compound 2-c (2.26 g, 10 mmol) to obtain compound 2-b (1.48 g, yield: 72%).

[0177] Referring to the synthesis method of compound H-1, compound 1-b was replaced by compound 2-b (2.06 g, 10 mmol), and compound 1-a was replaced by compound 2-a (3.63 g, 10 mmol) to obtain compound H-2 (3.32 g, yield: 68%), MS: m / z 488.28 [M+].

[0178] Synthesis Example 19: Synthesis of H-3

[0179]

[0180] Referring to the synthesis method of compound H-1, compound 1-b was replaced by compound 2-b (2.06 g, 10 mmol), and compound 1-a was replaced by compound 3-a (4.43 g, 10 mmol) to obtain compound H-3 (3.70 g, yield: 65%), MS: m / z 568.34 [M+].

[0181] Synthesis Example 20: Synthesis of H-4

[0182]

[0183] Referring to the synthesis method of compound 1-f, compound 1-g was replaced with compound 4-g (1.29 g, 10 mmol) to obtain compound 4-f (0.88 g, yield: 66%).

[0184] In a 100mL reaction bottle, add compound 4-f (1.33g, 10mmol), 20mL acetonitrile, concentrated sulfuric acid (1.08g, 11mmol), stir at room temperature for 5min, then slowly add NBS (1.96g, 11mmol), react at room temperature for 3h, add 20mL water, extract the aqueous phase 3 times with 30mL dichloromethane, combine the organic phases, dry the organic phases with anhydrous sodium sulfate, filter, distill under pressure, and pass through a silica gel column to obtain compound 4-e (1.60g, yield: 76%).

[0185] Referring to the synthesis method of compound 1-c, compound 1-e was replaced by compound 4-e (2.10 g, 10 mmol), and compound 1-d was replaced by compound 4-d (1.40 g, 10 mmol) to obtain compound 4-c (1.65 g, yield: 73%).

[0186] Referring to the synthesis method of compound 1-b, compound 1-c was replaced with compound 4-c (2.26 g, 10 mmol) to obtain compound 4-b (1.46 g, 71%).

[0187] Referring to the synthesis method of compound H-1, compound 1-b was replaced by compound 4-b (2.06 g, 10 mmol), and compound 1-a was replaced by compound 4-a (3.63 g, 10 mmol) to obtain compound H-4 (3.27 g, yield: 67%), MS: m / z 488.28 [M+].

[0188] Synthesis Example 21: Synthesis of H-5

[0189]

[0190] Referring to the synthesis method of compound H-1, compound 1-b was replaced by compound 4-b (2.06 g, 10 mmol), and compound 1-a was replaced by compound 5-a (4.32 g, 10 mmol) to obtain compound H-5 (3.85 g, yield: 69%), MS: m / z 557.27 [M+].

[0191] Synthesis Example 22: Synthesis of H-6

[0192]

[0193] In a 100mL reaction bottle, compound 6-h (1.42g, 10mmol) and 20mL tetrahydrofuran were added. Under nitrogen protection, the temperature was lowered to -40°C, 2M n-butyllithium (10mL, 20mmol) was slowly added dropwise, and the mixture was stirred for 1h after the addition was complete. Trimethyl borate (2.08g, 20mmol) was slowly added, and the mixture was stirred for 30min and then warmed to room temperature, stirred for 2h, and then lowered to -10°C. 30mL of dilute hydrochloric acid was slowly added, and the mixture was warmed to room temperature and stirred for 1h. 30mL of dichloromethane was added and stirred. The mixture was allowed to stand for phase separation, and the aqueous phase was extracted with 20mL of dichloromethane. The organic phases were combined, dried over anhydrous sodium sulfate, filtered, and evaporated under reduced pressure to obtain compound 6-g (1.52g, yield: 82%).

[0194] Referring to the synthesis method of compound 1-c, compound 1-e was replaced by compound 6-g (1.85 g, 10 mmol), and compound 1-d was replaced by compound 6-f (1.75 g, 10 mmol) to obtain compound 6-e (1.76 g, yield: 75%).

[0195] In a 250mL reaction bottle, compound 6-e (2.35g, 10mmol) and 25mL of dichloromethane were added under nitrogen protection, the temperature was lowered to -78°C, BBr3 (10.02g, 40mmol) was slowly added, the temperature was slowly raised to room temperature, the reaction was carried out for 2h, saturated NaHCO3 solution was added to terminate the reaction, the pH was adjusted to about 7, 20mL of water was added, stirred, and the liquid was separated by standing. The organic phase was taken, the aqueous phase was extracted with 30mL of dichloromethane, the organic phases were combined, the organic phases were dried over sodium sulfate, filtered and the solvent was removed under reduced pressure, and the mixture was passed through a silica gel column to obtain compound 6-d (1.53g, yield: 74%).

[0196] Referring to the synthesis method of compound 1-b, compound 1-c was replaced with compound 6-d (2.07 g, 10 mmol) to obtain compound 6-c (1.35 g, yield: 72%).

[0197] In a 100mL reaction bottle, compound 6-c (1.87g, 10mmol), 20mL tetradichloromethane, triethylamine (1.52g, 15mmol) were added. Under nitrogen protection, the temperature was lowered to 0°C, trifluoromethanesulfonic anhydride (4.23g, 15mmol) was slowly added, and the mixture was stirred for 30min. The mixture was warmed to room temperature and the reaction was continued for 4h. 30mL of saturated ammonium chloride solution was added, stirred, and allowed to stand for phase separation. The organic phase was then washed with 20mL of copper sulfate solution and then with 20mL of water. The organic phase was dried over anhydrous sodium sulfate, filtered and evaporated under reduced pressure to obtain compound 6-b (2.52g, yield: 79%).

[0198] Referring to the synthesis method of compound H-1, 1-b was replaced by 6-b (3.19 g, 10 mmol), 1-a was replaced by 6-a (3.56 g, 10 mmol), to obtain compound H-5 (3.03 g, yield: 63%), MS: m / z 481.24 [M+].

[0199] Synthesis Example 23: Synthesis of H-7

[0200]

[0201] Referring to the synthesis method of compound H-1, compound 1-b was replaced by compound 6-b (3.19 g, 10 mmol), and compound 1-a was replaced by compound 7-a (4.32 g, 10 mmol) to obtain compound H-7 (3.68 g, yield: 66%), MS: m / z 557.27 [M+].

[0202] Synthesis Example 24: Synthesis of H-8

[0203]

[0204] In a 100 mL reaction bottle, add compound 8-i (1.12 g, 10 mmol), 10 mL D2O, and 5 mL isopropanol. Under argon atmosphere, add Pt / C (0.12 g, 0.06 mmol). Raise the temperature to 180°C, react for 12 h, cool to room temperature, filter out Pt / C, and distill under reduced pressure to obtain compound 8-h (0.85 g, yield: 73%).

[0205] Referring to the synthesis method of compound 6-b, compound 6-c was replaced with compound 8-h (1.16 g, 10 mmol) to obtain compound 8-g (2.04 g, yield: 82%).

[0206] In a 250 ml reaction bottle, 35 ml of toluene, potassium acetate (1.96 g, 20 mmol), compound 8-g (2.48 g, 10 mmol), compound 8-f (3.05 g, 12 mmol), and palladium dichloride (0.07 g, 0.1 mmol) were added under nitrogen protection, the temperature was raised to reflux, the reaction was carried out for 8 h, the temperature was lowered to room temperature, 20 ml of water was added, the mixture was stirred, and the stratification was allowed to stand. The organic phase was taken, evaporated to dryness under reduced pressure, and passed through a silica gel column to obtain compound 8-e (1.63 g, yield: 72%).

[0207] Referring to the synthesis method of compound 1-c, compound 1-e was replaced by compound 8-e (2.26 g, 10 mmol), and compound 1-d was replaced by compound 8-d (2.07 g, 10 mmol) to obtain compound 8-c (1.68 g, yield: 74%).

[0208] Referring to the synthesis method of compound 1-b, compound 1-c was replaced with compound 8-c (2.27 g, 10 mmol) to obtain compound 8-b (1.45 g, yield: 70%).

[0209] Referring to the synthesis method of compound H-1, compound 1-b was replaced by compound 8-b (2.07 g, 10 mmol), and compound 1-a was replaced by compound 8-a (4.15 g, 10 mmol) to obtain compound H-8 (3.85 g, yield: 71%), MS: m / z 541.31 [M+].

[0210] Synthesis Example 25: Synthesis of H-9

[0211]

[0212] Referring to the synthesis method of compound 1-c, compound 1-e was replaced by compound 8-e (2.26 g, 10 mmol), and compound 1-d was replaced by compound 9-d (2.07 g, 10 mmol) to obtain compound 9-c (1.63 g, yield: 72%).

[0213] Referring to the synthesis method of compound 1-b, compound 1-c was replaced with compound 9-c (2.27 g, 10 mmol) to obtain compound 9-b (1.41 g, yield: 68%).

[0214] Referring to the synthesis method of compound H-1, compound 1-b was replaced by compound 9-b (2.07 g, 10 mmol), and compound 1-a was replaced by compound 9-a (3.63, 10 mmol) to obtain compound H-9 (3.38 g, yield: 69%), MS: m / z 489.29 [M+].

[0215] Synthesis Example 26: Synthesis of H-10

[0216]

[0217] Referring to the synthesis method of compound H-1, compound 1-b was replaced by compound 9-b (2.07 g, 10 mmol), and compound 1-a was replaced by compound 10-a (4.43 g, 10 mmol) to obtain compound H-10 (3.99 g, yield: 70%), MS: m / z 569.34 [M+].

[0218] Synthesis Example 27: Synthesis of H-11

[0219]

[0220] Referring to the synthesis method of compound 1-c, compound 1-e was replaced by compound 8-e (2.26 g, 10 mmol), and compound 1-d was replaced by compound 11-d (2.07 g, 10 mmol) to obtain compound 11-c (1.70 g, yield: 75%).

[0221] Referring to the synthesis method of compound 1-b, compound 1-c was replaced with compound 11-c (2.27 g, 10 mmol) to obtain compound 11-b (1.47 g, yield: 71%).

[0222] Referring to the synthesis method of compound H-1, compound 1-b was replaced by compound 11-b (2.07 g, 10 mmol), and compound 1-a was replaced by compound 11-a (3.63 g, 10 mmol) to obtain compound H-11 (3.62 g, yield: 74%), MS: m / z 489.29 [M+].

[0223] Synthesis Example 28: Synthesis of H-12

[0224]

[0225] Referring to the synthesis method of compound H-1, compound 1-b was replaced by compound 11-b (2.07 g, 10 mmol), and compound 1-a was replaced by compound 12-a (4.43 g, 10 mmol) to obtain compound H-12 (4.10 g, yield: 72%), MS: m / z 569.34 [M+].

[0226] Synthesis Example 29: Synthesis of H-13

[0227]

[0228] Referring to the synthesis method of compound 1-c, compound 1-e was replaced by compound 8-e (2.26 g, 10 mmol), and compound 1-d was replaced by compound 13-d (2.07 g, 10 mmol) to obtain compound 13-c (1.68 g, yield: 74%).

[0229] Referring to the synthesis method of compound 1-b, compound 1-c was replaced with compound 13-c (2.27 g, 10 mmol) to obtain compound 13-b (1.41 g, yield: 68%).

[0230] Referring to the synthesis method of compound H-1, compound 1-b was replaced by compound 13-b (2.07 g, 10 mmol), and compound 1-a was replaced by compound 13-a (3.56 g, 10 mmol) to obtain compound H-13 (3.23 g, yield: 67%), MS: m / z 482.24 [M+].

[0231] Comparative Example Compound

[0232] Some typical host-guest material structures that have been tried during the research are summarized as follows:

[0233]

[0234] Composition performance

[0235] In order to simulate and calculate the distance between the host material and the guest material of the present invention, the present invention uses gromacs 2019.3 software, based on the GAFF force field and RESP atomic charge, to construct a 10*10*10nm cubic box, control the host-guest material mass ratio to 98:2, and use the conjugate gradient method to randomly place the host-guest molecules into the box and minimize the energy to eliminate the repulsion caused by the unreasonable arrangement of molecules in the system, and then perform a 100ps equilibrium MD simulation under NVT (canonical ensemble) to fully balance the system. On the basis of this system, based on the NPT (isothermal and isobaric ensemble) with periodic boundary conditions, a 5ns generation MD simulation was performed under the external environment settings of 1atm and 298K, and the last 2ns MD trajectory was divided into 20 parts to calculate the average distance between the host and guest molecules in the present invention.

[0236] It should be noted that the host and guest molecular structures used in the MD simulation were obtained by using Gaussian 16C.01 software, based on the density functional theory (DFT) calculation method (the basis set level was set to: b3lyp / 6-31G(d), the charge number was 0), and the molecular structure was subjected to geometric optimization and vibration analysis (Opt+freq). During the calculation, the structures used did not have imaginary frequencies.

[0237] The results are shown in Table 1.

[0238] Table 1 Average distances between host and guest molecules in different compositions

[0239]

[0240]

[0241] Through calculation, it can be known that the distance between the host and guest molecules in the embodiment of the composition of the present invention is farther than the distance between the host and guest molecules in the comparative example of the composition, which is beneficial to prevent the aggregation of guest (BD) molecules, inhibit triplet Dexter energy transfer, reduce the energy loss of non-radiative transitions, and is beneficial to the energy transfer from S1 of the host material to S1 of the guest material, thereby improving the Forster energy transfer efficiency, thereby improving the efficiency of the prepared device, reducing the device operating voltage, and extending the device working life.

[0242] Fabrication and characterization of OLEDs

[0243] Device Embodiment

[0244] The organic electroluminescent device provided by the present invention comprises an anode, a hole transport region, a light-emitting layer, an electron transport region, and a cathode which are sequentially arranged on a substrate;

[0245] Furthermore, the hole transport region includes a hole injection layer, a hole transport layer and a light-emitting auxiliary layer; and the electron transport region includes an electron transport layer and an electron injection layer.

[0246] Furthermore, the light-emitting layer is composed of a host material and a guest material, and the host material of the light-emitting layer can be composed of one molecular material or multiple molecular materials.

[0247] The composition of the present invention can be used for the light-emitting layer of the above-mentioned organic electroluminescent device.

[0248] The anode in the embodiment adopts anode materials commonly used in the art, such as ITO, Ag or their multilayer structures. The hole injection layer adopts hole injection materials commonly used in the art, and F4TCNQ, HATCN, NDP-9, etc. are added for doping. The hole transport layer adopts hole transport materials commonly used in the art. The light-emitting layer adopts the host and guest material composition provided by the present invention. The electron transport layer adopts electron transport materials commonly used in the art. The electron injection layer adopts electron injection materials commonly used in the art, such as Liq, LiF, Yb, etc. The cathode adopts materials commonly used in the art, such as metal Al, Ag or metal mixtures (Ag-doped Mg, Ag-doped Ca, etc.).

[0249] The electrode preparation method and the deposition method of each functional layer in this embodiment are conventional methods in the art, such as vacuum thermal evaporation or inkjet printing, etc., which will not be described in detail here. Only some process details and test methods in the preparation process are supplemented as follows:

[0250] Device Example 1

[0251] The substrates used in the present invention were subjected to the following operations: the ITO substrate was patterned so that its luminous area had a size of 3 mm×3 mm, and then water / isopropanol ultrasound, UV / ozone irradiation, and then dried at 100°C. After that, the ITO substrate was mounted on a substrate holder of a vacuum deposition device and the pressure was adjusted so that the vacuum rate became 1×10 -7The following operations were then performed: first, on the ITO layer (anode) formed on the substrate, the compound HTL-01 and the compound p-dopant-01 (the mass ratio of HTL-01 to p-dopant-01 was 97:3) were vacuum deposited to form a hole injection layer with a thickness of 10 nm; secondly, on the hole injection layer, the compound HTL-01 was vacuum deposited to form a hole transport layer with a thickness of 120 nm; and then, on the hole transport layer, the compound B was vacuum deposited to form a hole transport layer with a thickness of 5 nm. prime-01 to form an electron blocking layer, and then on the above-mentioned electron blocking layer, a mixture of compound H-1 provided by the present invention and compound S3 is vacuum deposited with a thickness of 20nm to form a light-emitting layer, wherein H-1 serves as a host and S3 serves as a guest, and the mass ratio of the host to the guest is 98:2; then on the above-mentioned light-emitting layer, compound HBL-01 is vacuum deposited with a thickness of 5nm to form a hole blocking layer; then on the above-mentioned hole blocking layer, compound ETL-01 and compound Liq (the mass ratio of ETL-01 to Liq is 1:1) are vacuum deposited with a thickness of 20nm to form an electron transport layer; then on the above-mentioned electron transport layer, Yb is vacuum deposited with a thickness of 1nm to form an electron injection layer, and then on the above-mentioned electron injection layer, Mg and Ag (the mass ratio of Mg to Ag is 1:9) are deposited with a thickness of 15nm to form a cathode. Finally, the vapor-deposited substrate is packaged, and the cleaned cover is coated with UV glue using a glue coating device. The coated cover is then moved to the pressing section, and the vapor-deposited substrate is placed on the upper end of the cover. Finally, the substrate and the cover are bonded together using a bonding device, and the UV glue is light-cured to prepare an organic electroluminescent device.

[0252] Except for the host and guest materials of the light-emitting layer, the molecular structures of the materials in the remaining layers are as follows:

[0253]

[0254] Device Examples 2-25

[0255] The above method is used to prepare organic electroluminescent devices from the compositions described in other embodiments in Table 2, and the composition of the host and guest materials shown in the embodiments in Table 2 is used to replace the composition of H-1 and S3 in device embodiment 1 to prepare blue light organic electroluminescent device embodiments 2-25.

[0256] Device Comparison Examples 1-20

[0257] The above method is used to prepare the composition described in the comparative example in Table 2 into an organic electroluminescent device, and the host and guest material compositions shown in the comparative example in Table 2 are used to replace the composition of H-1 and S3 in device example 1 to prepare blue light organic electroluminescent device comparative examples 1-20.

[0258] The OLED devices described above were tested by standard methods. For this purpose, at J = 10 mA / cm 2 The driving voltage and luminous efficiency (EQE) of the organic electroluminescent device are determined at a current density of J = 10 mA / cm 2 When working under LT95, the luminous brightness drops to 95% of its initial value L0 after time LT95.

[0259] The test instruments and methods for testing the performance of the OLED devices in the above embodiments and comparative examples are as follows:

[0260] The external quantum efficiency was determined by using a voltage / current generator R6144 manufactured by Advantest, with a current of 10 mA / m 2 The element emits light by applying a voltage of . Using a spectroradiometer SR-3AR manufactured by TOPCON, the spectral radiance brightness in the visible light region is measured from the vertical direction to the luminous surface. Assuming that the luminous surface is a completely diffuse surface, the value of the spectral radiance brightness of each wavelength component measured is divided by the wavelength energy and multiplied by π to obtain the number of photons at each wavelength. Then, the number of photons is accumulated in the observed full wavelength region and set as the total number of photons released from the element. The value obtained by dividing the applied current value by the elementary charge is set as the number of carriers injected into the element, and the value obtained by dividing the total number of photons released from the element by the number of carriers injected into the element is the external quantum efficiency.

[0261] Current density and lighting voltage: tested using a digital source meter Keithley 2400;

[0262] Life test: Use silicon photoelectric OLED device life test system.

[0263] The performance test results of the above devices are listed in Table 2.

[0264] Table 2 Blue light device performance test results

[0265]

[0266]

[0267] It can be seen from the device performance test results in Table 2 above that by increasing the distance between the host and guest molecules, the prepared device does show significant changes in operating voltage, efficiency and life, and obtains lower operating voltage, higher device efficiency and working life, indicating that the luminescence performance of the device can be improved by reasonably adjusting the combination of host and guest materials.

[0268] Obviously, the above embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not limitations on the implementation methods of the present invention. For ordinary technicians in the relevant field, other different forms of changes or modifications can be made based on the above description. It is impossible to list all the implementation methods here. All obvious changes or modifications derived from the technical solution of the present invention are still within the protection scope of the present invention.

Claims

1. A blue light-emitting composition, characterized in that: The blue light-emitting composition comprises a compound having a general structural formula as shown in Formula I, and a compound having a general structural formula as shown in Formula II: In Formula I, Ar1 represents a substituted or unsubstituted phenyl group, naphthyl group, phenanthryl group or pyrenyl group; L1 represents a single bond, a substituted or unsubstituted phenylene group or naphthyl group; Ar2 represents the structure shown in formula A-1: R a1 To R a4 , R b1 To R b4 are each independently selected from hydrogen or deuterium; When the R a1 To R a4 When any one of the above is selected from deuterium, the R b1 To R b4 are all hydrogen; when the R a1 To R a4 When neither is selected from deuterium, the R b1 To R b4 At least one of them is selected from deuterium; and when the R a1 To R a4 , R b1 To R b4 When any one of is selected from deuterium, all hydrogen atoms in the same benzene ring are replaced by deuterium; R represents hydrogen or deuterium, and s represents an integer from 0 to 8; R a1 To R a4 Any one of which is bonded to the formula I; In formula II, R1 and R2 each independently represent one of hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 30 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 30 carbon atoms, substituted or unsubstituted aryl having 6 to 60 carbon atoms, and substituted or unsubstituted heteroaryl having 5 to 60 carbon atoms; R3 represents a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 60 carbon atoms, or a substituted or unsubstituted heteroaryl group having 5 to 60 carbon atoms; R4 represents one of a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, and a substituted or unsubstituted aryl group having 6 to 60 carbon atoms; R5 and R6 each independently represent one of hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 30 carbon atoms, substituted or unsubstituted alkoxy having 1 to 30 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 30 carbon atoms, substituted or unsubstituted aryl having 6 to 60 carbon atoms, substituted or unsubstituted heteroaryl having 5 to 60 carbon atoms, substituted or unsubstituted condensed ring aryl having 5 to 60 carbon atoms, substituted or unsubstituted heterocondensed ring aryl having 5 to 60 carbon atoms, and substituted or unsubstituted amine; two or more R5 and R6 may each be connected to form a ring structure; m and n each independently represent 0, 1, 2, 3 or 4; when m is 2, 3 or 4, R5 may be the same or different; when n is 2, 3 or 4, R6 may be the same or different; Ar3 represents one of the structures shown in formula B-1 to formula B-4: In formula B-1, X1 and X2 each independently represent O, NR 30 , S or Se, p represents 1, 2, 3, 4 or 5; R7 to R 11 Any one of which is bonded to the formula II; R7 to R 11 , R 30 Each independently represents one of hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 60 carbon atoms, and a substituted or unsubstituted heteroaryl group having 5 to 60 carbon atoms; In formula B-2, X3 and X4 each independently represent O, NR 31 , S or Se; R 12 To R 19 Any one of which is bonded to the formula II; R 12 To R 19 , R 31 Each independently represents hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 60 carbon atoms, or a substituted or unsubstituted heteroaryl group having 5 to 60 carbon atoms; R at adjacent positions 12 To R 19 can be connected to each other to form a ring structure; In formula B-3, X5 means O, NR 32 , S or Se; q represents 0, 1, 2, 3, 4 or 5; R 20 To R 24 Any one of which is bonded to the formula II; R 20 To R 24 , R 32 Each independently represents one of hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 60 carbon atoms, and a substituted or unsubstituted heteroaryl group having 5 to 60 carbon atoms; In formula B-4, R 25 To R 29 Any one of which is bonded to the formula II; R 25 To R 28 Each independently represents one of hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 60 carbon atoms, and a substituted or unsubstituted heteroaryl group having 5 to 60 carbon atoms; R 29 represents one of hydrogen, deuterium, and a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms; In formula I and formula II, any hydrogen can be replaced by deuterium, any nitrogen can be replaced by nitrogen-15, any sulfur can be replaced by sulfur-33, sulfur-34 or sulfur-36, any oxygen can be replaced by oxygen-17 or oxygen-18, and any carbon can be replaced by carbon-13.

2. The blue light-emitting composition according to claim 1, characterized in that: At least one of R1 and R2 is selected from a substituted or unsubstituted phenyl or biphenyl group having 6 to 60 carbon atoms; R3 represents a substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms; R4 represents one of a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms, and a substituted or unsubstituted aryl group having 6 to 30 carbon atoms; The R5 and R6 represent an alkyl group having 1 to 10 carbon atoms.

3. The blue light-emitting composition according to claim 1, characterized in that: The formula B-1 is selected from one of the following structures:

4. The blue light-emitting composition according to claim 1, characterized in that: The formula B-2 is selected from one of the structures shown below:

5. The blue light-emitting composition according to claim 1, characterized in that: The formula B-3 is selected from one of the structures shown below:

6. The blue light-emitting composition according to claim 1, characterized in that: Ar1 is selected from one of phenyl, biphenyl, naphthyl, phenyl-substituted naphthyl, phenanthrenyl, and pyrenyl; The Ar2 is selected from one of the structures shown below:

7. The blue light-emitting composition according to claim 1, characterized in that: The compound represented by formula I is selected from any one of the following structures:

8. The blue light-emitting composition according to claim 1, characterized in that: The compound represented by formula II is selected from any one of the following structures:

9. An organic electroluminescent device, characterized in that: It comprises an anode, a hole transport region, a light-emitting layer, an electron transport region, and a cathode which are sequentially arranged on a substrate; wherein the light-emitting layer comprises one or more blue light-emitting compositions as described in any one of claims 1 to 8.

10. The organic electroluminescent device according to claim 9, characterized in that: The light-emitting layer includes a host material and a guest material, wherein the host material includes one or more compounds with a general structural formula as shown in Formula I, and the guest material includes one or more compounds with a general structural formula as shown in Formula II.

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