A blue light-emitting composition and an organic electroluminescent device containing the same

Abstract

The present invention discloses a blue light-emitting composition and an organic electroluminescent device containing the same. The blue light-emitting composition comprises a host material having a general structural formula as shown in Formula I, and a guest material having a general structural formula as shown in Formula II. The present invention uses a compound containing a dibenzofuran group and a deuterium-substituted anthracene as a host material, and a compound containing a steric hindered group such as thiophene and a cycloalkyl group as a guest material. The composition can significantly enhance the stability and life of the blue light organic electroluminescent device through a reasonable combination, while enhancing the electron migration and transfer efficiency and eliminating the host luminescence phenomenon. Ⅰ, Ⅱ.

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, optoelectronic devices based on organic materials have become increasingly popular. Examples of such organic optoelectronic devices include organic light-emitting diodes (OLEDs), organic field effect transistors, organic photovoltaic cells, organic sensors, etc. Among them, OLED has developed particularly rapidly and has achieved commercial success in the field of information display. OLED can provide highly saturated red, green, and blue colors. Full-color display devices made of OLED do not require additional backlight sources and have the advantages of brilliant colors, short response time, wide color gamut, and high contrast.

[0003] OLED blue fluorescent devices adopt the form of a combination of host materials and guest materials, in which the host material is responsible for carrier transmission and recombination to form excitons, and transfers the exciton energy to the guest material. After receiving the energy transferred by the host material, the guest material emits light in the target wavelength range, and sometimes introduces a sensitizer to improve the energy transfer efficiency between the host and the guest. The energy transfer efficiency between different host and guest materials is different. When the energy transfer between the host and the guest is poor, the device performance will be reduced. In addition, the energy transfer between the host and the guest is also affected by the interaction between the host and the guest. The host materials commonly used at present are mainly anthracene-based main structures, and the substituents are usually fused ring structures such as naphthalene. Although some deuterium-substituted host material structures have been reported, due to the selection of substitution positions, the overall performance of the device has not been significantly improved. In addition, in the combination of host and guest materials, the interaction between the two has not been fully utilized to exert better functionality.

[0004] In addition, when the energy transmission between the host and guest materials is poor, deep blue light will appear in the 410-430nm region, which is the "host luminescence" phenomenon, see Figure 2 (The y-axis uses a logarithmic coordinate axis with a value range of 0.01 to 1). The generation of deep blue light can cause damage to the human eye and greatly reduce the efficiency of the device. This is another problem that currently needs to be solved in organic electroluminescent devices.

[0005] Therefore, it is necessary to adjust the structural configuration of the host material and the guest material and promote the reasonable combination of the two to improve the performance of organic light-emitting 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] Ⅰ. II;

[0010] In Formula I,

[0011] Ar1 represents one of deuterium-substituted or unsubstituted phenyl, deuterium-substituted or unsubstituted naphthyl, deuterium-substituted or unsubstituted phenanthrenyl, and deuterium-substituted or unsubstituted pyrenyl;

[0012] L1 represents a single bond, a deuterium-substituted or unsubstituted phenylene group, or a deuterium-substituted or unsubstituted naphthylene group;

[0013] Ar2 represents ;

[0014] R 11 To R 14 , R 21 To R 24 each independently represents hydrogen or deuterium;

[0015] R 11 To R 14 , R 21 To R 24 Any one of which is bonded to the anthracene structure of formula I;

[0016] When the R 11 To R 14 When any one of the following is selected from deuterium, the R 21 To R 24 are not selected from deuterium; when the R 11 To R 14 When neither is selected from deuterium, the R 21 To R 24 At least one of them is selected from deuterium, and when the R 11 To R 14 , R 21 To R 24 When any one of is selected from deuterium, all hydrogen atoms in the same benzene ring are replaced by deuterium;

[0017] In formula II,

[0018] Ring A represents a substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms; L2 represents a single bond;

[0019] R1, R2, R3, and R5 each independently represent any one of hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 30 carbon atoms, substituted or unsubstituted alkenyl having 2 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 aromatic group having 5 to 60 carbon atoms, substituted or unsubstituted heterocondensed aromatic group having 5 to 60 carbon atoms, and substituted or unsubstituted amine; two or more R1, R2, R3, and R5 may each be connected to form a ring structure;

[0020] R4 represents any 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;

[0021] X represents O or S;

[0022] m, n, q each independently represent 0, 1, 2, 3 or 4; when m is 2, 3 or 4, R1 may be the same or different; when n is 2, 3 or 4, R2 may be the same or different; when q is 2, 3 or 4, R5 may be the same or different;

[0023] p represents 0, 1, 2, 3, 4 or 5; when p is 2, 3, 4 or 5, R3 may be the same or different;

[0024] r represents 0 or 1;

[0025] The substituents in ring A, R1, R2, R3, R4, and R5 may be the same or different, and are independently selected from deuterium, halogen, cyano, alkyl having 1 to 10 carbon atoms, aryl having 6 to 60 carbon atoms, heteroaryl having 5 to 60 carbon atoms, condensed aromatic group having 5 to 60 carbon atoms, cycloalkyl having 3 to 30 carbon atoms, and amine, wherein two or more substituents may be connected to form an aliphatic ring, an aromatic ring, or a condensed ring;

[0026] In formula I and formula II, any hydrogen can be replaced by deuterium, and any nitrogen can be replaced by 15 N substitution, any sulfur can be 33 S. 34 S or 36 S is substituted, any oxygen can be 17 O or 18O substitution, any carbon can be 13 C substitution, any boron can be 11 B replaced.

[0027] Further, when the L1 represents a single bond, the Ar1 represents one of a deuterium-substituted or unsubstituted phenyl group, a deuterium-substituted or unsubstituted naphthyl group, a deuterium-substituted or unsubstituted phenanthrenyl group, and a deuterium-substituted or unsubstituted pyrenyl group;

[0028] When L1 represents a phenylene group, Ar1 represents a phenyl group or a naphthyl group;

[0029] When L1 represents a deuterium-substituted phenylene group, Ar1 represents one of a deuterium-substituted phenyl group and a deuterium-substituted naphthyl group;

[0030] When L1 represents a naphthylene group, Ar1 represents a phenyl group;

[0031] When the L1 represents a deuterium-substituted naphthylene group, the Ar1 represents a deuterium-substituted phenyl group.

[0032] Furthermore, Ar2 is selected from one of the structures shown in the following formula A-1 to formula A-8:

[0033] A-1, A-2, A-3, A-4, A-5, A-6, A-7, A-8;

[0034] Wherein, * represents the site where Ar2 is bonded to the anthracene structure of formula I.

[0035] Furthermore, the compound represented by formula II is selected from any one of formula II-1 to formula II-4:

[0036] Ⅱ-1, II-2;

[0037] Ⅱ-3, Ⅱ-4.

[0038] Further, the R1, R2, R3, and R5 each independently represent hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, and two or more R1, R2, R3, and R5 may each be connected to form a ring structure;

[0039] R4 represents hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 12 carbon atoms;

[0040] The substituents in the ring A, R1, R2, R3, R4, and R5 may be the same or different, and are independently selected from deuterium and an alkyl group having 1 to 10 carbon atoms.

[0041] Furthermore, the cycloalkyl group is a cyclohexyl group or a cyclopentyl group.

[0042] Furthermore, m, n, p, and q each independently represent 0, 1 or 2.

[0043] Furthermore, the compound represented by formula I is selected from any one of the following compounds:

[0044] .

[0045] Furthermore, the compound represented by formula II is selected from any one of the following compounds:

[0046] .

[0047] The second aspect of the present invention provides an organic electroluminescent device, comprising an anode, a hole transport region, a light-emitting layer, an electron transport region, and a cathode sequentially arranged on a substrate; wherein the light-emitting layer comprises one or more blue light-emitting compositions as described above.

[0048] 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.

[0049] Beneficial effects of the present invention:

[0050] The blue light host material (BH) provided by the present invention performs all deuteration on the anthracene structure in the parent core structure, so that the energy of the luminescent material is reduced, the stability and life of the luminescent device are significantly enhanced, and deuteration is introduced on the dibenzofuran structure and / or phenyl, naphthyl, phenanthrenyl, pyrene and other substituents, so that the device life is long without increasing the voltage, reducing energy loss, and after deuteration, it can work together with the cycloalkyl on the guest material to strengthen the dipole-dipole interaction between the host and the guest, thereby improving the exciton energy transfer. In the blue light guest material (BD) provided by the present invention, the introduction of steric hindering groups such as thiophene can inhibit the vibration of the parent core, so that the energy loss and FWHM generated during excitation are reduced; at the same time, the introduction of cycloalkyl in the structure can produce stereo interference, interfere with the encapsulation of the guest material and the guest material, thereby reducing the light loss between the guest materials and greatly improving the efficiency.

[0051] The present invention can effectively avoid the occurrence of host luminescence and reduce the occurrence of concentration quenching by reasonably matching the host and the guest, using a host with large polarity and a guest material with good dispersion. Therefore, by using the blue light-emitting composition provided in the present invention, the effects of improving the orientation of organic light-emitting materials, increasing lifespan, and reducing quenching can be achieved, and the organic electroluminescent device prepared using the blue light-emitting composition of the present invention has good performance in external quantum efficiency, lifespan, and driving voltage. BRIEF DESCRIPTION OF THE DRAWINGS

[0052] Figure 1 is a schematic structural diagram of an organic electroluminescent device of the present invention;

[0053] Figure 2 This is a UV-PL image showing the main luminescence phenomenon.

[0054] In the figure: 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

[0055] 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.

[0056] 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.

[0057] Experimental Section

[0058] 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.

[0059] Synthesis Example 1

[0060] This synthesis example provides a compound H-1, the synthesis route of which is as follows:

[0061]

[0062] In a 100 mL reaction bottle, compound 1-g (1.29 g, 10 mmol), 10 mL D2O, 2 mL isopropanol, and 2 mL n-hexane were added. Under an argon atmosphere, Pt / C (1.0 g, 0.5 mmol) was added. The temperature was raised to 90 °C and reacted for 24 h. The temperature was cooled to room temperature, Pt / C was removed by filtration, and 20 mL of dichloromethane was added. The mixture was stirred, allowed to stand, and the phases were separated. The lower layer was dried over anhydrous sodium sulfate, filtered, and distilled under reduced pressure to obtain 1-f (0.96 g, yield: 72%).

[0063] In a 250mL reaction bottle, 1-f (1.33 g, 10 mmol), diisopropylamine (0.10 g, 1 mmol), and 20 mL of dichloromethane were added, and N-bromosuccinimide (3.92 g, 22 mmol) was slowly added. The temperature was raised to 30°C, and the reaction was carried out for 12 h. The temperature was then lowered to room temperature. The pH of the system was adjusted to 5 with 1 mol / L hydrochloric acid solution. 20 mL of water was added, the mixture was stirred, and the mixture was allowed to stand for separation. The organic phase was taken, and the aqueous phase was extracted with 20 mL 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 1-e (1.30 g, yield: 62%).

[0064] 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. The mixture was heated to 80℃ 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 1-c (1.67g, yield: 74%).

[0065] In a 250mL three-necked flask, 1-c (2.26 g, 10 mmol), potassium carbonate (4.15 g, 30 mmol), and 30 mL of NMP were added under nitrogen protection, and the mixture was heated to 120°C for 16 h. After the reaction, the mixture was cooled to room temperature, 40 mL of water was added, and the mixture was stirred. The mixture was allowed to stand for stratification, and the aqueous phase was extracted with 30 mL of ethyl acetate. 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 1-b (1.46 g, yield: 71%).

[0066] In a 250mL three-necked flask, 40mL of 1,4-dioxane and 10mL of water were added under nitrogen protection, and then 1-b (2.06g, 10mmol), 1-a (3.56g, 10mmol), potassium phosphate (6.37g, 30mmol), and 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+].

[0067] Synthesis Example 2

[0068] This synthesis example provides a compound H-2, the synthesis route of which is as follows:

[0069]

[0070] Referring to the synthesis method of compound 1-f, 1-g was replaced by 2-g (1.29 g, 10 mmol) to obtain compound 2-f (0.92 g, yield: 69%).

[0071] In a 100mL reaction bottle, compound 2-f (1.33 g, 10 mmol), 20 mL of dichloromethane and 1 mL of glacial acetic acid were added, the temperature was lowered to 0°C, bromine (1.60 g, 10 mmol) was slowly added dropwise, and after the addition was completed, it was stirred at 0°C for 30 min, then warmed to room temperature and reacted for 16 h. 30 mL of sodium thiosulfate solution was added, stirred, and allowed to stand for phase separation. The aqueous phase was extracted with 20 mL of dichloromethane, the organic phases were combined, dried over anhydrous sodium sulfate, filtered, and then distilled under reduced pressure. Passed through a silica gel column to obtain 2-e (0.51 g, yield: 24%).

[0072] Referring to the synthesis method of compound 1-c, 1-e was replaced by 2-e (2.10 g, 10 mmol), 1-d was replaced by 2-d (1.40 g, 10 mmol), and compound 2-c (1.60 g, yield: 71%) was obtained.

[0073] Referring to the synthesis method of compound 1-b, 1-c was replaced by 2-c (2.26 g, 10 mmol) to obtain compound 2-b (1.48 g, yield: 72%).

[0074] Referring to the synthesis method of compound H-1, 1-b was replaced by 2-b (2.06 g, 10 mmol), 1-a was replaced by 2-a (3.63 g, 10 mmol), and compound H-2 (3.32 g, yield: 68%) was obtained, MS: m / z 488.28 [M+].

[0075] Synthesis Example 3

[0076] This synthesis example provides a compound H-3, the synthesis route of which is as follows:

[0077]

[0078] Referring to the synthesis method of compound H-1, 1-b was replaced by 2-b (2.06 g, 10 mmol), 1-a was replaced by 3-a (4.43 g, 10 mmol), and compound H-3 (3.70 g, yield: 65%) was obtained, MS: m / z 568.34 [M+].

[0079] Synthesis Example 4

[0080] This synthesis example provides a compound H-4, the synthesis route of which is as follows:

[0081]

[0082] Referring to the synthesis method of compound 1-f, 1-g was replaced with 4-g (1.29 g, 10 mmol) to obtain compound 4-f (0.88 g, yield: 66%).

[0083] In a 100 mL reaction bottle, compound 4-f (1.33 g, 10 mmol), 20 mL acetonitrile, and concentrated sulfuric acid (1.08 g, 11 mmol) were added. After stirring at room temperature for 5 min, NBS (1.96 g, 11 mmol) was slowly added. The reaction was carried out at room temperature for 3 h. 20 mL of water was added, and the aqueous phase was extracted three times with 30 mL of dichloromethane. The organic phases were combined, dried over anhydrous sodium sulfate, filtered, distilled under pressure, and passed through a silica gel column to obtain 4-e (1.60 g, yield: 76%).

[0084] Referring to the synthesis method of compound 1-c, 1-e was replaced by 4-e (2.10 g, 10 mmol), 1-d was replaced by 4-d (1.40 g, 10 mmol), and compound 4-c (1.65 g, yield: 73%) was obtained.

[0085] Referring to the synthesis method of compound 1-b, 1-c was replaced with 4-c (2.26 g, 10 mmol) to obtain compound 4-b (1.46 g, yield: 71%).

[0086] Referring to the synthesis method of compound H-1, 1-b was replaced by 4-b (2.06 g, 10 mmol), 1-a was replaced by 4-a (3.63 g, 10 mmol), and compound H-4 (3.27 g, yield: 67%) was obtained, MS: m / z 488.28 [M+].

[0087] Synthesis Example 5

[0088] This synthesis example provides a compound H-5, the synthesis route of which is as follows:

[0089]

[0090] Referring to the synthesis method of compound H-1, 1-b was replaced by 4-b (2.06 g, 10 mmol), 1-a was replaced by 5-a (4.32 g, 10 mmol), and compound H-5 (3.85 g, yield: 69%) was obtained, MS: m / z 557.27 [M+].

[0091] Synthesis Example 6

[0092] This synthesis example provides a compound H-6, the synthesis route of which is as follows:

[0093]

[0094] Compound 6-h (1.42 g, 10 mmol) and 20 mL of tetrahydrofuran were added to a 100 mL reaction bottle. Under nitrogen protection, the temperature was lowered to -40 °C, and 2 M n-butyl lithium (10 mL, 20 mmol) was slowly added dropwise. After the addition was complete, the mixture was stirred for 1 h. Trimethyl borate (2.08 g, 20 mmol) was slowly added. After stirring for 30 min, the mixture was warmed to room temperature and stirred for 2 h. The mixture was lowered to -10 °C, 30 mL of dilute hydrochloric acid was slowly added, the mixture was warmed to room temperature and stirred for 1 h. 30 mL of dichloromethane was added and stirred. The mixture was allowed to stand for phase separation. The aqueous phase was extracted with 20 mL of dichloromethane. The organic phases were combined, dried over anhydrous sodium sulfate, filtered, and distilled under reduced pressure to obtain 6-g (1.52 g, yield: 82%).

[0095] Referring to the synthesis method of compound 1-c, 1-e was replaced by 6-g (1.85 g, 10 mmol), and 1-d was replaced by 6-f (1.75 g, 10 mmol) to obtain compound 6-e (1.76 g, yield: 75%).

[0096] In a 250mL reaction bottle, 6-e (2.35 g, 10 mmol) and 25 mL of dichloromethane were added under nitrogen protection, the temperature was lowered to -78°C, BBr3 (10.02 g, 40 mmol) was slowly added, the temperature was slowly raised to room temperature, the reaction was carried out for 2 h, saturated NaHCO3 solution was added to terminate the reaction, the pH was adjusted to about 7, 20 mL of water was added, the mixture was stirred, and the mixture was allowed to stand for separation. The organic phase was taken, the aqueous phase was extracted with 30 mL of dichloromethane, the organic phases were combined, the organic phases were dried over sodium sulfate, filtered, the solvent was removed under reduced pressure, and the mixture was passed through a silica gel column to obtain 6-d (1.53 g, yield: 74%).

[0097] Referring to the synthesis method of compound 1-b, 1-c was replaced with 6-d (2.07 g, 10 mmol) to obtain compound 6-c (1.35 g, yield: 72%).

[0098] In a 100mL reaction bottle, compound 6-c (1.87g, 10mmol), 20mL tetradichloromethane, and triethylamine (1.52g, 15mmol) were added. Under nitrogen protection, the temperature was lowered to 0°C, trifluoromethanesulfonic anhydride (4.23g, 15mmol) was slowly added, stirred for 30min, 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 distilled under reduced pressure to obtain 6-b (2.52g, yield: 79%).

[0099] 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), and compound H-6 (3.03 g, yield: 63%) was obtained, MS: m / z 481.24 [M+].

[0100] Synthesis Example 7

[0101] This synthesis example provides a compound H-7, the synthesis route of which is as follows:

[0102]

[0103] 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 7-a (4.32 g, 10 mmol), and compound H-7 (3.68 g, yield: 66%) was obtained, MS: m / z 557.27 [M+].

[0104] Synthesis Example 8

[0105] This synthesis example provides a compound H-8, the synthesis route of the compound is as follows:

[0106]

[0107] In a 100 mL reaction bottle, 8-i (1.12 g, 10 mmol), 10 mL D2O, and 5 mL isopropanol were added. Under an argon atmosphere, Pt / C (0.12 g, 0.06 mmol) was added. The temperature was raised to 180 °C, reacted for 12 h, cooled to room temperature, filtered to remove Pt / C, and 8-h (0.85 g, yield: 73%) was obtained by distillation under reduced pressure.

[0108] Referring to the synthesis method of compound 6-b, 6-c was replaced by 8-h (1.16 g, 10 mmol) to obtain compound 8-g (2.04 g, yield: 82%).

[0109] In a 250 ml reaction bottle, 35 ml of toluene, potassium acetate (1.96 g, 20 mmol), 8-g (2.48 g, 10 mmol), 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 cooled 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 8-e (1.63 g, yield: 72%).

[0110] Referring to the synthesis method of compound 1-c, 1-e was replaced by 8-e (2.26 g, 10 mmol), 1-d was replaced by 8-d (2.07 g, 10 mmol), and compound 8-c (1.68 g, yield: 74%) was obtained.

[0111] Referring to the synthesis method of compound 1-b, 1-c was replaced with 8-c (2.27 g, 10 mmol) to obtain compound 8-b (1.45 g, yield: 70%).

[0112] Referring to the synthesis method of compound H-1, 1-b was replaced by 8-b (2.07 g, 10 mmol), 1-a was replaced by 8-a (4.15 g, 10 mmol), and compound H-8 (3.85 g, yield: 71%) was obtained, MS: m / z 541.31 [M+].

[0113] Synthesis Example 9

[0114] This synthesis example provides a compound H-9, the synthesis route of which is as follows:

[0115]

[0116] Referring to the synthesis method of compound 1-c, 1-e was replaced by 8-e (2.26 g, 10 mmol), 1-d was replaced by 9-d (2.07 g, 10 mmol), and compound 9-c (1.63 g, yield: 72%) was obtained.

[0117] Referring to the synthesis method of compound 1-b, 1-c was replaced with 9-c (2.27 g, 10 mmol) to obtain compound 9-b (1.41 g, yield: 68%).

[0118] Referring to the synthesis method of compound H-1, 1-b was replaced by 9-b (2.07 g, 10 mmol), 1-a was replaced by 9-a (3.63, 10 mmol), and compound H-9 (3.38 g, yield: 69%) was obtained, MS: m / z 489.29 [M+].

[0119] Synthesis Example 10

[0120] This synthesis example provides a compound H-10, the synthesis route of which is as follows:

[0121]

[0122] Referring to the synthesis method of compound H-1, 1-b was replaced by 9-b (2.07 g, 10 mmol), 1-a was replaced by 10-a (4.43 g, 10 mmol), and compound H-10 (3.99 g, yield: 70%) was obtained, MS: m / z 569.34 [M+].

[0123] Synthesis Example 11

[0124] This synthesis example provides a compound H-11, the synthesis route of the compound is as follows:

[0125]

[0126] Referring to the synthesis method of compound 1-c, 1-e was replaced by 8-e (2.26 g, 10 mmol), 1-d was replaced by 11-d (2.07 g, 10 mmol), and compound 11-c (1.70 g, yield: 75%) was obtained.

[0127] Referring to the synthesis method of compound 1-b, 1-c was replaced with 11-c (2.27 g, 10 mmol) to obtain compound 11-b (1.47 g, yield: 71%).

[0128] Referring to the synthesis method of compound H-1, 1-b was replaced by 11-b (2.07 g, 10 mmol), 1-a was replaced by 11-a (3.63 g, 10 mmol), and compound H-11 (3.62 g, yield: 74%) was obtained, MS: m / z 489.29 [M+].

[0129] Synthesis Example 12

[0130] This synthesis example provides a compound H-12, the synthesis route of which is as follows:

[0131]

[0132] Referring to the synthesis method of compound H-1, 1-b was replaced by 11-b (2.07 g, 10 mmol), 1-a was replaced by 12-a (4.43 g, 10 mmol), and compound H-12 (4.10 g, yield: 72%) was obtained, MS: m / z 569.34 [M+].

[0133] Synthesis Example 13

[0134] This synthesis example provides a compound H-13, the synthesis route of the compound is as follows:

[0135]

[0136] Referring to the synthesis method of compound 1-c, 1-e was replaced by 8-e (2.26 g, 10 mmol), and 1-d was replaced by 13-d (2.07 g, 10 mmol) to obtain compound 13-c (1.68 g, yield: 74%).

[0137] Referring to the synthesis method of compound 1-b, 1-c was replaced with 13-c (2.27 g, 10 mmol) to obtain compound 13-b (1.41 g, yield: 68%).

[0138] Referring to the synthesis method of compound H-1, 1-b was replaced by 13-b (2.07 g, 10 mmol), 1-a was replaced by 13-a (3.56 g, 10 mmol), and compound H-13 (3.23 g, yield: 67%) was obtained, MS: m / z 482.24 [M+].

[0139] Synthesis Example 14

[0140]

[0141] Y-1 (10.10 g; 10 mmol) was added to tert-butylbenzene (125 ml), and then the temperature was lowered to 0°C under nitrogen protection, 12.4 ml (21 mmol) of 1.7 M tert-butyl lithium pentane solution was added, the temperature was raised to 60°C and stirred for 2 h, and then the temperature was lowered to 0°C, 2.0 ml (21 mmol) of boron tribromide was added and stirred for 0.5 h, and the temperature was lowered to 0°C, 3.65 ml (21 mmol) of N,N-diisopropylethylamine was added, the temperature was raised to 60°C and stirred for 2 h, and then the temperature was lowered to room temperature, ice water was added to quench and the liquids were separated, the organic phase was filtered and dehydrated with anhydrous magnesium sulfate, the organic solvent was removed by rotation, and the compound Z-1 (0.85 g, yield: 9%) was finally obtained after recrystallization, MS: m / z 938.48 [M+].

[0142] Synthesis Example 15

[0143]

[0144] Referring to the synthesis method of compound Z-1, Y-1 was replaced by Y-2 (10.46 g, 10 mmol) to obtain compound Z-2 (1.07 g, yield: 11%), MS: m / z 974.63 [M+].

[0145] Synthesis Example 16

[0146]

[0147] Referring to the synthesis method of compound Z-1, Y-1 was replaced by Y-3 (10.80 g, 10 mmol) to obtain compound Z-3 (1.01 g, yield: 10%), MS: m / z 1008.56 [M+].

[0148] Synthesis Example 17

[0149]

[0150] Referring to the synthesis method of compound Z-1, Y-1 was replaced by Y-4 (9.48 g, 10 mmol) to obtain compound Z-4 (0.73 g, yield: 8%), MS: m / z 906.51 [M+].

[0151] Synthesis Example 18

[0152]

[0153] Referring to the synthesis method of compound Z-1, Y-1 was replaced by Y-5 (9.58 g, 10 mmol) to obtain compound Z-5 (0.89 g, yield: 10%), MS: m / z 886.50 [M+].

[0154] Synthesis Example 19

[0155]

[0156] Referring to the synthesis method of compound Z-1, Y-1 was replaced by Y-6 (10.88 g, 10 mmol) to obtain compound Z-6 (0.92 g, yield: 9%), MS: m / z 1016.62 [M+].

[0157] Synthesis Example 20

[0158]

[0159] Referring to the synthesis method of compound Z-1, Y-1 was replaced by Y-7 (10.06 g, 10 mmol) to obtain compound Z-7 (0.94 g, yield: 10%), MS: m / z 934.54 [M+].

[0160] Synthesis Example 21

[0161]

[0162] Referring to the synthesis method of compound Z-1, Y-1 was replaced by Y-8 (10.08 g, 10 mmol) to obtain compound Z-8 (0.84 g, yield: 9%), MS: m / z 936.52 [M+].

[0163] Synthesis Example 22

[0164]

[0165] Referring to the synthesis method of compound Z-1, Y-1 was replaced by Y-9 (10.28 g, 10 mmol) to obtain compound Z-9 (1.05 g, yield: 11%), MS: m / z 956.58 [M+].

[0166] Synthesis Example 23

[0167]

[0168] Referring to the synthesis method of compound Z-1, Y-1 was replaced by Y-10 (10.28 g, 10 mmol) to obtain compound Z-10 (1.05 g, yield: 11%), MS: m / z 956.52 [M+].

[0169] Composition performance

[0170] In order to illustrate that the composite material selected in the present invention has unique advantages in host-guest interaction, the molecular structure characteristics of the host material and the guest material were calculated respectively. The molecular structure was geometrically optimized (Optimization) by Gaussian 09W software based on the density functional theory (DFT) calculation method (the basis set level was set to: b3lyp / 6-31g(d), and the charge number was 0), and the dipole moments μ of the host material (BH) and the guest material (BD) in the ground state were obtained respectively. D , μ A , according to the probability formula of dipole-dipole interaction between host and guest:

[0171]

[0172] Among them, R DA is the distance between the host and the guest. Since the doping concentrations are the same, the distances between the host and the guest are assumed to be approximately the same. The orientations of the host and the guest are assumed to be the same, and the probability p of dipole-dipole interaction between the host and the guest is calculated.

[0173] In order to evaluate whether the device formed by the composition selected by the present invention produces the main luminescence phenomenon, according to the device preparation method, the mass concentration ratio of the guest material doping is reduced to 1%, and the electroluminescence spectrum is tested. The vertical axis adopts a logarithmic scale, and the presence of the luminescence peak is observed in the range of 400-440nm to evaluate whether the main luminescence phenomenon occurs.

[0174] The composition of the present invention was tested by the above method. For comparison, the main material can be BH-1 to BH-3, and the guest material can be BD-1 to BD-3. The test results of the composition performance are shown in Table 1 below:

[0175]

[0176]

[0177] Table 1 Composition performance test results

[0178]

[0179]

[0180] It can be seen from the above results that the probability of dipole-dipole interaction between the host and the guest provided by the present invention is greater than 3.5. This is because the host material provided by the present invention contains an asymmetric structure and polar groups, which significantly increase the dipole moment of the host material provided by the present invention. The guest material provided by the present invention contains benzothiophene fragments and cycloalkyl fragments to ensure that its polarity is more appropriate, avoiding too small polarity to be affected too little by the host force, and will not increase intermolecular aggregation due to excessive polarity.

[0181] It can also be seen that the composition of the present invention still does not exhibit host luminescence phenomenon at a low doping ratio, indicating that there is good energy transmission between the host and the guest in the composition of the present invention, which is beneficial to improving efficiency.

[0182] Fabrication and characterization of OLEDs

[0183] Device Embodiment

[0184] 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;

[0185] 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.

[0186] 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.

[0187] The composition of the present invention can be used for the light-emitting layer of the above-mentioned organic electroluminescent device.

[0188] 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.).

[0189] 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:

[0190] Device Example 1

[0191] The present embodiment provides a blue light organic electroluminescent device, and the preparation method thereof is as follows: first, on the ITO layer (anode) formed on the substrate, HTL-01 and p-dopant-01 (the mass ratio of HTL-01 to p-dopant-01 is 97:3) are vacuum deposited with a thickness of 10 nm to form a hole injection layer; secondly, on the hole injection layer, HTL-01 is vacuum deposited with a thickness of 120 nm to form a hole transport layer; and secondly, on the hole transport layer, B is vacuum deposited with a thickness of 5 nm. prime-01 forms a light-emitting auxiliary layer; again, on the above-mentioned light-emitting auxiliary layer, a composition of H-4 and Z-6 is vacuum deposited with a thickness of 20nm to form a light-emitting layer, wherein H-4 is used as a main material and Z-6 is used as a guest material, and the mass ratio of the main material to the guest material is 98:2; then, on the above-mentioned light-emitting layer, HBL-01 is vacuum deposited with a thickness of 5nm to form a hole blocking layer; a mixture of ET-01 and Liq (mass ratio of 1:1) is vacuum deposited with a thickness of 30nm to form an electron transport layer; then, on the above-mentioned electron transport layer, LiF is deposited with a thickness of 0.2nm to form an electron injection layer, and finally, on the above-mentioned electron injection layer, aluminum (Al) is deposited with a thickness of 150nm to form a cathode, and a blue light organic electroluminescent device is prepared.

[0192] 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:

[0193]

[0194]

[0195] Device Example 2-38

[0196] The above method is used to prepare organic electroluminescent devices from the compositions described in other embodiments in Table 1, and blue light organic electroluminescent device embodiments 2-38 are prepared by replacing the compositions of H-4 and Z-6 in device embodiment 1 with the host and guest material compositions shown in the embodiments in Table 1.

[0197] Device Comparison Examples 1-7

[0198] The above method is used to prepare the composition described in the comparative example in Table 1 into an organic electroluminescent device, and the host and guest material compositions shown in the comparative example in Table 1 are used to replace the compositions of H-4 and Z-6 in device example 1 to prepare blue light organic electroluminescent device comparative examples 1-7.

[0199] The OLED devices described above were tested by standard methods. For this purpose, at J = 10 mA / cm 2The driving voltage, brightness, electroluminescent current efficiency (measured in cd / A) and external quantum efficiency (EQE, measured in percentage) of the organic electroluminescent device are determined at a current density of , which is calculated from the current / voltage / luminous density characteristic line (IVL characteristic line) showing Lambertian emission characteristics as a function of luminous density. The lifetime LT is defined as the time after which the brightness drops from the initial luminous brightness L0 to a specific proportion L1 when operating at a constant current J; for example, J = 50 mA / cm 2 The expression L1 = 90% means that at 50 mA / cm 2 When working under LT, the luminance drops to 90% of its initial value L0 after time LT. Similarly, J = 20 mA / cm 2 , L1 = 80% means at 20mA / cm 2 When working under LT, the luminous brightness drops to 80% of its initial value L0 after time LT.

[0200] The data of various OLED devices are summarized in Table 2. Various parameters of the embodiments are compared with those of the comparative examples, and the performance data of various OLED devices are shown.

[0201] The test instruments and methods for testing the performance of the OLED devices in the above embodiments and comparative examples are as follows:

[0202] Brightness was tested using a spectral scanner PhotoResearch PR-635;

[0203] Current density and lighting voltage: tested using a digital source meter Keithley 2400;

[0204] Life test: Use LT-96ch life test device.

[0205] The performance test results of the above devices are listed in Table 2.

[0206] Table 2 Blue light device performance test results

[0207]

[0208] It can be seen from the device performance test results in Table 2 above that when the composition of the present invention is used in an organic electroluminescent device, the voltage is reduced, and the efficiency and life are significantly improved compared with the comparative example. This is because the present invention reasonably selects the host material and the guest material, fully utilizes the interaction between the host and the guest, and the combination of different host materials, so that the final device of the present invention shows significant advantages.

[0209] 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: Ⅰ、 Ⅱ； In Formula I, L1 represents a single bond, Ar1 represents a deuterium-substituted or unsubstituted naphthyl group; L1 represents a phenylene group, Ar1 represents a naphthyl group; L1 represents a deuterium-substituted phenylene group, and Ar1 represents a deuterium-substituted naphthyl group; L1 represents a naphthylene group, Ar1 represents a phenyl group; L1 represents a deuterium-substituted naphthylene group, and Ar1 represents a deuterium-substituted phenyl group; Ar2 represents ; R 11 To R 14 , R 21 To R 24 each independently represents hydrogen or deuterium; R 11 To R 14 , R 21 To R 24 Any one of which is bonded to the anthracene structure of formula I; When the R 11 To R 14 When any one of the above is selected from deuterium, the R 21 To R 24 are not selected from deuterium; when the R 11 To R 14 When neither is selected from deuterium, the R 21 To R 24 At least one of them is selected from deuterium, and when the R 11 To R 14 , R 21 To R 24 When any one of is selected from deuterium, all hydrogen atoms in the same benzene ring are replaced by deuterium; In formula II, Ring A represents a substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms; L2 represents a single bond; R1 represents a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, or a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms; R2 each independently represents a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, or a phenyl group; R3 and R5 each independently represent any one of hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 30 carbon atoms, and substituted or unsubstituted cycloalkyl having 3 to 30 carbon atoms; two or more R3 and R5 may each be connected to form a ring structure; R4 represents any one of hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 30 carbon atoms, and substituted or unsubstituted cycloalkyl having 3 to 30 carbon atoms; X represents O or S; m, n represent 1; q represents 0, 1, 2, 3 or 4; p represents 0, 1, 2, 3, 4 or 5; when p is 2, 3, 4 or 5, R3 may be the same or different; r represents 0 or 1; The substituents in ring A, R1, R2, R3, R4, and R5 may be the same or different, and are independently selected from deuterium, halogen, an alkyl group having 1 to 10 carbon atoms, and a cycloalkyl group having 3 to 30 carbon atoms, wherein two or more substituents may be connected to each other to form an aliphatic ring, an aromatic ring, or a condensed ring.

2. The blue light-emitting composition according to claim 1, characterized in that: The Ar2 is selected from one of the structures shown in the following formula A-1 to formula A-8: A-1、 A-2、 A-3、 A-4、 A-5、 A-6、 A-7、 A-8; Wherein, * represents the site where Ar2 is bonded to the anthracene structure of formula I.

3. The blue light-emitting composition according to claim 1, characterized in that: The compound represented by formula II is selected from any one of formula II-1 to formula II-4: Ⅱ-1、 Ⅱ-2； Ⅱ-3、 Ⅱ-4。 4. The blue light-emitting composition according to claim 1 or 3, characterized in that: The R3 and R5 each independently represent any one of hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, and a substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms, and two or more R3 and R5 may each be connected to form a ring structure; R4 represents any one of hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, and a substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms; The substituents in the ring A, R1, R2, R3, R4 and R5 may be the same or different, and are independently selected from deuterium and an alkyl group having 1 to 10 carbon atoms.

5. The blue light-emitting composition according to claim 1 or 4, characterized in that: The cycloalkyl group is cyclohexyl or cyclopentyl.

6. 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 compounds: 。 7. 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 compounds: 。 8. 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 7.

9. The organic electroluminescent device according to claim 8, 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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