Phosphorus-containing spirocyclic compounds and their applications

Abstract

The present invention relates to a phosphorus-containing spiro compound and its application, belonging to the technical field of organic optoelectronic devices. The present invention discloses a phosphorus-containing spiro compound having the following general formula I: The present invention also provides an application of the phosphorus-containing spiro compound: for use in an electroactive layer in an organic light-emitting device.

Description

Technical Field

[0001] The invention relates to a phosphorus-containing spiro compound and application thereof, belonging to the technical field of organic photoelectric devices. Background Art

[0002] Research and application of organic electroluminescent materials have been extensively pursued in academia and industry, resulting in the development of a large number of high-performance organic electroluminescent materials. Third-generation organic electroluminescent materials generally possess a small singlet-triplet energy level difference (ΔEST). Triplet excitons can be converted to singlet excitons via reverse intersystem crossing (RISC), emitting light. This allows for the simultaneous utilization of both singlet and triplet excitons formed by electrical excitation, resulting in devices with internal quantum efficiencies reaching 100%. Therefore, these materials are considered promising organic light-emitting materials for future applications. However, the operating lifetime of these devices, particularly for blue-emitting devices, remains an unresolved issue. Overall, the future development direction of organic electroluminescent devices is towards high-efficiency, long-life, and low-cost white light devices and full-color displays. However, the industrialization of this technology still faces many key challenges. Therefore, the design and search for stable and efficient compounds as novel materials for organic electroluminescent devices to overcome these shortcomings in practical applications remains a key focus and future research and development trend in organic electroluminescent device materials research.

[0003] In traditional OLED devices based on TADF materials, the performance of the luminescent materials is often unsatisfactory, hindering their industrialization. In the multi-layer structure of OLED devices, as the luminescent layer material, its chemical structure, thermal stability, photophysical properties, quantum yield (PLQY), etc. directly determine the device efficiency. In addition, molecular stacking and charge transfer can also affect the performance of the device. Due to the "insulating" effect of the P=O / S bond in the aromatic phosphorus oxygen / sulfur group, the formation of low-energy charge transfer states can be effectively suppressed, ensuring its blue or deep blue light emission; at the same time, its strong electron-withdrawing effect can effectively polarize the molecules, enhance the material's electrical transport properties and improve the material's quantum efficiency. In addition, due to its special tetrahedral configuration, the thermal stability of the material can be significantly improved. Therefore, the development of new luminescent materials containing P=O / S is particularly important.

[0004] Compound TSPO1, whose structural formula is Its currently known use is as an electron transport and exciton blocking material in blue light devices. (Adv Mater 2011, 23(12): 1436-1441.) Summary of the Invention

[0005] The technical problem to be solved by the present invention is to provide a synthesis and application of phosphorus-containing spirocyclic compounds.

[0006] In order to solve the above technical problems, the present invention provides a synthesis and application of a phosphorus-containing spirocyclic compound, which has the following general formula:

[0007]

[0008] in:

[0009] Ar1 is selected from hydrogen, deuterium, substituted or unsubstituted aryl, substituted or unsubstituted heterocyclic group containing one or more N, O or S atoms;

[0010] Ar2 and Ar3 are each independently selected from hydrogen, deuterium, a halogen group, a nitrile group, a nitro group, a hydroxyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted alkylthio group, a substituted or unsubstituted arylthio group, a substituted or unsubstituted alkylsulfinyl group, a substituted or unsubstituted arylsulfinyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted silyl group, a substituted or unsubstituted boron group, a substituted or unsubstituted alkylamino group, a substituted or unsubstituted aralkylamino group, a substituted or unsubstituted arylamino group, a substituted or unsubstituted heteroarylamino group, a substituted or unsubstituted aryl group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted carbazolyl group, and the like;

[0011] Ar4 and Ar5 are each independently selected from at least one of a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted condensed aryl group, a substituted or unsubstituted condensed heteroaryl group, a substituted or unsubstituted carbazolyl group and its derivatives, a substituted or unsubstituted diphenylamine group and its derivatives, a substituted or unsubstituted triphenylamine group and its derivatives, and an acridinium group and its derivatives;

[0012] The hydrogen atoms on the aromatic rings of Ar1, Ar2, Ar3, Ar4 and Ar5 may be fully deuterated, partially deuterated, or undeuterated;

[0013] X is selected from O or S or Se or Te;

[0014] Y is selected from Si or C;

[0015] In one embodiment, the hydrogen atoms on the Ar2 aromatic ring may be fully deuterated, partially deuterated, or undeuterated.

[0016] In one embodiment, the hydrogen atoms on the Ar3 aromatic ring may be fully deuterated, partially deuterated, or undeuterated.

[0017] In one embodiment, the hydrogen atoms on the Ar4 aromatic ring may be fully deuterated, partially deuterated, or undeuterated.

[0018] In one embodiment, all hydrogen atoms on the Ar5 aromatic ring may be fully deuterated, partially deuterated, or undeuterated.

[0019] In one embodiment, X is selected from O or S.

[0020] In one embodiment, Y is selected from Si.

[0021] In one embodiment, the spiro compound has a chemical structure shown in Chemical Formula II:

[0022]

[0023] In one embodiment, Ar4 and Ar5 are located in the para position relative to Si.

[0024] In one embodiment, a=1.

[0025] In one embodiment, b=c=0.

[0026] In one embodiment, d=1, e=0.

[0027] In one embodiment, the spiro compound has a chemical structure shown in Chemical Formula III:

[0028]

[0029] Preferably, in one embodiment, Ar1 is selected from the following groups, but is not limited thereto:

[0030]

[0031] Preferably, in one embodiment, Ar4, Ar5 are selected from the following groups, but are not limited thereto:

[0032]

[0033] In one embodiment, the specific structure of the compound is:

[0034]

[0035]

[0036]

[0037] In one embodiment, the phosphorus-containing spiro compound can be used as an electroactive layer of an organic light emitting diode.

[0038] In one embodiment, the phosphorus-containing spiro compound can be used as a host material of an electroactive layer.

[0039] In addition, the present invention provides an organic light emitting diode device comprising a first electrode, a second electrode and one or more organic material layers disposed between the first electrode and the second electrode, wherein the one or more organic material layers comprise any one of the above-mentioned specific structural compounds.

[0040] The organic electroluminescent device further includes a transparent substrate layer, an ITO anode layer, a hole injection layer, a hole transport layer, an electron blocking layer, a hole blocking / electron transport layer, an electron injection layer and a cathode reflective electrode layer. The transparent substrate layer, the ITO anode layer, the hole injection layer, the hole transport layer, the electron blocking layer, the light-emitting layer, the hole blocking / electron transport layer, the electron injection layer and the cathode reflective electrode layer are stacked in sequence from bottom to top.

[0041] The beneficial technical effects of the present invention are as follows: the compound of the present invention combines aryl phosphine oxide or aryl phosphine sulfide with spirofluorene, and the obtained compound serves as the main material of the light-emitting layer, has a high triplet energy level and a high glass transition temperature; in addition, the combination of an electron donor (donor, D) and an electron acceptor (acceptor, A) in the molecule can effectively improve the balanced migration of carriers, broaden the exciton recombination area, and enhance the luminous efficiency and life of the device.

[0042] The compound described in this invention can be used as the main material for the light-emitting layer in the fabrication of OLED light-emitting devices, achieving excellent device performance, significantly improving both the current efficiency and external quantum efficiency of the devices, and significantly increasing the device lifespan. The compound material described in this invention exhibits excellent application results in OLED light-emitting devices and has promising industrial prospects. BRIEF DESCRIPTION OF THE DRAWINGS

[0043] The specific embodiments of the present invention are further described in detail below with reference to the accompanying drawings.

[0044] Figure 1 is the device structure diagram;

[0045] A: organic light-emitting device; 10: substrate; 09: anode; 08: hole injection layer; 07: hole transport layer; 06: electron blocking layer; 05: light-emitting layer; 04: hole blocking layer; 03: electron transport layer; 02: electron injection layer; 01: cathode. DETAILED DESCRIPTION

[0046] The present invention is further described below with reference to specific embodiments, but the protection scope of the present invention is not limited thereto:

[0047] In order to more clearly illustrate the technical means and practical purposes of the present invention, examples and comparative examples are given for illustration.

[0048] General synthetic route of chemical formula III:

[0049]

[0050] Example 1: Synthesis of Compound P-1

[0051]

[0052] Synthesis of Intermediate 1: 2,2-diiodobiphenyl (8.12 g, 0.02 mol) was weighed into a dry three-necked flask, Pd(P(tBu)3)2I2 (0.46 g, 0.6 mmol) was added, and dry diisopropylethylamine (120 mL) was added to fully dissolve. The mixture was heated to 120°C, stirred for 12 hours, and returned to room temperature. The mixture was then extracted with dichloromethane (200 mL) and water (200 mL*3), and the organic phase was spin-dried to obtain a crude product. The crude product was recrystallized from petroleum ether (100 mL), filtered, and dried to obtain Intermediate 1 (8.17 g, 83%). 1 HNMR (400MHz) δ (ppm): 7.87 (d, 2H), 7.65-7.64 (m, 4H), 7.60 (dd, 2H), 7.52 (dd, 2H), 7.47 (m, 2H), 7.35 (d, 2H), 7.31 (m, 2H). HRMS(ESI,Positive)(m / z):[M]+Calcd for: C24H16Br2Si, 492.29, found: 492.26.

[0053] Synthesis of Intermediate 2: To a dry three-necked flask, add Intermediate 1 (4.92 g, 0.01 mol). Vacuum and refill with nitrogen for three cycles (so that the flask is filled with nitrogen and the reaction is carried out under nitrogen protection). Dry tetrahydrofuran (80 mL) is added to the reaction flask via syringe, and the temperature is cooled to -80°C and stirred for 30 minutes. Subsequently, n-butyllithium (1.35 g, 0.02 mol) is added to the reaction flask via syringe, and stirred for 6 hours. Subsequently, dichlorophenylphosphine (2.15 g, 0.012 mol) is added, and the temperature is cooled to -80°C and stirred for 12 hours. After the reaction is completed, the mixture is returned to room temperature and filtered through celite. The mixture is rinsed with petroleum ether (70 mL x 3). The solvents (tetrahydrofuran and petroleum ether) are removed under reduced pressure from the collected filtrate. 30% hydrogen peroxide (10 mL) and dichloromethane (50 mL) are then added to the flask and stirred at room temperature for 4 hours. The product was extracted with ethyl acetate (100 mL) and saturated aqueous sodium bicarbonate solution (100 mL * 3). The ethyl acetate phase was spin-dried to give a crude product. The crude product was purified by chromatography on a silica gel column (100-200 mesh) using petroleum ether / ethyl acetate (20 / 1) as the eluent. The organic phase (i.e., all the eluents obtained) was spin-dried to give pure intermediate 2 (3.56 g, 78%). 1HNMR (400MHz) δ (ppm): 7.87 (m, 4H), 7.77 (d, 2H), 7.66 (m, 4H), 7.61-7.60 (m, 6H), 7.51 (m, 3H), 7.47 (m, 2H). HRMS(ESI,Positive)(m / z):[M]+Calcd for:C30H21OPSi, 456.56, found: 456.55.

[0054] Synthesis of intermediate III-a: To a dry three-necked flask, add intermediate 2 (4.57 g, 0.01 mol) and dichloromethane (40 mL). Cover the reaction bottle with aluminum foil to protect it from light. Then add N-bromosuccinimide (1.87 g, 0.011 mol) to the reaction bottle, heat it to 50°C and stir for 4 hours, then return to room temperature and add water (50 mL) to quench the reaction. Use ethyl acetate (100 mL) and saturated sodium bicarbonate aqueous solution (120 mL * 3) to extract. Take the ethyl acetate phase and spin dry to obtain a crude product. The crude product is recrystallized using methanol, filtered and dried to obtain pure III-a (7.0 g, 83%). 1 HNMR (400MHz) δ (ppm): 7.87 (m, 3H), 7.77 (d, 2H), 7.74 (m, 2H), 7.66 (d, 2H), 7 .65(dd, 1H), 7.62-7.61(m, 4H), 7.60(m, 1H), 7.55-7.54(m, 2H), 7.51(m, 3H). HRMS(ESI,Positive)(m / z):[M]+Calcdfor:C30H20BrOPSi, 535.45, found: 535.42.

[0055] Synthesis of P-1: III-a (5.35 g, 0.01 mol) was added to a 250 mL three-necked flask, and then anhydrous 1,4-dioxane (100 mL) was added and stirred until clear, and then potassium carbonate (4.15 g, 0.03 mol) was added, followed by phenylboric acid (18.28 g, 0.015 mol) and tetrakis(triphenylphosphine)palladium (0.12 g, 0.1 mmol). Nitrogen was replaced three times to make the entire reaction flask nitrogen-free. The mixture was heated to 90 ° C. under an atmosphere of argon gas, stirred for 12 hours, cooled to room temperature, and extracted with dichloromethane (150 mL) and saturated sodium bicarbonate aqueous solution (3*150 mL). The organic phase was spin-dried and passed through a silica gel column (containing 30 g of 100-200 mesh silica gel) with petroleum ether / ethyl acetate (20 / 1 volume ratio) as the eluent. The obtained organic phase (i.e., all the eluents obtained) was spin-dried to obtain compound P-1 (4.79 g, yield 90%). 1HNMR (400MHz) δ (ppm): 8.04 (d, 1H), 7.97 (d, 1H), 7.87 (m, 3H), 7.84 (d, 1H), 7.77 (d, 2H) ), 7.66-7.65(m, 3H), 7.62-7.60(m, 5H), 7.51(m, 3H), 7.49-7.47(m, 5H), 7.41(dd, 1H). HRMS(ESI,Positive)(m / z):[M]+Calcd for: C36H25OPSi, 532.65, found: 532.60.

[0056] 2. Synthesis of compound P-2:

[0057]

[0058] To a 250mL two-necked flask was added III-a (5.35g, 10mmol), and anhydrous tetrahydrofuran (100mL) was added and stirred until dissolved, and zinc powder (3.2g, 0.5mmol) and bisacetonitrile palladium dichloride (0.03g, 0.1mmol) were added, and nitrogen was replaced three times. Then, a syringe was used to add Grignard reagent (2.1g, 11mmol), and the mixture was stirred at 60°C for 8 hours. After cooling to room temperature, saturated aqueous sodium bicarbonate solution was added to quench the mixture, and then dichloromethane (200mL) and water (3*200mL) were used for extraction. The organic phase was spin-dried, methanol was added for recrystallization, and the mixture was filtered and dried to obtain compound P-2 (5.03g, yield 93%). 1 HNMR (400MHz) δ (ppm): 8.04 (d, 1H), 7.87 (m, 3H), 7.77 (d, 2H), 7.66-7.65 (m, 4H), 7.62-7.60 (m, 5H), 7.52-7. 50(m, 4H), 7.47(dd, 1H), 2.72(d, 1H), 1.85(s, 2H), 1.60(s, 2H), 1.53(s, 2H), 1.46(s, 1H), 1.44-1.43(m, 3H). HRMS(ESI,Positive)(m / z):[M]+Calcd for: C36H31OPSi, 538.70, found: 538.67.

[0059] 3. Synthesis of compound P-3:

[0060]

[0061] To a 250mL three-necked flask was added III-a (5.35g, 10mmol), followed by anhydrous toluene (100mL) and stirring until clear, followed by potassium carbonate (4.15g, 30mmol), followed by 4-pyridine borate (1.84g, 15mmol) and tetrakistriphenylphosphine palladium (0.12g, 0.1mmol), and nitrogen was exchanged three times to give a nitrogen atmosphere to the entire reaction flask. The mixture was heated to 110°C and stirred for 18 hours. The mixture was cooled to room temperature and extracted with dichloromethane (150mL) and saturated aqueous sodium bicarbonate solution (3*150mL). The filtrate was dried and passed through a silica gel column (containing 60g of 100-200 mesh silica gel) with petroleum ether / ethyl acetate (18 / 1 volume ratio) as eluent. The obtained organic phase was dried to obtain compound P-3 (4.01g, 73% yield). 1 HNMR (400MHz) δ (ppm): 8.71 (d, 2H), 8.04 (d, 1H), 8.00 (d, 2H), 7.97 (d, 1H), 7.87 (m, 3H), 7. 84(d, 1H), 7.77(d, 2H), 7.66-7.65(m, 3H), 7.62-7.60(m, 5H), 7.51(m, 3H), 7.47(dd, 1H),. HRMS(ESI,Positive)(m / z):[M]+Calcd for: C35H24NOPSi, 533.64, found: 533.60.

[0062] 4. Synthesis of compound P-4:

[0063]

[0064] To a 250mL three-necked flask, III-a (5.35g, 10mmol) was added, followed by anhydrous toluene (100mL) and stirring until clarified. Sodium tert-butoxide (2.88g, 30mmol) and PdCl2(Amphos)2 (0.06g, 0.07mmol) were then added, followed by diphenylamine (2.2g, 13mmol), nitrogen was passed through the bottle for 30min, stirred and heated, and refluxed for 18h. After the reaction was completed, it was cooled to room temperature, filtered with diatomaceous earth, rinsed with dichloromethane (100mL), and the organic phase was spin-dried (normal temperature) to obtain a crude product. The crude product was purified by silica gel column chromatography, passed through a silica gel column (containing 100-200 mesh silica gel 30g), petroleum ether / ethyl acetate (13 / 1) as an eluent, and the obtained organic phase was spin-dried to obtain compound P-4 (5.31g, 85% yield). 1HNMR (400MHz) δ (ppm): 7.87 (m, 3H), 7.66-7.65 (m, 3H), 7.62-7.61 (m, 5H), 7.60 (dd, 1H) , 7.51 (m, 3H), 7.47 (dd, 1H), 7.38-7.37 (d, 2H), 7.24 (dd, 4H), 7.08 (d, 4H), 7.00 (m, 4H). HRMS(ESI,Positive)(m / z):[M]+Calcd for: C42H30NOPSi, 623.77, found: 623.70.

[0065] 5. Synthesis of compound P-5:

[0066]

[0067] To a 250 mL three-necked flask was added III-a (5.35 g, 10 mmol), followed by anhydrous DMPU (100 mL) and stirring until clear, followed by the addition of cuprous iodide (0.05 g, 1 mmol) and potassium carbonate (3.45 g, 25 mmol), followed by the addition of diphenylamine (2.2 g, 13 mmol), nitrogen was passed through the flask for 30 minutes, stirred and heated to 180 ° C., reacted for 18 hours, cooled to room temperature, filtered through diatomaceous earth, extracted with dichloromethane (150 mL) and water (3 * 150 mL), the organic phase was spin-dried and recrystallized by adding petroleum ether, filtered to obtain P-5 (5.41 g, yield 87%). 1 HNMR (400MHz) δ (ppm): 8.55 (d, 1H), 8.31 (s, 1H), 8.19 (d, 1H), 7.94-7.93 (d, 2H), 7.87 (m, 3H), 7.79 (d, 1H), 7.77 (d, 2H), 7.6 6-7.65 (m, 3H), 7.62-7.61 (m, 4H), 7.60-7.58 (dd, 2H), 7.51 (m, 4H), 7.50 (dd, 1H), 7.47 (dd, 1H), 7.35 (dd, 1H), 7.20 (d, 1H). HRMS(ESI,Positive)(m / z):[M]+Calcd for: C42H28NOPSi, 621.75, found: 621.73.

[0068] 6. Synthesis of compound P-6:

[0069]

[0070] To a 250 mL three-necked flask was added III-a (5.35 g, 10 mmol) and anhydrous DMF (120 mL) and stirred until clear. Cuprous iodide (0.05 g, 1 mmol) and potassium tert-butoxide (2.45 g, 25 mmol) were then added, followed by phenothiazine (2.39 g, 12 mmol). The mixture was stirred and heated to 120 ° C. After reacting for 12 hours, it was cooled to room temperature and extracted with dichloromethane (150 mL) and water (3*150). The organic phase was spin-dried and recrystallized by adding methanol and filtered to obtain P-6 (5.36 g, yield 83%). 1 HNMR (400MHz) δ (ppm): 7.87 (m, 3H), 7.77 (d, 2H), 7.66-7.65 (m, 3H), 7.62-7.60 (m, 5H), 7. 51 (m, 3H), 7.47 (dd, 2H), 7.38-7.37 (m, 2H), 7.21-7.20 (m, 4H), 7.16 (d, 2H), 6.97 (dd, 2H). HRMS(ESI,Positive)(m / z):[M]+Calcd for: C42H28NOPSSi, 653.81, found: 653.77.

[0071] 7. Synthesis of compound P-7:

[0072]

[0073] The synthetic route of this compound refers to compound P-6, that is, the phenothiazine in the "Synthesis of Compound P-6" is replaced with phenoxazine, the molar amount remains unchanged, and the rest is the same as the "Synthesis of Compound P-6".

[0074] The yield of compound P-7 was 86%. 1 HNMR (400MHz) δ (ppm): 7.87 (m, 3H), 7.77 (d, 2H), 7.66-7.65 (m, 3H), 7.62-7.60 (m, 6H), 7.38-7.37 (m, 2H), 7.14 (d, 2H), 7.01 (m, 4H), 6.96 (d, 2H). HRMS(ESI,Positive)(m / z):[M]+Calcd for: C42H28NO2PSi, 637.75, found: 637.73.

[0075] 8. Synthesis of compound P-8:

[0076]

[0077] III-a (5.35 g, 10 mmol) was added to a 250 mL three-necked flask, and then anhydrous toluene (100 mL) was added and stirred until clear, and then potassium carbonate (4.15 g, 30 mmol) was added, followed by 2,2-diphenyl(d)-4-pyridinium borate (5.51 g, 15 mmol), Aliquat 336 (0.02 g, 0.05 mmol) and Pd (dppf) 2 Cl 2 (0.08 g, 0.1 mmol), nitrogen was replaced three times to fill the entire reaction flask with nitrogen atmosphere, heated to 110 ° C, stirred for 12 hours, cooled to room temperature, added with dichloromethane (150 mL) and saturated sodium bicarbonate aqueous solution (3 * 150 mL) for extraction, the filtrate was spin-dried, passed through a silica gel column (containing 100-200 mesh silica gel 50 g), petroleum ether / ethyl acetate (18 / 1) as eluent, and the obtained organic phase was spin-dried to obtain compound P-8 (5.21 g, yield 75%). 1 HNMR (400MHz) δ (ppm): 8.20 (s, 2H), 8.04 (s, 1H), 7.97 (d, 1H), 7.87 (d, 3H), 7.84 (d, 1H), 7.77(d, 2H), 7.66-7.65(m, 3H), 7.62-7.60(m, 5H), 7.51(m, 3H), 7.47(dd, 1H). HRMS(ESI,Positive)(m / z):[M]+Calcd for: C47H22D10NOPSi, 695.90, found: 695.88.

[0078] The synthesis of other related compounds was the same as above. The molecular matrix was synthesized according to the general synthetic route of Chemical Formula III. The group in the para position of the silicon atom was incorporating the synthetic routes of reference compounds P-1 to P-8. The synthetic details of the compounds are shown in Table 1 below:

[0079] Table 1

[0080]

[0081]

[0082] The details are as follows:

[0083] (1) Compound P-11:

[0084]

[0085] Synthesis of Intermediate 3: Compared with the synthesis of Intermediate 2 in "1. Synthesis of Compound P-1", dichlorophenyl phosphine was replaced with dichlorophenyl (d5) phosphine, and the molar weight remained unchanged. Other conditions were the same to obtain Intermediate 3. 1HNMR (400MHz) δ (ppm): 7.87 (m, 4H), 7.66-7.65 (m, 4H), 7.62-7.60 (m, 6H), 7.47 (dd, 2H). HRMS(ESI,Positive)(m / z):[M]+Calcd for: C30H16D5OPSi, 461.59, found: 461.56.

[0086] Synthesis of intermediate III-b: Compared with the synthesis of intermediate III-a in "1. Synthesis of compound P-1", intermediate 2 was replaced by intermediate 3, the molar amount remained unchanged, and the rest were the same to obtain intermediate III-b. 1 HNMR (400MHz) δ (ppm): 7.87 (m, 3H), 7.74 (d, 1H), 7.66-7.65 (m, 3H), 7.62-7.60 (m, 5H), 7.55-7.54 (d, 2H), 7.47 (dd, 1H). HRMS(ESI,Positive)(m / z):[M]+Calcd for: C30H15D5BrOPSi, 540.48, found: 540.45.

[0087] Synthesis of P-11: Compared with "1. Synthesis of compound P-1", intermediate III-a was changed to intermediate III-b, the molar weight remained unchanged, phenylboronic acid was changed to p-pyridineboronic acid, and the rest were the same to obtain P-11. 1 HNMR (400MHz) δ (ppm): 8.71 (dd, 2H), 8.04 (s, 1H), 8.00 (dd, 2H), 7.97 (d, 1H), 7.87 (m , 3H), 7.84 (d, 1H), 7.75 (d, 2H), 7.66-7.65 (m, 3H), 7.62-7.60 (m, 3H), 7.47 (dd, 1H). HRMS(ESI,Positive)(m / z):[M]+Calcd for: C35H19D5NOPSi, 538.67, found: 538.14.

[0088] (2) Compound P-12:

[0089]

[0090] Synthesis of P-12: Compared with "4. Synthesis of compound P-4", intermediate III-a was changed to III-b, the molar amount remained unchanged, and the rest were the same to obtain compound P-12. 1HNMR (400MHz) δ (ppm): 7.87 (m, 3H), 7.66-7.65 (m, 3H), 7.62-7.60 (m, 6H), 7.47 (dd, 1H), 7.38-7.37 (dd, 2H), 7.24 (m, 4H), 7.08 (dd, 4H), 7.00 (dd, 2H). HRMS(ESI,Positive)(m / z):[M]+Calcd for: C42H25D5NOPSi, 628.80, found: 628.77.

[0091] (3) Compound P-14:

[0092]

[0093] Synthesis of compound P-14: Compared with "6. Synthesis of compound P-6", intermediate III-a was changed to III-b, the molar weight remained unchanged, and the rest were the same to obtain compound P-14. 1 HNMR (400MHz) δ (ppm): 7.87 (m, 3H), 7.66-7.65 (m, 4H), 7.62-7.60 (m, 5H), 7.4 7(dd, 1H), 7.38-7.37(dd, 2H), 7.21-7.20(m, 4H), 7.16(d, 2H), 6.97(dd, 2H). HRMS(ESI,Positive)(m / z):[M]+Calcd for: C42H23D5NOPSSi, 658.84, found: 658.82.

[0094] (4) Compound P-18:

[0095]

[0096] Synthesis of Intermediate 4: Compared with Intermediate 2 in "1. Synthesis of Compound P-1", dichlorophenylphosphine was replaced with dichlorocarbazolylphosphine, while the molar weight remained unchanged, and the rest were the same to obtain Intermediate 4. 1 HNMR (400MHz) δ (ppm): 8.55 (d, 1H), 8.19 (d, 1H), 7.94 (d, 1H), 7.87 (m, 4H), 7.66-7.65 (m, 4 H), 7.62-7.60 (m, 7H), 7.50 (dd, 1H), 7.47 (dd, 2H), 7.35 (dd, 1H), 7.20 (d, 1H), 7.15 (d, 1H). HRMS(ESI,Positive)(m / z):[M]+Calcd for: C36H24NOPSi, 545.65, found: 545.64.

[0097] Synthesis of intermediate III-c: Compared with intermediate III-a in "1. Synthesis of compound P-1", intermediate 2 was replaced by intermediate 4, the molar amount remained unchanged, and the rest were the same to obtain intermediate III-c. 1 HNMR (400MHz) δ (ppm):

[0098] 8.55(d, 1H), 8.19(d, 1H), 7.94(d, 1H), 7.87(m, 3H), 7.74(d, 1H), 7.66-7.65(m, 3H), 7.62-7.60(m, 5H) , 7.58 (d, 1H), 7.55-7.54 (m, 2H), 7.50 (dd, 1H), 7.47 (dd, 1H), 7.35 (dd, 1H), 7.20 (d, 1H), 7.15 (d, 1H). HRMS(ESI,Positive)(m / z):[M]+Calcd for: C36H23BrNOPSi, 624.55, found: 624.50.

[0099] Synthesis of compound P-18: Compared with "2. Synthesis of compound P-2", intermediate III-a was replaced with intermediate III-c, the molar weight remained unchanged, and the rest were the same to obtain P-18. 1 HNMR (400MHz) δ (ppm): 8.55 (d, 1H), 8.19 (d, 1H), 8.04 (s, 1H), 7.94 (d, 1H), 7.87 (m, 3H), 7.66-7.65 (m, 4H), 7.62-7.60 (m, 5H), 7.58 (d, 1 H), 7.52-7.50(m, 2H), 7.47(dd, 1H), 7.35(dd, 1H), 7.20(d, 1H), 7.18(d, 1H), 2.72(s, 1H), 1.85(s, 2H), 1.60(s, 2H), 1.53-1.44(m, 6H). HRMS(ESI,Positive)(m / z):[M]+Calcd for: C42H34NOPSi, 627.80, found: 627.70.

[0100] (5) Compound P-28:

[0101]

[0102] Synthesis of Intermediate 5: Compared with Intermediate 2 in "1. Synthesis of Compound P-1", dichlorophenylphosphine was replaced with 2-(dichlorophosphino)benzofuran, and the molar weight remained unchanged, and the rest were the same to obtain Intermediate 5. 1HNMR (400MHz) δ (ppm): 8.04 (d, 1H), 7.98 (d, 1H), 7.95 (s, 1H), 7.87 (m, 4H), 7.66-7. 65 (m, 5H), 7.62-7.60 (m, 6H), 7.54 (d, 1H), 7.47 (dd, 2H), 7.39 (dd, 1H), 7.31 (d, 1H). HRMS(ESI,Positive)(m / z):[M]+Calcd for: C36H23O2PSi, 546.64, found: 545.64.

[0103] Synthesis of intermediate III-d: Compared with intermediate III-a in "1. Synthesis of compound P-1", intermediate 2 was replaced by intermediate 5, the molar amount remained unchanged, and the rest were the same to obtain intermediate III-d. 1 HNMR (400MHz) δ (ppm): 8.04 (d, 1H), 7.98 (d, 1H), 7.95 (s, 1H), 7.87 (m, 3H), 7.74 (d, 1H), 7.66 -7.65(m, 3H), 7.62-7.60(m, 5H), 7.55-7.54(m, 3H), 7.47(dd, 2H), 7.39(dd, 1H), 7.31(d, 1H). HRMS(ESI,Positive)(m / z):[M]+Calcd for: C36H22BrO2PSi, 625.53, found: 625.53.

[0104] Synthesis of compound P-28: Compared with "4. Synthesis of compound P-4", intermediate III-a was replaced with intermediate III-d, the molar amount remained unchanged, and the rest were the same to obtain P-28. 1 HNMR (400MHz) δ (ppm): 8.04 (d, 1H), 7.98 (d, 1H), 7.95 (s, 1H), 7.87 (m, 3H), 7.66-7.65 (m, 4H), 7.62-7.60 (m , 6H), 7.54(d, 1H), 7.47(dd, 1H), 7.38-7.37(m, 2H), 7.39(dd, 1H), 7.31(dd, 1H), 7.24(dd, 4H), 7.08(m, 6H). HRMS(ESI,Positive)(m / z):[M]+Calcd for: C48H32NO2PSi, 713.85, found: 713.80.

[0105] (6) Compound P-46

[0106]

[0107] Synthesis of Intermediate 6: Compared with Intermediate 2 in "1. Synthesis of Compound P-1", dichlorophenylphosphine was replaced with 2-(dichlorophosphino)-9,9-dimethylfluorene, and the molar weight remained unchanged, and the rest were the same to obtain Intermediate 6. 1 HNMR (400MHz) δ (ppm): 8.10 (d, 1H), 8.08 (s, 1H), 7.91-7.90 (m, 2H), 7.87 (m, 4H), 7.66-7.65 ( m, 4H), 7.62-7.60 (m, 6H), 7.55 (d, 1H), 7.47 (dd, 2H), 7.38 (dd, 1H), 7.28 (d, 1H), 1.69 (s, 6H). HRMS(ESI,Positive)(m / z):[M]+Calcd for: C39H29OPSi, 572.72, found: 572.72.

[0108] Synthesis of intermediate III-e: Compared with intermediate III-a in "1. Synthesis of compound P-1", intermediate 2 was replaced by intermediate 6, the molar amount remained unchanged, and the rest were the same to obtain intermediate III-d. 1 HNMR (400MHz) δ (ppm): 8.10 (d, 1H), 8.08 (s, 1H), 7.91-7.90 (m, 2H), 7.87 (m, 3H), 7.74 (d, 1H), 7.66- 7.65 (m, 3H), 7.62-7.60 (m, 5H), 7.55 (m, 2H), 7.47 (dd, 2H), 7.38 (dd, 1H), 7.28 (d, 1H), 1.69 (s, 6H). HRMS(ESI,Positive)(m / z):[M]+Calcd for: C39H28BrOPSi, 651.61, found: 651.57.

[0109] Synthesis of compound P-46: Compared with "6. Synthesis of compound P-6", intermediate III-a was replaced with intermediate III-d, the molar weight remained unchanged, and the rest were the same to obtain P-46. 1HNMR (400MHz) δ (ppm): 8.10 (d, 1H), 8.08 (s, 1H), 7.91-7.90 (m, 2H), 7.87 (m, 3H), 7.66-7.65 (m, 3H), 7.62-7.6 0 (m, 6H), 7.55 (m, 1H), 7.47 (dd, 1H), 7.38-7.37 (m, 3H), 7.24 (dd, 4H), 7.08 (d, 4H), 7.00 (dd, 1H), 1.69 (s, 6H). HRMS(ESI,Positive)(m / z):[M]+Calcd forC51H36NOPSSi, 769.97, found: 769.93.

[0110] (7) Compound P-52:

[0111]

[0112] Synthesis of Intermediate 7: Compared with Intermediate 2 in "1. Synthesis of Compound P-1", dichlorophenylphosphine was replaced with dichlorophenoxazinephosphine, while the molar weight remained unchanged, and the rest were the same, to obtain Intermediate 7. 1 HNMR (400MHz) δ (ppm): 7.87 (m, 4H), 7.66-7.65 (m, 4H), 7.62-7.60 (m, 6H), 7.47 (dd, 2H), 7.14 (d, 2H), 7.01 (dd, 4H), 6.96 (d, 2H). HRMS(ESI,Positive)(m / z):[M]+Calcd for: C36H24NO2PSi, 561.65, found: 561.64.

[0113] Synthesis of intermediate III-f: Compared with intermediate III-a in "1. Synthesis of compound P-1", intermediate 2 was replaced by intermediate 7, the molar amount remained unchanged, and the rest were the same to obtain intermediate III-d. 1 HNMR (400MHz) δ (ppm): 7.87 (m, 3H), 7.74 (dd, 1H), 7.66-7.65 (m, 3H), 7.62-7.60 ( m, 5H), 7.55-7.54 (m, 2H), 7.47 (dd, 1H), 7.14 (d, 2H), 7.01 (dd, 4H), 6.96 (d, 2H). HRMS(ESI,Positive)(m / z):[M]+Calcdfor:C36H23BrNO2PSi, 640.55, found: 640.55.

[0114] Synthesis of compound P-52: Relative to "6. Synthesis of compound P-6", intermediate III-a was changed to intermediate III-d, the molar weight remained unchanged, and the rest were the same, to obtain P-46. 1HNMR (400MHz) δ (ppm): 7.87 (m, 3H), 7.66-7.65 (m, 3H), 7.62-7.60 (m, 6H), 7.47 (dd, 1H), 7.38-7.37 (m, 2H), 7.24 (dd, 4H), 7.14 (d, 2H), 7.08 (d, 4H), 7.01-7.00 (m, 6H), 6.96 (d, 2H). HRMS(ESI,Positive)(m / z):[M]+Calcd for: C48H33N2O2PSi, 728.86, found: 728.78.

[0115] The compounds of the present invention can be used as the main materials of the light-emitting layer. The thermal properties and triplet energy levels of the compounds P-2, P-4, P-5, P-6, P-8, P-11, P-12, P-14, P-18, P-28, P-46 and P-52 were measured respectively.

[0116] The determination method is conventional technology: Thermo-gravimetric apparatus (TGA, corresponding to the material's T d ), Differential scanning calorimeter (DSC, corresponding to the material's T g ) and triplet energy levels were measured and calculated according to Materials 2015, 8(12), 8793-8803, Thermochimica Acta 540(2012) 1-6, and Chemical Society Reviews 2013, 42(3), 845-856. The test results are shown in Table 2 below.

[0117] Table 2

[0118]

[0119]

[0120] Described comparative example 2 is:

[0121] As can be seen from the data in the above table, the compounds of the present invention have high thermal stability and high triplet energy levels, which improves the efficiency and life of OLED devices using the compounds of the present invention as the main material of the light-emitting layer.

[0122] Hereinafter, a method for preparing an OLED device including the compound according to the present disclosure and its characteristics will be explained in detail. However, the following examples only illustrate the characteristics of the OLED according to the present disclosure in detail, but the present disclosure is not limited to the following examples.

[0123] Based on the same inventive concept, embodiments of the present invention further provide an organic light-emitting device comprising the compounds of the above embodiments. An OLED is used as an example of an organic light-emitting device for illustration below. However, it should be understood that the following detailed description is not intended to limit the present invention, and those skilled in the art may extend the following detailed description to other organic light-emitting devices.

[0124] Device Examples

[0125] The OLED device includes a first electrode (anode) and a second electrode (cathode), and several organic material layers between the electrodes. The organic material layer can be divided into multiple regions. For example, the organic material layer can include a hole injection layer, a hole transport region, a light-emitting layer, an electron injection layer, and an electron transport region. In a specific embodiment, a substrate can be used below the first electrode or above the second electrode. The substrates are all glass or polymer materials with excellent mechanical strength, thermal stability, water resistance, and transparency.

[0126] Device Example 1:

[0127] The phosphorus-containing spiro compounds prepared according to the present invention can be used to prepare OLED devices, and the method of the published patent CN106831745A can be used for preparation.

[0128] The OLED device (ie, device A) is as follows Figure 1 The substrate 10, anode 09, hole injection layer 08, hole transport layer 07, electron blocking layer 06, light emitting layer 05, hole blocking layer 04, electron transport layer 03, electron injection layer 02, and cathode 01 are stacked in sequence from bottom to top; the substrate 10 and anode 09 are integrated.

[0129] The material of the hole injection layer 08 is HI; the material of the hole transport layer 07 is HT; the material of the electron blocking layer 06 is EB; the light-emitting layer 05 is composed of a host and a guest in a specific ratio, the host material is a spiro derivative prepared by the present invention, and the guest material is BD; the material of the hole blocking layer 04 is HB; the material of the electron transport layer 03 is ET; the material of the electron injection layer 02 is EI.

[0130]

[0131] The OLED device prepared has an anode 09 (ITO) with a thickness of 50 nm; a hole injection layer 08 (HI) with a thickness of 10 nm, a hole transport layer 07 (HT) with a thickness of 65 nm, an electron blocking layer 06 (EB) with a thickness of 25 nm, and a light-emitting layer 05 with a thickness of 20 nm. The material of the light-emitting layer 05 is a mixture of compound P-2 (as a host material) and BD (as a guest material) in a mass ratio of 90:10. The total thickness of the hole blocking layer 04 and the electron transport layer 03 is 40 nm, and the weight ratio of HB:ET is 1:1. The thickness of the electron injection layer 02 (EI) is 2 nm. The thickness of the cathode 01 (Al) is 80 nm.

[0132] Device Example 2-13

[0133] Compared with the device example device 1, only the host material used in the light-emitting layer 05 is changed (as described in Table 3), and the weight ratio of the host material to the guest material remains unchanged; the rest is the same as the device example device 1.

[0134] The results of the test were shown in Table 3 below:

[0135] Table 3

[0136]

[0137]

[0138] Note: LT95 is at 50℃ and 16.5mA / cm 2 The time (in hours) to reach 95% of the initial brightness at a current density of 100 nm was measured.

[0139] Comparative Example 2: TSPO1 is used as the electron transport layer and exciton blocking layer material of the device, but not the main material of the light-emitting layer. The light-emitting layer in Comparative Example 2 is composed of mCPPO1 and FCNIrpic.

[0140] As can be seen from the results of the Examples and the table above, the compounds of the present invention, which combine aryl phosphine oxides or aryl phosphine sulfides with spirofluorene, exhibit high triplet energy levels and high glass transition temperatures as the host material for the light-emitting layer, demonstrating excellent performance as a host material for blue light. Furthermore, the combination of an electron donor (D) and an electron acceptor (A) within the molecule effectively improves balanced carrier migration, broadens the exciton recombination zone, and enhances the device's luminous efficiency and lifetime. Compared to the comparative examples, both efficiency and lifetime are significantly improved over known OLED materials, with the device's efficiency being particularly significantly increased.

[0141] The compound of the present invention combines aryl phosphine oxide or aryl phosphine sulfide with spirofluorene. The obtained compound serves as the main material of the light-emitting layer, has a high triplet energy level and a high glass transition temperature, and has excellent performance as the main material of blue light. In addition, the combination of an electron donor (donor, D) and an electron acceptor (acceptor, A) in the molecule can effectively improve the balanced migration of carriers, widen the exciton recombination area, and enhance the luminous efficiency and life of the device.

[0142] Finally, it should be noted that the above examples are merely specific embodiments of the present invention. Obviously, the present invention is not limited to the above examples and is subject to numerous variations. All variations that can be directly derived or conceived by a person of ordinary skill in the art from the disclosure of the present invention are considered to be within the scope of protection of the present invention.

Claims

1. A phosphorus-containing spirocyclic compound, characterized in that: Is any of the following:

2. The use of the phosphorus-containing spiro compound according to claim 1, wherein: Electroactive layers for use in organic light-emitting devices.

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