A condensed ring organic compound and its preparation method and application

Abstract

This invention belongs to the field of light-emitting device technology. It provides a fused-ring organic compound, its preparation method, and its applications. Various aromatic ring derivatives are attached to electron-donating groups on a rigid plane via the Ullmann reaction, and further, a σ-single-bond linked ring structure is formed via the Heck reaction. The resulting molecular structure is flat, with a clear trend in the formation of electron clouds in the HOMO and LUMO energy levels, and a singlet-triplet band gap (ΔE). ST Larger, high-energy triplet excitons can form luminescent singlet excitons through reverse gap crossing (RISC), and this series of molecules exhibits significant hybridized local charge-transfer excited-state properties. Organic electroluminescent devices prepared from the fused-ring organic compounds of this invention exhibit high brightness, low start-up voltage, and high maximum external quantum efficiency. The fused-ring organic compounds of this invention also demonstrate excellent luminescent properties.

Description

Technical Field

[0001] This invention relates to the field of light-emitting device technology, and in particular to a fused-ring organic compound, its preparation method, and its application. Background Technology

[0002] Organic light-emitting diodes (OLEDs) are a type of device with a sandwich-like structure, consisting of positive and negative electrode layers and an organic functional material layer sandwiched between them. When a voltage is applied to the electrodes of an OLED device, positive charges are injected from the positive electrode and negative charges from the negative electrode. Under the influence of an electric field, the positive and negative charges migrate, meet, and recombine within the organic layer to emit light. Due to their advantages such as high brightness, fast response, wide viewing angle, simple manufacturing process, and flexibility, OLED devices have attracted significant attention in the fields of new display technology and new lighting technology. Currently, this technology is widely used in display panels for new lighting fixtures, smartphones, and tablets, and its application is expected to expand further into large-size display products such as televisions. It is a rapidly developing and technologically demanding new display technology.

[0003] Therefore, the discovery of a fused-ring organic compound that improves the electroluminescence performance of organic electroluminescent devices is of great significance. Summary of the Invention

[0004] The purpose of this invention is to overcome the shortcomings of the prior art by providing a fused-ring organic compound, its preparation method, and its application.

[0005] The beneficial effects of this invention include:

[0006] The fused-ring organic compounds of this invention are carbonyl-containing fused-ring organic compounds, and this series of molecules exhibits significant hybridized local charge-transfer excited-state properties. Organic electroluminescent devices prepared from the fused-ring organic compounds of this invention exhibit high brightness, low start-up voltage, and high maximum external quantum efficiency. The fused-ring organic compounds of this invention also demonstrate excellent luminescent properties.

[0007] Various aromatic ring derivatives are attached to electron-donating groups on a rigid plane via the Ullmann reaction, and further ring-closed structures linked by σ single bonds are formed via the Heck reaction. The resulting molecular structures are flat, with a clear trend in the formation of electron clouds in the HOMO and LUMO energy levels, and a singlet-triplet band gap (ΔE). ST Larger, high-energy triplet excitons can form luminescent singlet excitons through reverse gap crossing (RISC), and this series of organic light-emitting molecules can be applied in organic electroluminescent devices. Attached Figure Description

[0008] Figure 1 The EL spectrum of the organic electroluminescent device in Application Example 1;

[0009] Figure 2 The LVJ curve of the organic electroluminescent device in Application Example 1 is shown.

[0010] Figure 3 The graph shows the external quantum efficiency of the organic electroluminescent device in Application Example 1 as a function of brightness. Detailed Implementation

[0011] This invention provides a fused-ring organic compound, the structural formula of which is shown in formula (I):

[0012]

[0013] Among them, Z is preferably C-R1 or N; M is preferably a five-membered ring or a six-membered ring;

[0014] Each of the R1s is independently one of the following: hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C30 chain alkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C7-C30 aralkyl, substituted or unsubstituted C1-C30 alkoxy, substituted or unsubstituted C2-C30 aliphatic chain hydrocarbon amino, substituted or unsubstituted C4-C30 cycloaliphatic chain hydrocarbon amino, substituted or unsubstituted C6-C30 arylamino, substituted or unsubstituted C3-C30 heteroarylamino, substituted or unsubstituted C6-C30 aryloxy, substituted or unsubstituted C6-C60 arylboryl, substituted or unsubstituted C6-C60 aryl, and substituted or unsubstituted C3-C60 heteroaryl.

[0015] Adjacent R1s may form a cycle or not.

[0016] In this invention, the heteroatom of the heteroaryl group participates in conjugation and cyclization, preferably furan, benzofuran, thiophene, or thiadiazole, and the aryloxy group is preferably Ph-O-, phenoxy, or naphthoxy.

[0017] In this invention, the structural formula of the fused-ring organic compound is shown in formula (II) or formula (III):

[0018]

[0019] In formula (II), Z is preferably C-R1 or N; i is preferably 0 or 1; when i is 0, (C)0 is an unsubstituted single bond, and when i is 1, (C)1 is C-R2R3 or C=O;

[0020] In formula (III), Z is preferably C-R1 or N; X is preferably N-R4, Si-R5R6, O, S, O=S=O, Se or P-R7;

[0021] R1, R2, R3, R4, R5, R6, and R7 are each independently one of the following: hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C30 chain alkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C7-C30 aralkyl, substituted or unsubstituted C1-C30 alkoxy, substituted or unsubstituted C2-C30 aliphatic chain hydrocarbon amino, substituted or unsubstituted C4-C30 cycloaliphatic chain hydrocarbon amino, substituted or unsubstituted C6-C30 arylamino, substituted or unsubstituted C3-C30 heteroarylamino, substituted or unsubstituted C6-C30 aryloxy, substituted or unsubstituted C6-C60 arylboryl, substituted or unsubstituted C6-C60 aryl, and substituted or unsubstituted C3-C60 heteroaryl.

[0022] In this invention, R1, R2, R3, R4, R5, and R6 are not a ring, or R1, R2, R3, R4, R5, and R6 are a ring in one or more of the following ways: adjacent R1s form a ring, R2 and R3 form a ring, R4 and adjacent R1 form a ring, and R5 and R6 form a ring.

[0023] In this invention, R1, R2, R3, R4, R5, R6, and R7 are each independently methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, 2-methylbutyl, n-pentyl, sec-pentyl, cyclopentyl, neopentyl, n-hexyl, cyclohexyl, neohexyl, n-heptyl, cycloheptyl, n-octyl, cyclooctyl, 2-ethylhexyl, trifluoromethyl, pentafluoroethyl, 2,2,2-trifluoroethyl, cyano, halogen, phenyl, naphthyl, anthracene, benzo[a]anthrayl, phenanthrene, benzo[a]phenanthrene, pyrene, pyrene, peryl, fluoranyl, tetraphenyl, pentaphenyl, benzo[a]pyrene, biphenyl, amphylphenyl, terphenyl, triphenyl, tetraphenyl Fiberyl, spirodifluorenyl, dihydrophenanthrene, dihydropyrene, tetrahydropyrene, cis or trans indofluorenyl, trimerinyl, isotrimericininyl, spirotrimericininyl, spiroisotrimericininyl, furanyl, benzofuranyl, isobenzofuranyl, dibenzofuranyl, thiopheneyl, benzothiopheneyl, isobenzothiopheneyl, dibenzothiopheneyl, pyrroleyl, isoindoleyl, carbazoleyl, indocarbazoleyl, pyridinyl, quinolinyl, isoquinolinyl, acridineyl, phenanthridineyl, benzo-5,6-quinolinyl, benzo-6,7-quinolinyl, benzo-7,8-quinolinyl, pyrazolyl, indazoleyl, imidazoleyl, benzimidazoleyl, naphthizimidazoleyl, phenanthrenezimidazoleyl, pyridinium-imidazolyl, pyridinium-imidazolyl Azimidazolyl, quinoxalolinezimidazolyl, oxazolyl, benzoxoxazolyl, naphthoxoxazolyl, anthraxoxazolyl, phenanthoxazolyl, 1,2-thiazolyl, 1,3-thiazolyl, benzothiazolyl, pyridazinyl, benzopyridazinyl, pyrimidinyl, benzopyrimidinyl, quinoxalolineyl, 1,5-diazaanthrayl, 2,7-diazapyrene, 2,3-diazapyrene, 1,6-diazapyrene, 1,8-diazapyrene, 4,5-diazapyrene, 4,5,9,10-tetraazaperyl, pyrazinyl, phenazinyl, phenthiazinyl, naphridinyl, azacarbazolyl, benzocarbazoline, phenanthrolineyl, 1,2,3-triazolyl, 1,2,4-triazolyl Benzotriazolyl, 1,2,3-oxadiazolyl, 1,2,4-oxadiazolyl, 1,2,5-oxadiazolyl, 1,2,3-thiadiazolyl, 1,2,4-thiadiazolyl, 1,2,5-thiadiazolyl, 1,3,4-thiadiazolyl, 1,3,5-triazinyl, 1,2,4-triazinyl, 1,2,3-triazinyl, tetrazolyl, 1,2,4,5-tetraazinyl, 1,2,3,4-tetraazinyl, 1,2,3,5-tetraazinyl, purinyl, pteridyl, inazinyl, benzothiadiazolyl, diphenylboryl, dimilboryl, dipentafluorophenylboryl, and di(2,4,6-triisopropylphenyl)boryl.

[0024] In this invention, the preferred structural formula of the fused-ring organic compound is:

[0025]

[0026]

[0027]

[0028]

[0029]

[0030]

[0031]

[0032]

[0033]

[0034]

[0035]

[0036]

[0037]

[0038]

[0039] This invention also provides a method for preparing the aforementioned fused-ring organic compound, the preparation route of which is shown below:

[0040]

[0041] The preparation method of the present invention includes the following steps:

[0042] 2,3-dibromo-1,4-naphthoquinone and its derivatives, compound 1, sodium tert-butoxide, tritert-tert-butylphosphine tetrafluoroborate, tricyclohexylphosphine, tris(dibenzylacetone)dipalladium and o-xylene were reacted to give a fused-ring organic compound.

[0043] The molar ratio of 2,3-dibromo-1,4-naphthoquinone and its derivatives, compound 1, sodium tert-butoxide, tritert-tert-butylphosphine tetrafluoroborate, tricyclohexylphosphine, and tris(dibenzylideneacetone)palladium is 0.9–1.1: 2.2–2.6: 2.8–3.2: 0.09–0.11: 0.09–0.11: 0.04–0.06; the molar volume ratio of 2,3-dibromo-1,4-naphthoquinone and its derivatives to o-xylene is 0.9–1.1 mmol: 55–65 mL.

[0044] Compound 1 is an aromatic amine and its derivatives.

[0045] In this invention, the molar ratio of 2,3-dibromo-1,4-naphthoquinone and its derivatives, compound 1, sodium tert-butoxide, tritert-tert-butylphosphine tetrafluoroborate, tricyclohexylphosphine, and tris(dibenzylacetone)palladium is preferably 0.95–1.05: 2.3–2.5: 2.9–3.1: 0.095–0.105: 0.095–0.105: 0.045–0.055, more preferably 1.0: 2.4: 3.0: 0.10: 0.10: 0.05; the molar volume ratio of 2,3-dibromo-1,4-naphthoquinone and its derivatives to o-xylene is preferably 0.95–1.05 mmol: 58–62 mL, more preferably 1.0 mmol: 60 mL.

[0046] In this invention, the reaction temperature is preferably 130-150°C, more preferably 135-145°C, and even more preferably 140°C; the reaction time is preferably 65-80 h, more preferably 68-75 h, and even more preferably 70-72 h.

[0047] The present invention also provides the application of the fused-ring organic compound in an organic electronic device, the organic electronic device comprising a first electrode, a light-emitting functional layer, and a second electrode; the light-emitting functional layer comprising a hole transport region, a light-emitting layer, and an electron transport region, the light-emitting layer containing the fused-ring organic compound.

[0048] In this invention, the organic electronic devices are preferably organic electroluminescent devices, optical sensors, solar cells, lighting elements, organic thin-film transistors, organic field-effect transistors, organic thin-film solar cells, information tags, electronic artificial skin sheets, sheet-type scanners, or electronic paper.

[0049] In this invention, the fused-ring organic compound is the luminescent material in the luminescent layer; the luminescent functional layer is preferably inserted between the first electrode and the second electrode, and the luminescent functional layer is preferably one or more; the hole transport region is formed on the anode layer, the cathode layer is formed on the electron transport region, and the luminescent layer is located between the hole transport region and the electron transport region; the hole transport region is located between the anode and the luminescent layer.

[0050] In this invention, the anode material is preferably one or more of indium tin oxide (ITO), indium zinc oxide (IZO), tin dioxide (SnO2), and zinc oxide (ZnO); the cathode material is preferably one or more of magnesium (Mg), silver (Ag), aluminum (Al), aluminum-lithium (Al-Li), calcium (Ca), magnesium-indium (Mg-In), and magnesium-silver (Mg-Ag).

[0051] In this invention, the hole transport region is preferably a single-layer hole transport layer or a multi-layer hole transport layer. The single-layer hole transport layer includes a single-layer hole transport layer containing only one compound and a single-layer hole transport layer containing multiple compounds. The multi-layer hole transport layer includes one or more of the following structures: hole injection layer (HIL), hole transport layer (HTL), and electron blocking layer (EBL).

[0052] In this invention, the material of the hole transport region is preferably a phthalocyanine derivative, a conductive polymer, or a polymer containing a conductive dopant. The phthalocyanine derivative is preferably CuPc. The polymer containing a conductive dopant is preferably polyphenylene oxide, polyaniline / dodecylbenzenesulfonic acid, poly(3,4-ethylenedioxythiophene) / poly(4-styrenesulfonate), polyaniline / camphorsulfonic acid, polyaniline / poly(4-styrenesulfonate), or an aromatic amine derivative.

[0053] In this invention, the light-emitting layer preferably includes light-emitting dyes (i.e., dopants) that emit different wavelength spectra, and more preferably includes both sensitizers and host materials; the light-emitting layer is preferably a monochromatic light-emitting layer that emits a single color such as red, green, or blue; multiple monochromatic light-emitting layers of different colors can be arranged in a planar manner according to pixel patterns, or they can be stacked together to form a colored light-emitting layer; when light-emitting layers of different colors are stacked together, they can be separated from each other or connected to each other; the light-emitting layer is also preferably a single colored light-emitting layer that can emit different colors such as red, green, and blue simultaneously.

[0054] In this invention, the electron transport region is preferably a single-layer electron transport layer (ETL), including a single-layer electron transport layer containing only one compound and a single-layer electron transport layer containing multiple compounds; the electron transport region is also preferably a structure including one or more of an electron injection layer (EIL), an electron transport layer (ETL), and a hole blocking layer (HBL).

[0055] The preferred fabrication process of the organic electroluminescent device of the present invention is as follows: sequentially depositing an anode, a hole transport layer, a light-emitting layer, an electron transport layer, and a cathode on a substrate, followed by encapsulation. The light-emitting layer is prepared by co-evaporation of the host material and the fused-ring organic compound of the present invention, or by evaporation of a single fused-ring organic compound.

[0056] The preferred method for fabricating the organic electroluminescent device of the present invention includes the following steps:

[0057] 1) The glass plate coated with the anode material was ultrasonically treated in a commercial cleaning agent, rinsed in deionized water, then ultrasonically degreased in a mixed solvent of acetone and ethanol (volume ratio of 1:1), baked in a clean environment until all moisture was removed, cleaned with ultraviolet light and ozone, and bombarded with a low-energy cation beam.

[0058] 2) Place the glass plate with the anode inside the vacuum chamber and evacuate to a vacuum level of 1×10⁻⁶. -5 ~9×10 -3 Pa, a hole injection layer is vacuum-deposited on the above-mentioned anodic layer film at a deposition rate of 0.1 to 0.5 nm / s; a hole transport layer is vacuum-deposited on the hole injection layer at a deposition rate of 0.1 to 0.5 nm / s.

[0059] 3) Vacuum evaporation of a light-emitting layer on the hole transport layer. The light-emitting layer includes a host material and a fused-ring organic compound. Using a multi-source co-evaporation method, the evaporation rate of the host material and the evaporation rate of the fused-ring organic compound are adjusted to achieve a preset doping ratio for this fused-ring system material.

[0060] 4) Vacuum evaporation of electron transport layer material on the light-emitting layer at a deposition rate of 0.1–0.5 nm / s;

[0061] 5) A LiF layer is vacuum-deposited at 0.1–0.5 nm / s as the electron injection layer on the electron transport layer, and an Al layer is vacuum-deposited at 0.5–1.0 nm / s as the cathode of the device.

[0062] In this invention, the total thickness of the hole injection layer is preferably 5-30 nm, more preferably 10-25 nm, and even more preferably 15-20 nm; the total thickness of the hole transport layer is preferably 5-500 nm, more preferably 15-300 nm, and even more preferably 30-100 nm; the doping concentration of the luminescent material is preferably 0.8-1.2 wt%, more preferably 0.9-1.1 wt%, and even more preferably 1.0 wt%; the thickness of the organic light-emitting layer is preferably 1-200 nm, more preferably 10-100 nm, and even more preferably 30-50 nm; the thickness of the electron transport layer is preferably 5-300 nm, more preferably 15-200 nm, and even more preferably 30-100 nm; the thickness of the electron injection layer is preferably 0.8-1.2 nm, more preferably 0.9-1.1 nm, and even more preferably 1.0 nm; and the thickness of the cathode material is preferably 110-130 nm, more preferably 115-125 nm, and even more preferably 120 nm.

[0063] The technical solutions provided by the present invention will be described in detail below with reference to the embodiments, but they should not be construed as limiting the scope of protection of the present invention.

[0064] In the examples, dichloromethane was purchased from Shanghai Titan Technology Co., Ltd.; the mass spectrometer used for the following compounds was determined to be a GCT premier CAB048 mass spectrometer.

[0065] Example 1

[0066] Synthesis of compound C01

[0067]

[0068] 1.0 mmol of 2,3-dibromo-1,4-naphthoquinone, 2.4 mmol of carbazole, 3 mmol of sodium tert-butoxide, 0.1 mmol of tritert-tert-butylphosphine tetrafluoroborate, 0.1 mmol of tricyclohexylphosphine, and 0.05 mmol of tris(dibenzylacetone)dipalladium were added to a reaction flask, the mixture was purged three times, and finally 60 mL of o-xylene was added. The mixture was heated to 140 °C and refluxed, and reacted at 140 °C for 72 h. After extraction with dichloromethane and water, the concentrate was purified and column chromatography was performed to give the fused-ring organic compound C01 in 15% yield.

[0069] 1H NMR (500MHz, C2D2Cl4) δ (ppm) 8.71 (d, J = 8.0Hz, 1H), 8.30-8.23 (m, 3H) 8.06 (d, J = 7.4Hz, 1H) 8. 01(d,J=7.1Hz,1H)7.86-7.80(m,2H)7.71-7.68(m,1H)7.63-7.60(m,1H)7.51-7.47(m,1H).13C NMR (125MHz, C2D2Cl4) δ181.80,177.96,142.12,139.27,136.41,134.35,133.65,133.53,132.72,131. 51,128.55,127.70,126.86,126.85,126.16,125.53,123.91,123.51,122.23,120.92,117.13,116.99.

[0070] After high-resolution mass spectrometry, ESI source, and positive ion mode detection, the molecular formula of compound C01 is C 22 H 11 The detected value for NO2 was 321.0, which is the same as the theoretical value.

[0071] Example 2

[0072] Synthesis of compound C33

[0073]

[0074] 1.05 mmol of 2,3-dibromo-1,4-naphthoquinone, 2.5 mmol of 9,10-dihydro-9,9-dimethylacridine, 3.1 mmol of sodium tert-butoxide, 0.105 mmol of tritert-butylphosphine tetrafluoroborate, 0.105 mmol of tricyclohexylphosphine, and 0.055 mmol of tris(dibenzylacetone)dipalladium were added to a reaction flask, the atmosphere was purged three times, and finally 60 mL of o-xylene was added. The mixture was heated to 145 °C and refluxed, and reacted at 145 °C for 75 h. After extraction with dichloromethane and water, the concentrate was purified and column chromatography was performed to obtain the fused-ring organic compound C33 in 13% yield.

[0075] 1H NMR(500MHz,C2D2Cl4)δ(ppm)8.35-8.29(m,3H),8.27-8.24(m,1H),7.85-7.81( m,2H),7.71-7.69(m,1H),7.59-7.54(m,2H),7.45-7.38(m,2H),1.78(s,6H).13C NMR (125MHz, C2D2Cl4) δ182.11,178.13,137.02,136.63,136.09,134.53,133.97,133.68,133.49,133. 23,132.01,127.54,127.15,126.99,126.93,126.63,126.22,124.52,123.36,122.43,121.18,119.45.

[0076] After high-resolution mass spectrometry, ESI source, positive ion mode detection, the molecular formula of compound C33 is C 25 H 17 The detected value for NO2 was 363.1, which is the same as the theoretical value.

[0077] Example 3

[0078] Synthesis of compound C73

[0079]

[0080] 0.95 mmol of 2,3-dibromo-1,4-naphthoquinone, 2.3 mmol of phenoxazine, 2.9 mmol of sodium tert-butoxide, 0.095 mmol of tritert-tert-butylphosphine tetrafluoroborate, 0.095 mmol of tricyclohexylphosphine, and 0.045 mmol of tris(dibenzylacetone)dipalladium were added to a reaction flask, the mixture was purged three times, and finally 58 mL of o-xylene was added. The mixture was heated to 135 °C and refluxed, and reacted at 135 °C for 68 h. After extraction with dichloromethane and water, the concentrate was purified and column chromatography was performed to obtain the fused-ring organic compound C73 in 11% yield.

[0081] 1H NMR (500MHz, C2D2Cl4) δ (ppm) 9.03 (dd, J = 1.53, 1.41Hz, 1H), 8.25-8.22 (m, 1H), 8.18-8.15 (m, 1H), 7 .80-7.75(m,3H),7.25-7.21(m,2H),7.19-7.15(m,2H),7.11-7.09(m,1H),6.78(d,J=7.6Hz,1H).13C NMR (125MHz, C2D2Cl4) δ181.28,177.08,146.45,143.07,134.53,134.08,133.82,133.53,133.00,129. 36,128.65,127.89,127.61,126.08,125.70,124.47,124.14,122.61,120.78,118.03,116.07,108.88.

[0082] After high-resolution mass spectrometry, ESI source, positive ion mode detection, the molecular formula of compound C73 is C 22 H 11 The detected value for NO3 was 337.1, which is the same as the theoretical value.

[0083] Example 4

[0084] Synthesis of compound C113

[0085]

[0086] 1.0 mmol of 2,3-dibromo-1,4-naphthoquinone, 2.4 mmol of phenothiazine, 3.0 mmol of sodium tert-butoxide, 0.1 mmol of tritert-tert-butylphosphine tetrafluoroborate, 0.1 mmol of tricyclohexylphosphine, and 0.05 mmol of tris(dibenzylacetone)dipalladium were added to a reaction flask, the mixture was purged three times, and finally 60 mL of o-xylene was added. The mixture was heated to 140 °C and refluxed, and reacted at 140 °C for 72 h. After extraction with dichloromethane and water, the concentrate was purified and column chromatography was performed to give the fused-ring organic compound C113 in 16% yield.

[0087] 1H NMR (500MHz, C2D2Cl4) δ (ppm) 8.28-8.23 (m, 2H), 8.11 (d, J = 7.9Hz, 1H), 7.85-7.81 (m, 2 H),7.77-7.75(m,1H),7.36-7.31(m,3H),7.27-7.23(m,1H),7.16(d,J=7.4Hz,1H).13C NMR (125MHz, C2D2Cl4) δ181.48,177.57,139.33,136.24,134.17,133.82,133.39,133.16,128. 14,127.74,127.50,127.36,126.41,124.74,123.61,123.59,121.99,121.71,120.03,119.54.

[0088] After high-resolution mass spectrometry, ESI source, and positive ion mode detection, the molecular formula of compound C113 is C 22 H 11 The detected value for NO2S was 353.1, which is the same as the theoretical value.

[0089] Example 5

[0090] Synthesis of compound C325

[0091]

[0092] 1.0 mmol of 2,3-dibromo-1,4-naphthoquinone, 2.4 mmol of spirofluorene-acridine, 3.0 mmol of sodium tert-butoxide, 0.1 mmol of tritert-tert-butylphosphine tetrafluoroborate, 0.1 mmol of tricyclohexylphosphine, and 0.05 mmol of tris(dibenzylacetone)dipalladium were added to a reaction flask, the mixture was purged three times, and finally 60 mL of o-xylene was added. The mixture was heated to 140 °C and refluxed, and reacted at 140 °C for 72 h. After extraction with dichloromethane and water, the concentrate was purified and column chromatography was performed to give the fused-ring organic compound C325 in 16% yield.

[0093] 1H NMR (500MHz, C2D2Cl4) δ (ppm) 8.56 (d, J = 8.5Hz, 1H), 8.39-8.34 (m, 2H), 8.31-8.30 (m, 1H), 7.92-7.87 (m, 4H), 7.49-7.46 (m, 2H), 7.44-7.41(m,1H),7.30-7.25(m,3H),7.19(d,J=7.5Hz,2H),7.09-7.06(m,1H),6.71(d,J=7.8Hz,1H),6.66(d,J=7.4Hz,1H).13C NMR(125MHz,C2D2Cl4)δ182.16,178.27,153.41,139.89,137.79,136.69,134.77,134.53,134.12,133.83,133.23,131.86,128.65, 128.47,128.44,127.97,127.64,127.47,127.06,126.87,126.31,125.47,124.97,124.92,122.89,121.95,120.56,199.75,99.64.

[0094] After high-resolution mass spectrometry, ESI source, positive ion mode detection, the molecular formula of compound C325 is C 35 H 19 NO2, the detected value was 485.1, while the theoretical value was 485.1.

[0095] Example 6

[0096] Synthesis of compound C345

[0097]

[0098] 1.0 mmol of dibromo reactant, 2.4 mmol of spirofluorene-acrylidine, 3.0 mmol of sodium tert-butoxide, 0.1 mmol of tritert-tert-butylphosphine tetrafluoroborate, 0.1 mmol of tricyclohexylphosphine, and 0.05 mmol of tris(dibenzylacetone)dipalladium were added to a reaction flask, the mixture was purged three times, and finally 60 mL of o-xylene was added. The mixture was heated to 140 °C and refluxed, and reacted at 140 °C for 72 h. After extraction with dichloromethane and water, the concentrate was purified and column chromatography was performed to obtain the fused-ring organic compound C345 in 14% yield.

[0099] After high-resolution mass spectrometry, ESI source, positive ion mode detection, the molecular formula of compound C345 is C 37 H 17 The detected value of N3O2 was 535.1, which is the same as the theoretical value.

[0100] Example 7

[0101] Synthesis of compound C349

[0102]

[0103] 1.0 mmol of 6,7-dibromo-2,3-diphenyl-1,4-naphthoquinone, 2.4 mmol of oxaspirin acridine, 3.0 mmol of sodium tert-butoxide, 0.1 mmol of tritert-butylphosphine tetrafluoroborate, 0.1 mmol of tricyclohexylphosphine, and 0.05 mmol of tris(dibenzylacetone)dipalladium were added to a reaction flask, the atmosphere was purged three times, and finally 60 mL of o-xylene was added. The mixture was heated to 140 °C and refluxed, and reacted at 140 °C for 72 h. After extraction with dichloromethane and water, the concentrate was purified and column chromatography was performed to obtain the fused-ring organic compound C349 in 14% yield.

[0104] After high-resolution mass spectrometry, ESI source, positive ion mode detection, the molecular formula of compound C349 is C 47 H 27 The detected value for NO3 was 653.2, which is the same as the theoretical value.

[0105] Example 8

[0106] Synthesis of compound C365

[0107]

[0108] 1.0 mmol of dibromo reactant, 2.4 mmol of 3,6-di-tert-butyldimethylspirofluorene acridine, 3.0 mmol of sodium tert-butoxide, 0.1 mmol of tri-tert-butylphosphine tetrafluoroborate, 0.1 mmol of tricyclohexylphosphine, and 0.05 mmol of tris(dibenzylacetone)dipalladium were added to a reaction flask. The mixture was purged three times, and finally 60 mL of o-xylene was added. The mixture was heated to 140 °C and refluxed, and reacted at 140 °C for 72 h. After extraction with dichloromethane and water, the concentrate was purified and column chromatography was performed to obtain the fused-ring organic compound C365 in 18% yield.

[0109] After high-resolution mass spectrometry, ESI source, positive ion mode detection, the molecular formula of compound C365 is C 58 H 48 The detected value of N2O2 was 804.4, which is the same as the theoretical value.

[0110] The fused-ring organic compounds C01, C33, C73, C113, and C325 from Examples 1-5 were dissolved in toluene (each organic compound had a concentration of 10 g / L in toluene). -5 The photophysical properties of the mol / L toluene are shown in Table 1.

[0111] Table 1. Photophysical properties of the fused-ring organic compounds in Examples 1-5

[0112]

[0113]

[0114] Application Example 1

[0115] The organic electroluminescent device structure prepared in this application example is: ITO / HATCN (5nm) / TAPC (50nm) / TCTA (5nm) / 1wt% C325:CBP (20nm) / TmPyPB (50nm) / LiF (1nm) / Al (120nm). The anode is ITO; the hole injection layer is HATCN with a thickness of 5nm; the hole transport layer is TAPC with a thickness of 50nm; the electron blocking layer is TCTA with a thickness of 5nm; CBP is the main material for the wide bandgap organic light-emitting layer; the fused-ring organic compound C325 from Example 5 is the light-emitting material with a doping concentration of 1wt%, and the organic light-emitting layer (C325:CBP) has a thickness of 20nm; the electron transport layer is TmPyPB with a thickness of 50nm; the electron injection layer is LiF with a thickness of 1nm; and the cathode material is aluminum with a thickness of 120nm.

[0116] The structural formulas for HATCN, TAPC, TCTA, CBP, and TmPyPB are shown below:

[0117]

[0118] Figure 1 To obtain the EL spectrum of the organic electroluminescent device in Example 1, from Figure 1 As can be seen, the emission peak of the C325-based doped device is located at 576 nm.

[0119] Figure 2 The LVJ curve of the organic electroluminescent device in Application Example 1 is shown below. Figure 2 As can be seen, the organic electroluminescent device based on C325 has a high maximum brightness and a low start-up voltage, respectively, at 6173 cd / m². 2 and 3.6V.

[0120] Figure 3 The graph shows the external quantum efficiency of the organic electroluminescent device in Example 1 as a function of brightness. Figure 3 As can be seen, the maximum external quantum efficiency of the organic electroluminescent device based on C325 is 1.0%.

[0121] The fused ring system material of this invention, when applied to organic electroluminescent devices, achieves orange light emission under electroluminescence conditions. It is a high-performance organic light-emitting functional material and is expected to be promoted for commercial application.

[0122] The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. A fused-ring organic compound, characterized in that, The structural formula of the fused-ring organic compound is shown in formula (II): In equation (II), Z is independent and is C-R1; i is 0 or 1; when i is 0, (C)0 is an unsubstituted single bond, and when i is 1, (C)1 is C-R2R3; R1, R2, and R3 are each independently one of hydrogen, deuterium, halogen, cyano, or C1-C30 chain alkyl groups; Equation (II) is not 2. The fused-ring organic compound according to claim 1, characterized in that, R1, R2, and R3 are each independently one or more of the following: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, 2-methylbutyl, n-pentyl, sec-pentyl, neopentyl, n-hexyl, neohexyl, n-heptyl, n-octyl, 2-ethylhexyl, cyano, and halogen.

3. A fused-ring organic compound, characterized in that, The structural formula of the fused-ring organic compound is:

4. The method for preparing the fused-ring organic compound according to claim 1, characterized in that, It includes the following steps: 2,3-dibromo-1,4-naphthoquinone or its derivatives, compound 1, sodium tert-butoxide, tritert-tert-butylphosphine tetrafluoroborate, tricyclohexylphosphine, tris(dibenzylacetone)dipalladium and o-xylene were reacted to give a fused-ring organic compound. The molar ratio of 2,3-dibromo-1,4-naphthoquinone or its derivatives, compound 1, sodium tert-butoxide, tritert-tert-butylphosphine tetrafluoroborate, tricyclohexylphosphine, and tris(dibenzylacetone)palladium is 0.9–1.1: 2.2–2.6: 2.8–3.2: 0.09–0.11: 0.09–0.11: 0.04–0.06; the molar volume ratio of 2,3-dibromo-1,4-naphthoquinone or its derivatives and o-xylene is 0.9–1.1 mmol: 55–65 mL. Compound 1 is Among them, Z, M and Equation (II) have the same positional structure.

5. The preparation method according to claim 4, characterized in that, The reaction temperature is 130–150°C, and the reaction time is 65–80 h.

6. The application of the fused-ring organic compound according to any one of claims 1 to 3 in organic electronic devices, characterized in that, The organic electronic device includes a first electrode, a light-emitting functional layer, and a second electrode; the light-emitting functional layer includes a hole transport region, a light-emitting layer, and an electron transport region, and the light-emitting layer contains the fused-ring organic compound according to any one of claims 1 to 3.

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