WO2019114478A1 - 一种基于三嗪和苯并噁唑的有机化合物及其在有机电致发光器件上的应用 - Google Patents
一种基于三嗪和苯并噁唑的有机化合物及其在有机电致发光器件上的应用 Download PDFInfo
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- WO2019114478A1 WO2019114478A1 PCT/CN2018/115169 CN2018115169W WO2019114478A1 WO 2019114478 A1 WO2019114478 A1 WO 2019114478A1 CN 2018115169 W CN2018115169 W CN 2018115169W WO 2019114478 A1 WO2019114478 A1 WO 2019114478A1
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- 150000002894 organic compounds Chemical class 0.000 title claims abstract description 37
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 title claims abstract description 22
- BCMCBBGGLRIHSE-UHFFFAOYSA-N 1,3-benzoxazole Chemical compound C1=CC=C2OC=NC2=C1 BCMCBBGGLRIHSE-UHFFFAOYSA-N 0.000 title claims abstract description 19
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- CEWIMOICLLSMPQ-UHFFFAOYSA-N c(cc1)cc2c1[o]c(-c(cc1)ccc1-c1nc(-c(cc3)ccc3-c3nc(cccc4)c4[o]3)nc(-c3cncnc3)n1)n2 Chemical compound c(cc1)cc2c1[o]c(-c(cc1)ccc1-c1nc(-c(cc3)ccc3-c3nc(cccc4)c4[o]3)nc(-c3cncnc3)n1)n2 CEWIMOICLLSMPQ-UHFFFAOYSA-N 0.000 description 1
- ZJOUXTXOWLFLAF-UHFFFAOYSA-N c(cc1)cc2c1[o]c(cc1)c2cc1-c1nc(-c(cc2)ccc2-c2nc3ccccc3[o]2)nc(-c2ccc3[o]c(cccc4)c4c3c2)n1 Chemical compound c(cc1)cc2c1[o]c(cc1)c2cc1-c1nc(-c(cc2)ccc2-c2nc3ccccc3[o]2)nc(-c2ccc3[o]c(cccc4)c4c3c2)n1 ZJOUXTXOWLFLAF-UHFFFAOYSA-N 0.000 description 1
- DCAAMUWGOCGJGU-UHFFFAOYSA-N c(cc1)ccc1-c1nc2cc(-c3nc(-c(cc4)ccc4-[n]4c5ccccc5c5c4cccc5)nc(-c(cc4)ccc4-[n]4c(cccc5)c5c5c4cccc5)n3)ccc2[o]1 Chemical compound c(cc1)ccc1-c1nc2cc(-c3nc(-c(cc4)ccc4-[n]4c5ccccc5c5c4cccc5)nc(-c(cc4)ccc4-[n]4c(cccc5)c5c5c4cccc5)n3)ccc2[o]1 DCAAMUWGOCGJGU-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- JCWIWBWXCVGEAN-UHFFFAOYSA-L cyclopentyl(diphenyl)phosphane;dichloropalladium;iron Chemical compound [Fe].Cl[Pd]Cl.[CH]1[CH][CH][CH][C]1P(C=1C=CC=CC=1)C1=CC=CC=C1.[CH]1[CH][CH][CH][C]1P(C=1C=CC=CC=1)C1=CC=CC=C1 JCWIWBWXCVGEAN-UHFFFAOYSA-L 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011982 device technology Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- DKHNGUNXLDCATP-UHFFFAOYSA-N dipyrazino[2,3-f:2',3'-h]quinoxaline-2,3,6,7,10,11-hexacarbonitrile Chemical compound C12=NC(C#N)=C(C#N)N=C2C2=NC(C#N)=C(C#N)N=C2C2=C1N=C(C#N)C(C#N)=N2 DKHNGUNXLDCATP-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000005401 electroluminescence Methods 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 125000002183 isoquinolinyl group Chemical group C1(=NC=CC2=CC=CC=C12)* 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000004038 photonic crystal Substances 0.000 description 1
- 230000001902 propagating effect Effects 0.000 description 1
- 125000002943 quinolinyl group Chemical group N1=C(C=CC2=CC=CC=C12)* 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000002345 surface coating layer Substances 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- TVIVIEFSHFOWTE-UHFFFAOYSA-K tri(quinolin-8-yloxy)alumane Chemical compound [Al+3].C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1 TVIVIEFSHFOWTE-UHFFFAOYSA-K 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
- C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
- C07D251/04—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D498/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- H—ELECTRICITY
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/80—Constructional details
- H10K50/85—Arrangements for extracting light from the devices
- H10K50/858—Arrangements for extracting light from the devices comprising refractive means, e.g. lenses
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- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/30—Coordination compounds
- H10K85/321—Metal complexes comprising a group IIIA element, e.g. Tris (8-hydroxyquinoline) gallium [Gaq3]
- H10K85/322—Metal complexes comprising a group IIIA element, e.g. Tris (8-hydroxyquinoline) gallium [Gaq3] comprising boron
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/654—Aromatic compounds comprising a hetero atom comprising only nitrogen as heteroatom
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- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/656—Aromatic compounds comprising a hetero atom comprising two or more different heteroatoms per ring
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
- H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
- H10K85/6574—Polycyclic condensed heteroaromatic hydrocarbons comprising only oxygen in the heteroaromatic polycondensed ring system, e.g. cumarine dyes
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- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
- H10K85/6576—Polycyclic condensed heteroaromatic hydrocarbons comprising only sulfur in the heteroaromatic polycondensed ring system, e.g. benzothiophene
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/14—Carrier transporting layers
- H10K50/15—Hole transporting layers
- H10K50/155—Hole transporting layers comprising dopants
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/14—Carrier transporting layers
- H10K50/16—Electron transporting layers
Definitions
- the present invention relates to the field of semiconductor technology, and in particular to an organic compound based on triazine and benzoxazole and its use in an organic electroluminescent device.
- OLED Organic Light Emission Diodes
- the OLED light-emitting device is like a sandwich structure, including an electrode material film layer and an organic functional material sandwiched between different electrode film layers, and various functional materials are superposed on each other according to the purpose to form an OLED light-emitting device.
- the OLED light-emitting device functions as a current device.
- the positive and negative charges in the organic layer functional material film layer are applied by the electric field, the positive and negative charges are further recombined in the light-emitting layer, that is, the OLED electroluminescence is generated.
- OLED display technology has been applied in the fields of smart phones, tablet computers, etc., and will further expand to large-size applications such as television.
- the development of OLED is greatly restricted. Therefore, how to improve the light extraction efficiency of OLED has become a research hotspot.
- Total reflection occurs at the interface between the ITO film and the glass substrate and at the interface between the glass substrate and the air, and the light emitted to the external space of the OLED device accounts for about 20% of the total amount of the organic material film EL, and the rest is about 80% of the light.
- an important method to achieve an increase in the external quantum efficiency of OLEDs is to form structures such as wrinkles, photonic crystals, microlens arrays (MLAs), and surface covering layers on the light-emitting surface of the substrate.
- the first two structures will affect the angular distribution of the radiation spectrum of the OLED.
- the third structure has a complicated fabrication process, and the process of using the surface coating layer is simple, and the luminous efficiency is improved by more than 30%, which is particularly concerned.
- the absorption rate B can be calculated by the following formula:
- 2B 0.49.
- CPL capping layer
- the Applicant provides an organic compound based on triazine and benzoxazole and its use in an organic electroluminescent device.
- the compound of the invention contains a triazine and a benzoxazole structure, has a high glass transition temperature and molecular thermal stability, has low absorption in the visible light field, and has a high refractive index, and can effectively improve the OLED after being applied to the CPL layer of the OLED device.
- the light extraction efficiency of the device and because the triazine and benzoxazole have deep HOMO levels, a wide bandgap (Eg) level, can serve as a hole blocking/electron transport layer material for OLED devices, blocking holes from The luminescent layer is transferred to the side of the electron layer to improve the recombination of holes and electrons in the luminescent layer, thereby improving the luminous efficiency and the service life of the OLED device.
- Eg wide bandgap
- x is represented by the number 1 or 2;
- z is represented by the number 1 or 2;
- m, n are independently represented as the number 0, 1 or 2; and
- m + n + z 3;
- Ar 1 , Ar 2 and Ar 3 are each independently represented by a substituted or unsubstituted C 6-60 arylene group, a substituted or unsubstituted 5 to 60 member containing one or more hetero atoms. a heteroarylene; the hetero atom is nitrogen, oxygen or sulfur; Ar 1 , Ar 2 , and Ar 3 are each independently represented as a single bond; and Ar 1 , Ar 2 , and Ar 3 are the same or different;
- R 1 represents a hydrogen atom, a substituted or unsubstituted C 6-60 aryl group, a substituted or unsubstituted 5- to 60-membered heteroaryl group containing one or more hetero atoms or The hetero atom is nitrogen, oxygen or sulfur;
- Q 1 and Q 2 are each independently represented by a substituted or unsubstituted C 6-60 aryl group, a substituted or unsubstituted 5- to 60-membered heteroaryl group containing one or more hetero atoms; the hetero atom is nitrogen, Oxygen or sulfur;
- R 2 is represented by the structure represented by the formula (2) or the formula (3);
- R 3 is independently represented by the structure represented by the formula (4) or the formula (5);
- Ar 4 , Ar 5 , Ar 6 , Ar 7 , Ar 8 , Ar 9 , Ar 10 and Ar 11 are each independently represented by a hydrogen atom, a C 1-10 linear or branched alkyl group, a substituted or unsubstituted one.
- the Ar 1, Ar 2, Ar 3 each independently represents is a C 1-10 linear or branched alkyl group, a halogen atom, protium, deuterium, tritium atoms, a substituted or unsubstituted phenylene; C 1- 10 linear or branched alkyl, halogen atom, fluorene, fluorene, fluorene atom substituted or unsubstituted naphthylene; C 1-10 linear or branched alkyl, halogen atom, fluorene, fluorene, fluorene atom or Unsubstituted bis-biphenyl; C 1-10 straight or branched alkyl, halogen atom, fluorene, fluorene, fluorene atom substituted or unsubstituted pyridylene; carbazolyl; furanyl; pyrimidine a pyrazinyl group; a pyridazinyl group; a di
- the -Ar 1 -(R 1 ) x group contains at least one hetero atom, and the hetero atom is nitrogen, oxygen or sulfur.
- the structure of the organic compound is as shown in any one of the general formulae (I) to (VII):
- R 1 in the formula (1) is expressed as:
- the preferred structural formula of the organic compound is:
- a method for preparing the organic compound wherein the preparation method involves a reaction equation of:
- the raw material A and The molar ratio is 1:1.0-3, the molar ratio of palladium acetate to raw material A is 0.001-0.04:1, the molar ratio of potassium phosphate to raw material A is 1.0-4.0:1, and the ratio of raw material A to DMF is 1g: 10 to 30 ml;
- the intermediate I and The molar ratio is 1:1.0-3, the molar ratio of palladium acetate to intermediate I is 0.001-0.04:1, the molar ratio of potassium phosphate to intermediate I is 1.0-4.0:1, the ratio of intermediate I to DMF 1g: 10 to 40 ml;
- the intermediate II and The molar ratio is 1:1.0-3, the molar ratio of palladium acetate to intermediate II is 0.001-0.04:1, the molar ratio of potassium phosphate to intermediate II is 1.0-4.0:1, the ratio of intermediate II to DMF It is 1g: 15 to 50 ml.
- An application of the organic compound, the triazine-based and benzoxazole-based organic compound, is used to prepare an organic electroluminescent device.
- An organic electroluminescent device comprising the organic compound, the organic electroluminescent device comprising at least one functional layer comprising the triazine-based and benzoxazole-based organic compound.
- An organic electroluminescent device containing the organic compound comprising a hole blocking layer/electron transport layer, the hole blocking layer/electron transport layer containing the triazine-based and benzoxazole-based organic compound.
- An organic electroluminescent device comprising the organic compound, comprising a coating layer on the light-emitting side electrode, wherein the coating layer contains the triazine-based and benzoxazole-based organic compound.
- An illumination or display element comprising the organic electroluminescent device.
- the structure of the organic compound of the present invention contains two rigid groups of triazine and benzoxazole, which improves the structural stability of the material; the material of the present invention contains a strong electron triazine and a benzoxazole group in a spatial structure.
- the three groups are separated from each other to avoid free rotation of the group, so that the material has a higher density, a higher refractive index is obtained; at the same time, the material of the invention has a high Tg temperature; the material of the invention
- the vapor deposition temperature under vacuum is generally less than 350 ° C, which not only ensures that the material does not decompose for a long time in mass production, but also reduces the influence of heat radiation on the deformation of vapor deposited MASK due to the evaporation temperature.
- the material of the present invention is applied to the CPL layer in an OLED device, does not participate in electron and hole transport of the device, but has very high requirements for thermal stability of the material, film crystallinity, and light transmission (high refractive index).
- triazine and benzoxazole are rigid groups, which improve the stability of the material; high Tg temperature ensures that the material does not crystallize in the film state; low evaporation temperature is the material that can be used for mass production.
- high refractive index is the most important factor that can be applied to the CPL layer.
- the present invention is based on an organic compound of triazine and benzoxazole having a refractive index n ⁇ 2.1 between the wavelengths of 430 nm and 470 nm in the blue region.
- the material of the invention has a deep HOMO energy level and high electron mobility, and can effectively block holes or energy from being transmitted from the light-emitting layer to the electron layer side, thereby improving the recombination efficiency of holes and electrons in the light-emitting layer, thereby improving the OLED.
- the invention can effectively improve the light extraction efficiency of the OLED device after being applied to the CPL layer of the OLED device.
- the compounds of the present invention have good application effects and industrialization prospects in OLED light-emitting devices.
- FIG. 1 is a schematic structural view of a material exemplified in the present invention applied to an OLED device;
- FIG. 3 is a comparison diagram of a film acceleration experiment of Compound 1 and a known material CBP;
- Figure 4 is a graph showing the efficiency of the device measured at different temperatures.
- the obtained residue is separated and purified on a silica gel column to obtain Boric acid pinacol ester;
- the molar ratio to bis(pinacolyl)diboron is 1:1.0-3, Pd(dppf) 2 Cl 2 and The molar ratio is 0.001 ⁇ 0.04: 1, potassium acetate and The molar ratio is 1.0 to 4.0:1,
- the ratio of the amount to the amount of THF is 1 g: 10 to 30 ml.
- the raw material A is weighed and dissolved in N,N-dimethylformamide, DMF, and then And adding palladium acetate, stirring the mixture, adding potassium phosphate aqueous solution, and heating the mixed solution of the above reactants at a reaction temperature of 120-150 ° C for 5-15 hours; after the reaction is finished, cooling is added water, the mixture is filtered and dried under vacuum. Drying in a box, the residue obtained is purified by silica gel column to obtain compound intermediate I;
- the raw material A and The molar ratio is 1:1.0-3, the molar ratio of Pd(OAc) 2 to the raw material A is 0.001-0.04:1, the molar ratio of K 3 PO 4 to the raw material A is 1.0-4.0:1, the amount of DMF and the raw material A
- the dosage ratio is 1g: 10 ⁇ 30ml;
- Elemental analysis structure (Molecular Formula C 24 H 24 BNO 2 ): Theory C, 78.06; H, 6.55; B, 2.93; N, 3.79; O, 8.67; Tests: C, 78.09; H, 6.56; B, 2.91; N, 3.76; O, 8.68.
- ESI-MS (m/z) (M + ): calc.
- Elemental analysis structure (Molecular formula C 21 H 12 Cl 2 N 4 ): Theory C, 64.47; H, 3.09; Cl, 18.12; N, 14.32; Tests: C, 64.45; H, 3.07; Cl, 18.16; 14.34.
- Elemental analysis structure (Molecular formula C 21 H 22 BN 3 O 2 ): Theory C, 70.21; H, 6.17; B, 3.00; N, 11.70; O, 8.91; Tests: C, 70.23; H, 6.14; 3.01; N, 11.70; O, 8.92.
- ESI-MS (m/z) (M + ): 355.
- Elemental analysis structure (Molecular formula C 33 H 20 ClN 9 ): calcd. C, 68.57; H, 3.49; Cl, 6.13; N, 21.81; ⁇ / RTI> C, 68.55; H, 3.47; Cl, 6.15; N, 21.84.
- ESI-MS (m/z) (M + ): 553.
- Elemental analysis structure (Formula C 22 H 11 Cl 2 N 3 O 2): Theory C, 62.88; H, 2.64; Cl, 16.87; N, 10.00; test value: C, 62.86; H, 2.67 ; Cl, 16.85; N, 10.02.
- Elemental analysis structure (Molecular formula C 47 H 28 N 6 O 2 ): Theory C, 79.65; H, 3.98; N, 11.86; O, 4.51; Tests: C, 79.62; H, 3.99; N, 11.87; 4.52.
- Elemental analysis structure (Molecular formula C 46 H 28 N 10 O): Theory C, 74.99; H, 3.83; N, 19.1; O, 2.17; Tests: C, 74.95; H, 3.85N, 19.04; O, 2.16.
- Elemental analysis structure (Molecular formula C 27 H 16 ClN 5 O): Theory C, 70.21; H, 3.49; Cl, 7.67; N, 15.16; O, 3.46; Test value: C, 70.23; H, 3.45; Cl, 7.70 ;N, 15.17; O, 3.45.
- ESI-MS (m/z) (M + ): s.
- Elemental analysis structure (Molecular formula C 40 H 24 N 6 O 2 ): Theory C, 77.41; H, 3.90; N, 13.54; O, 5.16; Tests: C, 77.45; H, 3.88; N, 13.52; 5.15.
- Elemental analysis structure (Molecular formula C 44 H 26 N 6 O 2 ): Theory C, 78.79; H, 3.91; N, 12.53; O, 4.77; Tests: C, 78.77; H, 3.94; N, 12.51; 4.78.
- ESI-MS (m/z) (M + ): calc.
- Elemental analysis structure (Molecular formula C 52 H 32 N 6 O): Theory C, 82.52; H, 4.26; N, 11.10; O, 2.11; Test value: C, 82.53; H, 4.27; N, 11.07; O, 2.13 .
- Elemental analysis structure (Molecular formula C 59 H 36 N 6 O 2 ): Theory C, 82.31; H, 4.21.; N, 9.76; O, 3.72; Tests: C, 82.34; H, 4.19; N, 9.78; 3.69.
- the organic compound of the present invention is used as a CPL layer material in a light-emitting device, and has a high Tg (glass transition temperature) temperature and a high refractive index. Thermal properties and refractive index tests were carried out on the compound of the present invention and the existing materials, and the results are shown in Table 2. The refractive index test chart of Compound 8 is shown in Figure 2.
- the glass transition temperature Tg is determined by differential scanning calorimetry (DSC, DSC204F1 differential scanning calorimeter, Germany), the heating rate is 10 °C / min; the refractive index is determined by the ellipsometer (USA JAWoollam Co. model: ALPHA-SE) is measured and tested to the atmosphere.
- the organic compound of the present invention has high glass transition temperature and high refractive index compared with materials such as CBP, Alq3 and TPBi which are currently applied, and at the same time, it is ensured by containing a triazine and a benzoxazole rigid group.
- the thermal stability of the material. Therefore, the organic material with triazine and benzoxazole as the core of the invention can effectively improve the light extraction efficiency of the device after being applied to the CPL layer of the OLED device, and ensure the long life of the OLED device.
- the device examples 1 to 27 and the device comparative example 1 have the same fabrication process, and the same substrate material and electrode material are used, and the film thickness of the electrode material is also maintained. Consistently, the difference between the device examples 2 and 23 is that the CPL layer material in the device is changed; the device embodiments 24 to 27 change the hole blocking/electron transport layer material of the device, and the devices obtained in the respective embodiments are The performance test results are shown in Table 3.
- An electroluminescent device the preparation steps of which are as shown in FIG. 1 include:
- the thickness is 80 nm, the layer is the hole transport layer 4; d) the light-emitting layer 5 is evaporated on the hole transport layer 4, CBP is used as a host material, Ir(ppy) 3 is used as a doping material, Ir(ppy 3 ) The mass ratio of 3 and CBP is 1:9, and the thickness is 30 nm; e) On the light-emitting layer 5, the electron transport material TPBI is evaporated by vacuum evaporation to a thickness of 40 nm, and this organic material is used as a hole blocking/ The electron transport layer 6 is used; f) over the hole blocking/electron transport layer 6, vacuum-evaporating the electron injection layer LiF to a thickness of 1 nm, the layer being the electron injection layer 7; g) above the electron injection layer 7, Vacuum evaporation of the cathode Mg:Ag/Ag layer, Mg:Ag doping ratio of 9:1, thickness 15nm, Ag thickness 3nm, the layer is the
- Device Example 2 The CPL layer material of the electroluminescent device became the compound 8 of the present invention.
- Device Example 3 The CPL layer material of the electroluminescent device became the compound 12 of the present invention.
- Device Example 4 The CPL layer material of the electroluminescent device became the compound 16 of the present invention.
- Device Example 5 The CPL layer material of the electroluminescent device became the compound 28 of the present invention.
- Device Example 6 The CPL layer material of the electroluminescent device became the compound 30 of the present invention.
- Device Example 7 The CPL layer material of the electroluminescent device became the compound 35 of the present invention.
- Device Example 8 The CPL layer material of the electroluminescent device became the compound 38 of the present invention.
- Device Example 9 The CPL layer material of the electroluminescent device became the compound 39 of the present invention.
- Device Example 10 The CPL layer material of the electroluminescent device became the compound 47 of the present invention.
- Device Example 11 The CPL layer material of the electroluminescent device became the compound 59 of the present invention.
- Device Example 12 The CPL layer material of the electroluminescent device became the compound 69 of the present invention.
- Device Example 13 The CPL layer material of the electroluminescent device became the compound 71 of the present invention.
- Device Example 14 The CPL layer material of the electroluminescent device became the compound 78 of the present invention.
- Device Example 15 The CPL layer material of the electroluminescent device became the compound 85 of the present invention.
- Device Example 16 The CPL layer material of the electroluminescent device became the compound 153 of the present invention.
- Device Example 17 The CPL layer material of the electroluminescent device became the compound 164 of the present invention.
- Device Example 18 The CPL layer material of the electroluminescent device became the compound 173 of the present invention.
- Device Example 19 The CPL layer material of the electroluminescent device became the compound 175 of the present invention.
- Device Example 20 The CPL layer material of the electroluminescent device became the compound 191 of the present invention.
- Device Example 21 The CPL layer material of the electroluminescent device became the compound 227 of the present invention.
- Device Example 22 The CPL layer material of the electroluminescent device became the compound 270 of the present invention.
- Device Example 23 The CPL layer material of the electroluminescent device became the compound 360 of the present invention.
- Device Example 24 The hole blocking/electron transport layer material of the electroluminescent device became the compound 35 of the present invention, and the CPL layer material became the known material Alq 3 .
- Device Example 25 The hole blocking/electron transport layer material of the electroluminescent device became the compound 39 of the present invention, and the CPL layer material became the known material Alq 3 .
- Device Example 26 The hole blocking/electron transport layer material of the electroluminescent device became the compound 69 of the present invention, and the CPL layer material became the known material Alq 3 .
- Device Example 27 The hole blocking/electron transport layer material of the electroluminescent device became the compound 195 of the present invention, and the CPL layer material became the known material Alq 3 .
- Device Comparative Example 1 The CPL layer material of the electroluminescent device became a known material Alq 3 .
- the detection data of the obtained electroluminescent device is shown in Table 3.
- the material compound 1 of the present invention and the known material CBP were subjected to a film accelerated crystallization experiment: a vacuum evaporation method was used to vapor-deposit compound 1 and CBP on an alkali-free glass. And packaged in a glove box (water oxygen content ⁇ 0.1ppm), the packaged sample is placed in a double 85 (temperature 85 ° C, humidity 85%), periodically with a microscope (LEICA, DM8000M, 5 * 10 times Observe the crystal state of the material film. The experimental results are shown in Table 4. The surface morphology of the material is shown in Figure 3:
- the OLED device prepared by the material of the invention is more stable when operating at a low temperature, and the device examples 8, 17, 25 and the device comparative example 1 are tested in the range of -10 to 80 ° C, and the results are shown in Table 5 and Figure 4 shows.
- device embodiments 8, 17, and 25 are device structures in which the materials of the present invention and known materials are matched, and compared with the device of Comparative Example 1, not only the low temperature efficiency but also the temperature rise process. In the middle, efficiency has increased steadily.
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Abstract
一种基于三嗪和苯并噁唑的有机化合物及其在OLED器件上的应用，所述化合物具有较高的玻璃化温度和分子热稳定性；在可见光领域吸收低、折射率高，在应用于OLED器件的CPL层后，可有效提升OLED器件的光取出效率；所述化合物还具有深的HOMO能级和高的电子迁移率，可作为OLED器件的空穴阻挡/电子传输层材料，可有效阻挡空穴或能量从发光层传递至电子层一侧，从而提升空穴和电子在发光层的复合效率，进而提升OLED器件的发光效率和使用寿命。
Description
本发明涉及半导体技术领域，尤其是涉及一种基于三嗪和苯并噁唑的有机化合物及其在有机电致发光器件上的应用。
有机电致发光(OLED:Organic Light Emission Diodes)器件技术既可以用来制造新型显示产品，也可以用于制作新型照明产品，有望替代现有的液晶显示和荧光灯照明，应用前景十分广泛。OLED发光器件犹如三明治的结构，包括电极材料膜层以及夹在不同电极膜层之间的有机功能材料，各种不同功能材料根据用途相互叠加在一起共同组成OLED发光器件。OLED发光器件作为电流器件，当对其两端电极施加电压，并通过电场作用有机层功能材料膜层中的正负电荷时，正负电荷进一步在发光层中复合，即产生OLED电致发光。
当前，OLED显示技术已经在智能手机，平板电脑等领域获得应用，进一步还将向电视等大尺寸应用领域扩展。但是，由于OLED的外量子效率和内量子效率之间存在巨大差距，极大地制约了OLED的发展。因此，如何提高OLED的光取出效率成为研究热点。ITO薄膜和玻璃衬底的界面以及玻璃衬底和空气的界面处会发生全反射，出射到OLED器件前向外部空间的光约占有机材料薄膜EL总量的20％，其余约80％的光主要以导波形式限制在有机材料薄膜、ITO薄膜和玻璃衬底中。可见常规OLED器件的出光效率较低(约为20％)，这严重制约了OLED的发展和应用。如何减少OLED器件中的全反射效应、提高光耦合到器件前向外部空间的比例(出光效率)引起人们的广泛关注。
目前，实现提高OLED外量子效率的一类重要方法是在基底出光表面形成如褶皱、光子晶体、微透镜陈列(MLA)和添加表面覆盖层等结构。前两种结构会影响OLED的辐射光谱角度分布，第三种结构制作工艺复杂，使用表面覆盖层工艺简单，发光效率提高30％以上，尤为人们关注。根据光学原理，当光透射过折射率为n
1的物质到折射率为n
2的物质时(n
1＞n
2)，只有在arcsin(n
2/n
1)的角度内才能入射到折射率为n
2的物质里，吸收率B可以用以下的公式计算：
设n
1＝n
一般OLED有机材料＝1.70，n
2＝n
玻璃＝1.46，则2B＝0.49。假设向外传播的光全部被金属电极反射，则只有51％的光能被高折射率的有机膜和ITO层所波导，同样可以计算光从玻璃基底射 出到空气时的透过率。因此从有机层发出的光射出器件的外部时，只有约17％的光能被人们所看见。因此，针对目前OLED器件光取出效率低的现状，需要在器件结构中增加一层CPL(capping layer、覆盖)层，即光提取材料，根据光学吸收、折射原理，此表面覆盖层材料的折射率应该越高越好。
目前对OLED发光器件提高性能的研究包括：降低器件的驱动电压、提高器件的发光效率、提高器件的使用寿命等。为了实现OLED器件的性能的不断提升，不但需要从OLED器件结构和制作工艺的创新，更需要OLED光电功能材料不断研究和创新，创制出更高性能的OLED功能材料。
发明内容
针对现有技术存在的上述问题，本申请人提供了一种基于三嗪和苯并噁唑的有机化合物及其在有机电致发光器件上的应用。本发明化合物含有三嗪及苯并噁唑结构，具有较高的玻璃化温度和分子热稳定性，在可见光领域吸收低、折射率高，在应用于OLED器件的CPL层后，可有效提升OLED器件的光取出效率；并且由于三嗪和苯并噁唑具有深的HOMO能级，宽的禁带(Eg)能级，可作为OLED器件的空穴阻挡/电子传输层材料，阻挡空穴从发光层传递至电子层一侧，提高空穴和电子在发光层中的复合度，从而提升OLED器件的发光效率和使用寿命。
本发明的技术方案如下：
一种基于三嗪和苯并噁唑的有机化合物，所述有机化合物的结构如通式(1)所示：
通式(1)中，x表示为数字1或2；z表示为数字1或2；m、n分别独立的表示为数字0、1或2；且m+n+z＝3；
通式(1)中，Ar
1、Ar
2、Ar
3分别独立的表示为取代或未取代的C
6-60亚芳基、含有一个或多个杂原子的取代或未取代的5～60元杂亚芳基；所述杂原子为氮、氧或硫；Ar
1、Ar
2、Ar
3还分别独立的表示为单键；Ar
1、Ar
2、Ar
3相同或不同；
R
1表示为氢原子、取代或未取代的C
6-60芳基、含有一个或多个杂原子的取代或未取代的5～ 60元杂芳基或
所述杂原子为氮、氧或硫；
Q
1、Q
2分别独立的表示为取代或未取代的C
6-60芳基、含有一个或多个杂原子的取代或未取代的5～60元杂芳基；所述杂原子为氮、氧或硫；
R
2表示为通式(2)或通式(3)所示结构；
R
3分别独立的表示为通式(4)或通式(5)所示结构；
其中，Ar
4、Ar
5、Ar
6、Ar
7、Ar
8、Ar
9、Ar
10、Ar
11分别独立的表示为氢原子、C
1-10直链或支链烷基、取代或未取代的C
6-60芳基、含有一个或多个杂原子的取代或未取代的5～60元杂芳基；所述杂原子为氮、氧或硫。
优选，所述Ar
1、Ar
2、Ar
3分别独立的表示为C
1-10直链或支链烷基、卤素原子、氕、氘、氚原子取代或未取代的亚苯基；C
1-10直链或支链烷基、卤素原子、氕、氘、氚原子取代或未取代的亚萘基；C
1-10直链或支链烷基、卤素原子、氕、氘、氚原子取代或未取代的亚二联苯基；C
1-10直链或支链烷基、卤素原子、氕、氘、氚原子取代或未取代的亚吡啶基；亚咔唑基；亚呋喃基；亚嘧啶基；亚吡嗪基；亚哒嗪基；亚二苯并呋喃基；亚9,9-二甲基芴基；亚N-苯基咔唑基；亚喹啉基；亚异喹啉基或亚萘啶基中的一种；R
1、Ar
4、Ar
5、Ar
6、Ar
7、Ar
8、Ar
9、Ar
10、Ar
11、Q
1、Q
2表示为C
1-10直链或支链烷基、卤素原子、氕、氘、氚原子取代或未取代的苯基；C
1-10直链或支链烷基、卤素原子、氕、氘、氚原子取代或未取代的萘基；C
1-10直链或支链烷基、卤素原子、氕、氘、氚原子取代或未取代的二联苯基；C
1-10直链或支链烷基、卤素原子、氕、氘、氚原子取代或未取代的吡啶基；咔唑基；呋喃基；嘧啶基；吡嗪基；哒嗪基；二苯并呋喃基；9,9-二甲基芴基；N-苯基咔唑基；喹啉基；异喹啉基或萘啶基中的一种。
优选方案，当z表示为数字1时，-Ar
1-(R
1)
x基团至少含有1个杂原子，所述杂原子为氮、氧或硫。
所述有机化合物的结构如通式(Ⅰ)～(Ⅶ)中的任一种所示：
通式(1)中所述R
1表示为：
中的一种。
所述有机化合物优选的的具体结构式为：
一种所述有机化合物的制备方法，所述制备方法涉及的反应方程式为：
(1)氮气氛围下，称取原料A溶解于DMF中，再加入
醋酸钯，搅拌混合物，再加入磷酸钾水溶液，将上述反应物的混合溶液于120-150℃条件下加热回流5-15小时；反应结束后，冷却加水、将混合物过滤并在真空干燥箱中干燥，所得残余物过硅胶柱纯化，得到化合物中间体I；
所述原料A与
的摩尔比为1:1.0～3，醋酸钯与原料A的摩尔比为0.001～0.04:1，磷酸钾与原料A的摩尔比为1.0～4.0:1，原料A与DMF的用量比为1g:10～30ml；
(2)氮气氛围下，称取中间体I溶解于DMF中，再加入
及醋酸钯，搅拌混 合物，再加入磷酸钾水溶液，将上述反应物的混合溶液于120-150℃条件下加热回流10-24小时；反应结束后，冷却加水、将混合物过滤并在真空干燥箱中干燥，所得残余物过硅胶柱纯化，得到化合物中间体II；
所述中间体I与
的摩尔比为1:1.0～3，醋酸钯与中间体I的摩尔比为0.001～0.04:1，磷酸钾与中间体I的摩尔比为1.0～4.0:1，中间体I与DMF的用量比为1g:10～40ml；
(3)氮气氛围下，称取中间体II溶解于DMF中，再加入
及醋酸钯，搅拌混合物，再加入磷酸钾水溶液，将上述反应物的混合溶液于120-150℃条件下加热回流10-24小时；反应结束后，冷却加水、将混合物过滤并在真空干燥箱中干燥，所得残余物过硅胶柱纯化，得到目标化合物；
所述中间体II与
的摩尔比为1:1.0～3，醋酸钯与中间体II的摩尔比为0.001～0.04:1，磷酸钾与中间体II的摩尔比为1.0～4.0:1，中间体II与DMF的用量比为1g:15～50ml。
一种所述有机化合物的应用，所述基于三嗪和苯并噁唑的有机化合物用于制备有机电致发光器件。
一种含有所述有机化合物的有机电致发光器件，所述有机电致发光器件包括至少一层功能层含有所述基于三嗪和苯并噁唑的有机化合物。
一种含有所述有机化合物的有机电致发光器件，包括空穴阻挡层/电子传输层，所述空穴阻挡层/电子传输层含有所述基于三嗪和苯并噁唑的有机化合物。
一种含有所述有机化合物的有机电致发光器件，包括在出光一侧电极上的覆盖层，其特征在于，所述覆盖层含有所述基于三嗪和苯并噁唑的有机化合物。
一种含有所述有机电致发光器件的照明或显示元件。
本发明有益的技术效果在于：
本发明的有机化合物的结构含有三嗪和苯并噁唑两种刚性基团，提升了材料结构稳定性；本发明材料在空间结构上，含有强电子性的三嗪和苯并噁唑基团，并且3个基团相互交叉隔开，避免基团自由旋转，使得材料具有较高的密度，获得了较高的折射率；同时，使得本发明材料 都具有很高的Tg温度；本发明材料在真空状态下的蒸镀温度一般都小于350℃，既保证了材料在量产时长时间蒸镀材料不分解，又降低了由于蒸镀温度的热辐射对蒸镀MASK的形变影响。
本发明材料在OLED器件中应用在CPL层，不参与器件的电子和空穴传输，但对材料的热稳定性、膜结晶性及光传输(高折射率)具有非常高的要求。如上分析，三嗪和苯并噁唑为刚性基团，提高了材料的稳定性；高的Tg温度，保证了材料在薄膜状态下不结晶；低的蒸镀温度，是材料可应用于量产的前提；高的折射率则是本发明材料能应用于CPL层的最主要因素。本发明基于三嗪和苯并噁唑的有机化合物，在蓝光区域430nm-470nm波长之间的折射率n≥2.1。
本发明材料由于具有深的HOMO能级，高电子迁移率，可有效阻挡空穴或能量从发光层传递至电子层一侧，从而提高空穴和电子在发光层中的复合效率，从而提升OLED器件的发光效率和使用寿命。本发明在应用于OLED器件的CPL层后，可有效提升OLED器件的光取出效率。综上，本发明所述化合物在OLED发光器件中具有良好的应用效果和产业化前景。
图1为本发明所列举的材料应用于OLED器件的结构示意图；
其中，1、OLED器件基板，2、阳极层，3、空穴注入层，4、空穴传输层，5、发光层，6、空穴阻挡层/电子传输层，7、电子注入层，8、阴极层，9、CPL层；
图2为化合物8的折射率测试图；
图3为化合物1和公知材料CBP的膜加速实验对比图；
图4为器件在不同温度下测量的效率曲线图。
实施例1：中间体A的合成
氮气氛围下，称取
溴代物溶解于四氢呋喃(THF)中，再将双(频哪醇根基)二硼、(1,1’-双(二苯基膦)二茂铁)二氯钯(II)以及乙酸钾加入，搅拌混合物，将上述反应物的混合溶液于反应温度70-90℃下加热回流5-10小时；反应结束后，加水冷却、且将混合物过滤并在真空烘箱中干燥。将所获得的残余物过硅胶柱分离纯化，得到
的硼酸频哪醇酯；所述
与双(频哪醇根基)二硼的摩尔比为1:1.0～3，Pd(dppf)
2Cl
2与
的摩尔比为0.001～0.04:1，乙酸钾与
的摩尔比为1.0～4.0:1，
用量与THF的用量比为1g：10～30ml。
氮气氛围下，称取原料A溶解于N,N-二甲基甲酰胺即DMF中，再将
及醋酸钯加入，搅拌混合物，再加入磷酸钾水溶液，将上述反应物的混合溶液于反应温度120-150℃下加热回流5-15小时；反应结束后，冷却加水、将混合物过滤并在真空干燥箱中干燥，所得残余物过硅胶柱纯化，得到化合物中间体I；
所述原料A与
的摩尔比为1:1.0～3，Pd(OAc)
2与原料A的摩尔比为0.001～0.04:1，K
3PO
4与原料A的摩尔比为1.0～4.0:1，DMF用量与原料A的用量比为1g：10～30ml；
以中间体A1合成为例：
(1)在250mL三口瓶中，通入氮气，加入0.02mol中间体3-溴-9-苯基-9H-咔唑溶解于100ml四氢呋喃(THF)中，再将0.024mol双(频哪醇根基)二硼、0.0002mol(1,1’-双(二苯基膦)二茂铁)二氯钯(II)以及0.05mol乙酸钾加入，搅拌混合物，将上述反应物的混合溶液于反应温度80℃下加热回流5小时；反应结束后，冷却并加入100ml水、且将混合物过滤并在真空烘箱中干燥。将所获得的残余物过硅胶柱分离纯化，得到中间体D1；HPLC纯度99.8％，收率90.5％。
元素分析结构(分子式C
24H
24BNO
2)：理论值C,78.06；H,6.55；B,2.93；N,3.79；O,8.67；测试值：C,78.09；H,6.56；B,2.91；N,3.76；O,8.68。ESI-MS(m/z)(M
+)：理论值为369.19，实测值为369.27。
(2)在250mL三口瓶中，通入氮气，加入0.02mol原料2,4,6-三氯-1,3,5-三嗪，150mlDMF，0.024mol中间体D1，0.0002mol醋酸钯，搅拌，然后加入0.03mol K
3PO
4水溶液，加热至130℃，回流反应10小时，取样点板，反应完全。自然冷却，加水、将混合物过滤并在真空干燥箱中干燥，所得残余物过硅胶柱纯化，得到化合物中间体A1；HPLC纯度99.6％，收率73.3％。
元素分析结构(分子式C
21H
12Cl
2N
4)：理论值C,64.47；H,3.09；Cl,18.12；N,14.32；测试值： C,64.45；H,3.07；Cl,18.16；N,14.34。ESI-MS(m/z)(M
+)：理论值为390.04，实测值为390.13。
以中间体A12合成为例：
(1)在250mL三口瓶中，通入氮气，加入0.02mol中间体4'-溴-2,2’:6’,2’-三联吡啶溶解于100ml四氢呋喃(THF)中，再将0.024mol双(频哪醇根基)二硼、0.0002mol(1,1’-双(二苯基膦)二茂铁)二氯钯(II)以及0.05mol乙酸钾加入，搅拌混合物，将上述反应物的混合溶液于反应温度80℃下加热回流5小时；反应结束后，冷却并加入100ml水、且将混合物过滤并在真空烘箱中干燥。将所获得的残余物过硅胶柱分离纯化，得到中间体D2；HPLC纯度99.8％，收率88.5％。
元素分析结构(分子式C
21H
22BN
3O
2)：理论值C,70.21；H,6.17；B,3.00；N,11.70；O,8.91；测试值：C,70.23；H,6.14；B,3.01；N,11.70；O,8.92。ESI-MS(m/z)(M
+)：理论值为359.18，实测值为359.24。
(2)在250mL三口瓶中，通入氮气，加入0.02mol原料2,4,6-三氯-1,3,5-三嗪，150mlDMF，0.048mol中间体D2，0.0002mol醋酸钯，搅拌，然后加入0.03mol K
3PO
4水溶液，加热至130℃，回流反应10小时，取样点板，反应完全。自然冷却，加水、将混合物过滤并在真空干燥箱中干燥，所得残余物过硅胶柱纯化，得到化合物中间体A12；HPLC纯度99.5％，收率78.3％。
元素分析结构(分子式C
33H
20ClN
9)：理论值C,68.57；H,3.49；Cl,6.13；N,21.81；测试值：C,68.55；H,3.47；Cl,6.15；N,21.84。ESI-MS(m/z)(M
+)：理论值为577.15，实测值为577.23。
以中间体A20合成为例：
(1)在250mL三口瓶中，通入氮气，加入0.02mol原料Ⅰ-18溶解于100ml四氢呋喃(THF)中，再将0.024mol双(频哪醇根基)二硼、0.0002mol(1,1’-双(二苯基膦)二茂铁)二氯钯(II) 以及0.05mol乙酸钾加入，搅拌混合物，将上述反应物的混合溶液于反应温度80℃下加热回流5小时；反应结束后，冷却并加入100ml水、且将混合物过滤并在真空烘箱中干燥。将所获得的残余物过硅胶柱分离纯化，得到中间体D3；HPLC纯度99.4％，收率88.7％。
元素分析结构(分子式C
25H
23BO
4)：理论值C,75.40；H,5.82；B,2.71；O,16.07；测试值：C,75.41；H,5.85；B,2.69；O,16.05。ESI-MS(m/z)(M
+)：理论值为398.17，实测值为398.34。
(2)在250mL三口瓶中，通入氮气，加入0.02mol原料2,4,6-三氯-1,3,5-三嗪，150mlDMF，0.024mol中间体D3，0.0002mol醋酸钯，搅拌，然后加入0.03mol K
3PO
4水溶液，加热至130℃，回流反应12小时，取样点板，反应完全。自然冷却，加水、将混合物过滤并在真空干燥箱中干燥，所得残余物过硅胶柱纯化，得到化合物中间体A20；HPLC纯度99.2％，收率70.5％。
元素分析结构(分子式C
22H
11Cl
2N
3O
2)：理论值C,62.88；H,2.64；Cl,16.87；N,10.00；测试值：C,62.86；H,2.67；Cl,16.85；N,10.02。ESI-MS(m/z)(M
+)：理论值为419.02，实测值为419.33。
以中间体A1、A12和A20的合成方法制备中间体A，具体结构如表1所示。
表1
实施例2：化合物1的合成
在250mL三口瓶中，通入氮气，加入0.01mol中间体A1，150ml的DMF，0.03mol原料B1，0.0002mol醋酸钯，搅拌，然后加入0.02mol K
3PO
4水溶液，加热至150℃，回流反应24小时，取样点板，反应完全。自然冷却，用200ml二氯甲烷萃取，分层，萃取液用无水硫酸钠干燥，过滤，滤液旋蒸，过硅胶柱纯化，得到目标产物，HPLC纯度99.2％，收率53.6％。
元素分析结构(分子式C
47H
28N
6O
2)：理论值C,79.65；H,3.98；N,11.86；O,4.51；测试值：C,79.62；H,3.99；N,11.87；O,4.52。ESI-MS(m/z)(M
+)：理论值为708.23，实测值为708.31。
实施例3：化合物8的合成
化合物8的制备方法同实施例2，不同之处在于用中间体A2替换中间体A1。元素分析结构(分子式C
44H
29N
5O
2)：理论值C,80.10；H,4.43；N,10.62；O,4.85；测试值：C,80.09；H,4.45；N,10.65；O,4.81。ESI-MS(m/z)(M
+)：理论值为659.23，实测值为659.29。
实施例4：化合物12的合成
化合物12的制备方法同实施例2，不同之处在于用中间体A3替换中间体A1。元素分析结构(分子式C
41H
23N
5O
3)：理论值C,77.71；H,3.66；N,11.05；O,7.57；测试值：C,77.73；H,3.69；N,11.02；O,7.56。ESI-MS(m/z)(M
+)：理论值为633.18，实测值为633.24。
实施例5：化合物16的合成
化合物16的制备方法同实施例2，不同之处在于用中间体A4替换中间体A1。元素分析结构(分子式C
41H
23N
5O
2S)：理论值C,75.79；H,3.57；N,10.78；S,4.93；O,4.92；测试值：C,75.81；H,3.59；N,10.73；S,4.96；O,4.91。ESI-MS(m/z)(M
+)：理论值为649.16，实测值为649.23。
实施例6：化合物28的合成
化合物28的制备方法同实施例3，不同之处在于用中间体A5替换中间体A1。元素分析结 构(分子式C
33H
19N
7O
2)：理论值C,72.65；H,3.51；N,17.97；O,5.87；测试值：C,72.63；H,3.52；N,17.96；O,5.89。ESI-MS(m/z)(M
+)：理论值为545.16，实测值为545.37。
实施例7：化合物30的合成：
化合物30的制备方法同实施例2，不同之处在于用中间体A6替换中间体A1。元素分析结构(分子式C
34H
20N
6O
2)：理论值C,74.99；H,3.70；N,15.43；O,5.88；测试值：C,74.96；H,3.73；N,15.41；O,5.90。ESI-MS(m/z)(M
+)：理论值为544.16，实测值为544.24。
实施例8：化合物35的合成
化合物35的制备方法同实施例2，不同之处在于用中间体A7替换中间体A1。元素分析结构(分子式C
39H
23N
7O
2)：理论值C,75.35；H,3.73；N,15.77；O,5.15；测试值：C,75.34；H,3.75；N,15.76；O,5.15。ESI-MS(m/z)(M
+)：理论值为621.19，实测值为621.33。
实施例9：化合物38的合成
化合物38的制备方法同实施例2，不同之处在于用中间体A8替换中间体A1。元素分析结构(分子式C
40H
24N
6O
2)：理论值C,77.41；H,3.90；N,13.54；O,5.16；测试值：C,77.39；H,3.93；N,13.52；O,5.16。ESI-MS(m/z)(M
+)：理论值为620.20，实测值为620.47。
实施例10：化合物39的合成
化合物39的制备方法同实施例2，不同之处在于用中间体A8替换中间体A1。元素分析结构(分子式C
40H
24N
6O
2)：理论值C,77.41；H,3.90；N,13.54；O,5.16；测试值：C,77.45；H,3.87；N,13.51；O,5.17。ESI-MS(m/z)(M
+)：理论值为620.20，实测值为620.31。
实施例11：化合物47的合成
化合物47的制备方法同实施例2，不同之处在于用中间体A10替换中间体A1。元素分析结构(分子式C
46H
28N
6O
2)：理论值C,79.30；H,4.05；N,12.06；O,4.59；测试值：C,79.33；H,4.02；N,12.03；O,4.62。ESI-MS(m/z)(M
+)：理论值为695.23，实测值为695.32。
实施例12：化合物59的合成
化合物59的制备方法同实施例2，不同之处在于用中间体A11替换中间体A1。元素分析结构(分子式C
47H
30N
6O
2)：理论值C,79.42；H,4.25；N,11.82；O,4.50；测试值：C,79.44；H,4.22；N,11.83；O,4.51。ESI-MS(m/z)(M
+)：理论值为710.24，实测值为710.33。
实施例13：化合物69的合成
在250mL三口瓶中，通入氮气，加入0.01mol中间体A12，150mlDMF，0.012mol原料B1，0.0001mol醋酸钯，搅拌，然后加入0.012mol K
3PO
4水溶液，加热至150℃，回流反应24小时，取样点板，反应完全。自然冷却，用200ml二氯甲烷萃取，分层，萃取液用无水硫酸钠干燥，过滤，滤液旋蒸，过硅胶柱纯化，得到目标产物，HPLC纯度99.4％，收率60.8％。
元素分析结构(分子式C
46H
28N
10O)：理论值C,74.99；H,3.83；N,19.01；O,2.17；测试值：C,74.95；H,3.85N,19.04；O,2.16。ESI-MS(m/z)(M
+)：理论值为736.24，实测值为736.33。
实施例14：化合物71的合成
化合物71的制备方法同实施例13，不同之处在于用中间体A13替换中间体A12。元素分析结构(分子式C
40H
22N
4O
3)：理论值C,79.20；H,3.66；N,9.24；O,7.91；测试值：C,79.21；H,3.68；N,9.22；O,7.89。ESI-MS(m/z)(M
+)：理论值为606.17，实测值为606.23。
实施例15：化合物78的合成
化合物78的制备方法同实施例13，不同之处在于用中间体A14替换中间体A12。元素分析结构(分子式C
46H
38N
4O)：理论值C,83.35；H,5.78；N,8.45；O,2.41；测试值：C,83.38；H,5.74；N,8.43；O,2.45。ESI-MS(m/z)(M
+)：理论值为662.30，实测值为662.45。
实施例16：化合物85的合成
在250mL三口瓶中，通入氮气，加入0.01mol中间体A15，150ml的DMF，0.015mol原料B2，0.0001mol醋酸钯，搅拌，然后加入0.01mol K
3PO
4水溶液，加热至150℃，回流反应24小时，取样点板，反应完全。自然冷却，用200ml二氯甲烷萃取，分层，萃取液用无水硫酸钠干燥，过滤，滤液旋蒸，过硅胶柱纯化，得到中间体E1，HPLC纯度99.1％，收率70.3％。
元素分析结构(分子式C
27H
16ClN
5O)：理论值C,70.21；H,3.49；Cl,7.67；N,15.16；O,3.46；测试值：C,70.23；H,3.45；Cl,7.70；N,15.17；O,3.45。ESI-MS(m/z)(M
+)：理论值为461.10，实测值为461.37。
在250mL三口瓶中，通入氮气，加入0.01mol中间体E1，150ml的DMF，0.015mol中间体B1，0.0001mol醋酸钯，搅拌，然后加入0.01mol K
3PO
4水溶液，加热至150℃，回流反应24小时，取样点板，反应完全。自然冷却，用200ml二氯甲烷萃取，分层，萃取液用无水硫酸钠干燥，过滤，滤液旋蒸，过硅胶柱纯化，得到目标产物，HPLC纯度99.3％，收率58.7％。
元素分析结构(分子式C
40H
24N
6O
2)：理论值C,77.41；H,3.90；N,13.54；O,5.16；测试值：C,77.45；H,3.88；N,13.52；O,5.15。ESI-MS(m/z)(M
+)：理论值为620.20，实测值为620.27。
实施例17：化合物153的合成
在250mL三口瓶中，通入氮气，加入0.01mol中间体A16，150ml的DMF，0.028mol原料B3，0.0002mol醋酸钯，搅拌，然后加入0.02mol K
3PO
4水溶液，加热至150℃，回流反应24小时，取样点板，反应完全。自然冷却，用200ml二氯甲烷萃取，分层，萃取液用无水硫酸钠干燥，过滤，滤液旋蒸，过硅胶柱纯化，得到目标产物，HPLC纯度99.2％，收率53.6％。
元素分析结构(分子式C
44H
26N
6O
2)：理论值C,78.79；H,3.91；N,12.53；O,4.77；测试值：C,78.77；H,3.94；N,12.51；O,4.78。ESI-MS(m/z)(M
+)：理论值为670.21，实测值为670.35。
实施例18：化合物164的合成
在250mL三口瓶中，通入氮气，加入0.01mol中间体A17，150ml DMF，0.015mol原料B2，0.0001mol醋酸钯，搅拌，然后加入0.01mol K
3PO
4水溶液，加热至150℃，回流反应24小时，取样点板，反应完全。自然冷却，用200ml二氯甲烷萃取，分层，萃取液用无水硫酸钠干燥，过滤，滤液旋蒸，过硅胶柱纯化，得到目标产物，HPLC纯度99.1％，收率59.6％。
元素分析结构(分子式C
52H
32N
6O)：理论值C,82.52；H,4.26；N,11.10；O,2.11；测试值：C,82.53；H,4.27；N,11.07；O,2.13。ESI-MS(m/z)(M
+)：理论值为756.26，实测值为756.34。
实施例19：化合物173的合成
化合物173的制备方法同实施例13，不同之处在于用中间体A18替换中间体A12。元素分析结构(分子式C
52H
34N
4O)：理论值C,85.46；H,4.69；N,7.67；O,2.19；测试值：C,85.42；H,4.67；N,7.70；O,2.21。ESI-MS(m/z)(M
+)：理论值为730.27，实测值为730.35。
实施例20：化合物175的合成
化合物175的制备方法同实施例13，不同之处在于用中间体A19替换中间体A12。元素分析结构(分子式C
36H
22N
4O)：理论值C,82.11；H,4.21；N,10.64；O,3.04；测试值：C,82.13；H,4.23；N,10.63；O,3.01。ESI-MS(m/z)(M
+)：理论值为526.18，实测值为526.23。
实施例21：化合物191的合成
化合物191的制备方法同实施例2，不同之处在于用中间体A20替换中间体A1。元素分析结构(分子式C
47H
27N
5O
3)：理论值C,79.54；H,3.83；N,9.87；O,6.76；测试值：C,79.57；H,3.81；N,9.86；O,6.76。ESI-MS(m/z)(M
+)：理论值为709.21，实测值为709.43。
实施例22：化合物195的合成
化合物195的制备方法同实施例13，不同之处在于用中间体A21替换中间体A12。元素分析结构(分子式C
52H
32N
6O)：理论值C,82.52；H,4.26；N,11.10；O,2.11；测试值：C,82.53；H,4.27；N,11.13；O,2.07。ESI-MS(m/z)(M
+)：理论值为756.26，实测值为756.37。
实施例23：化合物227的合成
化合物227的制备方法同实施例2，不同之处在于用中间体A22替换中间体A1。元素分析结构(分子式C
59H
36N
6O
2)：理论值C,82.31；H,4.21；N,9.76；O,3.72；测试值：C,82.33；H,4.20；N,9.77；O,3.70。ESI-MS(m/z)(M
+)：理论值为860.29，实测值为860.46。
实施例24：化合物270的合成
在250mL三口瓶中，通入氮气，加入0.01mol原料P1，150ml DMF，0.012mol原料Q1，0.0001mol醋酸钯，搅拌，然后加入0.012mol K
3PO
4水溶液，加热至150℃，回流反应24小时，取样点板，反应完全。自然冷却，用200ml二氯甲烷萃取，分层，萃取液用无水硫酸钠干燥，过滤，滤液旋蒸，过硅胶柱纯化，得到中间体B4，HPLC纯度99.3％，收率70.8％。
在250mL三口瓶中，通入氮气，加入0.01mol中间体A1，150ml的DMF，0.03mol中间体B4，0.0002mol醋酸钯，搅拌，然后加入0.02mol K
3PO
4水溶液，加热至150℃，回流反应24小时，取样点板，反应完全。自然冷却，用200ml二氯甲烷萃取，分层，萃取液用无水硫酸钠干燥，过滤，滤液旋蒸，过硅胶柱纯化，得到目标产物，HPLC纯度99.1％，收率51.3％。
元素分析结构(分子式C
59H
36N
6O
2)：理论值C,82.31；H,4.21；N,9.76；O,3.72；测试值：C,82.34；H,4.19；N,9.78；O,3.69。ESI-MS(m/z)(M
+)：理论值为860.29，实测值为860.47。
实施例25：化合物360的合成
化合物360的制备方法同实施例2，不同之处在于用中间体A23替换中间体A1。元素分析结构(分子式C
51H
30N
6O
2)：理论值C,80.72；H,3.99；N,11.08；O,4.22；测试值：C,80.73；H,4.01；N,11.06；O,4.20。ESI-MS(m/z)(M
+)：理论值为758.24，实测值为758.47。
本发明的有机化合物在发光器件中使用作为CPL层材料，具有高的Tg(玻璃转化温度)温度和高折射率。对本发明化合物及现有材料分别进行热性能及折射率测试，结果如表2所示。其中化合物8的折射率测试图如图2所示。
表2
注：玻璃化温度Tg由示差扫描量热法(DSC，德国耐驰公司DSC204F1示差扫描量热仪)测定，升温速率10℃/min；折射率是由椭偏仪(美国J.A.Woollam Co.型号：ALPHA-SE)测量，测试为大气环境。
由表2数据可知，对比目前应用的CBP、Alq3及TPBi等材料，本发明的有机化合物具有高的玻璃转化温度、高折射率，同时由于含有三嗪和苯并噁唑刚性基团，保证了材料的热稳定性。因此，本发明以三嗪和苯并噁唑为核心的有机材料在应用于OLED器件的CPL层后，可有效提高器件的光取出效率，并且保证了OLED器件的长寿命。
以下通过器件实施例1～27和器件比较例1详细说明本发明合成的OLED材料在器件中的应用效果。本发明所述器件实施例2～27、器件比较例1与器件实施例1相比所述器件的制作工艺完全相同，并且所采用了相同的基板材料和电极材料，电极材料的膜厚也保持一致，所不同的是器件实施例2～23对器件中的CPL层材料做了变换；器件实施例24～27对器件的空穴阻挡/电子传输层材料做了变换，各实施例所得器件的性能测试结果如表3所示。
器件实施例1：一种电致发光器件，其制备步骤如图1所示包括：
a)清洗透明OLED器件基板1上的ITO阳极层2，分别用去离子水、丙酮、乙醇超声清洗各15分钟，然后在等离子体清洗器中处理2分钟；b)在ITO阳极层2上，通过真空蒸镀方式蒸镀空穴注入层材料HAT-CN，厚度为10nm，这层作为空穴注入层3；c)在空穴注入层3上，通过真空蒸镀方式蒸镀空穴传输材料NPB，厚度为80nm，该层为空穴传输层4；d)在空穴传输层4之上蒸镀发光层5，CBP作为作为主体材料，Ir(ppy)
3作为掺杂材料，Ir(ppy)
3和CBP的质量比为1:9，厚度为30nm；e)在发光层5之上，通过真空蒸镀方式蒸镀电子传输材料TPBI，厚度为40nm，这层有机材料作为空穴阻挡/电子传输层6使用；f)在空穴阻挡/电子传输层6之上，真空蒸镀电子注入层LiF，厚度为1nm，该层为电子注入层7；g)在电子注入层7之上，真空蒸镀阴极Mg：Ag/Ag层，Mg:Ag掺杂比例为9:1，厚度15nm，Ag厚度3nm，该层为阴极层8；h)在阴极层8之上，通过真空蒸镀方式蒸镀CPL材料化合物1，厚度为50nm，这层有机材料作为CPL层9使用。按照上述步骤完成电致发光器件的制作后，测量器件的电流效率和寿命，其结果见表3所示。相关材料的分子机构式如下所示：
器件实施例2：电致发光器件的CPL层材料变为本发明化合物8。器件实施例3：电致发光器件的CPL层材料变为本发明化合物12。器件实施例4：电致发光器件的CPL层材料变为本发明化合物16。器件实施例5：电致发光器件的CPL层材料变为本发明化合物28。器件实施例6：电致发光器件的CPL层材料变为本发明化合物30。器件实施例7：电致发光器件的CPL层材料变为本发明化合物35。器件实施例8：电致发光器件的CPL层材料变为本发明化合物38。器件实施例9：电致发光器件的CPL层材料变为本发明化合物39。器件实施例10：电致发光器件的CPL层材料变为本发明化合物47。器件实施例11：电致发光器件的CPL层材料变为本发明化合物59。器件实施例12：电致发光器件的CPL层材料变为本发明化合物69。器件实施例13：电致发光器件的CPL层材料变为本发明化合物71。器件实施例14：电致发光器件的CPL层材料变为本发明化合物78。器件实施例15：电致发光器件的CPL层材料变为本发明化合物85。器件实施例16：电致发光器件的CPL层材料变为本发明化合物153。器件实施例17：电致发光器件的CPL层材料变为本发明化合物164。器件实施例18：电致发光器件的CPL层材料变为本发明化合物173。器件实施例19：电致发光器件的CPL层材料变为本发明化合物175。器件实施例20：电致发光器件的CPL层材料变为本发明化合物191。器件实施例21：电致发光器件的CPL层材料变为本发明化合物227。器件实施例22：电致发光器件的CPL层材料变为本发明化合物270。器件实施例23：电致发光器件的CPL层材料变为本发明化合物360。器件实施例24：电致发光器件的空穴阻挡/电子传输层材料变为本发明化合物35，CPL层材料变为公知材料Alq
3。器件实施例25：电致发光器件的空穴阻挡/电子传输层材料变为本发明化合物39，CPL层材料变为公知材料Alq
3。器件实施例26：电致发光器件的空穴阻挡/电子传输层材料变为本发明化合物69，CPL层材料变为公知材料Alq
3。器件实施例27：电致发光器件的空穴阻挡/电子传输层材料变为本发明化合物195，CPL层材料变为公知材料Alq
3。器件比较例1：电致发光器件的CPL层材料变为公知材料Alq
3。所得电致发光器件的检测数据见表3所示。
表3
由表3的结果可以看出本发明所述以三嗪和苯并噁唑为核心的有机化合物应用于OLED发光器件制作后，与器件比较例1相比，光取出得到明显提升，相同电流密度下，器件亮度和器件效率都得到了提升，由于亮度及效率得到提升，OLED器件在定亮度下的功耗相对降低，使用寿命也得到提高。
为了说明本发明材料膜相态结晶稳定性能，将本发明材料化合物1和公知材料CBP进行了 膜加速结晶实验：采用真空蒸镀方式，分别蒸镀将化合物1和CBP蒸镀在无碱玻璃上，并在手套箱(水氧含量＜0.1ppm)中进行封装，将封装后样品在双85(温度85℃，湿度85％)条件下进行放置，定期用显微镜(LEICA，DM8000M，5*10倍率)观察材料膜的结晶状态，实验结果如表4所示，材料表面形态如图3所示：
表4
| 材料名称 | 化合物1 | CBP |
| 材料成膜后 | 表面形态光滑平整均匀 | 表面形态光滑平整均匀 |
| 实验72小时后 | 表面形态光滑平整均匀，无结晶 | 表面形成若干分散的圆形结晶面 |
| 实验600小时后 | 表面形态光滑平整均匀，无结晶 | 表面龟裂 |
以上实验说明，本发明材料的膜结晶稳定性远远高于公知材料，在应用于OLED器件后的使用寿命具有有益效果。
进一步的本发明材料制备的OLED器件在低温下工作时效率也比较稳定，将器件实施例8、17、25和器件比较例1在-10～80℃区间进行效率测试，所得结果如表5和图4所示。
表5
从表5和图4的数据可知，器件实施例8、17、25为本发明材料和已知材料搭配的器件结构，和器件比较例1相比，不仅低温效率高，而且在温度升高过程中，效率平稳升高。
综上，以上所述仅为本发明的较佳实施例，并不用以限制本发明，凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。
Claims (11)
- 一种基于三嗪和苯并噁唑的有机化合物，其特征在于，所述有机化合物的结构如通式(1)所示：
通式(1)中，x表示为数字1或2；z表示为数字1或2；m、n分别独立的表示为数字0、1或2；且m+n+z＝3；通式(1)中，Ar 1、Ar 2、Ar 3分别独立的表示为取代或未取代的C 6-60亚芳基、含有一个或多个杂原子的取代或未取代的5～60元杂亚芳基；所述杂原子为氮、氧或硫；Ar 1、Ar 2、Ar 3还分别独立的表示为单键；Ar 1、Ar 2、Ar 3相同或不同；R 1表示为氢原子、取代或未取代的C 6-60芳基、含有一个或多个杂原子的取代或未取代的5～60元杂芳基或所述杂原子为氮、氧或硫；
Q 1、Q 2分别独立的表示为取代或未取代的C 6-60芳基、含有一个或多个杂原子的取代或未取代的5～60元杂芳基；所述杂原子为氮、氧或硫；R 2表示为通式(2)或通式(3)所示结构；
R 3分别独立的表示为通式(4)或通式(5)所示结构；
其中，Ar 4、Ar 5、Ar 6、Ar 7、Ar 8、Ar 9、Ar 10、Ar 11分别独立的表示为氢原子、C 1-10直链或 支链烷基、取代或未取代的C 6-60芳基、含有一个或多个杂原子的取代或未取代的5～60元杂芳基；所述杂原子为氮、氧或硫。 - 根据权利要求1所述的有机化合物，其特征在于，所述Ar 1、Ar 2、Ar 3分别独立的表示为C 1-10直链或支链烷基、卤素原子、氕、氘、氚原子取代或未取代的亚苯基；C 1-10直链或支链烷基、卤素原子、氕、氘、氚原子取代或未取代的亚萘基；C 1-10直链或支链烷基、卤素原子、氕、氘、氚原子取代或未取代的亚二联苯基；C 1-10直链或支链烷基、卤素原子、氕、氘、氚原子取代或未取代的亚吡啶基；亚咔唑基；亚呋喃基；亚嘧啶基；亚吡嗪基；亚哒嗪基；亚二苯并呋喃基；亚9,9-二甲基芴基；亚N-苯基咔唑基；亚喹啉基；亚异喹啉基或亚萘啶基中的一种；R 1、Ar 4、Ar 5、Ar 6、Ar 7、Ar 8、Ar 9、Ar 10、Ar 11、Q 1、Q 2表示为C 1-10直链或支链烷基、卤素原子、氕、氘、氚原子取代或未取代的苯基；C 1-10直链或支链烷基、卤素原子、氕、氘、氚原子取代或未取代的萘基；C 1-10直链或支链烷基、卤素原子、氕、氘、氚原子取代或未取代的二联苯基；C 1-10直链或支链烷基、卤素原子、氕、氘、氚原子取代或未取代的吡啶基；咔唑基；呋喃基；嘧啶基；吡嗪基；哒嗪基；二苯并呋喃基；9,9-二甲基芴基；N-苯基咔唑基；喹啉基；异喹啉基或萘啶基中的一种。
- 根据权利要求1所述的有机化合物，其特征在于，所述z表示为数字1时，-Ar 1-(R 1) x基团至少含有1个杂原子，所述杂原子为氮、氧或硫。
- 根据权利要求1所述的有机化合物，其特征在于，所述有机化合物的结构如通式(Ⅰ)～(Ⅶ)中的任一种所示：
- 根据权利要求1所述的有机化合物，其特征在于，通式(1)中所述R 1表示为：
中的任一种。 - 根据权利要求1所述的有机化合物，其特征在于，所述有机化合物的具体结构式为：
中的任意一种。
- 一种权利要求1～6任一项所述有机化合物的制备方法，其特征在于，所述制备方法涉及的反应方程式为：
(1)氮气氛围下，称取原料A溶解于DMF中，再加入醋酸钯，搅拌混合物，再加入磷酸钾水溶液，将上述反应物的混合溶液于120-150℃条件下加热回流5-15小时；反应结束后，冷却加水、将混合物过滤并在真空干燥箱中干燥，所得残余物过硅胶柱纯化，得到化合物中间体I；
所述原料A与的摩尔比为1:1.0～3，醋酸钯与原料A的摩尔比为0.001～0.04:1，磷酸钾与原料A的摩尔比为1.0～4.0:1，原料A与DMF的用量比为1g:10～30ml；
(2)氮气氛围下，称取中间体I溶解于DMF中，再加入及醋酸钯，搅拌混合物，再加入磷酸钾水溶液，将上述反应物的混合溶液于120-150℃条件下加热回流10-24小时；反应结束后，冷却加水、将混合物过滤并在真空干燥箱中干燥，所得残余物过硅胶柱纯化，得到化合物中间体II；
所述中间体I与的摩尔比为1:1.0～3，醋酸钯与中间体I的摩尔比为0.001～0.04:1，磷酸钾与中间体I的摩尔比为1.0～4.0:1，中间体I与DMF的用量比为1g:10～40ml；
(3)氮气氛围下，称取中间体II溶解于DMF中，再加入及醋酸钯，搅拌混合物，再加入磷酸钾水溶液，将上述反应物的混合溶液于120-150℃条件下加热回流10-24小时；反应结束后，冷却加水、将混合物过滤并在真空干燥箱中干燥，所得残余物过硅胶柱纯化，得到目标化合物；
所述中间体II与的摩尔比为1:1.0～3，醋酸钯与中间体II的摩尔比为0.001～0.04:1，磷酸钾与中间体II的摩尔比为1.0～4.0:1，中间体II与DMF的用量比为1g:15～50ml。
- 一种含有权利要求1～6任一项所述有机化合物的有机电致发光器件，其特征在于，所述有机电致发光器件包括至少一层功能层含有所述基于三嗪和苯并噁唑的有机化合物。
- 一种含有权利要求1～6任一项所述有机化合物的有机电致发光器件，包括空穴阻挡层/电子传输层，其特征在于，所述空穴阻挡层/电子传输层含有所述基于三嗪和苯并噁唑的有机化合物。
- 一种含有权利要求1～6任一项所述有机化合物的有机电致发光器件，包括在出光一侧电极上的覆盖层，其特征在于，所述覆盖层含有所述基于三嗪和苯并噁唑的有机化合物。
- 一种照明或显示元件，其特征在于，所述元件含有权利要求8～10任一项所述的有机电致发光器件。
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| JP7519693B2 (ja) | 2020-12-22 | 2024-07-22 | 長春海譜潤斯科技股フン有限公司 | 複素環化合物及びそれを含む有機電界発光素子 |
| CN113234095A (zh) * | 2021-04-30 | 2021-08-10 | 武汉工程大学 | 含联三嗪基团的化合物及其作为三维电子受体材料的应用 |
| CN117229192A (zh) * | 2022-08-25 | 2023-12-15 | 江苏三月科技股份有限公司 | 含有三氟甲基或全氟异丙基的双邻苯二甲酰亚胺类有机化合物及包含其的有机电致发光器件 |
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| Publication number | Publication date |
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| US11555018B2 (en) | 2023-01-17 |
| US20210070717A1 (en) | 2021-03-11 |
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