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WO2018041123A1 - 以芴和含氮六元杂环为核心的化合物及在有机发光器件中的应用 - Google Patents

以芴和含氮六元杂环为核心的化合物及在有机发光器件中的应用 Download PDF

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WO2018041123A1
WO2018041123A1 PCT/CN2017/099587 CN2017099587W WO2018041123A1 WO 2018041123 A1 WO2018041123 A1 WO 2018041123A1 CN 2017099587 W CN2017099587 W CN 2017099587W WO 2018041123 A1 WO2018041123 A1 WO 2018041123A1
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张兆超
李崇
唐丹丹
张小庆
叶中华
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Jiangsu Sunera Technology Co Ltd
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Definitions

  • the invention relates to a compound based on ruthenium and a nitrogen-containing six-membered heterocyclic ring and its application in an organic light-emitting device, and belongs to the technical field of semiconductors.
  • 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.
  • a current device when a voltage is applied to the electrodes of both ends of the OLED light-emitting device, and the positive and negative charges in the film layer of the organic layer functional material are applied by the electric field, the positive and negative charges are further recombined in the light-emitting layer, that is, 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 televisions.
  • OLED devices have luminous efficiency and service life. Further improvement is needed.
  • Research on improving the performance of OLED light-emitting devices includes: reducing the driving voltage of the device, improving the luminous efficiency of the device, and improving the service life of the device.
  • it is not only necessary to innovate from the structure and fabrication process of OLED devices, but also to continuously research and innovate OLED photoelectric functional materials, and to create functional materials with higher performance OLEDs.
  • OLED photoelectric functional materials applied to OLED devices can be divided into two categories, namely, charge injection.
  • the charge injection transport material can also be divided into an electron injection transport material, an electron blocking material, a hole injection transport material and a hole blocking material, and the luminescent material can be divided into a host luminescent material and a blend. Miscellaneous materials.
  • organic functional materials are required to have good photoelectric characteristics.
  • a charge transport material it is required to have good carrier mobility, high glass transition temperature, etc., as a main body of the light-emitting layer.
  • Materials require materials with good bipolarity, appropriate HOMO/LUMO energy levels, and the like.
  • the OLED photoelectric functional material film layer constituting the OLED device includes at least two or more layers, and the industrially applied OLED device structure includes a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting layer, a hole blocking layer, and an electron.
  • a plurality of film layers such as a transport layer and an electron injection layer, that is, an optoelectronic functional material applied to an OLED device includes at least a hole injecting material, a hole transporting material, a luminescent material, an electron transporting material, etc., and the material type and the collocation form are rich. Characteristics of sex and diversity.
  • the optoelectronic functional materials used have strong selectivity, and the performance of the same materials in different structural devices may be completely different.
  • the photoelectric characteristics of the devices must be selected to be more suitable, and high-performance OLED functional materials or material combinations can achieve high efficiency and long device. Comprehensive characteristics of life and low voltage.
  • the development of OLED materials is still far from enough. It is lagging behind the requirements of panel manufacturers, and it is especially important to develop higher performance organic functional materials as material enterprises.
  • the technical problem to be solved by the present invention is to provide a compound having a ruthenium and a nitrogen-containing six-membered heterocyclic ring as its core and its use in an organic electroluminescent device.
  • the compound contains a ruthenium structure with high glass transition temperature and molecular thermal stability, suitable HOMO and LUMO energy levels, and high Eg.
  • the device structure is optimized to effectively improve the photoelectric performance of the OLED device and the lifetime of the OLED device.
  • R 1 , R 2 and R 3 are each a phenyl group, a biphenyl group, a naphthyl group, a pyridyl group, a quinolyl group, an isoquinolyl group, a phenanolyl group, a benzimidazolyl group, and a benzene group. And one of oxazolyl, pyridoindole, quinoxalinyl or naphthyridinyl;
  • Ar is represented by one of a phenyl group, a biphenyl group, a naphthyl group or a pyridyl group;
  • n 1, 2 or 3.
  • the invention has the beneficial effects that the nitrogen-containing six-membered heterocyclic ring is a strong electron group and is modified by a hydrazine or an aromatic group by a ruthenium group and a nitrogen-containing six-membered heterocyclic ring as a skeleton.
  • the HOMO level can be freely adjusted, used as an electronic luminescent material or used as a hole blocking/electron transport layer material, which can improve the photoelectric performance and service life of the device.
  • the present invention can also be improved as follows.
  • the present invention has a compound having a ruthenium and a nitrogen-containing six-membered heterocyclic ring as a core, and further, in the formula (1)
  • R 2 and R 3 are each independently represented by R 2 and R 3 are each a phenyl group, a biphenyl group, a naphthyl group, a pyridyl group, a quinolyl group, an isoquinolyl group, a phenanolyl group, a benzimidazolyl group, and a benzene group. And one of oxazolyl, pyridohydrazino, quinoxalinyl or naphthyridinyl.
  • the present invention has a compound having a ruthenium and a nitrogen-containing six-membered heterocyclic ring as a core, and further, in the formula (1)
  • the present invention has a compound having a ruthenium and a nitrogen-containing six-membered heterocyclic ring as a core, and further, the specific structural formula of the compound is:
  • the present invention has a compound having a ruthenium and a nitrogen-containing six-membered heterocyclic ring as a core, and further, the reaction equation in the preparation method is:
  • R 1 , R 2 and R 3 are each a phenyl group, a biphenyl group, a naphthyl group, a pyridyl group, a quinolyl group, an isoquinolyl group, a phenanolyl group, a benzimidazolyl group, a benzoxazolyl group, a pyridine group.
  • a mercapto group, a quinoxaline group or a naphthyridinyl group is a mercapto group, a quinoxaline group or a naphthyridinyl group;
  • the preparation method uses Br-Ar-Br as a raw material, obtains a Grignard reagent by Grignard reaction, and then reacts with 9-fluorenone to form a tertiary alcohol; then the tertiary alcohol and HR 1 are subjected to a Friedel-Craft reaction to obtain a Brominated compounds, then The compound was prepared by CC coupling.
  • the above preparation method specifically includes the following steps:
  • the crude product of the obtained tertiary alcohol is purified by using a petroleum ether: dichloromethane mixed solvent over a neutral silica gel column.
  • the alcohol purification product preferably the above petroleum ether: dichloromethane volume ratio of 3:2; the tetrahydrofuran in the step 2) is preferably used in an amount of 4-8 ml of tetrahydrofuran per 1 g of 9-fluorenone; 1 g of tertiary alcohol was added to 5-10 ml of diethyl ether.
  • the molar ratio of the Pd(PPh 3 ) 4 to the monobromo compound is (0.005 to 0.02): 1, and the molar ratio of the sodium carbonate to the monobromo compound is (1.5 to 3.0): ;
  • the mixed solution obtained in the step 5) is reacted at 95 to 110 ° C for 10 to 24 hours, naturally cooled to room temperature, and the reaction solution is filtered, and the filtrate is rotary-screwed to a solvent-free, neutral silica gel column.
  • the target product is obtained.
  • the invention relates to the above application of a compound having a ruthenium and a nitrogen-containing six-membered heterocyclic ring as cores in an organic light-emitting device.
  • the present invention provides an organic electroluminescence device comprising at least one functional layer containing the above-mentioned organic compound containing a dibenzo six-membered ring and a nitrogen-containing six-membered heterocyclic ring.
  • the present invention provides an organic light-emitting device comprising a hole blocking/electron transport layer which is a compound having a ruthenium and a nitrogen-containing six-membered heterocyclic ring as a core.
  • An organic light-emitting device as described above further comprising a transparent substrate layer, an ITO anode layer, a hole injection layer, a hole transport/electron barrier layer, a light-emitting layer, an electron injection layer, and a cathode reflective electrode layer, Transparent substrate layer, ITO anode layer, hole injection layer, hole transport/electron blocking layer, luminescent layer, The hole blocking/electron transporting layer, the electron injecting layer, and the cathode reflecting electrode layer are stacked in this order from bottom to top.
  • the ITO anode layer has a thickness of 130 to 150 nm; or/and the hole injection layer is a material HAT-CN having a thickness of 10 nm; or/and the hole
  • the transmission/electron blocking layer is a hole transporting material NPB having a thickness of 80 nm, or/and the light emitting layer is made of CBP as a host material, and Ir(ppy) is used as a phosphorescent doping material, the doping mass ratio is 10%, and the thickness is 30 nm.
  • the hole blocking/electron transport layer has a thickness of 40 nm
  • the electron injecting layer is a LiF material having a thickness of 1 nm
  • the cathode reflective electrode layer is a material Al, the thickness thereof It is 100 nm.
  • An organic light-emitting device comprises a light-emitting layer, wherein the light-emitting layer is a compound having a ruthenium and a nitrogen-containing six-membered heterocyclic ring as a core and a compound GHN as a host material, and the dopant material is Ir(ppy). 3 .
  • the mass ratio of the compound having the ruthenium and the nitrogen-containing six-membered heterocyclic ring as the core, the compound GHN and Ir(ppy) 3 is 60:30:10, wherein the structural formula of the compound GHN is
  • An organic light-emitting device as described above further comprising a transparent substrate layer, an ITO anode layer, a hole injection layer, a hole transport/electron barrier layer, a light-emitting layer, a hole blocking/electron transport layer, and 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/electron barrier layer, the light-emitting layer, the hole blocking/electron transport layer, the electron injection layer, and the cathode reflective electrode layer are The top is stacked in order.
  • An organic light-emitting device as described above further comprising a transparent substrate layer, an ITO anode layer, a hole injection layer, a hole transport/electron barrier layer, a light-emitting layer, a hole blocking/electron transport layer, and 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/electron barrier layer, the light-emitting layer, the hole blocking/electron transport layer, the electron injection layer, and the cathode reflective electrode layer are The top is stacked in order.
  • the ITO layer has an anode layer thickness of 130-150 nm; or/and the hole injection layer is a material HAT-CN having a thickness of 10 nm; or/and the hole transport/electron blocking
  • the layer is a hole transporting material NPB having a thickness of 80 nm, or/and the light emitting layer has a thickness of 30 nm, or/and the hole blocking/electron transporting layer material is TPBI, having a thickness of 40 nm, and/or the electron injecting
  • the layer is a LiF material having a thickness of 1 nm, and/or the cathode reflective electrode layer is a material Al having a thickness of 100 nm.
  • the invention provides a preparation method of an organic light emitting device, comprising the following steps:
  • Step c) depositing a hole transporting material NPB as a hole transporting layer/electron blocking layer on the hole injecting layer by vacuum evaporation;
  • Step d) evaporating a light-emitting layer on the hole transport/electron barrier layer, the light-emitting layer using CBP as a host material and Ir(ppy) as a phosphorescent dopant material;
  • Step e) above the light-emitting layer using the above-mentioned compound having a ruthenium and a nitrogen-containing six-membered heterocyclic ring as a core layer as a hole blocking layer/electron transport layer material;
  • Step g) On top of the electron injecting layer, a cathode Al is vacuum-evaporated as a cathode reflective electrode layer.
  • the compound of the present invention is composed of an anthracene group and a nitrogen-containing six-membered heterocyclic ring, wherein the nitrogen-containing six-membered heterocyclic ring is a strong electron group, and the HOMO level is freed by modification of a ruthenium or an aromatic group.
  • the adjustment can be used as an electron-type luminescent material or as a hole blocking/electron transport layer material.
  • each group is rigid, has high glass transition temperature and thermal stability, and the compound of the present invention is applied. In the case of OLED devices, the stability of the film after film formation can be maintained, and the service life of the OLED device can be improved.
  • FIG. 1 is a schematic structural view of a material exemplified in the present invention applied to an OLED device;
  • 1 is a transparent substrate layer
  • 2 is an ITO anode layer
  • 3 is a hole injection layer
  • 4 is a hole transport/electricity Sub-barrier layer
  • 5 is a light-emitting layer
  • 6 is a hole blocking/electron transport layer
  • 7 is an electron injection layer
  • 8 is a cathode reflective electrode layer.
  • the synthetic route is as follows:
  • the starting material A2 was prepared according to the synthesis method of the starting material A1 in Example 1, except that 1,4-dibromobenzene was used instead of 3,4'-dibromo-1,1'-biphenyl, and the third step was used in the reaction. Benzene instead of benzene;
  • the starting material A3 was prepared according to the synthesis method of the starting material A1 in Example 1, except that 1,4-dibromobenzene was used instead of 3,4'-dibromo-1,1'-biphenyl;
  • Raw material A4 was prepared according to the synthesis method of starting material A1 in Example 1, except that biphenyl was used instead of benzene in the third step reaction;
  • the starting material A5 was prepared according to the synthesis method of the starting material A1 in Example 1, except that 4,4'-dibromo-1,1'-biphenyl was used instead of 3,4'-dibromo-1,1'-biphenyl. ;
  • the starting material A2 was prepared according to the synthesis method of the starting material A1 in Example 1, except that 1,4-dibromobenzene was used instead of 3,4'-dibromo-1,1'-biphenyl, and the pyridine was used in the third step. Instead of benzene;
  • Elemental analysis structure (Molecular formula C 40 H 27 N 3 ): Theory C, 87.40; H, 4.95; N, 7.64; Tests: C, 87.41; H, 4.95; N, 7.63.
  • HPLC-MS The material had a molecular weight of 549.22 and a molecular weight of 549.45.
  • a 250 ml four-necked flask was charged with 0.01 mol of raw material A3, 0.012 mol of raw material B2, 0.02 mol of sodium carbonate, 1 ⁇ 10 -4 mol of Pd(PPh 3 ) 4 , 150 ml of toluene, and heated to 105 ° C under a nitrogen atmosphere. After refluxing for 24 hours, the spot plate was sampled, indicating that no bromine was left, and the reaction was complete; natural cooling, filtration, and the filtrate was rotary-steamed to a fraction without a fraction, and passed through a neutral silica gel column to obtain a target product with a purity of 99.5% and a yield of 79.2%.
  • HPLC-MS The material had a molecular weight of 548.23 and a molecular weight of 548.49.
  • a 250 ml four-necked flask was charged with 0.01 mol of raw material A1, 0.012 mol of raw material B3, 0.02 mol of sodium carbonate, 1 ⁇ 10 -4 mol of Pd(PPh 3 ) 4 , 150 ml of toluene, and heated to 105 ° C under a nitrogen atmosphere. After refluxing for 24 hours, the spot plate was sampled, indicating that there was no bromine residue remaining, and the reaction was complete; natural cooling, filtration, and the filtrate was rotary-steamed to a fraction without a fraction, and passed through a neutral silica gel column to obtain the desired product, purity 99.3%, yield 78.1%.
  • Elemental Analysis Structure (Molecular Formula C 48 H 33 N): Theory C, 92.42; H, 5.33; N, 2.25; ⁇ / RTI> C, 92.40; H, 5.34; N, 2.26.
  • HPLC-MS The material had a molecular weight of 623.26 and a molecular weight of 623.51.
  • a 250 ml four-necked flask was charged with 0.01 mol of raw material A2, 0.012 mol of raw material B3, 0.02 mol of sodium carbonate, 1 ⁇ 10 -4 mol of Pd(PPh 3 ) 4 , 150 ml of toluene, and heated to 105 ° C under a nitrogen atmosphere. After refluxing for 24 hours, the spot plate was sampled, indicating that there was no bromine residue remaining, and the reaction was completed; natural cooling, filtration, and the filtrate was rotary-steamed to a fraction without a fraction, and passed through a neutral silica gel column to obtain a target product with a purity of 99.5% and a yield of 74.3%.
  • Elemental Analysis Structure (Molecular Formula C 48 H 33 N): Theory C, 92.42; H, 5.33; N, 2.25; Tests: C, 92.43; H, 5.32; N, 2.25.
  • HPLC-MS The material had a molecular weight of 623.26 and a molecular weight of 623.53.
  • Elemental analysis structure (Molecular formula C 42 H 29 N): Theory C, 92.11; H, 5.34; N, 2.56; Tests: C, 92.10; H, 5.35; N, 2.55.
  • HPLC-MS The material had a molecular weight of 547.23 and a molecular weight of 547.49.
  • Elemental analysis structure (Molecular formula C 40 H 27 N 3 ): Theory C, 87.40; H, 4.95; N, 7.64; Tests: C, 87.41; H, 4.965; N, 7.63.
  • HPLC-MS The material had a molecular weight of 549.22 and a molecular weight of 549.47.
  • Elemental analysis structure (Molecular formula C 39 H 26 N 4 ): Theory C, 85.07; H, 4.76; N, 10.17; Tests: C, 85.06; H, 4.78; N, 10.16.
  • HPLC-MS The material had a molecular weight of 550.22 and a molecular weight of 550.43.
  • a 250 ml four-necked flask was charged with 0.01 mol of raw material A4, 0.012 mol of raw material C2, 0.02 mol of sodium carbonate, 1 ⁇ 10 -4 mol of Pd(PPh 3 ) 4 , 150 ml of toluene, and heated to 105 ° C under a nitrogen atmosphere. After refluxing for 24 hours, the spot plate was sampled, indicating that there was no bromine residue remaining, and the reaction was completed; natural cooling, filtration, and the filtrate was rotary-steamed to a fraction without a fraction, and passed through a neutral silica gel column to obtain the desired product, purity 99.1%, yield 65.1%.
  • Elemental Analysis Structure (Molecular Formula C 53 H 36 N 2 ): Theory C, 90.83; H, 5.18; N, 4.40; Tests: C, 90.81; H, 5.17; N, 4.02.
  • HPLC-MS The material had a molecular weight of 700.29 and a molecular weight of 700.55.
  • Elemental analysis structure (Molecular formula C 45 H 30 N 4 ): Theory C, 86.24; H, 4.82; N, 8.94; Tests: C, 86.22; H, 4.83; N, 8.95.
  • HPLC-MS The material had a molecular weight of 626.25 and a molecular weight of 626.52.
  • Elemental Analysis Structure (Molecular Formula C 47 H 32 N 2 ): Theory C, 90.35; H, 5.16; N, 4.48; Tests: C, 90.38; H, 5.15; N, 4.47.
  • HPLC-MS The material had a molecular weight of 624.26 and a molecular weight of 625.54.
  • Elemental analysis structure (Molecular formula C 47 H 32 N 2 ): Theory C, 90.35; H, 5.16; N, 4.48; Tests: C, 90.36; H, 5.17; N, 4.47.
  • HPLC-MS The material had a molecular weight of 624.26 and a molecular weight of 624.53.
  • Elemental Analysis Structure (Molecular Formula C 47 H 32 N 2 ): Theory C, 90.35; H, 5.16; N, 4.48; Tests: C, 90.37; H, 5.15; N, 4.48.
  • HPLC-MS The material had a molecular weight of 624.26 and a molecular weight of 624.57.
  • Elemental analysis structure (molecular formula C 40 H 27 N 3 ): calcd. C, 87.40; H, 4.95; N, 7.64; C, 87.40; H, 4.95; N, 7.65.
  • HPLC-MS The material had a molecular weight of 549.22 and a molecular weight of 549.45.
  • Elemental analysis structure (Molecular formula C 46 H 31 N 3 ): Theory C, 88.29; H, 4.99; N, 6.72; ??????, C, 88.30; H, 5.00; N, 6.70.
  • HPLC-MS The material had a molecular weight of 625.25 and a molecular weight of 625.56.
  • Elemental Analysis Structure (Molecular Formula C 46 H 31 N 3 ): Theory C, 88.29; H, 4.49; N, 6.72; Tests: C, 88.27; H, 5.00; N, 6.73.
  • HPLC-MS The material had a molecular weight of 625.25 and a molecular weight of 625.59.
  • a 250 ml four-necked flask was charged with 0.01 mol of raw material A6, 0.012 mol of raw material D1, 0.02 mol of sodium carbonate, 1 ⁇ 10 -4 mol of Pd(PPh 3 ) 4 , 150 ml of toluene, and heated to 105 ° C under a nitrogen atmosphere. After refluxing for 24 hours, the spot plate was sampled, indicating that there was no bromine residue remaining, and the reaction was complete; natural cooling, filtration, and the filtrate was rotary-steamed to a fraction without a fraction, and passed through a neutral silica gel column to obtain a target product with a purity of 99.4% and a yield of 71.7%.
  • Elemental analysis structure (Molecular formula C 39 H 26 N 4 ): Theory C, 85.07; H, 4.76; N, 10.17; Tests: C, 85.07; H, 4.75; N, 10.18.
  • HPLC-MS The material had a molecular weight of 550.22 and a molecular weight of 550.47.
  • the compound provided by the present invention will be described in detail as a hole blocking or electron transporting layer material and a light emitting layer material by the device examples 1-10 and the device comparative example 1, and applied to an electroluminescent device, and proved by the comparative example 1. Its beneficial effect.
  • the performance test results of the devices obtained in the respective examples are shown in Table 1.
  • An electroluminescent device the preparation steps comprising:
  • the hole injection layer material HAT-CN is deposited by vacuum evaporation, the thickness is 10nm, this layer serves as the hole injection layer 3;
  • the hole transport material NPB is evaporated by vacuum evaporation, the thickness is 80nm, the layer is a hole transport layer or electron blocking layer 4;
  • the layer is the cathode reflective electrode layer 8;
  • the molecular organization of the relevant material is as follows:
  • This embodiment is different from Device Embodiment 1 in that the hole blocking or electron transport layer 6 material of the electroluminescent device becomes the compound 4 of the present invention.
  • the detection data of the obtained electroluminescent device is shown in Table 1.
  • This embodiment differs from Device Embodiment 1 in that the hole blocking or electron transport layer 6 material of the electroluminescent device becomes the compound 15 of the present invention.
  • the detection data of the obtained electroluminescent device is shown in Table 1.
  • This embodiment differs from Device Embodiment 1 in that the material of the hole blocking or electron transport layer 6 of the electroluminescent device becomes the compound 26 of the present invention.
  • the detection data of the obtained electroluminescent device is shown in Table 1.
  • This embodiment is different from Device Embodiment 1 in that the material of the hole blocking/electron transport layer 6 of the electroluminescent device becomes the compound 35 of the present invention.
  • the detection data of the obtained electroluminescent device is shown in Table 1.
  • This embodiment differs from Device Embodiment 1 in that the hole blocking or electron transport layer 6 material of the electroluminescent device becomes TPBI, the light emitting layer host material becomes the compound 5 of the present invention, and the doping material is Ir (ppy). 3 ) The mass ratio of the compound 5 of the present invention and the doping material Ir(ppy) 3 was 9:1, and the detection data of the obtained electroluminescent device are shown in Table 1.
  • This embodiment differs from Device Embodiment 1 in that the hole blocking or electron transport layer 6 material of the electroluminescent device becomes TPBI, the light emitting layer host material becomes the compound 42 of the present invention, and the doping material is Ir (ppy). 3 , the mass ratio of the compound 42 of the present invention and the doping material Ir(ppy) 3 is 9:1, and the detection data of the obtained electroluminescent device are shown in Table 1.
  • This embodiment differs from Device Embodiment 1 in that the hole blocking or electron transport layer 6 material of the electroluminescent device becomes TPBI, and the light emitting layer host material becomes the compound 51 and the compound GHN of the present invention, and the doping material is Ir(ppy) 3 , the mass ratio of the compound 51 of the present invention, the compound GHN and the doping material to Ir(ppy) 3 is 60:30:10, and the detection data of the obtained electroluminescent device are shown in Table 1.
  • This embodiment differs from Device Embodiment 1 in that the hole blocking or electron transporting layer 6 material of the electroluminescent device becomes TPBI, and the light emitting layer host material becomes the compound 53 and the compound GHN of the present invention, and the doping material is Ir(ppy) 3 , the mass ratio of the compound 53 of the present invention, the compound GHN and the doping material to Ir(ppy) 3 is 60:30:10, and the detection data of the obtained electroluminescent device are shown in Table 1.
  • This embodiment differs from Device Embodiment 1 in that the hole blocking or electron transport layer 6 material of the electroluminescent device becomes two layers, wherein the compound 58 of the present invention is used alone as a hole blocking layer, having a thickness of 5 nm.
  • the following structural compound A and compound B were mixed with each other at a mass ratio of 1:1 as an electron transport layer, and the thickness thereof was 35 nm.
  • the detection data of the obtained electroluminescent device is shown in Table 1.
  • This comparative example is different from Device Embodiment 1 in that the hole blocking or electron transport layer 6 material of the electroluminescent device becomes TPB I.
  • the detection data of the obtained electroluminescent device is shown in Table 1.
  • the device test performance is based on device comparison example 1, and the performance index of the device of comparison example 1 is set to 1.0.
  • the current efficiency of Comparative Example 1 was 28 cd/A (@10 mA/cm 2 ); the CIE color coordinate was (0.33, 0.63); the LT95 lifetime decay at 5000 luminance was 2.5 Hr.
  • the above hole blocking layer is also referred to as an electron transport layer.

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Abstract

本发明公开了一种以芴和含氮六元杂环为核心的化合物，该具有结构通式（1），通式（1）中，R 1、R 2、R 3分别为苯基、联苯基、萘基、吡啶基、喹啉基、异喹啉基、菲罗啉基、苯并咪唑基、苯并恶唑基、吡啶并吲哚基、喹喔啉基或萘啶基中的一种；通式（1）中，Ar表示为苯基、联苯基、萘基或吡啶基中的一种；通式（1）中， aa表示为含氮六元杂环，n＝1、2或3。本发明以芴和含氮六元杂环为骨架，通过芳香基团连接，其中的含氮六元杂环为强电子性基团，通过芴或芳香基团的修饰，使HOMO能级自由调整，作为电子型发光材料使用或作为空穴阻挡/电子传输层材料使用，可以提高器件的光电性能及使用寿命。

Description

以芴和含氮六元杂环为核心的化合物及在有机发光器件中的应用 技术领域
本发明涉及一种以芴和含氮六元杂环为核心的化合物及在有机发光器件中的应用，属于半导体技术领域。
背景技术
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。作为电流器件，当对OLED发光器件的两端电极施加电压，并通过电场作用有机层功能材料膜层中的正负电荷，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，和实际的产品应用要求相比，OLED器件的发光效率，使用寿命等性能还需要进一步提升。
对于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OLED的功能材料。
应用于OLED器件的OLED光电功能材料从用途上可划分为两大类，即电荷注 入传输材料和发光材料，进一步，还可将电荷注入传输材料分为电子注入传输材料、电子阻挡材料、空穴注入传输材料和空穴阻挡材料，还可以将发光材料分为主体发光材料和掺杂材料。
为了制作高性能的OLED发光器件，要求各种有机功能材料具备良好的光电特性，譬如，作为电荷传输材料，要求具有良好的载流子迁移率，高玻璃化转化温度等，作为发光层的主体材料要求材料具有良好双极性，适当的HOMO/LUMO能阶等。
构成OLED器件的OLED光电功能材料膜层至少包括两层以上结构，产业上应用的OLED器件结构，则包括空穴注入层、空穴传输层、电子阻挡层、发光层、空穴阻挡层、电子传输层、电子注入层等多种膜层，也就是说应用于OLED器件的光电功能材料至少包含空穴注入材料，空穴传输材料，发光材料，电子传输材料等，材料类型和搭配形式具有丰富性和多样性的特点。另外，对于不同结构的OLED器件搭配而言，所使用的光电功能材料具有较强的选择性，相同的材料在不同结构器件中的性能表现，也可能完全迥异。
因此，针对当前OLED器件的产业应用要求，以及OLED器件的不同功能膜层，器件的光电特性需求，必须选择更适合，具有高性能的OLED功能材料或材料组合，才能实现器件的高效率、长寿命和低电压的综合特性。就当前OLED显示照明产业的实际需求而言，目前OLED材料的发展还远远不够，落后于面板制造企业的要求，作为材料企业开发更高性能的有机功能材料显得尤为重要。
发明内容
本发明所要解决的技术问题是提供一种以芴和含氮六元杂环为核心的化合物及其在有机电致发光器件上的应用。该化合物含有芴结构，具有较高的玻璃化温度和分子热稳定性，合适的HOMO和LUMO能级，较高Eg，通过器件结构优化，可有效提升OLED器件的光电性能以及OLED器件的寿命。
本发明解决上述技术问题的技术方案如下：一种以芴和含氮六元杂环为核心 的化合物，所述化合物具有如下结构通式(1)：
Figure PCTCN2017099587-appb-000001
所述通式(1)中，R1、R2、R3分别为苯基、联苯基、萘基、吡啶基、喹啉基、异喹啉基、菲罗啉基、苯并咪唑基、苯并恶唑基、吡啶并吲哚基、喹喔啉基或萘啶基中的一种；
通式(1)中，Ar表示为苯基、联苯基、萘基或吡啶基中的一种；
通式(1)中，
Figure PCTCN2017099587-appb-000002
表示为含氮六元杂环，n＝1、2或3。
本发明的有益效果是：在以芴和含氮六元杂环为骨架，通过芳香基团连接，其中的含氮六元杂环为强电子性基团，通过芴或芳香基团的修饰，使HOMO能级自由调整，作为电子型发光材料使用或作为空穴阻挡/电子传输层材料使用，可以提高器件的光电性能及使用寿命。
在上述技术方案的基础上，本发明还可以做如下改进。
本发明如上所述一种以芴和含氮六元杂环为核心的化合物，进一步，通式(1)中的
Figure PCTCN2017099587-appb-000003
为通式(2)、通式(3)、通式(4)、通式(5)或通式(6)表示：
Figure PCTCN2017099587-appb-000004
其中，R2、R3分别独立的表示为R2、R3分别为苯基、联苯基、萘基、吡啶基、喹啉基、异喹啉基、菲罗啉基、苯并咪唑基、苯并恶唑基、吡啶并吲哚基、喹喔 啉基或萘啶基中的一种。
本发明如上所述一种以芴和含氮六元杂环为核心的化合物，进一步，通式(1)中的
Figure PCTCN2017099587-appb-000005
表示为：
Figure PCTCN2017099587-appb-000006
Figure PCTCN2017099587-appb-000007
Figure PCTCN2017099587-appb-000008
Figure PCTCN2017099587-appb-000009
Figure PCTCN2017099587-appb-000010
Figure PCTCN2017099587-appb-000011
Figure PCTCN2017099587-appb-000012
或
Figure PCTCN2017099587-appb-000013
中的任一种。
本发明如上所述一种以芴和含氮六元杂环为核心的化合物，进一步，所述化合物的具体结构式为：
Figure PCTCN2017099587-appb-000014
Figure PCTCN2017099587-appb-000015
Figure PCTCN2017099587-appb-000016
Figure PCTCN2017099587-appb-000017
Figure PCTCN2017099587-appb-000018
Figure PCTCN2017099587-appb-000019
中的任一种。
本发明如上所述一种以芴和含氮六元杂环为核心的化合物，进一步，该制备方法中的反应方程式为：
Figure PCTCN2017099587-appb-000020
Figure PCTCN2017099587-appb-000021
其中，R1、R2、R3分别为苯基、联苯基、萘基、吡啶基、喹啉基、异喹啉基、菲罗啉基、苯并咪唑基、苯并恶唑基、吡啶并吲哚基、喹喔啉基或萘啶基中的一种；
所述制备方法以Br-Ar-Br为原料，通过格氏反应，制得格氏试剂，然后和9-芴酮反应，生成叔醇；随后叔醇和H-R1通过傅-克反应，制得一溴代化合物，然后和
Figure PCTCN2017099587-appb-000022
通过C-C偶联制得所述化合物。
上述制备方法具体地包括以下步骤：
1)Br-Ar-Br和镁粉为原料，所述Br-Ar-Br和镁粉摩尔比例为1:1，加入四氢呋喃，氮气氛围下，加热至70℃，回流反应3-5小时，无镁粉剩余，反应完全，生成格式试剂；上述的所述四氢呋喃的用量优选为1gBr-Ar-Br加入3-6ml四氢呋喃，
2)称取9-芴酮溶于四氢呋喃中，所述9-芴酮和所述Br-Ar-Br摩尔比为1:1，然后滴加步骤1)制备的格式试剂，滴加结束后，加热至60-70℃，回流反应10-25小时，生成大量白色的格式盐沉淀，反应结束，然后滴加饱和NHCl4溶液，将所述格式盐转化为叔醇；再用乙醚萃取获得萃取液，所述萃取液用无水硫酸钠干燥，然后旋蒸脱溶剂至无馏分，获得叔醇粗产物，所得叔醇粗产物用石油醚：二氯甲烷混合溶剂过中性硅胶柱，得到固体叔醇纯化产物；优选地上述的石油醚：二氯甲烷的体积比3:2；步骤2)中的所述四氢呋喃的用量优选为每1g9-芴酮溶于4-8ml四氢呋喃；所述乙醚的用量为1g叔醇加入5-10ml乙醚中。
3)按1:2当量称取固体叔醇纯化产物和R1-H，溶于二氯甲烷中，所述二氯甲烷的用量为1g固体叔醇纯化产物溶于5-8ml二氯甲烷中，室温条件下再滴加三 氟化硼·乙醚络合物，所述固体叔醇纯化产物与三氟化硼·乙醚络合物摩尔比例为1:1.5，反应30-60分钟，然后加入乙醇和水淬灭反应，然后用二氯甲烷萃取，无水硫酸钠干燥，旋蒸脱溶剂至馏分，石油醚过中性硅胶柱，乙醇：二氯甲烷混合溶剂重结晶，得一溴代化合物；优选地，所述乙醇：二氯甲烷混合溶剂中乙醇和二氯甲烷体积比1:1。
4)以一溴代化合物和硼酸化合物
Figure PCTCN2017099587-appb-000023
为原料，甲苯溶解，所述甲苯用量为1g一溴代化合物使用30-50ml甲苯，其中，所述一溴代化合物与硼酸化合物
Figure PCTCN2017099587-appb-000024
的摩尔比为1:(1.2～1.5)；
5)向步骤4)最终的反应体系中加入Pd(PPh3)4和碳酸钠；
其中，优选地，所述Pd(PPh3)4与一溴代化合物的摩尔比为(0.005～0.02):1，所述碳酸钠与一溴代化合物的摩尔比为(1.5～3.0):1；
6)在氮气保护下，将步骤5)获得的混合溶液于95～110℃，反应10～24小时，自然冷却至室温，并过滤反应溶液，滤液旋蒸至无溶剂，过中性硅胶柱，得到目标产物。
本发明一种上述以芴和含氮六元杂环为核心的化合物在有机发光器件中的应用。
本发明提供一种有机电致发光器件，所述有机电致发光器件包括至少一层功能层含有上述的含有二苯并六元环和含氮六元杂环的有机化合物。
本发明提供一种有机发光器件，包括空穴阻挡/电子传输层层，所述空穴阻挡/电子传输层为上述以芴和含氮六元杂环为核心的化合物。
本发明如上所述一种有机发光器件，进一步，还包括透明基板层、ITO阳极层、空穴注入层、空穴传输/电子阻挡层、发光层、电子注入层及阴极反射电极层，所述透明基板层、ITO阳极层、空穴注入层、空穴传输/电子阻挡层、发光层、 空穴阻挡/电子传输层、电子注入层及阴极反射电极层从下至上依次层叠布置。
本发明如上所述一种有机发光器件，进一步，所述ITO阳极层厚度为130-150nm；或/和所述空穴注入层为材料HAT-CN，厚度为10nm；或/和所述空穴传输/电子阻挡层为穴传输材料NPB，厚度为80nm，或/和所述发光层以CBP作为主体材料，Ir(ppy)作为磷光掺杂材料，掺杂质量比为10％，厚度为30nm，或/和所述空穴阻挡/电子传输层的厚度为40nm，和/或所述电子注入层的为LiF材料，其厚度为1nm，和/或所述阴极反射电极层为材料Al，其厚度为100nm。
本发明如上所述一种有机发光器件，包括发光层，所述发光层为以上述以芴和含氮六元杂环为核心的化合物和化合物GHN为主体材料，掺杂材料为Ir(ppy)3，所述以芴和含氮六元杂环为核心的化合物、化合物GHN及Ir(ppy)3的混掺质量比为60:30:10，其中，所述化合物GHN的结构式为
Figure PCTCN2017099587-appb-000025
本发明如上所述一种有机发光器件，进一步，还包括透明基板层、ITO阳极层、空穴注入层、空穴传输/电子阻挡层、发光层、空穴阻挡/电子传输层、电子注入层及阴极反射电极层，所述透明基板层、ITO阳极层、空穴注入层、空穴传输/电子阻挡层、发光层、空穴阻挡/电子传输层、电子注入层及阴极反射电极层从下至上依次层叠布置。
本发明如上所述一种有机发光器件，进一步，还包括透明基板层、ITO阳极层、空穴注入层、空穴传输/电子阻挡层、发光层、空穴阻挡/电子传输层、电子注入层及阴极反射电极层，所述透明基板层、ITO阳极层、空穴注入层、空穴传输/电子阻挡层、发光层、空穴阻挡/电子传输层、电子注入层及阴极反射电极层从下至上依次层叠布置。上述优选地所述ITO层为阳极层厚度为130-150nm；或/和所述空穴注入层为材料HAT-CN，厚度为10nm；或/和所述空穴传输/电子阻挡 层为穴传输材料NPB，厚度为80nm，或/和所述发光层厚度为30nm，或/和所述空穴阻挡/电子传输层材料为TPBI，其厚度为40nm，和/或所述电子注入层的为LiF材料，其厚度为1nm，和/或所述阴极反射电极层为材料Al，其厚度为100nm。
本发明提供一种有机发光器件的制备方法，包括以下步骤：
步骤a)清洗透明基板层上的ITO阳极层；
步骤b)在ITO阳极层上，通过真空蒸镀方式蒸镀空穴注入层材料HAT-CN作为空穴注入层；
步骤c)在空穴注入层上，通过真空蒸镀方式蒸镀空穴传输材料NPB作为空穴传输层/电子阻挡层；
步骤d)在空穴传输/电子阻挡层之上蒸镀发光层，所述发光层以CBP作为主体材料，Ir(ppy)作为磷光掺杂材料；
步骤e)在发光层之上，使用上述以芴和含氮六元杂环为核心的化合物作为空穴阻挡层/电子传输层材料；
步骤f)在空穴阻挡/电子传输层之上，真空蒸镀电子注入层LiF；
步骤g)在电子注入层之上，真空蒸镀阴极Al作为阴极反射电极层。
本发明化合物以芴和含氮六元杂环为骨架，通过芳香基团连接，其中的含氮六元杂环为强电子性基团，通过芴或芳香基团的修饰，使HOMO能级自由调整，可以作为电子型发光材料使用，也可以作为空穴阻挡/电子传输层材料使用。且由于芴的9位引入不同基团，破坏分子对称性，避免分子间的聚集作用，分子结构中，各基团刚性较强，具有高的玻璃化温度及热稳定性，本发明化合物应用于OLED器件时，可保持材料成膜后的膜层稳定性，提高OLED器件使用寿命。
附图说明
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为透明基板层，2为ITO阳极层，3为空穴注入层，4为空穴传输/电 子阻挡层，5为发光层，6为空穴阻挡/电子传输层，7为电子注入层，8为阴极反射电极层。
具体实施方式
以下结合附图对本发明的原理和特征进行描述，所举实例只用于解释本发明，并非用于限定本发明的范围。
实施例1
原料A1的合成：
合成路线如下：
Figure PCTCN2017099587-appb-000026
250ml的四口瓶，在通入氮气的气氛下，加入15.6g 3,4'-二溴-1,1'-联苯(0.05mol)和1.33gMg粉(0.05mol)，60ml四氢呋喃，加热至70℃，回流反应4小时，无镁粉剩余，反应完全，生成格式试剂；
9.01g 9-芴酮(0.05mol)溶于50ml四氢呋喃中，滴加上述格式试剂，60℃反应24小时，生成大量白色沉淀，最后加入饱和NHCl4将格式盐转化为醇；反应完毕后，乙醚萃取，干燥旋蒸，石油醚：二氯甲烷混合溶剂(3:2)硅胶柱纯化，得到略带黄色的固体叔醇(收率为91％)；使用DEI-MS来识别该化合物，分子式C25H17BrO，检测值[M+1]+＝413.02，计算值412.05；
按1:2当量取16.5g上述叔醇(0.04mol)和6.24g苯(0.08mol)溶于100ml二氯甲烷中，在室温条件下滴加8ml三氟化硼·乙醚络合物，反应30分钟，加入20ml乙醇和20ml水淬灭反应，用二氯甲烷(20ml*3)萃取，干燥旋蒸，石油醚硅胶柱纯化，用乙醇：二氯甲烷重结晶，收率为72％；使用DEI-MS来识别该化合物，分子式C31H21Br，检测值[M+1]+＝473.04，计算值472.08。
实施例2
原料A2的合成：
合成路线：
Figure PCTCN2017099587-appb-000027
按实施例1中的原料A1的合成方法制备原料A2，不同点在于用1,4-二溴苯代替3,4'-二溴-1,1'-联苯，第三步反应中用联苯代替苯；
使用DEI-MS来识别该化合物，分子式C31H21Br，检测值[M+1]+＝473.06，计算值472.08。
实施例3
原料A3的合成：
合成路线：
Figure PCTCN2017099587-appb-000028
Figure PCTCN2017099587-appb-000029
按实施例1中的原料A1的合成方法制备原料A3，不同点在于用1,4-二溴苯代替3,4'-二溴-1,1'-联苯；
使用DEI-MS来识别该化合物，分子式C25H17Br，检测值[M+1]+＝397.11，计算值396.05。
实施例4
原料A4的合成：
合成路线：
Figure PCTCN2017099587-appb-000030
按实施例1中的原料A1的合成方法制备原料A4，不同点在于第三步反应中用联苯代替苯；
使用DEI-MS来识别该化合物，分子式C37H25Br，检测值[M+1]+＝549.08，计算值548.11。
实施例5
原料A5的合成：
合成路线：
Figure PCTCN2017099587-appb-000031
按实施例1中的原料A1的合成方法制备原料A5，不同点在于用4,4'-二溴-1,1'-联苯代替3,4'-二溴-1,1'-联苯；
使用DEI-MS来识别该化合物，分子式C31H21Br，检测值[M+1]+＝473.15，计算值472.08。
实施例6
原料A6的合成：
合成路线：
Figure PCTCN2017099587-appb-000032
Figure PCTCN2017099587-appb-000033
按实施例1中的原料A1的合成方法制备原料A2，不同点在于用1,4-二溴苯代替3,4'-二溴-1,1'-联苯，第三步反应中用吡啶代替苯；
使用DEI-MS来识别该化合物，分子式C24H16BrN，检测值[M+1]+＝397.98，计算值397.05。
实施例7化合物3的合成：
合成路线：
Figure PCTCN2017099587-appb-000034
250ml的四口瓶，在通入氮气的气氛下，加入0.01mol原料A3，0.012mol原料B1，0.02mol碳酸钠，1×10-4mol Pd(PPh3)4，150ml甲苯，加热至105℃回流24小时，取样点板，显示无溴代物剩余，反应完全；自然冷却，过滤，滤液旋蒸至无馏分，过中性硅胶柱，得到目标产物，纯度99.4％，收率77.5％。
元素分析结构(分子式C40H27N3)：理论值C,87.40；H,4.95；N,7.64；测试值：C,87.41；H,4.95；N,7.63。
HPLC-MS：材料分子量为549.22，实测分子量549.45。
实施例8化合物4的合成：
合成路线：
Figure PCTCN2017099587-appb-000035
250ml的四口瓶，在通入氮气的气氛下，加入0.01mol原料A3，0.012mol原料B2，0.02mol碳酸钠，1×10-4mol Pd(PPh3)4，150ml甲苯，加热至105℃回流24小时，取样点板，显示无溴代物剩余，反应完全；自然冷却，过滤，滤液旋蒸至无馏分，过中性硅胶柱，得到目标产物，纯度99.5％，收率79.2％。
元素分析结构(分子式C41H28N2)：理论值C,89.75；H,5.14；N,5.11；测试值：C,89.76；H,5.12；N,5.12。
HPLC-MS：材料分子量为548.23，实测分子量548.49。
实施例9化合物5的合成：
合成路线：
Figure PCTCN2017099587-appb-000036
250ml的四口瓶，在通入氮气的气氛下，加入0.01mol原料A1，0.012mol原料B3，0.02mol碳酸钠，1×10-4mol Pd(PPh3)4，150ml甲苯，加热至105℃回流24小时，取样点板，显示无溴代物剩余，反应完全；自然冷却，过滤，滤液旋蒸至无馏分，过中性硅胶柱，得到目标产物，纯度99.3％，收率78.1％。
元素分析结构(分子式C48H33N)：理论值C,92.42；H,5.33；N,2.25；测试值：C,92.40；H,5.34；N,2.26。
HPLC-MS：材料分子量为623.26，实测分子量623.51。
实施例10化合物7的合成：
合成路线：
Figure PCTCN2017099587-appb-000037
250ml的四口瓶，在通入氮气的气氛下，加入0.01mol原料A2，0.012mol原料B3，0.02mol碳酸钠，1×10-4mol Pd(PPh3)4，150ml甲苯，加热至105℃回流24小时，取样点板，显示无溴代物剩余，反应完全；自然冷却，过滤，滤液旋蒸至无馏分，过中性硅胶柱，得到目标产物，纯度99.5％，收率74.3％。
元素分析结构(分子式C48H33N)：理论值C,92.42；H,5.33；N,2.25；测试值：C,92.43；H,5.32；N,2.25。
HPLC-MS：材料分子量为623.26，实测分子量623.53。
实施例11化合物13的合成：
合成路线：
Figure PCTCN2017099587-appb-000038
250ml的四口瓶，在通入氮气的气氛下，加入0.01mol原料A3，0.012mol原料B4，0.02mol碳酸钠，1×10-4mol Pd(PPh3)4，150ml甲苯，加热至105℃回流24小时，取样点板，显示无溴代物剩余，反应完全；自然冷却，过滤，滤液旋蒸至无馏分，过中性硅胶柱，得到目标产物，纯度99.7％，收率78.9％。
元素分析结构(分子式C42H29N)：理论值C,92.11；H,5.34；N,2.56；测试值：C,92.10；H,5.35；N,2.55。
HPLC-MS：材料分子量为547.23，实测分子量547.49。
实施例12化合物15的合成：
合成路线：
Figure PCTCN2017099587-appb-000039
250ml的四口瓶，在通入氮气的气氛下，加入0.01mol原料A3，0.012mol原料B5，0.02mol碳酸钠，1×10-4mol Pd(PPh3)4，150ml甲苯，加热至105℃回流24小时，取样点板，显示无溴代物剩余，反应完全；自然冷却，过滤，滤液旋蒸至无馏分，过中性硅胶柱，得到目标产物，纯度99.2％，收率77.8％。
元素分析结构(分子式C40H27N3)：理论值C,87.40；H,4.95；N,7.64；测试值：C,87.41；H,4.965；N,7.63。
HPLC-MS：材料分子量为549.22，实测分子量549.47。
实施例13化合物26的合成：
合成路线：
Figure PCTCN2017099587-appb-000040
250ml的四口瓶，在通入氮气的气氛下，加入0.01mol原料A3，0.012mol原料C1，0.02mol碳酸钠，1×10-4mol Pd(PPh3)4，150ml甲苯，加热至105℃回流24小时，取样点板，显示无溴代物剩余，反应完全；自然冷却，过滤，滤液旋蒸至无馏分，过中性硅胶柱，得到目标产物，纯度99.6％，收率77.3％。
元素分析结构(分子式C39H26N4)：理论值C,85.07；H,4.76；N,10.17；测试值：C,85.06；H,4.78；N,10.16。
HPLC-MS：材料分子量为550.22，实测分子量550.43。
实施例14化合物28的合成：
合成路线：
Figure PCTCN2017099587-appb-000041
250ml的四口瓶，在通入氮气的气氛下，加入0.01mol原料A4，0.012mol原料C2，0.02mol碳酸钠，1×10-4mol Pd(PPh3)4，150ml甲苯，加热至105℃回流24小时，取样点板，显示无溴代物剩余，反应完全；自然冷却，过滤，滤液旋蒸至无馏分，过中性硅胶柱，得到目标产物，纯度99.1％，收率65.1％。
元素分析结构(分子式C53H36N2)：理论值C,90.83；H,5.18；N,4.00；测试值：C,90.81；H,5.17；N,4.02。
HPLC-MS：材料分子量为700.29，实测分子量700.55。
实施例15化合物35的合成：
合成路线：
Figure PCTCN2017099587-appb-000042
250ml的四口瓶，在通入氮气的气氛下，加入0.01mol原料A5，0.012mol原料C1，0.02mol碳酸钠，1×10-4mol Pd(PPh3)4，150ml甲苯，加热至105℃回流24小时，取样点板，显示无溴代物剩余，反应完全；自然冷却，过滤，滤液旋蒸至无馏分，过中性硅胶柱，得到目标产物，纯度99.4％，收率71.7％。
元素分析结构(分子式C45H30N4)：理论值C,86.24；H,4.82；N,8.94；测试 值：C,86.22；H,4.83；N,8.95。
HPLC-MS：材料分子量为626.25，实测分子量626.52。
实施例16化合物40的合成：
合成路线：
Figure PCTCN2017099587-appb-000043
按实施例9中化合物5的合成方法制备，不同点在于用原料C3代替原料B3；
元素分析结构(分子式C47H32N2)：理论值C,90.35；H,5.16；N,4.48；测试值：C,90.38；H,5.15；N,4.47。
HPLC-MS：材料分子量为624.26，实测分子量625.54。
实施例17化合物42的合成：
合成路线：
Figure PCTCN2017099587-appb-000044
按实施例10中化合物7的合成方法制备，不同点在于用原料C3代替原料B3；
元素分析结构(分子式C47H32N2)：理论值C,90.35；H,5.16；N,4.48；测试值：C,90.36；H,5.17；N,4.47。
HPLC-MS：材料分子量为624.26，实测分子量624.53。
实施例18化合物44的合成：
合成路线：
Figure PCTCN2017099587-appb-000045
按实施例7中化合物3的合成方法制备，不同点在于用原料C4代替原料B1；
元素分析结构(分子式C47H32N2)：理论值C,90.35；H,5.16；N,4.48；测试值：C,90.37；H,5.15；N,4.48。
HPLC-MS：材料分子量为624.26，实测分子量624.57。
实施例19化合物47的合成：
合成路线：
Figure PCTCN2017099587-appb-000046
按实施例7中化合物3的合成方法制备，不同点在于用原料D1代替原料B1；
元素分析结构(分子式C40H27N3)：理论值C,87.40；H,4.95；N,7.64；测试值：C,87.40；H,4.95；N,7.65。
HPLC-MS：材料分子量为549.22，实测分子量549.45。
实施例20化合物51的合成：
合成路线：
Figure PCTCN2017099587-appb-000047
按实施例9中化合物5的合成方法制备，不同点在于用原料D1代替原料B3；
元素分析结构(分子式C46H31N3)：理论值C,88.29；H,4.99；N,6.72；测试值：C,88.30；H,5.00；N,6.70。
HPLC-MS：材料分子量为625.25，实测分子量625.56。
实施例21化合物53的合成：
合成路线：
Figure PCTCN2017099587-appb-000048
按实施例10中化合物7的合成方法制备，不同点在于用原料D1代替原料B3；
元素分析结构(分子式C46H31N3)：理论值C,88.29；H,4.99；N,6.72；测试值：C,88.27；H,5.00；N,6.73。
HPLC-MS：材料分子量为625.25，实测分子量625.59。
实施例22化合物58的合成：
合成路线：
Figure PCTCN2017099587-appb-000049
250ml的四口瓶，在通入氮气的气氛下，加入0.01mol原料A6，0.012mol原料D1，0.02mol碳酸钠，1×10-4mol Pd(PPh3)4，150ml甲苯，加热至105℃回流24小时，取样点板，显示无溴代物剩余，反应完全；自然冷却，过滤，滤液旋蒸至无馏分，过中性硅胶柱，得到目标产物，纯度99.4％，收率71.7％。
元素分析结构(分子式C39H26N4)：理论值C,85.07；H,4.76；N,10.17；测试值：C,85.07；H,4.75；N,10.18。
HPLC-MS：材料分子量为550.22，实测分子量550.47。
以下，通过器件实施例1-10和器件比较例1详细说明本发明所提供的化合物作为空穴阻挡或电子传输层材料以及发光层材料，应用在电致发光器件上，并以比较例1证明其有益效果。各实施例所得器件的性能测试结果如表1所示。
器件实施例1
一种电致发光器件，其制备步骤包括：
a)清洗透明基板层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，该层为空穴传输层或电子阻挡层4；
d)在空穴传输或电子阻挡层4之上蒸镀发光层5，CBP作为主体材料，Ir(ppy)3作为磷光掺杂材料，Ir(ppy)3和CBP的质量比为1:9，厚度为30nm；
e)在发光层5之上，使用本发明化合物3作为空穴阻挡层或电子传输层材料，厚度为40nm，这层有机材料作为空穴阻挡或电子传输层6使用；
f)在空穴阻挡或电子传输层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Al(100nm)，该层为阴极反射电极层8；
按照上述步骤完成电致发光器件的制作后，测量器件的驱动电压，电流效率，其结果见表1所示。
相关材料的分子机构式如下所示：
Figure PCTCN2017099587-appb-000050
器件实施例2
本实施例与器件实施例1的不同之处在于：电致发光器件的空穴阻挡或电子传输层6材料变为本发明化合物4。所得电致发光器件的检测数据见表1所示。
器件实施例3
本实施例与器件实施例1的不同之处在于：电致发光器件的空穴阻挡或电子传输层6材料变为本发明化合物15。所得电致发光器件的检测数据见表1所示。
器件实施例4
本实施例与器件实施例1的不同之处在于：电致发光器件的空穴阻挡或电子传输层6材料变为本发明化合物26。所得电致发光器件的检测数据见表1所示。
器件实施例5
本实施例与器件实施例1的不同之处在于：电致发光器件的空穴阻挡/电子传输层6材料变为本发明化合物35。所得电致发光器件的检测数据见表1所示。
器件实施例6
本实施例与器件实施例1的不同之处在于：电致发光器件的空穴阻挡或电子传输层6材料变为TPBI，发光层主体材料变为本发明化合物5，掺杂材料为Ir(ppy)3，本发明化合物5及掺杂材料Ir(ppy)3的质量比为9：1，所得电致发光 器件的检测数据见表1所示。
器件实施例7
本实施例与器件实施例1的不同之处在于：电致发光器件的空穴阻挡或电子传输层6材料变为TPBI，发光层主体材料变为本发明化合物42，掺杂材料为Ir(ppy)3，本发明化合物42及掺杂材料Ir(ppy)3的质量比为9：1，所得电致发光器件的检测数据见表1所示。
器件实施例8
本实施例与器件实施例1的不同之处在于：电致发光器件的空穴阻挡或电子传输层6材料变为TPBI，发光层主体材料变为本发明化合物51和化合物GHN，掺杂材料为Ir(ppy)3，本发明化合物51、化合物GHN及掺杂材料为Ir(ppy)3的混掺质量比为60:30:10，所得电致发光器件的检测数据见表1所示。
器件实施例9
本实施例与器件实施例1的不同之处在于：电致发光器件的空穴阻挡或电子传输层6材料变为TPBI，发光层主体材料变为本发明化合物53和化合物GHN，掺杂材料为Ir(ppy)3，本发明化合物53、化合物GHN及掺杂材料为Ir(ppy)3混掺的质量比为60:30:10，所得电致发光器件的检测数据见表1所示。
器件实施例10
本实施例与器件实施例1的不同之处在于：电致发光器件的空穴阻挡或电子传输层6材料变为两层，其中本发明化合物58单独作为空穴阻挡层使用，厚度为5nm，所述下列结构化合物A和化合物B按照质量比1:1的比例相互混合作为电子传输层使用，其厚度为35nm。所得电致发光器件的检测数据见表1所示。
Figure PCTCN2017099587-appb-000051
器件比较例1
本比较例与器件实施例1的不同之处在于：电致发光器件的空穴阻挡或电子传输层6材料变为TPB I。所得电致发光器件的检测数据见表1所示。
表1
编号 电流效率 色彩 LT95寿命
器件实施例1 1.3 绿光 3.3
器件实施例2 1.2 绿光 2.9
器件实施例3 1.4 绿光 3.5
器件实施例4 1.3 绿光 3.1
器件实施例5 1.4 绿光 3.4
器件实施例6 1.5 绿光 5.1
器件实施例7 1.4 绿光 4.5
器件实施例8 1.7 绿光 8.2
器件实施例9 1.6 绿光 7.5
器件实施例10 1.5 绿光 4.5
器件比较例1 1.0 绿光 1.0
注：器件测试性能以器件比较例1作为参照，比较例1器件各项性能指标设为1.0。比较例1的电流效率为28cd/A(@10mA/cm2)；CIE色坐标为(0.33,0.63)；5000亮度下LT95寿命衰减为2.5Hr。
上述的空穴阻挡层也称为电子传输层。
由表1的结果可以看出本发明有机化合物可应用于OLED发光器件制作，并且与比较例相比，无论是效率还是寿命均比已知OLED材料获得较大改观，特别是器件的使用寿命获得较大的提升。
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 (12)

  1. 一种以芴和含氮六元杂环为核心的化合物，其特征在于，所述化合物具有如下结构通式(1)：
    Figure PCTCN2017099587-appb-100001
    所述通式(1)中，R1、R2、R3分别独立的表示为苯基、联苯基、萘基、吡啶基、喹啉基、异喹啉基、菲罗啉基、苯并咪唑基、苯并恶唑基、吡啶并吲哚基、喹喔啉基或萘啶基中的一种；
    通式(1)中，Ar表示为苯基、联苯基、萘基或吡啶基中的一种；
    通式(1)中，
    Figure PCTCN2017099587-appb-100002
    表示为含氮六元杂环，n＝1、2或3。
  2. 根据权利要求1所述一种以芴和含氮六元杂环为核心的化合物，其特征在于，通式(1)中的
    Figure PCTCN2017099587-appb-100003
    为通式(2)、通式(3)、通式(4)、通式(5)或通式(6)表示：
    Figure PCTCN2017099587-appb-100004
    其中，R2、R3分别独立的表示为苯基、联苯基、萘基、吡啶基、喹啉基、异喹啉基、菲罗啉基、苯并咪唑基、苯并恶唑基、吡啶并吲哚基、喹喔啉基或萘啶基中的一种。
  3. 根据权利要求1所述一种以芴和含氮六元杂环为核心的化合物，其特征 在于，通式(1)中的
    Figure PCTCN2017099587-appb-100005
    表示为：
    Figure PCTCN2017099587-appb-100006
    Figure PCTCN2017099587-appb-100007
    Figure PCTCN2017099587-appb-100008
    Figure PCTCN2017099587-appb-100009
    Figure PCTCN2017099587-appb-100010
    Figure PCTCN2017099587-appb-100011
    Figure PCTCN2017099587-appb-100012
    中的任一种
  4. 根据权利要求1所述的化合物，其特征在于，所述化合物的具体结构式为：
    Figure PCTCN2017099587-appb-100013
    Figure PCTCN2017099587-appb-100014
    Figure PCTCN2017099587-appb-100015
    Figure PCTCN2017099587-appb-100016
    Figure PCTCN2017099587-appb-100017
    Figure PCTCN2017099587-appb-100018
    中的任一种。
  5. 一种权利要求1所述有机化合物的制备方法，其特征在于该制备方法中的反应方程式为：
    Figure PCTCN2017099587-appb-100019
    其中，R1、R2、R3分别为苯基、联苯基、萘基、吡啶基、喹啉基、异喹啉基、菲罗啉基、苯并咪唑基、苯并恶唑基、吡啶并吲哚基、喹喔啉基或萘啶基中的一 种；
    Ar为苯基、联苯基、萘基或吡啶基中的一种；
    Figure PCTCN2017099587-appb-100020
    为含氮六元杂环，n＝1、2或3；
    所述制备方法以Br-Ar-Br为原料，通过格氏反应，制得格氏试剂，然后和9-芴酮反应，生成叔醇；随后叔醇和H-R1通过傅-克反应，制得一溴代化合物，然后和
    Figure PCTCN2017099587-appb-100021
    通过C-C偶联制得所述化合物。
  6. 一种权利要求1至5任一项所述以芴和含氮六元杂环为核心的化合物在有机发光器件中的应用。
  7. 一种有机电致发光器件，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权利要求1至4任一项所述的含有二苯并六元环和含氮六元杂环的有机化合物。
  8. 一种有机发光器件，包括空穴阻挡/电子传输层6，其特征在于，所述空穴阻挡/电子传输层为权利要求1至5任一项所述以芴和含氮六元杂环为核心的化合物。
  9. 根据权利要求8所述一种有机发光器件，其特征在于，还包括透明基板层、ITO阳极层、空穴注入层、空穴传输/电子阻挡层、发光层、电子注入层及阴极反射电极层，所述透明基板层、ITO阳极层、空穴注入层、空穴传输/电子阻挡层、发光层、空穴阻挡/电子传输层、电子注入层及阴极反射电极层从下至上依次层叠布置。
  10. 根据权利要求9所述一种有机发光器件，其特征在于，所述空穴注入层为材料HAT-CN，厚度为10nm；或/和所述空穴传输/电子阻挡层为穴传输材料NPB，厚度为80nm，或/和所述发光层5以CBP作为主体材料，Ir(ppy)3作为磷光掺杂材料，掺杂质量比为10％，厚度为30nm，或/和所述空穴阻挡/电子传输层的厚度为40nm，和/或所述电子注入层的为LiF材料，其厚度为1nm，和/或所述阴极反 射电极层为材料Al，其厚度为100nm。
  11. 一种有机发光器件，包括发光层，其特征在于，所述发光层为以权利要求1至5任一项所述以芴和含氮六元杂环为核心的化合物和化合物GHN为主体材料，掺杂材料为Ir(ppy)3，所述权利要求1至5任一项所述以芴和含氮六元杂环为核心的化合物、化合物GHN及Ir(ppy)3的混掺质量比为60:30:10，其中，所述化合物GHN的结构式为
    Figure PCTCN2017099587-appb-100022
  12. 一种有机发光器件的制备方法，其特征在于，包括以下步骤：
    步骤a)清洗透明基板层上的ITO阳极层；
    步骤b)在ITO阳极层上，通过真空蒸镀方式蒸镀空穴注入层材料HAT-CN作为空穴注入层；
    步骤c)在空穴注入层上，通过真空蒸镀方式蒸镀空穴传输材料NPB作为空穴传输层/电子阻挡层；
    步骤d)在空穴传输/电子阻挡层之上蒸镀发光层，以CBP作为主体材料，Ir(ppy)3作为磷光掺杂材料；
    步骤e)在发光层之上，使用权利要求1至5任一项所述以芴和含氮六元杂环为核心的化合物作为空穴阻挡层/电子传输层材料；
    步骤f)在空穴阻挡/电子传输层之上，真空蒸镀电子注入层LiF；
    步骤g)在电子注入层之上，真空蒸镀阴极Al作为阴极反射电极层。
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