WO2022068528A1 - Light-emitting material and use thereof, and organic electroluminescent device comprising same - Google Patents

Light-emitting material and use thereof, and organic electroluminescent device comprising same Download PDF

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WO2022068528A1
WO2022068528A1 PCT/CN2021/116592 CN2021116592W WO2022068528A1 WO 2022068528 A1 WO2022068528 A1 WO 2022068528A1 CN 2021116592 W CN2021116592 W CN 2021116592W WO 2022068528 A1 WO2022068528 A1 WO 2022068528A1
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ring
compound
light
fused
monocyclic
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Chinese (zh)
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段炼
张跃威
张东东
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清华大学
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Priority to KR1020237003354A priority patent/KR20230048311A/en
Publication of WO2022068528A1 publication Critical patent/WO2022068528A1/en

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    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
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Definitions

  • the present invention relates to the technical field of organic electroluminescence, in particular to an organic compound and its application and an organic electroluminescence device comprising the compound.
  • OLED Organic Light Emission Diodes
  • OLED Organic Light Emission Diodes
  • MR-TADF materials have the advantages of high color purity and high luminous efficiency, which have attracted extensive attention in scientific research and industrial circles.
  • peripheral substituents have little effect on the S 1 energy level, that is, it is difficult to control the emission color of the material, and its light color has always been limited to the blue-deep blue light region, which greatly limits the high-resolution display of MR-TADF materials. , full-color display and further applications in the field of white lighting.
  • the present invention provides a kind of organic compound, and the specific general formula of the compound of the present invention is shown in the following formula (1):
  • ring A, ring B, ring C, and ring D each independently represent any of a C5-C20 monocyclic aromatic ring or a condensed aromatic ring, a C4-C20 monocyclic heterocyclic ring or a condensed heterocyclic ring.
  • Ring E represents an aromatic ring of C5 ⁇ C20;
  • the ring A and the ring B can be connected by a single bond, and the ring C and the ring D can be connected by a single bond;
  • Said Y 1 and Y 2 are each independently N or B;
  • Said X 1 , X 2 , X 3 and X 4 are each independently NR 1 , BR 2 , O or S;
  • the R 1 and R 2 are independently selected from one of the following substituted or unsubstituted groups: C1-C36 chain alkyl, C3-C36 cycloalkyl, C6-C30 arylamino, C3 ⁇ C30 heteroarylamino, C6-C60 monocyclic aryl, C6-C60 fused-ring aryl, C6-C60 aryloxy, C5-C60 monocyclic heteroaryl or C5-C60 fused-ring heteroaryl Aryl;
  • the R 1 can be connected to the adjacent ring A, ring B, ring C or ring D through a single bond, or can be condensed with the adjacent ring A, ring B, ring C or ring D to bond with each other to form a ring ;
  • the R 2 can be connected with the adjacent ring A, ring B, ring C or ring D through a single bond, or can be fused with the adjacent ring A, ring B, ring C or ring D to form a bond with each other ring;
  • the X 1 and X 3 can be connected by a single bond, or can be fused to form a ring; the X 2 and X 4 can be connected by a single bond, or can be fused to form a mutual bond ring;
  • the R a , R b , R c and R d each independently represent a mono-substituent to the maximum allowable substituent, and are each independently selected from hydrogen, deuterium, or one of the following groups, substituted or unsubstituted: Halogen, C1-C36 chain alkyl, C3-C36 cycloalkyl, C1-C10 alkoxy, C1-C10 thioalkoxy, carbonyl, carboxyl, nitro, cyano, amino, C6 ⁇ C30 arylamino, C3 ⁇ C30 heteroarylamino, C6-C60 monocyclic aryl, C6-C60 fused-ring aryl, C6-C60 aryloxy, C5-C60 monocyclic heteroaryl , a C5-C60 condensed ring heteroaryl; the adjacent two of the R a , R b , R c and R d can optionally be connected by a single bond or can be fused
  • the substituents are independently selected from deuterium, halogen, C1-C30 chain alkyl, C3-C30 cycloalkyl, C1-C10 alkoxy, C1-C10 thioalkoxy, carbonyl, carboxyl, nitro, cyano, amino, C6-C30 arylamino, C3-C30 heteroarylamino, C6-C60 monocyclic aryl, C6-C60 fused ring Any of an aryl group, a C6-C60 aryloxy group, a C5-C60 monocyclic heteroaryl group, and a C5-C60 condensed ring heteroaryl group.
  • the ring A, ring B, ring C and ring D each independently represent a C5-C10 monocyclic aromatic ring or a condensed aromatic ring, a C4-C10 monocyclic heterocyclic ring or a condensed aromatic ring Any of the heterocyclic rings, the ring E represents a C5-C10 monocyclic aromatic ring or a condensed aromatic ring.
  • the ring A, ring B, ring C and ring D are each independently selected from any one of a benzene ring, a naphthalene ring or a fluorene ring, and the ring E is selected from a benzene ring , any one of naphthalene ring or fluorene ring.
  • each independent X 1 , X 2 , X 3 , and X 4 have the following preferred solutions:
  • X 1 , X 2 , X 3 and X 4 are BR 2 , and the other two are NR 1 ;
  • X 1 , X 2 , X 3 , and X 4 are BR 2 , and the other two are O;
  • X 1 , X 2 , X 3 , and X 4 are BR 2 , and the other two are S;
  • X 1 , X 2 , X 3 , and X 4 are BR 2 and the other is NR 1 ;
  • one of X 1 , X 2 , X 3 , and X 4 is BR 2 , and the other three are NR 1 ;
  • two of X 1 , X 2 , X 3 , and X 4 are BR 2 , one is NR 1 , and the other is O;
  • one of X 1 , X 2 , X 3 , and X 4 is BR 2 , two are NR 1 , and the other is O;
  • two of X 1 , X 2 , X 3 , and X 4 are BR 2 , one is NR 1 , and the other is O;
  • two of X 1 , X 2 , X 3 , and X 4 are BR 2 , one is NR 1 , and the other is O;
  • X 1 , X 2 , X 3 , and X 4 are all S;
  • one of X 1 , X 2 , X 3 , and X 4 is O, and the other three are S;
  • one of X 1 , X 2 , X 3 , and X 4 is NR 1 , and the other three are NR 1 .
  • R a , R b , R c and R d are independently selected from hydrogen, deuterium or substituted or unsubstituted following One of the substituent groups: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, 2-methylbutyl, n-pentyl, sec Pentyl, cyclopentyl, neopentyl, n-hexyl, cyclohexyl, neohexyl, n-heptyl, cycloheptyl, n-octyl, cyclooctyl, 2-ethylhexyl, trifluoromethyl, pentafluoroethyl base, 2,2,2-trifluoroethyl, phenyl, naphthyl, anth
  • substituted group refers to the selection range of the substituent when the “substituted or unsubstituted” group is substituted, and the number is not specifically limited, as long as it meets the requirements of compound bonds. There may be 1, 2, 3, 4 or 5, and when the number of substituents is 2 or more, the 2 or more substituents may be the same or different.
  • halogen represents a chlorine atom, a fluorine atom, a bromine atom or the like.
  • the expressions of Ca-Cb represent that the number of carbon atoms of the group is a-b, unless otherwise specified, generally the number of carbon atoms does not include the number of carbon atoms of the substituent.
  • the expression of the ring structure crossed by "—" means that the connection site is at any position on the ring structure that can form a bond.
  • the heteroatoms mentioned in the present invention generally refer to atoms or atomic groups selected from N, O, S, P, Si and Se, preferably selected from N, O, S.
  • the atom names described in the present invention include their corresponding isotopes, for example, hydrogen (H) includes 1 H (protium or H), 2 H (deuterium or D), etc.; carbon (C) includes 12C , 13C , etc.
  • the compounds described in the general formula (1) of the present invention can preferably be the following specific structure compounds 1 to 180, and these compounds are only representative:
  • the second object of the present invention is to provide an application of the compound described in one of the objects, and the compound is used in an organic electroluminescent device.
  • the compound is used as a light-emitting layer material, preferably a light-emitting dye, in the organic electroluminescent device.
  • the third object of the present invention is to provide an organic electroluminescent device.
  • embodiments of the present invention provide an organic electroluminescent device, comprising a substrate, and an anode layer, a plurality of light-emitting functional layers and a cathode layer sequentially formed on the substrate;
  • the light-emitting functional layer includes A hole injection layer, a hole transport layer, a light-emitting layer, and an electron transport layer, the hole injection layer is formed on the anode layer, and the hole transport layer is formed on the hole injection layer , the cathode layer is formed on the electron transport layer, and a light-emitting layer is formed between the hole transport layer and the electron transport layer; wherein, preferably, the light-emitting layer contains the above
  • the compound of the general formula of the present invention represented by any one of the general formula (1) to the formula (7), or the light-emitting layer contains at least any one of the above-mentioned specific compounds 1 to 180.
  • the compound of the general formula of the present invention (see the following formula), introduced into the special structure of linear donor- ⁇ -donor, linear donor- ⁇ -acceptor or linear acceptor- ⁇ -acceptor, maintains multiple resonances Under the premise of , an effective red shift is generated through the energy level splitting of the frontier orbitals, so that the target molecule has both high luminous efficiency and high color purity.
  • this series of materials achieves a huge red shift in light color, and can obtain orange-red light, red light to near-infrared emission.
  • the electroluminescence spectrum of the OLED device prepared by using the compound of the present invention has a narrow half-peak width and exhibits an obvious multiple resonance effect, thereby greatly enriching the material system and emission color range of multiple resonance-thermal activated delayed fluorescence; and It has low starting voltage, high luminous efficiency and better service life, which can meet the requirements of current panel manufacturers for high-performance materials, and shows good application prospects.
  • Fig. 1 structural schematic diagram of the organic electroluminescent device prepared by the present invention, in the figure, 1 is a substrate, 2 is an anode, 3 is a hole transport layer, 4 is an organic light-emitting layer, 5 is an electron transport layer, and 6 is a cathode .
  • Various chemicals used in the present invention such as petroleum ether, tert-butylbenzene, ethyl acetate, sodium sulfate, toluene, dichloromethane, potassium carbonate, boron tribromide, N,N-diisopropylethylamine, reaction Basic chemical raw materials such as intermediates were purchased from Shanghai Titan Technology Co., Ltd. and Xilong Chemical Co., Ltd.
  • the mass spectrometer used to identify the following compounds was a ZAB-HS mass spectrometer (manufactured by Micromass, UK).
  • the synthesis method of the compound of the present invention will be briefly described below.
  • First, the hydrogen and Cl atoms between/on X 1 , X 2 , X 3 and X 4 are subjected to ortho-metallization by n-butyllithium or tert-butyllithium, etc. change.
  • boron tribromide is added to perform lithium-boron metal exchange, and then a Bronsted base such as N,N-diisopropylethylamine is added to perform a tandem boronza Fried-Kla. Crafts Reaction (Tandem Bora-Friedel-Crafts Reaction) to obtain the target.
  • N,N-diisopropylethylamine (7.00 mL, 40.20 mmol) was added at room temperature and the reaction was continued at 145°C for 5 hours and then stopped.
  • MALDI-TOF-MS results Molecular ion peak: 762.53 Elemental analysis results: Theoretical value: C, 85.06; H, 4.76; B, 2.84; N, 7.35(%); Experimental value: C, 85.16; H, 4.66; B , 2.64; N, 7.55 (%).
  • This example is basically the same as the synthesis of compound 1, the difference is that: in this example, 1-1 needs to be replaced with 5-1 in an equivalent amount.
  • the target compound 5 (0.68 g, 38% yield, 99.55% purity by HPLC analysis) was a yellow solid.
  • MALDI-TOF-MS results Molecular ion peak: 754.47 Elemental analysis results: Theoretical value: C, 85.97; H, 3.74; B, 2.87; N, 7.43(%); Experimental value: C, 85.87; H, 3.84; B , 2.77; N, 7.53 (%).
  • This example is basically the same as the synthesis of compound 1, the difference is that: in this example, 1-1 needs to be replaced with 8-1 in the same amount of substance.
  • the target compound 8 (0.66 g, 25% yield, 99.65% purity by HPLC analysis) was a yellow solid.
  • MALDI-TOF-MS results Molecular ion peak: 1203.33 Elemental analysis results: Theoretical value: C, 85.84; H, 7.71; B, 1.80; N, 4.66(%); Experimental value: C, 85.81; H, 7.74; B , 1.70; N, 4.766 (%).
  • This example is basically the same as the synthesis of compound 1, the difference is that: in this example, 1-1 needs to be replaced with 18-1 in an equivalent amount.
  • the target compound 18 (1.00 g, 32% yield, 99.43% purity by HPLC analysis) was a yellow solid.
  • MALDI-TOF-MS results Molecular ion peak: 1419.70 Elemental analysis results: Theoretical value: C, 86.29; H, 8.24; B, 1.52; N, 3.95(%); Experimental value: C, 86.19; H, 8.34; B , 1.32; N, 4.15 (%).
  • This example is basically the same as the synthesis of compound 1, the difference is that: in this example, 1-1 needs to be replaced with 82-1 in the same amount of substances.
  • the target compound 82 (0.41 g, 30% yield, 99.53% purity by HPLC analysis) was a yellow solid.
  • MALDI-TOF-MS results Molecular ion peak: 606.30 Elemental analysis results: Theoretical value: C, 83.20; H, 3.99; B, 3.57; N, 9.24(%); Experimental value: C, 83.27; H, 3.92; B , 3.67; N, 9.14 (%).
  • This example is basically the same as the synthesis of compound 1, the difference is that: in this example, 1-1 needs to be replaced with 87-1 in an equivalent amount.
  • the target compound 87 (0.42 g, 32% yield, 99.67% purity by HPLC analysis) was a yellow solid.
  • N,N-diisopropylethylamine (2.56g, 19.82mmol) was added at room temperature, and the reaction was continued at 145°C for 12 hours and then cooled to room temperature. In this state, phenylmagnesium bromide (3.59g, 19.82mmol) was added. ), continue to react for 2 hours and then stop.
  • MALDI-TOF-MS results Molecular ion peak: 756.14 Elemental analysis results: Theoretical value: C, 85.78; H, 4.80; B, 5.72; N, 3.70(%); Experimental value: C, 85.78; H, 4.80; B , 5.72; N, 3.70 (%).
  • This example is basically the same as the synthesis of compound 1, the difference is that: in this example, 1-1 needs to be replaced with 113-1 in the same amount of substance.
  • the target compound 113 (0.55 g, 41% yield, 99.33% purity by HPLC analysis) was a yellow solid.
  • MALDI-TOF-MS results Molecular ion peak: 612.22 Elemental analysis results: Theoretical value: C, 82.39; H, 4.28; B, 3.53; N, 4.58; O, 5.23 (%); Experimental value: C, 82.19; H , 4.25; B, 3.73; N, 4.57; O, 5.27 (%).
  • This example is basically the same as the synthesis of compound 1, the difference is that: in this example, 1-1 needs to be replaced with 114-1 in an equivalent amount.
  • the target compound 114 (0.42 g, 36% yield, 99.54% purity by HPLC analysis) was a yellow solid.
  • MALDI-TOF-MS results Molecular ion peak: 537.19 Elemental analysis results: Theoretical value: C, 80.49; H, 3.94; B, 4.02; N, 2.61; O, 8.93(%); Experimental value: C, 80.59; H , 3.74; B, 4.12; N, 2.71; O, 8.83 (%).
  • This example is basically the same as the synthesis of compound 1, the difference is that: in this example, 1-1 needs to be replaced with 132-1 in an equivalent amount.
  • the target compound 132 (0.37 g, 26% yield, 99.52% purity by HPLC analysis) was a yellow solid.
  • MALDI-TOF-MS results Molecular ion peak: 644.42 Elemental analysis results: Theoretical value: C, 78.28; H, 4.07; B, 3.35; N, 4.35; S, 9.95(%); Experimental value: C, 78.28; H , 4.07; B, 3.35; N, 4.35; S, 9.95 (%).
  • This example is basically the same as the synthesis of compound 1, the difference is that: in this example, 1-1 needs to be replaced with 149-1 in an equivalent amount.
  • the target compound 149 (0.52 g, 36% yield, 99.42% purity by HPLC analysis) was a yellow solid.
  • MALDI-TOF-MS results Molecular ion peak: 662.41 Elemental analysis results: Theoretical value: C, 83.41; H, 4.87; B, 3.26; N, 8.46(%); Experimental value: C, 83.40; H, 4.88; B , 3.25; N, 8.47 (%).
  • This example is basically the same as the synthesis of compound 102, the difference is that: in this example, 102-1 needs to be replaced with 180-1 in an equivalent amount.
  • the target compound 180 (0.72 g, 19% yield, 99.35% purity by HPLC analysis) was an orange-red solid.
  • the organic electroluminescent device includes a first electrode, a second electrode, and an organic material layer between the two electrodes.
  • the organic material can be further divided into multiple regions.
  • the organic material layer can include a hole transport region, a light-emitting layer, and an electron transport region.
  • the material of the anode can be transparent conductive oxide materials such as indium tin oxide (ITO), indium zinc oxide (IZO), tin dioxide (SnO2), zinc oxide (ZnO), and any combination thereof.
  • the material of the cathode can be magnesium (Mg), silver (Ag), aluminum (Al), aluminum-lithium (Al-Li), calcium (Ca), magnesium-indium (Mg-In), magnesium-silver (Mg-Ag) ) and other metals or alloys and any combination between them.
  • the hole transport region is located between the anode and the light emitting layer.
  • the hole transport region may be a hole transport layer (HTL) with a single-layer structure, including a single-layer hole-transport layer containing only one compound and a single-layer hole-transport layer containing multiple compounds.
  • the hole transport region may also be a multilayer structure including at least one of a hole injection layer (HIL), a hole transport layer (HTL), and an electron blocking layer (EBL).
  • HIL hole injection layer
  • HTL hole transport layer
  • EBL electron blocking layer
  • the material of the hole transport region can be selected from, but not limited to, phthalocyanine derivatives such as CuPc, conductive polymers or polymers containing conductive dopants such as polyphenylene vinylene, polyaniline/dodecylbenzenesulfonic acid (Pani/dodecylbenzenesulfonic acid).
  • DBSA poly(3,4-ethylenedioxythiophene)/poly(4-styrenesulfonate)
  • PEDOT/PSS polyaniline/camphorsulfonic acid
  • Pani/CSA polyaniline/poly(4 - Styrene sulfonate
  • aromatic amine derivatives etc.
  • the light-emitting layer includes light-emitting dyes (ie dopant, dopant) that can emit different wavelength spectra, and may also include a host material (Host).
  • the light-emitting layer may be a monochromatic light-emitting layer that emits a single color such as red, green, and blue.
  • the monochromatic light-emitting layers of a plurality of different colors can be arranged in a plane according to a pixel pattern, or can be stacked together to form a colored light-emitting layer. When light-emitting layers of different colors are stacked together, they can be spaced from each other or connected to each other.
  • the light-emitting layer may also be a single-color light-emitting layer capable of simultaneously emitting different colors such as red, green, and blue.
  • the electron transport region may be an electron transport layer (ETL) with a single-layer structure, including a single-layer electron transport layer containing only one compound and a single-layer electron transport layer containing multiple compounds.
  • the electron transport region may also be a multilayer structure including at least one of an electron injection layer (EIL), an electron transport layer (ETL), and a hole blocking layer (HBL).
  • EIL electron injection layer
  • ETL electron transport layer
  • HBL hole blocking layer
  • an anode 2 a hole transport layer 3, an organic light emitting layer 4, an electron transport layer 5, and a cathode 6 are sequentially deposited on a substrate 1, and then packaged.
  • the organic light-emitting layer 4 is formed by co-evaporating a wide bandgap material source, an electron donor material source, an electron acceptor material source and a resonance TADF material source.
  • the preparation method of the organic electroluminescent device of the present invention comprises the following steps:
  • the glass plate coated with anode material was ultrasonically treated in commercial cleaning agent, rinsed in deionized water, ultrasonically degreasing in acetone:ethanol mixed solvent, baked in a clean environment until water was completely removed, and UV light was used. Light and ozone cleaning, and bombarding the surface with a beam of low-energy cations;
  • Vacuum evaporation of a hole transport material on the hole injection layer to form a hole transport layer the evaporation rate is 0.1-0.5nm/s
  • the electron blocking layer is vacuum evaporated on the hole transport layer, and the evaporation rate is 0.1-0.5nm/s;
  • the organic light-emitting layer of the device is vacuum-evaporated on the electron blocking layer.
  • the organic light-emitting layer material includes the host material and TADF dye, and the multi-source co-evaporation method is used to adjust the evaporation rate of the host material and the sensitizer material. The evaporation rate and the evaporation rate of the dye make the dye reach the preset doping ratio;
  • the electron transport material of the device is vacuum evaporated on the hole blocking layer to form an electron transport layer, and the evaporation rate is 0.1-0.5nm/s;
  • An embodiment of the present invention further provides a display device, the display device includes the organic electroluminescence device provided above.
  • the display device may be a display device such as an OLED display, as well as any product or component with a display function, such as a TV, a digital camera, a mobile phone, and a tablet computer including the display device.
  • the display device and the above organic electroluminescent device have the same advantages over the prior art, which will not be repeated here.
  • organic electroluminescent device of the present invention will be further introduced below through specific examples.
  • the structure of the organic electroluminescent device prepared in this example is as follows:
  • the material of the anode is ITO; the material of the hole injection layer is HI, and the total thickness is generally 5-30 nm, which is 10 nm in this embodiment; the material of the hole transport layer is HT, and the total thickness is generally 5-500 nm.
  • Host is the host material of the wide bandgap of the organic light-emitting layer, the compound 1 of the present invention is a dye and the doping concentration is 3wt%, the thickness of the organic light-emitting layer is generally 1-200nm, 30nm in this embodiment; the material of the electron transport layer is ET, the thickness is generally 5-300nm, this embodiment is 30nm; the electron injection layer and cathode materials are selected from LiF (0.5nm) and metal aluminum (150nm).
  • the preparation method is the same as that of Device Example 1, except that the wide-bandgap host material Host used in the light-emitting layer is replaced with a TADF-type host TD, and the specific device structure is as follows:
  • the preparation method is the same as that of Device Example 1, except that the dye used in the light-emitting layer is replaced from 1 to 5.
  • the device structure is as follows:
  • the preparation method is the same as that of Device Example 1, except that the wide-bandgap host material Host in the light-emitting layer is replaced with a TADF-type host TD, and the dye is replaced from 1 to 5.
  • the device structure is as follows:
  • the preparation method is the same as that of Device Example 1, except that the dye in the light-emitting layer is replaced from 1 to 82.
  • the device structure is as follows:
  • the preparation method is the same as that of Device Example 1, except that the wide-bandgap host material Host in the light-emitting layer is replaced with a TADF-type host TD, and the dye is replaced from 1 to 82.
  • the device structure is as follows:
  • the preparation method is the same as that of Device Example 1, except that the dye in the light-emitting layer is replaced from 1 to 87.
  • the device structure is as follows:
  • the preparation method is the same as that of Device Example 1, except that the wide band gap type host material Host in the light-emitting layer is replaced with a TADF type host TD, and the dye is replaced from 1 to 87.
  • the device structure is as follows:
  • the preparation method is the same as that of Device Example 1, except that the dye in the light-emitting layer is replaced from 1 to 102.
  • the device structure is as follows:
  • the preparation method is the same as that of Device Example 1, except that the wide-bandgap host material Host in the light-emitting layer is replaced with a TADF-type host TD, and the dye is replaced from 1 to 102.
  • the device structure is as follows:
  • the preparation method is the same as that of Device Example 1, except that the dye in the light-emitting layer is replaced from 1 to 113.
  • the device structure is as follows:
  • the preparation method is the same as that of Device Example 1, except that the wide-bandgap host material Host in the light-emitting layer is replaced with a TADF-type host TD, and the dye is replaced with 113.
  • the device structure is as follows:
  • the preparation method is the same as that of Device Example 1, except that the dye in the light-emitting layer is replaced from 1 to 114.
  • the device structure is as follows:
  • the preparation method is the same as that of Device Example 1, except that the wide band gap type host material Host in the light-emitting layer is replaced with a TADF type host TD, and the dye is replaced from 1 to 114.
  • the device structure is as follows:
  • the preparation method is the same as that of Device Example 1, except that the dye in the light-emitting layer is replaced from 1 to 180.
  • the device structure is as follows:
  • the preparation method is the same as that of Device Example 1, except that the wide-bandgap host material Host in the light-emitting layer is replaced with a TADF-type host TD, and the dye is replaced from 1 to 180.
  • the device structure is as follows:
  • the preparation method is the same as that of Device Example 1, except that the compound 1 of the present invention used in the light-emitting layer is replaced with the compound P1 in the prior art, and the specific device structure is as follows:
  • the preparation method is the same as that of Device Example 2, except that the compound 1 of the present invention used in the light-emitting layer is replaced with the compound P1 in the prior art, and the specific device structure is as follows:
  • the preparation method is the same as that of Device Example 1, except that the compound 1 of the present invention used in the light-emitting layer is replaced with the compound P2 in the prior art, and the specific device structure is as follows:
  • the preparation method is the same as that of Device Example 2, except that the compound 1 of the present invention used in the light-emitting layer is replaced with the compound P2 in the prior art, and the specific device structure is as follows:
  • the preparation method is the same as that of Device Example 1, except that the compound 1 of the present invention used in the light-emitting layer is replaced by the compound P3 in the prior art, and the specific device structure is as follows:
  • the preparation method is the same as that of Device Example 2, except that the compound 1 of the present invention used in the light-emitting layer is replaced with the compound P3 in the prior art, and the specific device structure is as follows:

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Abstract

The present invention relates to the technical field of organic electroluminescence, and particularly relates to an organic compound and the use thereof, and an organic electroluminescence device comprising the compound. A general formula compound of the present invention has a structure as represented by formula (I), wherein ring A, ring B, ring C and ring D each independently represent any one of a C5-C20 monocyclic aromatic ring or fused aromatic ring, and a C4-C20 monocyclic heterocyclic ring or fused heterocyclic ring; ring E represents a C5-C20 aromatic ring; Y1 and Y2 independently are N or B, respectively; and X1, X2, X3 and X4 independently are NR1, BR2, O or S, respectively. The compound of the present invention exhibits excellent device performance and stability when used as a light-emitting material in an OLED device. The present invention also claims an organic electroluminescence device using the general formula compound.

Description

一种发光材料及其应用以及包含其的有机电致发光器件A light-emitting material and its application and an organic electroluminescent device comprising the same 技术领域technical field
本发明涉及有机电致发光技术领域，特别涉及一种有机化合物及其应用以及包含该化合物的有机电致发光器件。The present invention relates to the technical field of organic electroluminescence, in particular to an organic compound and its application and an organic electroluminescence device comprising the compound.
背景技术Background technique
有机电致发光器件(OLED:Organic Light Emission Diodes)是一类具有类三明治结构的器件，包括正负电极膜层及夹在电极膜层之间的有机功能材料层。由于OLED器件具有亮度高、响应快、视角宽、工艺简单、可柔性化等优点,在新型显示技术领域和新型照明技术领域备受关注。目前，该技术已被广泛应用于新型照明灯具、智能手机及平板电脑等产品的显示面板，进一步还将向电视等大尺寸显示产品应用领域扩展，是一种发展快、技术要求高的新型显示技术。Organic electroluminescent device (OLED: Organic Light Emission Diodes) is a kind of device with a sandwich-like structure, including positive and negative electrode film layers and organic functional material layers sandwiched between the electrode film layers. Due to the advantages of high brightness, fast response, wide viewing angle, simple process and flexibility, OLED devices have attracted much attention in the field of new display technology and new lighting technology. At present, this technology has been widely used in the display panels of new lighting fixtures, smart phones and tablet computers, and will be further expanded to the application field of large-size display products such as TVs. It is a new type of display with fast development and high technical requirements. technology.
随着OLED在照明和显示两大领域的不断推进，人们对于其核心材料的研究也更加关注，因为一个效率好、寿命长的OLED器件通常是器件结构以及各种有机材料的优化搭配的结果。为了制备驱动电压更低、发光效率更好、器件使用寿命更长的OLED发光器件，实现OLED器件的性能不断提升，不仅需要对OLED器件结构和制作工艺进行创新，更需要对OLED器件中的光电功能材料不断研究和创新，以制备出具有更高性能的功能材料。基于此，OLED材料界一直致力于开发新的有机电致发光材料以实现器件低启动电压、高发光效率和更优的使用寿命。With the continuous advancement of OLED in the two fields of lighting and display, people pay more attention to the research of its core materials, because an OLED device with good efficiency and long life is usually the result of the optimized combination of device structure and various organic materials. In order to prepare OLED light-emitting devices with lower driving voltage, better luminous efficiency, and longer device service life, and realize the continuous improvement of the performance of OLED devices, it is not only necessary to innovate the structure and production process of OLED devices, but also need to innovate the optoelectronic devices in OLED devices. Functional materials are continuously researched and innovated to prepare functional materials with higher performance. Based on this, the OLED material community has been devoted to developing new organic electroluminescent materials to achieve low startup voltage, high luminous efficiency and better lifetime of devices.
在OLED材料的选择上，单线态发光的荧光材料寿命好，价格低廉，但是效率低；三线态发光的磷光材料效率高，但是价格昂贵，而且蓝光材料的寿命问题一直没有解决。日本九州大学的Adachi提出了一类新的有机发光材料，即热活化延迟荧光(TADF)材料。该类材料的单线态-三线态能隙(ΔE ST)非常小(<0.3eV)，三线态激子可以通过反向系间窜越(RISC)转变成单线态激子发光，因此器件的内量子效率可以达到100％。 In the selection of OLED materials, singlet light-emitting fluorescent materials have good lifespan and low price, but low efficiency; triplet light-emitting phosphorescent materials have high efficiency, but are expensive, and the lifespan of blue light materials has not been solved. Adachi of Kyushu University in Japan proposed a new class of organic light-emitting materials, namely thermally activated delayed fluorescence (TADF) materials. The singlet-triplet energy gap (ΔE ST ) of this type of material is very small (<0.3 eV), and triplet excitons can be converted into singlet excitons through reverse intersystem crossing (RISC) to emit light. The quantum efficiency can reach 100%.
MR-TADF材料具有高色纯度和高发光效率的优点，引起了科研界和产业界的广泛关注。但是，由于外围取代基对S 1能级影响很小，即很难对材料的发光颜色进行调控，其光色也一直局限在蓝光-深蓝光区域，大大限制了MR-TADF材料在高分辨显示、全彩显示以及白光照明领域等的进一步应用。 MR-TADF materials have the advantages of high color purity and high luminous efficiency, which have attracted extensive attention in scientific research and industrial circles. However, because the peripheral substituents have little effect on the S 1 energy level, that is, it is difficult to control the emission color of the material, and its light color has always been limited to the blue-deep blue light region, which greatly limits the high-resolution display of MR-TADF materials. , full-color display and further applications in the field of white lighting.
发明内容SUMMARY OF THE INVENTION
为解决上述技术问题，本发提供了一种有机化合物，本发明化合物的具体通式如下式(1)所示：In order to solve the above-mentioned technical problems, the present invention provides a kind of organic compound, and the specific general formula of the compound of the present invention is shown in the following formula (1):
Figure PCTCN2021116592-appb-000001
Figure PCTCN2021116592-appb-000001
式(1)中，环A、环B、环C、环D各自独立地表示C5～C20的单环芳环或稠合芳环、C4～C20单环杂环或稠合杂环中的任意一种；环E表示C5～C20的芳环；In formula (1), ring A, ring B, ring C, and ring D each independently represent any of a C5-C20 monocyclic aromatic ring or a condensed aromatic ring, a C4-C20 monocyclic heterocyclic ring or a condensed heterocyclic ring. One; Ring E represents an aromatic ring of C5～C20;
所述环A与环B之间可通过单键连接，所述环C与环D之间可通过单键连接；The ring A and the ring B can be connected by a single bond, and the ring C and the ring D can be connected by a single bond;
所述Y 1和Y 2分别独立地为N或B； Said Y 1 and Y 2 are each independently N or B;
所述X 1、X 2、X 3和X 4分别独立地为NR 1、BR 2、O或S； Said X 1 , X 2 , X 3 and X 4 are each independently NR 1 , BR 2 , O or S;
当Y 1和Y 2均为B时，X 1、X 2、X 3和X 4不同时为NR 1； When Y 1 and Y 2 are both B, X 1 , X 2 , X 3 and X 4 are not NR 1 at the same time;
所述R 1、R 2分别独立地选自取代或未取代的下述基团中的一种：C1-C36链状烷基、C3-C36环烷基、C6～C30的芳基氨基、C3～C30杂芳基氨基、C6-C60的单环芳基、C6-C60的稠环芳基、C6-C60的芳氧基、C5-C60的单环杂芳基或C5-C60的稠环杂芳基； The R 1 and R 2 are independently selected from one of the following substituted or unsubstituted groups: C1-C36 chain alkyl, C3-C36 cycloalkyl, C6-C30 arylamino, C3 ~C30 heteroarylamino, C6-C60 monocyclic aryl, C6-C60 fused-ring aryl, C6-C60 aryloxy, C5-C60 monocyclic heteroaryl or C5-C60 fused-ring heteroaryl Aryl;
所述R 1可通过单键与相邻的环A、环B、环C或环D连接，或者可与相邻的环A、环B、环C或环D稠合而相互键合形成环；所述R 2可通过单键与相邻的环A、环B、环C或环D连接，或者可与相邻的环A、环B、环C或环D稠合而相互键合形成环； The R 1 can be connected to the adjacent ring A, ring B, ring C or ring D through a single bond, or can be condensed with the adjacent ring A, ring B, ring C or ring D to bond with each other to form a ring ; The R 2 can be connected with the adjacent ring A, ring B, ring C or ring D through a single bond, or can be fused with the adjacent ring A, ring B, ring C or ring D to form a bond with each other ring;
所述X 1与X 3之间可通过单键连接，或者可稠合而相互键合形成环；所述X 2与X 4之间可通过单键连接，或者可稠合而相互键合形成环； The X 1 and X 3 can be connected by a single bond, or can be fused to form a ring; the X 2 and X 4 can be connected by a single bond, or can be fused to form a mutual bond ring;
所述R a、R b、R c和R d分别独立地表示单取代基到最大允许取代基，并且各自独立地选自氢、氘或者取代或未取代的下述基团中的一种：卤素、C1～C36的链状烷基、C3～C36的环烷基、C1～C10的烷氧基、C1～C10的硫代烷氧基、羰基、羧基、硝基、氰基、氨基、C6～C30的芳基氨基、C3～C30杂芳基氨基、C6-C60的单环芳基、C6-C60的稠环芳基、C6-C60的芳氧基、C5-C60的单环杂芳基、C5-C60的稠环杂芳基中的一种；所述R a、R b、R  c和R d中的相邻的两个之间任选可通过单键连接或者可稠合而相互键合形成环； The R a , R b , R c and R d each independently represent a mono-substituent to the maximum allowable substituent, and are each independently selected from hydrogen, deuterium, or one of the following groups, substituted or unsubstituted: Halogen, C1-C36 chain alkyl, C3-C36 cycloalkyl, C1-C10 alkoxy, C1-C10 thioalkoxy, carbonyl, carboxyl, nitro, cyano, amino, C6 ～C30 arylamino, C3～C30 heteroarylamino, C6-C60 monocyclic aryl, C6-C60 fused-ring aryl, C6-C60 aryloxy, C5-C60 monocyclic heteroaryl , a C5-C60 condensed ring heteroaryl; the adjacent two of the R a , R b , R c and R d can optionally be connected by a single bond or can be fused to each other bond to form a ring;
当上述基团存在取代基时，所述取代基团分别独立选自氘、卤素、C1～C30的链状烷基、C3～C30的环烷基、C1～C10的烷氧基、C1～C10的硫代烷氧基、羰基、羧基、硝基、氰基、氨基、C6～C30的芳基氨基、C3～C30杂芳基氨基、C6～C60的单环芳基、C6～C60的稠环芳基、C6～C60的芳氧基、C5～C60的单环杂芳基、C5～C60的稠环杂芳基中的任一种。When the above groups have substituents, the substituents are independently selected from deuterium, halogen, C1-C30 chain alkyl, C3-C30 cycloalkyl, C1-C10 alkoxy, C1-C10 thioalkoxy, carbonyl, carboxyl, nitro, cyano, amino, C6-C30 arylamino, C3-C30 heteroarylamino, C6-C60 monocyclic aryl, C6-C60 fused ring Any of an aryl group, a C6-C60 aryloxy group, a C5-C60 monocyclic heteroaryl group, and a C5-C60 condensed ring heteroaryl group.
优选的，式(1)中，所述环A、环B、环C和环D各自独立地表示C5～C10的单环芳环或稠合芳环、C4～C10的单环杂环或稠合杂环中的任意一种，所述环E表示C5～C10的单环芳环或稠合芳环。Preferably, in formula (1), the ring A, ring B, ring C and ring D each independently represent a C5-C10 monocyclic aromatic ring or a condensed aromatic ring, a C4-C10 monocyclic heterocyclic ring or a condensed aromatic ring Any of the heterocyclic rings, the ring E represents a C5-C10 monocyclic aromatic ring or a condensed aromatic ring.
更优选的，式(1)中，所述环A、环B、环C和环D各自独立地选自苯环、萘环或芴环中的任意一种，所述环E选自苯环、萘环或芴环中的任意一种。More preferably, in formula (1), the ring A, ring B, ring C and ring D are each independently selected from any one of a benzene ring, a naphthalene ring or a fluorene ring, and the ring E is selected from a benzene ring , any one of naphthalene ring or fluorene ring.
优选的，本发明化合物的具体通式如下式(2)至式(7)中的任一所示：Preferably, the specific general formula of the compound of the present invention is shown in any one of the following formulas (2) to (7):
Figure PCTCN2021116592-appb-000002
Figure PCTCN2021116592-appb-000002
Figure PCTCN2021116592-appb-000003
Figure PCTCN2021116592-appb-000003
式(2)至式(7)中，X 1、X 2、X 3、X 4、R a、R b、R c和R d的定义均与在式(1)中的定义相同。 In formula (2) to formula (7), the definitions of X 1 , X 2 , X 3 , X 4 , R a , R b , R c and R d are the same as those in formula (1).
进一步的，本发明的式(2)、式(3)和式(4)中，各自独立的X 1、X 2、X 3、X 4具有如下所述的优选方案： Further, in formula (2), formula (3) and formula (4) of the present invention, each independent X 1 , X 2 , X 3 , and X 4 have the following preferred solutions:
X 1、X 2、X 3、X 4中的两个为BR 2，另两个为NR 1； Two of X 1 , X 2 , X 3 and X 4 are BR 2 , and the other two are NR 1 ;
或者，X 1、X 2、X 3、X 4中的两个为BR 2，另两个为O； Or, two of X 1 , X 2 , X 3 , and X 4 are BR 2 , and the other two are O;
或者，X 1、X 2、X 3、X 4中的两个为BR 2，另两个为S； Or, two of X 1 , X 2 , X 3 , and X 4 are BR 2 , and the other two are S;
或者，X 1、X 2、X 3、X 4中的三个为BR 2，另一个为NR 1； Or, three of X 1 , X 2 , X 3 , and X 4 are BR 2 and the other is NR 1 ;
或者，X 1、X 2、X 3、X 4中的一个为BR 2，另三个为NR 1； Or, one of X 1 , X 2 , X 3 , and X 4 is BR 2 , and the other three are NR 1 ;
或者，X 1、X 2、X 3、X 4中的两个为BR 2，一个为NR 1，另一个为O； Or, two of X 1 , X 2 , X 3 , and X 4 are BR 2 , one is NR 1 , and the other is O;
或者，X 1、X 2、X 3、X 4中的一个为BR 2，两个为NR 1，另一个为O； Or, one of X 1 , X 2 , X 3 , and X 4 is BR 2 , two are NR 1 , and the other is O;
或者，X 1、X 2、X 3、X 4中的两个为BR 2，一个为NR 1，另一个为O； Or, two of X 1 , X 2 , X 3 , and X 4 are BR 2 , one is NR 1 , and the other is O;
或者，X 1、X 2、X 3、X 4中的两个为BR 2，一个为NR 1，另一个为O； Or, two of X 1 , X 2 , X 3 , and X 4 are BR 2 , one is NR 1 , and the other is O;
或者，X 1、X 2、X 3、X 4均为S； Or, X 1 , X 2 , X 3 , and X 4 are all S;
或者，X 1、X 2、X 3、X 4中的一个为O，另三个为S； Or, one of X 1 , X 2 , X 3 , and X 4 is O, and the other three are S;
或者，X 1、X 2、X 3、X 4中的一个为NR 1，另三个为NR 1。 Alternatively, one of X 1 , X 2 , X 3 , and X 4 is NR 1 , and the other three are NR 1 .
再进一步的，式(1)中、式(2)至式(7)中，所述R a、R b、R c和R d分别独立地选自氢、氘或者取代或未取代的下述取代基团中的一种：甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基、叔丁基、2-甲基丁基、正戊基、仲戊基、环戊基、新戊基、正己基、环己基、新己基、正庚基、环庚基、正辛基、环辛基、2-乙基己基、三氟甲基、五氟乙基、2,2,2-三氟乙基、苯基、萘基、蒽基、苯并蒽基、菲基、苯并菲基、芘基、窟基、茈基、荧蒽基、并四苯基、并五苯基、苯并芘基、联苯基、偶苯基、三联苯基、三聚苯基、四联苯基、芴基、螺二芴基、二氢菲基、二氢芘基、四氢芘基、顺式或反式茚并芴基、三聚茚基、异三聚茚基、螺三聚茚基、螺异三聚茚基、呋喃基、苯并呋喃基、异苯并呋喃基、二苯并呋喃基、噻吩基、苯并噻吩基、异苯并噻吩基、二苯并噻吩基、吡咯基、异吲哚基、咔唑基、茚并咔唑基、吡啶基、喹啉基、异喹啉基、吖啶基、菲啶基、苯并-5,6-喹啉基、苯并-6,7-喹啉基、苯并-7,8-喹啉基、吡唑基、吲唑基、咪唑基、苯并咪唑基、萘并咪唑基、菲并咪唑基、吡啶并咪唑基、吡嗪并咪唑基、喹喔啉并咪唑基、嗯唑基、苯并嗯唑基、萘并嗯唑基、蒽并嗯唑基、菲并嗯唑基、1，2-噻唑基、1，3-噻唑基、苯并噻唑基、哒嗪基、苯并哒嗪基、嘧啶基、苯并嘧啶基、喹喔啉基、1，5-二氮杂蒽基、2,7-二氮杂芘基、2,3-二氮杂芘基、1,6-二氮杂芘基、1,8-二氮杂芘基、4,5-二氮杂芘基、4,5,9,10-四氮杂茈基、吡嗪基、吩嗪基、吩噻嗪基、萘啶基、氮杂咔唑基、苯并咔啉基、菲咯啉基、1,2,3-三唑基、1,2,4-三唑基、苯并三唑基、1,2,3-噁二唑基、1,2,4-嗯二唑基、1,2,5_嗯二唑基、1,2,3-噻二唑基、1,2,4-噻二唑基、1,2,5-噻二唑 基、1,3,4-噻二唑基、1,3,5-三嗪基、1,2,4-三嗪基、1,2,3-三嗪基、四唑基、1,2,4,5-四嗪基、1,2,3,4-四嗪基、1,2,3,5-四嗪基、嘌呤基、蝶啶基、吲嗪基、苯并噻二唑基、9,9-二甲基吖啶基、三芳胺基、金刚烷、氟代苯基、甲基苯基、三甲基苯基、氰基苯基、四氢吡咯、哌啶、甲氧基、硅基，或者选自以上两种取代基团的组合。 Still further, in formula (1), formula (2) to formula (7), said R a , R b , R c and R d are independently selected from hydrogen, deuterium or substituted or unsubstituted following One of the substituent groups: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, 2-methylbutyl, n-pentyl, sec Pentyl, cyclopentyl, neopentyl, n-hexyl, cyclohexyl, neohexyl, n-heptyl, cycloheptyl, n-octyl, cyclooctyl, 2-ethylhexyl, trifluoromethyl, pentafluoroethyl base, 2,2,2-trifluoroethyl, phenyl, naphthyl, anthracenyl, benzanthracene, phenanthryl, triphenylene, pyrenyl, cavernyl, perylene, fluoranthyl, naphthyl Phenyl, pentacyl, benzopyrene, biphenyl, biphenyl, terphenyl, triphenyl, tetraphenyl, fluorenyl, spirobifluorenyl, dihydrophenanthryl, dihydro Pyrenyl, tetrahydropyrenyl, cis- or trans-indenofluorenyl, trimerindenyl, heterotrimerindenyl, spirotrimerindenyl, spiroheterotrimerindenyl, furanyl, benzofuranyl, Isobenzofuranyl, dibenzofuranyl, thienyl, benzothienyl, isobenzothienyl, dibenzothienyl, pyrrolyl, isoindolyl, carbazolyl, indenocarbazolyl, Pyridyl, quinolinyl, isoquinolinyl, acridinyl, phenanthridine, benzo-5,6-quinolinyl, benzo-6,7-quinolinyl, benzo-7,8-quinoline Linoyl, pyrazolyl, indazolyl, imidazolyl, benzimidazolyl, naphthimidazolyl, phenanthroimidazolyl, pyridimidazolyl, pyrazinimidazolyl, quinoxalineimidazolyl, oxazolyl , benzoxazolyl, naphthazolyl, anthraxazolyl, phenanthazolyl, 1,2-thiazolyl, 1,3-thiazolyl, benzothiazolyl, pyridazinyl, benzoyl Pyridazinyl, pyrimidinyl, benzopyrimidinyl, quinoxalinyl, 1,5-diazaanthryl, 2,7-diazapyrenyl, 2,3-diazapyrenyl, 1,6 - Diazapyrenyl, 1,8-diazapyrenyl, 4,5-diazapyrenyl, 4,5,9,10-tetraazaperpenyl, pyrazinyl, phenazinyl, phen Thiazinyl, naphthyridinyl, azacarbazolyl, benzocarbolinyl, phenanthroline, 1,2,3-triazolyl, 1,2,4-triazolyl, benzotriazolyl , 1,2,3-oxadiazolyl, 1,2,4-oxadiazolyl, 1,2,5-oxadiazolyl, 1,2,3-thiadiazolyl, 1,2,4 - Thiadiazolyl, 1,2,5-thiadiazolyl, 1,3,4-thiadiazolyl, 1,3,5-triazinyl, 1,2,4-triazinyl, 1, 2,3-triazinyl, tetrazolyl, 1,2,4,5-tetrazinyl, 1,2,3,4-tetrazinyl, 1,2,3,5-tetrazinyl, purinyl , pteridyl, indolizinyl, benzothiadiazolyl, 9,9-dimethylacridinyl, triarylamine, adamantane, fluorophenyl, methylphenyl, trimethylphenyl, Cyanophenyl, tetrahydropyrrole, piperidine, methoxy, silicon, or a combination of the above two substituents.
本发明中，“取代的基团”指的是“取代或未取代”的基团被取代时取代基的选择范围，个数不做具体限定，只要满足化合物键要求即可，示例性地，可以为1个、2个、3个、4个或5个，且当取代基的个数为2个及以上时，这2个及以上取代基可以相同也可以不同。In the present invention, "substituted group" refers to the selection range of the substituent when the "substituted or unsubstituted" group is substituted, and the number is not specifically limited, as long as it meets the requirements of compound bonds. There may be 1, 2, 3, 4 or 5, and when the number of substituents is 2 or more, the 2 or more substituents may be the same or different.
本发明中，卤素代表氯原子、氟原子、溴原子等。In the present invention, halogen represents a chlorine atom, a fluorine atom, a bromine atom or the like.
本发明中，Ca～Cb的表达方式代表该基团具有的碳原子数为a～b，除非特殊说明，一般而言该碳原子数不包括取代基的碳原子数。In the present invention, the expressions of Ca-Cb represent that the number of carbon atoms of the group is a-b, unless otherwise specified, generally the number of carbon atoms does not include the number of carbon atoms of the substituent.
本发明中，“—”划过的环结构的表达方式，表示连接位点于该环结构上任意能够成键的位置。In the present invention, the expression of the ring structure crossed by "—" means that the connection site is at any position on the ring structure that can form a bond.
本发明中所述的杂原子，通常指选自N、O、S、P、Si和Se中的原子或原子团，优选选自N、O、S。本发明中所述的原子名称，包括其对应的各种同位素，例如，氢(H)则包括 1H(氕或作H)、 2H(氘或作D)等；碳(C)则包括 12C、 13C等。 The heteroatoms mentioned in the present invention generally refer to atoms or atomic groups selected from N, O, S, P, Si and Se, preferably selected from N, O, S. The atom names described in the present invention include their corresponding isotopes, for example, hydrogen (H) includes 1 H (protium or H), 2 H (deuterium or D), etc.; carbon (C) includes 12C , 13C , etc.
更进一步的，本发明的通式(1)所述的化合物可以优选出下述具体结构化合物1至化合物180，这些化合物仅为代表性的：Further, the compounds described in the general formula (1) of the present invention can preferably be the following specific structure compounds 1 to 180, and these compounds are only representative:
Figure PCTCN2021116592-appb-000004
Figure PCTCN2021116592-appb-000004
Figure PCTCN2021116592-appb-000005
Figure PCTCN2021116592-appb-000005
Figure PCTCN2021116592-appb-000006
Figure PCTCN2021116592-appb-000006
Figure PCTCN2021116592-appb-000007
Figure PCTCN2021116592-appb-000007
Figure PCTCN2021116592-appb-000008
Figure PCTCN2021116592-appb-000008
Figure PCTCN2021116592-appb-000009
Figure PCTCN2021116592-appb-000009
Figure PCTCN2021116592-appb-000010
Figure PCTCN2021116592-appb-000010
Figure PCTCN2021116592-appb-000011
Figure PCTCN2021116592-appb-000011
Figure PCTCN2021116592-appb-000012
Figure PCTCN2021116592-appb-000012
本发明的目的之二在于提供一种目的之一所述的化合物的应用，所述化合物用于有机电致发光器 件。优选地，所述化合物在所述有机电致发光器件中作为发光层材料，优选发光染料。The second object of the present invention is to provide an application of the compound described in one of the objects, and the compound is used in an organic electroluminescent device. Preferably, the compound is used as a light-emitting layer material, preferably a light-emitting dye, in the organic electroluminescent device.
本发明的目的之三在于提供一种有机电致发光器件。具体而言，本发明的实施方案提供了一种有机电致发光器件，包括基板，以及依次形成在所述基板上的阳极层、多个发光功能层和阴极层；所述的发光功能层包括空穴注入层、空穴传输层、发光层、电子传输层，所述的空穴注入层形成在所述的阳极层上，所述的空穴传输层形成在所述的空穴注入层上，所述的阴极层形成在所述的电子传输层上，所述的空穴传输层与所述的电子传输层之间为发光层；其中，优选的，所述的发光层中含有上述通式通式(1)至式(7)中任一所示的本发明的通式化合物，或者所述的发光层中含有上述具体化合物1至化合物180中的至少任一个。The third object of the present invention is to provide an organic electroluminescent device. Specifically, embodiments of the present invention provide an organic electroluminescent device, comprising a substrate, and an anode layer, a plurality of light-emitting functional layers and a cathode layer sequentially formed on the substrate; the light-emitting functional layer includes A hole injection layer, a hole transport layer, a light-emitting layer, and an electron transport layer, the hole injection layer is formed on the anode layer, and the hole transport layer is formed on the hole injection layer , the cathode layer is formed on the electron transport layer, and a light-emitting layer is formed between the hole transport layer and the electron transport layer; wherein, preferably, the light-emitting layer contains the above The compound of the general formula of the present invention represented by any one of the general formula (1) to the formula (7), or the light-emitting layer contains at least any one of the above-mentioned specific compounds 1 to 180.
上述本发明化合物用作有机电致发光器件中的电子传输层材料性能优异的具体原因尚不明确，推测可能是以下的原因：The specific reasons why the above-mentioned compounds of the present invention are used as electron transport layer materials in organic electroluminescent devices are not clear, but the following reasons are presumed:
本发明的通式化合物(见下式)，引入直线型给体-Π-给体、直线型给体-Π-受体或直线型受体-Π-受体的特殊结构，在保持多重共振的前提下，通过前线轨道的能级裂分产生有效的红移，从而使目标分子兼具高发光效率和高色纯度。该系列材料相比目前MR-TADF材料实现光色的巨大红移，能够得到橙红光、红光至近红外的发射。The compound of the general formula of the present invention (see the following formula), introduced into the special structure of linear donor-Π-donor, linear donor-Π-acceptor or linear acceptor-Π-acceptor, maintains multiple resonances Under the premise of , an effective red shift is generated through the energy level splitting of the frontier orbitals, so that the target molecule has both high luminous efficiency and high color purity. Compared with the current MR-TADF materials, this series of materials achieves a huge red shift in light color, and can obtain orange-red light, red light to near-infrared emission.
Figure PCTCN2021116592-appb-000013
Figure PCTCN2021116592-appb-000013
采用本发明化合物制备的OLED器件电致发光光谱，具有较窄的半峰宽，表现出明显的多重共振效果，从而极大地丰富了多重共振-热活化延迟荧光的材料体系和发光颜色范围；并且具有低启动电压、高发光效率和更优的使用寿命，能够满足当前面板制造企业对高性能材料的要求，表现出良好的应用前景。The electroluminescence spectrum of the OLED device prepared by using the compound of the present invention has a narrow half-peak width and exhibits an obvious multiple resonance effect, thereby greatly enriching the material system and emission color range of multiple resonance-thermal activated delayed fluorescence; and It has low starting voltage, high luminous efficiency and better service life, which can meet the requirements of current panel manufacturers for high-performance materials, and shows good application prospects.
附图说明Description of drawings
图1：本发明所制备的有机电致发光器件的结构示意图，图中，1为基板，2为阳极、3为空穴传输层、4为有机发光层、5为电子传输层、6为阴极。Fig. 1: structural schematic diagram of the organic electroluminescent device prepared by the present invention, in the figure, 1 is a substrate, 2 is an anode, 3 is a hole transport layer, 4 is an organic light-emitting layer, 5 is an electron transport layer, and 6 is a cathode .
具体实施方式Detailed ways
下面将以多个合成实施例为例来详述本发明的上述新化合物的具体制备方法，但本发明的制备方法并不限于这些合成实施例。The specific preparation methods of the above-mentioned novel compounds of the present invention will be described in detail below by taking multiple synthesis examples as examples, but the preparation methods of the present invention are not limited to these synthesis examples.
本发明中所用的各种化学药品如石油醚、叔丁苯、乙酸乙酯、硫酸钠、甲苯、二氯甲烷、碳酸钾、三溴化硼、N，N-二异丙基乙胺、反应中间体等基础化工原料均购自上海泰坦科技股份有限公司和西陇化工股份有限公司。确定下述化合物所用的质谱仪采用的是ZAB-HS型质谱仪测定(英国 Micromass公司制造)。Various chemicals used in the present invention such as petroleum ether, tert-butylbenzene, ethyl acetate, sodium sulfate, toluene, dichloromethane, potassium carbonate, boron tribromide, N,N-diisopropylethylamine, reaction Basic chemical raw materials such as intermediates were purchased from Shanghai Titan Technology Co., Ltd. and Xilong Chemical Co., Ltd. The mass spectrometer used to identify the following compounds was a ZAB-HS mass spectrometer (manufactured by Micromass, UK).
下面对本发明化合物的合成方法进行简要的说明，首先，利用正丁基锂或叔丁基锂等对X 1、X 2、X 3与X 4之间/上的氢、Cl原子进行邻位金属化。继而，添加三溴化硼进行锂-硼的金属交换后，添加N，N-二异丙基乙基胺等布朗斯特碱(Bronsted base)，由此进行串联式硼杂弗里德-克拉夫茨反应(Tandem Bora-Friedel-Crafts Reaction)，而可获得目标物。 The synthesis method of the compound of the present invention will be briefly described below. First, the hydrogen and Cl atoms between/on X 1 , X 2 , X 3 and X 4 are subjected to ortho-metallization by n-butyllithium or tert-butyllithium, etc. change. Next, boron tribromide is added to perform lithium-boron metal exchange, and then a Bronsted base such as N,N-diisopropylethylamine is added to perform a tandem boronza Fried-Kla. Crafts Reaction (Tandem Bora-Friedel-Crafts Reaction) to obtain the target.
Figure PCTCN2021116592-appb-000014
Figure PCTCN2021116592-appb-000014
更具体地，以下给出本发明的代表性具体化合物的合成方法。More specifically, synthetic methods of representative specific compounds of the present invention are given below.
合成实施例Synthesis Example
合成实施例1：Synthesis Example 1:
Figure PCTCN2021116592-appb-000015
Figure PCTCN2021116592-appb-000015
化合物1的合成Synthesis of Compound 1
Figure PCTCN2021116592-appb-000016
Figure PCTCN2021116592-appb-000016
将叔丁基锂的戊烷溶液(7.9mL，1.70M，13.38mmol)缓慢加入到0℃的1-1(1.79g，2.20mmol)的叔丁苯(60mL)溶液中，而后依次升温至60℃各反应3小时。反应结束后降温至-30℃，缓慢加入三溴化硼(2.5mL，26.80mmol)，室温继续搅拌0.5小时。室温下加入N，N-二异丙基乙胺(7.00mL，40.20mmol)，并在145℃下继续反应5小时后停止。真空旋干溶剂，过硅胶柱(展开剂：乙酸乙酯：石油醚＝50:1)，得目标化合物1(0.64g，38％收率，HPLC分析纯度99.43％)，为黄色固体。MALDI-TOF-MS结果：分子离子峰：762.53元素分析结果：理论值：C,85.06；H,4.76；B,2.84；N,7.35(％)；实验值：C,85.16；H,4.66；B,2.64；N,7.55(％)。A solution of tert-butyllithium in pentane (7.9 mL, 1.70 M, 13.38 mmol) was slowly added to a solution of 1-1 (1.79 g, 2.20 mmol) in tert-butylbenzene (60 mL) at 0 °C, and then the temperature was increased to 60 °C. °C for each reaction for 3 hours. After the reaction, the temperature was lowered to -30°C, boron tribromide (2.5 mL, 26.80 mmol) was slowly added, and stirring was continued at room temperature for 0.5 hour. N,N-diisopropylethylamine (7.00 mL, 40.20 mmol) was added at room temperature and the reaction was continued at 145°C for 5 hours and then stopped. The solvent was spin-dried in vacuo and passed through a silica gel column (developing solvent: ethyl acetate: petroleum ether=50:1) to obtain the target compound 1 (0.64 g, 38% yield, 99.43% purity by HPLC) as a yellow solid. MALDI-TOF-MS results: Molecular ion peak: 762.53 Elemental analysis results: Theoretical value: C, 85.06; H, 4.76; B, 2.84; N, 7.35(%); Experimental value: C, 85.16; H, 4.66; B , 2.64; N, 7.55 (%).
合成实施例2：Synthesis Example 2:
Figure PCTCN2021116592-appb-000017
Figure PCTCN2021116592-appb-000017
化合物5的合成Synthesis of compound 5
Figure PCTCN2021116592-appb-000018
Figure PCTCN2021116592-appb-000018
本实施例与化合物1合成基本相同，其不同之处在于：本例中需将1-1换为等物质的量的5-1。目标化合物5(0.68g，38％收率，HPLC分析纯度99.55％)，为黄色固体。MALDI-TOF-MS结果：分子离子峰：754.47元素分析结果：理论值：C,85.97；H,3.74；B,2.87；N,7.43(％)；实验值：C,85.87；H,3.84；B,2.77；N,7.53(％)。This example is basically the same as the synthesis of compound 1, the difference is that: in this example, 1-1 needs to be replaced with 5-1 in an equivalent amount. The target compound 5 (0.68 g, 38% yield, 99.55% purity by HPLC analysis) was a yellow solid. MALDI-TOF-MS results: Molecular ion peak: 754.47 Elemental analysis results: Theoretical value: C, 85.97; H, 3.74; B, 2.87; N, 7.43(%); Experimental value: C, 85.87; H, 3.84; B , 2.77; N, 7.53 (%).
合成实施例3：Synthesis Example 3:
Figure PCTCN2021116592-appb-000019
Figure PCTCN2021116592-appb-000019
化合物8的合成Synthesis of Compound 8
Figure PCTCN2021116592-appb-000020
Figure PCTCN2021116592-appb-000020
本实施例与化合物1合成基本相同，其不同之处在于：本例中需将1-1换为等物质的量的8-1。目标化合物8(0.66g，25％收率，HPLC分析纯度99.65％)，为黄色固体。MALDI-TOF-MS结果：分子离子峰：1203.33元素分析结果：理论值：C,85.84；H,7.71；B,1.80；N,4.66(％)；实验值：C,85.81；H,7.74；B,1.70；N,4.766(％)。This example is basically the same as the synthesis of compound 1, the difference is that: in this example, 1-1 needs to be replaced with 8-1 in the same amount of substance. The target compound 8 (0.66 g, 25% yield, 99.65% purity by HPLC analysis) was a yellow solid. MALDI-TOF-MS results: Molecular ion peak: 1203.33 Elemental analysis results: Theoretical value: C, 85.84; H, 7.71; B, 1.80; N, 4.66(%); Experimental value: C, 85.81; H, 7.74; B , 1.70; N, 4.766 (%).
合成实施例4：Synthesis Example 4:
Figure PCTCN2021116592-appb-000021
Figure PCTCN2021116592-appb-000021
化合物18的合成Synthesis of compound 18
Figure PCTCN2021116592-appb-000022
Figure PCTCN2021116592-appb-000022
本实施例与化合物1合成基本相同，其不同之处在于：本例中需将1-1换为等物质的量的18-1。目标化合物18(1.00g，32％收率，HPLC分析纯度99.43％)，为黄色固体。MALDI-TOF-MS结果：分子离子峰：1419.70元素分析结果：理论值：C,86.29；H,8.24；B,1.52；N,3.95(％)；实验值：C,86.19；H,8.34；B,1.32；N,4.15(％)。This example is basically the same as the synthesis of compound 1, the difference is that: in this example, 1-1 needs to be replaced with 18-1 in an equivalent amount. The target compound 18 (1.00 g, 32% yield, 99.43% purity by HPLC analysis) was a yellow solid. MALDI-TOF-MS results: Molecular ion peak: 1419.70 Elemental analysis results: Theoretical value: C, 86.29; H, 8.24; B, 1.52; N, 3.95(%); Experimental value: C, 86.19; H, 8.34; B , 1.32; N, 4.15 (%).
合成实施例5：Synthesis Example 5:
Figure PCTCN2021116592-appb-000023
Figure PCTCN2021116592-appb-000023
化合物82的合成Synthesis of Compound 82
Figure PCTCN2021116592-appb-000024
Figure PCTCN2021116592-appb-000024
本实施例与化合物1合成基本相同，其不同之处在于：本例中需将1-1换为等物质的量的82-1。目标化合物82(0.41g，30％收率，HPLC分析纯度99.53％)，为黄色固体。MALDI-TOF-MS结果：分子离子峰：606.30元素分析结果：理论值：C,83.20；H,3.99；B,3.57；N,9.24(％)；实验值：C,83.27；H,3.92；B,3.67；N,9.14(％)。This example is basically the same as the synthesis of compound 1, the difference is that: in this example, 1-1 needs to be replaced with 82-1 in the same amount of substances. The target compound 82 (0.41 g, 30% yield, 99.53% purity by HPLC analysis) was a yellow solid. MALDI-TOF-MS results: Molecular ion peak: 606.30 Elemental analysis results: Theoretical value: C, 83.20; H, 3.99; B, 3.57; N, 9.24(%); Experimental value: C, 83.27; H, 3.92; B , 3.67; N, 9.14 (%).
合成实施例6：Synthesis Example 6:
Figure PCTCN2021116592-appb-000025
Figure PCTCN2021116592-appb-000025
化合物87的合成Synthesis of compound 87
Figure PCTCN2021116592-appb-000026
Figure PCTCN2021116592-appb-000026
本实施例与化合物1合成基本相同，其不同之处在于：本例中需将1-1换为等物质的量的87-1。目标化合物87(0.42g，32％收率，HPLC分析纯度99.67％)，为黄色固体。MALDI-TOF-MS结果：分子离子峰：598.24元素分析结果：理论值：C,84.32；H,2.70；B,3.61；N,9.37(％)；实验值：C,84.42；H,2.60；B,3.51；N,9.47(％)。This example is basically the same as the synthesis of compound 1, the difference is that: in this example, 1-1 needs to be replaced with 87-1 in an equivalent amount. The target compound 87 (0.42 g, 32% yield, 99.67% purity by HPLC analysis) was a yellow solid. MALDI-TOF-MS results: Molecular ion peak: 598.24 Elemental analysis results: Theoretical value: C, 84.32; H, 2.70; B, 3.61; N, 9.37(%); Experimental value: C, 84.42; H, 2.60; B , 3.51; N, 9.47 (%).
合成实施例7：Synthesis Example 7:
Figure PCTCN2021116592-appb-000027
Figure PCTCN2021116592-appb-000027
化合物102的合成Synthesis of Compound 102
Figure PCTCN2021116592-appb-000028
Figure PCTCN2021116592-appb-000028
将叔丁基锂的戊烷溶液(18.59mL，1.60M，29.75mmol)缓慢加入到0℃的102-1(3.61g，4.96mmol)的叔丁苯(60mL)溶液中，而后依次升温至60℃各反应3小时。反应结束后降温至-30℃，缓慢加入三溴化硼(4.97g，19.82mmol)，室温继续搅拌0.5小时。室温下加入N，N-二异丙基乙胺(2.56g，19.82mmol)，并在145℃下继续反应12小时后冷却至室温，此状态下加入苯基溴化镁(3.59g，19.82mmol)，继续反应2小时后停止。真空旋干溶剂，过硅胶柱(展开剂：乙酸乙酯：石油醚＝50:1)，得目标化合物102(0.34g，10％收率，HPLC分析纯度99.22％)，为黄色固体。MALDI-TOF-MS结果：分子离子峰：756.14元素分析结果：理论值：C,85.78；H,4.80；B,5.72；N,3.70(％)；实验值：C,85.78；H,4.80；B,5.72；N,3.70(％)。A solution of tert-butyllithium in pentane (18.59 mL, 1.60 M, 29.75 mmol) was slowly added to a solution of 102-1 (3.61 g, 4.96 mmol) in tert-butylbenzene (60 mL) at 0 °C, and then the temperature was increased to 60 °C. °C for each reaction for 3 hours. After the reaction, the temperature was lowered to -30°C, boron tribromide (4.97 g, 19.82 mmol) was slowly added, and stirring was continued at room temperature for 0.5 hour. N,N-diisopropylethylamine (2.56g, 19.82mmol) was added at room temperature, and the reaction was continued at 145°C for 12 hours and then cooled to room temperature. In this state, phenylmagnesium bromide (3.59g, 19.82mmol) was added. ), continue to react for 2 hours and then stop. The solvent was spin-dried in vacuo and passed through a silica gel column (developing solvent: ethyl acetate: petroleum ether=50:1) to obtain the target compound 102 (0.34 g, 10% yield, 99.22% purity by HPLC) as a yellow solid. MALDI-TOF-MS results: Molecular ion peak: 756.14 Elemental analysis results: Theoretical value: C, 85.78; H, 4.80; B, 5.72; N, 3.70(%); Experimental value: C, 85.78; H, 4.80; B , 5.72; N, 3.70 (%).
合成实施例8：Synthesis Example 8:
Figure PCTCN2021116592-appb-000029
Figure PCTCN2021116592-appb-000029
化合物113的合成Synthesis of Compound 113
Figure PCTCN2021116592-appb-000030
Figure PCTCN2021116592-appb-000030
本实施例与化合物1合成基本相同，其不同之处在于：本例中需将1-1换为等物质的量的113-1。目标化合物113(0.55g，41％收率，HPLC分析纯度99.33％)，为黄色固体。MALDI-TOF-MS结果：分子离子峰：612.22元素分析结果：理论值：C,82.39；H,4.28；B,3.53；N,4.58；O,5.23(％)；实验值：C,82.19；H,4.25；B,3.73；N,4.57；O,5.27(％)。This example is basically the same as the synthesis of compound 1, the difference is that: in this example, 1-1 needs to be replaced with 113-1 in the same amount of substance. The target compound 113 (0.55 g, 41% yield, 99.33% purity by HPLC analysis) was a yellow solid. MALDI-TOF-MS results: Molecular ion peak: 612.22 Elemental analysis results: Theoretical value: C, 82.39; H, 4.28; B, 3.53; N, 4.58; O, 5.23 (%); Experimental value: C, 82.19; H , 4.25; B, 3.73; N, 4.57; O, 5.27 (%).
合成实施例9：Synthesis Example 9:
Figure PCTCN2021116592-appb-000031
Figure PCTCN2021116592-appb-000031
化合物114的合成Synthesis of compound 114
Figure PCTCN2021116592-appb-000032
Figure PCTCN2021116592-appb-000032
本实施例与化合物1合成基本相同，其不同之处在于：本例中需将1-1换为等物质的量的114-1。目标化合物114(0.42g，36％收率，HPLC分析纯度99.54％)，为黄色固体。MALDI-TOF-MS结果：分子离子峰：537.19元素分析结果：理论值：C,80.49；H,3.94；B,4.02；N,2.61；O,8.93(％)；实验值：C,80.59；H,3.74；B,4.12；N,2.71；O,8.83(％)。This example is basically the same as the synthesis of compound 1, the difference is that: in this example, 1-1 needs to be replaced with 114-1 in an equivalent amount. The target compound 114 (0.42 g, 36% yield, 99.54% purity by HPLC analysis) was a yellow solid. MALDI-TOF-MS results: Molecular ion peak: 537.19 Elemental analysis results: Theoretical value: C, 80.49; H, 3.94; B, 4.02; N, 2.61; O, 8.93(%); Experimental value: C, 80.59; H , 3.74; B, 4.12; N, 2.71; O, 8.83 (%).
合成实施例10：Synthesis Example 10:
Figure PCTCN2021116592-appb-000033
Figure PCTCN2021116592-appb-000033
化合物132的合成Synthesis of Compound 132
Figure PCTCN2021116592-appb-000034
Figure PCTCN2021116592-appb-000034
本实施例与化合物1合成基本相同，其不同之处在于：本例中需将1-1换为等物质的量的132-1。目标化合物132(0.37g，26％收率，HPLC分析纯度99.52％)，为黄色固体。MALDI-TOF-MS结果：分子离子峰：644.42元素分析结果：理论值：C,78.28；H,4.07；B,3.35；N,4.35；S,9.95(％)；实验值：C,78.28；H,4.07；B,3.35；N,4.35；S,9.95(％)。This example is basically the same as the synthesis of compound 1, the difference is that: in this example, 1-1 needs to be replaced with 132-1 in an equivalent amount. The target compound 132 (0.37 g, 26% yield, 99.52% purity by HPLC analysis) was a yellow solid. MALDI-TOF-MS results: Molecular ion peak: 644.42 Elemental analysis results: Theoretical value: C, 78.28; H, 4.07; B, 3.35; N, 4.35; S, 9.95(%); Experimental value: C, 78.28; H , 4.07; B, 3.35; N, 4.35; S, 9.95 (%).
合成实施例11：Synthesis Example 11:
Figure PCTCN2021116592-appb-000035
Figure PCTCN2021116592-appb-000035
化合物149的合成Synthesis of compound 149
Figure PCTCN2021116592-appb-000036
Figure PCTCN2021116592-appb-000036
本实施例与化合物1合成基本相同，其不同之处在于：本例中需将1-1换为等物质的量的149-1。目标化合物149(0.52g，36％收率，HPLC分析纯度99.42％)，为黄色固体。MALDI-TOF-MS结果：分子离子峰：662.41元素分析结果：理论值：C,83.41；H,4.87；B,3.26；N,8.46(％)；实验值：C,83.40；H,4.88；B,3.25；N,8.47(％)。This example is basically the same as the synthesis of compound 1, the difference is that: in this example, 1-1 needs to be replaced with 149-1 in an equivalent amount. The target compound 149 (0.52 g, 36% yield, 99.42% purity by HPLC analysis) was a yellow solid. MALDI-TOF-MS results: Molecular ion peak: 662.41 Elemental analysis results: Theoretical value: C, 83.41; H, 4.87; B, 3.26; N, 8.46(%); Experimental value: C, 83.40; H, 4.88; B , 3.25; N, 8.47 (%).
合成实施例12：Synthesis Example 12:
Figure PCTCN2021116592-appb-000037
Figure PCTCN2021116592-appb-000037
化合物150的合成Synthesis of Compound 150
Figure PCTCN2021116592-appb-000038
Figure PCTCN2021116592-appb-000038
合成实施例12：Synthesis Example 12:
Figure PCTCN2021116592-appb-000039
Figure PCTCN2021116592-appb-000039
化合物180的合成Synthesis of Compound 180
Figure PCTCN2021116592-appb-000040
Figure PCTCN2021116592-appb-000040
本实施例与化合物102合成基本相同，其不同之处在于：本例中需将102-1换为等物质的量的180-1。目标化合物180(0.72g，19％收率，HPLC分析纯度99.35％)，为橙红色固体。MALDI-TOF-MS结果：分子离子峰：759.33元素分析结果：理论值：C,85.42；H,4.78；B,4.27；N,5.53(％)；实验值：C,85.42；H,4.78；B,4.27；N,5.53(％)。This example is basically the same as the synthesis of compound 102, the difference is that: in this example, 102-1 needs to be replaced with 180-1 in an equivalent amount. The target compound 180 (0.72 g, 19% yield, 99.35% purity by HPLC analysis) was an orange-red solid. MALDI-TOF-MS results: Molecular ion peak: 759.33 Elemental analysis results: Theoretical value: C, 85.42; H, 4.78; B, 4.27; N, 5.53(%); Experimental value: C, 85.42; H, 4.78; B , 4.27; N, 5.53 (%).
下通过将本发明的化合物具体应用到有机电致发光器件中测试实际使用性能来展示和验证本发明的技术效果和优点。Next, the technical effects and advantages of the present invention are demonstrated and verified by applying the compounds of the present invention to organic electroluminescent devices and testing the actual performance.
有机电致发光器件包括第一电极、第二电极，以及位于两个电极之间的有机材料层。该有机材料又可以分为多个区域，比如该有机材料层可以包括空穴传输区、发光层、电子传输区。The organic electroluminescent device includes a first electrode, a second electrode, and an organic material layer between the two electrodes. The organic material can be further divided into multiple regions. For example, the organic material layer can include a hole transport region, a light-emitting layer, and an electron transport region.
阳极的材料可以采用铟锡氧(ITO)、铟锌氧(IZO)、二氧化锡(SnO2)、氧化锌(ZnO)等氧化物透明导电材料和它们的任意组合。阴极的材料可以采用镁(Mg)、银(Ag)、铝(Al)、铝-锂(Al-Li)、钙(Ca)、镁-铟(Mg-In)、镁-银(Mg-Ag)等金属或合金以及它们之间的任意组合。The material of the anode can be transparent conductive oxide materials such as indium tin oxide (ITO), indium zinc oxide (IZO), tin dioxide (SnO2), zinc oxide (ZnO), and any combination thereof. The material of the cathode can be magnesium (Mg), silver (Ag), aluminum (Al), aluminum-lithium (Al-Li), calcium (Ca), magnesium-indium (Mg-In), magnesium-silver (Mg-Ag) ) and other metals or alloys and any combination between them.
空穴传输区位于阳极和发光层之间。空穴传输区可以为单层结构的空穴传输层(HTL)，包括只含有一种化合物的单层空穴传输层和含有多种化合物的单层空穴传输层。空穴传输区也可以为包括空穴注入层(HIL)、空穴传输层(HTL)、电子阻挡层(EBL)中的至少一层的多层结构。The hole transport region is located between the anode and the light emitting layer. The hole transport region may be a hole transport layer (HTL) with a single-layer structure, including a single-layer hole-transport layer containing only one compound and a single-layer hole-transport layer containing multiple compounds. The hole transport region may also be a multilayer structure including at least one of a hole injection layer (HIL), a hole transport layer (HTL), and an electron blocking layer (EBL).
空穴传输区的材料可以选自但不限于酞菁衍生物如CuPc、导电聚合物或含导电掺杂剂的聚合物如聚苯撑乙烯、聚苯胺/十二烷基苯磺酸(Pani/DBSA)、聚(3,4-乙撑二氧噻吩)/聚(4-苯乙烯磺酸盐)(PEDOT/PSS)、聚苯胺/樟脑磺酸(Pani/CSA)、聚苯胺/聚(4-苯乙烯磺酸盐)(Pani/PSS)、芳香胺衍生物等。The material of the hole transport region can be selected from, but not limited to, phthalocyanine derivatives such as CuPc, conductive polymers or polymers containing conductive dopants such as polyphenylene vinylene, polyaniline/dodecylbenzenesulfonic acid (Pani/dodecylbenzenesulfonic acid). DBSA), poly(3,4-ethylenedioxythiophene)/poly(4-styrenesulfonate) (PEDOT/PSS), polyaniline/camphorsulfonic acid (Pani/CSA), polyaniline/poly(4 - Styrene sulfonate) (Pani/PSS), aromatic amine derivatives, etc.
发光层包括可以发射不同波长光谱的的发光染料(即掺杂剂，dopant)，还可以同时包括主体材料(Host)。发光层可以是发射红、绿、蓝等单一颜色的单色发光层。多种不同颜色的单色发光层可以按照像素图形进行平面排列，也可以堆叠在一起而形成彩色发光层。当不同颜色的发光层堆叠在一起时，它们可以彼此隔开，也可以彼此相连。发光层也可以是能同时发射红、绿、蓝等不同颜色的单一彩色发光层。The light-emitting layer includes light-emitting dyes (ie dopant, dopant) that can emit different wavelength spectra, and may also include a host material (Host). The light-emitting layer may be a monochromatic light-emitting layer that emits a single color such as red, green, and blue. The monochromatic light-emitting layers of a plurality of different colors can be arranged in a plane according to a pixel pattern, or can be stacked together to form a colored light-emitting layer. When light-emitting layers of different colors are stacked together, they can be spaced from each other or connected to each other. The light-emitting layer may also be a single-color light-emitting layer capable of simultaneously emitting different colors such as red, green, and blue.
电子传输区可以为单层结构的电子传输层(ETL)，包括只含有一种化合物的单层电子传输层和含有多种化合物的单层电子传输层。电子传输区也可以为包括电子注入层(EIL)、电子传输层(ETL)、空穴阻挡层(HBL)中的至少一层的多层结构。The electron transport region may be an electron transport layer (ETL) with a single-layer structure, including a single-layer electron transport layer containing only one compound and a single-layer electron transport layer containing multiple compounds. The electron transport region may also be a multilayer structure including at least one of an electron injection layer (EIL), an electron transport layer (ETL), and a hole blocking layer (HBL).
结合附图1说明有机电致发光器件制备过程如下：在基板1上依次沉积阳极2、空穴传输层3、有机发光层4、电子传输层5、阴极6，然后封装。其中，在制备有机发光层4时，通过宽带隙材料源、电子给体型材料源、电子受体型材料源和共振型TADF材料源共同蒸镀的方法形成有机发光层4。The preparation process of the organic electroluminescent device is described with reference to FIG. 1 as follows: an anode 2, a hole transport layer 3, an organic light emitting layer 4, an electron transport layer 5, and a cathode 6 are sequentially deposited on a substrate 1, and then packaged. Wherein, when preparing the organic light-emitting layer 4, the organic light-emitting layer 4 is formed by co-evaporating a wide bandgap material source, an electron donor material source, an electron acceptor material source and a resonance TADF material source.
具体地，本发明的有机电致发光器件的制备方法包括以下步骤：Specifically, the preparation method of the organic electroluminescent device of the present invention comprises the following steps:
1、将涂布了阳极材料的玻璃板在商用清洗剂中超声处理，在去离子水中冲洗，在丙酮：乙醇混合溶剂中超声除油，在洁净环境下烘烤至完全除去水份，用紫外光和臭氧清洗，并用低能阳离子束轰击表面；1. The glass plate coated with anode material was ultrasonically treated in commercial cleaning agent, rinsed in deionized water, ultrasonically degreasing in acetone:ethanol mixed solvent, baked in a clean environment until water was completely removed, and UV light was used. Light and ozone cleaning, and bombarding the surface with a beam of low-energy cations;
2、把上述带有阳极的玻璃板置于真空腔内，抽真空至1×10 -5～9×10 -3Pa，在上述阳极层膜上真空蒸镀空穴注入材料形成空穴注入层，蒸镀速率为0.1-0.5nm/s； 2. Place the above-mentioned glass plate with anode in a vacuum chamber, evacuate to 1 × 10 -5 to 9 × 10 -3 Pa, and vacuum-deposit hole injection material on the above-mentioned anode film to form a hole injection layer , the evaporation rate is 0.1-0.5nm/s;
3、在空穴注入层之上真空蒸镀空穴传输材料形成空穴传输层，蒸镀速率为0.1-0.5nm/s，3. Vacuum evaporation of a hole transport material on the hole injection layer to form a hole transport layer, the evaporation rate is 0.1-0.5nm/s,
4、在空穴传输层之上真空蒸镀电子阻挡层，蒸镀速率为0.1-0.5nm/s；4. The electron blocking layer is vacuum evaporated on the hole transport layer, and the evaporation rate is 0.1-0.5nm/s;
5、在电子阻挡层之上真空蒸镀器件的有机发光层，有机发光层材料中包括主体材料和TADF染料，利用多源共蒸的方法，调节主体材料的蒸镀速率、敏化剂材料的蒸镀速度和染料的蒸镀速率使染料达到预设掺杂比例；5. The organic light-emitting layer of the device is vacuum-evaporated on the electron blocking layer. The organic light-emitting layer material includes the host material and TADF dye, and the multi-source co-evaporation method is used to adjust the evaporation rate of the host material and the sensitizer material. The evaporation rate and the evaporation rate of the dye make the dye reach the preset doping ratio;
6、在有机发光层之上真空蒸镀空穴阻挡层，其蒸镀速率为0.1-0.5nm/s；6. Vacuum evaporation of a hole blocking layer on the organic light-emitting layer, the evaporation rate of which is 0.1-0.5nm/s;
7、在空穴阻挡层之上真空蒸镀器件的电子传输材料形成电子传输层，其蒸镀速率为0.1-0.5nm/s；7. The electron transport material of the device is vacuum evaporated on the hole blocking layer to form an electron transport layer, and the evaporation rate is 0.1-0.5nm/s;
8、在电子传输层上以0.1-0.5nm/s真空蒸镀LiF作为电子注入层，以0.5-1nm/s真空蒸镀Al层作为器件的阴极。8. On the electron transport layer, 0.1-0.5nm/s vacuum evaporation LiF is used as the electron injection layer, and 0.5-1nm/s vacuum evaporation Al layer is used as the cathode of the device.
本发明实施例还提供一种显示装置，所述显示装置包括如上述提供的有机电致发光器件。该显示装置具体可以为OLED显示器等显示器件，以及包括该显示器件的电视、数码相机、手机、平板电脑等任何具有显示功能的产品或者部件。该显示装置与上述有机电致发光器件相对于现有技术所具有的优势相同，在此不再赘述。An embodiment of the present invention further provides a display device, the display device includes the organic electroluminescence device provided above. Specifically, the display device may be a display device such as an OLED display, as well as any product or component with a display function, such as a TV, a digital camera, a mobile phone, and a tablet computer including the display device. The display device and the above organic electroluminescent device have the same advantages over the prior art, which will not be repeated here.
以下通过具体实施例对本发明的有机电致发光器件进行进一步的介绍。The organic electroluminescent device of the present invention will be further introduced below through specific examples.
器件实施例1Device Example 1
本实施例制备的有机电致发光器件结构如下所示：The structure of the organic electroluminescent device prepared in this example is as follows:
ITO/HI(10nm)/HT(30nm)/EBL(10nm)/Host:3wt％1(30nm)/HBL(10nm)ET(30nm)/LiF(0.5nm)/Al(150nm)ITO/HI(10nm)/HT(30nm)/EBL(10nm)/Host:3wt%1(30nm)/HBL(10nm)ET(30nm)/LiF(0.5nm)/Al(150nm)
其中，阳极材料为ITO；空穴注入层材料为HI，一般总厚度为5-30nm，本实施例为10nm；空穴传输层的材料为HT，总厚度一般为5-500nm，本实施例为40nm；Host为有机发光层宽带隙的主体材料，本发明化合物1为染料且掺杂浓度为3wt％，有机发光层的厚度一般为1-200nm，本实施例为30nm；电子传输层的材料为ET，厚度一般为5-300nm，本实施例为30nm；电子注入层及阴极材料选择LiF(0.5nm)和金属铝(150nm)。The material of the anode is ITO; the material of the hole injection layer is HI, and the total thickness is generally 5-30 nm, which is 10 nm in this embodiment; the material of the hole transport layer is HT, and the total thickness is generally 5-500 nm. 40nm; Host is the host material of the wide bandgap of the organic light-emitting layer, the compound 1 of the present invention is a dye and the doping concentration is 3wt%, the thickness of the organic light-emitting layer is generally 1-200nm, 30nm in this embodiment; the material of the electron transport layer is ET, the thickness is generally 5-300nm, this embodiment is 30nm; the electron injection layer and cathode materials are selected from LiF (0.5nm) and metal aluminum (150nm).
针对本实施例制备得到的有机电致发光器件D1施加直流电压，测定10cd/m 2发光时的特性，可获得波长605nm、半峰宽42nm、CIE色坐标(x,y)＝(0.68,0.31)、外量子效率EQE为25.8％的红色发光(驱动电压为2.3V)。 Apply a DC voltage to the organic electroluminescent device D1 prepared in this example, and measure the characteristics when emitting light at 10 cd/m 2 . The wavelength at 605 nm, the width at half maximum of 42 nm, and the CIE color coordinates (x, y)=(0.68, 0.31) can be obtained. ) and red light emission with external quantum efficiency EQE of 25.8% (driving voltage of 2.3V).
器件实施例2Device Example 2
与器件实施例1的制备方法相同，区别在于，将发光层中采用的宽带隙型主体材料Host替换为TADF型主体TD，具体器件结构如下：The preparation method is the same as that of Device Example 1, except that the wide-bandgap host material Host used in the light-emitting layer is replaced with a TADF-type host TD, and the specific device structure is as follows:
ITO/HI(10nm)/HT(30nm)/EBL(10nm)/TD:3wt％1(30nm)/HBL(10nm)ET(30nm)/LiF(0.5nm)/Al(150nm)ITO/HI(10nm)/HT(30nm)/EBL(10nm)/TD:3wt%1(30nm)/HBL(10nm)ET(30nm)/LiF(0.5nm)/Al(150nm)
针对本实施例制备得到的有机电致发光器件D2测定器件性能结果如下：施加直流电压，测定10cd/m 2发光时的特性，可获得波长605nm、半峰宽43nm、CIE色坐标(x,y)＝(0.69,0.30)、外量子效率EQE为31.4％的红色发光(驱动电压为2.2V)。 For the organic electroluminescent device D2 prepared in this example, the results of measuring the device performance are as follows: applying a DC voltage, measuring the characteristics when 10cd/m 2 emits light, the wavelength of 605nm, the half-peak width of 43nm, and the CIE color coordinates (x, y) can be obtained. )=(0.69, 0.30), red light emission with external quantum efficiency EQE of 31.4% (driving voltage of 2.2V).
器件实施例3Device Example 3
与器件实施例1的制备方法相同，区别在于，将发光层中所采用的染料由1替换为5。器件结构如下：The preparation method is the same as that of Device Example 1, except that the dye used in the light-emitting layer is replaced from 1 to 5. The device structure is as follows:
ITO/HI(10nm)/HT(30nm)/EBL(10nm)/Host:3wt％5(30nm)/HBL(10nm)ET(30nm)/LiF(0.5nm)/Al(150nm)ITO/HI(10nm)/HT(30nm)/EBL(10nm)/Host:3wt%5(30nm)/HBL(10nm)ET(30nm)/LiF(0.5nm)/Al(150nm)
针对本实施例制备得到的有机电致发光器件D3测定器件性能结果如下：施加直流电压，测定10cd/m 2发光时的特性，可获得波长664nm、半峰宽48nm、CIE色坐标(x,y)＝(0.71,0.29)、 外量子效率EQE为24.2％的深红色发光(驱动电压为2.2V)。 For the organic electroluminescent device D3 prepared in this example, the results of measuring the device performance are as follows: applying a DC voltage, measuring the characteristics when 10cd/m 2 emits light, the wavelength of 664 nm, the half-peak width of 48 nm, and the CIE color coordinates (x, y) can be obtained. )=(0.71, 0.29), deep red emission with external quantum efficiency EQE of 24.2% (driving voltage of 2.2V).
器件实施例4Device Example 4
与器件实施例1的制备方法相同，区别在于，将发光层中的宽带隙型主体材料Host替换为TADF型主体TD、将染料由1替换为5。器件结构如下：The preparation method is the same as that of Device Example 1, except that the wide-bandgap host material Host in the light-emitting layer is replaced with a TADF-type host TD, and the dye is replaced from 1 to 5. The device structure is as follows:
ITO/HI(10nm)/HT(30nm)/EBL(10nm)/TD:3wt％5(30nm)/HBL(10nm)ET(30nm)/LiF(0.5nm)/Al(150nm)ITO/HI(10nm)/HT(30nm)/EBL(10nm)/TD:3wt%5(30nm)/HBL(10nm)ET(30nm)/LiF(0.5nm)/Al(150nm)
针对本实施例制备得到的有机电致发光器件D4测定器件性能结果如下：施加直流电压，测定10cd/m 2发光时的特性，可获得波长664nm、半峰宽48nm、CIE色坐标(x,y)＝(0.71,0.29)、外量子效率EQE为29.2％的深红色发光(驱动电压为2.1V)。 For the organic electroluminescent device D4 prepared in this example, the results of measuring the device performance are as follows: applying a DC voltage, measuring the characteristics when emitting light at 10cd/ m2 , the wavelength of 664nm, the half-peak width of 48nm, and the CIE color coordinates (x, y) can be obtained. )=(0.71, 0.29), deep red emission with external quantum efficiency EQE of 29.2% (driving voltage 2.1V).
器件实施例5Device Example 5
与器件实施例1的制备方法相同，区别在于，将发光层中的染料由1替换为82。器件结构如下：The preparation method is the same as that of Device Example 1, except that the dye in the light-emitting layer is replaced from 1 to 82. The device structure is as follows:
ITO/HI(10nm)/HT(30nm)/EBL(10nm)/Host:3wt％82(30nm)/HBL(10nm)ET(30nm)/LiF(0.5nm)/Al(150nm)ITO/HI(10nm)/HT(30nm)/EBL(10nm)/Host:3wt%82(30nm)/HBL(10nm)ET(30nm)/LiF(0.5nm)/Al(150nm)
针对本实施例制备得到的有机电致发光器件D5测定器件性能结果如下：施加直流电压，测定10cd/m 2发光时的特性，可获得波长755nm、半峰宽50nm、CIE色坐标(x,y)＝(0.72,0.28)、外量子效率EQE为20.3％的近红外发光(驱动电压为2.1V)。 For the organic electroluminescent device D5 prepared in this example, the results of measuring the device performance are as follows: applying a DC voltage, measuring the characteristics when 10cd/m 2 emits light, the wavelength of 755nm, the half-peak width of 50nm, and the CIE color coordinates (x, y) can be obtained. )=(0.72, 0.28) and near-infrared light emission with external quantum efficiency EQE of 20.3% (driving voltage of 2.1V).
器件实施例6Device Example 6
与器件实施例1的制备方法相同，区别在于，将发光层中的宽带隙型主体材料Host替换为TADF型主体TD、将染料由1替换为82。器件结构如下：The preparation method is the same as that of Device Example 1, except that the wide-bandgap host material Host in the light-emitting layer is replaced with a TADF-type host TD, and the dye is replaced from 1 to 82. The device structure is as follows:
ITO/HI(10nm)/HT(30nm)/EBL(10nm)/TD:3wt％82(30nm)/HBL(10nm)ET(30nm)/LiF(0.5nm)/Al(150nm)ITO/HI(10nm)/HT(30nm)/EBL(10nm)/TD:3wt%82(30nm)/HBL(10nm)ET(30nm)/LiF(0.5nm)/Al(150nm)
针对本实施例制备得到的有机电致发光器件D6测定器件性能结果如下：施加直流电压，测定10cd/m 2发光时的特性，可获得波长755nm、半峰宽50nm、CIE色坐标(x,y)＝(0.72,0.28)、外量子效率EQE为25.3％的近红外发光(驱动电压为2.0V)。 For the organic electroluminescent device D6 prepared in this example, the results of measuring the device performance are as follows: applying a DC voltage, measuring the characteristics when 10cd/m 2 emits light, the wavelength of 755nm, the half-peak width of 50nm, and the CIE color coordinates (x, y) can be obtained. )=(0.72, 0.28) and near-infrared emission with external quantum efficiency EQE of 25.3% (driving voltage of 2.0V).
器件实施例7Device Example 7
与器件实施例1的制备方法相同，区别在于，将发光层中的染料由1替换为87。器件结构如下：The preparation method is the same as that of Device Example 1, except that the dye in the light-emitting layer is replaced from 1 to 87. The device structure is as follows:
ITO/HI(10nm)/HT(30nm)/EBL(10nm)/Host:3wt％87(30nm)/HBL(10nm)ET(30nm)/LiF(0.5nm)/Al(150nm)ITO/HI(10nm)/HT(30nm)/EBL(10nm)/Host:3wt%87(30nm)/HBL(10nm)ET(30nm)/LiF(0.5nm)/Al(150nm)
针对本实施例制备得到的有机电致发光器件D7测定器件性能结果如下：施加直流电压，测定10cd/m 2发光时的特性，可获得波长875nm、半峰宽52nm、CIE色坐标(x,y)＝(0.74,0.26)、外量子效率EQE为15.3％的近红外发光(驱动电压为2.0V)。 For the organic electroluminescent device D7 prepared in this example, the results of measuring the device performance are as follows: applying a DC voltage, measuring the characteristics when 10cd/m 2 emits light, the wavelength of 875nm, the half-peak width of 52nm, and the CIE color coordinates (x, y) can be obtained. )=(0.74, 0.26), near-infrared emission with external quantum efficiency EQE of 15.3% (driving voltage of 2.0V).
器件实施例8Device Example 8
与器件实施例1的制备方法相同，区别在于，将发光层中的宽带隙型主体材料Host替换为TADF型主体TD、将染料由1替换为87。器件结构如下：The preparation method is the same as that of Device Example 1, except that the wide band gap type host material Host in the light-emitting layer is replaced with a TADF type host TD, and the dye is replaced from 1 to 87. The device structure is as follows:
ITO/HI(10nm)/HT(30nm)/EBL(10nm)/TD:3wt％87(30nm)/HBL(10nm)ET(30nm)/LiF(0.5nm)/Al(150nm)ITO/HI(10nm)/HT(30nm)/EBL(10nm)/TD:3wt%87(30nm)/HBL(10nm)ET(30nm)/LiF(0.5nm)/Al(150nm)
针对本实施例制备得到的有机电致发光器件D8测定器件性能结果如下：施加直流电压，测定10cd/m 2发光时的特性，可获得波长875nm、半峰宽52nm、CIE色坐标(x,y)＝(0.74,0.26)、外量子效率EQE为19.3％的近红外发光(驱动电压为1.9V)。 For the organic electroluminescent device D8 prepared in this example, the results of measuring the device performance are as follows: applying a DC voltage, measuring the characteristics when 10cd/m 2 emits light, the wavelength of 875nm, the half-peak width of 52nm, and the CIE color coordinates (x, y) can be obtained. )=(0.74, 0.26) and near-infrared emission with external quantum efficiency EQE of 19.3% (driving voltage of 1.9V).
器件实施例9Device Example 9
与器件实施例1的制备方法相同，区别在于，将发光层中的染料由1替换为102。器件结构如下：The preparation method is the same as that of Device Example 1, except that the dye in the light-emitting layer is replaced from 1 to 102. The device structure is as follows:
ITO/HI(10nm)/HT(30nm)/EBL(10nm)/Host:3wt％102(30nm)/HBL(10nm)ET(30nm)/LiF(0.5nm)/Al(150nm)ITO/HI(10nm)/HT(30nm)/EBL(10nm)/Host:3wt%102(30nm)/HBL(10nm)ET(30nm)/LiF(0.5nm)/Al(150nm)
针对本实施例制备得到的有机电致发光器件D9测定器件性能结果如下：施加直流电压，测定10cd/m 2发光时的特性，可获得波长626nm、半峰宽44nm、CIE色坐标(x,y)＝(0.69,0.31)、外量子效率EQE为24.3％的红色发光(驱动电压为2.3V)。 For the organic electroluminescent device D9 prepared in this example, the results of measuring the device performance are as follows: applying a DC voltage, measuring the characteristics when 10cd/m 2 emits light, the wavelength of 626 nm, the half-peak width of 44 nm, the CIE color coordinates (x, y) can be obtained. )=(0.69, 0.31), red light emission with external quantum efficiency EQE of 24.3% (driving voltage of 2.3V).
器件实施例10Device Example 10
与器件实施例1的制备方法相同，区别在于，将发光层中的宽带隙型主体材料Host替换为TADF型主体TD、将染料由1替换为102。器件结构如下：The preparation method is the same as that of Device Example 1, except that the wide-bandgap host material Host in the light-emitting layer is replaced with a TADF-type host TD, and the dye is replaced from 1 to 102. The device structure is as follows:
ITO/HI(10nm)/HT(30nm)/EBL(10nm)/TD:3wt％102(30nm)/HBL(10nm)ET(30nm)/LiF(0.5nm)/Al(150nm)ITO/HI(10nm)/HT(30nm)/EBL(10nm)/TD:3wt%102(30nm)/HBL(10nm)ET(30nm)/LiF(0.5nm)/Al(150nm)
针对本实施例制备得到的有机电致发光器件D10测定器件性能结果如下：施加直流电压，测定10cd/m 2发光时的特性，可获得波长626nm、半峰宽44nm、CIE色坐标(x,y)＝(0.69,0.31)、外量子效率EQE为29.3％的红色发光(驱动电压为2.2V)。 For the organic electroluminescent device D10 prepared in this example, the device performance measurement results are as follows: applying a DC voltage, measuring the characteristics when 10cd/m 2 emits light, the wavelength of 626 nm, the half-peak width of 44 nm, and the CIE color coordinates (x, y) can be obtained. )=(0.69, 0.31), red light emission with external quantum efficiency EQE of 29.3% (driving voltage 2.2V).
器件实施例11Device Example 11
与器件实施例1的制备方法相同，区别在于，将发光层中的染料由1替换为113。器件结构如下：The preparation method is the same as that of Device Example 1, except that the dye in the light-emitting layer is replaced from 1 to 113. The device structure is as follows:
ITO/HI(10nm)/HT(30nm)/EBL(10nm)/Host:3wt％113(30nm)/HBL(10nm)ET(30nm)/LiF(0.5nm)/Al(150nm)ITO/HI(10nm)/HT(30nm)/EBL(10nm)/Host:3wt%113(30nm)/HBL(10nm)ET(30nm)/LiF(0.5nm)/Al(150nm)
针对本实施例制备得到的有机电致发光器件D11测定器件性能结果如下：施加直流电压，测定10cd/m 2发光时的特性，可获得波长580nm、半峰宽39nm、CIE色坐标(x,y)＝(0.58,0.42)、外量子效率EQE为26.3％的橙黄色发光(驱动电压为2.5V)。 For the organic electroluminescent device D11 prepared in this example, the device performance measurement results are as follows: applying a DC voltage, measuring the characteristics when 10cd/m 2 emits light, the wavelength of 580nm, the half-peak width of 39nm, and the CIE color coordinates (x, y) can be obtained. )=(0.58, 0.42), orange-yellow emission with external quantum efficiency EQE of 26.3% (driving voltage of 2.5V).
器件实施例12Device Example 12
与器件实施例1的制备方法相同，区别在于，将发光层中的宽带隙型主体材料Host替换为TADF型主体TD、将染料由1替换为113。器件结构如下：The preparation method is the same as that of Device Example 1, except that the wide-bandgap host material Host in the light-emitting layer is replaced with a TADF-type host TD, and the dye is replaced with 113. The device structure is as follows:
ITO/HI(10nm)/HT(30nm)/EBL(10nm)/TD:3wt％113(30nm)/HBL(10nm)ET(30nm)/LiF(0.5nm)/Al(150nm)ITO/HI(10nm)/HT(30nm)/EBL(10nm)/TD:3wt%113(30nm)/HBL(10nm)ET(30nm)/LiF(0.5nm)/Al(150nm)
针对本实施例制备得到的有机电致发光器件D12测定器件性能结果如下：施加直流电压，测定10cd/m 2发光时的特性，可获得波长580nm、半峰宽39nm、CIE色坐标(x,y)＝(0.58,0.42)、外量子效率EQE为34.3％的橙黄色发光(驱动电压为2.4V)。 For the organic electroluminescent device D12 prepared in this example, the device performance measurement results are as follows: applying a DC voltage, measuring the characteristics when 10cd/m 2 emits light, the wavelength of 580nm, the half-peak width of 39nm, and the CIE color coordinates (x, y) can be obtained. )=(0.58, 0.42), orange-yellow emission with external quantum efficiency EQE of 34.3% (driving voltage of 2.4V).
器件实施例13Device Example 13
与器件实施例1的制备方法相同，区别在于，将发光层中的染料由1替换为114。器件结构如下：The preparation method is the same as that of Device Example 1, except that the dye in the light-emitting layer is replaced from 1 to 114. The device structure is as follows:
ITO/HI(10nm)/HT(30nm)/EBL(10nm)/Host:3wt％114(30nm)/HBL(10nm)ET(30nm)/LiF(0.5nm)/Al(150nm)ITO/HI(10nm)/HT(30nm)/EBL(10nm)/Host:3wt%114(30nm)/HBL(10nm)ET(30nm)/LiF(0.5nm)/Al(150nm)
针对本实施例制备得到的有机电致发光器件D13测定器件性能结果如下：施加直流电压，测定10cd/m 2发光时的特性，可获得波长565nm、半峰宽38nm、CIE色坐标(x,y)＝(0.57,0.43)、外量子效率EQE为24.6％的橙黄色发光(驱动电压为2.5V)。 For the organic electroluminescent device D13 prepared in this example, the results of measuring the device performance are as follows: apply a DC voltage, measure the characteristics when 10cd/m 2 emits light, and can obtain a wavelength of 565 nm, a half-peak width of 38 nm, and CIE color coordinates (x, y )=(0.57, 0.43), orange-yellow emission with external quantum efficiency EQE of 24.6% (driving voltage of 2.5V).
器件实施例14Device Example 14
与器件实施例1的制备方法相同，区别在于，将发光层中的宽带隙型主体材料Host替换为TADF型主体TD、将染料由1替换为114。器件结构如下：The preparation method is the same as that of Device Example 1, except that the wide band gap type host material Host in the light-emitting layer is replaced with a TADF type host TD, and the dye is replaced from 1 to 114. The device structure is as follows:
ITO/HI(10nm)/HT(30nm)/EBL(10nm)/TD:3wt％114(30nm)/HBL(10nm)ET(30nm)/LiF(0.5nm)/Al(150nm)ITO/HI(10nm)/HT(30nm)/EBL(10nm)/TD:3wt%114(30nm)/HBL(10nm)ET(30nm)/LiF(0.5nm)/Al(150nm)
针对本实施例制备得到的有机电致发光器件D14测定器件性能结果如下：施加直流电压，测定10cd/m 2发光时的特性，可获得波长565nm、半峰宽38nm、CIE色坐标(x,y)＝(0.57,0.43)、外量子效率EQE为32.6％的橙黄色发光(驱动电压为2.4V)。 The results of measuring device performance for the organic electroluminescent device D14 prepared in this example are as follows: applying a DC voltage, measuring the characteristics when emitting light at 10cd/ m2 , the wavelength of 565nm, the half-peak width of 38nm, and the CIE color coordinates (x, y) can be obtained. )=(0.57, 0.43), orange-yellow emission with external quantum efficiency EQE of 32.6% (driving voltage of 2.4V).
器件实施例15Device Example 15
与器件实施例1的制备方法相同，区别在于，将发光层中的染料由1替换为180。器件结构如下：The preparation method is the same as that of Device Example 1, except that the dye in the light-emitting layer is replaced from 1 to 180. The device structure is as follows:
ITO/HI(10nm)/HT(30nm)/EBL(10nm)/Host:3wt％180(30nm)/HBL(10nm)ET(30nm)/LiF(0.5nm)/Al(150nm)ITO/HI(10nm)/HT(30nm)/EBL(10nm)/Host:3wt%180(30nm)/HBL(10nm)ET(30nm)/LiF(0.5nm)/Al(150nm)
针对本实施例制备得到的有机电致发光器件D15测定器件性能结果如下：施加直流电压，测定10cd/m 2发光时的特性，可获得波长635nm、半峰宽46nm、CIE色坐标(x,y)＝(0.70,0.30)、外量子效率EQE为25.6％的红色发光(驱动电压为2.3V)。 For the organic electroluminescent device D15 prepared in this example, the device performance measurement results are as follows: applying a DC voltage, measuring the characteristics when 10cd/m 2 emits light, the wavelength of 635nm, the half-peak width of 46nm, and the CIE color coordinates (x, y) can be obtained. )=(0.70, 0.30), red light emission with external quantum efficiency EQE of 25.6% (driving voltage of 2.3V).
器件实施例16Device Example 16
与器件实施例1的制备方法相同，区别在于，将发光层中的宽带隙型主体材料Host替换为TADF型主体TD、将染料由1替换为180。器件结构如下：The preparation method is the same as that of Device Example 1, except that the wide-bandgap host material Host in the light-emitting layer is replaced with a TADF-type host TD, and the dye is replaced from 1 to 180. The device structure is as follows:
ITO/HI(10nm)/HT(30nm)/EBL(10nm)/TD:3wt％180(30nm)/HBL(10nm)ET(30nm)/LiF(0.5nm)/Al(150nm)ITO/HI(10nm)/HT(30nm)/EBL(10nm)/TD:3wt%180(30nm)/HBL(10nm)ET(30nm)/LiF(0.5nm)/Al(150nm)
针对本实施例制备得到的有机电致发光器件D16测定器件性能结果如下：施加直流电压，测定10cd/m 2发光时的特性，可获得波长635nm、半峰宽46nm、CIE色坐标(x,y)＝(0.70,0.30)、外量子效率EQE为31.6％的红色发光(驱动电压为2.2V)。 For the organic electroluminescent device D16 prepared in this example, the device performance measurement results are as follows: applying a DC voltage, measuring the characteristics when 10cd/m 2 emits light, the wavelength of 635nm, the half-peak width of 46nm, and the CIE color coordinates (x, y) can be obtained. )=(0.70, 0.30), red light emission with external quantum efficiency EQE of 31.6% (driving voltage of 2.2V).
对比器件实施例1Comparative Device Example 1
与器件实施例1的制备方法相同，区别在于，将发光层中采用的本发明的化合物1替换为现有技术中的化合物P1，具体器件结构如下：The preparation method is the same as that of Device Example 1, except that the compound 1 of the present invention used in the light-emitting layer is replaced with the compound P1 in the prior art, and the specific device structure is as follows:
ITO/HI(10nm)/HT(40nm)/Host:3wt％P1(30nm)/ET(30nm)/LiF(0.5nm)/Al(150nm)ITO/HI(10nm)/HT(40nm)/Host:3wt%P1(30nm)/ET(30nm)/LiF(0.5nm)/Al(150nm)
针对本实施例制备得到的有机电致发光器件DD1测定器件性能结果如下：施加直流电压，测定10cd/m2发光时的特性，可获得波长459nm、半峰宽28nm、CIE色坐标(x,y)＝(0.13,0.09)、外量子效率EQE为13.5％的蓝色发光(驱动电压为3.6V)。For the organic electroluminescent device DD1 prepared in this example, the device performance measurement results are as follows: apply a DC voltage, measure the characteristics when 10cd/m2 emits light, and obtain a wavelength of 459nm, a half-peak width of 28nm, and CIE color coordinates (x, y) =(0.13, 0.09), blue light emission with external quantum efficiency EQE of 13.5% (driving voltage of 3.6V).
对比器件实施例2Comparative Device Example 2
与器件实施例2的制备方法相同，区别在于，将发光层中采用的本发明的化合物1替换为现有技术中的化合物P1，具体器件结构如下：The preparation method is the same as that of Device Example 2, except that the compound 1 of the present invention used in the light-emitting layer is replaced with the compound P1 in the prior art, and the specific device structure is as follows:
ITO/HI(10nm)/HT(40nm)/TD:3wt％P1(30nm)/ET(30nm)/LiF(0.5nm)/Al(150nm)ITO/HI(10nm)/HT(40nm)/TD:3wt%P1(30nm)/ET(30nm)/LiF(0.5nm)/Al(150nm)
针对本实施例制备得到的有机电致发光器件DD2测定器件性能结果如下：施加直流电压，测定10cd/m 2发光时的特性，可获得波长460nm、半峰宽28nm、CIE色坐标(x,y)＝(0.13,0.09)、外量子效率EQE为18.4％的蓝色发光(驱动电压为3.3V)。 For the organic electroluminescent device DD2 prepared in this example, the results of measuring the device performance are as follows: apply a DC voltage, measure the characteristics when 10cd/m 2 emits light, and can obtain a wavelength of 460 nm, a half-peak width of 28 nm, and CIE color coordinates (x, y )=(0.13, 0.09), blue light emission with external quantum efficiency EQE of 18.4% (driving voltage of 3.3V).
对比器件实施例3Comparative Device Example 3
与器件实施例1的制备方法相同，区别在于，将发光层中采用的本发明的化合物1替换为现有技术中的化合物P2，具体器件结构如下：The preparation method is the same as that of Device Example 1, except that the compound 1 of the present invention used in the light-emitting layer is replaced with the compound P2 in the prior art, and the specific device structure is as follows:
ITO/HI(10nm)/HT(40nm)/Host:3wt％P2(30nm)/ET(30nm)/LiF(0.5nm)/Al(150nm)ITO/HI(10nm)/HT(40nm)/Host:3wt%P2(30nm)/ET(30nm)/LiF(0.5nm)/Al(150nm)
针对本实施例制备得到的有机电致发光器件DD1测定器件性能结果如下：施加直流电压，测定10cd/m2发光时的特性，可获得波长519nm、半峰宽38nm、CIE色坐标(x,y)＝(0.27,0.69)、外量子效率EQE为19.5％的绿色发光(驱动电压为2.6V)。For the organic electroluminescent device DD1 prepared in this example, the device performance measurement results are as follows: apply a DC voltage, measure the characteristics when emitting light at 10cd/m2, and obtain a wavelength of 519nm, a half-peak width of 38nm, and CIE color coordinates (x, y) =(0.27, 0.69), green light emission with external quantum efficiency EQE of 19.5% (driving voltage: 2.6V).
对比器件实施例4Comparative Device Example 4
与器件实施例2的制备方法相同，区别在于，将发光层中采用的本发明的化合物1替换为现有技术中的化合物P2，具体器件结构如下：The preparation method is the same as that of Device Example 2, except that the compound 1 of the present invention used in the light-emitting layer is replaced with the compound P2 in the prior art, and the specific device structure is as follows:
ITO/HI(10nm)/HT(40nm)/TD:3wt％P2(30nm)/ET(30nm)/LiF(0.5nm)/Al(150nm)ITO/HI(10nm)/HT(40nm)/TD:3wt%P2(30nm)/ET(30nm)/LiF(0.5nm)/Al(150nm)
针对本实施例制备得到的有机电致发光器件DD2测定器件性能结果如下：施加直流电压，测定10cd/m 2发光时的特性，可获得波长519nm、半峰宽38nm、CIE色坐标(x,y)＝(0.27,0.69)、外量子效率EQE为25.5％的绿色发光(驱动电压为2.5V)。 For the organic electroluminescent device DD2 prepared in this example, the device performance measurement results are as follows: apply a DC voltage, measure the characteristics when 10cd/m 2 emits light, and can obtain a wavelength of 519 nm, a half-peak width of 38 nm, and CIE color coordinates (x, y )=(0.27, 0.69), green light emission with external quantum efficiency EQE of 25.5% (driving voltage of 2.5V).
对比器件实施例5Comparative Device Example 5
与器件实施例1的制备方法相同，区别在于，将发光层中采用的本发明的化合物1替换为现有技术中的化合物P3，具体器件结构如下：The preparation method is the same as that of Device Example 1, except that the compound 1 of the present invention used in the light-emitting layer is replaced by the compound P3 in the prior art, and the specific device structure is as follows:
ITO/HI(10nm)/HT(40nm)/Host:3wt％P3(30nm)/ET(30nm)/LiF(0.5nm)/Al(150nm)ITO/HI(10nm)/HT(40nm)/Host:3wt%P3(30nm)/ET(30nm)/LiF(0.5nm)/Al(150nm)
针对本实施例制备得到的有机电致发光器件DD1测定器件性能结果如下：施加直流电压，测定10cd/m2发光时的特性，可获得波长459nm、半峰宽29nm、CIE色坐标(x,y)＝(0.13,0.12)、外量子效率EQE为12.5％的蓝色发光(驱动电压为3.4V)。For the organic electroluminescent device DD1 prepared in this example, the results of measuring the device performance are as follows: apply a DC voltage, measure the characteristics when emitting light at 10cd/m2, and obtain a wavelength of 459nm, a half-peak width of 29nm, and CIE color coordinates (x, y) =(0.13, 0.12), blue light emission with external quantum efficiency EQE of 12.5% (driving voltage of 3.4V).
对比器件实施例6Comparative Device Example 6
与器件实施例2的制备方法相同，区别在于，将发光层中采用的本发明的化合物1替换为现有技术中的化合物P3，具体器件结构如下：The preparation method is the same as that of Device Example 2, except that the compound 1 of the present invention used in the light-emitting layer is replaced with the compound P3 in the prior art, and the specific device structure is as follows:
ITO/HI(10nm)/HT(40nm)/TD:3wt％P3(30nm)/ET(30nm)/LiF(0.5nm)/Al(150nm)ITO/HI(10nm)/HT(40nm)/TD:3wt%P3(30nm)/ET(30nm)/LiF(0.5nm)/Al(150nm)
针对本实施例制备得到的有机电致发光器件DD2测定器件性能结果如下：施加直流电压， 测定10cd/m 2发光时的特性，可获得波长459nm、半峰宽29nm、CIE色坐标(x,y)＝(0.13,0.12)、外量子效率EQE为12.5％的蓝色发光(驱动电压为3.3V)。 For the organic electroluminescent device DD2 prepared in this example, the device performance measurement results are as follows: applying a DC voltage, measuring the characteristics when 10cd/m 2 emits light, the wavelength of 459nm, the half-peak width of 29nm, and the CIE color coordinates (x, y) can be obtained. )=(0.13, 0.12), blue light emission with external quantum efficiency EQE of 12.5% (driving voltage of 3.3V).
上述各个实施例中所采用的各类有机材料的结构式如下：The structural formulas of the various organic materials used in the above-mentioned embodiments are as follows:
Figure PCTCN2021116592-appb-000041
Figure PCTCN2021116592-appb-000041
Figure PCTCN2021116592-appb-000042
Figure PCTCN2021116592-appb-000042
上述各个器件实施例所制备的的有机电致发光器件D1至器件D16以及器件DD1和DD6的具体性能数据详见下表1。The specific performance data of the organic electroluminescent devices D1 to D16 and the devices DD1 and DD6 prepared by the above respective device embodiments are shown in Table 1 below.
表1：Table 1:
Figure PCTCN2021116592-appb-000043
Figure PCTCN2021116592-appb-000043
Figure PCTCN2021116592-appb-000044
Figure PCTCN2021116592-appb-000044
以上实验数据表明，本发明的化合物通过引入直线型给体-Π-给体、直线型给体-Π-受体或直线型受体-Π-受体的特殊结构，在保持多重共振的前提下，通过前线轨道的能级裂分产生有效的红移，从而使目标分子兼具高发光效率和高色纯度。该系列材料相比目前MR-TADF材料实现光色的巨大红移，能够得到橙红光、红光至近红外的发射，从而极大地丰富了多重共振-热活化延迟荧光的材料体系和发光颜色范围，具有良好的应用前景。The above experimental data show that the compound of the present invention can maintain multiple resonances by introducing special structures of linear donor-Π-donor, linear donor-Π-acceptor or linear acceptor-Π-acceptor. , an effective red shift is generated through the energy level splitting of the frontier orbitals, so that the target molecule has both high luminous efficiency and high color purity. Compared with the current MR-TADF materials, this series of materials achieves a huge red shift in light color, and can obtain orange-red light, red light to near-infrared emission, thus greatly enriching the material system and emission color range of multiple resonance-thermal activated delayed fluorescence. Has a good application prospect.
尽管结合实施例对本发明进行了说明，但本发明并不局限于上述实施例，应当理解，在本发明构思的引导下，本领域技术人员可进行各种修改和改进，所附权利要求概括了本发明的范围。Although the present invention has been described in conjunction with the embodiments, the present invention is not limited to the above-mentioned embodiments, and it should be understood that various modifications and improvements can be made by those skilled in the art under the guidance of the inventive concept. The appended claims summarize the scope of the present invention.
显然，上述实施例仅仅是为清楚地说明所作的举例，而并非对实施方式的限定。对于所属领域的普通技术人员来说，在上述说明的基础上还可以做出其它不同形式的变化或变动。这里无需也无法对所有的实施方式予以穷举。而由此所引伸出的显而易见的变化或变动仍处于本发明创造的保护范围之中。Obviously, the above-mentioned embodiments are only examples for clear description, and are not intended to limit the implementation manner. For those of ordinary skill in the art, changes or modifications in other different forms can also be made on the basis of the above description. There is no need and cannot be exhaustive of all implementations here. And the obvious changes or changes derived from this are still within the protection scope of the present invention.

Claims (10)

  1. 一种通式化合物，具有如下式(1)所示的结构：A compound of general formula has the structure shown in the following formula (1):
    Figure PCTCN2021116592-appb-100001
    Figure PCTCN2021116592-appb-100001
    式(1)中，In formula (1),
    环A、环B、环C、环D各自独立地表示C5～C20的单环芳环或稠合芳环、C4～C20单环杂环或稠合杂环中的任意一种；环E表示C5～C20的芳环；Ring A, Ring B, Ring C, and Ring D each independently represent any one of a C5-C20 monocyclic aromatic ring or a condensed aromatic ring, a C4-C20 monocyclic heterocyclic ring or a condensed heterocyclic ring; Ring E represents Aromatic rings of C5～C20;
    所述环A与环B之间可通过单键连接，所述环C与环D之间可通过单键连接；The ring A and the ring B can be connected by a single bond, and the ring C and the ring D can be connected by a single bond;
    所述Y 1和Y 2分别独立地为N或B； Said Y 1 and Y 2 are each independently N or B;
    所述X 1、X 2、X 3和X 4分别独立地为NR 1、BR 2、O或S； Said X 1 , X 2 , X 3 and X 4 are each independently NR 1 , BR 2 , O or S;
    当Y 1和Y 2均为B时，X 1、X 2、X 3和X 4不同时为NR 1； When Y 1 and Y 2 are both B, X 1 , X 2 , X 3 and X 4 are not NR 1 at the same time;
    所述R 1、R 2分别独立地选自取代或未取代的下述基团中的一种：C1-C36链状烷基、C3-C36环烷基、C6～C30的芳基氨基、C3～C30杂芳基氨基、C6-C60的单环芳基、C6-C60的稠环芳基、C6-C60的芳氧基、C5-C60的单环杂芳基或C5-C60的稠环杂芳基； The R 1 and R 2 are independently selected from one of the following substituted or unsubstituted groups: C1-C36 chain alkyl, C3-C36 cycloalkyl, C6-C30 arylamino, C3 ~C30 heteroarylamino, C6-C60 monocyclic aryl, C6-C60 fused-ring aryl, C6-C60 aryloxy, C5-C60 monocyclic heteroaryl or C5-C60 fused-ring heteroaryl Aryl;
    所述R 1可通过单键与相邻的环A、环B、环C或环D连接，或者可与相邻的环A、环B、环C或环D稠合而相互键合形成环；所述R 2可通过单键与相邻的环A、环B、环C或环D连接，或者可与相邻的环A、环B、环C或环D稠合而相互键合形成环； The R 1 can be connected to the adjacent ring A, ring B, ring C or ring D through a single bond, or can be condensed with the adjacent ring A, ring B, ring C or ring D to bond with each other to form a ring ; The R 2 can be connected with the adjacent ring A, ring B, ring C or ring D through a single bond, or can be fused with the adjacent ring A, ring B, ring C or ring D to form a bond with each other ring;
    所述X 1与X 3之间可通过单键连接，或者可稠合而相互键合形成环；所述X 2与X 4之间可通过单键连接，或者可稠合而相互键合形成环； The X 1 and X 3 can be connected by a single bond, or can be fused to form a ring; the X 2 and X 4 can be connected by a single bond, or can be fused to form a mutual bond ring;
    所述R a、R b、R c和R d分别独立地表示单取代基到最大允许取代基，并且各自独立地选自氢、氘或者取代或未取代的下述基团中的一种：卤素、C1～C36的链状烷基、C3～C36的环烷基、C1～C10的烷氧基、C1～C10的硫代烷氧基、羰基、羧基、硝基、氰基、氨基、C6～C30的芳基氨基、C3～C30杂芳基氨基、C6-C60的单环芳基、C6-C60的稠环芳基、C6-C60的芳氧基、C5-C60的单环杂芳基、C5-C60的稠环杂芳基中的一种；所述R a、R b、R c和R d中的相邻的两个之间任选可通过单键连接或者可稠合而相互键合形成环； The R a , R b , R c and R d each independently represent a mono-substituent to the maximum allowable substituent, and are each independently selected from hydrogen, deuterium, or one of the following groups, substituted or unsubstituted: Halogen, C1-C36 chain alkyl, C3-C36 cycloalkyl, C1-C10 alkoxy, C1-C10 thioalkoxy, carbonyl, carboxyl, nitro, cyano, amino, C6 ～C30 arylamino, C3～C30 heteroarylamino, C6-C60 monocyclic aryl, C6-C60 fused-ring aryl, C6-C60 aryloxy, C5-C60 monocyclic heteroaryl , a C5-C60 condensed ring heteroaryl; the adjacent two of the R a , R b , R c and R d can optionally be connected by a single bond or can be fused to each other bond to form a ring;
    当上述基团存在取代基时，所述取代基团分别独立选自氘、卤素、C1～C30的链状烷基、C3～C30的环烷基、C1～C10的烷氧基、C1～C10的硫代烷氧基、羰基、羧基、硝基、氰基、氨基、C6～C30的芳基氨基、C3～C30杂芳基氨基、C6～C60的单环芳基、C6～C60的稠环芳基、C6～C60的芳氧基、C5～C60的单环杂芳基、C5～C60的稠环杂芳基中的任一种。When the above groups have substituents, the substituents are independently selected from deuterium, halogen, C1-C30 chain alkyl, C3-C30 cycloalkyl, C1-C10 alkoxy, C1-C10 thioalkoxy, carbonyl, carboxyl, nitro, cyano, amino, C6-C30 arylamino, C3-C30 heteroarylamino, C6-C60 monocyclic aryl, C6-C60 fused ring Any of an aryl group, a C6-C60 aryloxy group, a C5-C60 monocyclic heteroaryl group, and a C5-C60 condensed ring heteroaryl group.
  2. 根据权利要求1所述的通式化合物，式(1)中，所述环A、环B、环C和环D各自独立地表示C5～C10的单环芳环或稠合芳环、C4～C10的单环杂环或稠合杂环中的任意一种，所述环E表示C5～C10的单环芳环或稠合芳环；The compound of the general formula according to claim 1, in formula (1), the ring A, ring B, ring C and ring D each independently represent a C5-C10 monocyclic aromatic ring or a condensed aromatic ring, a C4- Any one of a C10 monocyclic heterocycle or a fused heterocycle, and the ring E represents a C5-C10 monocyclic aromatic ring or a fused aromatic ring;
    优选的，所述环A、环B、环C和环D各自独立地选自苯环、萘环或芴环中的任意一种，所述环E选自苯环、萘环或芴环中的任意一种。Preferably, the ring A, the ring B, the ring C and the ring D are each independently selected from any one of a benzene ring, a naphthalene ring or a fluorene ring, and the ring E is selected from a benzene ring, a naphthalene ring or a fluorene ring any of the .
  3. 根据权利要求1所述的通式化合物，具有如下式(2)至式(4)中任一所示的结构：The compound of the general formula according to claim 1 has the structure shown in any one of the following formulas (2) to (4):
    Figure PCTCN2021116592-appb-100002
    Figure PCTCN2021116592-appb-100002
    式(2)至式(7)中，X 1、X 2、X 3、X 4、R a、R b、R c和R d的定义均与在式(1)中的定义相同。 In formula (2) to formula (7), the definitions of X 1 , X 2 , X 3 , X 4 , R a , R b , R c and R d are the same as those in formula (1).
  4. 根据权利要求3所述的通式化合物，式(2)中：The compound of general formula according to claim 3, in formula (2):
    X 1、X 2、X 3、X 4中的两个为BR 2，另两个为NR 1； Two of X 1 , X 2 , X 3 and X 4 are BR 2 , and the other two are NR 1 ;
    或者，X 1、X 2、X 3、X 4中的两个为BR 2，另两个为O； Or, two of X 1 , X 2 , X 3 , and X 4 are BR 2 , and the other two are O;
    或者，X 1、X 2、X 3、X 4中的两个为BR 2，另两个为S； Or, two of X 1 , X 2 , X 3 , and X 4 are BR 2 , and the other two are S;
    或者，X 1、X 2、X 3、X 4中的三个为BR 2，另一个为NR 1； Or, three of X 1 , X 2 , X 3 , and X 4 are BR 2 and the other is NR 1 ;
    或者，X 1、X 2、X 3、X 4中的一个为BR 2，另三个为NR 1； Or, one of X 1 , X 2 , X 3 , and X 4 is BR 2 , and the other three are NR 1 ;
    或者，X 1、X 2、X 3、X 4中的两个为BR 2，一个为NR 1，另一个为O； Or, two of X 1 , X 2 , X 3 , and X 4 are BR 2 , one is NR 1 , and the other is O;
    或者，X 1、X 2、X 3、X 4中的一个为BR 2，两个为NR 1，另一个为O； Or, one of X 1 , X 2 , X 3 , and X 4 is BR 2 , two are NR 1 , and the other is O;
    或者，X 1、X 2、X 3、X 4中的两个为BR 2，一个为NR 1，另一个为O； Or, two of X 1 , X 2 , X 3 , and X 4 are BR 2 , one is NR 1 , and the other is O;
    或者，X 1、X 2、X 3、X 4中的两个为BR 2，一个为NR 1，另一个为O； Or, two of X 1 , X 2 , X 3 , and X 4 are BR 2 , one is NR 1 , and the other is O;
    或者，X 1、X 2、X 3、X 4均为S； Or, X 1 , X 2 , X 3 , and X 4 are all S;
    或者，X 1、X 2、X 3、X 4中的一个为O，另三个为S； Or, one of X 1 , X 2 , X 3 , and X 4 is O, and the other three are S;
    或者，X 1、X 2、X 3、X 4中的一个为NR 1，另三个为NR 1。 Alternatively, one of X 1 , X 2 , X 3 , and X 4 is NR 1 , and the other three are NR 1 .
  5. 根据权利要求3所述的通式化合物，式(3)中：The compound of general formula according to claim 3, in formula (3):
    X 1、X 2、X 3、X 4中的两个为BR 2，另两个为NR 1； Two of X 1 , X 2 , X 3 and X 4 are BR 2 , and the other two are NR 1 ;
    或者，X 1、X 2、X 3、X 4中的两个为BR 2，另两个为O； Or, two of X 1 , X 2 , X 3 , and X 4 are BR 2 , and the other two are O;
    或者，X 1、X 2、X 3、X 4中的两个为BR 2，另两个为S； Or, two of X 1 , X 2 , X 3 , and X 4 are BR 2 , and the other two are S;
    或者，X 1、X 2、X 3、X 4中的三个为BR 2，另一个为NR 1； Or, three of X 1 , X 2 , X 3 , and X 4 are BR 2 and the other is NR 1 ;
    或者，X 1、X 2、X 3、X 4中的一个为BR 2，另三个为NR 1； Or, one of X 1 , X 2 , X 3 , and X 4 is BR 2 , and the other three are NR 1 ;
    或者，X 1、X 2、X 3、X 4中的两个为BR 2，一个为NR 1，另一个为O； Or, two of X 1 , X 2 , X 3 , and X 4 are BR 2 , one is NR 1 , and the other is O;
    或者，X 1、X 2、X 3、X 4中的一个为BR 2，两个为NR 1，另一个为O； Or, one of X 1 , X 2 , X 3 , and X 4 is BR 2 , two are NR 1 , and the other is O;
    或者，X 1、X 2、X 3、X 4中的两个为BR 2，一个为NR 1，另一个为O； Or, two of X 1 , X 2 , X 3 , and X 4 are BR 2 , one is NR 1 , and the other is O;
    或者，X 1、X 2、X 3、X 4中的两个为BR 2，一个为NR 1，另一个为O； Or, two of X 1 , X 2 , X 3 , and X 4 are BR 2 , one is NR 1 , and the other is O;
    或者，X 1、X 2、X 3、X 4均为S； Or, X 1 , X 2 , X 3 , and X 4 are all S;
    或者，X 1、X 2、X 3、X 4中的一个为O，另三个为S； Or, one of X 1 , X 2 , X 3 , and X 4 is O, and the other three are S;
    或者，X 1、X 2、X 3、X 4中的一个为NR 1，另三个为NR 1。 Alternatively, one of X 1 , X 2 , X 3 , and X 4 is NR 1 , and the other three are NR 1 .
  6. 根据权利要求3所述的通式化合物，式(4)中：The compound of general formula according to claim 3, in formula (4):
    X 1、X 2、X 3、X 4中的两个为BR 2，另两个为NR 1； Two of X 1 , X 2 , X 3 and X 4 are BR 2 , and the other two are NR 1 ;
    或者，X 1、X 2、X 3、X 4中的两个为BR 2，另两个为O； Or, two of X 1 , X 2 , X 3 , and X 4 are BR 2 , and the other two are O;
    或者，X 1、X 2、X 3、X 4中的两个为BR 2，另两个为S； Or, two of X 1 , X 2 , X 3 , and X 4 are BR 2 , and the other two are S;
    或者，X 1、X 2、X 3、X 4中的三个为BR 2，另一个为NR 1； Or, three of X 1 , X 2 , X 3 , and X 4 are BR 2 and the other is NR 1 ;
    或者，X 1、X 2、X 3、X 4中的一个为BR 2，另三个为NR 1； Or, one of X 1 , X 2 , X 3 , and X 4 is BR 2 , and the other three are NR 1 ;
    或者，X 1、X 2、X 3、X 4中的两个为BR 2，一个为NR 1，另一个为O； Or, two of X 1 , X 2 , X 3 , and X 4 are BR 2 , one is NR 1 , and the other is O;
    或者，X 1、X 2、X 3、X 4中的一个为BR 2，两个为NR 1，另一个为O； Or, one of X 1 , X 2 , X 3 , and X 4 is BR 2 , two are NR 1 , and the other is O;
    或者，X 1、X 2、X 3、X 4中的两个为BR 2，一个为NR 1，另一个为O； Or, two of X 1 , X 2 , X 3 , and X 4 are BR 2 , one is NR 1 , and the other is O;
    或者，X 1、X 2、X 3、X 4中的两个为BR 2，一个为NR 1，另一个为O； Or, two of X 1 , X 2 , X 3 , and X 4 are BR 2 , one is NR 1 , and the other is O;
    或者，X 1、X 2、X 3、X 4均为S； Or, X 1 , X 2 , X 3 , and X 4 are all S;
    或者，X 1、X 2、X 3、X 4中的一个为O，另三个为S； Or, one of X 1 , X 2 , X 3 , and X 4 is O, and the other three are S;
    或者，X 1、X 2、X 3、X 4中的一个为NR 1，另三个为NR 1。 Alternatively, one of X 1 , X 2 , X 3 , and X 4 is NR 1 , and the other three are NR 1 .
  7. 根据权利要求1所述的通式化合物，式(1)中，所述R a、R b、R c和R d分别独立地选自氢、氘或者取代或未取代的下述取代基团中的一种：甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基、叔丁基、2-甲基丁基、正戊基、仲戊基、环戊基、新戊基、正己基、环己基、新己基、正庚基、环庚基、正辛基、环辛基、2-乙基己基、三氟甲基、五氟乙基、2,2,2-三氟乙基、苯基、萘基、蒽基、苯并蒽基、菲基、苯并菲基、芘基、窟基、茈基、荧蒽基、并四苯基、并五苯基、苯并芘基、联苯基、偶苯基、三联苯基、三聚苯基、四联苯基、芴基、螺二芴基、二氢菲基、二氢芘基、四氢芘基、顺式或反式茚并芴基、三聚茚基、异三聚茚基、螺三聚茚基、螺异三聚茚基、呋喃基、苯并呋喃基、异苯并呋喃基、二苯并呋喃基、噻吩基、苯并噻吩基、异苯并噻吩基、二苯并噻吩基、吡咯基、异吲哚基、咔唑基、茚并咔唑基、吡啶基、喹啉基、异喹啉基、吖啶基、菲啶基、苯并-5,6-喹啉基、苯并-6,7-喹啉基、苯并-7,8-喹啉基、吡唑基、吲唑基、咪唑基、苯并咪唑基、萘并咪唑基、菲并咪唑基、吡啶并咪唑基、吡嗪并咪唑基、喹喔啉并咪唑基、嗯唑基、苯并嗯唑基、萘并嗯唑基、蒽并嗯唑基、菲并嗯唑基、1，2-噻唑基、1，3-噻唑基、苯并噻唑基、哒嗪基、苯并哒嗪基、嘧啶基、苯并嘧啶基、喹喔啉基、1，5-二氮杂蒽基、2,7-二氮杂芘基、2,3-二氮杂芘基、1,6-二氮杂芘基、1,8-二氮杂芘基、4,5-二氮杂芘基、4,5,9,10-四氮杂茈基、吡嗪基、吩嗪基、吩噻嗪基、萘啶基、氮杂咔唑基、苯并咔啉基、菲咯啉基、1,2,3-三唑基、1,2,4-三唑基、苯并三唑基、1,2,3-噁二唑基、1,2,4-嗯二唑基、1,2,5_嗯二唑基、1,2,3-噻二唑基、1,2,4-噻二唑基、1,2,5-噻二唑基、1,3,4-噻二唑基、1,3,5-三嗪基、1,2,4-三嗪基、1,2,3-三嗪基、四唑基、1,2,4,5-四嗪基、1,2,3,4-四嗪基、1,2,3,5-四嗪基、嘌呤基、蝶啶基、吲嗪基、苯并噻二唑基、9,9-二甲基吖啶基、三芳胺基、金刚烷、氟代苯基、甲基苯基、三甲基苯基、氰基苯基、四氢吡咯、哌啶、甲氧基、硅基，或者选自以上两种取代基团的组合； The compound of the general formula according to claim 1, in formula (1), the R a , R b , R c and R d are independently selected from hydrogen, deuterium or substituted or unsubstituted following substituent groups A kind of: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, 2-methylbutyl, n-pentyl, sec-pentyl, ring Pentyl, neopentyl, n-hexyl, cyclohexyl, neohexyl, n-heptyl, cycloheptyl, n-octyl, cyclooctyl, 2-ethylhexyl, trifluoromethyl, pentafluoroethyl, 2, 2,2-Trifluoroethyl, phenyl, naphthyl, anthracenyl, benzanthracene, phenanthryl, triphenylanthryl, pyrenyl, cavernyl, perylene, fluoranthene, tetraphenyl, and Pentaphenyl, benzopyrenyl, biphenyl, biphenyl, terphenyl, triphenyl, tetraphenyl, fluorenyl, spirobifluorenyl, dihydrophenanthryl, dihydropyrenyl, tetraphenyl Hydropyrenyl, cis- or trans-indenofluorenyl, trimerindenyl, heterotrimerindenyl, spirotrimerindenyl, spiroheterotrimerindenyl, furanyl, benzofuranyl, isobenzofuran base, dibenzofuranyl, thienyl, benzothienyl, isobenzothienyl, dibenzothienyl, pyrrolyl, isoindolyl, carbazolyl, indenocarbazolyl, pyridyl, quinoline olinyl, isoquinolinyl, acridinyl, phenanthridine, benzo-5,6-quinolinyl, benzo-6,7-quinolinyl, benzo-7,8-quinolinyl, pyridine azolyl, indazolyl, imidazolyl, benzimidazolyl, naphthimidazolyl, phenanthroimidazolyl, pyridimidazolyl, pyrazinimidazolyl, quinoxalineimidazolyl, oxazolyl, benzimidazolyl azolyl, naphthazolyl, anthraxazolyl, phenanthazolyl, 1,2-thiazolyl, 1,3-thiazolyl, benzothiazolyl, pyridazinyl, benzopyridazinyl, Pyrimidyl, benzopyrimidinyl, quinoxalinyl, 1,5-diazaanthryl, 2,7-diazapyrenyl, 2,3-diazapyrenyl, 1,6-diazapyrenyl Pyrenyl, 1,8-diazapyrenyl, 4,5-diazapyrenyl, 4,5,9,10-tetraazaperpenyl, pyrazinyl, phenazinyl, phenothiazinyl, Naphthyridinyl, azacarbazolyl, benzocarbolinyl, phenanthroline, 1,2,3-triazolyl, 1,2,4-triazolyl, benzotriazolyl, 1,2 ,3-oxadiazolyl, 1,2,4-oxadiazolyl, 1,2,5-oxadiazolyl, 1,2,3-thiadiazolyl, 1,2,4-thiadiazole base, 1,2,5-thiadiazolyl, 1,3,4-thiadiazolyl, 1,3,5-triazinyl, 1,2,4-triazinyl, 1,2,3- Triazinyl, tetrazolyl, 1,2,4,5-tetrazinyl, 1,2,3,4-tetrazinyl, 1,2,3,5-tetrazinyl, purinyl, pteridyl , indolizinyl, benzothiadiazolyl, 9,9-dimethylacridinyl, triarylamine, adamantane, fluorophenyl, methylphenyl, trimethylphenyl, cyanophenyl , tetrahydropyrrole, piperidine, methoxy, silicon, or a combination of the above two substituent groups;
    当上述基团存在取代基时，所述取代基团分别独立选自卤素、C1～C12的链状烷基、C3-C12的环烷基、C1～C6的烷氧基或硫代烷氧基、C6～C30芳基氨基、C3～C30杂芳基氨基、C6-C30的单环芳 烃或稠环芳烃基团、C3-C30的单环杂芳烃或稠环杂芳烃基团中的任一种。When the above groups have substituents, the substituents are independently selected from halogen, C1-C12 chain alkyl, C3-C12 cycloalkyl, C1-C6 alkoxy or thioalkoxy , any one of C6～C30 arylamino, C3～C30 heteroarylamino, C6-C30 monocyclic aromatic hydrocarbon or fused ring aromatic hydrocarbon group, C3-C30 monocyclic heteroaromatic hydrocarbon or fused ring heteroaromatic hydrocarbon group .
  8. 根据权利要求1所述的通式化合物，选自下述具体结构化合物：The compound of general formula according to claim 1 is selected from the following specific structural compounds:
    Figure PCTCN2021116592-appb-100003
    Figure PCTCN2021116592-appb-100003
    Figure PCTCN2021116592-appb-100004
    Figure PCTCN2021116592-appb-100004
    Figure PCTCN2021116592-appb-100005
    Figure PCTCN2021116592-appb-100005
    Figure PCTCN2021116592-appb-100006
    Figure PCTCN2021116592-appb-100006
    Figure PCTCN2021116592-appb-100007
    Figure PCTCN2021116592-appb-100007
    Figure PCTCN2021116592-appb-100008
    Figure PCTCN2021116592-appb-100008
    Figure PCTCN2021116592-appb-100009
    Figure PCTCN2021116592-appb-100009
    Figure PCTCN2021116592-appb-100010
    Figure PCTCN2021116592-appb-100010
    Figure PCTCN2021116592-appb-100011
    Figure PCTCN2021116592-appb-100011
  9. 权利要求1-8中任一所述的化合物的应用，其特征在于，所述化合物用于有机电致发光器件；The use of the compound according to any one of claims 1-8, wherein the compound is used in an organic electroluminescent device;
    优选地，所述化合物在有机电致发光器件中作为发光层材料，优选作为发光染料。Preferably, the compound is used as a light-emitting layer material, preferably a light-emitting dye, in an organic electroluminescent device.
  10. 一种有机电致发光器件，该器件包括第一电极、第二电极和插入所述第一电极和第二电极之间的一层或多层有机层，其特征在于，所述有机层中包括至少一种由权利要求1-8中任一所述的化合物；An organic electroluminescence device comprising a first electrode, a second electrode and one or more organic layers interposed between the first electrode and the second electrode, wherein the organic layer includes at least one compound of any one of claims 1-8;
    优选的，所述的有机层包括空穴注入层、空穴传输层、发光层、电子传输层，所述的空穴注入层形成在所述的阳极层上，所述的空穴传输层形成在所述的空穴注入层上，所述的阴极层形成在所述的电子传输层上，所述的空穴传输层与所述的电子传输层之间为发光层，其中，所述的发光层中含有权利要求1-8中任一所述的化合物。Preferably, the organic layer includes a hole injection layer, a hole transport layer, a light-emitting layer, and an electron transport layer, the hole injection layer is formed on the anode layer, and the hole transport layer is formed on the anode layer. On the hole injection layer, the cathode layer is formed on the electron transport layer, and a light-emitting layer is formed between the hole transport layer and the electron transport layer, wherein the The light-emitting layer contains the compound according to any one of claims 1-8.
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ZHANG YUEWEI, ZHANG DONGDONG, HUANG TIANYU, GILLETT ALEXANDER J., LIU YANG, HU DEPING, CUI LINSONG, BIN ZHENGYANG, LI GUOMENG, WEI: "Multi‐Resonance Deep‐Red Emitters with Shallow Potential‐Energy Surfaces to Surpass Energy‐Gap Law**", ANGEWANDTE CHEMIE INTERNATIONAL EDITION, VERLAG CHEMIE, vol. 60, no. 37, 6 September 2021 (2021-09-06), pages 20498 - 20503, XP055917758, ISSN: 1433-7851, DOI: 10.1002/anie.202107848 *

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Publication number Priority date Publication date Assignee Title
CN114621269A (en) * 2020-12-09 2022-06-14 清华大学 Fused aromatic compound and application thereof in electroluminescent device

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