CN119930498B - 9, 9-Bifluorenoindole derivative and electroluminescent device thereof - Google Patents
9, 9-Bifluorenoindole derivative and electroluminescent device thereofInfo
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Abstract
The invention belongs to the technical field of organic luminescent materials and semiconductors, and provides 9, 9-bifluous indole derivatives and electroluminescent devices thereof, wherein the structural formula of the 9, 9-bifluous indole derivatives is as follows. The 9, 9-bifluorenyl indole derivative provided by the invention is used as a luminescent layer material for preparing the electroluminescent device, so that the luminescent performance of the electroluminescent device can be effectively improved, and the service life of the electroluminescent device can be prolonged.
Description
Technical Field
The invention belongs to the technical field of organic luminescent materials and semiconductors, and particularly relates to a 9, 9-bifluorenoindole derivative and an electroluminescent device thereof.
Background
In recent years, organic light emitting diodes (Organic LIGHT EMITTING DISPLAY, OLED) have been a popular research direction in the fields of illumination and display by virtue of their excellent characteristics of self-luminescence, high brightness, high contrast, perspective, wearable, foldable, low power consumption, wide viewing angle, low temperature resistance, and the like.
OLED devices typically consist of functional layers such as an anode, a cathode, a hole transport layer (Hole Transport Layer, HTL), a light emitting layer (Emission MATERIAL LAYER, EML), an electron transport layer (Electron Transport Layer, ETL), etc. The selection and matching of the materials of the hole transport layer, the light emitting layer and other functional layers have a significant impact on the current efficiency, the driving voltage, the light emission color purity, the light emission brightness and the service life of the OLED device, so the exploration of the functional layer materials with higher performance is still a critical task for the current development of the OLED industry.
Chinese patent No. 106187861B discloses a spirobifluoreno indole derivative, a preparation method and application thereof, but the current efficiency and the service life of an OLED device prepared based on the spirobifluoreno indole derivative are not ideal.
Therefore, in order to meet the higher demands of OLED devices, there is a need in the art to develop higher performance functional layer materials.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a 9, 9-bifluorenoindole derivative and an electroluminescent device thereof, and the electroluminescent device based on the 9, 9-bifluorenoindole derivative has improved current efficiency, service life and other comprehensive performances.
The invention is realized by the following technical scheme:
In a first aspect, the present invention provides a 9, 9-bifluorenoindole derivative, wherein the structural formula of the 9, 9-bifluorenoindole derivative is shown as formula (1):
Wherein L is selected from the group consisting of substituted or unsubstituted aryl of C 6~C40 and substituted or unsubstituted heteroaryl of C 4~C40, L is bonded to the main structure by a single bond, the heteroatom in the heteroaryl group comprises at least one of O, S and N, and the main structure is 。
Preferably, the substituted or unsubstituted aryl of C 6~C40 means that the aryl of C 6~C40 may or may not be further substituted with a substituent, and when the aryl of C 6~C40 is substituted with a substituent selected from the group consisting of phenyl, naphthyl, biphenyl, phenanthryl, benzo [9,10] phenanthryl, methyl, 9-dimethyl-9, 10-dihydro-anthracyl and fluoranthenyl.
Preferably, the substituted or unsubstituted heteroaryl group of C 4~C40 means that the heteroaryl group of C 4~C40 may be further substituted or unsubstituted, and when the heteroaryl group of C 4~C40 is substituted with a substituent selected from the group consisting of phenyl, biphenyl, naphthyl, phenanthryl, anthracenyl, methyl, ethyl, isopropyl, tert-butyl, carbonyl, benzofuranyl, naphtho [2,1-B ] benzofuranyl, fluorenyl, oxaanthracenyl, thiaanthracenyl, 1-methylpiperidin-4-enyl, N-dimethyl-3-enyl, carbazolyl, N-phenylcarbazolyl, dibenzothiophenyl, dibenzofuranyl, deuterophenyl, methylthio, methoxy, cyano, ethylcyano, tolyl, xylyl, ethylphenyl, cyclohexylphenyl, pyridyl, cyclopropyl, pyrimidinyl, methylsulfonyl, morpholinyl, phenanthroline.
In the present invention, the term "aryl" refers to an all-carbon monocyclic or fused-polycyclic (i.e., rings that share adjacent pairs of carbon atoms) group having a conjugated pi-electron system.
In the present invention, the term "heteroaryl" refers to the collective term for groups in which one or more of the aromatic nucleus carbon atoms or non-aromatic nucleus carbon atoms in the aryl group are replaced with heteroatoms, and the heteroaryl group may be a monocyclic heteroaryl group, a polycyclic heteroaryl group, or a fused ring heteroaryl group.
Preferably, in the 9, 9-bifluorenoindole derivative, the L is selected from one of the following groups L1-1 to L1-19:
The group L1-1 to L1-19 is' "Means the position at which L is bonded to the host structure, wherein the groups L1-9, L1-10, L1-12, L1-13, L1-14, L1-16, L1-17, L1-18 and L1-19 are each bonded to the host structure by only one" group ""Bonded to the body structure".
Preferably, in the 9, 9-bifluorenoindole derivative, the L is selected from one of the following groups L2-1 to L2-32:
The group L2-1 to L2-32 is' "Means the position at which L is bonded to the host structure, wherein the groups L2-4, L2-7, L2-8, L2-9, L2-10, L2-18, L2-19, L2-21, L2-24, L2-27 and L2-28 are each bonded to the host structure by only one" means ""Bonded to the body structure".
Preferably, in the 9, 9-bifluorenoindole derivative, the L is selected from one of the following groups L3-1 to L3-89:
the group L3-1 to L3-89 is' "Means the position at which L is bonded to the host structure, wherein the groups L3-4, L3-5, L3-19, L3-45, L3-78, L3-79, L3-87 and L3-88 are all bonded to the host structure by only one" group ""Bonded to the body structure".
Preferably, the 9, 9-bifluorenoindole derivative is selected from one of the following compounds H1-1 to H3-99:
In a second aspect, the invention provides an electroluminescent device comprising a cathode, an anode and an organic layer between the cathode and the anode, wherein the organic layer comprises a hole transport layer, a luminescent layer and an electron transport layer, the hole transport layer is positioned between the anode and the luminescent layer, the electron transport layer is positioned between the cathode and the luminescent layer, and the luminescent layer comprises 9, 9-bifena indole derivatives shown in a formula (1).
Preferably, the component of the hole transport layer comprises 9, 9-bifluorenoindole derivatives shown in formula (1).
In some embodiments of the present invention, L of the 9, 9-bifluorenoindole derivative is selected from the group L2-1 to L2-32 in the hole transport layer. The 9, 9-bifluorenoindole derivative with L being selected from the groups L2-1-L2-32 has an extended conjugated pi electron system, is beneficial to hole transmission and luminescence, and simultaneously contains electron donating groups, so that the hole injection and transmission capacity can be improved.
Preferably, the components of the light-emitting layer comprise a Host light-emitting material (Host) and a guest light-emitting material (Dopant), wherein the Host light-emitting material comprises 9, 9-bifluous indolyl derivatives shown as a formula (1), and the guest light-emitting material can be selected from the group consisting of excellent performance、、AndOne of them.
In some embodiments of the present invention, the host luminescent material comprises a first host luminescent material and a second host luminescent material, wherein the first host luminescent material and the second host luminescent material are both 9, 9-bifluorenoindole derivatives shown in formula (1), L of the 9, 9-bifluorenoindole derivatives in the first host luminescent material is selected from groups L2-1 to L2-32, and L of the 9, 9-bifluorenoindole derivatives in the second host luminescent material is selected from groups L3-1 to L3-89.L is selected from 9, 9-bifluorenoindole derivatives of groups L2-1-L2-32 as hole transport type main luminescent materials, contains electron donating groups (such as groups containing O, S, N atoms and the like with lone electron pairs) and improves hole injection and transport capacity. L is selected from 9, 9-bifluorenoindole derivatives of groups L3-1-L3-89 which are used as electron-transporting main luminescent materials and contain electron-deficient groups (such as cyano, carbonyl, triazine, pyrimidine, pyridine, phenanthroline, pyridazine, pyrazine and the like) so as to facilitate electron transport.
Preferably, the composition of the light emitting layer comprises a host light emitting material and a guest light emitting material, wherein the guest light emitting material comprises 9, 9-bifluorenoindole derivatives shown as a formula (1), and the host light emitting material is selected fromAndOr the host luminescent material comprises a first host luminescent material and a second host luminescent material;
the first main luminescent material is selected from any one of the following RH1-1 to RH1-4:
the second main luminescent material is selected from any one of the following RH2-1 to RH 2-4:
。
In some embodiments of the present invention, in the guest light emitting material, L of the 9, 9-bifluorenoindole derivative is selected from the group L3-1 to L3-89.L is selected from 9, 9-bifluorenoindole derivatives of groups L3-1-L3-89, and has both electron donating groups and electron withdrawing groups, so that the material can be used as a THERMALLY ACTIVATED DELAYED Fluorescence delay (TADF) material, and the TADF material can be used as a guest luminescent material.
Preferably, the mass of the guest luminescent material accounts for 0.1% -3.0% of the mass of the whole luminescent layer.
Preferably, the electroluminescent device of the present invention further comprises a hole injection layer (Hole Injection Layer, HIL), an electron blocking layer (Electron Blocking Layer, EBL), a hole blocking layer (Hole Blocking Layer, HBL) and an electron injection layer (Electron Injection Layer, EIL), wherein the hole injection layer is positioned between the anode and the hole transport layer, the electron blocking layer is positioned between the hole transport layer and the light emitting layer, the hole blocking layer is positioned between the light emitting layer and the electron transport layer, and the electron injection layer is positioned between the electron transport layer and the cathode.
As an anode in an electroluminescent device, in general, an anode material is preferably a material having a large work function in order to allow holes to be smoothly injected into an organic layer. Specific examples of the anode material that can be used in the present invention include metals such as vanadium, chromium, copper, zinc and gold, or alloys thereof, oxides such as zinc oxide, aluminum oxide or tin dioxide, and conductive polymers such as polypyrrole and polyaniline.
The hole injection layer, the hole transport layer, the electron blocking layer, the hole blocking layer, the electron transport layer and the electron injection layer are made of corresponding materials with excellent cost performance in industry, and the suitability of the layers is determined through series testing and screening processes.
Preferably, the material of the hole injection layer in the present invention is preferably MoO 3.
Preferably, the hole transport layer in the present invention is selected from one of the following materials:
。
preferably, the material of the electron blocking layer in the present invention is selected from one of the following materials:
。
Preferably, the material of the hole blocking layer in the present invention is selected from one of the following materials:
。
preferably, the electron transport layer in the present invention is selected from one of the following materials:
。
As the cathode, in general, a cathode material is preferably a material having a small work function in order to facilitate injection of electrons into the organic layer. Specific examples of the cathode material that can be used in the present invention include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, and lead, or alloys thereof.
The electroluminescent device of the invention can be provided with a substrate outside the anode and a cover protection layer (Covering Protection Layer, CPL) outside the cathode.
The substrate is required to have high mechanical strength, excellent thermal stability, excellent water repellency, and excellent transparency.
As a cover protective layer, the refractive index of the cathode surface can be improved, and the light extraction rate can be improved, preferably。
The hole injection layer, the hole transport layer, the electron blocking layer, the light emitting layer, the hole blocking layer, the electron transport layer and the electron injection layer can be prepared by various means or methods such as vacuum thermal evaporation, spin coating, printing and the like.
In a third aspect, the present invention provides a method for preparing the electroluminescent device, wherein an anode is adhered to a substrate after pretreatment and cleaning, and then a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron transport layer and an electron injection layer with set thicknesses are sequentially evaporated under a low temperature condition, and then a cathode and a cover protection layer are continuously sputtered at a low temperature, and finally a test device is packaged by using a conventional device test packaging means, so as to prepare the electroluminescent device.
In a fourth aspect, the present invention provides a display panel comprising an electroluminescent device as described above.
Compared with the prior art, the invention has the following beneficial effects:
In the 9, 9-bifenamine derivative provided by the invention, the 9, 9-bifenamine structure is obtained by connecting two fluorenyl groups through unsaturated double bonds, so that the 9, 9-bifenamine structure has higher unsaturation degree, a conjugation system is larger, an electron delocalization range is larger, a conjugation effect is stronger, and an absorption spectrum is stronger, and meanwhile, the 9, 9-bifenamine structure is obtained by connecting two fluorenyl groups through unsaturated double bonds, so that the 9, 9-bifenamine structure has better flexibility and adaptability, relatively more extension of the conjugation system, stronger intermolecular interaction, better stability (namely service life improvement) and consistency in a charge transmission process, and can realize efficient charge transmission when being used as an organic photoelectric material, thereby being beneficial to improving the comprehensive performance of an electroluminescent device.
The electroluminescent device provided by the invention adopts 9, 9-bifluorenyl indole derivatives as the luminescent layer material, so that the luminescent performance of the electroluminescent device can be effectively improved, and the service life of the electroluminescent device can be prolonged.
Furthermore, the electroluminescent device adopts 9, 9-bifluorenoindole derivatives as hole transport layer materials, so that the starting voltage can be further reduced, and the comprehensive performance of the electroluminescent device is improved.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a schematic diagram of an electroluminescent device according to an embodiment of the present invention;
FIG. 2 is a nuclear magnetic resonance spectrum of the compound H1-5 prepared in preparation example 1 of the present invention;
FIG. 3 is a nuclear magnetic resonance spectrum of the compound H1-19 prepared in preparation example 2 of the present invention;
FIG. 4 is a nuclear magnetic resonance spectrum of the compound H2-25 prepared in preparation example 3 of the present invention;
FIG. 5 is a nuclear magnetic resonance spectrum of the compound H2-43 prepared in preparation example 4 of the present invention;
FIG. 6 is a nuclear magnetic resonance spectrum of the compound H3-2 prepared in preparation example 5 of the present invention;
FIG. 7 is a nuclear magnetic resonance spectrum of Compound H3-37 prepared in preparation example 6 of the present invention.
Reference numerals illustrate:
1-base plate, 2-anode, 3-hole injection layer, 4-hole transport layer, 5-electron blocking layer, 6-luminescent layer, 7-hole blocking layer, 8-electron transport layer, 9-electron injection layer, 10-cathode, 11-cover protective layer.
Detailed Description
Other advantages and effects of the present invention will become apparent to those skilled in the art from the following disclosure, which describes the embodiments of the present invention with reference to specific examples. The invention may be practiced or carried out in other embodiments that depart from the specific details, and the details of the present description may be modified or varied from the spirit and scope of the present invention.
The following examples use instrumentation conventional in the art. The experimental methods, in which specific conditions are not noted in the following examples, are generally conducted under conventional conditions or under conditions recommended by the manufacturer. The various materials used in the examples below, unless otherwise indicated, were conventional commercial products, the specifications of which are conventional in the art.
The synthesis process of 9, 9-bifluorenoindole derivatives of the present invention is described below.
Synthesis of intermediate M1:
step one:
In the operation process, 9H-fluorene (166 g,1.0 mol) and tetrahydrofuran (Tetrahydrofuran, THF) 2.5L are added into a 10L three-neck flask under inert atmosphere, stirring is started, the temperature of the reaction solution is reduced to below-78 ℃, 2.5mol/L of n-butyllithium (n-BuLi) (400 mL,1.0 mol) is dropwise added, after the dropwise addition is finished, the reaction solution is continuously stirred for 1H, 800mL of THF solution of 1-bromo-9-fluorenone (272 g,1.05 mol) is slowly dropwise added, stirring is carried out for 1H after the dropwise addition is finished, the reaction solution is transferred to room temperature, and the reaction is continued for 2H until the reaction is complete. After the reaction, the reaction system is concentrated at low temperature to remove most THF, 3L of dichloromethane is added for dilution, 3L of water is used for washing, the organic phase is dried and concentrated to obtain a residue, the residue is purified by silica gel column chromatography (dichloromethane/petroleum ether) to obtain an intermediate M1-1, the weight is 306g, the yield is 72%, the purity of HPLC (high performance liquid chromatography ) is 98%, and the molecular weight is 425.1 by LC-MS (liquid chromatography-mass spectrometer, liquid Chromatograph-Mass Spectrometer).
Step two:
the operation procedure is that a 5L three-neck flask is added with an intermediate M1-1 (298 g,0.7 mol), 2.5L mixed solution of sulfuric acid and acetic acid (V Sulfuric acid :V Acetic acid =2:8), stirring is started, the temperature of the reaction solution is raised to 60 ℃, and the reaction is continued for 1h until the reaction is completed. The reaction solution was cooled to room temperature, 3L of water was added, the reaction solution was extracted 3 times with 6L of diethyl ether, 2L of each time was used, the organic phases were combined, dried, filtered, and concentrated to give a residue, which was purified by silica gel column chromatography (dichloromethane/petroleum ether) to give intermediate M1-2, which was 205g in weight, 72% in yield, 98% in HPLC purity, and LC-MS showed molecular weight 407.0.
Step three:
In the operation process, an intermediate M1-2 (204 g,0.5 mol), 2-nitrobenzeneboronic acid pinacol ester (131 g,0.53 mol), potassium carbonate (138 g,1.0 mol), 500mL deionized water and 2.0L THF are added into a 5L three-port bottle under inert atmosphere, stirring is started, pd (PPh 3)4 (11.6 g,0.01 mol) is added, the temperature of the system is raised to 80 ℃, the reflux reaction is carried out for 10 hours until the reaction is completed, the reaction liquid is washed by water and separated, the filtrate is collected after passing through a diatomite funnel, the filtrate is concentrated under reduced pressure to obtain a solid crude product, and the solid crude product is purified by silica gel column chromatography (dichloromethane/petroleum ether) to obtain the intermediate M1-3, the weight of 178g, the yield of 79%, the HPLC content of 99% and the LC-MS molecular weight of 450.2.
Step four:
In the operation process, an intermediate M1-3 (157 g,0.35 mol), 2.5L o-dichlorobenzene and triphenylphosphine (PPh 3) (230 g,0.875 mol) are added into a 5L three-necked flask under an inert atmosphere, stirring is started, and the reaction solution is heated to 180 ℃ and refluxed for 10 hours until the reaction is completed. The reaction solution is cooled to room temperature, the solvent is concentrated under reduced pressure to obtain a solid crude product, and the solid crude product is purified by silica gel column chromatography (ethyl acetate/petroleum ether) to obtain an intermediate M1, wherein the weight is 133g, the yield is 91%, the HPLC purity is 99%, and the LC-MS shows the molecular weight of 418.2.
Those skilled in the art can refer to the structural formula of the above formula (1) and the following specific examples, and prepare the compounds H1-1 to H3-99 by combining the intermediates M1.
Preparation example 1
Synthesis of compound H1-5:
In the operation process, an intermediate M1 (4.2 g,0.01 mol), 1-chloro-4-phenylnaphthalene (3.7 g,0.0105 mol) and 50mL of toluene are added into a 100mL three-necked flask under an inert atmosphere, stirred until the solution is clear, pd 2(dba)3 (0.18 g,0.2 mmol), am-phos ([ (4- (N, N-dimethylamino) phenyl ] di-tert-butylphosphine) (0.13 g,0.5 mmol) and sodium tert-butoxide (3.8 g,0.04 mmol) are added, the reaction solution is heated to 120 ℃ for 10H, after the reaction is completed, the mixture is filtered while hot by using diatomite, the filtrate is cooled to room temperature, purified water is added for washing, an organic phase is reserved after the separation, the aqueous phase is extracted by ethyl acetate, the organic phase is combined, anhydrous magnesium sulfate is dried and concentrated, and the mixture is subjected to column (dichloromethane/petroleum ether) to obtain a compound H1-5, the weight of 4.7g, the yield is 76%, the HPLC content of 99%, and LC-MS shows a nuclear compound H1-2 with a molecular weight of 620.2, and a magnetic spectrum chart is shown in FIG. 2.
Nuclear magnetic hydrogen spectrum data of compound H1-5 ：1H NMR (500 MHz, CD3OD) δ 8.95 (s, 1H), 8.55 (s, 1H), 8.12 (d,J= 39.6 Hz, 4H), 7.89 (s, 1H), 7.79 (s, 2H), 7.60 – 7.29 (m, 18H), 7.13 (d,J= 25.0 Hz, 2H).
Preparation example 2
Synthesis of Compound H1-19:
The operation procedure refers to the synthesis process of the compound H1-5, 1-chloro-4-phenyl naphthalene is replaced by 4-bromophenanthrene (2.7 g,0.0105 mol) to obtain the compound H1-19, the weight is 4.4g, the yield is 74%, the HPLC content is 99%, and the LC-MS shows molecular weight 594.3. The nuclear magnetic pattern of the compound H1-19 is shown in FIG. 3.
Nuclear magnetic hydrogen spectrum data of compound H1-19 ：1H NMR (500 MHz, CD3OD) δ 8.98 (dd,J= 7.3, 1.6 Hz, 1H), 8.55 (dd,J= 7.4, 1.5 Hz, 1H), 8.35 (dd,J= 7.4, 1.5 Hz, 1H), 8.20 – 8.12 (m, 3H), 7.94 – 7.83 (m, 3H), 7.80 – 7.72 (m, 2H), 7.65 (dtd,J= 26.2, 7.4, 1.5 Hz, 2H), 7.59 – 7.54 (m, 3H), 7.53 – 7.48 (m, 2H), 7.46 – 7.39 (m, 7H), 7.13 (dtd,J= 26.0, 7.5, 1.5 Hz, 2H).
Preparation example 3
Synthesis of compound H2-25:
the operation process refers to the synthesis process of the compound H1-5, 1-chloro-4-phenyl naphthalene is replaced by 2-bromo-9, 9' -spirodioxy anthracene (4.5 g,0.0105 mol), and the compound H2-25 is obtained, the weight is 5.6g, the yield is 73%, the HPLC content is 99%, and the LC-MS displays molecular weight 764.3. The nuclear magnetic spectrum of the compound H2-25 is shown in FIG. 4.
Nuclear magnetic hydrogen spectrum data of compound H2-25 ：1H NMR (500 MHz, CD3OD) δ 8.55 (s, 1H), 8.16 (s, 3H), 7.74 (s, 1H), 7.58 (d,J= 10.0 Hz, 4H), 7.51 (d,J= 10.0 Hz, 2H), 7.43 (d,J= 10.0 Hz, 7H), 7.31 (s, 3H), 7.22 – 7.14 (m, 7H), 7.11 (d,J= 5.0 Hz, 2H), 7.00 (s, 3H).
Preparation example 4
Synthesis of Compound H2-43:
the operation procedure refers to the synthesis process of the compound H1-5, 1-chloro-4-phenyl naphthalene is replaced by 8-chloronaphtho [1,2-b ] benzofuran (2.65 g,0.0105 mol) to obtain the compound H2-43, the weight is 4.8g, the yield is 76%, the HPLC content is 99%, and the LC-MS shows molecular weight 634.3. The nuclear magnetic pattern of the compound H2-43 is shown in FIG. 5.
Nuclear magnetic hydrogen spectrum data of compound H2-43 ：1H NMR (500 MHz, CD3OD) δ 8.55 (s, 1H), 8.37 (s, 1H), 8.16 (s, 3H), 8.02 (s, 1H), 7.84 (s, 2H), 7.64 (s, 1H), 7.58 (d,J= 10.0 Hz, 4H), 7.54 – 7.46 (m, 4H), 7.43 (d,J= 10.0 Hz, 7H), 7.23 (s, 1H), 7.13 (d,J= 25.0 Hz, 2H).
Preparation example 5
Synthesis of compound H3-2:
the procedure is as follows, referring to the synthesis of compound H1-5, 1-chloro-4-phenyl naphthalene is replaced by 2-chloro-4- (2-naphthyl) -6-phenyl-1, 3, 5-triazine (3.3 g,0.0105 mol) to give compound H3-2, weighing 5.0g, yield 72%, HPLC content 99%, LC-MS shows molecular weight 699.3. The nuclear magnetic spectrum of the compound H3-2 is shown in FIG. 6.
Nuclear magnetic hydrogen spectrum data of compound H3-2 ：1H NMR (500 MHz, CD3OD) δ 9.09 (s, 1H), 8.52 (d,J= 30.0 Hz, 2H), 8.36 (s, 2H), 8.16 (s, 4H), 8.08 (s, 1H), 8.00 (s, 1H), 7.65 – 7.39 (m, 17H), 7.13 (d,J= 25.0 Hz, 2H).
Preparation example 6
Synthesis of Compound H3-37:
The procedure refers to the synthesis of compound H1-5, substituting 1-chloro-4-phenyl naphthalene with 2-cyano-4-bromopyrimidine (1.9 g,0.0105 mol) to give compound H3-37, weighing 3.7g, 71% yield, 99% HPLC content, LC-MS indicated a molecular weight of 521.2. The nuclear magnetic pattern of the compound H3-37 is shown in FIG. 7.
Nuclear magnetic hydrogen spectrum data of compound H3-37 ：1H NMR (500 MHz, CD3OD) δ 9.25 (s, 1H), 8.55 (s, 1H), 8.31 (s, 1H), 8.16 (s, 3H), 7.61 – 7.48 (m, 5H), 7.43 (d,J= 10.0 Hz, 7H), 7.13 (d,J= 25.0 Hz, 2H).
The electroluminescent devices of examples 1 to 44 and comparative examples 1 to 5 were prepared according to the structural information of the light emitting layers of the electroluminescent devices given in table 1 below.
The electroluminescent devices of the examples and comparative examples of the present invention are schematically shown in fig. 1, and comprise a substrate 1, an anode 2, a hole injection layer 3, a hole transport layer 4, an electron blocking layer 5, a light emitting layer 6, a hole blocking layer 7, an electron transport layer 8, an electron injection layer 9, a cathode 10, and a cover protection layer 11.
Example 1 electroluminescent device comprising Compounds H1-7
The electroluminescent device containing the compound H1-7 in this example comprises polyethylene terephthalate (Polyethylene Terephthalate, PET) plastic, indium Tin Oxide (ITO) conductive glass, moO 3, HT-2, EB-2, luminescent layer, HB-1, ET-2, liF, al-Mg (Al: mg=9:1) and CPL in order from anode to cathode, wherein the CPL is made of the following materials;
Wherein the light-emitting layer consists of H1-7 and Ir (ppy) 3 in a mass ratio of 99:1.
The preparation method of the electroluminescent device containing the compound H1-7 comprises the following steps:
1. The PET plastic with the thickness of 1.5mm is taken as a substrate 1, the ITO conductive glass with the thickness of 0.15mm is taken as an anode 2, and washing is sequentially carried out in a mode of alkali washing, pure water washing, drying and ultraviolet-ozone washing, so that organic residues on the surfaces of the PET plastic and the ITO conductive glass are removed.
2. Adhering a layer of ITO conductive glass on PET plastic, evaporating MoO 3 with the thickness of 20nm to serve as a hole injection layer 3, evaporating HT-2 with the thickness of 110nm to serve as a hole transport layer 4, evaporating EB-2 with the thickness of 30nm to serve as an electron blocking layer 5, continuously evaporating a luminescent layer 6 formed by a compound H1-7 (a host luminescent material) and Ir (ppy) 3 (a guest luminescent material) with the mass ratio of 99:1 with the thickness of 60nm on the EB-2, continuously evaporating HB-1 with the thickness of 10nm to serve as a hole blocking layer 7 on the luminescent layer 6, continuously evaporating ET-2 with the thickness of 30nm to serve as an electron transport layer 8, continuously evaporating LiF with the thickness of 16nm on the electron transport layer 8 to serve as an electron injection layer 9, continuously evaporating CPL with the thickness of 10nm in a low-temperature sputtering mode to serve as a cathode 10 after the evaporation of the electron injection layer 9 is completed, and finally continuously evaporating CPL with the thickness of 40nm on the cathode 10 to serve as a cover protection layer 11.
3. And vacuum packaging MoO 3, HT-2, EB-2, a luminescent layer 6, HB-1, ET-2 and LiF to obtain the electroluminescent device.
Example 2 to example 18
The difference from example 1 is that examples 2 to 18 use compounds H1 to 18, H1 to 25, H2 to 31, H2 to 32, H1 to 13, H1 to 14, H2 to 1, H2 to 2, H2 to 4, H2 to 5, H2 to 9, H2 to 12, H2 to 27, H2 to 28, H2 to 30, H2 to 35, H2 to 41 as the main luminescent materials of the luminescent layer 6.
Examples 19 to 40
The difference from example 1 is that in each of examples 19 to 40, BH-1 is used as a host light-emitting material of the light-emitting layer 6, and in each of examples 19 to 40, compound H3-10、H3-43、H3-90、H3-4、H3-13、H3-14、H3-20、H3-21、H3-26、H3-28、H3-34、H3-50、H3-56、H3-58、H3-66、H3-69、H3-75、H3-76、H3-80、H3-86、H3-95、H3-99 is used as a guest light-emitting material of the light-emitting layer 6.
Examples 41 to 44
The difference from embodiment 1 is that in the light-emitting layer 6 of embodiment 41 to embodiment 44, the compounds H2-21, H2-25, H2-33, and H2-36 are respectively used as the first host light-emitting material, the compound H3-90 is used as the second host light-emitting material, and the mass ratio of the first host light-emitting material, the second host light-emitting material, and the guest light-emitting material is 40:60:1, and simultaneously the materials of the hole transport layers corresponding to embodiment 41 to embodiment 44 are the compounds H2-21, H2-25, H2-33, and H2-36 in sequence.
Comparative example 1
The difference from example 1 is that HB-1 is used as the host light-emitting material in the light-emitting layer 6.
Comparative example 1 electroluminescent device has a structure of PET substrate /ITO/MoO3(20nm)/HT-2(110nm)/EB-2(30nm)/BH-1:Ir(ppy)3=99:1(60nm)/HB-1(10nm)/ET-2(30nm)/LiF(16nm)/Al:Mg=9:1(10nm)/CPL(40nm).
Comparative example 2
The difference from example 1 is that BH-2 was used as the host light-emitting material in the light-emitting layer 6.
The structure of the electroluminescent device of comparative example 2 is that a PET substrate /ITO/MoO3(20nm)/HT-2(110nm)/EB-2(30nm)/BH-2:Ir(ppy)3=99:1(60nm)/HB-1(10nm)/ET-2(30nm)/LiF(16nm)/Al:Mg=9:1(10nm)/CPL(40nm).
Comparative example 3
The difference from example 1 is that BH-1 was used as the host light-emitting material and C545T was used as the guest light-emitting material in the light-emitting layer 6.
Comparative example 3 electroluminescent device has a structure of PET substrate /ITO/MoO3(20nm)/HT-2(110nm)/EB-2(30nm)/BH-1:C545T=99:1(60nm)/HB-1(10nm)/ET-2(30nm)/LiF(16nm)/Al:Mg=9:1(10nm)/CPL(40nm).
Comparative example 4
The difference from example 1 is that BH-1 was used as the host light-emitting material in the light-emitting layer 6, and Compound 41 of Chinese patent No. CN106187861B was usedAs a guest light emitting material.
The structure of the electroluminescent device of comparative example 4 was PET substrate/ITO/MoO 3 (20 nm)/HT-2 (110 nm)/EB-2 (30 nm)/BH-1:41=99:1 (60 nm)/HB-1 (10 nm)/ET-2 (30 nm)/LiF (16 nm)/Al:Mg=9:1 (10 nm)/CPL (40 nm).
Comparative example 5
The difference from example 1 is that in the light-emitting layer 6, RH1-3 is selected as the first host light-emitting material, RH2-2 is selected as the second host light-emitting material, and the mass ratio of the first host light-emitting material, the second host light-emitting material, and the guest light-emitting material is 40:60:1.
The structure of the electroluminescent device of comparative example 5 is that a PET substrate /ITO/MoO3(20nm)/HT-2(110nm)/EB-2(30nm)/RH1-3:RH2-2:Ir(ppy)3=40:60:1(60nm)/HB-1(10nm)/ET-2(30nm)/LiF(16nm)/Al:Mg=9:1(10nm)/CPL(40nm).
The electroluminescent devices of the above examples and comparative examples were prepared as 30mm×30mm samples, and the anode and cathode were connected by a driving circuit well known in the industry, and each luminous performance index was tested. The test results are shown in Table 2.
As can be seen from the test results of Table 2, the electroluminescent devices prepared in examples 1 to 44 using the preferred 9, 9-bifluorenoindole derivatives of the present invention have significant advantages in overall luminous efficacy as compared with comparative examples 1 to 4. As can be seen from examples 1 to 18, the electroluminescent device prepared by using the preferred compound of the present invention as the main luminescent material has a current efficiency improved by about 50% and a service life LT95 prolonged by about 40% compared with comparative example 1. As can be seen from examples 19 to 40, the electroluminescent device prepared by using the preferred compound of the present invention as a guest light emitting material has a current efficiency improved by about 45% and a service life LT95 prolonged by about 80% relative to comparative example 3, and a current efficiency improved by about 80% and a service life LT95 prolonged by about 100% relative to comparative example 4. As can be seen from examples 41 to 44, the electroluminescent device prepared by using the preferred compound of the present invention as a dual-host light-emitting material and a hole transport layer material simultaneously has a significantly reduced starting voltage and a prolonged service life LT95 by approximately 2 times compared with comparative example 5.
The foregoing is merely illustrative of the technical idea of the present invention, and the scope of the present invention is not limited thereto, but any modification made on the basis of the technical scheme according to the technical idea of the present invention falls within the scope of the present invention.
Claims (7)
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