CN109824684B - Spirofluorene derivative organic compound and application thereof in organic electroluminescent device - Google Patents

Spirofluorene derivative organic compound and application thereof in organic electroluminescent device Download PDF

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CN109824684B
CN109824684B CN201711180427.4A CN201711180427A CN109824684B CN 109824684 B CN109824684 B CN 109824684B CN 201711180427 A CN201711180427 A CN 201711180427A CN 109824684 B CN109824684 B CN 109824684B
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唐丹丹
张兆超
李崇
张小庆
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Jiangsu Sunera Technology Co Ltd
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Valiant Co Ltd
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Abstract

The invention relates to a spirofluorene derivative organic compound and application thereof in an organic electroluminescent device, wherein the compound has a structure that spirofluorene is connected with an indole fused ring structure in a ring way through a carbon-carbon bond, the carbon-carbon bond ring-forming connection not only improves the chemical stability of materials, but also avoids the exposure of active positions of branched chain groups, and the whole molecule is a larger rigid structure and has a high triplet state energy level (T1); the steric hindrance is large, the rotation is not easy, and the three-dimensional structure is more stable, so that the compound has higher glass transition temperature and molecular thermal stability; in addition, the HOMO and LUMO distribution positions of the compound are separated from each other, so that the compound has proper HOMO and LUMO energy levels; therefore, after the compound is applied to an OLED device, the luminous efficiency of the device can be effectively improved, and the service life of the device can be effectively prolonged.

Description

Spirofluorene derivative organic compound and application thereof in organic electroluminescent device
Technical Field
The invention relates to the technical field of semiconductors, in particular to a spirofluorene derivative organic compound and application thereof in an organic electroluminescent device.
Background
The Organic Light Emission Diodes (OLED) device technology can be used for manufacturing novel display products and novel lighting products, is expected to replace the existing liquid crystal display and fluorescent lamp lighting, and has wide application prospect. The OLED light-emitting device is like a sandwich structure and comprises electrode material film layers and organic functional materials clamped between different electrode film layers, and various different functional materials are mutually overlapped together according to purposes to form the OLED light-emitting device. When voltage is applied to electrodes at two ends of the OLED light-emitting device and positive and negative charges in the organic layer functional material film layer are acted through an electric field, the positive and negative charges are further compounded in the light-emitting layer, and OLED electroluminescence is generated.
Currently, the OLED display technology is already applied in the fields of smart phones, tablet computers, and the like, and is further expanded to the large-size application field of televisions, and the like, but compared with the actual product application requirements, the performance of the OLED device, such as light emitting efficiency, service life, and the like, needs to be further improved. Current research into improving the performance of OLED light emitting devices includes: the driving voltage of the device is reduced, the luminous efficiency of the device is improved, the service life of the device is prolonged, and the like. In order to realize the continuous improvement of the performance of the OLED device, not only the innovation of the structure and the manufacturing process of the OLED device but also the continuous research and innovation of the photoelectric functional material of the OLED are required to create the functional material of the OLED with higher performance.
The photoelectric functional materials of the OLED applied to the OLED device can be divided into two categories from the aspect of application, namely charge injection transmission materials and luminescent materials. Further, the charge injection transport material may be classified into an electron injection transport material, an electron blocking material, a hole injection transport material, and a hole blocking material, and the light emitting material may be classified into a host light emitting material and a doping material.
In order to fabricate a high-performance OLED light-emitting device, various organic functional materials are required to have good photoelectric properties, for example, as a charge transport material, good carrier mobility, high glass transition temperature, etc. are required, as a host material of a light-emitting layer, good bipolar, appropriate HOMO/LUMO energy level, etc. are required.
The OLED photoelectric functional material film layer for forming the OLED device at least comprises more than two layers of structures, the OLED device structure applied in industry comprises a hole injection layer, a hole transmission layer, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron transmission layer, an electron injection layer and other various film layers, namely the photoelectric functional material applied to the OLED device at least comprises a hole injection material, a hole transmission material, a light emitting material, an electron transmission material and the like, and the material type and the matching form have the characteristics of richness and diversity. In addition, for the collocation of OLED devices with different structures, the used photoelectric functional material has stronger selectivity, and the performance of the same material in the devices with different structures can be completely different.
Therefore, aiming at the industrial application requirements of the current OLED device and the requirements of different functional film layers and photoelectric characteristics of the OLED device, a more suitable OLED functional material or material combination with higher performance needs to be selected to realize the comprehensive characteristics of high efficiency, long service life and low voltage of the device. In terms of the actual demand of the current OLED display lighting industry, the development of the current OLED material is far from enough, and lags behind the requirements of panel manufacturing enterprises, and it is very important to develop a higher-performance organic functional material as a material enterprise.
Disclosure of Invention
In view of the above problems in the prior art, the present applicant provides a spirofluorene derivative organic compound and its application in an organic electroluminescent device. The compound contains a spirofluorene structure, has higher glass transition temperature and molecular thermal stability, proper HOMO and LUMO energy levels, higher Eg and triplet state energy level T1, and can effectively improve the photoelectric property of an OLED device and the service life of the OLED device through device structure optimization.
The technical scheme of the invention is as follows:
a spirofluorene derivative organic compound has a structure shown in a general formula (1):
Figure BDA0001479060120000021
in the general formula (1) above,
Figure BDA0001479060120000022
through CL1-CL2Bond or CL2-CL3A bond is linked to spirofluorene;
in the general formula (1), Ar represents substituted or unsubstituted C6-60One of an aryl group, a substituted or unsubstituted 5-60 membered heteroaryl group containing one or more heteroatoms; the heteroatom is nitrogen, oxygen or sulfur;
ar is also represented by a structure represented by general formula (2):
Figure BDA0001479060120000023
in the general formula (2), X represents an oxygen atom, a sulfur atom, C1-10One of linear chain or branched alkyl substituted alkylidene, aryl substituted alkylidene, alkyl substituted imino, aryl substituted imino or heteroaryl substituted imino;
in the general formula (1), R represents a structure shown in a general formula (3), a general formula (4) or a general formula (5);
Figure BDA0001479060120000024
in the general formulae (3) and (4), X1、X2、X3Each independently represents an oxygen atom, a sulfur atom, C1-10Straight chain or C1-10One of a branched alkyl substituted alkylene group, an aryl substituted alkylene group, an alkyl substituted imino group or an aryl substituted imino group;
the general formula (3) and the general formula (4) are respectively and independently passed through CL’1-CL’2Key, CL’2-CL’3Key, CL’3-CL’4Bond' with in the general formula (1)
Figure BDA0001479060120000031
Connecting;
in the general formula (5), R1、R2Each independently represents substituted or unsubstituted C6-60One of an aryl group, a substituted or unsubstituted 5-60 membered heteroaryl group containing one or more heteroatoms; the heteroatom is nitrogen, oxygen or sulfur.
The structure of the organic compound is shown as a general formula (6), a general formula (7), a general formula (8) or a general formula (9):
Figure BDA0001479060120000032
the structure of the organic compound is shown as a general formula (10), a general formula (11) or a general formula (12):
Figure BDA0001479060120000033
the structure of the organic compound is shown as a general formula (13), a general formula (14) or a general formula (15):
Figure BDA0001479060120000034
the structure of the organic compound is shown as a general formula (16), a general formula (17) or a general formula (18):
Figure BDA0001479060120000035
the structure of the organic compound is shown as a general formula (19), a general formula (20) or a general formula (21):
Figure BDA0001479060120000041
ar represents one of phenyl, biphenyl, terphenyl, pyridyl, pyrimidyl, pyridazinyl, pyrazinyl or triazinyl; r1、R2Each independently represents one of phenyl, naphthyl, biphenyl, terphenyl, naphthyl, dibenzofuran, dibenzothiophene, 9-dimethylfluorene or N-phenylcarbazole.
In the general formula (1)
Figure BDA0001479060120000042
Expressed as:
Figure BDA0001479060120000043
Figure BDA0001479060120000051
Figure BDA0001479060120000061
Figure BDA0001479060120000062
any one of them. The specific structural formula of the organic compound is as follows:
Figure BDA0001479060120000063
Figure BDA0001479060120000071
Figure BDA0001479060120000081
Figure BDA0001479060120000091
Figure BDA0001479060120000101
Figure BDA0001479060120000111
Figure BDA0001479060120000121
Figure BDA0001479060120000122
any one of them. A method for producing the organic compound, the method involving a reaction equation:
1) when R is represented by a structure shown in a general formula (3) or a general formula (4), a specific reaction equation is as follows:
Figure BDA0001479060120000131
the preparation method comprises the following steps:
(1) weighing the raw material I and the intermediate II, and dissolving the raw material I and the intermediate II in a toluene/ethanol mixed solvent with a volume ratio of 1.5-3.0: 1; then adding Na2CO3Aqueous solution, Pd (PPh)3)4(ii) a Under the protection of nitrogen, stirring the mixed solution at 90-110 ℃ for reaction for 10-24 hours, then cooling to room temperature, filtering the reaction solution, carrying out rotary evaporation on the filtrate, and passing through a silica gel column to obtain an intermediate III; the molar ratio of the raw material I to the intermediate II is 1: 1.5-3.0; pd (PPh)3)4The molar ratio of the raw material I to the raw material I is 0.006-0.02: 1, and Na2CO3The molar ratio of the raw material I to the raw material I is 2.0-3.0: 1;
(2) under the protection of nitrogen, dissolving the intermediate III in o-dichlorobenzene, adding triphenylphosphine, stirring and reacting at 170-190 ℃ for 12-16 hours, cooling to room temperature after the reaction is finished, filtering, carrying out reduced pressure rotary evaporation on the filtrate, and passing through a neutral silica gel column to obtain an intermediate IV; the molar ratio of the intermediate III to triphenylphosphine is 1: 1-2;
(3) under the protection of nitrogen, sequentially weighing the intermediate IV, the raw material V, sodium tert-butoxide and Pd2(dba)3Stirring and mixing tri-tert-butylphosphine with toluene, heating to 100-120 ℃, performing reflux reaction for 12-24 hours, and sampling a sample point plate to show that no intermediate IV remains and the reaction is complete; naturally cooling to room temperature, filtering, decompressing and rotary steaming the filtrate until no fraction is produced, and passing through a neutral silica gel column to obtain a target product; the molar ratio of the intermediate IV to the raw material V is 1: 1-2; the Pd2(dba)3The molar ratio of the tri-tert-butylphosphine to the intermediate IV is 0.006-0.02: 1, and the molar ratio of the tri-tert-butylphosphine to the intermediate IV is 0.006-0.02: 1; the molar ratio of the sodium tert-butoxide to the intermediate IV is 2.0-3.0: 1;
2) when R is represented by the structure shown in the general formula (5), the specific reaction equation is as follows:
Figure BDA0001479060120000132
under the protection of nitrogen, sequentially weighing the intermediate VI, the raw material VII, sodium tert-butoxide and Pd2(dba)3Stirring and mixing tri-tert-butylphosphine with toluene, heating to 100-120 ℃, carrying out reflux reaction for 12-24 hours, and sampling a sample point plate to show that no intermediate VI remains and the reaction is complete; naturally cooling to roomWarming, filtering, decompressing and rotary steaming the filtrate until no fraction is produced, and passing through a neutral silica gel column to obtain a target product; the molar ratio of the intermediate VI to the raw material VII is 1: 1-2; the Pd2(dba)3The molar ratio of the tri-tert-butylphosphine to the intermediate VI is 0.006-0.02: 1, and the molar ratio of the tri-tert-butylphosphine to the intermediate VI is 0.006-0.02: 1; the molar ratio of the sodium tert-butoxide to the intermediate VI is 2.0-3.0: 1.
The application of the organic compound is used for preparing an organic electroluminescent device.
An organic electroluminescent device containing the organic compound comprises at least one functional layer containing the spirofluorene derivative organic compound.
An organic electroluminescent device containing the organic compound comprises an electron blocking layer, wherein the electron blocking layer is made of the spirofluorene derivative organic compound.
An organic electroluminescent device containing the organic compound comprises a light-emitting layer, wherein the light-emitting layer contains the spirofluorene derivative organic compound.
An illumination or display element comprising the organic electroluminescent device.
The beneficial technical effects of the invention are as follows:
the compound of the invention takes spirofluorene as a framework, and is connected with an indole fused ring structure in a ring-forming way through a carbon-carbon bond, and the carbon-carbon bond ring-forming connection not only improves the stability of the material, but also avoids the exposure of the active position of a branched chain group; besides the greater rigidity of the spirofluorene, the indole fused ring structure is also a large pi-bond conjugated rigid structure, the steric hindrance is large, and the compound material is not easy to rotate, so that the three-dimensional structure of the compound material is more stable. The spin density distribution of the triplet state energy level T1 of the compound is basically on a branch chain, and the branch chain has a high T1 energy level, so that the compound also has a high T1 energy level; when the compound is used as an electron blocking layer material of an OLED, the high T1 energy level can effectively block energy from being transferred from a light emitting layer to a hole transport layer, energy loss is reduced, and the energy of a main material of the light emitting layer is fully transferred to a doping material, so that the light emitting efficiency of the material applied to a device is improved.
The organic compound has a structure which enables the distribution of electrons and holes in the light-emitting layer to be more balanced, and under the proper HOMO energy level, the hole injection and transmission performance is improved; under a proper LUMO energy level, the organic electroluminescent material plays a role in blocking electrons, and improves the recombination efficiency of excitons in the luminescent layer; when the spirofluorene derivative is used as a light-emitting functional layer material of an OLED light-emitting device, the spirofluorene derivative can be matched with the branched chain in the range of the spirofluorene derivative to effectively improve the exciton utilization rate and the high fluorescence radiation efficiency, reduce the efficiency roll-off under high current density, reduce the voltage of the device, improve the current efficiency of the device and prolong the service life of the device. When the organic compound is applied to an OLED device, the structure of the device is optimized, so that high film stability can be kept, and the photoelectric property of the OLED device and the service life of the OLED device can be effectively improved. The compound has good application effect and industrialization prospect in OLED light-emitting devices.
Drawings
FIG. 1 is a schematic structural diagram of an OLED device using the materials listed in the present invention; the organic electroluminescent device comprises a transparent substrate layer 1, a transparent substrate layer 2, an ITO anode layer 3, a hole injection layer 4, a hole transport layer 5, an electron blocking layer 6, a light emitting layer 7, a hole blocking/electron transport layer 8, an electron injection layer 9 and a cathode reflection electrode layer.
Fig. 2 is a graph of efficiency of devices measured at different temperatures.
Detailed Description
Example 1: synthesis of intermediate II and intermediate VI
a. Synthesis of intermediate II
Figure BDA0001479060120000151
(1) Weighing a raw material A, dissolving the raw material A in tetrahydrofuran under the protection of nitrogen, cooling to-78 ℃, adding 1.6mol/L n-butyllithium tetrahydrofuran solution into a reaction system, reacting at-78 ℃ for 3h, adding triisopropyl borate, reacting for 2h, raising the temperature of the reaction system to 0 ℃, adding 2mol/L hydrochloric acid solution, stirring for 3h, completely reacting, adding diethyl ether for extraction, adding anhydrous magnesium sulfate into an extract liquid, drying, performing rotary evaporation, and recrystallizing by using an ethanol solvent to obtain an intermediate B; the molar ratio of the raw material A to n-butyllithium is 1: 1-1.5; the molar ratio of the intermediate S4 to triisopropyl borate is 1: 1-1.5.
(2) Weighing intermediate B, Fe (NO) under nitrogen protection3)3.9H2O, dissolving with toluene; heating to 90-110 ℃, reacting for 10-24 hours, taking a sample, naturally cooling to room temperature until no intermediate B remains, carrying out reduced pressure rotary evaporation until no fraction is obtained, and passing through a silica gel column to obtain an intermediate C; said Fe (NO)3)3.9H2The molar ratio of O to the intermediate B is 0.4-0.8: 1.
(1) Weighing the intermediate C, dissolving the intermediate C in acetic acid, and cooling to 0 ℃ by using an ice salt bath; weighing liquid bromine, dissolving the liquid bromine in glacial acetic acid, slowly dropwise adding the liquid bromine into an acetic acid solution of the intermediate C, stirring for 5 hours at room temperature, sampling a sample point plate, and displaying that no intermediate C remains and the reaction is complete; after the reaction is finished, adding alkali liquor into the reaction liquid for neutralization, extracting by using dichloromethane, layering, taking an organic phase for filtration, decompressing and rotary-steaming the filtrate until no fraction is produced, and passing through a silica gel column to obtain an intermediate II; the molar ratio of the intermediate C to the liquid bromine is 1: 1-1.5;
synthesis example of intermediate II-1:
Figure BDA0001479060120000152
Figure BDA0001479060120000161
(1) a250 mL three-necked flask is filled with 0.05mol of raw material A-1 under the atmosphere of nitrogen, dissolved by 50mL of tetrahydrofuran, cooled to-78 ℃, added with 1.6mol/L of n-butyllithium tetrahydrofuran solution (45mL) into a reaction system, reacted for 3h at-78 ℃, added with 0.075mol of triisopropyl borate for reaction for 2h, raised to 0 ℃, added with 2mol/L of hydrochloric acid solution, stirred for 3h, reacted completely, added with diethyl ether for extraction, added with anhydrous magnesium sulfate into an extract for drying, rotary evaporated and recrystallized by ethanol solvent to obtain an intermediate B-1, the HPLC purity is 99.3%, and the yield is 79.9%.
Elemental analysis Structure (molecular formula C)15H15BO3): theoretical value C, 70.91; h, 5.95; b, 4.25; o, 18.89; test values are: c, 70.92; h, 5.93; b, 4.24; and O, 18.91. ESI-MS (M/z) (M)+): theoretical value is 254.11, found 254.32.
(2) A250 mL three-neck flask was charged with nitrogen and 0.03mol of intermediate B-1, 0.015mol of Fe (NO)3)3.9H2O, dissolving with toluene; heating to 100 ℃, reacting for 24 hours, taking a sample, naturally cooling to room temperature until no intermediate B-1 remains, decompressing, rotary-steaming until no fraction is obtained, and passing through a silica gel column to obtain an intermediate C-1. HPLC purity 99.1%, yield 74.7%.
Elemental analysis Structure (molecular formula C)15H13NO3): theoretical value C, 70.58; h, 5.13; n, 5.49; o, 18.80; test values are: c, 70.56; h, 5.14; n, 5.48; o, 18.82. ESI-MS (M/z) (M)+): theoretical value is 255.09, found 255.29.
(3) Adding 0.02mol of intermediate C-1 into a 100mL three-necked bottle, dissolving with 30mL acetic acid, and cooling to 0 ℃ by using an ice salt bath; dropwise adding 1.6ml (0.03mol) of liquid bromine dissolved in 20ml of glacial acetic acid into the reaction system at 0 ℃, heating to room temperature, and stirring for 5 hours; sampling the spot plate, showing no intermediate C-1 remained and complete reaction; after the reaction is finished, adding a sodium carbonate solution into the reaction liquid for neutralization, extracting by using dichloromethane, layering, taking an organic phase, drying and filtering, decompressing and rotary-steaming the filtrate until no fraction is produced, and passing through a silica gel column to obtain an intermediate II-1, wherein the HPLC purity is 99.4%, and the yield is 66.8%.
Elemental analysis Structure (molecular formula C)15H12BrNO3): theoretical value C, 53.91; h, 3.62; br, 23.91; n, 4.19; o, 14.36; test values are: c, 53.93; h, 3.63; br, 23.92; n, 4.19; o, 14.33. ESI-MS (M/z) (M)+): theoretical value is 333.00, found 333.22.
Intermediate II was prepared by the synthetic method of intermediate II-1, the specific structure of which is shown in Table 1.
TABLE 1
Figure BDA0001479060120000162
Figure BDA0001479060120000171
b. Synthesis of intermediate VI
Figure BDA0001479060120000172
Figure BDA0001479060120000181
(1) Weighing raw materials I and 1-bromo-2-nitrobenzene, and dissolving the raw materials I and 1-bromo-2-nitrobenzene in a toluene-ethanol mixed solvent with a volume ratio of 1.5-3.0: 1; then adding Na2CO3Aqueous solution, Pd (PPh)3)4(ii) a Under the protection of nitrogen, stirring the mixed solution at 90-110 ℃ for reaction for 10-24 hours, then cooling to room temperature, filtering the reaction solution, carrying out rotary evaporation on the filtrate, and passing through a silica gel column to obtain an intermediate P; the molar ratio of the raw material I to the 1-bromo-2-nitrobenzene is 1: 1.5-3.0; pd (PPh)3)4The molar ratio of the raw material I to the raw material I is 0.006-0.02: 1, and Na2CO3The molar ratio of the raw material I to the raw material I is 2.0-3.0: 1;
(2) under the protection of nitrogen, dissolving the intermediate N prepared in the previous step in o-dichlorobenzene, adding triphenylphosphine, stirring and reacting at 170-190 ℃ for 12-16 hours, cooling to room temperature after the reaction is finished, filtering, decompressing and rotary-steaming the filtrate, and passing through a neutral silica gel column to obtain an intermediate P; the molar ratio of the intermediate N to the triphenylphosphine is 1: 1-2;
(3) under the protection of nitrogen, intermediate P, Ar-Br, sodium tert-butoxide and Pd are weighed in sequence2(dba)3And tri-tert-butylphosphine, stirring and mixing with toluene, heating to 100-120 ℃, refluxing and reacting for 12-24 hours, taking a sample, and displaying no intermediateThe body IV is remained and the reaction is complete; naturally cooling to room temperature, filtering, carrying out reduced pressure rotary evaporation on the filtrate until no fraction is obtained, and passing through a neutral silica gel column to obtain an intermediate Q; the molar ratio of the intermediate P to Ar-Br is 1: 1-2; the Pd2(dba)3The molar ratio of the tri-tert-butylphosphine to the intermediate P is 0.006-0.02: 1, and the molar ratio of the tri-tert-butylphosphine to the intermediate P is 0.006-0.02: 1; the molar ratio of the sodium tert-butoxide to the intermediate P is 2.0-3.0: 1;
(4) weighing an intermediate Q, dissolving the intermediate Q in acetic acid, and cooling to 0 ℃ by using an ice salt bath; weighing liquid bromine, dissolving the liquid bromine in glacial acetic acid, slowly dropwise adding the liquid bromine into an acetic acid solution of the intermediate Q, stirring for 5 hours at room temperature, sampling a sample point plate, and displaying that no intermediate Q remains and the reaction is complete; after the reaction is finished, adding alkali liquor into the reaction liquid for neutralization, extracting by using dichloromethane, layering, taking an organic phase for filtration, decompressing and rotary-steaming the filtrate until no fraction is produced, and passing through a silica gel column to obtain an intermediate VI; the molar ratio of the intermediate Q to the liquid bromine is 1: 1-1.5.
Synthesis of intermediate VI-1 as an example:
Figure BDA0001479060120000182
Figure BDA0001479060120000191
(1) in a 250ml three-necked flask, under the protection of nitrogen, 0.05mol of raw material I-1, 0.075mol of 1-bromo 2-nitrobenzene is added, dissolved in a mixed solvent (90ml of toluene, 45ml of ethanol), and then 0.15mol of Na is added2CO3The aqueous solution (2M) was stirred under nitrogen for 1 hour, then 0.0005mol Pd (PPh) was added3)4And heating and refluxing for 15 hours, sampling a sample point plate, and completely reacting. Naturally cooling, filtering, rotatably steaming the filtrate, and passing through a silica gel column to obtain an intermediate N-1 with the purity of 99.5 percent and the yield of 82.3 percent. Elemental analysis Structure (molecular formula C)31H19NO2): theoretical value C, 85.11; h, 4.38; n, 3.20; o, 7.31; test values are: c, 85.12; h, 4.36; n, 3.21; o, 7.31. ESI-MS (M/z) (M)+): theoretical value of 437.14, found valueIs 437.33.
(2) Adding 0.03mol of intermediate N-1 and 0.036mol of triphenylphosphine into a 100ml three-necked bottle under the protection of nitrogen, dissolving the mixture by using 50ml of o-dichlorobenzene, heating the mixture to 170 ℃, reacting for 15 hours, sampling a sample point plate, and completely reacting. Naturally cooling, filtering, rotatably steaming the filtrate, and passing through a silica gel column to obtain an intermediate P-1 with the purity of 99.2 percent and the yield of 78.4 percent. Elemental analysis Structure (molecular formula C)31H19N): theoretical value C, 91.82; h, 4.72; n, 3.45; test values are: c, 91.81; h, 4.73; and N, 3.46. ESI-MS (M/z) (M)+): theoretical value is 405.15, found 405.46.
(3) In a 250ml three-mouth bottle, 0.02mol of intermediate P-1, 0.024mol of bromobenzene, 0.06mol of sodium tert-butoxide and 1 multiplied by 10 are added under the protection of nitrogen-4mol Pd2(dba)3，1×10-4Dissolving the tri-tert-butylphosphine in 150ml of toluene, heating and refluxing for 24 hours, sampling a sample, and completely reacting; naturally cooling, filtering, rotatably steaming the filtrate, and passing through a silica gel column to obtain an intermediate Q-1, wherein the HPLC purity is 99.6 percent, and the yield is 79.6 percent; elemental analysis Structure (molecular formula C)37H23N): theoretical value C, 92.28; h, 4.81; n, 2.91; test values are: c, 92.25; h, 4.83; and N, 2.92. ESI-MS (M/z) (M)+): the theoretical value was 481.18, found 481.44.
(4) Adding 0.01mol of intermediate Q-1 into a 100mL three-necked bottle, dissolving with 30mL acetic acid, and cooling to 0 ℃ by using an ice salt bath; dropwise adding 0.8ml (0.015mol) of liquid bromine dissolved in 20ml of glacial acetic acid into the reaction system at the temperature of 0 ℃, heating to room temperature, and stirring for 5 hours; sampling the spot plate, showing no intermediate Q-1 remained and complete reaction; after the reaction is finished, adding a sodium carbonate solution into the reaction liquid for neutralization, extracting by using dichloromethane, layering, taking an organic phase, drying and filtering, decompressing and rotary-steaming the filtrate until no fraction is produced, and passing through a silica gel column to obtain an intermediate VI-1, wherein the HPLC purity is 99.4%, and the yield is 66.3%. Elemental analysis Structure (molecular formula C)37H22BrN): theoretical value C, 79.29; h, 3.96; br, 14.26; n, 2.50; test values are: c, 79.27; h, 3.95; br, 14.27; n, 2.53. ESI-MS (M/z) (M)+): theoretical value is 559.09, found 559.37.
Intermediate VI was prepared by the synthetic method of intermediate VI-1, the specific structure is shown in Table 2.
TABLE 2
Figure BDA0001479060120000192
Figure BDA0001479060120000201
Example 2: synthesis of Compound 5:
Figure BDA0001479060120000202
(1) in a 250ml three-necked flask, 0.05mol of the raw material I-1, 0.075mol of the intermediate II-1 was added under nitrogen protection, dissolved in a mixed solvent (90ml of toluene, 45ml of ethanol), and then 0.15mol of Na was added2CO3The aqueous solution (2M) was stirred under nitrogen for 1 hour, then 0.0005mol Pd (PPh) was added3)4And heating and refluxing for 15 hours, sampling a sample point plate, and completely reacting. Naturally cooling, filtering, rotatably steaming the filtrate, and passing through a silica gel column to obtain an intermediate III-1 with the purity of 99.0 percent and the yield of 78.1 percent. Elemental analysis Structure (molecular formula C)40H27NO3): theoretical value C, 84.34; h, 4.78; n, 2.46; o, 8.43; test values are: c, 84.32; h, 4.77; n, 2.47; and O, 8.44. ESI-MS (M/z) (M)+): theoretical value is 569.20, found 569.44.
(2) Adding 0.03mol of intermediate III-1 and 0.036mol of triphenylphosphine into a 100ml three-neck flask under the protection of nitrogen, dissolving the mixture by using 50ml of o-dichlorobenzene, heating the mixture to 170 ℃, reacting for 15 hours, sampling a sample, and completely reacting. Naturally cooling, filtering, rotatably steaming the filtrate, and passing through a silica gel column to obtain an intermediate IV-1 with the purity of 99.3 percent and the yield of 76.6 percent. Elemental analysis Structure (molecular formula C)40H27NO): theoretical value C, 89.36; h, 5.06; n, 2.61; o, 2.98; test values are: c, 89.33; h, 5.07; n, 2.63; o, 2.97. ESI-MS (M/z) (M)+): theoretical value is 537.21, found 537.48.
(3) In a 250ml three-mouth bottle, 0.01mol of intermediate IV-1, 0.012mol of bromobenzene, 0.03mol of sodium tert-butoxide and 5X 10 are added under the protection of nitrogen-5mol Pd2(dba)3，5×10-5Dissolving the tri-tert-butylphosphine in 150ml of toluene, heating and refluxing for 24 hours, sampling a sample, and completely reacting; naturally cooling, filtering, rotatably evaporating filtrate, and passing through a silica gel column to obtain a target product, wherein the HPLC purity is 99.7%, and the yield is 79.3%; elemental analysis Structure (molecular formula C)46H31NO): theoretical value C, 90.02; h, 5.09; n, 2.28; o, 2.61; test values are: c, 90.01; h, 5.07; n, 2.29; o, 2.63. ESI-MS (M/z) (M)+): theoretical value is 613.24, found 613.51.
Example 3: synthesis of compound 12:
Figure BDA0001479060120000211
(1) in a 250ml three-necked flask, under the protection of nitrogen, 0.05mol of the raw material I-1, 0.075mol of the intermediate II-2 was added, dissolved in a mixed solvent (90ml of toluene, 45ml of ethanol), and then 0.15mol of Na was added2CO3The aqueous solution (2M) was stirred under nitrogen for 1 hour, then 0.0005mol Pd (PPh) was added3)4And heating and refluxing for 15 hours, sampling a sample point plate, and completely reacting. Naturally cooling, filtering, rotatably evaporating filtrate, and passing through a silica gel column to obtain an intermediate III-2 with the purity of 99.6 percent and the yield of 77.4 percent. Elemental analysis Structure (molecular formula C)40H27NO2S): theoretical value C, 82.03; h, 4.65; n, 2.39; o, 5.46; s, 5.47; test values are: c, 82.05; h, 4.67; n, 2.40; o, 5.44; s, 5.44. ESI-MS (M/z) (M)+): theoretical value is 585.18, found 585.38.
(2) Adding 0.03mol of intermediate III-2 and 0.036mol of triphenylphosphine into a 100ml three-neck flask under the protection of nitrogen, dissolving the mixture by using 50ml of o-dichlorobenzene, heating the mixture to 170 ℃, reacting for 15 hours, sampling a sample, and completely reacting. Naturally cooling, filtering, rotatably steaming the filtrate, and passing through a silica gel column to obtain an intermediate IV-2 with the purity of 99.4 percent and the yield of 75.7 percent. Elemental analysis Structure (molecular formula C)40H27NS): theoretical value C, 86.77; h, 4.92; n, 2.53; s, 5.79; test values are: c, 86.78; h, 4.91; n, 2.54; s, 5.77. ESI-MS (M/z) (M +): theoretical value is 553.19, found 553.49.
(3) In a 250ml three-mouth bottle, 0.01mol of intermediate IV-2, 0.012mol of bromobenzene, 0.03mol of sodium tert-butoxide and 5X 10 are added under the protection of nitrogen-5mol Pd2(dba)3，5×10-5Dissolving the tri-tert-butylphosphine in 150ml of toluene, heating and refluxing for 24 hours, sampling a sample, and completely reacting; naturally cooling, filtering, rotatably evaporating filtrate, and passing through a silica gel column to obtain a target product, wherein the HPLC purity is 99.6%, and the yield is 77.4%; elemental analysis Structure (molecular formula C)46H31NS): theoretical value C, 87.72; h, 4.96; n, 2.22; s, 5.09; test values are: c, 87.74; h, 4.97; n, 2.21; and S, 5.08. ESI-MS (M/z) (M)+): theoretical value is 629.22, found 629.51.
Example 4: synthesis of compound 24:
Figure BDA0001479060120000221
the preparation method of the intermediate III-3 is the same as that of the intermediate III-1, except that the intermediate II-3 is used for replacing the intermediate II-1; the preparation method of the intermediate IV-3 is the same as that of the intermediate IV-1, except that the intermediate III-3 is used for replacing the intermediate III-1;
compound 24 was prepared as compound 5, except that intermediate IV-3 was used in place of intermediate IV-1. Elemental analysis Structure (molecular formula C)49H37N): theoretical value C, 91.98; h, 5.83; n, 2.19; test values are: c, 91.96; h, 5.85; and N, 2.19. ESI-MS (M/z) (M)+): theoretical value is 639.29, found 639.62.
Example 5: synthesis of compound 42:
Figure BDA0001479060120000222
the preparation method of the intermediate III-4 is the same as that of the intermediate III-1, except that the raw material I-2 is used for replacing the raw material I-1 and the intermediate II-4 is used for replacing the intermediate II-1; the preparation method of the intermediate IV-4 is the same as that of the intermediate IV-1, except that the intermediate III-4 is used for replacing the intermediate III-1;
compound 42 was prepared as compound 5 except intermediate IV-4 was used in place of intermediate IV-1. Elemental analysis Structure (molecular formula C)46H31NO): theoretical value C, 90.02; h, 5.09; n, 2.28; o, 2.61; test values are: c, 90.03; h, 5.08; n, 2.27; o, 2.62. ESI-MS (M/z) (M)+): theoretical value is 613.24, found 613.47.
Example 6: synthesis of compound 53:
Figure BDA0001479060120000231
the preparation method of the intermediate III-5 is the same as that of the intermediate III-1, except that the raw material I-2 is used for replacing the raw material I-1 and the intermediate II-5 is used for replacing the intermediate II-1; the preparation method of the intermediate IV-5 is the same as that of the intermediate IV-1, except that the intermediate III-5 is used for replacing the intermediate III-1;
compound 53 was prepared as compound 5, except that intermediate IV-5 was used in place of intermediate IV-1. Elemental analysis Structure (molecular formula C)46H31NO): theoretical value C, 90.02; h, 5.09; n, 2.28; o, 2.61; test values are: c, 90.03; h, 5.08; n, 2.29; o, 2.60. ESI-MS (M/z) (M)+): theoretical value is 613.24, found 613.51.
Example 7: synthesis of compound 60:
Figure BDA0001479060120000232
the preparation method of the intermediate III-6 is the same as that of the intermediate III-1, except that the raw material I-2 is used for replacing the raw material I-1 and the intermediate II-6 is used for replacing the intermediate II-1; the preparation method of the intermediate IV-6 is the same as the intermediate IV-1, except that the intermediate III-6 is used for replacing the intermediate III-1;
process for the preparation of compound 60Compound 5 was used except that intermediate IV-6 was used in place of intermediate IV-1. Elemental analysis Structure (molecular formula C)49H37N): theoretical value C, 91.98; h, 5.83; n, 2.19; test values are: c, 91.97; h, 5.82; n, 2.21. ESI-MS (M/z) (M)+): theoretical value is 639.29, found 639.57.
Example 8: synthesis of compound 67:
Figure BDA0001479060120000241
the preparation method of the intermediate III-7 is the same as that of the intermediate III-1, except that the raw material I-2 is used for replacing the raw material I-1 and the intermediate II-7 is used for replacing the intermediate II-1; the preparation method of the intermediate IV-7 is the same as that of the intermediate IV-1, except that the intermediate III-7 is used for replacing the intermediate III-1;
compound 67 was prepared as compound 5, except that intermediate IV-7 was used in place of intermediate IV-1. Elemental analysis Structure (molecular formula C)49H30N2O): theoretical value C, 88.80; h, 4.56; n, 4.23; o, 2.41; test values are: c, 88.81; h, 4.55; n, 4.22; o, 2.42. ESI-MS (M/z) (M)+): theoretical value is 662.24, found 662.57.
Example 9: synthesis of compound 81:
Figure BDA0001479060120000242
the preparation method of the intermediate III-8 is the same as that of the intermediate III-1, except that the raw material I-2 is used for replacing the raw material I-1 and the intermediate II-8 is used for replacing the intermediate II-1; the preparation method of the intermediate IV-8 is the same as that of the intermediate IV-1, except that the intermediate III-8 is used for replacing the intermediate III-1;
compound 81 was prepared as compound 5 except intermediate IV-8 was used in place of intermediate IV-1 and 2-bromobiphenyl was used in place of bromobenzene. Elemental analysis Structure (molecular formula C)52H35NO): theoretical value C, 90.54; h, 5.11; n, 2.03; o, 2.32; test values are: c, 90.53; h, 5.12; n,2.01；O,2.34。ESI-MS(m/z)(M+): theoretical value is 689.27, found 689.53.
Example 10: synthesis of compound 99:
Figure BDA0001479060120000251
the preparation method of the intermediate III-6 is the same as that of the intermediate III-1, except that the raw material I-2 is used for replacing the raw material I-1 and the intermediate II-6 is used for replacing the intermediate II-1; the preparation method of the intermediate IV-6 is the same as the intermediate IV-1, except that the intermediate III-6 is used for replacing the intermediate III-1;
compound 99 is prepared as compound 5, except that intermediate IV-6 is used instead of intermediate IV-1 and 4-bromodibenzofuran is used instead of bromobenzene. Elemental analysis Structure (molecular formula C)55H39NO): theoretical value C, 90.50; h, 5.39; n, 1.92; o, 2.19; test values are: c, 90.51; h, 5.37; n, 1.94; o, 2.18. ESI-MS (M/z) (M)+): theoretical value is 729.30, found 729.55.
Example 11: synthesis of compound 110:
Figure BDA0001479060120000252
the preparation method of the intermediate III-9 is the same as that of the intermediate III-1, except that the raw material I-3 is adopted to replace the raw material I-1 and the intermediate II-4 is adopted to replace the intermediate II-1; the preparation method of the intermediate IV-9 is the same as the intermediate IV-1, except that the intermediate III-9 is used for replacing the intermediate III-1;
compound 110 was prepared as compound 5, except that intermediate IV-9 was used in place of intermediate IV-1. Elemental analysis Structure (molecular formula C)46H31NO): theoretical value C, 90.02; h, 5.09; n, 2.28; o, 2.61; test values are: c, 90.01; h, 5.08; n, 2.29; o, 2.62. ESI-MS (M/z) (M)+): theoretical value is 613.24, found 613.51.
Example 12: synthesis of compound 121:
Figure BDA0001479060120000261
the preparation method of the intermediate III-10 is the same as that of the intermediate III-1, except that the raw material I-3 is adopted to replace the raw material I-1 and the intermediate II-8 is adopted to replace the intermediate II-1; the preparation method of the intermediate IV-10 is the same as that of the intermediate IV-1, except that the intermediate III-10 is used for replacing the intermediate III-1;
compound 121 was prepared as compound 5, except that intermediate IV-10 was used in place of intermediate IV-1. Elemental analysis Structure (molecular formula C)46H31NO): theoretical value C, 90.02; h, 5.09; n, 2.28; o, 2.61; test values are: c, 90.04; h, 5.07; n, 2.27; o, 2.62. ESI-MS (M/z) (M)+): theoretical value is 613.24, found 613.57.
Example 13: synthesis of compound 128:
Figure BDA0001479060120000262
the preparation method of the intermediate III-11 is the same as that of the intermediate III-1, except that the raw material I-3 is adopted to replace the raw material I-1 and the intermediate II-9 is adopted to replace the intermediate II-1; the preparation method of the intermediate IV-11 is the same as the intermediate IV-1, except that the intermediate III-11 is used for replacing the intermediate III-1;
compound 128 was prepared as compound 5, except intermediate IV-11 was used in place of intermediate IV-1. Elemental analysis Structure (molecular formula C)52H36N2): theoretical value C, 90.67; h, 5.27; n, 4.07; test values are: c, 90.65; h, 5.26; and N, 4.09. ESI-MS (M/z) (M)+): theoretical value is 688.29, found 688.62.
Example 14: synthesis of compound 135:
Figure BDA0001479060120000271
the preparation method of the intermediate III-12 is the same as that of the intermediate III-1, except that the raw material I-3 is adopted to replace the raw material I-1 and the intermediate II-10 is adopted to replace the intermediate II-1; the preparation method of the intermediate IV-12 is the same as the intermediate IV-1, except that the intermediate III-12 is used for replacing the intermediate III-1;
compound 135 was prepared as compound 5, except that intermediate IV-12 was used in place of intermediate IV-1. Elemental analysis Structure (molecular formula C)52H36N2): theoretical value C, 90.67; h, 5.27; n, 4.07; test values are: c, 90.65; h, 5.28; and N, 4.07. ESI-MS (M/z) (M)+): theoretical value is 688.29, found 688.61.
Example 15: synthesis of compound 145:
Figure BDA0001479060120000272
the preparation method of the intermediate III-13 is the same as that of the intermediate III-1, except that the raw material I-3 is adopted to replace the raw material I-1 and the intermediate II-5 is adopted to replace the intermediate II-1; the preparation method of the intermediate IV-13 is the same as the intermediate IV-1, except that the intermediate III-13 is used for replacing the intermediate III-1;
compound 145 is prepared as compound 5, except that intermediate IV-13 is used instead of intermediate IV-1 and 4-bromobiphenyl is used instead of bromobenzene. Elemental analysis Structure (molecular formula C)52H35NO): theoretical value C, 90.54; h, 5.11; n, 2.03; o, 2.32; test values are: c, 90.55; h, 5.12; n, 2.02; o, 2.31. ESI-MS (M/z) (M)+): theoretical value is 689.27, found 689.51.
Example 16: synthesis of compound 155:
Figure BDA0001479060120000281
the preparation method of the intermediate III-14 is the same as that of the intermediate III-1, except that the intermediate II-11 is used for replacing the intermediate II-1; the preparation method of the intermediate IV-14 is the same as that of the intermediate IV-1, except that the intermediate III-14 is used for replacing the intermediate III-1;
compound 155 was prepared as compound 5, except that intermediate IV-14 was used in place of intermediate IV-1. Elemental analysis Structure (molecular formula C)46H31NO): theoretical value C, 90.02; h, 5.09; n, 2.28; o, 2.61; test values are: c, 90.03; h, 5.07; n, 2.27; o, 2.63. ESI-MS (M/z) (M)+): theoretical value is 613.24, found 613.55.
Example 17: synthesis of compound 165:
Figure BDA0001479060120000282
the intermediate III-15 is prepared by the same method as the intermediate III-1 except that the intermediate II-8 replaces the intermediate II-1; the preparation method of the intermediate IV-15 is the same as that of the intermediate IV-1, except that the intermediate III-15 is used for replacing the intermediate III-1;
compound 165 is prepared as compound 5, except that intermediate IV-15 is used in place of intermediate IV-1. Elemental analysis Structure (molecular formula C)46H31NO): theoretical value C, 90.02; h, 5.09; n, 2.28; o, 2.61; test values are: c, 90.03; h, 5.07; n, 2.26; o, 2.64. ESI-MS (M/z) (M)+): theoretical value is 613.24, found 613.52.
Example 18: synthesis of compound 172:
Figure BDA0001479060120000291
the preparation method of the intermediate III-3 is the same as that of the intermediate III-1, except that the intermediate II-3 is used for replacing the intermediate II-1; the preparation method of the intermediate IV-16 is the same as that of the intermediate IV-1, except that the intermediate III-3 is used for replacing the intermediate III-1;
compound 172 was prepared as compound 5, except that intermediate IV-16 was used in place of intermediate IV-1. Elemental analysis Structure (molecular formula C)49H37N): theoretical value C, 91.98; h, 5.83; n, 2.19; test values are: c, 91.97; h, 5.85; and N, 2.18. ESI-MS (M/z) (M)+)：Theoretical value is 639.29, found 639.58.
Example 19: synthesis of compound 182:
Figure BDA0001479060120000292
the intermediate III-16 is prepared by the same method as the intermediate III-1 except that the intermediate II-1 is replaced by the intermediate II-9; the preparation method of the intermediate IV-17 is the same as that of the intermediate IV-1, except that the intermediate III-16 is used for replacing the intermediate III-1;
compound 182 is prepared as compound 5, except that intermediate IV-17 is used in place of intermediate IV-1. Elemental analysis Structure (molecular formula C)52H36N2): theoretical value C, 90.67; h, 5.27; n, 4.07; test values are: c, 90.66; h, 5.26; and N, 4.08. ESI-MS (M/z) (M)+): theoretical value is 688.29, found 688.65.
Example 20: synthesis of compound 191:
Figure BDA0001479060120000293
Figure BDA0001479060120000301
the preparation method of the intermediate III-17 is the same as that of the intermediate III-1, except that the raw material I-2 is used for replacing the raw material I-1 and the intermediate II-12 is used for replacing the intermediate II-1; the preparation method of the intermediate IV-18 is the same as that of the intermediate IV-1, except that the intermediate III-17 is adopted to replace the intermediate III-1;
compound 191 is prepared as described for compound 5, except that intermediate IV-18 is used in place of intermediate IV-1. Elemental analysis Structure (molecular formula C)45H27NO): theoretical value C, 90.43; h, 4.55; n, 2.34; o, 2.68; test values are: c, 90.44; h, 4.56; n, 2.32; o, 2.68. ESI-MS (M/z) (M)+): theoretical value is 597.21, found 597.54.
Example 21: synthesis of compound 204:
Figure BDA0001479060120000302
in a 250ml three-mouth bottle, 0.01mol of intermediate VI-1, 0.012mol of raw material VII-1, 0.03mol of sodium tert-butoxide and 5X 10 mol are added under the protection of nitrogen-5mol Pd2(dba)3，5×10-5Dissolving the tri-tert-butylphosphine in 150ml of toluene, heating and refluxing for 24 hours, sampling a sample, and completely reacting; naturally cooling, filtering, rotatably evaporating filtrate, and passing through a silica gel column to obtain a target product with the HPLC purity of 99.8 percent and the yield of 81.4 percent. Elemental analysis Structure (molecular formula C)49H32N2): theoretical value C, 90.71; h, 4.97; n, 4.32; test values are: c, 90.72; h, 4.95; n, 4.33. ESI-MS (M/z) (M)+): theoretical value is 648.26, found 648.53.
Example 22: synthesis of compound 216:
Figure BDA0001479060120000303
compound 216 was prepared as compound 204 except intermediate VI-2 was used instead of intermediate VI-1 and starting material VII-2 was used instead of starting material VII-1 in an HPLC purity of 99.9% with a yield of 80.8%. Elemental analysis Structure (molecular formula C)58H40N2): theoretical value C, 91.07; h, 5.27; n, 3.66; test value C, 91.05; h, 5.28; n, 3.67. ESI-MS (M/z) (M)+): theoretical value is 764.32, found 764.65.
Example 23: synthesis of compound 226:
Figure BDA0001479060120000311
compound 226 can be prepared by replacing intermediate VI-1 with intermediate VI-3 and replacing raw material VII-1 with raw material VII-3, with HPLC purity of 99.8% and yield of 79.9% of the total weight of the composition. Elemental analysis Structure (molecular formula C)55H34N2O): theoretical value C, 89.41; h, 4.64; n, 3.79; o, 2.17; test values are: c, 89.43; h, 4.62; n, 3.77; o, 2.18. ESI-MS (M/z) (M)+): theoretical value is 738.27, found 738.67.
Example 24: synthesis of compound 245:
Figure BDA0001479060120000312
compound 245 is prepared as compound 204 except intermediate VI-3 is used in place of intermediate VI-1 in HPLC purity of 99.5% and yield of 83.1%. Elemental analysis Structure (molecular formula C)55H34N2O): theoretical value C, 89.41; h, 4.64; n, 3.79; o, 2.17; test values are: c, 89.43; h, 4.61; n, 3.81; o, 2.15. ESI-MS (M/z) (M)+): theoretical value is 738.27, found 738.58.
The organic compound of the present invention is used in a light-emitting device, and can be used as an electron blocking layer material or a light-emitting layer host material. The compounds of the present invention were tested for thermal properties, HOMO energy levels, and cyclic voltammetric stability, as shown in Table 3.
TABLE 3
Figure BDA0001479060120000313
Figure BDA0001479060120000321
Note: the triplet energy level T1 was measured by Hitachi F4600 fluorescence spectrometer under the conditions of 2X 10-5A toluene solution of (4); the glass transition temperature Tg is determined by differential scanning calorimetry (DSC, DSC204F1 DSC, Germany Chi corporation), the heating rate is 10 ℃/min; the thermogravimetric temperature Td was a temperature at which 1% of the weight loss was observed in a nitrogen atmosphere, and was measured on a TGA-50H thermogravimetric analyzer of Shimadzu corporation, Japan, and the nitrogen flow rate was20 mL/min; the highest occupied molecular orbital HOMO energy level was tested by the ionization energy testing system (IPS3) in an atmospheric environment. The cyclic voltammetry stability is characterized by observing the redox characteristics of the material by cyclic voltammetry; and (3) testing conditions are as follows: the test sample was dissolved in a mixed solvent of dichloromethane and acetonitrile at a volume ratio of 2:1 at a concentration of 1mg/mL, and the electrolyte was 0.1M of an organic solution of tetrabutylammonium tetrafluoroborate or hexafluorophosphate. The reference electrode is an Ag/Ag + electrode, the counter electrode is a titanium plate, the working electrode is an ITO electrode, and the cycle time is 20 times.
The data in the table show that the organic compound has different HOMO energy levels and can be applied to different functional layers, and the spirofluorene derivative organic compound has higher triplet state energy level, higher thermal stability and chemical stability, so that the efficiency and the service life of the manufactured OLED device containing the organic compound are improved.
The application effect of the synthesized OLED material in the device is explained in detail through device examples 1-23 and device comparative example 1. Compared with the device embodiment 1, the device embodiments 2 to 23 and the device comparative example 1 have the same manufacturing process, adopt the same substrate material and electrode material, and keep the film thickness of the electrode material consistent, except that the device embodiments 2 to 13 use the material of the invention as an electron blocking layer; device examples 14 to 23 changed the host material of the light emitting layer in the device. The results of the performance tests of the devices obtained in the examples are shown in table 4.
Device example 1: as shown in fig. 1, an electroluminescent device is prepared by the steps of:
a) cleaning the ITO anode layer 2 on the transparent substrate layer 1, respectively ultrasonically cleaning the ITO anode layer 2 with deionized water, acetone and ethanol for 15 minutes, and then treating the ITO anode layer 2 in a plasma cleaner for 2 minutes; b) evaporating a hole injection layer material HAT-CN on the ITO anode layer 2 in a vacuum evaporation mode, wherein the thickness of the hole injection layer material HAT-CN is 10nm, and the layer is used as a hole injection layer 3; c) evaporating a hole transport material NPB (N-propyl bromide) on the hole injection layer 3 in a vacuum evaporation mode, wherein the thickness of the hole transport material NPB is 60nm, and the hole transport layer is a hole transport layer 4; d) in thatThe compound 42 of the invention as an electron blocking layer material is evaporated on the hole transport layer 4 in a vacuum evaporation mode, the thickness is 20nm, and the layer is an electron blocking layer 5; e) depositing a light-emitting layer 6 on the electron blocking layer 5, using CBP as a host material, Ir (ppy)3As doping material, Ir (ppy)3The mass ratio of CBP to CBP is 10:90, and the thickness is 30 nm; f) an electron transport material TPBI is evaporated on the light-emitting layer 6 in a vacuum evaporation mode, the thickness of the TPBI is 40nm, and the organic material of the TPBI layer is used as a hole blocking/electron transport layer 7; g) vacuum evaporating an electron injection layer LiF with the thickness of 1nm on the hole blocking/electron transport layer 7, wherein the layer is an electron injection layer 8; h) vacuum evaporating cathode Al (100nm) on the electron injection layer 8, which is a cathode reflection electrode layer 9; electroluminescent devices were fabricated as described above, and the current efficiency and lifetime of the devices were measured, and the results are shown in table 4. The molecular structural formula of the related material is shown as follows:
Figure BDA0001479060120000331
device example 2: this embodiment differs from device embodiment 1 in that: the electron blocking layer material of the electroluminescent device is the compound 67 of the present invention. Device example 3: this embodiment differs from device embodiment 1 in that: the electron blocking layer material of the electroluminescent device is the compound 81 of the present invention. Device example 4: this embodiment differs from device embodiment 1 in that: the electron blocking layer material of the electroluminescent device is the compound 110 of the present invention. Device example 5: this embodiment differs from device embodiment 1 in that: the electron blocking layer material of the electroluminescent device is the compound 121 of the present invention. Device example 6: this embodiment differs from device embodiment 1 in that: the electron blocking layer material of the electroluminescent device is the compound 128 of the present invention. Device example 7: this embodiment differs from device embodiment 1 in that: the electron blocking layer material of the electroluminescent device is the compound 135 of the present invention. Device example 8: this embodiment differs from device embodiment 1 in that: the electron barrier material of the electroluminescent device isA compound 165. Device example 9: this embodiment differs from device embodiment 1 in that: the electron blocking layer material of the electroluminescent device is compound 182 of the present invention. Device example 10: this embodiment differs from device embodiment 1 in that: the electron blocking layer material of the electroluminescent device is the compound 204 of the present invention. Device example 11: this embodiment differs from device embodiment 1 in that: the electron blocking layer material of the electroluminescent device is the compound 216 of the present invention. Device example 12: this embodiment differs from device embodiment 1 in that: the electron blocking layer material of the electroluminescent device is the compound 226 of the present invention. Device example 13: this embodiment differs from device embodiment 1 in that: the electron blocking layer material of the electroluminescent device is the compound 245 of the present invention. Device example 14: this embodiment differs from device embodiment 1 in that: the material of the electron barrier layer of the electroluminescent device is NPB, the main material of the luminescent layer of the electroluminescent device is changed into the compound 5 of the invention, and the doping material is Ir (ppy)3，Ir(ppy)3And compound 5 in a mass ratio of 10: 90. Device example 15: this embodiment differs from device embodiment 1 in that: the material of the electron barrier layer of the electroluminescent device is NPB, the main material of the luminescent layer of the electroluminescent device is changed into the compound 12 of the invention, and the doped material is Ir (ppy)3，Ir(ppy)3And compound 12 in a mass ratio of 10: 90. Device example 16: this embodiment differs from device embodiment 1 in that: the material of the electron barrier layer of the electroluminescent device is NPB, the main material of the luminescent layer of the electroluminescent device is changed into the compound 53 of the invention, and the doping material is Ir (ppy)3，Ir(ppy)3And compound 53 in a mass ratio of 10: 90. . Device example 17: this embodiment differs from device embodiment 1 in that: the material of the electron barrier layer of the electroluminescent device is NPB, the main material of the luminescent layer of the electroluminescent device is changed into the compound 145 of the invention, and the doping material is Ir (ppy)3，Ir(ppy)3And compound 145 in a mass ratio of 10: 90. Device example 18: this embodiment differs from device embodiment 1 in that: the electron-blocking layer material of the electroluminescent device is NPB, the electroluminescent deviceThe host material of the light-emitting layer was changed to the compound 155 of the present invention, and the dopant material was Ir (ppy)3，Ir(ppy)3And compound 155 in a mass ratio of 10: 90. Device example 19: this embodiment differs from device embodiment 1 in that: the material of the electron barrier layer of the electroluminescent device is NPB, the main material of the luminescent layer of the electroluminescent device is changed into the compound 191 of the invention, and the doping material is Ir (ppy)3，Ir(ppy)3And compound 191 at a mass ratio of 10: 90. Device example 20: this embodiment differs from device embodiment 1 in that: the material of the electron barrier layer of the electroluminescent device is NPB, the main material of the luminescent layer of the electroluminescent device is changed into the compound 24 and the compound GHN, and the doping material is Ir (ppy)3Compound 24, GHN and Ir (ppy)3The mass ratio of the three components is 60:30: 10. Device example 21: this embodiment differs from device embodiment 1 in that: the material of the electron barrier layer of the electroluminescent device is NPB, the main material of the luminescent layer of the electroluminescent device is changed into the compound 60 and the compound GHN, and the doping material is Ir (ppy)3 Compound 60, GHN and Ir (ppy)3The mass ratio of the three components is 60:30: 10. Device example 22: this embodiment differs from device embodiment 1 in that: the material of the electron barrier layer of the electroluminescent device is NPB, the main material of the luminescent layer of the electroluminescent device is changed into the compound 99 and the compound GHN, and the doping material is Ir (ppy)3Compound 99, GHN and Ir (ppy)3The mass ratio of the three components is 60:30: 10. Device example 23: this embodiment differs from device embodiment 1 in that: the material of the electron barrier layer of the electroluminescent device is NPB, the main material of the luminescent layer of the electroluminescent device is changed into the compound 172 and the compound GHN of the invention, and the doping material is Ir (ppy)3Compound 172, GHN and Ir (ppy)3The mass ratio of the three components is 60:30: 10. Device comparative example 1: this embodiment differs from device embodiment 1 in that: the material of the electron barrier layer of the electroluminescent device is NPB, the main material of the luminescent layer of the electroluminescent device is known compound CBP, and the doping material is Ir (ppy)3，Ir(ppy)3The mass ratio of CBP to CBP was 10:90, and the inspection data of the obtained electroluminescent device are shown in Table 4.
TABLE 4
Figure BDA0001479060120000341
Figure BDA0001479060120000351
Note: the life test system is an OLED device life tester which is researched by the owner of the invention together with Shanghai university.
From the results in table 4, it can be seen that the spirofluorene derivative organic compound of the present invention can be applied to the fabrication of an OLED light emitting device, and compared with comparative device example 1, the voltage of the device is significantly reduced, and the efficiency and the lifetime of the device are both improved greatly compared with those of the known OLED material, especially the lifetime decay of the device is greatly improved.
Further, the OLED devices prepared from the material of the present invention can maintain long life at high temperature, and the device examples 1-23 and the device comparative example 1 were subjected to a high temperature driving life test at 85 ℃, and the results are shown in Table 5.
TABLE 5
Figure BDA0001479060120000352
Figure BDA0001479060120000361
As can be seen from the data in Table 5, the OLED device provided by the invention has a very good driving life at high temperature compared with the device comparative example 1 in the device structures of the device examples 1-23 in which the material of the invention is matched with the known material.
In order to compare the efficiency attenuation conditions of different devices under high current density, the efficiency attenuation coefficient is defined
Figure BDA0001479060120000364
To carry out the expression；
Figure BDA0001479060120000362
It indicates a drive current of 100mA/cm2Maximum efficiency mu of time device100Maximum efficiency of the devicemaxDifference between the maximum efficiency mu and themaxThe ratio of the amount of the first and the second,
Figure BDA0001479060120000365
the larger the value, the more serious the efficiency roll-off of the device is, and conversely, the problem that the device rapidly decays under high current density is controlled.
The organic compound of the present invention is used in a light-emitting device, and can be used as an electron blocking layer material or a light-emitting layer host material. The efficiency attenuation coefficients of the device examples 1 to 23 and the device comparative example 1 were measured
Figure BDA0001479060120000366
The measurement results are shown in Table 6.
TABLE 6
Figure BDA0001479060120000363
Figure BDA0001479060120000371
As can be seen from the data in table 6, compared with comparative device 1, the OLED device provided by the present invention has a relatively gentle roll-off trend of efficiency at high current density, and provides a good prospect for industrialization.
Further, the efficiency of the OLED device prepared by the material is stable when the OLED device works at low temperature, the efficiency test is carried out on the device examples 4, 16 and 23 and the device comparative example 1 at the temperature of-10-80 ℃, and the obtained results are shown in the table 7 and the figure 2.
TABLE 7
Figure BDA0001479060120000372
As can be seen from the data in table 7 and fig. 2, device examples 4, 16, and 23 are device structures in which the material of the present invention and the known material are combined, and compared with device comparative example 1, the efficiency is high at low temperature, and the efficiency is smoothly increased during the temperature increase process.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.

Claims (7)

1. A spirofluorene derivative organic compound is characterized in that the structure of the organic compound is shown as a general formula (1):
Figure FDA0002922984730000011
in the general formula (1) above,
Figure FDA0002922984730000012
through CL1-CL2Bond or CL2-CL3A bond is linked to spirofluorene;
in the general formula (1) above,
Figure FDA0002922984730000013
expressed as:
Figure FDA0002922984730000014
Figure FDA0002922984730000021
Figure FDA0002922984730000022
any one of them.
2. The spirofluorene derivative organic compound is characterized in that the specific structural formula of the organic compound is as follows:
Figure FDA0002922984730000023
Figure FDA0002922984730000031
Figure FDA0002922984730000041
Figure FDA0002922984730000051
Figure FDA0002922984730000061
Figure FDA0002922984730000071
Figure FDA0002922984730000072
any one of them.
3. Use of an organic compound according to any one of claims 1 to 2 for the preparation of an organic electroluminescent device.
4. An organic electroluminescent element comprising the organic compound according to any one of claims 1 to 2, wherein the organic electroluminescent element comprises at least one functional layer comprising the spirofluorene derivative-based organic compound.
5. An organic electroluminescent device comprising the organic compound according to any one of claims 1 to 2, comprising an electron blocking layer, wherein the electron blocking layer is made of the spirofluorene derivative organic compound.
6. An organic electroluminescent element comprising the organic compound according to any one of claims 1 to 2, comprising a light-emitting layer, wherein the light-emitting layer contains the spirofluorene derivative organic compound.
7. A lighting or display element comprising the organic electroluminescent device as claimed in any one of claims 4 to 6, characterized in that the lighting or display element comprises the organic electroluminescent device.
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