CN113801109B - Compound containing biscarbazole structure and organic electroluminescent device - Google Patents

Compound containing biscarbazole structure and organic electroluminescent device Download PDF

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CN113801109B
CN113801109B CN202110943249.6A CN202110943249A CN113801109B CN 113801109 B CN113801109 B CN 113801109B CN 202110943249 A CN202110943249 A CN 202110943249A CN 113801109 B CN113801109 B CN 113801109B
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CN113801109A (en
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钱超
许军
朱东林
黄明辉
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Nanjing Topto Materials Co Ltd
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Abstract

The invention discloses a compound containing a biscarbazole structure and an organic electroluminescent device, and relates to the technical field of organic electroluminescence. The 1-position of the dibenzofuran group in the compounds of the invention is via L 1 After the material is connected with the triazole, the chemical stability and the thermal stability of material molecules can be effectively improved, the luminous efficiency can be greatly improved, the service life can be greatly prolonged, and the efficiency and the service life of a device can be improved.
Figure DDA0003215923410000011

Description

Compound containing biscarbazole structure and organic electroluminescent device
Technical Field
The invention relates to the technical field of organic electroluminescence, in particular to a compound containing a biscarbazole structure and an organic electroluminescent device.
Background
Organic Light-emitting Devices (OLEDs) are spontaneous Light-emitting Devices that utilize the following principles: when an electric field is applied, the fluorescent substance emits light by recombination of holes injected from the anode and electrons injected from the cathode. The self-luminous device has the characteristics of low voltage, high brightness, wide viewing angle, quick response, good temperature adaptability and the like, is ultrathin, can be manufactured on a flexible panel and the like, and is widely applied to the fields of mobile phones, tablet computers, televisions, illumination and the like.
The organic plastic layer of the OLED is thinner, lighter, and more flexible than the crystal layer of the LED (light emitting diode) or LCD (liquid crystal display);
the organic plastic layer of the OLED is thinner, lighter, and more flexible than the crystal layer of the LED (light emitting diode) or LCD (liquid crystal display);
the light-emitting layer of the OLED is light, so that the base layer can be made of a material with high flexibility instead of a rigid material, the OLED base layer is made of a plastic material, and the LED and the LCD are made of a glass base layer;
the OLED is a current-type organic light emitting device, and emits light by injection and recombination of carriers, and the intensity of light emission is proportional to the injected current. Under the action of an electric field, holes generated by an anode and electrons generated by a cathode move, are respectively injected into a hole transport layer and an electron transport layer, and migrate to a light emitting layer. When the two meet at the light emitting layer, energy excitons are generated, thereby exciting the light emitting molecules to finally generate visible light.
As a next-generation flat panel display technology, organic light-emitting diodes (OLEDs) have advantages of active light emission, low driving voltage, fast response speed, wide viewing angle, thin and light device, and flexible display, and have recently received wide attention from academia and industry. If the full-color display of the OLED is to be realized, red, green and blue three-primary-color light-emitting materials are indispensable. Among them, a blue light material is particularly important, which can provide not only necessary blue emission light but also green and red light by energy transfer. Moreover, the blue light material is also the key to effectively reduce the energy consumption of the full-color OLED. However, since the energy gap of the blue light material is wide, the energy level matching between the electron orbital level and the carrier injection/transmission material is poor, and the working stability of the material is reduced by the high excited state energy level, so that the development of a high-performance blue light material luminescent device is very difficult. At present, the research on red light and green light materials is mature, the performance of devices of the red light and green light materials reaches the level of practical application, the performance of blue light OLEDs still needs to be further improved, and factors which have large influence on the performance of the blue light OLEDs are more, wherein the doped materials are hot spots of the current research.
Disclosure of Invention
The invention aims to provide a compound containing a biscarbazole structure, which can be used as an organic electroluminescent material on the basis of the prior art.
Another object of the present invention is to provide an organic electroluminescent device containing a compound having a biscarbazole structure.
The technical scheme of the invention is as follows:
a compound containing a biscarbazole structure shown as a structure in a formula (I),
Figure BDA0003215923390000021
wherein the content of the first and second substances,
Ar 1 ～Ar 6 each independently is hydrogen, deuterium or substituted or unsubstituted C 5～20 Aromatic group, wherein the substituent is selected from deuterium, C 1-6 One or more of alkyl or phenyl;
L 1 is a carbon-carbon single bond or substituted or unsubstituted C 5～20 Aromatic group, wherein the substituent is selected from deuterium, C 5～20 Aromatic group or deuterated C 5～20 An aromatic group;
x is O or S.
In a preferred embodiment, ar 1 ～Ar 6 Each independently is hydrogen, deuterium, or the following group, deuterated or non-deuterated: phenyl, biphenyl, terphenyl, anthracenyl, naphthyl, phenanthrenyl, fluorenyl, dibenzofuranyl, dibenzothiophenyl or 9, 9-dimethylfluorenyl.
In a preferred embodiment, L 1 Is a carbon-carbon single bond or substituted or unsubstituted phenyl, and the substituent is selected from deuterium, phenyl, deuterated phenyl, biphenyl, terphenyl, anthracenyl, naphthyl, phenanthrenyl or fluorenyl.
In a more preferred embodiment, ar 1 ～Ar 6 Each independently is hydrogen, phenyl or deuterated phenyl.
In another preferred embodiment, ar 1 Or Ar 2 Each independently is hydrogen, phenyl, pentadeuterated phenyl, or biphenyl.
In another preferred embodiment, ar 3 、Ar 4 、Ar 5 、Ar 6 Each independently is hydrogen, phenyl, pentadeuterated phenyl, or biphenyl.
In a more preferred embodiment, L 1 Is a carbon-carbon single bond orA substituted or unsubstituted phenyl, said substituent being selected from deuterium, phenyl or deuterated phenyl.
In another preferred embodiment, L 1 Is a carbon-carbon single bond, phenyl, tetradeuterated phenyl, phenyl substituted phenyl or phenyl substituted by deuterated phenyl.
In another preferred embodiment, L 1 Is a carbon-carbon single bond, phenyl, 2,4,5, 6-tetradeuterated phenyl, phenyl substituted phenyl or pentadeuterated phenyl substituted phenyl.
In a preferred embodiment, when L 1 When it is a substituted or unsubstituted phenyl group, L 1 The triazole and the dibenzofuran at two ends are arranged in a meta position.
Further, the compound containing a biscarbazole structure in the present invention may be selected from any one of the following compounds:
Figure BDA0003215923390000031
Figure BDA0003215923390000041
Figure BDA0003215923390000051
Figure BDA0003215923390000061
Figure BDA0003215923390000071
Figure BDA0003215923390000081
Figure BDA0003215923390000091
the synthetic route of the compound containing the biscarbazole structure shown in the formula (I) is as follows:
Figure BDA0003215923390000092
wherein each group is as defined above.
An organic electroluminescent element comprising a first electrode, a second electrode, and an organic layer formed between the first electrode and the second electrode, wherein the organic layer contains the compound having a biscarbazole structure.
Further, the organic layer includes a hole injection layer, a first hole transport layer, a second hole transport layer, a light emitting layer, a hole blocking layer, an electron transport layer, and an electron injection layer; wherein at least one of the hole injection layer, the first hole transport layer, the second hole transport layer, the light-emitting layer, the hole blocking layer, the electron transport layer, and the electron injection layer contains the compound containing a biscarbazole structure.
Further, the light-emitting layer contains the above-described compound containing a biscarbazole structure.
Further, the light-emitting layer further contains at least one of the following compounds G1 to G56:
Figure BDA0003215923390000101
Figure BDA0003215923390000111
the invention discloses an electronic display device which comprises the organic electroluminescent device.
The invention discloses an OLED lighting device which comprises the organic electroluminescent device.
Unless otherwise indicated, the following terms used in the claims and specification have the following meanings.
By "carbon-carbon single bond", it is meant that it is "between two C atoms in a C-C group", such as L 1 When it is a carbon-carbon single bond, it represents L 1 The triazole and the dibenzofuran at two ends are directly connected by a single bond (-), and do not contain other substituent groups.
"Hydrogen" means protium (1H), which is the predominant stable isotope of hydrogen.
"deuterium", which is a stable isotope of hydrogen, also known as deuterium, has the elemental symbol D.
An "aromatic group," abbreviated as "aryl," refers to a monocyclic, linked, or fused polycyclic group containing multiple carbon atoms, or also containing one or more ring heteroatoms (e.g., N, O, or S), all or a portion of which have a completely conjugated pi-electron system. The number of carbon ring atoms in the aromatic group may be represented by C5-20, C6-20 or the like, e.g. C 5-20 By aromatic group is meant that the number of carbon ring atoms in the aromatic group can be 5,6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, etc., up to 20. The aromatic group can adopt C according to the number of carbon ring atoms 5-20 Aromatic group, C 6-20 Aromatic group, C 5-16 Aromatic group, C 6-16 Aromatic group, C 5-12 Aromatic group, C 6-12 Aromatic group, C 5-10 Aromatic group, C 6-10 Aromatic group, C 5-9 Aromatic group, C 6-9 Aromatic group, C 5-8 Aromatic group, C 6-8 Aromatic group, C 5-7 Aromatic group, C 6-7 Aromatic group, C 8-16 Aromatic groups, and the like. Non-limiting examples of aromatic groups are pyridyl, phenyl, biphenyl, terphenyl, anthracenyl, naphthyl, phenanthrenyl, fluorenyl, dibenzofuranyl, dibenzothienyl, 9-dimethylfluorenyl, benzimidazolyl, quinolyl, isoquinolyl, and the like.
"substituted or unsubstituted" means that the subsequent groups may or may not have a substituent. As used herein, in "substituted" or "unsubstituted," the term "substituted" means that at least one hydrogen in the group is re-coordinated to a hydrocarbyl group, hydrocarbon derivative group, halogen, cyano (-CN), or other substituent. The term "unsubstituted" means that none of the hydrogens in the group are reconciled with hydrocarbyl, hydrocarbon derivative groups, halogens, cyano (-CN) or other substituents. Examples of the hydrocarbon group or hydrocarbon derivative group may include, but are not limited to, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C2 to C20 alkynyl group, a C6 to C20 aryl group, a C5 to C20 heteroaryl group, a C1 to C20 alkylamino group, a C6 to C20 arylamino group, a C6 to C20 heteroarylamino group, a C6 to C20 arylheteroarylamino group, and the like.
"deuterated phenyl" means that at least one hydrogen atom on the phenyl group is replaced by a deuterium atom, which can be mono-deuterated phenyl, di-deuterated phenyl, tri-deuterated phenyl, tetra-deuterated phenyl, penta-deuterated phenyl. Specific examples thereof include 2-deuterated phenyl, 3-deuterated phenyl, 4-deuterated phenyl, 2,4,5, 6-tetradeuterated phenyl, and 2,3,4,5, 6-pentadeuterated phenyl.
The room temperature of the invention is 25 +/-5 ℃.
By adopting the technical scheme of the invention, the advantages are as follows:
the invention has the beneficial effects that:
the invention designs a compound used as an organic electroluminescent material, which has the following characteristics:
firstly, the material molecule in the application contains two carbazole structures, and the carbazole group has a higher triplet state energy level, so that the compound also has the higher triplet state energy level, and the characteristic effectively avoids the reverse transfer of energy from the doping material to the main material, thereby improving the luminous efficiency of the device.
Secondly, the compound designed by the invention breaks the conjugated effect in the molecular layers of the electron donor and the electron acceptor by increasing the steric hindrance and the torque among the molecules, further increases the triplet state energy level of the material molecules, and is beneficial to improving the luminous efficiency of the device.
Thirdly, we have found that the 1-position of the dibenzofuran group in the compounds of the invention passes through L 1 After bonding with triazole, bonding with other sites and triazoleCompared with the connected compound, the chemical stability and the thermal stability of material molecules can be effectively improved, the luminous efficiency can be greatly improved, the service life of the device can be greatly prolonged, and the efficiency and the service life of the device can be improved.
The organic electroluminescent device prepared by using the compound designed by the invention has better luminous efficiency and service life.
Drawings
Fig. 1 is a schematic structural view of an organic electroluminescent device of the present invention.
In the figure: 1-anode, 2-hole injection layer, 3-first hole transport layer, 4-second hole transport layer, 5-luminescent layer, 6-hole barrier layer, 7-electron transport layer, 8-electron injection layer and 9-cathode.
FIG. 2 is an HPLC chart of Compound 6 prepared in example 1 of the present invention.
FIG. 3 is a DSC chart of Compound 6 prepared in example 1 of the present invention, and from FIG. 3, the Tm of Compound 6 is 344.33 ℃.
Fig. 4 is a TGA spectrum of compound 6 prepared in example 1 of the present invention, and it can be seen from fig. 4 that the thermal weight loss temperature Td value is 464.19 ℃.
FIG. 5 is a graph showing the life of organic electroluminescent devices in application example 1 and comparative example 1 of the present invention; as can be seen from fig. 5, the T97% lifetimes of the organic electroluminescent devices prepared in application example 1 and comparative example 1 of the present invention were 609h and 427h, respectively. Detailed Description
Embodiments of the various aspects are further illustrated and described below. It should be understood that the description herein is not intended to limit the claims to the particular aspects described. On the contrary, it is intended to cover alternatives, modifications, and equivalents as may be included within the spirit and scope of the disclosure as defined by the appended claims.
As used herein, in "substituted" or "unsubstituted," the term "substituted" means that at least one hydrogen in the group is re-coordinated to a hydrocarbyl group, a hydrocarbon derivative group, a halogen group, or a cyano (-CN) group. The term "unsubstituted" means that at least one hydrogen in the group does not re-coordinate with the hydrocarbyl, hydrocarbon derivative group, halogen, or cyano (-CN). Examples of the hydrocarbon group or hydrocarbon derivative group may include, but are not limited to, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C2 to C20 alkynyl group, a C6 to C20 aryl group, a C5 to C20 heteroaryl group, a C1 to C20 alkylamino group, a C6 to C20 arylamino group, a C6 to C20 heteroarylamino group, a C6 to C20 arylheteroarylamino group, and the like.
The examples, in which specific conditions are not specified, were carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are conventional products which are not indicated by manufacturers and are commercially available.
Example 1:
Figure BDA0003215923390000141
the synthesis of compound 6 is as follows:
Figure BDA0003215923390000142
compound 1-a (1.1eq, 9.13g,478.34g/mol,24.67 mmol), compound 1-b (1eq, 10g,445.9g/mol,22.43 mmol) were dissolved in 200mL of toluene under nitrogen protection, palladium acetate (0.25g, 224.51g/mol,1.12 mmol), X-phos (0.26g, 476.72g/mol,1.12 mmol), potassium carbonate (9.3g, 138.21g/mol,67.28 mmol) were added, 100mL of ethanol and 50mL of water were added, the reaction was stirred at 82 ℃ overnight, and the progress of the reaction was monitored by HPLC.
After HPLC monitoring compound 1-b completely reacts, stopping the reaction, cooling the reaction solution to room temperature, adding 60mL of water, stirring for 20min, performing suction filtration to obtain a filter cake, rinsing the filter cake with water and ethanol for 2 times, drying at 80 ℃ for 6 hours in vacuum, adding the dried filter cake into a 250mL three-neck flask, adding 100mL of o-dichlorobenzene, heating to 120 ℃ until the solid is completely dissolved, passing through a silica gel and an active carbon funnel while the solution is hot after the solid is completely dissolved to obtain a filtrate, naturally cooling the filtrate to room temperature, separating out a white solid, performing suction filtration to obtain a filter cake, and performing recrystallization twice on the filter cake to obtain a final target product compound 6 (6.64g, 10.169mol, yield 45.3%), ESI-MS (M/z) (M +): theoretical 653.73, found 653.42, elemental analysis (formula C45H27N 5O): theoretical value C,82.68; h,4.16; n,10.71; o,2.45; found C,82.62; h,4.19; n,10.68; o,2.51.
Example 2:
Figure BDA0003215923390000151
the synthesis of compound 11 is as follows:
Figure BDA0003215923390000152
the preparation was carried out in essentially the same manner as in example 1, giving the final desired product compound 11 in 41.4% yield, ESI-MS (M/z) (M +): theoretical value 729.82, found value 729.31, elemental analysis result (molecular formula C51H31N 5O): theoretical value C,83.93; h,4.28; n,9.60; o,2.19; found C,83.98; h,4.29; n,9.57; o,2.16.
Example 3:
Figure BDA0003215923390000153
the synthesis of compound 12 is as follows:
Figure BDA0003215923390000154
the preparation method is basically the same as that of example 1, and the final target compound 12 is obtained with 47.6% yield, ESI-MS (M/z) (M +): theoretical value 729.82, found value 729.15, elemental analysis result (molecular formula C51H31N 5O): theoretical value C,83.93; h,4.28; n,9.60; o,2.19; found C,83.99; h,4.22; n,9.64; o,2.15.
Example 4:
Figure BDA0003215923390000161
the synthesis of compound 16 is as follows:
Figure BDA0003215923390000162
the preparation method is basically the same as that of example 1, and the final target compound 16 is obtained with the yield of 40.8%, ESI-MS (M/z) (M +): theoretical 653.73, found 653.28, elemental analysis (formula C45H27N 5O): theoretical value C,82.68; h,4.16; n,10.71; o,2.45; found C,82.62; h,4.11; n,10.76; o,2.51.
Example 5:
Figure BDA0003215923390000163
the synthesis of compound 21 is as follows:
Figure BDA0003215923390000164
the preparation method is essentially the same as in example 1, and the final target compound, compound 21, is obtained in 51.2% yield, ESI-MS (M/z) (M +): theoretical 729.82, found 729.45, elemental analysis result (molecular formula C51H31N 5O): theoretical value C,83.93; h,4.28; n,9.60; o,2.19; found C,83.97; h,4.24; n,9.67; o,2.12.
Example 6:
Figure BDA0003215923390000171
the synthesis of compound 24 is as follows:
Figure BDA0003215923390000172
the preparation method is basically the same as that of example 1, and the final target compound 24 is obtained with the yield of 45.7%, ESI-MS (M/z) (M +): theoretical 653.73, found 653.31, elemental analysis (formula C45H27N 5O): theoretical value C,82.68; h,4.16; n,10.71; o,2.45; found 82.62; h,4.19; n,10.77; o,2.42.
Example 7:
Figure BDA0003215923390000173
the synthesis of compound 29 is as follows:
Figure BDA0003215923390000181
the preparation was essentially the same as in example 1, giving the final target compound 29 in 48.3% yield, ESI-MS (M/z) (M +): theoretical value 729.82, found 729.26, elemental analysis result (molecular formula C51H31N 5O): theoretical value C,83.93; h,4.28; n,9.60; o,2.19; found C,83.87; h,4.34; n,9.65; o,2.14.
Example 8:
Figure BDA0003215923390000182
the synthesis of compound 32 is as follows:
Figure BDA0003215923390000183
the preparation was carried out in essentially the same manner as in example 1, giving the final desired compound 32 in 48.1% yield, ESI-MS (M/z) (M +): theoretical 653.73, found 653.26, elemental analysis (formula C45H27N 5O): theoretical value C,82.68; h,4.16; n,10.71; o,2.45; found C,82.62; h,4.22; n,10.65; o,2.51.
Example 9:
Figure BDA0003215923390000191
the synthesis of compound 45 is as follows:
Figure BDA0003215923390000192
the preparation was carried out in essentially the same manner as in example 1, giving the final desired compound 45 in 42.4% yield, ESI-MS (M/z) (M +): theoretical value 729.82, found 729.36, elemental analysis result (molecular formula C51H31N 5O): theoretical value C,83.93; h,4.28; n,9.60; o,2.19; found C,83.85; h,4.20; n,9.68; o,2.27.
Example 10:
Figure BDA0003215923390000193
the synthesis of compound 52 is as follows:
Figure BDA0003215923390000194
the preparation was carried out in essentially the same manner as in example 1, giving the final desired compound 52 in 51.8% yield, ESI-MS (M/z) (M +): theoretical 653.73, found 653.48, elemental analysis (formula C45H27N 5O): theoretical value C,82.68; h,4.16; n,10.71; o,2.45; found C,82.75; h,4.11; n,10.69; o,2.45.
Example 11:
Figure BDA0003215923390000201
the synthesis of compound 54 was as follows:
Figure BDA0003215923390000202
the preparation was essentially the same as in example 1 to give 54, a final target compound in 44.6% yield, ESI-MS (M/z) (M +): theoretical value 729.82, found 729.41, elemental analysis result (molecular formula C51H31N 5O): theoretical value C,83.93; h,4.28; n,9.60; o,2.19; found C,83.90; h,4.23; n,9.63; o,2.24.
Example 12:
Figure BDA0003215923390000203
the synthesis of compound 58 is as follows:
Figure BDA0003215923390000204
the preparation was carried out in essentially the same manner as in example 1, giving the final desired compound 58 in 38.3% yield, ESI-MS (M/z) (M +): theoretical value 729.82, found 729.06, elemental analysis result (molecular formula C51H31N 5O): theoretical value C,83.93; h,4.28; n,9.60; o,2.19; found C,83.84; h,4.27; n,9.64; o,2.25.
Example 13:
Figure BDA0003215923390000211
the synthesis of compound 65 was as follows:
Figure BDA0003215923390000212
the preparation was essentially the same as in example 1, giving 65 as the final target product in 49.5% yield, ESI-MS (M/z) (M +): theoretical 658.76, found 657.98, elemental analysis (molecular formula C45H22D5N 5O): theoretical value C,82.05; h,4.89; n,10.63; o,2.43; found C,82.07; h,4.87; n,10.66; o,2.40.
Example 14:
Figure BDA0003215923390000213
the synthesis of compound 75 was as follows:
Figure BDA0003215923390000221
the preparation was carried out in essentially the same manner as in example 1, giving the final desired compound, compound 75, in 48.8% yield, ESI-MS (M/z) (M +): theoretical 658.76, found 659.42, elemental analysis (molecular formula C45H22D5N 5O): theoretical value C,82.05; h,4.89; n,10.63; o,2.43; found C,82.09; h,4.94; n,10.59; o,2.38.
Example 15:
Figure BDA0003215923390000222
the synthesis of compound 88 is as follows:
Figure BDA0003215923390000223
the preparation method is essentially the same as in example 1, and the final target compound 88 is obtained in 39.6% yield, ESI-MS (M/z) (M +): theoretical 734.86, observed 735.35, elemental analysis (formula C51H26D5N 5O): theoretical value C,83.36; h,4.94; n,9.53; o,2.18; found C,83.30; h,4.99; n,9.51; o,2.20.
Example 16:
Figure BDA0003215923390000231
the synthesis of compound 111 is as follows:
Figure BDA0003215923390000232
the preparation was carried out in essentially the same manner as in example 1, giving the final desired compound 111 in 46.8% yield, ESI-MS (M/z) (M +): theoretical 657.75, found 657.66, elemental analysis result (molecular formula C45H23D4N 5O): theoretical value C,82.17; h,4.75; n,10.65; o,2.43; found C,82.12; h,4.80; n,10.61; o,2.47.
Example 17:
Figure BDA0003215923390000233
the synthesis of compound 117 is as follows:
Figure BDA0003215923390000234
the preparation was carried out in essentially the same manner as in example 1, giving the final desired product, compound 117, in 37.3% yield, ESI-MS (M/z) (M +): theoretical 734.86, found 735.21, elemental analysis (molecular formula C51H26D5N 5O): theoretical value C,83.36; h,4.94; n,9.53; o,2.18; found C,83.31; h,4.99; n,9.56; o,2.14.
Example 18:
Figure BDA0003215923390000241
the synthesis of compound 124 is as follows:
Figure BDA0003215923390000242
the preparation was carried out in essentially the same manner as in example 1, giving the final desired compound 124 in 48.4% yield, ESI-MS (M/z) (M +): theoretical 669.79, found 669.45, elemental analysis result (molecular formula C45H27N 5S): theoretical value C,80.69; h,4.06; n,10.46; s,4.79; found C,80.63; h,4.00; n,10.52; and S,4.85.
Example 19:
Figure BDA0003215923390000243
the synthesis of compound 125 is as follows:
Figure BDA0003215923390000244
the preparation method is essentially the same as in example 1, and the final target compound 125 is obtained in 52.7% yield, ESI-MS (M/z) (M +): theoretical 669.79, found 669.47, elemental analysis result (molecular formula C45H27N 5S): theoretical value C,80.69; h,4.06; n,10.46; s,4.79; found C,80.61; h,4.02; n,10.53; and S,4.84.
Example 20:
Figure BDA0003215923390000251
the synthesis of compound 126 is as follows:
Figure BDA0003215923390000252
the preparation was essentially the same as in example 1, giving the final target compound 126 in 35.1% yield, ESI-MS (M/z) (M +): theoretical value 745.89, observed value 745.61, elemental analysis result (molecular formula C51H31N 5S): theoretical value C,82.12; h,4.19; n,9.39; s,4.30; found C,82.17; h,4.24; n,9.34; and S,4.25.
Example 21:
Figure BDA0003215923390000253
the synthesis of compound 127 is as follows:
Figure BDA0003215923390000261
the preparation was carried out in essentially the same manner as in example 1, giving the final desired compound 127 in 40.4% yield, ESI-MS (M/z) (M +): theoretical 750.92, found 751.43, elemental analysis result (molecular formula C51H26D5N 5S): theoretical value C,81.57; h,4.83; n,9.33; s,4.27; found C,81.53; h,4.87; n,9.38; and S,4.22.
And (3) testing the material properties:
compounds 6, 11, 12, 16, 21, 24, 29, 32, 45, 52, 54, 58, 65, 75, 88, 111, 117, 124, 125, 126, 127 of the present invention were tested for weight loss on heating temperature Td and melting point Tm, with the results shown in table 1 below.
Note: the thermal weight loss temperature Td is a temperature at which the weight loss is 5% in a nitrogen atmosphere, and is measured on a TGAN-1000 thermogravimetric analyzer, the nitrogen flow is 10mL/min during measurement, the melting point Tm is measured by differential scanning calorimetry (DSC, new DSC N-650), and the temperature rise rate is 10 ℃/min.
Table 1:
Figure BDA0003215923390000262
Figure BDA0003215923390000271
from the data, the compound synthesized by the invention has excellent thermal stability, which indicates that the compounds according to the structural general formula of the invention have excellent thermal stability and can meet the use requirements of organic electroluminescent materials.
Testing the performance of the device:
application example 1:
adopting ITO as the anode substrate material of the reflecting layer, and sequentially using water, acetone and N 2 Carrying out surface treatment on the glass substrate by plasma;
depositing 10nm of HT-1 doped with 5% (mass percent) HAT-CN on the ITO anode substrate to form a Hole Injection Layer (HIL);
evaporating HT-1 with the thickness of 100nm above the Hole Injection Layer (HIL) to form a first Hole Transport Layer (HTL);
vacuum evaporating GP above the first Hole Transport Layer (HTL) to form a second hole transport layer (GPL) with the thickness of 30 nm;
carrying out co-evaporation on the compound 6 and the G1 designed by the invention as a green host material according to the mass ratio of 5;
evaporating HB-1 onto the light-emitting layer to obtain a Hole Blocking Layer (HBL) with the thickness of 20 nm;
co-evaporating ET-1 and LiQ on a Hole Blocking Layer (HBL) according to the mass ratio of 5;
mixing magnesium (Mg) and silver (Ag) according to a mass ratio of 9;
thereafter, silver (Ag) was evaporated over the electron injection layer to form a cathode having a thickness of 100nm, DNTPD having a thickness of 50nm was deposited on the above-mentioned cathode sealing layer, and further, the surface of the cathode was sealed with a UV hardening adhesive and a sealing film (seal cap) containing a moisture scavenger to protect the organic electroluminescent device from oxygen or moisture in the atmosphere, thereby preparing an organic electroluminescent device.
Figure BDA0003215923390000281
Application examples 2 to 21
The organic electroluminescent devices of application examples 2 to 24 were produced by using compounds 11, 12, 16, 21, 24, 29, 32, 45, 52, 54, 58, 65, 75, 88, 111, 117, 124, 125, 126 and 127 in examples 2 to 24 of the present invention as green host materials, respectively, and the rest of the materials were the same as in application example 1.
Comparative examples 1 to 2:
the difference from application example 1 is that GH-1 and GH-2 in CN112079824A are respectively used as green light host materials instead of the compound 1, and the rest is the same as application example 1.
The characteristics of the organic electroluminescent element produced in the above application example and the organic electroluminescent element produced in the comparative example were that the current density was 10mA/cm 2 The results of measurements under the conditions of (1) are shown in Table 2.
Table 2:
Figure BDA0003215923390000291
as can be seen from the above Table 2, when the compound of the present invention is applied to an organic electroluminescent device, the luminous efficiency is greatly improved under the same current density, the start voltage of the device is reduced, the power consumption of the device is relatively reduced, and the service life of the device is correspondingly improved.
The organic electroluminescent devices prepared in the comparative examples 1 to 2 and the application examples 1 to 10 were subjected to a light emission life test to obtain data of light emission life T97% (time for which the light emission luminance was reduced to 97% of the initial luminance), and the test apparatus was a TEO light emitting device life test system. The results are shown in Table 3:
table 3:
Figure BDA0003215923390000301
as shown in the above table 3, when the compound of the present invention is applied to an organic electroluminescent device, the service life is greatly prolonged under the same current density, and the compound has a wide application prospect.

Claims (10)

1. A compound containing a bis-carbazole structure shown as a structure in a formula (I),
Figure FDA0003860980150000011
wherein the content of the first and second substances,
Ar 1 is hydrogen, ar 2 Is phenyl, pentadeuterated phenyl or biphenyl; or
Ar 1 Is phenyl, pentadeuterated phenyl or biphenyl, ar 2 Is hydrogen; or
Ar 1 Or Ar 2 Each independently is phenyl, pentadeutrophenyl, or biphenyl;
Ar 3 、Ar 4 、Ar 5 、Ar 6 each independently is hydrogen, phenyl, pentadeuterated phenyl or biphenyl;
l1 is a carbon-carbon single bond or substituted or unsubstituted C 5～20 Aromatic group, wherein the substituent is selected from deuterium and C 5～20 Aromatic group or deuterated C 5～20 An aromatic group;
x is O or S.
2. The compound of claim 1,
L 1 is a carbon-carbon single bond or substituted or unsubstituted phenyl, and the substituent is selected from deuterium, phenyl, deuterated phenyl, biphenyl, terphenyl, anthryl, naphthyl, phenanthryl or fluorenyl.
3. The compound of claim 1,
L 1 is a carbon-carbon single bond or substituted or unsubstituted phenyl, and the substituent is selected from deuterium, phenyl or deuterated phenyl.
4. An organic compound according to claim 1, which is any one of the following compounds:
Figure FDA0003860980150000012
Figure FDA0003860980150000021
Figure FDA0003860980150000031
Figure FDA0003860980150000041
Figure FDA0003860980150000051
Figure FDA0003860980150000061
Figure FDA0003860980150000071
5. an organic electroluminescent device comprising a first electrode, a second electrode, and an organic layer formed between the first electrode and the second electrode, wherein the organic layer contains the compound according to any one of claims 1 to 3.
6. The organic electroluminescent device according to claim 5, wherein the organic layer comprises a hole injection layer, a first hole transport layer, a second hole transport layer, a light emitting layer, a hole blocking layer, an electron transport layer, an electron injection layer; at least one of the hole injection layer, the first hole transport layer, the second hole transport layer, the light-emitting layer, the hole blocking layer, the electron transport layer, and the electron injection layer contains the compound according to any one of claims 1 to 3.
7. The organic electroluminescent element as claimed in claim 6, wherein the compound as claimed in any one of claims 1 to 3 is contained in the light-emitting layer.
8. The organic electroluminescent device according to claim 7, wherein the light-emitting layer further contains at least one of the following compounds G1 to G56:
Figure FDA0003860980150000072
Figure FDA0003860980150000081
Figure FDA0003860980150000091
9. an electronic display device comprising the organic electroluminescent element according to claim 5.
10. An OLED lighting device comprising the organic electroluminescent device as claimed in claim 5.
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