CN109232474B - 1,2, 4-thiadiazole compound and preparation method and application thereof - Google Patents

1,2, 4-thiadiazole compound and preparation method and application thereof Download PDF

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CN109232474B
CN109232474B CN201811130417.4A CN201811130417A CN109232474B CN 109232474 B CN109232474 B CN 109232474B CN 201811130417 A CN201811130417 A CN 201811130417A CN 109232474 B CN109232474 B CN 109232474B
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CN109232474A (en
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穆广园
庄少卿
任春婷
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Wuhan Shangsai Optoelectronics Technology Co ltd
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Abstract

The invention discloses a 1,2, 4-thiadiazole compound and a preparation method and application thereof. The 1,2, 4-thiadiazole compound serving as a light-emitting layer material of the OLED device can remarkably improve the performances of the device in the aspects of luminous intensity, current efficiency, power efficiency, external quantum efficiency, chromaticity and the like, and prolong the service life of the device.

Description

1,2, 4-thiadiazole compound and preparation method and application thereof
Technical Field
The invention relates to the field of photoelectric materials, in particular to a 1,2, 4-thiadiazole compound serving as a light-emitting layer material and a preparation method and application thereof.
Background
OLEDs, i.e., organic light emitting diodes, are also known as organic electroluminescent displays. The OLED has a self-luminous characteristic, adopts a very thin organic material coating layer and a glass substrate, emits light when current passes through the organic material coating layer, has a large viewing angle of an OLED display screen, and can significantly save electric energy, so the OLED is regarded as one of the most promising products in the 21 st century. However, to date, OLED devices have not achieved widespread use, where device efficiency is an important reason that limits their popularity.
External quantum efficiency (eta), an important parameter characterizing the efficiency of OLEDsEQE) Expressed by the following equation (1.1):
ηEQE＝γ·ηr·qeff·ηout (1.1)
wherein gamma represents the carrier balance, etarRepresents the radiative exciton constant, qeffRepresenting the luminescence quantum efficiency, ηoutRepresenting the light coupling-out efficiency, if an excellent functional layer material is adopted, the efficiency is excellentDevices with a balanced charge carrier, the balance gamma of which can be considered as 1, and an exciton constant η of radiationrAt 100% in the material qeffWhen the lift is close to 1, etaoutThe luminous efficiency is limited to a large extent.
The light coupling-out efficiency is a ratio of external modes to all modes, and therefore, the light coupling-out efficiency is improved by minimizing an influence of other modes than the external modes on the device and increasing the ratio of the external modes as much as possible. EtaoutThe phenomenon that light emitted from the organic layer interferes with reflected light is caused by total reflection due to a difference in refractive index between the organic material and the substrate.
At present, the main ways of improving the light coupling-out efficiency are to increase the roughness of a glass substrate, coat microspheres, cover microlenses and implant low-refractive index substances to reduce the optical waveguide effect, and the methods improve the light extraction efficiency and increase the device preparation process.
In an optical device, a dielectric film can be evaporated on the surface of the device to reduce the reflection loss of the surface, the principle is the destructive interference effect of the film, and further, the principle can be explained that in the process of transmitting light waves, the distribution of energy is changed at the interface of two different transmission media due to different boundary conditions. Therefore, the light-out coupling layer material is introduced outside the light-out side metal electrode of the organic electroluminescent device, which basically does not affect the electrical performance of the device, and only changes the transmission and reflection energy distribution of light waves to enhance the light output coupling capability. As the light-out coupling layer material of the microcavity OLED, the characteristics of high refractive index, low light absorption rate in a visible light range, relatively easy evaporation growth mode and the like of the material are mainly considered, the light coupling-out capability is enhanced, the external quantum efficiency of the device is improved, and the loss of light in the device is reduced. However, the light-emitting layer materials of the existing OLEDs still remain to be improved.
Disclosure of Invention
In one aspect of the invention, a compound is provided. According to an embodiment of the invention, the compound has a structure shown in formula (I),
Figure BDA0001813398750000021
wherein the content of the first and second substances,
R1and R2Each independently hydrogen, cyano, nitro, amidino, sulfonyl, optionally substituted sulfinate, optionally substituted C1～20Alkyl, optionally substituted amino, optionally substituted C1～20Heteroalkyl, optionally substituted C1～20Silyl, optionally substituted C6～30Aryl, optionally substituted C3～30Heteroaryl, optionally substituted C6～30Aryloxy, optionally substituted C6～30Arylthio, optionally substituted C6～30Arylamino or optionally substituted C2～30A heterocyclic group;
L1and L2Each independently is optionally substituted C6～30Aryl or optionally substituted C3～30Heteroaryl, d and e are each independently 0 or 1, and d and e are not both 0.
The compound provided by the embodiment of the invention is used as a light-emitting layer material of an OLED device, so that the performances of the device in the aspects of luminous intensity, current efficiency, power efficiency, external quantum efficiency, chromaticity and the like can be obviously improved, and the service life of the device is prolonged.
In some embodiments of the invention, R1And R2At least one of which is
Figure BDA0001813398750000022
Figure BDA0001813398750000023
Wherein Ar is optionally substituted C6～50Aryl, optionally substituted C3～50Heteroaryl, optionally substituted C6～50Aryloxy, optionally substituted C6～50Arylthio, optionally substituted C6～50Arylamino or optionally substituted C2～50A heterocyclic group; a is optionally substituted C1～20Alkyl, optionally substituted amino, optionally substituted C6～50Aryl, optionally substituted C3～50Heteroaryl, optionally substituted C6～50Aryloxy, optionally substituted C6～50Arylthio, optionally substituted C6～50Arylamino or optionally substituted C2～50A heterocyclic group; each X is independently optionally substituted C, N, or each X is independently optionally substituted C, N and two adjacent X are optionally substituted C6～50Aryl, optionally substituted C3～50Heteroaryl, optionally substituted C6～50Aryloxy, optionally substituted C6～50Arylthio, optionally substituted C6～50Arylamine group and optionally substituted C2～50At least one of the heterocyclic groups forms a fused ring; y is1And Y2Each independently is optionally substituted C, N, O or S, f is 0 or 1; a. the1And A2Each independently is optionally substituted C1～20Heteroalkyl, optionally substituted C6～50Aryl, optionally substituted amino, optionally substituted C3～50Heteroaryl, optionally substituted C6～50Aryloxy, optionally substituted C6～50Arylthio, optionally substituted C6～50Arylamino or optionally substituted C2～50A heterocyclic group.
In some embodiments of the invention, R1And R2At least one of which is of the sub-structure:
Figure BDA0001813398750000024
Figure BDA0001813398750000031
wherein R is3、R4、R5、R6、R7And R8Each independently is optionally substituted C1～20Alkyl, optionally substituted amino, optionally substituted C1～50Heteroalkyl, optionally substituted C1～20Silyl, optionally substituted C6～50Aryl, optionally substituted C3～50Heteroaryl, optionally substituted C6～50Aryloxy, optionally substituted C6～50Arylthio, optionally substituted C6～50Arylamino or optionally substituted C2～50Heterocyclyl, X is as previously described, Y1And Y2Each independently is optionally substituted C, N, O or S;
A1and A2At least one of which is
Figure BDA0001813398750000032
Wherein Ar, A and X are as previously described.
In some embodiments of the invention, R1And R2At least one of which is of the sub-structure:
Figure BDA0001813398750000033
Figure BDA0001813398750000041
Figure BDA0001813398750000051
Figure BDA0001813398750000061
Figure BDA0001813398750000071
in some embodiments of the invention, the compound has the structure of one of:
Figure BDA0001813398750000072
Figure BDA0001813398750000081
Figure BDA0001813398750000091
Figure BDA0001813398750000101
Figure BDA0001813398750000111
Figure BDA0001813398750000121
Figure BDA0001813398750000131
Figure BDA0001813398750000141
Figure BDA0001813398750000151
Figure BDA0001813398750000161
Figure BDA0001813398750000171
Figure BDA0001813398750000181
Figure BDA0001813398750000191
Figure BDA0001813398750000201
Figure BDA0001813398750000211
according to the embodiment of the invention, the compound with the structure takes 1,2, 4-thiadiazole with strong electron pulling capacity as a parent nucleus, and a fused ring system is introduced to the 3-position and/or the 5-position of the parent nucleus to form a bipolar compound. The condensed ring system with higher conjugation degree is in key joint with the thiadiazole mother nucleus with the vacant 3d orbit, and the conjugation degree can be extended through S, so that the compactness of the compound in a solid state is greatly improved, the refractive index of the compound is improved, and meanwhile, the non-metal heavy atom S changes the orbital delocalization degree of a donor group, so that the vibration absorption intensity in molecules is improved, the loss of light caused by total reflection of the light in the device is effectively weakened, and the performances of the device in the aspects of current efficiency, power efficiency, external quantum efficiency, chromaticity and the like are improved. In addition, a rigid group, a carbazole group and the like with higher thermal stability are introduced into the 3-position and/or the 5-position of the 1,2, 4-thiadiazole, so that the thermal stability of the whole molecule is further ensured, and the service life of the device is prolonged. In general, a bipolar compound formed by the 1,2, 4-thiadiazole parent-nucleus bonded fused ring system is a compound with high conjugation, high refraction, low reflection and good thermal stability, and is an ideal light extraction layer material.
In some embodiments of the invention, the compound has the structure of one of:
Figure BDA0001813398750000221
Figure BDA0001813398750000231
Figure BDA0001813398750000241
Figure BDA0001813398750000251
Figure BDA0001813398750000261
Figure BDA0001813398750000271
Figure BDA0001813398750000281
Figure BDA0001813398750000291
Figure BDA0001813398750000301
Figure BDA0001813398750000311
Figure BDA0001813398750000321
Figure BDA0001813398750000331
Figure BDA0001813398750000341
Figure BDA0001813398750000351
Figure BDA0001813398750000361
Figure BDA0001813398750000371
Figure BDA0001813398750000381
according to the embodiment of the invention, the compound with the structure takes 1,2, 4-thiadiazole with strong electron-withdrawing capability as a mother nucleus, and is connected with an N site with small electron cloud density of a condensed ring system through a pi bridge at the 3-position and/or the 5-position, so that on one hand, the effective adjustment of molecular dipole moment is realized by a chain structure of D-pi-A or D-pi-A-pi-D, and the thiadiazole mother nucleus with asymmetric electron-withdrawing capability presents directional arrangement orientation among molecules, thereby being beneficial to forming a compact packing structure and improving the integral refractive index of the compound in a packing state; on the other hand, the thiadiazole parent nucleus with larger proton number is further bonded with N-containing groups with different atomic numbers at the 3-position and/or the 5-position, the spin-orbit effect of electrons effectively improves the absorption of molecules to light, reduces the light loss caused by total reflection of light near a cathode, and improves the performances of the device in the aspects of current efficiency, power efficiency, external quantum efficiency, chromaticity and the like from a physical level. In addition, the pi bridge is connected with a relatively active N site in a fused heterocyclic system, so that the length of molecules is effectively extended and the overall thermal stability of the compound is improved on the premise of reducing the process difficulty, thereby effectively avoiding the damage of heat accumulation to the structure of the device, effectively improving the non-radiative coupling degree of the device and prolonging the service life of the device. In general, the 1,2, 4-thiadiazole parent nucleus is bonded with a fused heterocyclic ring system through an N site, and the formed compound is a compound with larger proton number, high refraction, low reflection and good thermal stability, and is an ideal light extraction layer material.
In some embodiments of the invention, the compound has the structure of one of:
Figure BDA0001813398750000382
Figure BDA0001813398750000391
Figure BDA0001813398750000401
Figure BDA0001813398750000411
Figure BDA0001813398750000421
Figure BDA0001813398750000431
Figure BDA0001813398750000441
Figure BDA0001813398750000451
according to the embodiment of the invention, the compound with the structure takes 1,2, 4-thiadiazole with strong electron pulling capacity as a mother nucleus, and arylamine groups with strong electron donating capacity are introduced to the 3-position and/or the 5-position of the compound, so that on one hand, the introduction of arylamine groups with high glass transition temperature improves the overall thermal stability of molecules, and the influence of heat accumulation caused by light conversion into heat on the service life and stability of a device is effectively avoided; on the other hand, branched chain structures of the arylamine are arranged in a crossed manner to form a dense accumulation structure, thiadiazole cores with asymmetric electron pulling capacity are arranged in a directional manner among the branched chain structures with stronger electron donating groups, and the integral refractive index of the compound in a accumulation state is improved, so that the light coupling output efficiency of the device is further improved, and the comprehensive performance of the device in the aspects of current efficiency, power efficiency, external quantum efficiency, chromaticity and the like is improved. In general, the 1,2, 4-thiadiazole mother nucleus is bonded with arylamine groups with branched structures at the 3-position and/or the 5-position, and the formed compound is a compound which is arranged in a cross way and is densely packed and has good thermal stability, and is an ideal light extraction layer material.
It is noted that, in the present context, the term "heteroaryl" refers to a substituent containing a heteroatom in an aromatic ring, such as pyridyl. The terms "aryloxy", "arylthio" and "arylamino" refer to substituents which do not contain heteroatoms in the aromatic ring, but which are substituted on the aromatic ring with substituents containing O, S or N, such as methoxy-substituted phenyl, mercapto-substituted phenyl, amino-substituted phenyl.
In another aspect of the invention, the invention provides a method of making the compounds of the above examples. According to an embodiment of the invention, the method comprises: the compound of formula (a), the compound of formula (b) and the compound of formula (c) are contacted to obtain the compounds of the above examples,
Figure BDA0001813398750000461
wherein Z is1And Z2Each independently Cl or Br, R1And R2、L1、L2D and e are as previously described. Thus, the above examples can be efficiently prepared by this methodA compound is provided.
According to an embodiment of the present invention, the compound of the present invention can be prepared by a Suzuki reaction using a compound represented by formula (a), a compound represented by formula (b), and a compound represented by formula (c). Specifically, the method comprises the following steps:
according to an embodiment of the present invention, the above contacting is performed in a mixed solvent in the presence of a palladium catalyst and a base. The specific kinds of the palladium catalyst and the base, and the mixed solvent for the reaction are not particularly limited, and those skilled in the art can select them according to actual needs. According to a preferred embodiment of the present invention, the palladium catalyst may be at least one of [1, 1' -bis (diphenylphosphino) ferrocene ] dichloropalladium, tetratriphenylphosphine palladium, tris (dibenzylideneacetone) dipalladium, and palladium acetate. The base may be at least one of cesium carbonate, cesium fluoride, potassium carbonate, potassium phosphate, lithium phosphate, sodium carbonate, tetrabutylammonium fluoride, and sodium tert-butoxide. The mixed solvent may include at least one of toluene, xylene, ethanol, N-dimethylformamide, N-dimethylacetamide, and water.
It should be noted that the features and advantages described above for the compounds apply to the method for preparing the compounds at the same time, and are not described in detail here.
The methods of preparing the compounds according to the embodiments of the present invention are further described in detail below:
according to an embodiment of the invention, in the compound of formula (a), Z1And Z2Each independently Cl or Br. According to a preferred embodiment of the invention, Z1And Z2When not simultaneously Cl or Br, the compound of formula (b) or the compound of formula (c) can be reacted with Z in the compound of formula (a) stepwise using the difference in reactivity between Cl and Br1And Z2And (4) carrying out substitution. Specifically, R may be introduced into the compound represented by the formula (a) as follows1-(L1)dAnd R2-(L2)e：
Figure BDA0001813398750000462
According to the examples of the invention, R is under the action of a palladium catalyst and a base1-(L1)dAnd R2-(L2)eThe boric acid compound of (2) can substitute halogen in 1,2, 4-thiadiazole, thereby enabling R to be substituted1-(L1)dAnd R2-(L2)eIs introduced into the structure of 1,2, 4-thiadiazole. According to a specific embodiment of the present invention, in [1, 1' -bis (diphenylphosphino) ferrocene]Palladium dichloride (PdCl)2(dppf)) and cesium carbonate (Cs)2CO3) With the action of (A), the boric acid compound is firstly reacted with Cl and then palladium (Pd (PPh) triphenylphosphine3)4) And potassium carbonate (K)2CO3) Reacting the boric acid compound with Br to complete R in the 1,2, 4-thiadiazole structure1-(L1)dAnd R2-(L2)eThe introduction of (1).
According to an embodiment of the invention, in the reactions of formula (I) and formula (II), the dihalide of 1,2, 4-thiadiazole, R1-(L1)d-B(OH)2And cesium carbonate can be fed according to the molar ratio of 1 (1-1.5) to (1-3), proper toluene is added, and 1-10% of [1, 1' -bis (diphenylphosphino) ferrocene is added in the nitrogen atmosphere]Heating palladium dichloride (calculated according to the amount of the dihalogen substance) to 50-100 ℃ for reaction for 4-48h, monitoring the completion of the reaction by a liquid phase, cooling to room temperature, and processing to obtain R1-(L1)dA monohalide of the corresponding substituted 1,2, 4-thiadiazole; further, adding R1-(L1)dMonohalides of correspondingly substituted 1,2, 4-thiadiazoles with R2-(L2)e-B(OH)2And feeding potassium carbonate according to a molar ratio of 1 (1-1.5) to 2-4, adding a proper amount of toluene, ethanol and water, adding 1-1% of tetrakis (triphenylphosphine) palladium (based on the amount of a halide) in a nitrogen atmosphere, heating to 50-100 ℃ for reaction for 4-48h, monitoring the completion of the reaction in a liquid phase, cooling to room temperature, and processing to obtain a final product.
According to other embodiments of the invention, R1-(L1)dAnd R2-(L2)eThe substituents may be of the same structure, and R may be introduced into the compound represented by the formula (a) as follows1And R2：
Figure BDA0001813398750000471
According to an embodiment of the invention, in the reaction of formula (III), the dihalide of 1,2, 4-thiadiazole, R1-(L1)d-B(OH)2、R2-(L2)e-B(OH)2And feeding potassium carbonate according to a molar ratio of 1 (1-1.5) to 2-4, adding a proper amount of toluene, ethanol and water, adding 1 thousandth-1% of tetrakis (triphenylphosphine) palladium (based on the amount of a dihalogenate substance) in a nitrogen atmosphere, heating to 50-100 ℃ for reaction for 4-48h, monitoring the completion of the reaction in a liquid phase, cooling to room temperature, and processing to obtain a final product.
According to an embodiment of the present invention, R is1-(L1)d-B(OH)2、R2-(L2)e-B(OH)2Can be prepared by the following method (as R)1Is composed of
Figure BDA0001813398750000472
Preparation R1-(L1)d-B(OH)2For example):
Figure BDA0001813398750000473
in the reaction of formula (IV), (L)1)dCorresponding haloboronic acid derivatives, R1Corresponding amines, sodium tert-butoxide (t-BuONa), tri-tert-butylphosphine tetrafluoroborate (t-Bu)3BF4P) is added according to the molar ratio of 1 (1-1.5) to 2-4 (1-10 per thousand), proper amount of toluene is added, and 0.5-10 per thousand of palladium acetate (Pd (OAc) is added under the nitrogen atmosphere2) (according to (L)1)dAmount of substance corresponding to halogenated boronic acid derivative) and the temperature is raised to 60 deg.cReacting at 150 ℃ for 4-48h, monitoring the completion of the reaction by a liquid phase, cooling to room temperature, and treating to obtain R1-(L1)d-B(OH)2。
According to an embodiment of the present invention, R is1-(L1)d-B(OH)2、R2-(L2)e-B(OH)2Can also be prepared by the following method (as R)1Is composed of
Figure BDA0001813398750000481
Preparation R1-(L1)d-B(OH)2For example):
Figure BDA0001813398750000482
in the reaction of the formula (V), A2Corresponding halide, A1Corresponding amide, sodium tert-butoxide (t-BuONa), tri-tert-butylphosphine tetrafluoroborate (t-Bu)3BF4P) is added according to the mol ratio of 1 (1.5-3) to 2-4 (0.5-2 percent), proper amount of toluene is added, and 3 per thousand-1 percent of tris (dibenzylideneacetone) dipalladium (Pd) is added under the nitrogen atmosphere2(dba)3)(A2The amount of the corresponding halide substance), heating to 80-150 ℃, reacting for 4-48h, monitoring the completion of the reaction by a liquid phase, cooling to 35-70 ℃, adding the halide substance and the A in a nitrogen atmosphere2Amount of halide or the like (L)1)dHeating the corresponding halogenated boric acid derivative to 80-150 ℃, continuing to react for 4-48h, and treating to obtain R1-(L1)d-B(OH)2。
In yet another aspect of the present invention, an electronic component is provided. According to an embodiment of the present invention, the electronic component includes: the light-emitting layer is formed on one side surface of the cathode far away from the anode, and is formed by the compound of the embodiment.
According to the electronic element provided by the embodiment of the invention, the light-emitting layer formed by adopting the compound of the embodiment can effectively reduce the loss of light caused by total reflection of light near the cathode, and the performances of the device in the aspects of current efficiency, power efficiency, external quantum efficiency, chromaticity and the like are improved.
Meanwhile, according to the electronic component of the embodiment of the invention, the compound of the embodiment is used as a light-emitting layer material, and is applied to an organic light-emitting component by a material thermal evaporation process which is simple and convenient to operate and has small damage to a device structure, so that the problem of loss of 80% of light of the organic light-emitting component in the device is solved in a physical layer.
According to the embodiment of the invention, the thickness of the light emitting layer in the electronic component is 1-100 nm. This further contributes to the exertion of the aforementioned excellent properties of the 1,2, 4-thiadiazole compound, thereby further improving the device properties.
It should be noted that the features and advantages described above for the compounds and the methods for preparing the compounds apply to the electronic components at the same time, and are not described in detail here.
Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
Drawings
The above and/or additional aspects and advantages of the present invention will become apparent and readily appreciated from the following description of the embodiments, taken in conjunction with the accompanying drawings of which:
FIG. 1 is a graph of wavelength versus luminous intensity characteristics for device No. A9 and a control and blank device;
FIG. 2 is a graph of voltage-current density-luminance characteristics for device No. A9 and a control and blank set of devices;
FIG. 3 is a graph of current density-current efficiency-power efficiency characteristics for device No. A9 and a control and blank set of devices;
FIG. 4 is a graph of luminance versus external quantum efficiency characteristics for device No. A9 and for control and blank devices;
FIG. 5 is a wavelength-index plot of the device No. A9 versus the control;
FIG. 6 is a graph of wavelength versus luminous intensity characteristics for device No. B11 and a control and blank set of devices;
FIG. 7 is a graph of voltage-current density-luminance characteristics for device No. B11 and a control and blank set of devices;
FIG. 8 is a graph of current density-current efficiency-power efficiency characteristics for device No. B11 and a control and blank set of devices;
FIG. 9 is a graph of luminance versus external quantum efficiency characteristics for device No. B11 and for a control and blank set of devices;
FIG. 10 is a wavelength-index plot of the device No. B11 versus the control device;
FIG. 11 is a graph of wavelength versus luminous intensity characteristics for device No. C5 and a control and blank set of devices;
FIG. 12 is a graph of voltage-current density-luminance characteristics for device No. C5 and a control and blank set of devices;
FIG. 13 is a graph of current density-current efficiency-power efficiency characteristics for device No. C5 and a control and blank set of devices;
FIG. 14 is a graph of luminance versus external quantum efficiency characteristics for device number C5 and for control and blank devices;
fig. 15 is a wavelength-index plot of the device No. C5 versus the control.
Detailed Description
The following describes embodiments of the present invention in detail. The following examples are illustrative only and are not to be construed as limiting the invention. The examples, where specific techniques or conditions are not indicated, are to be construed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
Example 1
Figure BDA0001813398750000491
(1) Putting 5-bromo-3-chloro-1, 2, 4-thiadiazole (19.94g, 100mmol), phenanthrene-9-yl boric acid (22.20g, 100mmol) and cesium carbonate (48.87g, 150mmol) into a 500mL three-necked bottle, adding 200mL toluene, adding [1, 1' -bis (diphenylphosphino) ferrocene ] palladium dichloride (1.46g, 2mmol) under nitrogen atmosphere, heating to 50-100 ℃ for reacting for 4-48h, monitoring the reaction completion of a liquid phase, cooling to room temperature, washing with water, filtering, concentrating, and separating by column chromatography to obtain 25.25g of 5-bromo-3- (phenanthrene-9-yl) -1,2, 4-thiadiazole with yield of 74%;
(2) putting 5-bromo-3- (phenanthrene-9-yl) -1,2, 4-thiadiazole (17.06g, 50mmol), 4-tert-butylboronic acid (8.90g, 50mmol) and potassium carbonate (13.82g, 100mmol) into a 500mL three-necked bottle, adding 150mL toluene, 50mL ethanol and 50mL water, adding tetrakis (triphenylphosphine) palladium (0.12g, 0.1mmol) under nitrogen atmosphere, heating to 50-100 ℃, reacting for 4-48h, monitoring the reaction completion by liquid phase, cooling to room temperature, washing with water, filtering, and separating by column chromatography to obtain a final product 17.16g with a yield of 87%.
Mass spectrometer MALDI-TOF-MS (m/z) ═ 394.5352, theoretical molecular weight: 394.5360, respectively; call for C26H22N2(％):C 79.15,H 5.62,N 7.10,Found:C 79.15,H 5.60,N 7.10。
Example 2
Figure BDA0001813398750000501
The objective compound in the above formula was prepared in the same manner as in example 1 (the reactants in each corresponding step were different as compared with example 1, but the molar ratios of the reactants and the reaction conditions were the same), to obtain 17.62g of the final product in a yield of 85%. Mass spectrometer MALDI-TOF-MS (m/z) ═ 414.5266, theoretical molecular weight: 414.5260, respectively; call for C28H18N2(％):C 81.13,H 4.38,N 6.67,Found:C 81.14,H 4.38,N 6.65。
Example 3
Figure BDA0001813398750000502
The objective compound in the above formula was prepared in the same manner as in example 1 (the reactants in each corresponding step may be different as compared with example 1, but the molar ratios of the reactants and the reaction conditions are the same), to obtain 20.52g of the final product in a yield of 81%. Mass spectrometer MALDI-TOF-MS (m/z) ═ 506.6664, theoretical molecular weight: 506.6670, respectively; call for C35H26N2(％):C 82.97,H 5.17,N 5.53,Found:C 82.95,H 5.18,N 5.53。
Example 4
Figure BDA0001813398750000503
The objective compound in the above formula was prepared in the same manner as in example 1 (the reactants in each corresponding step may be different as compared with example 1, but the molar ratios of the reactants and the reaction conditions were the same), to obtain 18.62g of a final product in 89% yield. Mass spectrometer MALDI-TOF-MS (m/z) ═ 418.5577, theoretical molecular weight: 418.5580, respectively; call for C28H22N2(％):C 80.35,H 5.30,N 6.69,Found:C 80.36,H 5.30,N 6.70。
Example 5
Figure BDA0001813398750000504
The objective compound in the above formula was prepared in the same manner as in example 1 (the reactants in each corresponding step may be different as compared with example 1, but the molar ratios of the reactants and the reaction conditions were the same), to obtain 18.20g of the final product in 83% yield. Mass spectrometer MALDI-TOF-MS (m/z) ═ 438.5487, theoretical molecular weight: 438.5480, respectively; call for C30H18N2(％):C 82.16,H 4.14,N 6.39,Found:C 82.16,H 4.15,N 6.40。
Example 6
Figure BDA0001813398750000511
Putting 3-bromo-5-chloro-1, 2, 4-thiadiazole (19.94g, 50mmol), phenanthrene-3-yl boric acid (22.20g, 100mmol) and potassium carbonate (13.82g, 100mmol) into a 500mL three-necked bottle, adding 150mL toluene, 50mL ethanol and 50mL water, adding tetrakis (triphenylphosphine) palladium (0.12g, 0.1mmol) under nitrogen atmosphere, heating to 85 ℃ for reaction for 28h, monitoring the completion of the reaction by liquid phase, cooling to room temperature, washing with water, filtering, and separating by column chromatography to obtain a final product of 18.64g with a yield of 85%. Mass spectrometer MALDI-TOF-MS (m/z) ═ 438.5487, theoretical molecular weight: 438.5480, respectively; call for C30H18N2(％):C 82.16,H 4.14,N 6.39,Found:C 82.15,H 4.14,N 6.41。
Example 7
Figure BDA0001813398750000512
The objective compound in the above formula was prepared in the same manner as in example 1 (the reactants in each corresponding step were different as compared with example 1, but the molar ratios of the reactants and the reaction conditions were the same), to obtain 18.82g of the final product in 83% yield. Mass spectrometer MALDI-TOF-MS (m/z) ═ 453.5624, theoretical molecular weight: 453.5630, respectively; call for C30H19N3(％):C 79.44,H 4.22,N 9.26,Found:C 79.45,H 4.23,N 9.26。
Example 8
Figure BDA0001813398750000513
The title compound was obtained in the same manner as in example 1 (the reactants in each corresponding step were different but the molar ratios of the reactants and the reaction conditions were the same as in example 1) to obtain 18.90g of a final productThe rate was 81%. Mass spectrometer MALDI-TOF-MS (m/z) ═ 466.5625, theoretical molecular weight: 466.5620, respectively; call for C30H18N4(％):C 77.23,H 3.89,N 12.01,Found:C 77.23,H 3.90,N 12.00。
Example 9
Figure BDA0001813398750000521
(1) Putting (9H-carbazole-3-yl) boric acid (25.32g, 150mmol), 5-bromo-2-phenylpyrimidine (28.21g, 120mmol), sodium tert-butoxide (23.04g, 240mmol) and tri-tert-butylphosphine tetrafluoroborate (0.21g, 0.72mmol) into a 500mL three-necked flask, adding 250mL toluene, adding tris (dibenzylideneacetone) dipalladium (0.33g, 0.36mmol) under nitrogen atmosphere, heating to 50-150 ℃ for reaction for 4-48H, monitoring the completion of the reaction by a liquid phase, cooling to room temperature, washing with water, filtering, and separating by column chromatography to obtain (9- (2-phenylpyrimidine-5-yl) -9H-carbazole-3-yl) boric acid 40.31g with the yield of 92%;
(2) putting 5-bromo-3-chloro-1, 2, 4-thiadiazole (19.94g, 100mmol), (9- (2-phenylpyrimidin-5-yl) -9H-carbazol-3-yl) boric acid (36.52g, 100mmol) and cesium carbonate (48.87g, 150mmol) into a 500mL three-necked bottle, adding 200mL toluene, adding [1, 1' -bis (diphenylphosphino) ferrocene ] palladium dichloride (1.46g, 2mmol) under nitrogen atmosphere, heating to 50-100 ℃ for reaction for 4-48H, monitoring the completion of the reaction by a liquid phase, cooling to room temperature, washing with water, filtering, concentrating, separating by column chromatography to obtain 5-bromo-3- (9- (2-phenylpyrimidin-5-yl) -9H-carbazol-4-yl) -1, 34.87g of 2, 4-thiadiazole, and the yield is 72%;
(3) putting 5-bromo-3- (9- (2-phenylpyrimidin-5-yl) -9H-carbazol-4-yl) -1,2, 4-thiadiazole (24.22g and 50mmol), (3- (naphthalene-1-yl) phenyl) boric acid (12.40g and 50mmol) and potassium carbonate (13.82g and 100mmol) into a 500mL three-necked bottle, adding 150mL of toluene, 50mL of ethanol and 50mL of water, adding 0.12g and 0.1mmol of tetrakis (triphenylphosphine) palladium (0.1 mmol) in a nitrogen atmosphere, heating to 50-100 ℃, reacting for 4-48H, monitoring the reaction completion of a liquid phase, cooling to room temperature, washing with water, filtering, and separating by column chromatography to obtain 25.83g of a final product with a yield of 85%.
Mass spectrometer MALDI-TOF-MS (m/z) ═ 607.7348, theoretical molecular weight: 607.7350, respectively; call for C40H25N5(％):C 79.05,H 4.15,N 11.52,Found:C 79.05,H 4.17,N 11.51。
Example 10
Figure BDA0001813398750000522
The objective compound in the above formula was prepared in the same manner as in example 9 (the reactants in each corresponding step may be different as compared with example 9, but the molar ratios of the reactants and the reaction conditions were the same), to obtain 23.91g of the final product in 87% yield. Mass spectrometer MALDI-TOF-MS (m/z) ═ 549.6914, theoretical molecular weight: 549.6920, respectively; call for C36H27N3(％):C 78.66,H 4.95,N 7.64,Found:C 78.66,H 4.93,N 7.65。
Example 11
Figure BDA0001813398750000531
The objective compound in the above formula was prepared in the same manner as in example 9 (the reactants in each corresponding step may be different as compared with example 9, but the molar ratios of the reactants and the reaction conditions are the same), to obtain 20.69g of the final product in a yield of 82%. Mass spectrometer MALDI-TOF-MS (m/z) ═ 504.6114, theoretical molecular weight: 504.6110, respectively; call for C33H20N4(％):C 78.55,H 4.00,N 11.10,Found:C 78.56,H 4.00,N 11.10。
Example 12
Figure BDA0001813398750000532
(1) Putting (9H-carbazole-3-yl) boric acid (25.32g, 120mmol), 3-bromodibenzothiophene (31.58g, 120mmol), sodium tert-butoxide (23.04g, 240mmol) and tri-tert-butylphosphine tetrafluoroborate (0.21g, 0.72mmol) into a 500mL three-necked flask, adding 250mL toluene, adding tris (dibenzylideneacetone) dipalladium (0.33g, 0.36mmol) under nitrogen atmosphere, heating to 115 ℃ for reaction for 16H, monitoring the completion of the reaction by a liquid phase, cooling to room temperature, washing with water, filtering, and separating by column chromatography to obtain 38.70g of (9- (dibenzothiophene-3-yl) -9H-carbazole-3-yl) boric acid with the yield of 82%;
(2) 3-bromo-5-chloro-1, 2, 4-thiadiazole (19.94g, 50mmol), (9- (dibenzothiophene-3-yl) -9H-carbazol-3-yl) boric acid (39.33g, 100mmol) and potassium carbonate (13.82g, 100mmol) are put into a 500mL three-necked bottle, 150mL of toluene, 50mL of ethanol and 50mL of water are added, tetrakis (triphenylphosphine) palladium (0.12g, 0.1mmol) is added under nitrogen atmosphere, the temperature is raised to 85 ℃ for reaction for 28H, the reaction is monitored to be completed by a liquid phase, the solution is cooled to room temperature, washed by water, filtered and separated by column chromatography, and the final product 32.02g with the yield of 82% can be obtained.
Mass spectrometer MALDI-TOF-MS (m/z) ═ 780.9815, theoretical molecular weight: 780.9820, respectively; call for C50H28N4(％):C 76.90,H 3.61,N 7.17,Found:C 76.90,H 3.60,N 7.18。
Example 13
Figure BDA0001813398750000533
The objective compound in the above formula was prepared in the same manner as in example 9 (the reactants in each corresponding step may be different, but the molar ratios of the reactants, the reaction conditions are the same, compared to example 9). 30.54g of the final product was obtained in 82% yield. Mass spectrometer MALDI-TOF-MS (m/z) ═ 744.9156, theoretical molecular weight: 744.9160, respectively; call for C52H32N4(％):C 83.84,H 4.33,N 7.52,Found:C 83.85,H 4.34,N 7.52。
Example 14
Figure BDA0001813398750000541
The objective compound in the above formula (for each corresponding step, compared to example 1) was prepared in the same manner as in example 1The reactants may be different, but the molar ratios of the reactants and the reaction conditions are the same), 19.09g of the final product is obtained, and the yield is 84%. Mass spectrometer MALDI-TOF-MS (m/z) ═ 454.5473, theoretical molecular weight: 454.5470, respectively; call for C30H18N2(％):C 79.27,H 3.99,N 6.16,Found:C 79.26,H 3.40,N 6.16。
Example 15
Figure BDA0001813398750000542
The objective compound in the above formula was prepared in the same manner as in example 1 (the reactants in each corresponding step may be different as compared with example 1, but the molar ratios of the reactants and the reaction conditions were the same), to obtain 23.14g of the final product in 83% yield. Mass spectrometer MALDI-TOF-MS (m/z) ═ 557.6748, theoretical molecular weight: 557.6750, respectively; call for C36H23N5(％):C 77.54,H 4.16,N 12.56,Found:C 77.54,H 4.15,N 12.56。
Example 16
Figure BDA0001813398750000543
The objective compound in the above formula was prepared in the same manner as in example 6 (the reactants in each corresponding step may be different as compared with example 6, but the molar ratios of the reactants and the reaction conditions were the same), to obtain 19.76g of the final product in a yield of 84%. Mass spectrometer MALDI-TOF-MS (m/z) ═ 470.6337, theoretical molecular weight: 470.6340, respectively; call for C32H26N2(％):C 81.67,H 5.57,N 5.95,Found:C 81.66,H 5.58,N 5.95。
Example 17
Figure BDA0001813398750000544
The objective compound in the above formula was prepared in the same manner as in example 1 (the reactant in each corresponding step may be different as compared with example 1)However, the molar ratio of the reactants and the reaction conditions were the same), 23.11g of the final product was obtained in a yield of 81%. Mass spectrometer MALDI-TOF-MS (m/z) ═ 570.7264, theoretical molecular weight: 570.7280, respectively; call for C38H22N2(％):C 79.97,H 3.89,N 4.91,Found:C 79.97,H 3.90,N 4.89。
Example 18
Figure BDA0001813398750000551
(1) Putting 2-bromo-5, 10-dihydrophenazine (23.50g, 90mmol), bromobenzene (28.26g, 180mmol), sodium tert-butoxide (17.28g, 180mmol) and tri-tert-butylphosphine tetrafluoroborate (0.16g, 0.55mmol) into a 500mL three-necked bottle, adding 250mL toluene, adding palladium acetate (0.06g, 0.27mmol) under nitrogen atmosphere, heating to 50-150 ℃ for reaction for 4-48h, monitoring the reaction completion of liquid phase, cooling to room temperature, adding 125mL petroleum ether, filtering, and pulping the solid with mixed solution of hexane and dichloromethane once to obtain 32.36g of 2-bromo-5, 10-diphenyl-5, 10-dihydrophenazine with the yield of 87%;
(2) adding 2-bromo-5, 10-diphenyl-5, 10-dihydrophenazine (28.93g, 70mmol) and 200mL of tetrahydrofuran into a 500mL three-necked bottle, stirring for dissolving, cooling to-78 ℃ under the protection of nitrogen, dropwise adding 15mL of n-butyllithium by using a constant-pressure dropping funnel, after the reaction is finished for 45min, adding trimethyl borate (15.58g, 150mmol), recovering to room temperature after the reaction is carried out for 1h, continuing the reaction for 10h, cooling to 0 ℃, adding 100mL of 1.0M hydrochloric acid aqueous solution for hydrolysis, extracting by using dichloromethane, and concentrating to obtain 21.18g of (5, 10-diphenyl-5, 10-dihydrophenazine-2-yl) boric acid with the yield of 80%;
(3) putting 5-bromo-3-chloro-1, 2, 4-thiadiazole (9.97g, 50mmol), (5, 10-diphenyl-5, 10-dihydrophenazine-2-yl) boric acid (18.91g, 50mmol) and cesium carbonate (24.43g, 75mmol) into a 250mL three-necked bottle, adding 100mL toluene, adding [1, 1' -bis (diphenylphosphino) ferrocene ] palladium dichloride (0.73g, 1mmol) under nitrogen atmosphere, heating to 50-100 ℃ for reaction for 4-48h, monitoring the completion of the reaction by liquid phase, cooling to room temperature, washing with water, filtering, concentrating, and separating by column chromatography to obtain 17.66g of 5-bromo-3- (5, 10-diphenyl-5, 10-dihydrophenazine-2-yl) -1,2, 4-thiadiazole, the yield is 71%;
(4) putting 5-bromo-3- (5, 10-diphenyl-5, 10-dihydrophenazine-2-yl) -1,2, 4-thiadiazole (12.43g, 25mmol), 4-tert-butylbenzoic acid (4.45g, 25mmol) and potassium carbonate (6.91g, 50mmol) into a 250mL three-necked bottle, adding 80mL of toluene, 40mL of ethanol and 40mL of water, adding 0.06g of tetrakis (triphenylphosphine) palladium (0.05 mmol) under nitrogen atmosphere, heating to 50-100 ℃, reacting for 4-48h, monitoring the completion of the reaction by liquid phase, cooling to room temperature, washing with water, filtering, and separating by column chromatography to obtain the final product 11.98g with the yield of 87%.
Mass spectrometer MALDI-TOF-MS (m/z) ═ 550.7247, theoretical molecular weight: 550.7240, respectively; call for C36H30N4(％):C 78.51,H 5.49,N 10.17,Found:C 78.50,H 5.50,N 10.17。
Example 19
Figure BDA0001813398750000552
The objective compound in the above formula was prepared in the same manner as in example 18 (the reactants in each corresponding step were different as compared with example 18, but the molar ratios of the reactants and the reaction conditions were the same), to obtain 12.34g of a final product in 83% yield. Mass spectrometer MALDI-TOF-MS (m/z) ═ 594.7366, theoretical molecular weight: 594.7360, respectively; call for C40H26N4(％):C 80.78,H 4.41,N 9.42,Found:C 80.79,H 4.40,N 9.42。
Example 20
Figure BDA0001813398750000561
The objective compound in the above formula was prepared in the same manner as in example 18 (the reactants in each corresponding step were different as compared with example 18, but the molar ratios of the reactants and the reaction conditions were the same), to obtain 14.42g of the final product in 86% yield. Mass spectrometer MALDI-TOF-MS (m/z) ═ 670.8332, theoretical scoreAnd (2) sub-amount: 670.8340, respectively; call for C46H30N4(％):C 82.36,H 4.51,N 8.35,Found:C 82.36,H 4.50,N 8.35。
Example 21
Figure BDA0001813398750000562
(1) Putting 2-bromo-5, 10-dihydrophenazine (23.50g, 90mmol), bromobenzene (28.26g, 180mmol), sodium tert-butoxide (17.28g, 180mmol) and tri-tert-butylphosphine tetrafluoroborate (0.16g, 0.55mmol) into a 500mL three-necked bottle, adding 250mL toluene, adding palladium acetate (0.06g, 0.27mmol) under nitrogen atmosphere, heating to 115 ℃ for reaction for 10h, monitoring the reaction completion of liquid phase, cooling to room temperature, adding 125mL petroleum ether, filtering, and pulping the solid with a mixed solution of hexane and dichloromethane to obtain 2-bromo-5, 10-diphenyl-5, 10-dihydrophenazine 32.36g with a yield of 87%;
(2) adding 2-bromo-5, 10-diphenyl-5, 10-dihydrophenazine (28.93g, 70mmol) and 200mL of tetrahydrofuran into a 500mL three-necked bottle, stirring for dissolving, cooling to-78 ℃ under the protection of nitrogen, dropwise adding 15mL of n-butyllithium by using a constant-pressure dropping funnel, after the reaction is finished for 45min, adding trimethyl borate (15.58g, 150mmol), recovering to room temperature after the reaction is carried out for 1h, continuing the reaction for 10h, cooling to 0 ℃, adding 100mL of 1.0M hydrochloric acid aqueous solution for hydrolysis, extracting by using dichloromethane, and concentrating to obtain 21.18g of (5, 10-diphenyl-5, 10-dihydrophenazine-2-yl) boric acid with the yield of 80%.
(3) Putting 3-bromo-5-chloro-1, 2, 4-thiadiazole (9.97g, 25mmol), (5, 10-diphenyl-5, 10-dihydrophenazine-2-yl) boric acid (18.91g, 50mmol) and potassium carbonate (6.91g, 50mmol) into a 250mL three-necked bottle, adding 80mL of toluene, 40mL of ethanol and 40mL of water, adding tetrakis (triphenylphosphine) palladium (0.06g, 0.05mmol) under nitrogen atmosphere, heating to 85 ℃, reacting for 28h, monitoring the reaction completion by liquid phase, cooling to room temperature, washing with water, filtering, and separating by column chromatography to obtain 15.95g of a final product with a yield of 85%.
Mass spectrometer MALDI-TOF-MS (m/z) ═ 750.9235, theoretical molecular weight: 750.9240, respectively; ca of anallcd for C50H34N6(％):C 79.97,H 4.56,N 11.19,Found:C 79.99,H 4.55,N 11.20。
Example 22
Figure BDA0001813398750000571
The objective compound in the above formula was prepared in the same manner as in example 21 (the reactants in each corresponding step were different as compared with example 21, but the molar ratios of the reactants and the reaction conditions were the same), to obtain 15.64g of a final product in a yield of 84%. Mass spectrometer MALDI-TOF-MS (m/z) ═ 745.0347, theoretical molecular weight: 745.0340, respectively; call for C46H40N4(％):C 74.16,H 5.41,N 7.52,Found:C 74.15,H 5.39,N 7.52。
Example 23
Figure BDA0001813398750000572
The objective compound in the above formula was prepared in the same manner as in example 18 (the reactants in each corresponding step were different as compared with example 18, but the molar ratios of the reactants and the reaction conditions were the same), to obtain 13.23g of the final product in 83% yield. Mass spectrometer MALDI-TOF-MS (m/z) ═ 637.8193, theoretical molecular weight: 637.8190, respectively; call for C42H27N3(％):C 79.09,H 4.27,N 6.59,Found:C 79.10,H 4.27,N 6.60。
Example 24
Figure BDA0001813398750000573
The objective compound in the above formula was prepared in the same manner as in example 18 (the reactants in each corresponding step were different as compared with example 18, but the molar ratios of the reactants and the reaction conditions were the same), to obtain 12.42g of the final product in 86% yield. Mass spectrometer MALDI-TOF-MS (m/z) ═ 577.7996, theoretical molecular weight: 577.7900, respectively; call for C39H35N3(％):C 81.07,H 6.11,N 7.27,Found:C 81.06,H 6.10,N 7.27。
Example 25
Figure BDA0001813398750000574
The objective compound in the above formula was prepared in the same manner as in example 1 (the reactants in each corresponding step were different as compared with example 1, but the molar ratios of the reactants and the reaction conditions were the same), to obtain 17.82g of the final product in 86% yield. Mass spectrometer MALDI-TOF-MS (m/z) ═ 414.5267, theoretical molecular weight: 414.5260, respectively; call for C28H18N2(％):C 81.13,H 4.38,N 6.76,Found:C 81.12,H 4.40,N 6.76。
Example 26
Figure BDA0001813398750000581
The objective compound in the above formula was prepared in the same manner as in example 6 (the reactants in each corresponding step may be different as compared with example 6, but the molar ratios of the reactants and the reaction conditions were the same), to obtain 19.71g of the final product in a yield of 81%. Mass spectrometer MALDI-TOF-MS (m/z) ═ 486.5917, theoretical molecular weight: 486.5920, respectively; call for C34H18N2(％):C 83.93,H 3.73,N 5.76,Found:C 83.92,H 3.75,N 5.75。
Example 27
Figure BDA0001813398750000582
The objective compound in the above formula was prepared in the same manner as in example 18 (the reactants in each corresponding step were different as compared with example 18, but the molar ratios of the reactants and the reaction conditions were the same), to obtain 9.69g of a final product in 87% yield. Mass spectrometer MALDI-TOF-MS (m/z) ═ 445.5846, theoretical molecular weight: 445.5840, respectively; call for C29H23N3(％):C 78.17,H 5.20,N 9.43,Found:C 78.15,H 5.20,N 9.42。
Example 28
Figure BDA0001813398750000583
The objective compound in the above formula was prepared in the same manner as in example 18 (the reactants in each corresponding step were different as compared with example 18, but the molar ratios of the reactants and the reaction conditions were the same), to obtain 12.46g of the final product in a yield of 82%. Mass spectrometer MALDI-TOF-MS (m/z) ═ 607.8335, theoretical molecular weight: 607.8340, respectively; call for C39H33N3(％):C 77.07,H 5.47,N 6.91,Found:C 77.07,H 5.48,N 6.90。
Example 29
Figure BDA0001813398750000591
The objective compound in the above formula was prepared in the same manner as in example 9 (the reactants in each corresponding step were different as compared with example 9, but the molar ratios of the reactants and the reaction conditions were the same), to obtain 26.13g of the final product in 83% yield. Mass spectrometer MALDI-TOF-MS (m/z) ═ 629.7807, theoretical molecular weight: 629.7810, respectively; call for C44H27N3(％):C 83.92,H 4.32,N 6.67,Found:C 83.92,H 4.30,N 6.68。
Example 30
Figure BDA0001813398750000592
The objective compound in the above formula was prepared in the same manner as in example 18 (the reactants in each corresponding step were different as compared with example 18, but the molar ratios of the reactants and the reaction conditions were the same), to obtain 12.47g of the final product in a yield of 84%. Mass spectrometer MALDI-TOF-MS (m/z) ═ 593.7038, theoretical molecular weight: 593.7040, respectively; call for C40H23N3(％):C 80.92,H 3.90,N 7.08,Found:C 80.90,H 3.90,N 7.09。
Example 31
Figure BDA0001813398750000593
The objective compound in the above formula was prepared in substantially the same manner as in example 1 (the reactants in each corresponding step may be different as compared with example 1, but the molar ratios of the reactants and the reaction conditions were the same), to obtain 16.96g of a final product in a yield of 86%. Mass spectrometer MALDI-TOF-MS (m/z) ═ 394.5095, theoretical molecular weight: 394.5100, respectively; call for C24H14N2(％):C 73.07,H 3.58,N 7.10,Found:C 73.06,H 3.60,N 7.10。
Example 32
Figure BDA0001813398750000594
The objective compound in the above formula was prepared in the same manner as in example 9 (the reactants in each corresponding step may be different as compared with example 9, but the molar ratios of the reactants and the reaction conditions were the same), to obtain 25.36g of the final product in 83% yield. Mass spectrometer MALDI-TOF-MS (m/z) ═ 603.7430, theoretical molecular weight: 603.7430, respectively; call for C42H25N3(％):C 83.56,H 4.17,N 6.96,Found:C 83.55,H 4.19,N 6.96。
Example 33
Figure BDA0001813398750000601
The objective compound in the above formula was prepared in the same manner as in example 21 (the reactants in each corresponding step were different as compared with example 21, but the molar ratios of the reactants and the reaction conditions were the same), to obtain 15.24g of a final product in a yield of 81%. Mass spectrometer MALDI-TOF-MS (m/z) ═ 752.9806, theoretical molecular weight: 752.9800, respectively; call for C52H40N4(％):C 82.95,H 5.35,N 7.44,Found:C 82.94,H 5.35,N 7.45。
Example 34
Figure BDA0001813398750000602
The objective compound in the above formula was prepared in the same manner as in example 12 (the reactants in each corresponding step may be different as compared with example 12, but the molar ratios of the reactants and the reaction conditions were the same), to obtain 28.09g of a final product in 84% yield. Mass spectrometer MALDI-TOF-MS (m/z) ═ 668.8177, theoretical molecular weight: 668.8180, respectively; call for C46H28N4(％):C 82.61,H 4.22,N 8.38,Found:C 82.60,H 4.24,N 8.38。
Example 35
The method comprises the following steps of sequentially ultrasonically cleaning an Indium Tin Oxide (ITO) glass substrate in a cleaning agent and deionized water for 1h, then continuously ultrasonically cleaning the ITO glass substrate by acetone and isopropanol for 15min, carrying out vacuum drying for 2h (105 ℃), then carrying out UV ozone treatment for 15min, and conveying the ITO glass substrate to a vacuum evaporator.
Mixing molybdenum trioxide (MoO)3) Vacuum deposition was performed to a thickness of 10nm on the ITO glass substrate to form a hole injection layer.
N, N '-diphenyl-N, N' - (1-naphthyl) -1,1 '-biphenyl-4, 4' -diamine (NPB) was vacuum deposited on the hole injection layer to a thickness of 60nm to form a hole transport layer.
1, 3-bis (9H-carbazol-9-yl) benzene (mCP) (as a light-emitting layer host material) and 4,4 '-bis (9-ethyl-3-carbazolenyl) -1, 1' -biphenyl (BCzVBi) (as a light-emitting layer guest material) were co-vacuum deposited on the hole transport layer at a weight ratio of 95:5 to a thickness of 20nm to form a light-emitting layer.
1,3, 5-tris (1-phenyl-1H-benzimidazol-2-yl) benzene (TPBi) was vacuum deposited on the light-emitting layer to a thickness of 30nm to form an electron transport layer material.
Lithium fluoride (LiF) was vacuum-deposited on the electron transport layer to a thickness of 1nm to form an electron injection layer.
Aluminum (Al) was vacuum-deposited on the electron injection layer to a thickness of 100nm to form a cathode.
The compounds prepared in the embodiments 2,4, 6, 7 to 12, 14, 15, 17 to 19 and 21 to 34 are respectively adopted to be deposited on the cathode in vacuum to a thickness of 60nm to form a light emitting layer material, so that the preparation of the organic light emitting element is completed. The performance of the prepared light-emitting element is detected, fig. 1 to 4 are respectively a wavelength-luminous intensity characteristic curve graph, a voltage-current density-brightness characteristic curve graph, a current density-current efficiency-power efficiency characteristic curve graph and a brightness-external quantum efficiency characteristic curve graph of the device No. A9, a comparison group and a blank group, and fig. 5 is a wavelength-refractive index curve graph of the device No. A9 and the comparison group. Specific detection data are shown in table 1:
TABLE 1 characterization of organic electroluminescent device Properties
Figure BDA0001813398750000611
Figure BDA0001813398750000621
The detection results show that the light-emitting elements prepared by using the compounds prepared in examples 1 to 34 as the light-emitting layer material have excellent performances in the aspects of current efficiency, power efficiency, external quantum efficiency, chromaticity and the like, and are significantly superior to a control group (device number D, and TPBi is used as the electron transport layer and the light-emitting layer material) and a blank group (device number K). In addition, the asymmetric 1,2, 4-thiadiazole with high thermal stability formed by the introduction of the S atom and the synergistic effect of the rigid group, the carbazole group and the like with high thermal stability further guarantee the thermal stability of the whole molecule and prolong the service life of the device.
Example 36
Figure BDA0001813398750000622
(1) Putting 3-bromo-9H-carbazole (24.61g, 100mmol), naphthalene-2-yl boric acid (17.20g, 100mmol) and potassium carbonate (27.64g, 200mmol) into a 500mL three-necked bottle, adding 250mL of toluene, adding tetrakis (triphenylphosphine) palladium (0.23g, 0.2mmol) in a nitrogen atmosphere, heating to 50-150 ℃ for reacting for 4-48H, monitoring the reaction completion in a liquid phase, cooling to room temperature, washing with water, filtering, and separating by column chromatography to obtain 23.76g of 3- (naphthalene-2-yl) -9H-carbazole with a yield of 81%;
(2) putting 3- (naphthalene-2-yl) -9H-carbazole (17.60g, 60mmol), (4-bromophenyl) boric acid (12.05g, 60mmol), sodium tert-butoxide (11.52g, 120mmol) and tri-tert-butylphosphine tetrafluoroborate (0.07g, 0.24mmol) into a 500mL three-necked flask, adding 200mL toluene, adding palladium acetate (0.03g, 0.12mmol) under nitrogen atmosphere, heating to 50-150 ℃ for reaction for 4-48H, monitoring the reaction completion by liquid phase, cooling to room temperature, washing with water, filtering, and separating by column chromatography to obtain 21.82g ((4- (3- (naphthalene-2-yl) -9H-carbazol-9-yl) phenyl) boric acid with yield of 88%;
(3) putting 3-bromo-5-chloro-1, 2, 4-thiadiazole (5.98g, 30mmol), ((4- (3- (naphthalene-2-yl) -9H-carbazole-9-yl) phenyl) boric acid (12.40g, 30mmol) and cesium carbonate (14.66g, 45mmol) into a 250mL three-necked flask, adding 120mL toluene, adding [1, 1' -bis (diphenylphosphino) ferrocene ] palladium dichloride (0.44g, 6mmol) under nitrogen atmosphere, heating to 90 ℃ for reaction for 24H, monitoring the completion of the reaction by liquid phase, cooling to room temperature, washing with water, filtering, concentrating, and separating by column chromatography to obtain 3-bromo-5- (4- (3- (naphthalene-2-yl) -9H-carbazole-9-yl) phenyl) -1, 12.30g of 2, 4-thiadiazole, and the yield is 77%;
(4) putting 3-bromo-5- (4- (3- (naphthalene-2-yl) -9H-carbazole-9-yl) phenyl) -1,2, 4-thiadiazole (5.32g, 10mmol), naphthalene-2-yl boric acid (1.72g, 10mmol) and potassium carbonate (2.76g, 20mmol) into a 250mL three-necked bottle, adding 50mL of toluene, 25mL of ethanol and 25mL of water, adding 0.02g of tetrakis (triphenylphosphine) palladium (0.02 mmol) under nitrogen atmosphere, heating to 50-100 ℃, reacting for 4-48H, monitoring reaction completion of a liquid phase, cooling to room temperature, washing with water, filtering, and separating by column chromatography to obtain a final product of 4.70g with a yield of 81%.
Mass spectrometer MALDI-TOF-MS (m/z) ═ 579.7204, theoretical molecular weight: 579.7210, respectively; call for C40H25N3(％):C 82.87,H 4.35,N 7.25,Found:C 82.86,H 4.35,N 7.25。
Example 37
Figure BDA0001813398750000631
The objective compound in the above formula was prepared in the same manner as in example 36 (the reactants in each corresponding step were different as compared with example 36, but the molar ratios of the reactants and the reaction conditions were the same), to obtain 6.43g of the final product in 79% yield. Mass spectrometer MALDI-TOF-MS (m/z) ═ 814.0366, theoretical molecular weight: 814.0370, respectively; call for C56H35N3(％):C 82.63,H 4.33,N 5.16,Found:C 82.64,H 4.34,N 5.15。
Example 38
Figure BDA0001813398750000632
The objective compound in the above formula was prepared in the same manner as in example 36 (the reactants in each corresponding step were different as compared with example 36, but the molar ratios of the reactants and the reaction conditions were the same), to obtain 6.04g of the final product in 86% yield. Mass spectrometer MALDI-TOF-MS (m/z) ═ 701.8877, theoretical molecular weight: 701.8880, respectively; call for C48H35N3(％):C 82.14,H 5.03,N 5.99,Found:C 82.14,H 5.02,N 6.00。
Example 39
Figure BDA0001813398750000633
(1) Putting 9, 9-dimethyl-9, 10-dihydroacridine (12.56g, 60mmol), (3-bromophenyl) boric acid (12.05g, 60mmol), sodium tert-butoxide (11.52g, 120mmol) and tri-tert-butylphosphine tetrafluoroborate (0.07g, 0.24mmol) into a 500mL three-necked flask, adding 200mL of toluene, adding palladium acetate (0.03g, 0.12mmol) under nitrogen atmosphere, heating to 50-150 ℃ for reaction for 4-48H, monitoring the reaction completion by liquid phase, cooling to room temperature, adding 50-200 mL of petroleum ether, filtering, and pulping the solid once with a mixed solution of hexane and dichloromethane to obtain 17.38g of (3- (9, 9-dimethylacridin-10 (9H) -yl) phenyl) boric acid with the yield of 88%;
(2) putting 5-bromo-3-chloro-1, 2, 4-thiadiazole (5.98g, 30mmol), (3- (9, 9-dimethylacridin-10 (9H) -yl) phenyl) boric acid (9.88g, 30mmol) and cesium carbonate (14.66g, 45mmol) into a 250mL three-necked flask, adding 120mL toluene, adding [1, 1' -bis (diphenylphosphino) ferrocene ] palladium dichloride (0.44g, 6mmol) under nitrogen atmosphere, heating to 50-100 ℃ for reaction for 4-48H, monitoring the completion of the reaction by liquid phase, cooling to room temperature, washing with water, filtering, concentrating, and separating by column chromatography to obtain 10.36g of 5-bromo-3- (3- (9, 9-dimethylacridin-10 (9H) -yl) phenyl) -1,2, 4-thiadiazole, the yield is 77%;
(3) adding 5-bromo-3- (3- (9, 9-dimethylacridin-10 (9H) -yl) phenyl) -1,2, 4-thiadiazole (4.48g, 10mmol), (3- (naphthalene-1-yl) phenyl) boric acid (2.48g, 10mmol) and potassium carbonate (2.76g, 20mmol) into a 250mL three-necked flask, adding 20-80 mL of toluene, 20-50 mL of ethanol and 20-50 mL of water, adding 0.02g of tetrakis (triphenylphosphine) palladium (0.02 mmol), heating to 50-100 ℃ for reacting for 4-48H under a nitrogen atmosphere, monitoring the reaction completion of a liquid phase, cooling to room temperature, washing with water, filtering, and separating by column chromatography to obtain a final product of 6.04g with a yield of 86%.
Mass spectrometer MALDI-TOF-MS (m/z) ═ 571.7424, theoretical molecular weight: 571.7420, respectively; call for C39H29N3(％):C 81.93,H 5.11,N 7.35,Found:C 81.94,H 5.10,N 7.35。
Example 40
Figure BDA0001813398750000641
The objective compound in the above formula was prepared in the same manner as in example 39 (the reactants in each corresponding step were different as compared with example 39, but the molar ratios of the reactants and the reaction conditions were the same), to obtain 5.93g of the final product in a yield of 82%. Mass spectrometer MALDI-TOF-MS (m/z) ═ 723.8973, theoretical molecular weight: 723.8980, respectively; call for C49H33N5(％):C 81.30,H 4.60,N 9.67,Found:C 81.30,H 4.58,N 9.68。
EXAMPLE 41
Figure BDA0001813398750000642
(1) Putting 9, 9-dimethyl-9, 10-dihydroacridine (12.56g, 60mmol), (3-bromophenyl) boric acid (12.05g, 60mmol), sodium tert-butoxide (11.52g, 120mmol) and tri-tert-butylphosphine tetrafluoroborate (0.07g, 0.24mmol) into a 500mL three-necked flask, adding 200mL toluene, adding palladium acetate (0.03g, 0.12mmol) under nitrogen atmosphere, heating to 50-150 ℃ for reaction for 4-48H, monitoring the reaction completion by liquid phase, cooling to room temperature, adding 100mL petroleum ether, filtering, and pulping the solid with a mixed solution of hexane and dichloromethane to obtain 17.38g of (3- (9, 9-dimethylacridin-10 (9H) -yl) phenyl) boric acid with a yield of 88%;
(2) putting 3-bromo-5-chloro-1, 2, 4-thiadiazole (5.98g, 30mmol), (3- (9, 9-dimethylacridin-10 (9H) -yl) phenyl) boric acid (19.75g, 60mmol) and potassium carbonate (8.28g, 60mmol) into a 500mL three-necked flask, adding 50-200 mL of toluene, 50-100 mL of ethanol and 50-100 mL of water, adding 0.07g, 0.06mmol of tetrakis (triphenylphosphine) palladium under nitrogen atmosphere, heating to 50-100 ℃, reacting for 4-48H, monitoring the reaction completion of a liquid phase, cooling to room temperature, washing with water, filtering, and separating by column chromatography to obtain a final product of 16.65g with a yield of 85%.
Mass spectrometer MALDI-TOF-MS (m/z) ═ 652.8597, theoretical molecular weight: 652.8600, respectively; call for C44H36N4(％):C 80.95,H 5.56,N 8.58，Found:C 80.95,H 5.55,N 8.58。
Example 42
Figure BDA0001813398750000651
The objective product in the above formula was prepared in the same manner as in example 39 (the reactants in each corresponding step may be different, but the reactants are molar compared to example 39)The ratio and the reaction conditions were the same), 4.81g of the final product was obtained in 80% yield. Mass spectrometer MALDI-TOF-MS (m/z) ═ 600.7575, theoretical molecular weight: 600.7580, respectively; call for C38H24N4(％):C 75.97,H 4.03,N 9.33,Found:C 75.98,H 4.03,N 9.34。
Example 43
Figure BDA0001813398750000652
The objective compound in the above formula was prepared in the same manner as in example 39 (the reactants in each corresponding step were different as compared with example 39, but the molar ratios of the reactants and the reaction conditions were the same), to obtain 4.58g of the final product in a yield of 84%. Mass spectrometer MALDI-TOF-MS (m/z) ═ 545.6608, theoretical molecular weight: 545.6600, respectively; call for C36H23N3(％):C 79.24,H 4.25,N 7.70,Found:C 79.24,H 4.27,N 7.70。
Example 44
Figure BDA0001813398750000653
The objective compound in the above formula was prepared in the same manner as in example 39 (the reactants in each corresponding step were different as compared with example 39, but the molar ratios of the reactants and the reaction conditions were the same), to obtain 4.89g of the final product in a yield of 80%. Mass spectrometer MALDI-TOF-MS (m/z) ═ 611.7625, theoretical molecular weight: 611.7630, respectively; call for C41H29N3(％):C 80.50,H 4.78,N 6.87,Found:C 80.48,H 4.78,N 6.88。
Example 45
Figure BDA0001813398750000661
The objective product in the above formula was prepared in the same manner as in example 36 (in comparison with example 36, the reactants in each corresponding step were different, but the molar ratios of the reactants and the reaction conditions were the same),5.74g of the final product was obtained in 86% yield. Mass spectrometer MALDI-TOF-MS (m/z) ═ 667.8883, theoretical molecular weight: 667.8890, respectively; call for C44H33N3(％):C 79.13,H 4.98,N 6.29,Found:C 79.12,H 5.00,N 6.29。
Example 46
Figure BDA0001813398750000662
The objective compound in the above formula was prepared in the same manner as in example 41 (the reactants in each corresponding step were different as compared with example 41, but the molar ratios of the reactants and the reaction conditions were the same), to obtain 5.50g of the final product in a yield of 87%. Mass spectrometer MALDI-TOF-MS (m/z) ═ 632.8177, theoretical molecular weight: 632.8180, respectively; call for C38H24N4(％):C 72.12,H 3.82,N 8.85,Found:C 72.12,H 3.84,N 8.84。
Example 47
Figure BDA0001813398750000663
(1) Adding 10H-phenothiazine (19.93g, 100mmol), dichloromethane (200mL), hydrogen peroxide (20mL) and acetic acid (100mL) into a 500mL reaction bottle, heating to 50-100 ℃, reacting for 4-48H, monitoring by a liquid phase that 10H-phenothiazine is not left, and cooling to stop the reaction. Filtering the reaction solution by using a silica gel funnel, washing the filtrate with water, layering, and concentrating to obtain 20.81g of 10H-dioxyphenothiazine with the yield of 90%;
(2) putting 10H-dioxyphenothiazine (13.88g, 60mmol), (6-bromonaphthalene-2-yl) boric acid (15.05g, 60mmol), sodium tert-butoxide (11.52g, 120mmol) and tri-tert-butylphosphine tetrafluoroborate (0.07g, 0.24mmol) into a 500mL three-necked bottle, adding 50-200 mL toluene, adding palladium acetate (0.03g, 0.12mmol) under nitrogen atmosphere, heating to 50-150 ℃ for reaction for 4-48H, monitoring the reaction completion of a liquid phase, cooling to room temperature, adding 100mL petroleum ether, filtering, and pulping the solid with a mixed solution of hexane and dichloromethane to obtain 18.54g of (6- (10H-dioxyphenothiazin-10-yl) naphthalene-2-yl) boric acid with a yield of 77%;
(3) putting 5-bromo-3-chloro-1, 2, 4-thiadiazole (5.98g, 30mmol), (6- (10H-dioxophenothiazin-10-yl) naphthalen-2-yl) boronic acid (12.04g, 30mmol) and cesium carbonate (14.66g, 45mmol) into a 250mL three-necked flask, adding 120mL toluene, adding [1, 1' -bis (diphenylphosphino) ferrocene ] palladium dichloride (0.44g, 6mmol) under nitrogen atmosphere, heating to 50-100 ℃ for reaction for 4-48H, monitoring the completion of the reaction by liquid phase, cooling to room temperature, washing with water, filtering, concentrating, and separating by column chromatography to obtain 10.93g of 10- (6- (5-bromo-1, 2, 4-thiadiazol-3-yl) naphthalen-2-yl) -10H-dioxophenothiazine, the yield is 70%;
(4) putting 10- (6- (5-bromo-1, 2, 4-thiadiazole-3-yl) naphthalene-2-yl) -10H-dioxyphenothiazine (5.20g, 10mmol), 1' -biphenyl ] -3-yl boric acid (1.98g, 10mmol) and potassium carbonate (2.76g, 20mmol) into a 250mL three-necked bottle, adding 50mL of toluene, 25mL of ethanol and 25mL of water, adding 0.02g of palladium (triphenylphosphine) (0.02 mmol), heating to 50-100 ℃, reacting for 4-48H, monitoring the reaction completion of a liquid phase, cooling to room temperature, washing with water, filtering, and separating by column chromatography to obtain a final product of 4.98g with a yield of 84%.
Mass spectrometer MALDI-TOF-MS (m/z) ═ 593.7187, theoretical molecular weight: 593.7190, respectively; call for C36H23N3(％):C 72.83,H 3.90,N 7.08,Found:C 72.82,H 3.90,N 7.09。
Example 48
Figure BDA0001813398750000671
The objective compound in the above formula was prepared in the same manner as in example 47 (the reactants in each corresponding step were different as compared with example 47, but the molar ratios of the reactants and the reaction conditions were the same), to obtain 5.15g of the final product in a yield of 80%. Mass spectrometer MALDI-TOF-MS (m/z) ═ 643.7787, theoretical molecular weight: 643.7790, respectively; call for C40H25N3(％):C 74.63,H 3.91,N 6.53.Found:C 74.63,H 3.90,N 6.55。
Example 49
Figure BDA0001813398750000672
The objective compound in the above formula was prepared in the same manner as in example 39 (the reactants in each corresponding step were different as compared with example 39, but the molar ratios of the reactants and the reaction conditions were the same), to obtain 4.98g of the final product in a yield of 84%. Mass spectrometer MALDI-TOF-MS (m/z) ═ 594.7353, theoretical molecular weight: 594.7360, respectively; call for C40H26N4(％):C 80.78,H 4.41,N 9.42,Found:C 80.77,H 4.40,N 9.42。
Example 50
Figure BDA0001813398750000681
(1) Adding 5, 10-dihydrophenazine (29.15g, 160mmol), bromobenzene (23.55g, 150mmol), sodium tert-butoxide (28.80g, 300mmol), tri-tert-butylphosphine tetrafluoroborate (0.18g, 0.6mmol) and 250mL of toluene into a 500mL three-necked flask, adding palladium acetate (0.06g, 0.3mmol) under nitrogen atmosphere, heating to 50-150 ℃, reacting for 4-48h, monitoring the completion of the reaction in a liquid phase, cooling to room temperature, washing with water, filtering, concentrating, and separating by column chromatography to obtain 21.70g of 5-phenyl-5, 10-dihydrophenazine with a yield of 56%;
(2) putting 5-phenyl-5, 10-dihydrophenazine (15.50g, 60mmol), (4-bromophenyl) boric acid (12.05g, 60mmol), sodium tert-butoxide (11.52g, 120mmol) and tri-tert-butylphosphine (0.07g, 0.24mmol) into a 500mL three-necked bottle, adding 200mL toluene, adding palladium acetate (0.03g, 0.12mmol) under nitrogen atmosphere, heating to 50-150 ℃ for reaction for 4-48H, monitoring the reaction completion of a liquid phase, cooling to room temperature, adding 100mL petroleum ether, filtering, and pulping the solid with a mixed solution of hexane and dichloromethane to obtain 19.06g of (4- (10-phenazine-5 (10H) -yl) phenyl) boric acid with a yield of 84%;
(3) putting 5-bromo-3-chloro-1, 2, 4-thiadiazole (1.99g, 10mmol), (4- (10-phenazine-5 (10H) -yl) phenyl) boric acid (7.56g, 20mmol) and potassium carbonate (2.76g, 20mmol) into a 250mL three-necked bottle, adding 50mL of toluene, 25mL of ethanol and 25mL of water, adding tetrakis (triphenylphosphine) palladium (0.02g, 0.02mmol) under nitrogen atmosphere, heating to 50-100 ℃, reacting for 4-48H, monitoring the reaction completion by liquid phase, cooling to room temperature, washing with water, filtering, and separating by column chromatography to obtain a final product of 4.98g with a yield of 84%.
Mass spectrometer MALDI-TOF-MS (m/z) ═ 750.9247, theoretical molecular weight: 750.9240, respectively; call for C50H34N6(％):C 79.97,H 4.56,N 11.19,Found:C 79.98,H 4.56,N 11.20。
Example 51
Figure BDA0001813398750000682
The objective compound in the above formula was prepared in the same manner as in example 36 (the reactants in each corresponding step were different as compared with example 36, but the molar ratios of the reactants and the reaction conditions were the same), to obtain 5.29g of the final product in a yield of 80%. Mass spectrometer MALDI-TOF-MS (m/z) ═ 661.8412, theoretical molecular weight: 661.8410, respectively; call for C44H27N3(％):C 79.85,H 4.11,N 6.35,Found:C 79.86,H 4.10,N 6.35。
Example 52
Figure BDA0001813398750000691
The objective compound in the above formula was prepared in the same manner as in example 36 (the reactants in each corresponding step were different as compared with example 36, but the molar ratios of the reactants and the reaction conditions were the same), to obtain 5.44g of the final product in 83% yield. Mass spectrometer MALDI-TOF-MS (m/z) ═ 655.8185, theoretical molecular weight: 655.8190, respectively; call for C46H29N3(％):C 84.25,H 4.46,N 6.41,Found:C 84.25,H 4.45,N 6.40。
Example 53
Figure BDA0001813398750000692
The objective compound in the above formula was prepared in the same manner as in example 39 (the reactants in each corresponding step were different as compared with example 39, but the molar ratios of the reactants and the reaction conditions were the same), to obtain 4.02g of the final product in a yield of 80%. Mass spectrometer MALDI-TOF-MS (m/z) ═ 503.6234, theoretical molecular weight: 503.6230, respectively; call for C34H21N3(％):C 81.09,H 4.20,N 8.34,Found:C 81.08,H 4.20,N 8.35。
Example 54
Figure BDA0001813398750000693
The objective compound in the above formula was prepared in the same manner as in example 36 (the reactants in each corresponding step were different as compared with example 36, but the molar ratios of the reactants and the reaction conditions were the same), to obtain 5.60g of the final product in a yield of 81%. Mass spectrometer MALDI-TOF-MS (m/z) ═ 691.8844, theoretical molecular weight: 691.8850, respectively; call for C44H25N3(％):C 76.38,H 3.64,N 6.07,Found:C 76.38,H 3.66,N 6.06。
Example 55
Figure BDA0001813398750000694
The objective compound in the above formula was prepared in the same manner as in example 39 (the reactants in each corresponding step were different as compared with example 39, but the molar ratios of the reactants and the reaction conditions were the same), to obtain 4.04g of the final product in a yield of 85%. Mass spectrometer MALDI-TOF-MS (m/z) ═ 475.6097, theoretical molecular weight: 475.6100, respectively; call for C30H25N3(％):C 75.76,H 5.30,N 8.84,Found:C 75.76,H 5.32,N 8.82。
Example 56
Figure BDA0001813398750000701
The objective compound in the above formula was prepared in the same manner as in example 36 (the reactants in each corresponding step were different as compared with example 36, but the molar ratios of the reactants and the reaction conditions were the same), to obtain 6.40g of the final product in 80% yield. Mass spectrometer MALDI-TOF-MS (m/z) ═ 799.9927, theoretical molecular weight: 799.9920, respectively; call for C56H37N3(％):C 84.08,H 4.66,N 5.25,Found:C 84.08,H 4.67,N 5.23。
Example 57
Figure BDA0001813398750000702
The objective compound in the above formula was prepared in the same manner as in example 39 (the reactants in each corresponding step were different as compared with example 39, but the molar ratios of the reactants and the reaction conditions were the same), to obtain 4.58g of the final product in a yield of 85%. Mass spectrometer MALDI-TOF-MS (m/z) ═ 545.6600, theoretical molecular weight: 545.6600, respectively; call for C36H23N3(％):C 79.24,H 4.25,N 7.70,Found:C 79.23,H 4.27,N 7.70。
Example 58
Figure BDA0001813398750000703
The objective compound in the above formula was prepared in the same manner as in example 39 (the reactants in each corresponding step were different as compared with example 39, but the molar ratios of the reactants and the reaction conditions were the same), to obtain 4.47g of the final product in a yield of 82%. Mass spectrometer MALDI-TOF-MS (m/z) ═ 545.7046, theoretical molecular weight: 545.7040, respectively; call for C37H27N3(％):C 81.44,H 4.99,N 7.70,Found:C 81.45,H 5.00,N 7.70。
Example 59
Figure BDA0001813398750000704
The objective compound in the above formula was prepared in the same manner as in example 39 (the reactants in each corresponding step were different as compared with example 39, but the molar ratios of the reactants and the reaction conditions were the same), to obtain 5.48g of the final product in a yield of 80%. Mass spectrometer MALDI-TOF-MS (m/z) ═ 685.8893, theoretical molecular weight: 685.8890, respectively; call for C48H35N3(％):C 84.06,H 5.14,N 6.13,Found:C 84.05,H 5.15,N 6.14。
Example 60
Figure BDA0001813398750000711
The objective compound in the above formula was prepared in the same manner as in example 39 (the reactants in each corresponding step were different as compared with example 39, but the molar ratios of the reactants and the reaction conditions were the same), to obtain 4.59g of the final product in a yield of 82%. Mass spectrometer MALDI-TOF-MS (m/z) ═ 559.7047, theoretical molecular weight: 559.7050, respectively; call for C36H21N3(％):C 77.25,H 3.78,N 7.51,Found:C 77.25,H 3.80,N 7.50。
Example 61
Figure BDA0001813398750000712
The objective compound in the above formula was prepared in the same manner as in example 39 (the reactants in each corresponding step were different as compared with example 39, but the molar ratios of the reactants and the reaction conditions were the same), to obtain 4.98g of the final product in a yield of 84%. Mass spectrometer MALDI-TOF-MS (m/z) ═ 646.8122, theoretical molecular weight: 646.8120, respectively; call for C44H30N4(％):C 81.71,H 4.68,N 8.66,Found:C 81.70,H 4.69,N 8.66。
Example 62
Figure BDA0001813398750000713
The objective compound in the above formula was prepared in the same manner as in example 36 (the reactants in each corresponding step were different as compared with example 36, but the molar ratios of the reactants and the reaction conditions were the same), to obtain 5.07g of the final product in 83% yield. Mass spectrometer MALDI-TOF-MS (m/z) ═ 611.7807, theoretical molecular weight: 611.7810, respectively; call for C40H25N3(％):C 78.53,H 4.12,N 6.87,Found:C 78.52,H 4.14,N 6.86。
Example 63
Figure BDA0001813398750000714
The objective compound in the above formula was prepared in the same manner as in example 47 (the reactants in each corresponding step were different as compared with example 47, but the molar ratios of the reactants and the reaction conditions were the same), to obtain 4.74g of the final product in a yield of 85%. Mass spectrometer MALDI-TOF-MS (m/z) ═ 557.6424, theoretical molecular weight: 557.6420, respectively; call for C32H19N3(％):C 68.92,H 3.43,N 7.54,Found:C 68.92,H 3.44,N 7.55。
Example 64
Figure BDA0001813398750000721
The objective compound in the above formula was prepared in the same manner as in example 39 (the reactants in each corresponding step were different as compared with example 39, but the molar ratios of the reactants and the reaction conditions were the same), to obtain 4.67g of the final product in a yield of 82%. Mass spectrometer MALDI-TOF-MS (m/z) ═ 569.7260, theoretical molecular weight: 569.7260, respectively; call for C39H27N3(％):C 82.22,H 4.78,N 7.38,Found:C 82.21,H 4.80,N 7.38。
Example 65
Figure BDA0001813398750000722
The objective compound in the above formula was prepared in the same manner as in example 39 (the reactants in each corresponding step were different as compared with example 39, but the molar ratios of the reactants and the reaction conditions were the same), to obtain 5.63g of the final product in a yield of 84%. Mass spectrometer MALDI-TOF-MS (m/z) ═ 669.8465, theoretical molecular weight: 669.8460, respectively; call for C47H31N3(％):C 84.28,H 4.66,N 6.27,Found:C 84.28,H 4.65,N 6.27。
Example 66
Figure BDA0001813398750000723
(1) Putting 3-bromo-9H-carbazole (39.37g, 160mmol), naphthalene-2-yl boric acid (19.51g, 160mmol) and potassium carbonate (44.44g, 320mmol) into a 500mL three-necked bottle, adding 250mL of toluene, adding tetrakis (triphenylphosphine) palladium (0.37g, 0.32mmol) in a nitrogen atmosphere, heating to 50-150 ℃ for reacting for 4-48H, monitoring the reaction completion in a liquid phase, cooling to room temperature, washing with water, filtering, and separating by column chromatography to obtain 32.70g of 3-phenyl-9H-carbazole with a yield of 84%;
(2) putting 3-phenyl-9H-carbazole (14.60g, 60mmol), (4-bromophenyl) boric acid (12.05g, 60mmol), sodium tert-butoxide (11.52g, 120mmol) and tri-tert-butylphosphine tetrafluoroborate (0.07g, 0.24mmol) into a 500mL three-necked flask, adding 200mL toluene, adding palladium acetate (0.03g, 0.12mmol) under nitrogen atmosphere, heating to 50-150 ℃ for reaction for 4-48H, monitoring the reaction completion of a liquid phase, cooling to room temperature, washing with water, filtering, and separating by column chromatography to obtain 18.96g of (4- (3-phenyl-9H-carbazole-9-yl) phenyl) boric acid with the yield of 87%;
(3) putting 3-bromo-5-chloro-1, 2, 4-thiadiazole (1.99g, 10mmol), (4- (3-phenyl-9H-carbazole-9-yl) phenyl) boric acid (7.26g, 20mmol) and potassium carbonate (2.76g, 20mmol) into a 250mL three-necked bottle, adding 50mL of toluene, 25mL of ethanol and 25mL of water, adding tetrakis (triphenylphosphine) palladium (0.02g, 0.02mmol) under a nitrogen atmosphere, heating to 50-100 ℃, reacting for 4-48H, monitoring the reaction completion by a liquid phase, cooling to room temperature, washing with water, filtering, and separating by column chromatography to obtain a final product 5.84g with a yield of 81%.
Mass spectrometer MALDI-TOF-MS (m/z) ═ 720.8944, theoretical molecular weight: 720.8940, respectively; call for C50H32N4(％):C 83.31,H 4.47,N 7.77,Found:C 83.30,H 4.48，N 7.77。
Example 67
The method comprises the following steps of sequentially ultrasonically cleaning an Indium Tin Oxide (ITO) glass substrate in a cleaning agent and deionized water for 1h, then continuously ultrasonically cleaning the ITO glass substrate by acetone and isopropanol for 15min, carrying out vacuum drying for 2h (105 ℃), then carrying out UV ozone treatment for 15min, and conveying the ITO glass substrate to a vacuum evaporator.
Mixing molybdenum trioxide (MoO)3) Vacuum deposition was performed to a thickness of 10nm on the ITO glass substrate to form a hole injection layer.
N, N '-diphenyl-N, N' - (1-naphthyl) -1,1 '-biphenyl-4, 4' -diamine (NPB) was vacuum deposited on the hole injection layer to a thickness of 60nm to form a hole transport layer.
1, 3-bis (9H-carbazol-9-yl) benzene (mCP) as a host material of a light emitting layer and 4,4 '-bis (9-ethyl-3-carbazolenyl) -1,' -biphenyl (BCzVBi) as a guest material of the light emitting layer were co-vacuum deposited on the hole transport layer at a weight ratio of 95:5 to a thickness of 20nm to form a light emitting layer.
1,3, 5-tris (1-phenyl-1H-benzimidazol-2-yl) benzene (TPBi) was vacuum deposited on the light-emitting layer to a thickness of 30nm to form an electron transport layer material.
Lithium fluoride (LiF) was vacuum-deposited on the electron transport layer to a thickness of 1nm to form an electron injection layer.
Aluminum (Al) was vacuum-deposited on the electron injection layer to a thickness of 100nm to form a cathode.
The compounds prepared in examples 36 to 65 were deposited on the cathode in vacuum to a thickness of 60nm to form a light-emitting layer material, thereby completing the preparation of the organic light-emitting device. The performance of the prepared light-emitting element is detected, fig. 6 to 9 are respectively a wavelength-luminous intensity characteristic curve, a voltage-current density-brightness characteristic curve, a current density-current efficiency-power efficiency characteristic curve and a brightness-external quantum efficiency characteristic curve of the device No. B11, a comparison group and a blank group, and fig. 10 is a wavelength-refractive index curve of the device No. B11 and the comparison group. Specific detection data are shown in table 2:
TABLE 2 characterization of organic electroluminescent device Properties
Figure BDA0001813398750000731
Figure BDA0001813398750000741
The detection results show that the light-emitting element prepared by using the compound prepared in examples 36 to 65 as the light-emitting layer material has excellent performance in the aspects of current efficiency, power efficiency, external quantum efficiency, chromaticity and the like, and is significantly superior to a control group (device number D, and TPBi is used as the electron transport layer and the light-emitting layer material) and a blank group (device number K). In addition, the pi bridge is connected with a relatively active N site in a fused heterocyclic system, so that the length of molecules is effectively extended and the overall thermal stability of the compound is improved on the premise of reducing the process difficulty, thereby effectively avoiding the damage of heat accumulation to the structure of the device, effectively improving the non-radiative coupling degree of the device and prolonging the service life of the device.
Example 68
Figure BDA0001813398750000742
(1) Putting 9.42g of bromobenzene (60 mmol), 11.18g of aniline (120 mmol), 11.53g of sodium tert-butoxide (120 mmol) and 0.15g of tri-tert-butylphosphine tetrafluoroborate (0.6 mmol) into a 500mL three-necked bottle, adding 250mL of toluene, adding 0.29g of tris (dibenzylideneacetone) dipalladium (0.3 mmol) under nitrogen atmosphere, heating to 50-150 ℃ for reaction for 4-48h, monitoring the reaction completion of liquid phase, cooling to 50 ℃, adding 12.05g of (4-bromophenyl) boric acid (60 mmol) under nitrogen atmosphere, heating to 50-150 ℃ for continuous reaction for 4-48h, monitoring the reaction completion of liquid phase, cooling to room temperature, washing with water, filtering, concentrating the filtrate, mixing with filter residue, recrystallizing twice with ethanol in an ice bath to obtain 11.27g of (4-diphenylamine-phenyl) boric acid, wherein the yield is 65%;
(2) putting 3-bromo-5-chloro-1, 2, 4-thiadiazole (5.98g, 30mmol), (4-diphenylaminophenyl) boric acid (8.67g, 30mmol) and cesium carbonate (14.66g, 45mmol) into a 250mL three-necked bottle, adding 120mL toluene, adding [1, 1' -bis (diphenylphosphino) ferrocene ] palladium dichloride (0.44g, 0.6mmol) under nitrogen atmosphere, heating to 50-100 ℃ for reacting for 4-48h, monitoring the reaction completion of a liquid phase, cooling to room temperature, washing with water, filtering, concentrating, and separating by column chromatography to obtain 8.82g of 4- (3-bromo-1, 2, 4-thiadiazole-5-yl) -N, N-diphenylaniline with a yield of 72%;
(3) putting 4- (3-bromo-1, 2, 4-thiadiazol-5-yl) -N, N-diphenylaniline (4.08g, 10mmol), phenylboronic acid (1.22g, 10mmol) and potassium carbonate (2.76g, 20mmol) into a 250mL three-necked bottle, adding 50mL of toluene, 25mL of ethanol and 25mL of water, adding 0.02g of palladium tetrakis (triphenylphosphine) under nitrogen atmosphere, heating to 50-100 ℃, reacting for 4-48h, monitoring the reaction completion by a liquid phase, cooling to room temperature, washing with water, filtering, and separating by column chromatography to obtain a final product of 3.60g, wherein the yield is 89%.
Mass spectrometer MALDI-TOF-MS (m/z) ═ 405.5186, theoretical molecular weight: 405.5190, respectively; call for C26H19N3(％):C 77.01,H 4.72,N 10.36,Found:C 77.00,H 4.72,N 10.35。
Example 69
Figure BDA0001813398750000751
The objective compound in the above formula was prepared in the same manner as in example 68 (the reactants in each corresponding step were different compared to example 68, but the molar ratios of the reactants and the reaction conditions were the same), to obtain 5.00g of the final product in 86% yield. Mass spectrometer MALDI-TOF-MS (m/z) ═ 581.7374, theoretical molecular weight: 581.7370, respectively; call for C40H27N3(％):C 82.59,H 4.68,N 7.22,Found:C 82.60,H 4.66,N 7.22。
Example 70
Figure BDA0001813398750000752
The objective compound in the above formula was prepared in the same manner as in example 68 (the reactants in each corresponding step were different compared to example 68, but the molar ratios of the reactants and the reaction conditions were the same), and 4.74g of the final product was obtained in 86% yield. Mass spectrometer MALDI-TOF-MS (m/z) ═ 551.7067, theoretical molecular weight: 551.7080, respectively; call for C36H29N3(％):C 78.37,H 5.30,N 7.62,Found:C 78.38,H 5.30,N 7.60。
Example 71
Figure BDA0001813398750000761
The objective compound in the above formula was prepared in the same manner as in example 68 (the reactants in each corresponding step were different compared to example 68, but the molar ratios of the reactants and the reaction conditions were the same), to obtain 5.31g of the final product in a yield of 84%. Mass spectrometer MALDI-TOF-MS (m/z) ═ 631.7965, theoretical molecular weight: 631.7970, respectively; call for C44H29N3(％):C 83.65,H 4.63,N 6.65,Found:C 83.65,H 4.62,N 6.65。
Example 72
Figure BDA0001813398750000762
(1) Putting 2-bromodibenzothiophene (15.79g, 60mmol), aniline (11.18g, 120mmol), sodium tert-butoxide (11.53g, 120mmol) and tri-tert-butylphosphine tetrafluoroborate (0.15g, 0.6mmol) into a 500mL three-necked bottle, adding 250mL toluene, adding tris (dibenzylideneacetone) dipalladium (0.29g, 0.3mmol) under nitrogen atmosphere, heating to 50-150 ℃ for reaction for 4-48h, monitoring the reaction completion of liquid phase, cooling to 50 ℃, adding (3-bromophenyl) boric acid (12.05g, 60mmol) under nitrogen atmosphere, heating to 50-150 ℃ for further reaction for 4-48h, monitoring the reaction completion of liquid phase, cooling to room temperature, washing with water, filtering, concentrating the filtrate, mixing with filter residue, recrystallizing twice with ethanol in an ice bath to obtain 15.65g of (3- (dibenzothiophene-2-yl (phenyl) amine) phenyl) boric acid, the yield is 66%;
(2) putting 3-bromo-5-chloro-1, 2, 4-thiadiazole (1.99g, 10mmol), (3- (dibenzothiophene-2-yl (phenyl) amine) phenyl) boric acid (7.91g, 20mmol) and potassium carbonate (2.76g, 20mmol) into a 250mL three-necked bottle, adding 50mL toluene, 25mL ethanol and 25mL water, adding tetrakis (triphenylphosphine) palladium (0.02g, 0.02mmol) under nitrogen atmosphere, heating to 50-100 ℃, reacting for 4-48h, monitoring the reaction completion by liquid phase, cooling to room temperature, washing with water, filtering, and separating by column chromatography to obtain the final product 6.28g with yield of 80%.
Mass spectrometer MALDI-TOF-MS (m/z) ═ 785.0144, theoretical molecular weight: 785.0140, respectively; call for C50H32N4(％):C 76.50,H 4.11,N 7.14,Found:C 76.50,H 4.10,N 7.15。
Example 73
Figure BDA0001813398750000763
The objective compound in the above formula was prepared in the same manner as in example 68 (the reactants in each corresponding step were different compared to example 68, but the molar ratios of the reactants and the reaction conditions were the same), to obtain 5.62g of a final product in a yield of 81%. Mass spectrometer MALDI-TOF-MS (m/z) ═ 693.9535, theoretical molecular weight: 693.9530, respectively; call for C48H43N3(％):C 83.08,H 6.25,N 6.06,Found:C 83.08,H 6.26,N 6.07。
Example 74
Figure BDA0001813398750000771
The objective compound in the above formula was prepared in the same manner as in example 68 (in comparison with example 68, the reactants in each corresponding step were different, but the molar ratios of the reactants and the reaction conditions were the same),5.62g of the final product are obtained in a yield of 81%. Mass spectrometer MALDI-TOF-MS (m/z) ═ 673.8786, theoretical molecular weight: 673.8780, respectively; call for C47H35N3(％):C 83.77,H 5.24,N 6.24,Found:C 83.76,H 5.24,N 6.25。
Example 75
Figure BDA0001813398750000772
The objective compound in the above formula was prepared in the same manner as in example 68 (the reactants in each corresponding step were different compared to example 68, but the molar ratios of the reactants and the reaction conditions were the same), to obtain 5.21g of the final product in 79% yield. Mass spectrometer MALDI-TOF-MS (m/z) ═ 659.8106, theoretical molecular weight: 659.8110, respectively; call for C44H29N5(％):C 80.10,H 4.43,N 10.61,Found:C 80.09,H 4.44,N 10.60。
Example 76
Figure BDA0001813398750000773
The objective compound in the above formula was prepared in the same manner as in example 72 (the reactants in each corresponding step were different as compared with example 72, but the molar ratios of the reactants and the reaction conditions were the same), to obtain 4.58g of a final product in a yield of 80%. Mass spectrometer MALDI-TOF-MS (m/z) ═ 572.7297, theoretical molecular weight: 572.7300, respectively; call for C38H28N4(％):C 79.69,H 4.93,N 9.78,Found:C 79.68,H 4.95,N 9.78。
Example 77
Figure BDA0001813398750000781
(1) Putting 9.42g of bromobenzene (60 mmol), 11.18g of aniline (120 mmol), 11.53g of sodium tert-butoxide (120 mmol) and 0.15g of tri-tert-butylphosphine tetrafluoroborate (0.6 mmol) into a 500mL three-necked bottle, adding 250mL of toluene, adding 0.29g of tris (dibenzylideneacetone) dipalladium (0.3 mmol) under nitrogen atmosphere, heating to 80-150 ℃ for reaction for 4-48h, monitoring the reaction completion of liquid phase, cooling to 50 ℃, adding 12.05g of (4-bromophenyl) boric acid (60 mmol) under nitrogen atmosphere, heating to 80-150 ℃ for continuous reaction for 4-48h, monitoring the reaction completion of liquid phase, cooling to room temperature, washing with water, filtering, concentrating the filtrate, mixing with filter residue, recrystallizing twice with ethanol in an ice bath to obtain 11.27g of (4-diphenylamine-phenyl) boric acid, wherein the yield is 65%;
(2) putting 3-bromo-5-chloro-1, 2, 4-thiadiazole (5.98g, 30mmol), (4-diphenylaminophenyl) boric acid (8.67g, 30mmol) and cesium carbonate (14.66g, 45mmol) into a 250mL three-necked bottle, adding 120mL toluene, adding [1, 1' -bis (diphenylphosphino) ferrocene ] palladium dichloride (0.44g, 0.6mmol) under nitrogen atmosphere, heating to 50-100 ℃ for reacting for 4-48h, monitoring the reaction completion of a liquid phase, cooling to room temperature, washing with water, filtering, concentrating, and separating by column chromatography to obtain 8.82g of 4- (3-bromo-1, 2, 4-thiadiazole-5-yl) -N, N-diphenylaniline with a yield of 72%;
(3) putting 4-bromodibenzothiophene (15.79g, 60mmol), aniline (11.18g, 120mmol), sodium tert-butoxide (11.53g, 120mmol) and tri-tert-butylphosphine tetrafluoroborate (0.15g, 0.6mmol) into a 500mL three-necked bottle, adding 250mL toluene, adding tris (dibenzylideneacetone) dipalladium (0.29g, 0.3mmol) under nitrogen atmosphere, heating to 80-150 ℃ for reaction for 4-48h, monitoring the reaction completion of liquid phase, cooling to 50 ℃, adding (4-bromophenyl) boric acid (12.05g, 60mmol) under nitrogen atmosphere, heating to 80-150 ℃ for further reaction for 4-48h, monitoring the reaction completion of liquid phase, cooling to room temperature, washing with water, filtering, concentrating the filtrate, mixing with filter residue, recrystallizing twice with ethanol in an ice bath to obtain 16.12g of (4- (dibenzothiophene-4-yl (phenyl) amine) phenyl) boric acid, the yield is 68 percent;
(4) putting 4- (3-bromo-1, 2, 4-thiadiazol-5-yl) -N, N-diphenylaniline (4.08g, 10mmol), (4- (dibenzothiophene-4-yl (phenyl) amine) phenyl) boric acid (3.95g, 10mmol) and potassium carbonate (2.76g, 20mmol) into a 250mL three-necked bottle, adding 50mL of toluene, 25mL of ethanol and 25mL of water, adding 0.02g of tetrakis (triphenylphosphine) palladium (0.02 mmol) under nitrogen atmosphere, heating to 50-100 ℃, reacting for 4-48h, monitoring the reaction completion of a liquid phase, cooling to room temperature, washing with water, filtering, and separating by column chromatography to obtain a final product of 5.43g with a yield of 80%.
Mass spectrometer MALDI-TOF-MS (m/z) ═ 678.8725, theoretical molecular weight: 678.8720, respectively; call for C44H30N4(％):C 77.85,H 4.45,N 8.25,Found:C 77.85,H 4.47,N 8.24。
Example 78
Figure BDA0001813398750000782
The objective compound in the above formula was prepared in the same manner as in example 68 (the reactants in each corresponding step were different compared to example 68, but the molar ratios of the reactants and the reaction conditions were the same), to obtain 4.71g of the final product in 83% yield. Mass spectrometer MALDI-TOF-MS (m/z) ═ 567.7687, theoretical molecular weight: 567.7690, respectively; call for C36H29N3(％):C 76.16,H 5.15,N 7.40,Found:C 76.16,H 5.17,N 7.40。
Example 79
Figure BDA0001813398750000791
The objective compound in the above formula was prepared in the same manner as in example 68 (the reactants in each corresponding step were different compared to example 68, but the molar ratios of the reactants and the reaction conditions were the same), to obtain 5.30g of the final product in a yield of 84%. Mass spectrometer MALDI-TOF-MS (m/z) ═ 631.7976, theoretical molecular weight: 631.7970, respectively; call for C44H29N3(％):C 83.65,H 4.63,N 6.65,Found:C 83.64,H 4.65,N 6.65。
Example 80
Figure BDA0001813398750000792
Prepared according to the same method as the example 68The target compound in the formula (in comparison with example 68, reactants in each corresponding step may be different, but the molar ratio of the reactants and the reaction conditions are the same) was obtained in a yield of 80% to obtain 4.76g of the final product. Mass spectrometer MALDI-TOF-MS (m/z) ═ 595.7204, theoretical molecular weight: 595.7200, respectively; call for C40H25N3(％):C 80.65,H 4.23,N 7.05,Found:C 80.66,H 4.22,N 7.05。
Example 81
Figure BDA0001813398750000793
The objective compound in the above formula was prepared in the same manner as in example 68 (the reactants in each corresponding step were different compared to example 68, but the molar ratios of the reactants and the reaction conditions were the same), to obtain 4.88g of the final product in 83% yield. Mass spectrometer MALDI-TOF-MS (m/z) ═ 587.7590, theoretical molecular weight: 587.7590, respectively; call for C38H25N3(％):C 77.65,H 4.29,N 7.15,Found:C 77.65,H 4.30,N 7.16。
Example 82
Figure BDA0001813398750000794
The objective compound in the above formula was prepared in the same manner as in example 68 (the reactants in each corresponding step were different compared to example 68, but the molar ratios of the reactants and the reaction conditions were the same), to obtain 4.93g of the final product in 86% yield. Mass spectrometer MALDI-TOF-MS (m/z) ═ 573.8432, theoretical molecular weight: 573.8430, respectively; call for C38H43N3(％):C 79.54,H 7.55,N 7.32,Found:C 79.55,H 7.55,N 7.30。
Example 83
Figure BDA0001813398750000801
Targeted version of the above formula was prepared in the same manner as in example 68Compound (in comparison with example 68, the reactants of each corresponding step can be different, but the molar ratio of the reactants and the reaction conditions are the same), and 5.02g of the final product is obtained, with a yield of 82%. Mass spectrometer MALDI-TOF-MS (m/z) ═ 611.7815, theoretical molecular weight: 611.7810, respectively; call for C40H25N3(％):C 78.53,H 4.12,N 6.87,Found:C 79.55,H 7.55,N 7.30。
Example 84
Figure BDA0001813398750000802
The objective compound in the above formula was prepared in the same manner as in example 68 (the reactants in each corresponding step were different compared to example 68, but the molar ratios of the reactants and the reaction conditions were the same), to obtain 5.10g of the final product in a yield of 80%. Mass spectrometer MALDI-TOF-MS (m/z) ═ 637.8450, theoretical molecular weight: 637.8450, respectively; call for C44H35N3(％):C 82.85,H 5.53,N 6.59,Found:C 82.86,H 5.53,N 6.60。
Example 85
Figure BDA0001813398750000803
The objective compound in the above formula was prepared in the same manner as in example 72 (the reactants in each corresponding step were different as compared with example 72, but the molar ratios of the reactants and the reaction conditions were the same), to obtain 6.03g of a final product in a yield of 78%. Mass spectrometer MALDI-TOF-MS (m/z) ═ 772.9703, theoretical molecular weight: 772.9700, respectively; call for C54H36N4(％):C 83.91,H 4.69,N 7.25,Found:C 83.90,H 4.69,N 7.25。
Example 86
Figure BDA0001813398750000811
The objective compound in the above formula (comparative to example 72) was prepared in the same manner as in example 72Example 72, the reactants of each corresponding step can be different, but the molar ratio of the reactants and the reaction conditions are the same), the final product 6.96g is obtained, and the yield is 79%. Mass spectrometer MALDI-TOF-MS (m/z) ═ 881.0736, theoretical molecular weight: 881.0740, respectively; call for C58H40N8(％):C 79.07,H 4.58,N 12.72,Found:C 79.06,H 4.59,N 12.71。
Example 87
Figure BDA0001813398750000812
The objective compound in the above formula was prepared in the same manner as in example 77 (the reactants in each corresponding step may be different compared to example 77, but the molar ratios of the reactants and the reaction conditions were the same), to obtain 5.76g of a final product in a yield of 77%. Mass spectrometer MALDI-TOF-MS (m/z) ═ 748.9484, theoretical molecular weight: 748.9480, respectively; call for C52H36N4(％):C 83.39,H 4.85,N 7.48,Found:C 83.40,H 4.85,N 7.47。
Example 88
The method comprises the following steps of sequentially ultrasonically cleaning an Indium Tin Oxide (ITO) glass substrate in a cleaning agent and deionized water for 1h, then continuously ultrasonically cleaning the ITO glass substrate by acetone and isopropanol for 15min, carrying out vacuum drying for 2h (105 ℃), then carrying out UV ozone treatment for 15min, and conveying the ITO glass substrate to a vacuum evaporator.
Mixing molybdenum trioxide (MoO)3) Vacuum deposition was performed to a thickness of 10nm on the ITO glass substrate to form a hole injection layer.
N, N '-diphenyl-N, N' - (1-naphthyl) -1,1 '-biphenyl-4, 4' -diamine (NPB) was vacuum deposited on the hole injection layer to a thickness of 60nm to form a hole transport layer.
1, 3-bis (9H-carbazol-9-yl) benzene (mCP) (as a light-emitting layer host material) and BCzVBi (as a light-emitting layer guest material) were co-vacuum deposited on the hole transport layer at a weight ratio of 95:5 to a thickness of 20nm to form a light-emitting layer.
1,3, 5-tris (1-phenyl-1H-benzimidazol-2-yl) benzene (TPBi) was vacuum deposited on the light-emitting layer to a thickness of 30nm to form an electron transport layer material.
Lithium fluoride (LiF) was vacuum-deposited on the electron transport layer to a thickness of 1nm to form an electron injection layer.
Aluminum (Al) was vacuum-deposited on the electron injection layer to a thickness of 100nm to form a cathode.
The compounds prepared in examples 68 to 87 were deposited on the cathode in vacuum to a thickness of 60nm to form a light-emitting layer material, thereby completing the preparation of the organic light-emitting device. The performance of the prepared light-emitting element is detected, fig. 11 to 14 are respectively a wavelength-luminous intensity characteristic curve, a voltage-current density-brightness characteristic curve, a current density-current efficiency-power efficiency characteristic curve and a brightness-external quantum efficiency characteristic curve of the device No. C5, a comparison group and a blank group, and fig. 15 is a wavelength-refractive index curve of the device No. C5 and the comparison group. Specific detection data are shown in table 3:
TABLE 3 characterization of organic electroluminescent device Properties
Figure BDA0001813398750000821
The detection results show that the light-emitting element prepared by using the compound of example 68-87 as the light-emitting layer material has excellent performance in the aspects of current efficiency, power efficiency, external quantum efficiency, chromaticity and the like, and is significantly superior to a control group (device number D, and TPBi is used as the electron transport layer and the light-emitting layer material at the same time) and a blank group (device number K). Due to the introduction of the arylamine group, the overall thermal stability of the molecule is improved, and the influence of heat accumulation caused by the conversion of light into heat on the service life and stability of the device is effectively avoided. In addition, the compound is integrally arranged in a cross mode to form a dense packing structure, the 1,2, 4-thiadiazole group of the core regulates the arrangement orientation among molecules, and the integral refractive index and extinction coefficient of the compound in a packing state are improved, so that the light coupling output efficiency of the device is further improved, and the comprehensive performance of the device in the aspects of current efficiency, power efficiency, external quantum efficiency, chromaticity and the like is improved.
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.

Claims (6)

1. A compound is characterized in that the compound has a structure shown in a formula (I),
Figure FDA0003101423410000011
wherein the content of the first and second substances,
L1and L2Are each independently C6～30Aryl or C3～30Heteroaryl, d and e are each independently 0 or 1, and d and e are not both 0;
R1and R2At least one of which is of the sub-structure:
Figure FDA0003101423410000012
Figure FDA0003101423410000021
Figure FDA0003101423410000031
2. a process for preparing the compound of claim 1, comprising:
contacting a compound of formula (a), a compound of formula (b), and a compound of formula (c) to obtain a compound of claim 1,
Figure FDA0003101423410000032
wherein Z is1And Z2Each independently Cl or Br, R1And R2As defined in claim 1, L1、L2D and e are as defined in claim 1.
3. The method of claim 2, wherein the contacting is performed in a mixed solvent in the presence of a palladium catalyst and a base.
4. The method of claim 3, wherein the palladium catalyst is at least one of [1, 1' -bis (diphenylphosphino) ferrocene ] dichloropalladium, tetratriphenylphosphine palladium, tris (dibenzylideneacetone) dipalladium, and palladium acetate;
optionally, the base is at least one of cesium carbonate, cesium fluoride, potassium carbonate, potassium phosphate, lithium phosphate, sodium carbonate, tetrabutylammonium fluoride, and sodium tert-butoxide;
optionally, the mixed solvent includes at least one of toluene, xylene, ethanol, N-dimethylformamide, N-dimethylacetamide, and water.
5. An electronic component, comprising: a light emitting layer, a cathode and an anode, wherein the light emitting layer is formed on one side surface of the cathode away from the anode, and the light emitting layer is formed by the compound of claim 1.
6. The electronic component according to claim 5, wherein the light-emitting layer has a thickness of 1 to 100 nm.
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