CN110128372B - Benzothiadiazole derivative, application thereof and organic electroluminescent device - Google Patents
Benzothiadiazole derivative, application thereof and organic electroluminescent device Download PDFInfo
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- CN110128372B CN110128372B CN201810108438.XA CN201810108438A CN110128372B CN 110128372 B CN110128372 B CN 110128372B CN 201810108438 A CN201810108438 A CN 201810108438A CN 110128372 B CN110128372 B CN 110128372B
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Abstract
The invention relates to a benzothiadiazole derivative, application thereof and an organic electroluminescent device, wherein the compound has a structure shown in the following general formula (1):
wherein R is 1 、R 2 、R 3 And R is 4 Each independently selected from hydrogen atoms, C 1 ～C 12 Aliphatic alkyl, C 3 ～C 12 Cycloalkyl, halogen, cyano, substituted or unsubstituted C 6 ～C 30 Aryl and substituted or unsubstituted C 2 ～C 30 At least one of heteroaryl, and R 1 、R 2 、R 3 And R is 4 At least one of them is selected from the group represented by the following general formula (2) or (3):
Description
Technical Field
The present disclosure relates to the field of organic electroluminescent materials, and in particular, to a benzothiadiazole derivative, an application thereof, and an organic electroluminescent device.
Background
The organic electroluminescent display (OLED) has the advantages of self-luminescence, low voltage DC drive, full solidification, wide viewing angle, light weight, simple composition and process, and the like, compared with the liquid crystal display, the organic electroluminescent display does not need a backlight source, has large viewing angle and low power, has response speed which can be 1000 times that of the liquid crystal display, and has lower manufacturing cost than that of the liquid crystal display with the same resolution, so the organic electroluminescent device has wide application prospect.
With the continuous advancement of OLED technology in illumination and display fields, people pay more attention to research on efficient organic materials affecting the performance of OLED devices, and an organic electroluminescent device with good efficiency and long service life is usually the result of optimized collocation of device structures and various organic materials. In the most common OLED device structures, the following classes of organic materials are typically included: a hole injection material, a hole transport material, an electron transport material, a light emitting material (dye or doped guest material) of each color, a corresponding host material, and the like.
The electron transport material conventionally used in electroluminescent devices is Alq3, but Alq3 has relatively low electron mobility (about 10 -6 cm 2 /Vs). In order to improve the electron transport performance of the electroluminescent device, researchers have made a great deal of research work.
An ideal electron transport material should have the following characteristics: has reversible electrochemical reduction reaction, proper HOMO and LUMO energy levels, high electron mobility, good film forming property, high Tg and better hole blocking performance. The performance of the currently known electron transport materials is not ideal, and there is still an urgent need in the industry to develop new electron transport materials.
Disclosure of Invention
The purpose of the disclosure is to provide a benzothiadiazole derivative, application thereof and an organic electroluminescent device, wherein the benzothiadiazole derivative can reduce the working voltage of the device when being applied to the organic electroluminescent device, and improve the luminous efficiency and the service life of the device.
In order to achieve the above object, a first aspect of the present disclosure provides a benzothiadiazole derivative, which has a structure represented by the following general formula (1):
wherein R is 1 、R 2 、R 3 And R is 4 Each independently selected from hydrogen atoms, C 1 ～C 12 Aliphatic alkyl, C 3 ～C 12 Cycloalkyl, halogen, cyano, substituted or unsubstituted C 6 ～C 30 Aryl and substituted or unsubstituted C 2 ～C 30 At least one of heteroaryl, and R 1 、R 2 、R 3 And R is 4 At least one of them is selected from the group represented by the following general formula (2) or (3):
wherein, represents the site of attachment;
R 5 、R 6 and R is 7 Each independently selected from hydrogen atoms, C 1 ～C 12 Aliphatic alkyl, C 3 ～C 12 Cycloalkyl, halogen, cyano, substituted or unsubstituted C 6 ～C 30 Aryl and substituted or unsubstituted C 2 ～C 30 At least one of heteroaryl;
L 1 and L 2 Each independently selected from the group consisting of a bond, a substituted or unsubstituted C 6 ～C 30 Arylene and substituted or unsubstituted C 2 ～C 30 At least one of heteroarylene;
Ar 1 、Ar 2 and Ar is a group 3 Each independently selected from substituted or unsubstituted C 6 ～C 30 Aryl or substituted or unsubstituted C 2 ～C 30 Heteroaryl groups.
A second aspect of the present disclosure provides an application of the benzothiadiazole derivative in preparing an organic electroluminescent device.
A third aspect of the present disclosure provides an organic electroluminescent device, including a substrate, an anode layer, a cathode layer, and at least one organic functional layer interposed between the anode layer and the cathode layer, where the organic functional layer includes a hole injection layer, a hole transport layer, an organic light emitting layer, an electron transport layer, and an electron injection layer, and an electron transport layer material of the electron transport layer contains the benzothiadiazole derivative of the first aspect of the present disclosure.
Through the technical scheme, the parent structure of the benzothiadiazole derivative has good coplanarity, so that the compounds are ensured to have higher carrier transmission property, the working voltage of an organic electroluminescent device using the compounds can be obviously reduced, meanwhile, the high mobility of the compounds also enables the thickness control of the material to have wider adjustment range, and the increase of the film thickness of the material can not obviously influence the working voltage of the device; the compound disclosed by the invention is most suitable for being used as an electron transport material in an organic electroluminescent device, and can be better matched with the LUMO energy level of a main body material of a luminescent layer, so that the working voltage of the device can be effectively reduced, the luminescent efficiency of the device can be improved, the service life of the device can be prolonged, and the compound has very important practical significance in the manufacture of the organic electroluminescent device.
Additional features and advantages of the present disclosure will be set forth in the detailed description which follows.
Detailed Description
The following describes specific embodiments of the present disclosure in detail. It should be understood that the detailed description and specific examples, while indicating and illustrating the disclosure, are not intended to limit the disclosure.
The first aspect of the present disclosure provides a benzothiadiazole derivative, which has a structure represented by the following general formula (1):
wherein R is 1 、R 2 、R 3 And R is 4 Each independently selected from hydrogen atoms, C 1 ～C 12 Aliphatic alkyl, C 3 ～C 12 Cycloalkyl, halogen, cyano, substituted or unsubstituted C 6 ～C 30 Aryl and substituted or unsubstituted C 2 ～C 30 At least in heteroaryl groupsAnd R is 1 ～R 4 At least one of them is selected from the group represented by the following general formula (2) or (3): />
Wherein, represents the site of attachment; r is R 5 、R 6 And R is 7 Each independently selected from hydrogen atoms, C 1 ～C 12 Aliphatic alkyl, C 3 ～C 12 Cycloalkyl, halogen, cyano, substituted or unsubstituted C 6 ～C 30 Aryl and substituted or unsubstituted C 2 ～C 30 At least one of heteroaryl; l (L) 1 And L 2 Each independently selected from the group consisting of a bond, a substituted or unsubstituted C 6 ～C 30 Arylene and substituted or unsubstituted C 2 ～C 30 At least one of heteroarylene; ar (Ar) 1 、Ar 2 And Ar is a group 3 Each independently selected from substituted or unsubstituted C 6 ～C 30 Aryl or substituted or unsubstituted C 2 ～C 30 Heteroaryl groups.
The mother structure of the benzothiadiazole derivative has good coplanarity, thus ensuring that the compound has higher carrier transmission property, thereby obviously reducing the working voltage of an organic electroluminescent device using the compound, simultaneously the high mobility of the compound ensures that the thickness control of the material has wider adjustment range, and the increase of the film thickness of the material can not obviously influence the working voltage of the device; the compound disclosed by the invention is most suitable for being used as an electron transport material in an organic electroluminescent device, and can be better matched with the LUMO energy level of a main body material of a luminescent layer, so that the working voltage of the device can be effectively reduced, the luminescent efficiency of the device can be improved, the service life of the device can be prolonged, and the compound has very important practical significance in the manufacture of the organic electroluminescent device.
According to the present disclosure, substituted C 6 ～C 30 Aryl, substituted C 2 ～C 30 Heteroaryl, substituted C 6 ～C 30 Arylene and substituted C 2 ～C 30 The substituents in the heteroarylene group may each independently beHalogen radicals, cyano radicals, C 1 ～C 6 Alkyl, C of (2) 1 ～C 6 Alkoxy, C 6 ～C 30 Aromatic groups or C of (2) 2 ～C 30 Heteroaryl, wherein the halogen group may be at least one of-F, -Cl, -Br, -I, C 1 ～C 6 The alkyl group of (C) is preferably at least one of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, n-hexyl, cyclopentyl and cyclohexyl 1 ～C 6 The alkoxy group of (a) is preferably at least one of methoxy, ethoxy, propoxy and isopropoxy.
According to the present disclosure, C 6 ～C 30 Aryl groups are well known to the person skilled in the art, i.e. aryl groups having 6 to 30 backbone carbon atoms, preferably having 6 to 20 backbone carbon atoms, and may be selected from phenyl, biphenyl, terphenyl, naphthyl, anthracenyl, fluoranthracenyl, phenanthrenyl, indenyl, benzofluorenyl, fluorenyl, triphenylenyl, pyrenyl, perylenyl,
at least one of a group and a tetracenyl group, wherein the biphenyl group may include a group selected from the group consisting of a 2-biphenyl group, a 3-biphenyl group and a 4-biphenyl group; the terphenyl group may include at least one of a p-terphenyl-4-yl group, a p-terphenyl-3-yl group, a p-terphenyl-2-yl group, a m-terphenyl-4-yl group, a m-terphenyl-3-yl group, and a m-terphenyl-2-yl group, the naphthyl group may include at least one of a 1-naphthyl group and a 2-naphthyl group, the anthryl group may include at least one of a 1-anthryl group, a 2-anthryl group, and a 9-anthryl group, the fluorenyl derivative may include at least one of 9,9 '-dimethylfluorene, 9' -spirobifluorene, benzofluorene, and indenofluorene, and the pyrenyl group may include at least one selected from a 1-pyrenyl group, a 2-pyrenyl group, and a 4-pyrenyl group.
Heteroaryl means, according to the present disclosure, a monocyclic or fused ring aromatic group having at least one heteroatom and having a number of ring backbone atoms, which heteroatom may comprise one or more heteroatoms selected from B, N, O, S, P (=o), si and P; preferably, the heteroatoms may comprise one or more heteroatoms selected from O, S and N. C (C) 2 ～C 30 Heteroaryl groupHaving 2 to 30 skeleton carbon atoms, preferably having 4 to 20 skeleton carbon atoms, may be, for example, at least one selected from the group consisting of furyl, thienyl, thiazolyl, pyrrolyl, pyridyl, carbazolyl, benzofuryl, benzothienyl, benzothiazolyl, isobenzofuryl, indolyl, quinolinyl, isoquinolinyl, dibenzofuranyl, dibenzothienyl, phenylpyridyl, pyridylphenyl, 9-phenylcarbazolyl, 9-naphthylcarbazolyl, benzocarbazolyl, dibenzocarbazolyl, indolocarbazolyl and benzodioxolyl, and is preferably pyridyl.
According to the present disclosure, C 1 ～C 12 The aliphatic alkyl group is well known to those skilled in the art, i.e., an aliphatic alkyl group having 1 to 12 carbon atoms, and may be selected from the group consisting of methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl and dodecyl, wherein the alkyl group may be a straight-chain alkyl group or an alkyl group having a branched chain, and further preferably at least one of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl and n-hexyl.
According to the present disclosure, C 3 ～C 12 Cycloalkyl groups are well known to those skilled in the art, i.e. cycloalkyl groups having 3 to 12 carbon atoms, preferably cyclopentyl or cyclohexyl.
According to the present disclosure, the benzothiadiazole derivative may have a structure represented by any one of the following formulas (4) - (7):
wherein R is 2 、R 3 、R 4 、R 5 、R 6 、R 7 、L 1 、L 2 、Ar 1 、Ar 2 And Ar is a group 3 May have the same definition as described above.
Further, having a structure represented by the formula (4)The benzothiadiazole derivative may have a structure represented by the following formula (8):
wherein R is 2’ 、R 3’ 、R 4’ 、R 2 ”、R 3 "and R 4 "may be each independently selected from hydrogen atoms, C 1 ～C 12 Aliphatic alkyl, C 3 ～C 12 Cycloalkyl, halogen, cyano, substituted or unsubstituted C 6 ～C 30 Aryl and substituted or unsubstituted C 2 ～C 30 At least one of heteroaryl; l 'and L' may each be independently selected from a bond, a substituted or unsubstituted C 6 ～C 30 Arylene and substituted or unsubstituted C 2 ～C 30 At least one of heteroarylene groups. Wherein C is 1 ～C 12 Aliphatic alkyl, C 3 ～C 12 Cycloalkyl, substituted or unsubstituted C 6 ～C 30 Aryl, substituted or unsubstituted C 2 ～C 30 Heteroaryl groups may have the same ranges of choice as described above, and the meaning of heteroarylene and heteroarylene is also well known to those skilled in the art and will not be described in detail herein. />
May be the same or different, preferably the same.
In one embodiment of the present disclosure, R 1 May have a structure represented by formula (2) or (3), R 2 、R 3 、R 4 、R 5 And R is 6 Each independently selected from at least one of H, cyano, halo, methyl, ethyl, propyl, N-butyl, N-pentyl, N-hexyl, phenyl, methylphenyl, ethylphenyl, biphenyl, naphthyl, pyridinyl, carbazolyl, carbazolylphenyl, fluorenyl, N-fluorenylcarbazolyl, methoxy, ethoxy, and trifluoromethyl, preferably at least one of H, cyano, phenyl, and pyridinyl, further R 2 、R 3 And R is 4 One of which is cyano, phenyl or pyridylAt least one, the rest is H; in another embodiment of the present disclosure, R 2 May have a structure represented by formula (2) or (3), R 1 、R 3 、R 4 、R 5 And R is 6 Each independently selected from at least one of H, cyano, halo, methyl, ethyl, propyl, N-butyl, N-pentyl, N-hexyl, phenyl, methylphenyl, ethylphenyl, biphenyl, naphthyl, pyridinyl, carbazolyl, carbazolylphenyl, fluorenyl, N-fluorenylcarbazolyl, methoxy, ethoxy, and trifluoromethyl, preferably at least one of H, cyano, phenyl, and pyridinyl, further R 1 、R 3 And R is 4 One of them is at least one of cyano, phenyl and pyridyl, and the rest is H. Further, in one embodiment of the present disclosure, R 5 And R is 6 May be the same or different, and R is preferably 5 And R is 6 Is the same and is selected from at least one of H, cyano, phenyl and pyridyl.
Ar according to the present disclosure 1 、Ar 2 And Ar is a group 3 Each independently selected from at least one of phenyl, methylphenyl, ethylphenyl, biphenyl, naphthyl, pyridyl, carbazolyl, thiazolyl, carbazolylphenyl, benzothiazolyl, fluorenyl and N-fluorenylcarbazolyl, preferably at least one of phenyl, biphenyl and naphthyl. Ar (Ar) 2 And Ar is a group 3 May be the same or different, and is preferably Ar 2 And Ar is a group 3 And is the same and is selected from at least one of phenyl, biphenyl and naphthyl. Preferably Ar 1 Is at least one of phenyl, biphenyl and naphthyl.
According to the present disclosure, when L 1 And L 2 When not a bond, L 1 And L 2 Can be independently selected from one of the structures shown in the following formulas (8) - (13):
according to the present disclosure, the benzothiadiazole derivative is preferably selected from one of the following structural formulas:
a second aspect of the present disclosure provides an application of the benzothiadiazole derivative in preparing an organic electroluminescent device.
A third aspect of the present disclosure provides an organic electroluminescent device, which includes a substrate, an anode layer, a cathode layer, and at least one organic functional layer interposed between the anode layer and the cathode layer, where the organic functional layer includes a hole injection layer, a hole transport layer, an organic light emitting layer, an electron transport layer, and an electron injection layer, the hole transport layer, the organic light emitting layer, the electron transport layer, and the electron injection layer are formed on the anode layer, the cathode layer is formed on the electron transport layer, and an electron transport layer material of the electron transport layer contains the benzothiadiazole derivative of the first aspect of the present disclosure, preferably contains compounds A1 to a39.
The organic electroluminescent device disclosed by the disclosure can reduce the working voltage of the device, improve the luminous efficiency and prolong the service life of the device based on the excellent performance of the compound disclosed by the disclosure.
The substrate of the organic electroluminescent device of the present disclosure may use a substrate in a conventional organic light emitting device, for example: glass, polymer material, glass with TFT components, polymer material, and the like are preferably used as the glass substrate.
The anode layer material can be Indium Tin Oxide (ITO), indium Zinc Oxide (IZO), or tin dioxide (SnO) 2 ) Transparent conductive materials such as zinc oxide (ZnO), metallic materials such as silver and its alloys, aluminum and its alloys, organic conductive materials such as PEDOT, and multilayer structures of the above materials. The cathode layer material can be magnesium-silver mixture, liF/Al, ITO and other metals, metal mixture and oxide.
The hole injection layer material and the hole transport layer material may each be independently selected from at least one of the following compounds HT-1 to HT-31:
according to the present disclosure, the organic light emitting layer of the organic electroluminescent device may be a single light emitting layer or a multi-light emitting layer structure; the emission color is not limited, and may be red, yellow, blue, green, etc., and the organic emission layer may include a host material and a doping dye, wherein the blue fluorescent host may include at least one of the following compounds BFH-1 to BFH-14:
the blue fluorescent dye may include at least one of the following compounds BFD-1 to BFD-9:
the compounds of the present invention may be used in combination with one or more of the electron transport materials listed below, but are not limited thereto.
The electron injection layer material includes, but is not limited to, a combination of one or more of the following.
LiQ,LiF,NaCl,CsF,Li 2 O,Cs 2 CO 3 ,BaO,Na,Li,Ca。
The synthetic methods of the compounds of the present disclosure are briefly described below.
The benzothiadiazole derivative is obtained by coupling halogenated benzothiadiazole represented by a general formula Q with boric acid ester represented by a general formula M;
representative synthetic route 1 is as follows, which corresponds to the benzothiadiazole derivatives represented by the synthetic formulas (1), (2) and (3):
wherein X represents halogen (chlorine, bromine or iodine); l is L 1 Or L 2 The method comprises the steps of carrying out a first treatment on the surface of the A has a structure represented by formula (M1) or formula (M2), R 2 、R 3 、R 4 、R 5 、R 6 And R is 7 Each independently selected from hydrogen atoms, C 1 ～C 12 Aliphatic alkyl, halogen, cyano, substituted or unsubstituted C 6 ～C 30 Aryl and substituted or unsubstituted C 2 ～C 30 At least one of heteroaryl; l (L) 1 、L 2 、Ar 1 、Ar 2 And Ar is a group 3 The definition is as defined in claim 1;
representative synthetic pathway 2 is as follows:
wherein X represents halogen (chlorine, bromine or iodine); l is L 1 Or L 2 The method comprises the steps of carrying out a first treatment on the surface of the A has a structure represented by formula (M1) or formula (M2), R 2 、R 3 、R 4 、R 5 And R is 6 Each independently selected from hydrogen atoms, C 1 ～C 12 Aliphatic alkyl, halogen, cyano, substituted or unsubstituted C 6 ～C 30 Aryl and substituted or unsubstituted C 2 ～C 30 At least one of heteroaryl; l (L) 1 、L 2 、Ar 1 、Ar 2 And Ar is a group 3 The definition is as defined in claim 1;
by replacing different
(sometimes referred to in the art as borates) or a-Br may yield different target compounds. In the above synthesis method, the substituent a is bonded to the benzothiadiazole by using a Suzuki coupling, but the method is not limited to this coupling method, and those skilled in the art may select other methods, for example, a Stille coupling method, a grignard reagent method, a Kumada-Tamao method, and the like, but the method is not limited to these methods, and any equivalent synthesis method may be used to achieve the purpose of bonding the substituent a to the benzothiadiazole, and may be selected as needed.
Unless specified otherwise, all raw materials and intermediates used in the present disclosure are commercial products; mass spectrometry in this disclosure was measured using a ZAB-HS type mass spectrometer (manufactured by Micromass corporation, uk), and elemental analysis was measured using a vario EL type elemental analyzer (manufactured by Elementar Analysensysteme GmbH corporation, uk).
Synthesis example 1: synthesis of Compound A1
50g (0.09 mol,1 eq) of the product 9, 10-bis (2-naphthyl) anthracene-2-pinacolatoborate (compound B1), 21.3g (0.0992 eq) of 4-bromo-2, 1, 3-benzothiadiazole (compound C1), 500mL of dioxane, 80mL of water were added to a 1000mL four-necked flask equipped with a mechanical stirrer, a thermometer, and a condenser under nitrogen atmosphere, and the reaction mixture was refluxed for 6h, followed by TLC to monitor the completion of the reaction.
After cooling to room temperature, directly carrying out suction filtration, and washing a filter cake once by water and once by ethanol; chloroform (30 eq) was dissolved by heating and concentrated on silica gel to give a yellow solid. Adding ethyl acetate, heating, boiling, washing for 2 hours, filtering, refluxing with normal hexane, boiling, washing for 2 hours, and filtering to obtain a bright yellow powdery product.
Nuclear magnetic spectrum data of the product: 1 H NMR(500MHz,Chloroform)δ8.96(d,J＝2.9Hz,1H),8.34(d,J＝15.0Hz,1H),8.27–8.13(m,3H),8.13–7.95(m,6H),7.72–7.51(m,9H),7.43–7.26(m,4H)；
elemental analysis data C for the product: 85.08%, H:4.28%, N:4.96%.
Synthesis example 2: synthesis of Compound A5
Under nitrogen protection, 50g (0.09 mol,1 eq) of the product 9, 10-bis (2-naphthyl) anthracene-2-pinacolatoborate (compound B1), 28.8g (0.099 mol,1.1 eq) of 4- (4-bromophenyl) -2,1, 3-benzothiadiazole (compound C5), pd (PPh) were put into a 1000mL four-necked flask equipped with a mechanical stirrer, a thermometer and a condenser 3 ) 4 0.5g (0.0045 mol, 0.5%), potassium carbonate 22.3g (1.62 mol,2 eq), dioxane500mL, 80mL of water, the reaction mixture was refluxed for 6h, and TLC monitored the completion of the reaction.
Cooling to room temperature, directly suction filtering, and washing the filter cake with water and ethanol once respectively; chloroform (30 eq) was dissolved by heating and concentrated on silica gel to give a yellow solid. Adding ethyl acetate, heating, boiling, washing for 2 hours, filtering, refluxing with normal hexane, boiling, washing for 2 hours, and filtering to obtain a pale yellow powdery product.
Nuclear magnetic spectrum data of the product: 1 H NMR(500MHz,Chloroform)δ8.96(d,J＝2.9Hz,1H),8.34(d,J＝15.0Hz,1H),8.27–8.14(m,3H),8.13–8.03(m,4H),7.99(dd,J＝15.0,2.9Hz,2H),7.72–7.48(m,9H),7.42–7.28(m,4H),7.25(s,4H)；
elemental analysis data C for the product: 86.22%, H:4.40%, N:4.37%.
Synthesis example 3: synthesis of Compound A12
Under nitrogen protection, 50g (0.09 mol,1 eq) of the product 9, 10-bis (2-naphthyl) anthracene-2-pinacolatoborate (compound B1), 28.8g (0.099 mol,1.1 eq) of 4- (3-bromophenyl) -2,1, 3-benzothiadiazole (compound C11), pd (PPh 3) were introduced into a 1000mL four-necked flask equipped with a mechanical stirrer, a thermometer and a condenser 4 0.5g (0.0045 mol, 0.5%) potassium carbonate 22.3g (1.62 mol,2 eq), dioxane 500mL, water 80mL, the reaction mixture was refluxed for 6h, and TLC monitored for reaction completion.
After cooling to room temperature, directly carrying out suction filtration, and washing a filter cake once by water and once by ethanol; chloroform (30 eq) was dissolved by heating and concentrated on silica gel to give a yellow solid. Adding ethyl acetate, heating, boiling, washing for 2 hours, filtering, refluxing with normal hexane, boiling, washing for 2 hours, and filtering to obtain a pale yellow powdery product.
Nuclear magnetic spectrum data of the product: 1 H NMR(500MHz,Chloroform)δ8.96(d,J＝2.9Hz,1H),8.34(d,J＝15.0Hz,1H),8.29–8.14(m,3H),8.14–7.95(m,7H),7.75–7.47(m,12H),7.43–7.27(m,4H)；
elemental analysis data C for the product: 86.22%, H:4.40%, N:4.37%.
Synthesis example 4: synthesis of Compound A13
28.8g (0.098 mol,1.0 eq) of 4- (4-bromophenyl) -2,1, 3-benzothiadiazole (Compound C5), 37g (0.15 mol,1.5 eq) of pinacol bisborate, pd (dppf) Cl were placed in a 1000mL four-necked flask equipped with magnetic stirring, thermometer, condenser under nitrogen 2 (0.37 g, 0.5%), potassium acetate 19.6g (0.2 mol,2 eq), dioxane 500mL, the reaction mixture reacted for 6h under reflux, tlc monitored the reaction to completion (PE/ea=10:1). Cooling the reaction solution to room temperature, adding water and dichloromethane for extraction, concentrating an organic phase, pulping and washing with ethanol, and filtering to obtain an off-white solid (a compound D13);
under the protection of nitrogen, 30g (0.09 mol,1 eq) of 9, 10-dibromoanthracene (compound E13), 1364g (0.189 mol,2.1 eq) of compound D and Pd (PPh 3) are added into a 1000mL four-necked flask equipped with a magnetic force, a thermometer and a condenser tube 4 0.5g (0.0045 mol, 0.5%) potassium carbonate 22.3g (1.62 mol,2 eq), dioxane 500mL, water 80mL, the reaction mixture was refluxed for 6h, and TLC monitored for reaction completion.
After cooling to room temperature, water and dichloromethane were added to extract, the organic phase was concentrated as a grey solid, which was dissolved in dichloromethane and filtered by flash column chromatography to remove palladium residue from the solid, the product was concentrated as a yellow solid, a13.
Nuclear magnetic spectrum data of the product: 1 H NMR(500MHz,Chloroform)δ8.26–8.12(m,6H),7.75–7.62(m,4H),7.48–7.38(m,4H),7.25(s,8H)；
elemental analysis data C for the product: 76.23%, H:3.70%, N:9.36%.
Synthesis example 5: synthesis of Compound A25
The procedure of Synthesis example 4 was followed except that compound E13 was replaced with the corresponding equivalent of 9- (2-naphthyl) -10-bromoanthracene (compound E25) to give a powdery product.
Nuclear magnetic spectrum data of the product: 1 H NMR(500MHz,Chloroform)δ8.26–8.13(m,5H),8.13–8.03(m,2H),7.99(dd,J＝15.0,2.9Hz,1H),7.72–7.51(m,5H),7.49–7.33(m,5H),7.25(s,4H)；
elemental analysis data for the product: elemental analysis (b) C:84.02%, H:4.31%, N:5.44%.
Synthesis example 6: synthesis of Compound A33
The procedure of Synthesis example 1 was followed except that 4-bromo-2, 1, 3-benzothiadiazole (Compound C1) was replaced with the corresponding equivalent of 5-bromo-2, 1, 3-benzothiadiazole (Compound C33), to give a powdery product.
Nuclear magnetic spectrum data of the product: 1 H NMR(500MHz,Chloroform)δ8.96(d,J＝2.9Hz,1H),8.34(d,J＝15.0Hz,1H),8.24(ddd,J＝19.2,14.3,6.7Hz,3H),8.14–8.03(m,4H),8.02–7.91(m,3H),7.68–7.49(m,8H),7.43–7.27(m,4H)；
elemental analysis data C for the product: 85.08%, H:4.28%, N:4.96%.
Device example 1.
The compound A1 in the invention is used as an electron transport layer material.
The glass plate coated with the ITO transparent conductive layer was sonicated in commercial cleaners, rinsed in deionized water, and rinsed in acetone: ultrasonic degreasing in ethanol mixed solvent, baking in clean environment to completely remove water, cleaning with ultraviolet light and ozone, and bombarding surface with low-energy cation beam;
placing the above glass substrate with anode in vacuum chamber, and vacuumizing to 1×10 -5 ～9×10 -3 Pa, vacuum evaporating HT-11 as a hole injection layer on the anode layer film, wherein the evaporation rate is 0.1nm/s, and the thickness of the evaporation film is 10nm;
vacuum evaporation HT-2 is carried out on the hole injection layer to serve as a hole transmission layer of the device, the evaporation rate is 0.1nm/s, and the total film thickness of evaporation is 80nm;
vacuum evaporating a luminescent layer of the device on the hole transport layer, wherein the luminescent layer comprises a main material and a dye material, the evaporation rate of the main material BFH-4 is regulated to be 0.1nm/s by utilizing a multi-source co-evaporation method, the evaporation rate of the dye BFD-1 is set to be 3 percent, and the total film thickness of the evaporation is 30nm;
vacuum evaporating an electron transport layer material (compound A1) of the device on the light emitting layer, wherein the evaporation rate is 0.1nm/s, and the total evaporation film thickness is 30nm;
LiF with the thickness of 0.5nm is vacuum evaporated on an Electron Transport Layer (ETL) to serve as an electron injection layer, an Al layer with the thickness of 150nm serves as a cathode of the device, and the organic electroluminescent device of the embodiment is obtained, and the measurement results of the device performance are shown in Table 1.
Device examples 2 to 7
Organic electroluminescent devices were prepared in the same manner as in device example 1 except that the compounds A2, A5, a12, a13, a25, a33 and a36 were used as electron transport layer materials in place of A1, respectively obtaining device examples 2 to 7, and the measurement results of the device properties are shown in table 1.
Device comparative example 1
An organic electroluminescent device was prepared in the same manner as in device example 1, except that the electron transport layer material compound A1 was replaced with the compound ET-38, and the measurement results of the device properties were shown in Table 1.
Device comparative example 2
An organic electroluminescent device was prepared in the same manner as in device example 1, except that the electron transport layer material compound A1 was replaced with the compound ET-43, and the measurement results of the device properties were shown in Table 1.
Test examples
The organic electroluminescent device prepared by the above procedure was subjected to the following performance measurement:
the organic electronics obtained in examples 1 to 7 and comparative examples 1 to 2 were measured at the same brightness using a digital source meter and a brightness meterThe driving voltage and current efficiency of the light emitting device and the lifetime of the device. Specifically, the luminance of the organic electroluminescent device was measured to reach 1000cd/m by increasing the voltage at a rate of 0.1V per second 2 The voltage at the time is the driving voltage, and the current density at the time is measured; the ratio of brightness to current density is the current efficiency; the lifetime test of LT95 is as follows: at 1000cd/m using a luminance meter 2 Under the condition of brightness, constant current is kept, and the brightness of the organic electroluminescent device is measured to be reduced to 950cd/m 2 Time in hours.
TABLE 1
| Device embodiment | Numbering of compounds | The required brightness cd/m 2 | Voltage mV | Current efficiency cd/a | T95h |
| Example 1 | A1 | 1000.00 | 4300 | 8.7 | 85 |
| Example 2 | A5 | 1000.00 | 4300 | 8.5 | 87 |
| Example 3 | A12 | 1000.00 | 4600 | 8.5 | 90 |
| Example 4 | A13 | 1000.00 | 4500 | 8.6 | 82 |
| Example 5 | A25 | 1000.00 | 4300 | 8.5 | 85 |
| Example 6 | A33 | 1000.00 | 4500 | 8.7 | 86 |
| Example 7 | A36 | 1000.00 | 4500 | 8.5 | 82 |
| Comparative example 1 | ET-38 | 1000.00 | 5700 | 8.3 | 64 |
| Comparative example 2 | ET-43 | 1000.00 | 5500 | 8.5 | 67 |
The result shows that the novel organic material is used for an organic electroluminescent device, can effectively reduce the voltage at take off and landing, and is an electron transport material with good performance.
The result shows that the novel organic material is used for an organic electroluminescent device, can effectively reduce the voltage at take off and landing, and is an electron transport material with good performance.
The preferred embodiments of the present disclosure have been described in detail above, but the present disclosure is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solutions of the present disclosure within the scope of the technical concept of the present disclosure, and all the simple modifications belong to the protection scope of the present disclosure.
In addition, the specific features described in the above embodiments may be combined in any suitable manner without contradiction. The various possible combinations are not described further in this disclosure in order to avoid unnecessary repetition.
Moreover, any combination between the various embodiments of the present disclosure is possible as long as it does not depart from the spirit of the present disclosure, which should also be construed as the disclosure of the present disclosure.
Claims (9)
1. The benzothiadiazole derivative is characterized by having a structure shown in any one of the following general formulas (4) - (8):
in the formula (4) or (7), R 1 、R 2 、R 3 And R is 4 Each independently is H or cyano; or alternatively
In the formula (5) or (6), R 1 、R 2 、R 3 And R is 4 Each independently is H or cyano;
in the formula (8), R 2’ 、R 3’ 、R 4’ 、R 2” 、R 3” And R is 4” Each independently is a hydrogen atom or a cyano group;
l ', L' are each independently selected from at least one of a bond, a substituted or unsubstituted phenylene group, and a substituted or unsubstituted naphthylene group, a substituted or unsubstituted pyridylene group;
R 5 、R 6 and R is 7 Is a hydrogen atom;
L 1 and L 2 Each independently selected from the group consisting of a bond, a substituted or unsubstituted phenyl group, and a substituted or unsubstituted naphthyl group, a substituted or unsubstituted pyridinyl group;
Ar 1 、Ar 2 and Ar is a group 3 Each independently selected from at least one of a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted pyridyl group; wherein the substituents in the above-mentioned substitution or unsubstituted are each independently halogen group, cyano group, C 1 ～C 6 Alkyl, C of (2) 1 ～C 6 Alkoxy groups of (a).
2. The benzothiadiazole derivative according to claim 1, wherein Ar 1 、Ar 2 And Ar is a group 3 Each independently selected from at least one of phenyl, methylphenyl, ethylphenyl, biphenyl, naphthyl, pyridinyl, and the like.
3. The benzothiadiazole derivative according to claim 2, wherein Ar 2 And Ar is a group 3 Identical, and Ar 2 And Ar is a group 3 Each independently selected from at least one of phenyl, biphenyl, and naphthyl.
4. The benzothiadiazole derivative according to claim 2, wherein Ar 1 Is at least one of phenyl, biphenyl and naphthyl.
5. The benzothiadiazole derivative according to claim 1, wherein L 1 And L 2 Each independently selected from one of structures represented by the following formulas (8 a) - (13):
6. the benzothiadiazole derivative according to claim 1, wherein said benzothiadiazole derivative is selected from one of the following structural formulas:
7. use of a benzothiadiazole derivative according to any of claims 1 to 6 for the preparation of an organic electroluminescent device.
8. The use according to claim 7, characterized in that the benzothiadiazole derivative is used as an electron transport layer material for the organic electroluminescent device.
9. An organic electroluminescent device comprising a substrate, an anode layer, a cathode layer, and at least one organic functional layer interposed between the anode layer and the cathode layer, the organic functional layer comprising a hole injection layer, a hole transport layer, an organic light emitting layer, an electron transport layer, and an electron injection layer, characterized in that an electron transport layer material of the electron transport layer contains the benzothiadiazole derivative of any one of claims 1 to 6.
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| CN101392174A (en) * | 2008-10-27 | 2009-03-25 | 华南理工大学 | Soluble electro-green light organic molecule glass material and preparation method and use thereof |
| KR20130090726A (en) * | 2012-02-06 | 2013-08-14 | 주식회사 엘지화학 | Nitrogen-containing heterocyclic compound and organic electronic device using the same |
| CN103804640A (en) * | 2012-11-08 | 2014-05-21 | 海洋王照明科技股份有限公司 | Electron transfer polymer, and preparation method and application thereof |
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| CN101392174A (en) * | 2008-10-27 | 2009-03-25 | 华南理工大学 | Soluble electro-green light organic molecule glass material and preparation method and use thereof |
| KR20130090726A (en) * | 2012-02-06 | 2013-08-14 | 주식회사 엘지화학 | Nitrogen-containing heterocyclic compound and organic electronic device using the same |
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