CN112266361A - Organic luminescent material based on phenanthroimidazole derivative and application of organic luminescent material in electroluminescent device - Google Patents

Organic luminescent material based on phenanthroimidazole derivative and application of organic luminescent material in electroluminescent device Download PDF

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CN112266361A
CN112266361A CN202011266915.9A CN202011266915A CN112266361A CN 112266361 A CN112266361 A CN 112266361A CN 202011266915 A CN202011266915 A CN 202011266915A CN 112266361 A CN112266361 A CN 112266361A
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phenanthroimidazole
luminescent material
organic luminescent
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李成龙
王悦
刘宇
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Jilin University
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Abstract

An organic luminescent material based on phenanthroimidazole derivatives and application thereof in electroluminescent devices, belonging to the technical field of organic electroluminescence. The structural formula of the organic luminescent material is shown as (I), R1‑R4The same or different, C1-C30 alkyl, C3-C10 cycloalkyl, C6-C48 aryl, C2-C30 heteroaryl with one or more atoms selected from O, N, Se and S, and C6-C40 arylamine. The phenanthroimidazole derivative has good bipolar transmission capability, excellent thermal stability, higher glass transition temperature and good film forming property. The derivatives can be used in the field of organic electroluminescence, and the organic electroluminescent diode device prepared by the derivatives has the advantages of low turn-on, low roll-off, high efficiency and the like, and is further used for preparing organic electroluminescent displays, organic electroluminescent lighting sources or decorative light sources.
Figure DDA0002776351900000011

Description

Organic luminescent material based on phenanthroimidazole derivative and application of organic luminescent material in electroluminescent device
Technical Field
The invention belongs to the technical field of organic electroluminescence, and particularly relates to a phenanthroimidazole derivative-based organic luminescent material and application thereof in an electroluminescent device.
Background
In 1963, Pope et al, university of new york, usa, first discovered that by applying several hundred volts to an organic aromatic anthracene crystal, a weak blue emission of anthracene was observed (see m.pope, h.kallmann and p.magnane, j.chem.phys.,1963,38, 2042). However, the driving voltage is too high, and the light emitting efficiency is low, so that no attention is paid at that time. Tang et al, C.W. of Kodak corporation, first used vacuum evaporation to deposit 4,4' -cyclohexylbis [ N, N-bis (4-methylphenyl) aniline](TAPC) As hole transport layer, tris (8-hydroxyquinoline) aluminum (AlQ)3) The double-layer device is prepared as an electron transport layer and a luminescent layer, the external quantum efficiency of the device is improved to 1 percent, and the power efficiency reaches 1.5lm W-1Up to 1000cd m at operating voltages below 10V-2Brightness (see c.w.tang and s.a.vanslyke, appl.phys.lett., 1987, 51, 913). This result has led to a wide range of worldwide resultsAttention is paid to the method. From this point on, the organic electroluminescence technology enters the inoculation practical stage. Baldo and Forrest et al, Princeton university in 1998[5]A transition metal complex platinum octaethylporphyrin (PtOEP) is reported, which is doped into AlQ3In the host, phosphorescent emission from triplet excitons is obtained, which discovery breaks the 25% limit of quantum efficiency within fluorescent devices, making the realization of quantum efficiency within 100% possible (see m.a. baldo, d.f. o' brienetal, Nature, 1998, 395, 151). However, on one hand, the phosphorescent material generally uses noble metals such as iridium and platinum, and is expensive, and on the other hand, the deep blue phosphorescent material still has the problems of chemical instability, large efficiency roll-off of the device under high current density, and the like, so that the development of an OLED device which uses cheap and stable organic small molecular materials and can realize high-efficiency light emission is very important.
The phenanthroimidazole compound has the advantages of simple synthesis, easy modification, wider forbidden band, high photoluminescence efficiency, good thermal stability, balanced carrier injection/transmission capability and the like, so the phenanthroimidazole compound is concerned by researchers in the field of photoelectricity.
Disclosure of Invention
The invention provides a phenanthroimidazole derivative-based organic luminescent material, a preparation method thereof and application thereof in an electroluminescent device. The phenanthroimidazole derivative has good bipolar transmission capability, excellent thermal stability, higher glass transition temperature and good film forming property. The derivatives can be used in the field of organic electroluminescence. The organic electroluminescent diode device prepared by the derivative has the advantages of low turn-on, low roll-off, high efficiency and the like.
The invention aims to provide a novel organic electroluminescent material based on phenanthroimidazole derivative and application thereof in preparing electroluminescent devices.
The compound of the invention has the following general formula (I):
Figure BDA0002776351880000011
wherein R is1-R4The aromatic amine group may be the same or different and is C1-C30 alkyl, C3-C10 cycloalkyl, C6-C48 aryl, C2-C30 heteroaryl with one or more atoms selected from O, N, Se and S, or C6-C40 aromatic amine.
Preferably, the phenanthroimidazole derivative shown in the general formula (I) is any one of the following compounds:
Figure BDA0002776351880000021
Figure BDA0002776351880000031
Figure BDA0002776351880000041
Figure BDA0002776351880000051
Figure BDA0002776351880000061
Figure BDA0002776351880000071
Figure BDA0002776351880000081
Figure BDA0002776351880000091
Figure BDA0002776351880000101
Figure BDA0002776351880000111
Figure BDA0002776351880000121
Figure BDA0002776351880000131
Figure BDA0002776351880000141
Figure BDA0002776351880000151
Figure BDA0002776351880000161
Figure BDA0002776351880000171
Figure BDA0002776351880000181
the compound of the general formula (I) can be prepared according to the conventional chemical synthesis method in the field, and the steps and conditions can refer to the steps and conditions of similar reactions in the field.
The invention provides a preparation method of a compound shown as a general formula (I), which can comprise the following scheme:
Figure BDA0002776351880000182
wherein R is1、R2、R3And R4Is as defined above.
In one embodiment of the present invention, the compound of formula (I) is synthesized from the following raw materials:
Figure BDA0002776351880000191
Figure BDA0002776351880000201
Figure BDA0002776351880000211
Figure BDA0002776351880000221
Figure BDA0002776351880000231
Figure BDA0002776351880000241
the present invention also provides an organic electroluminescent device (OLED) composed of a cathode, a transparent anode, and one or more organic compound layers interposed between the two electrodes; the organic compound layer at least comprises a hole transport layer, an electron blocking layer, a light emitting layer and an electron transport layer, and the phenanthroimidazole derivative provided by the invention is used as the light emitting layer.
In the OLED device, the transparent anode may be formed by using an electrode material known per se, that is, by vapor-depositing an electrode material having a large work function, such as ITO or gold, on a substrate (a transparent substrate such as a glass substrate).
As the material for the device of the present invention, any material known in the art for organic electroluminescent devices can be used
The organic electroluminescent device is used for preparing organic electroluminescent displays, organic electroluminescent lighting sources and decorative light sources.
Description of the terms
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
As used herein, the term "comprising" or "includes" can be open, semi-closed, and closed. In other words, the term also includes "consisting essentially of …," or "consisting of ….
Radical definition
In the present specification, groups and substituents thereof may be selected by one skilled in the art to provide stable moieties and compounds. When a substituent is described by a general formula written from left to right, the substituent also includes chemically equivalent substituents obtained when the formula is written from right to left.
The section headings used in this specification are for organizational purposes only and are not to be construed as limiting the subject matter described. All documents, or portions of documents, cited in this application, including but not limited to patents, patent applications, articles, books, operating manuals, and treatises, are hereby incorporated by reference in their entirety.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as is standard in the art to which the claimed subject matter belongs. In case there are multiple definitions for a term, the definitions herein control.
It should be understood that as used herein, singular forms, such as "a", "an", include plural references unless the context clearly dictates otherwise. Furthermore, the term "comprising" is open-ended, i.e. including what is specified in the invention, but not excluding other aspects.
The present invention employs conventional methods of mass spectrometry, elemental analysis, and the various steps and conditions can be referred to those conventional in the art unless otherwise indicated.
Unless otherwise indicated, the present invention employs standard nomenclature for analytical chemistry, organic synthetic chemistry, and optics, and standard laboratory procedures and techniques. In some cases, standard techniques are used for chemical synthesis, chemical analysis, light emitting device performance detection.
The compounds of the present invention may contain unnatural proportions of atomic isotopes at one or more of the atoms that constitute such compounds. For example, the compounds may be labelled with radioisotopes, such as deuterium (g) ((R))2H) In that respect All isotopic variations of the compounds of the present invention, whether radioactive or not, are intended to be encompassed within the scope of the present invention.
The above preferred conditions can be arbitrarily combined to obtain preferred embodiments of the present invention without departing from the common general knowledge in the art. The reagents and starting materials used in the present invention are commercially available.
Drawings
Fig. 1 is a schematic diagram of a device structure used in an effect embodiment.
In fig. 1, 1 is an ITO glass substrate (ITO is deposited on the glass substrate), 2 is a hole injection layer, 3 is a hole transport layer, 4 is a light emitting layer, 5 is an electron transport layer, 6 is an electron injection layer, and 7 is a metal cathode.
Fig. 2 shows photoluminescence spectra of compound No. 13 in a toluene solution.
FIG. 3 shows an electroluminescence spectrum of a solid thin film formed from Compound No. 13.
Detailed Description
The invention is further illustrated by the following representative examples, which are not intended to limit the invention thereto. The experimental methods without specifying specific conditions in the following examples were selected according to the conventional methods and conditions, or according to the commercial instructions.
Example 1:
the specific preparation method of the phenanthroimidazole intermediate is as follows:
Figure BDA0002776351880000251
adding 2, 7-dibromo phenanthrenequinone (10mmol), R1-CHO (i.e. R)1-1 to R1-10)(10mmol)，R2-NH2(i.e., R)2-1 to R2-25) (50mmol), ammonium acetate (40mmol) and acetic acid (50mL) were added to a three-necked flask and heated to reflux for 12h under nitrogen at 130 ℃ in an oil bath. Stopping the reaction, pouring the reaction mixture into distilled water, stirring and filtering, washing the obtained gray filter cake with water, glacial acetic acid and ethanol in sequence, and drying to obtain the para-bromine substituted phenanthroimidazole intermediate.
The specific preparation method of the carbon-carbon coupling compound is as follows
The p-bromo-substituted phenanthroimidazole intermediate (3mmol), an organic boronic acid (i.e. R)3-1 to R3-58) (7mmol), potassium carbonate (24mmol), tetrakis (triphenylphosphine) palladium (0.1mmol), toluene (45mL), water (7.5mL) were added to a three-necked flask, N2Under protection, heating and refluxing for 12h at 100 ℃ in an oil bath to stop the reaction, pouring the reaction mixture into distilled water, extracting with dichloromethane, concentrating, and separating by column chromatography (silica gel and dichloromethane) to obtain a powdery target product.
The specific preparation method of the carbon-carbon coupling compound is as follows
Specific details of the synthesis examples are illustrated by compound 1: adding 2, 7-dibromo phenanthrenequinone (10mmol), R1-1(10mmol)，R2-1(50mmol), ammonium acetate (40mmol), acetic acid (50mL) were added to a three-necked flask and heated to reflux for 12h under nitrogen at 130 ℃ in an oil bath. Stopping the reaction, pouring the reaction mixture into distilled water, stirring and filtering, washing the obtained gray filter cake with water, glacial acetic acid and ethanol in sequence, and drying to obtain the phenanthroimidazole intermediate (4.12g, the yield is 78%) which has the following molecular ion mass determined by mass spectrometry: 525.88 (calculated value: 525.97); theoretical element content (%) C27H16Br2N2: c, 61.39; h, 3.05; br, 30.25; n, 5.30; measured elemental content (%): c, 60.29;H,3.10；N,5.38。
the p-bromo-substituted phenanthroimidazole intermediate (3mmol), R3-1(7mmol), potassium carbonate (24mmol), tetrakis (triphenylphosphine) palladium (0.1mmol), toluene (45mL), water (7.5mL) were added to a three-necked flask, N2Under protection, the reaction was stopped by heating under reflux at 100 ℃ in an oil bath for 12h, the reaction mixture was poured into distilled water, extracted with dichloromethane, concentrated and separated by column chromatography (silica gel, dichloromethane) to give the desired product (1.07g, 68% yield) as a powder. The mass of the molecular ions determined by mass spectrometry was: 522.24 (calculated value: 522.21); theoretical element content (%) C39H26N2: c, 89.63; h, 5.01; n, 5.36, measured elemental content (%): c, 89.65; h, 5.05; n, 5.32. The above analysis results show that the obtained product is the expected product.
Examples 2 to 27:
compounds 2 to 27 were prepared as in example 1, using different starting materials.
Example 28:
the phenanthroimidazole intermediate was prepared as in example 1.
The specific preparation method of the carbon-nitrogen coupling compound is as follows
The p-bromo-substituted phenanthroimidazole intermediate (3mmol), an aromatic amine (i.e., R)4-1 to R4-21) (7mmol), cesium carbonate (24mmol), tris (dibenzylideneacetone) dipalladium (0.1mmol), tri-tert-butylphosphine (0.1mmol), o-xylene (30mL) were added to a three-necked flask, N2Under protection, heating and refluxing at 130 deg.C in oil bath for 12 hr to stop reaction, pouring the reaction mixture into distilled water, extracting with dichloromethane, concentrating, and separating by column chromatography (silica gel, dichloromethane) to obtain powdery target product
Specific details of the synthesis examples are illustrated by compound 28: the p-bromo-substituted phenanthroimidazole intermediate (3mmol), R4-3(7mmol), cesium carbonate (24mmol), tris (dibenzylideneacetone) dipalladium (0.1mmol), tri-tert-butylphosphine (0.1mmol), o-xylene (30mL) were added to a three-necked flask, N2Under protection, the reaction was stopped by heating and refluxing in an oil bath at 130 ℃ for 12h, the reaction mixture was poured into distilled water and treated with dichloro-benzeneExtraction with methane, concentration and separation by column chromatography (silica gel, dichloromethane) gave the desired product as a powder (1.07g, 68% yield). The mass of the molecular ions determined by mass spectrometry was: 707.89 (calculated value: 706.89); theoretical element content (%) C51H38N4: c, 86.66; h, 5.42; n,7.93, measured elemental content (%): c, 86.64; h, 5.44; and N, 7.96. The above analysis results show that the obtained product is the expected product.
Examples 29 to 42:
compounds 29 to 42 were prepared using different starting materials as in example 28.
Examples 43 to 69:
compounds 43 to 69 were prepared as in example 1, using different starting materials.
Examples 70 to 84:
compounds 70 to 84 were prepared using different starting materials as in example 28.
Examples 85 to 96:
compounds 85 to 96 were prepared as in example 1, using different starting materials.
Examples 97 to 99:
compounds 97 to 99 were prepared using different starting materials as in example 28.
Examples 100 to 114:
compounds 100 to 114 were prepared as in example 1, using different starting materials.
Example 115:
the phenanthroimidazole intermediate was prepared as in example 1.
The specific preparation method of the compound for carbon-nitrogen coupling and carbon-carbon coupling comprises the following steps:
the p-bromo-substituted phenanthroimidazole intermediate (3mmol), an aromatic amine (i.e., R)4-1 to R4-21) (7mmol) (3.5mmol), cesium carbonate (24mmol), tris (dibenzylideneacetone) dipalladium (0.1mmol), tri-tert-butylphosphine (0.1mmol), o-xylene (30mL) were added to a three-necked flask, N2Heating and refluxing for 12h at 130 ℃ in an oil bath under protection to stop the reaction, pouring the reaction mixture into distilled water,extracting with dichloromethane, concentrating, and separating by column chromatography (silica gel, dichloromethane) to obtain powder product.
Mixing the above powdered product (3mmol), organic boric acid (i.e. R)3-1 to R3-58) (7mmol), (3.5mmol), potassium carbonate (24mmol), tetrakis (triphenylphosphine) palladium (0.1mmol), toluene (45mL), water (7.5mL) were added to a three-necked flask, N2Under protection, heating and refluxing for 12h at 100 ℃ in an oil bath to stop the reaction, pouring the reaction mixture into distilled water, extracting with dichloromethane, concentrating, and separating by column chromatography (silica gel and dichloromethane) to obtain a powdery target product.
Specific details of the synthesis examples are illustrated by compound 115 as an example: the p-bromo-substituted phenanthroimidazole intermediate (3mmol), R4-3(3.5mmol), cesium carbonate (24mmol), tris (dibenzylideneacetone) dipalladium (0.1mmol), tri-tert-butylphosphine (0.1mmol), o-xylene (30mL) were added to a three-necked flask, N2Under protection, the reaction is stopped by heating and refluxing for 12h at 130 ℃ in an oil bath, the reaction mixture is poured into distilled water, extracted by dichloromethane, concentrated and separated by column chromatography (silica gel, dichloromethane) to obtain a powdery product (2.1g, yield 80%) with the mass of molecular ions determined by mass spectrometry: 630.69 (calculated value: 630.59); theoretical element content (%) C40H28BrN3: c, 76.19; h, 4.48; br, 12.67; n, 6.66; measured elemental content (%): c, 76.29; h, 4.58; n, 6.67. The above analysis results show that the obtained product is the expected product.
The powdery product (3mmol), R in the previous step311(3.5mmol), Potassium carbonate (24mmol), tetrakis (triphenylphosphine) palladium (0.1mmol), toluene (45mL), Water (7.5mL) in a three-necked flask, N2Under protection, the reaction is stopped after heating and refluxing for 12h at 100 ℃ in an oil bath, the reaction mixture is poured into distilled water, extracted by dichloromethane, concentrated and separated by column chromatography (silica gel and dichloromethane) to obtain a powdery target product (3.50g, the yield is 92%), and the mass of molecular ions determined by mass spectrometry is as follows: 795.00 (calculated value: 795.34); theoretical element content (%) C58H42N4: c, 87.63; h, 5.33; n, 7.05; measured elemental content (%): c, 87.65; h, 5.36; and N, 7.07. The above pointsThe analysis result shows that the obtained product is the expected product.
Examples 116 to 165:
compounds 116 to 165 were prepared using different starting materials as in example 115.
Examples 166 to 180:
compounds 166 to 180 were prepared using different starting materials as in example 1.
Examples 181 to 201:
compounds 181 to 201 were prepared using different starting materials as in example 115.
Examples 202 to 339:
compounds 202 to 339 were prepared as in example 1 using different starting materials.
Table 1. the data of the products obtained by the carbon-carbon coupling and carbon-nitrogen coupling reactions according to the synthetic route in the scheme are summarized below:
Figure BDA0002776351880000281
Figure BDA0002776351880000291
Figure BDA0002776351880000301
Figure BDA0002776351880000311
Figure BDA0002776351880000321
Figure BDA0002776351880000331
Figure BDA0002776351880000341
Figure BDA0002776351880000351
Figure BDA0002776351880000361
Figure BDA0002776351880000371
Figure BDA0002776351880000381
Figure BDA0002776351880000391
effect examples 1 to 115
The following embodiments of the electroluminescent device prepared by using the material of the present invention have the following specific device preparation process and device performance test experimental operations: the preparation method of the device comprises the following steps: the ITO glass substrate used by the device has the thickness of 180nm and the sheet resistance of 10 omega, and is pretreated before use. The treatment process comprises respectively ultrasonically cleaning the substrate for three times by using an ITO cleaning agent, an aqueous solution, acetone and isopropanol for 30min each time, and then treating the substrate for 5min by using Plasma. The evaporation process of the device is 5 multiplied by 10-4The evaporation speed of the organic layer of the device is completed under Pa
Figure BDA0002776351880000394
Lithium fluoride is
Figure BDA0002776351880000395
Aluminum is
Figure BDA0002776351880000396
The device tests are all completed in the atmospheric environment at normal temperature, and the used instruments are PHOTO RESEARCH SpectraScan PR655 and KEITHLEY 2400Source Meter constant current source.
The names of the components are: the material comprises a transparent glass or other transparent substrates, an ITO (indium tin oxide) anode, an NPB (N, N ' -di (naphthalene-1-yl) -N, N ' -bis (phenyl) benzidine) hole transport layer, a TCTA (4,4' -tris (carbazole-9-yl) triphenylamine) electron blocking layer, a luminescent layer (a deep blue light and sky blue light electroluminescent device obtained by directly preparing a luminescent layer from a phenanthroimidazole derivative), a TPBi (1,3, 5-tris (1-phenyl-1H-benzimidazole-2-yl) benzene) electron transport layer, a LiF electron injection layer and metal Al as a cathode, wherein the ITO anode, the NPB (N, N ' -di (naphthalene-1-yl) -N, N ' -bis (phenyl) benzidine) hole transport layer and the TCTA (4, 4. Comparative effect examples the organic electroluminescent device structure was [ ITO/NPB (400nm)/TCTA (5nm)/EML (25nm)/TPBI (40nm)/LiF (1nm)/Al (100nm) ], EML representing the light-emitting layer, and the results of the effect examples are shown in table 2
Figure BDA0002776351880000392
In an effect embodiment, basic performance indexes of the OLED device are characterized by a conventional method, including a turn-on voltage, a light emission peak position, a light emission maximum luminance, and a device efficiency (%).
Table 2 effects example data
Figure BDA0002776351880000393
Figure BDA0002776351880000401
Figure BDA0002776351880000411
Figure BDA0002776351880000421

Claims (4)

1. A phenanthroimidazole derivative-based organic light-emitting material has a structural formula as follows:
Figure FDA0002776351870000011
wherein R is1-R4The same or different, C1-C30 alkyl, C3-C10 cycloalkyl, C6-C48 aryl, C2-C30 heteroaryl with one or more atoms selected from O, N, Se and S, and C6-C40 arylamine.
2. The phenanthroimidazole derivative-based organic light-emitting material of claim 1, having a structural formula shown as one of the following:
Figure FDA0002776351870000012
Figure FDA0002776351870000021
Figure FDA0002776351870000031
Figure FDA0002776351870000041
Figure FDA0002776351870000051
Figure FDA0002776351870000061
Figure FDA0002776351870000071
Figure FDA0002776351870000081
Figure FDA0002776351870000091
Figure FDA0002776351870000101
Figure FDA0002776351870000111
Figure FDA0002776351870000121
Figure FDA0002776351870000131
Figure FDA0002776351870000141
Figure FDA0002776351870000151
Figure FDA0002776351870000161
Figure FDA0002776351870000171
3. an organic electroluminescent device comprising a cathode, a transparent anode and one or more organic compound layers interposed between the two electrodes, the organic compound layers comprising at least a hole transport layer, an electron blocking layer, a light emitting layer and an electron transport layer, characterized in that: the light-emitting layer is the phenanthroimidazole derivative-based organic light-emitting material according to claim 1 or 2.
4. The organic electroluminescent device as claimed in claim 3 is used for producing an organic electroluminescent display, an organic electroluminescent lighting source or a decorative lighting source.
CN202011266915.9A 2020-11-13 2020-11-13 Organic luminescent material based on phenanthroimidazole derivative and application of organic luminescent material in electroluminescent device Pending CN112266361A (en)

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