CN116082318B - Blue light luminescent auxiliary material, preparation method thereof and organic electroluminescent device - Google Patents
Blue light luminescent auxiliary material, preparation method thereof and organic electroluminescent device Download PDFInfo
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Abstract
The invention discloses a blue light luminescent auxiliary material, a preparation method thereof and an organic electroluminescent device, belonging to the technical field of organic electroluminescent materials, wherein the structural general formula of the blue light luminescent auxiliary material is shown in the specification, and Ar is selected from the group consisting of 1 ，Ar 2 Each independently selected from substituted or unsubstituted C6-C30 aryl or substituted or unsubstituted 3-to 30-membered heteroaryl, ar 1 ，Ar 2 Adjacent substituents cannot be linked to each other to form a ring, and the heteroatoms in the heteroaryl groups are each independently selected from any one of oxygen, nitrogen or sulfur. The invention provides a blue light luminescent auxiliary material containing aromatic amine of dibenzofuran, wherein the aromatic amine is connected at the 1 position of the dibenzofuran, and 9-phenyl-9H-carbazole is connected at the 3 position of the dibenzofuran. The organic electroluminescent device prepared from the blue light luminescent auxiliary material provided by the invention has excellent effect on the service life of the device, and simultaneously improves the luminous efficiency and the driving voltage.
Description
Technical Field
The invention belongs to the technical field of organic light-emitting materials, and particularly relates to a blue light-emitting auxiliary material, a preparation method thereof and an organic light-emitting device.
Background
Organic electroluminescence is a process in which an organic substance emits light under the action of an electric field, and its device is also called an Organic Light Emitting Diode (OLED). The research of OLED is started from the problem group Pope in 1963 to find the electroluminescent phenomenon of anthracene single crystal, and the multilayer structure organic electroluminescent fluorescent device is truly developed in the company Deng Qingyun of Izeman Kodak in 1987. To date, OLEDs have undergone many technological innovations, penetrating into various fields with advantages that are incomparable with conventional display and lighting technologies such as light weight, low energy consumption, high efficiency, softness, no glare, flexibility, and become a new star in the lighting and display fields.
The OLED presents multilayer as "sandwich type structural feature, specifically includes electrode material rete and presss from both sides the organic functional material between different electrode retes, includes: a Hole Injection Layer (HIL), a Hole Transport Layer (HTL), an emission layer (EML), an Electron Transport Layer (ETL), and an Electron Injection Layer (EIL). In the current research, in order to reduce the potential barrier between the HTL and the EML and reduce the driving voltage of the OLED, a light-emitting auxiliary layer is generally disposed between the HTL and the EML to increase the utilization rate of holes, thereby improving the light-emitting efficiency, stability and lifetime of the OLED.
In recent years, research on materials of light-emitting auxiliary layers has been carried out, but materials with excellent device performance have been found, so that there is still a great development space for research on OLED light-emitting auxiliary materials. Finding luminescent auxiliary materials that are developed to match current or future OLED technologies is a matter of urgent need for those skilled in the art.
Disclosure of Invention
In view of the above, the invention provides a blue light emitting auxiliary material, a preparation method thereof and an organic electroluminescent device.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
the structural general formula of the blue light luminescent auxiliary material is shown as formula I:
wherein Ar is 1 ，Ar 2 Each independently selected from a substituted or unsubstituted C6-C30 aryl group, or a substituted or unsubstituted 3-to 30-membered heteroaryl group, ar as described above 1 ，Ar 2 Adjacent substituents cannot be linked to each other to form a ring, and each heteroatom in the heteroaryl is independently selected from any one of oxygen, nitrogen, or sulfur.
Further, ar is as described above 1 ，Ar 2 Each independently selected from substituted or unsubstituted C6-C18 aryl, or substituted or unsubstituted 3-to 24-membered heteroaryl.
Further, ar is as described above 1 ，Ar 2 Each independently selected from phenyl, methylphenyl, m-dimethylphenyl, ethylphenyl, t-butylphenyl, biphenyl, terphenyl, naphthyl, phenylnaphthyl, naphthylphenyl, phenylterphenyl, fluorenyl, dimethylfluorenyl, diphenylfluorenyl, benzofluorenyl, dibenzofluorenyl, phenanthryl, phenylphenanthryl, indenyl, triphenylenyl, pyrenyl, perylenyl, chrysene -yl, naphthaceneyl, fluoranthryl, spirobifluorenyl, azulenyl, methoxyphenyl or cyanophenyl.
Further, ar is as described above 1 ，Ar 2 Each independently selected from the group consisting of furyl, thienyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, thiadiazolyl, isothiazolyl, isoxazolyl, oxazolyl, oxadiazolyl, triazinyl, tetrazinyl, triazolyl, tetrazolyl, furazanyl, pyridyl, bipyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, benzofuranyl, benzothienyl, isobenzofuranyl, dibenzofuranyl, dibenzothienyl, benzimidazolyl, benzothiazolyl, benzisothiazolyl, benzisoxazolyl, benzoxazolyl, isoindolyl, indolyl, benzindolyl, indazolyl, benzothiadiazolyl, quinolinyl, isoquinolinyl, cinnolinyl, quinazolinyl, benzoquinazolinyl, quinoxalinyl, benzoquinoxalinyl, naphthyridinyl, carbazolyl, benzocarbazolyl, phenoxazinyl, phenothiazinyl, phenanthridinyl, azabiphenyl, benzodioxolyl, or dihydroacridinyl.
Further, ar is as described above 1 ，Ar 2 Each independently selected from phenyl, naphthyl, anthracenyl, phenanthryl, methylphenyl, m-dimethylphenyl, ethylphenyl, t-butylphenyl, cyanophenyl, methoxyphenyl, phenylpyridyl, phenylpyrimidinyl, biphenyl, terphenyl, phenylnaphthyl, dibenzofuranyl, dibenzothienyl, carbazolyl, 9-phenyl-9H-carbazolyl, diphenylfluorenyl, dimethylfluorenyl or azabiphenyl;
the structural general formula I comprises a structure shown in a formula I-1-formula I-3:
。
in the above-mentioned technical scheme, the method comprises the steps of,
the substitution positions are defined as follows:
the term "substitution" means that a hydrogen atom bonded to a carbon atom of a compound becomes an additional substituent, and the position of substitution is not limited as long as the position is a position where the hydrogen atom is substituted, i.e., a position where the substituent can be substituted, and when two or more substituents are substituted, two or more substituents may be the same or different from each other.
The terms "substituted or unsubstituted C6-C30 aryl", "substituted or unsubstituted 3-to 30-membered heteroaryl", "substituted or unsubstituted C6-C18 aryl", "substituted or unsubstituted 3-to 24-membered heteroaryl", the number of carbon atoms in the aryl or heteroaryl representing the number of carbon atoms making up the unsubstituted aryl or the total number of heteroatoms and carbon atoms making up the heteroaryl, irrespective of the number of carbon atoms in the substituent.
The term "substituted or unsubstituted" means substituted with one, two or more substituents selected from the group consisting of: deuterium; halogen; a nitrile group; isocyano; a hydroxyl group; a mercapto group; a carbonyl group; a carboxylic acid group; an acyl group; an ester group; a silyl group; a boron base; C1-C30 alkyl; cycloalkyl of C3-C30; C1-C30 heteroalkyl; a C1-C30 arylalkyl group; an alkoxy group; aryl of C6-C30; heteroaryl groups of 3-to 30-membered, or substituted with a substituent to which two or more of the substituents shown above are attached, or not having a substituent.
Cycloalkyl means monocyclic, polycyclic or spiroalkyl;
aryl refers to a monocyclic aromatic hydrocarbon group or a polycyclic aromatic ring system, polycyclic having two or more rings in which two carbons are common to two adjoining rings (the rings described above being "fused");
heteroaryl groups include monocyclic aromatic groups or polycyclic aromatic ring systems of at least one heteroatom including, but not limited to O, S, N, P, B, si and Se.
Further, the blue light emitting auxiliary material is selected from any one of the compounds represented by the following structural formulas:
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the invention also provides a preparation method of the blue light luminescent auxiliary material, which comprises the following steps:
(1) Under the protection of nitrogen, sequentially adding reactants A-I, reactants B-I, potassium carbonate, tetra (triphenylphosphine) palladium, toluene, ethanol and water into a reaction container, heating and refluxing, cooling to room temperature, adding water, filtering after the solid is separated out, drying a filter cake, purifying the residual substances by using a column chromatography, removing the solvent from the filtrate by using a rotary evaporator, and drying the obtained solid to obtain an intermediate C-I;
(2) After intermediate C-I and reactant D-I are completely dissolved in xylene in a reaction vessel under the protection of nitrogen, sodium tert-butoxide, bis (tri-tert-butylphosphine) palladium and tri-tert-butylphosphine are added, the obtained product is heated and stirred, the obtained product is filtered by using kieselguhr while the obtained product is hot, after the obtained filtrate is cooled to room temperature, water is added into the obtained filtrate for washing, an organic phase is reserved after separation, and an aqueous phase is extracted by ethyl acetate; drying the combined organic layers with magnesium sulfate, and purifying the remaining material by column chromatography to obtain a compound of formula-I;
wherein R' isOr->。
Further, in the step (1), the molar ratio of the reactants A-I, B-I, potassium carbonate and tetrakis (triphenylphosphine) palladium is 1.0 (1.0-1.2): 2.0-2.3): 0.01-0.02.
Further, in the step (2), the molar ratio of the intermediate C-I, the reactant D-I, the sodium tert-butoxide, the bis (tri-tert-butylphosphine) palladium and the tri-tert-butylphosphine is 1.0 (1.1-1.3): (2.0-2.4): (0.01-0.05): (0.02-0.15).
In the step (1), the volume ratio of toluene, ethanol and water is (2-4): 1:1.
Further, in the step (1), the temperature is raised to 80-100 ℃ and the mixture is refluxed for 8-12 hours.
Further, in the step (2), the above is heated to 130-140℃and stirred for 8-12 hours.
The invention also provides an organic electroluminescent device, which comprises the blue light luminescent auxiliary material or the blue light luminescent auxiliary material prepared by the method.
The invention has the beneficial effects that: the invention provides a blue light luminescent auxiliary material containing aromatic amine of dibenzofuran, wherein the aromatic amine is connected at the 1 position of the dibenzofuran, and 9-phenyl-9H-carbazole is connected at the 3 position of the dibenzofuran. The organic electroluminescent device prepared from the blue light luminescent auxiliary material provided by the invention has excellent effect on the service life of the device, and simultaneously improves the luminous efficiency and the driving voltage.
The arylamine has better electron donating property and higher hole mobility, so the invention is applied to the light-emitting auxiliary layer; on the basis, the dibenzofuran with higher triplet state is combined to further achieve the performance of the blue light luminescent auxiliary material; meanwhile, 9-phenyl-9H-carbazolyl is introduced to the meta position of the same benzene ring of the aromatic amine group substituted dibenzofuran to twist the configuration, so that the defects of overlarge intermolecular acting force and poor fluidity caused by molecular aggregation are avoided, and the service life is prolonged.
Drawings
FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of intermediate C-29.
FIG. 2 is a nuclear magnetic resonance hydrogen spectrum of compound 29.
Description of the embodiments
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The invention carries out a series of palladium catalytic coupling reactions, on one hand, utilizes the difference that the activity of Br is larger than that of Cl, on the other hand, controls the reaction sites by controlling the reaction conditions, and uses column chromatography or silica gel funnel purification reaction to remove byproducts, thus obtaining the target compound. The following are referred to in the common general knowledge:
transition metal organic chemistry (original sixth edition), robert H-Crabtree (Robert H. Crabtree), press: publication time of Shanghai Shandong university Press: 2017-09-00, ISBN:978-7-5628-5111-0, page 388.
Organic chemistry and photoelectric Material Experimental Instructions, chen Runfeng, press: university of east south Press, publication time: 2019-11-00, ISBN:9787564184230, page 174.
Example 1: synthesis of Compound 29
Under the protection of nitrogen, the reaction is sequentially added into a round bottom flaskThe preparation method comprises the steps of (1) carrying out heating to 95 ℃ for 10 hours, cooling to room temperature, adding water, filtering after solid precipitation is finished, drying a filter cake, purifying the residual substances by using a column chromatography, removing a solvent from the filtrate by using a rotary evaporator, and drying the obtained solid to obtain an intermediate C-29, wherein the reaction product A-29 (50 mmol), the reaction product B-I (60 mmol), potassium carbonate (110 mmol), tetrakis (triphenylphosphine) palladium (0.5 mmol), 150mL toluene, 50mL ethanol and 50mL water are heated to the temperature of 95 ℃. (15.54 g, yield: 70%, test value MS (ESI, M/Z): [ M+H ]] + = 444.14）。
The nuclear magnetic resonance hydrogen spectrum of the intermediate C-29 is shown in figure 1;
after intermediate C-29 (40 mmol) and reactant D-29 (45 mmol) were completely dissolved in xylene (200 mL) in a round bottom flask under nitrogen, sodium tert-butoxide (80 mmol), bis (tri-tert-butylphosphine) palladium (0.4 mmol), tri-tert-butylphosphine (0.8 mmol) were added thereto, and then the resultant was heated to 135℃and stirred for 10 hours. Filtering with diatomaceous earth while hot, cooling the filtrate to room temperature, adding water into the filtrate, washing, separating to obtain organic phase, and extracting water phase with ethyl acetate; the combined organic layers were then dried over magnesium sulfate and the remaining material was purified by column chromatography to give compound 29. (22.16 g, yield: 76%, test value MS (ESI, M/Z): [ M+H ]] + = 729.18）。
The nuclear magnetic resonance hydrogen spectrum of compound 29 is shown in fig. 2;
characterization:
HPLC purity: > 99.8%.
Elemental analysis:
theoretical value: c, 88.98, H, 4.98, N, 3.84, O, 2.19
Test value: c, 88.88, H, 5.05, N, 3.86, O, 2.23
Example 2: synthesis of Compound 142
CAS: reactant D-142:1647103-35-2
Under nitrogen protection, in a round bottom flaskReactant A-142 (50 mmol), reactant B-I (60 mmol), potassium carbonate (110 mmol), tetrakis (triphenylphosphine) palladium (0.5 mmol), 150mL toluene, 50mL ethanol and 50mL water are added sequentially, the temperature is raised to 95 ℃, the mixture is refluxed for 10 hours, cooled to room temperature, water is added, after the solid is precipitated, the mixture is filtered, the filter cake is dried, the remaining material is purified by column chromatography, the solvent is removed from the filtrate by a rotary evaporator, and the obtained solid is dried to obtain intermediate C-142. (15.76 g, yield: 71%, test value MS (ESI, M/Z): [ M+H ]] + = 444.13）。
After intermediate C-142 (40 mmol) and reactant D-142 (45 mmol) were completely dissolved in xylene (200 mL) in a round bottom flask under nitrogen, sodium tert-butoxide (80 mmol), bis (tri-tert-butylphosphine) palladium (0.4 mmol), tri-tert-butylphosphine (0.8 mmol) were added thereto, and then the resultant was heated to 135℃and stirred for 10 hours. Filtering with diatomaceous earth while hot, cooling the filtrate to room temperature, adding water into the filtrate, washing, separating to obtain organic phase, and extracting water phase with ethyl acetate; the combined organic layers were then dried over magnesium sulfate and the remaining material was purified by column chromatography to give compound 142. (23.49 g, yield: 75%, test value MS (ESI, M/Z): [ M+H ]] + = 783.21）。
Characterization:
HPLC purity: > 99.8%.
Elemental analysis:
theoretical value: c, 87.44; H, 4.89; N, 3.58; O, 4.09
Test value: c, 87.38, H, 4.95, N, 3.59, O, 4.12
Example 3: synthesis of Compound 155
CAS reactant D-155:1613331-98-8
Under the protection of nitrogen, reactants A-155 (50 mmol), reactants B-I (60 mmol), potassium carbonate (110 mmol), tetrakis (triphenylphosphine) palladium (0.5 mmol) and 150m are added in sequence into a round bottom flaskL toluene, 50mL ethanol and 50mL water, heating to 95 ℃, refluxing for 10 hours, cooling to room temperature, adding water, filtering after the solid is separated out, drying a filter cake, purifying the residual substances by using a column chromatography, removing the solvent from the filtrate by using a rotary evaporator, and drying the obtained solid to obtain an intermediate C-155. (15.76 g, yield: 71%, test value MS (ESI, M/Z): [ M+H ]] + = 444.16）。
After intermediate C-155 (40 mmol) and reactant D-155 (45 mmol) were completely dissolved in xylene (200 mL) in a round bottom flask under nitrogen, sodium tert-butoxide (80 mmol), bis (tri-tert-butylphosphine) palladium (0.4 mmol), tri-tert-butylphosphine (0.8 mmol) were added thereto, and then the resultant was heated to 135℃and stirred for 10 hours. Filtering with diatomaceous earth while hot, cooling the filtrate to room temperature, adding water into the filtrate, washing, separating to obtain organic phase, and extracting water phase with ethyl acetate; the combined organic layers were then dried over magnesium sulfate and the remaining material was purified by column chromatography to give compound 155. (26.37 g, yield: 78%, test value MS (ESI, M/Z): [ M+H ]] + = 845.34）。
Characterization:
HPLC purity: > 99.8%.
Elemental analysis:
theoretical value: c, 89.54, H, 5.25, N, 3.32, O, 1.89
Test value: c, 89.44, H, 5.31, N, 3.35, O, 1.93
Examples 4 to 65
The synthesis of the following compounds, whose molecular formulas and mass spectra are shown in table 1 below, was accomplished with reference to the synthesis methods of examples 1 to 3.
Table 1 molecular formula and mass spectrum
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Further, since other compounds of the present invention can be obtained by referring to the synthetic methods of the above-described examples, they are not exemplified herein.
The invention provides an organic electroluminescent device, which specifically comprises a hole injection layer, a hole transport layer, an electron blocking layer, a light-emitting auxiliary layer, a light-emitting layer, a hole blocking layer, an electron transport layer, an electron injection layer, a capping layer and the like which are used as organic layers. In one embodiment, the organic light emitting element may be described as an "organic layer" disposed between the cathode and the anode, which may be achieved by combining the above layers, or some layers may be omitted or added entirely.
According to one embodiment of the present specification, the compound of formula I prepared according to the present invention is used as a light-emitting auxiliary layer material.
The anode is made of a conductor such as a metal, metal oxide, and/or conductive polymer that has a higher work function to aid in hole injection. The metal is selected from nickel, platinum, vanadium, chromium, copper, zinc, gold, silver or alloys thereof; the metal oxide is selected from zinc oxide, indium Tin Oxide (ITO) and indium zinc oxide; the combination of metal and oxide is ZnO and A1 or SnO 2 Sb or ITO and Ag; the conductive polymer is selected from poly (3-methylthiophene), poly (3, 4- (ethylene-1, 2-dioxy) thiophene), polypyrrole and polyaniline, but is not limited thereto.
The hole injection layer and the hole transport layer efficiently inject or transport holes from the anode between the electrodes to which an electric field has been applied, and preferably have high hole injection efficiency and efficiently transport the injected holes. Therefore, a substance having a small ionization potential, a large hole mobility, and excellent stability, and which is less likely to cause impurities that become traps during production and use, is selected. The hole injection layer is selected to be a p-doped hole injection layer; the hole transport material is selected from arylamine derivatives, conductive polymers, block copolymers having conjugated and non-conjugated portions at the same time, and the like.
A light-emitting auxiliary layer (multi-layer hole transporting layer) is interposed between the hole transporting layer and the light-emitting layer, and functions to smoothly move holes from the anode to the light-emitting layer and block electrons from the cathode.
The light-emitting layer is a compound that emits light by excitation by recombination of holes and electrons, and is selected to have a stable thin film shape and to exhibit high light-emitting efficiency in a solid state. The light emitting layer is a single layer or multiple layers and comprises a host material and a dopant material. The amounts of the host material and the dopant material to be used may be determined in accordance with the respective material characteristics. The doping method may be realized by co-evaporation with the host material, or may be formed by simultaneous evaporation after mixing with the host material.
The electron transport layer and the electron injection layer efficiently transport or inject electrons from the anode and cathode between the electrodes to which an electric field has been applied. An impurity substance which has high electron affinity, high electron mobility, excellent stability and is not liable to generate traps is selected.
The anode is a substance capable of injecting electrons with good efficiency, and the same material as that of the anode is selected. If a low work function metal is chosen that facilitates efficient electron injection, it is often necessary to dope trace amounts of lithium, cesium or magnesium to avoid its instability in the atmosphere.
There are no particular restrictions on other layer materials in an OLED device, except that the light-emitting auxiliary layer disclosed herein comprises formula I.
The organic electroluminescent composition and the organic electroluminescent device according to the present invention are described in detail below with reference to specific examples.
Application example 1 preparation of organic electroluminescent device:
a. ITO anode: washing ITO (indium tin oxide) -Ag-ITO (indium tin oxide) glass substrate with the coating thickness of 150nm in distilled water for 2 times, washing with ultrasonic waves for 30min, washing with distilled water for 2 times repeatedly, washing with ultrasonic waves for 10min, baking with a vacuum oven at 220 ℃ for 2 hours after washing, and cooling after baking is finished, so that the glass substrate can be used. The substrate is used as an anode, a vapor deposition device process is performed by using a vapor deposition machine, and other functional layers are sequentially vapor deposited on the substrate.
b. HIL (hole injection layer): vacuum evaporation of hole injection layer materials HT and P-dopant at an evaporation rate of 1 Å/s, wherein the ratio of the evaporation rates of HT and P-dopant is 97:3, the thickness is 10nm.
c. HTL (hole transport layer): HT of 120nm was vacuum deposited as a hole transport layer on top of the hole injection layer at a deposition rate of 1.5 Å/s.
d. Prime (light-emitting auxiliary layer): the compound 29 of the present invention was vacuum-deposited as a light-emitting auxiliary layer on top of the hole transport layer at a deposition rate of 0.5 Å/s at 10nm.
e. EML (light emitting layer): then, on the above light-emitting auxiliary layer, a Host material (Host) and a Dopant material (Dopant) having a thickness of 25nm were vacuum-evaporated as light-emitting layers at an evaporation rate of 1 Å/s, wherein the ratio of the evaporation rates of Host and Dopant was 97:3.
f. HB (hole blocking layer): a hole blocking layer having a thickness of 5.0nm was vacuum deposited at a deposition rate of 0.5. 0.5 Å/s.
g. ETL (electron transport layer): ET and Liq with a thickness of 35nm were vacuum-evaporated as electron transport layers at an evaporation rate of 1 Å/s. Wherein the evaporation rate ratio of ET to Liq is 50:50.
h. EIL (electron injection layer): an electron injection layer was formed by vapor deposition of 1.0nm on a Yb film layer at a vapor deposition rate of 0.5. 0.5 Å/s.
i. And (3) cathode: and evaporating magnesium and silver at 18nm at an evaporation rate ratio of 1 Å/s, wherein the evaporation rate ratio is 1:9, so as to obtain the OLED device.
j. Light extraction layer: CPL with a thickness of 70nm was vacuum deposited as a light extraction layer on the cathode at a deposition rate of 1 Å/s.
k. And packaging the substrate subjected to evaporation. Firstly, a gluing device is adopted to carry out a coating process on a cleaned cover plate by UV glue, then the coated cover plate is moved to a lamination working section, a substrate subjected to vapor deposition is placed at the upper end of the cover plate, and finally the substrate and the cover plate are bonded under the action of a bonding device, and meanwhile, the UV glue is cured by illumination.
The device structure is as follows:
ITO/Ag/ITO/HT P-dose (10 nm)/HT (120 nm)/prime (10 nm)/Host: dose (25 nm)/HB (5 nm)/ET: liq (35 nm)/Yb (1 nm)/Mg: ag (18 nm)/CPL (70 nm).
The structural formula of the compound in the device is as follows:
application examples 2 to 65
The organic electroluminescent devices of application examples 2 to 65 were prepared according to the above-described preparation method of the organic electroluminescent device, except that the compound 29 of application example 1 was replaced with the corresponding compound, respectively, to form a light-emitting auxiliary layer.
Comparative example 1
An organic electroluminescent device was prepared according to the above-described preparation method of an organic electroluminescent device, except that compound 29 in application example 1 was replaced with comparative compound 1, wherein the structural formula of comparative compound 1 is as follows:
comparative example 2
An organic electroluminescent device was prepared according to the above-described preparation method of an organic electroluminescent device, except that compound 29 in application example 1 was replaced with comparative compound 2, wherein the structural formula of comparative compound 2 is as follows:
comparative example 3
An organic electroluminescent device was prepared according to the above-described preparation method of an organic electroluminescent device, except that compound 29 in application example 1 was replaced with comparative compound 3, wherein the structural formula of comparative compound 3 is as follows:
comparative example 4
An organic electroluminescent device was prepared according to the above-described preparation method of an organic electroluminescent device, except that compound 29 in application example 1 was replaced with comparative compound 4, wherein the structural formula of comparative compound 4 is as follows:
comparative example 5
An organic electroluminescent device was prepared according to the above-described preparation method of an organic electroluminescent device, except that compound 29 in application example 1 was replaced with comparative compound 5, wherein the structural formula of comparative compound 5 is as follows:
comparative example 6
An organic electroluminescent device was prepared according to the above-described preparation method of an organic electroluminescent device, except that compound 29 in application example 1 was replaced with comparative compound 6, wherein the structural formula of comparative compound 6 is as follows:
the organic electroluminescent devices obtained in the above device examples 1 to 65 and device comparative examples 1 to 6 were characterized in terms of driving voltage, luminous efficiency, BI value and lifetime at a luminance of 1000 (nits), and the test results are shown in table 2 below:
TABLE 2 luminescence property test results (brightness value 1000 nits)
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Since the blue-light organic electroluminescent device is affected by microcavity effect, the luminous efficiency is greatly affected by chromaticity, so that a BI value is introduced as a basis for the efficiency of the blue-light luminescent material, bi=luminous efficiency/CIEy.
As can be seen from table 2, compared with the existing organic electroluminescent devices provided in comparative examples 1 to 6, the organic electroluminescent devices prepared by using the blue light emitting auxiliary material provided in the embodiments of the present invention have the technical effects of improving the driving voltage and lifetime while exhibiting an ultra-long device lifetime.
The compound 1 provided by the embodiment of the invention is similar to the comparative compound 1 and the comparative compound 2 in the mother nucleus, and the difference is that the substitution positions of the diphenylamino group and the 9-phenyl-9H-carbazolyl group on the dibenzofuran are different. The triplet energy of comparative compound 1 was found to be 2.82eV, and the triplet energy of comparative compound 1 and comparative compound 2 were found to be 2.77eV and 2.64eV, respectively, by structural optimization of compound 1, comparative compound 1 and comparative compound 2 at the calculated level of B3LYP/6-31G (d) using the Gaussian16 procedure and calculation of the excited states thereof. The change of the substitution position of the group makes the compound have higher triplet energy and contributes to the improvement of luminous efficiency, and it can be found from Table 2 that the luminous efficiency of the compound 1 is improved to 9.7cd/A compared with the luminous efficiencies of the comparative compound 1 and the comparative compound 2 of 8.7cd/A and 8.9cd/A, respectively. In addition, the lifetime of compound 1 (582 h) was significantly increased over that of comparative compound 1 (420 h) and comparative compound 2 (423 h).
Compared with the comparative compound 3, the compound 28 provided by the embodiment of the invention has the mother nucleus of dibenzofuran, and the substitution positions of the dianiline and the 9-phenyl-9H-carbazolyl on the mother nucleus are different, and the luminous efficiency of the compound 28 is improved by 0.7cd/A and the service life is prolonged by 125 hours as shown in the table 2; the difference between compound 28 and comparative compound 4 is that the substitution positions of the dianiline and 9-phenyl-9H-carbazolyl on the mother nucleus are different, and whether a bridged benzene ring exists between the dianiline and dibenzofuran, and it is known from Table 2 that the luminous efficiency of compound 28 is improved by 0.8cd/A, and meanwhile, the direct connection of the dianiline and the dibenzofuran increases the configuration torsion of the compound, so that the intermolecular interaction is reduced, and the service life is prolonged by 120H.
The comparative structures of the compound 89 and the comparative compound 5 and the compound 341 and the comparative compound 6 provided in the examples of the present invention show that the difference is that the substitution positions of the arylamine group and the 9-phenyl-9H-carbazolyl group on the dibenzofuran are different, and the luminous efficiencies of the compounds 89 and 341 of the present invention are improved by 0.2cd/A and 0.6cd/A compared with the comparative compound 5 and the comparative compound 6, respectively, as shown in Table II. Further comparison shows that the substitution of the arylamine group and the 9-phenyl-9H-carbazolyl group in the dibenzofuran 1 and 3 positions increases the torsion relative to the substitution of the 1,4 positions of the comparison compound, and avoids the excessive intermolecular action, so that the service life of the compound 89 is prolonged by 174H compared with the service life of the comparison compound 5, and the service life of the compound 341 is prolonged by 114H compared with the service life of the comparison compound 6.
In conclusion, the blue light luminescent auxiliary material provided by the invention has the advantages that the proper substitution positions of the aromatic amine group and the 9-phenyl-9H-carbazole on the dibenzofuran are selected, so that the prepared organic electroluminescent device has excellent effect on the aspect of service life of the device, and meanwhile, the luminous efficiency and the driving voltage are improved. It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. While still being apparent from variations or modifications that may be made by those skilled in the art are within the scope of the invention.
Claims (7)
1. The blue light luminescent auxiliary material is characterized by having a structural general formula shown in formula I:
wherein the Ar is 1 ，Ar 2 Each independently selected from phenyl, methylphenyl, m-dimethylphenyl, ethylphenyl, t-butylphenyl, biphenyl, terphenyl, naphthyl, phenylnaphthyl, naphthylphenyl, phenylterphenyl, fluorenyl, dimethylfluorenyl, diphenylFluorenyl, benzofluorenyl, dibenzofluorenyl, phenanthryl, phenylphenanthryl, anthracenyl, indenyl, triphenylenyl, pyrenyl, perylenyl,A group, naphthacene group, fluoranthenyl group, spirobifluorenyl group, azulenyl group, methoxyphenyl group, cyanophenyl group, furyl group, thienyl group, pyrrolyl group, imidazolyl group, pyrazolyl group, thiazolyl group, thiadiazolyl group, isothiazolyl group, isoxazolyl group, oxazolyl group, oxadiazolyl group, pyridyl group, bipyridyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl group, benzofuryl group, benzothienyl group, isobenzofuranyl group, dibenzofuranyl group, dibenzothienyl group, benzimidazolyl group, benzothiazolyl group, benzisothiazolyl group, benzisoxazolyl group, benzoxazolyl group, isoindolyl group, indolyl group, benzindolyl group, indazolyl group, benzothiadiazolyl group, quinolinyl group, isoquinolinyl group, quinazolinyl group, quinoxalinyl group, benzoquinoxalinyl group, naphthyridinyl group, carbazolyl group, benzocarbazolyl group, dibenzocarbazolyl group, phenoxazinyl group, phenothiazinyl group, phenanthridinyl group, or azabiphenyl group.
2. A blue light emitting auxiliary material according to claim 1, wherein said Ar 1 ，Ar 2 Each independently selected from phenyl, naphthyl, anthracenyl, phenanthryl, methylphenyl, m-dimethylphenyl, ethylphenyl, t-butylphenyl, cyanophenyl, methoxyphenyl, phenylpyridyl, phenylpyrimidinyl, biphenyl, terphenyl, phenylnaphthyl, dibenzofuranyl, dibenzothienyl, carbazolyl, 9-phenyl-9H-carbazolyl, diphenylfluorenyl, dimethylfluorenyl or azabiphenyl;
the structural general formula I comprises a structure shown in a formula I-1-formula I-3:
3. the blue light emitting auxiliary material is characterized by being selected from any one of the compounds shown in the following structural formulas:
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4. a method for preparing the blue light emitting auxiliary material according to claim 1, comprising the steps of:
(1) Under the protection of nitrogen, sequentially adding reactants A-I, reactants B-I, potassium carbonate, tetra (triphenylphosphine) palladium, toluene, ethanol and water into a reaction container, heating and refluxing, cooling to room temperature, adding water, filtering after the solid is separated out, drying a filter cake, purifying the residual substances by using a column chromatography, removing the solvent from the filtrate by using a rotary evaporator, and drying the obtained solid to obtain an intermediate C-I;
(2) After intermediate C-I and reactant D-I are completely dissolved in xylene in a reaction vessel under the protection of nitrogen, sodium tert-butoxide, bis (tri-tert-butylphosphine) palladium and tri-tert-butylphosphine are added, the obtained product is heated and stirred, the obtained product is filtered by using kieselguhr while the obtained product is hot, after the obtained filtrate is cooled to room temperature, water is added into the obtained filtrate for washing, an organic phase is reserved after separation, and an aqueous phase is extracted by ethyl acetate; drying the combined organic layers with magnesium sulfate, and purifying the remaining material by column chromatography to obtain a compound of formula-I;
the synthetic route is as follows:
wherein R' is
Ar 1 ，Ar 2 The radicals being as claimed in claim 1.
5. The method of preparing a blue light emitting phosphor according to claim 4, wherein in the step (1), the molar ratio of the reactant A-I, the reactant B-I, the potassium carbonate and the tetrakis (triphenylphosphine) palladium is 1.0 (1.0-1.2): 2.0-2.3): 0.01-0.02.
6. The method for preparing a blue light emitting auxiliary material according to claim 4, wherein in the step (2), the molar ratio of the intermediate C-I, the reactant D-I, the sodium tert-butoxide, the bis (tri-tert-butylphosphine) palladium and the tri-tert-butylphosphine is 1.0 (1.1-1.3): (2.0-2.4): (0.01-0.05): (0.02-0.15).
7. An organic electroluminescent device comprising the blue light emitting auxiliary material according to any one of claims 1 to 3 or the blue light emitting auxiliary material prepared by the method according to any one of claims 4 to 6.
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