CN114634494B - Dicyanopyrazine compound, preparation method and application thereof, organic electroluminescent device and application thereof - Google Patents
Dicyanopyrazine compound, preparation method and application thereof, organic electroluminescent device and application thereof Download PDFInfo
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Abstract
The invention provides a dicyanopyrazine compound, a preparation method and application thereof, an organic electroluminescent device and application thereof, and relates to the technical field of organic electroluminescent materials. According to the invention, electronegative functional groups (diphenylamine) are introduced as electron donor groups and thiophene (pi bridge) are used for carrying out chemical modification on the 5-position and 8-position of dicyanopyrazine, the electron donating ability of substituent groups and the connection of pi bridge can influence the intramolecular charge transfer effect and the spatial distribution of molecular front line orbitals, the adjustment of the front line molecular orbital energy level of molecules is realized, the adjustment of the luminescent color of dicyanopyrazine compounds in a red light area is further realized, the luminescent material with the luminescent wavelength of near infrared emission is obtained, and the near infrared emission of dicyanopyrazine compounds is realized. The dicyanopyrazine compound provided by the invention can emit red light, has high luminous efficiency and has good application prospect in organic electroluminescent devices.
Description
Technical Field
The invention relates to the technical field of organic electroluminescent materials, in particular to dicyanopyrazine compounds, a preparation method and application thereof, an organic electroluminescent device and application thereof.
Background
Near infrared organic light emitting diodes (NIR-OLEDs) have been widely studied in recent years due to their special applications in night vision displays, chemical sensing and medical diagnostics. Organic NIR-OLEDs materials mainly include transition metal complexes, organic dyes, low band gap polymers, and organic donor-acceptor (D-A) small molecules. Although near infrared phosphorescent OLEDs have been reported to reach the highest External Quantum Efficiency (EQE) of about 24%, instability and severe efficiency roll-off also exist at high current densities due to their long-lived triplet exciton quenching effect. Therefore, in view of the characteristics of chemical modification, easy synthesis, low cost, etc. of organic materials, it is necessary to develop metal-free organic materials.
To achieve near infrared emission, two molecular design strategies are typically employed to reduce the optical bandgap. One is to obtain a more red-shifted chromophore by extending pi-conjugation, but the red shift is limited, which is problematic in multi-step synthesis, purification and device fabrication. The second approach is to construct near infrared chromophores with D-a structures. This is a very promising class of materials for near infrared OLED applications because their bandgap levels can be easily adjusted according to the emission state of the CT features, bipolar charge transport, and the ability to fabricate devices by vacuum evaporation.
But D-a materials face further development problems. First, the overlap between the highest unoccupied molecular orbital (HOMO) and the Lowest Unoccupied Molecular Orbital (LUMO) in the D-a chromophore is typically very limited, inevitably resulting in a lower radiation transition rate, ultimately resulting in lower luminous efficiency, and even no emission at all. Second, near infrared luminescent materials also face the inherent limitations of the energy gap law. Furthermore, when D-a molecules are used to fabricate near infrared electroluminescent devices, the non-radiative transition rate further increases due to the stacking and dipole interactions of the solid state, resulting in reduced light emission performance of near infrared emitting OLEDs. Therefore, decreasing the non-radiative transition or increasing the radiative transition rate has become an important direction for improving near infrared luminescent materials.
To solve the above problems, the near infrared material design should be based on the following molecular design principles: (1) Selecting a suitable donor-acceptor group combination to obtain an electronic structure of the separated HOMO and LUMO, and enabling the molecule to have a CT state to achieve near infrared emission; (2) Selecting proper electron donor acceptor group connecting group, balancing the space separation and overlapping degree of HOMO and LUMO, and improving radiation transition rate; (3) The molecules with rigid structures are selected, so that the non-radiative transition can be restrained with large steric hindrance, and the fluorescence emission efficiency is improved.
The N-substituted aromatic heterocyclic compound with a condensed ring structure is used as a good electron acceptor group, has a rigid plane structure, can be connected with different donors and pi bridge groups through Suzuki reaction and Ullman reaction, and is widely applied to acceptor-type organic near infrared emission materials. The material has the advantages of simple synthesis, good thermal stability and the like, but still has the problem of low luminous efficiency.
Disclosure of Invention
The invention aims to provide a dicyanopyrazine compound, a preparation method and application thereof, an organic electroluminescent device and application thereof.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a dicyanopyrazine compound, which has a structure shown in a formula I:
the invention provides a preparation method of dicyanopyrazine compounds, which comprises the following steps:
mixing halogenated dicyanopyrazine, a compound II, a palladium catalyst, an alkaline reagent and a mixed solvent in a protective atmosphere, and performing a coupling reaction to obtain dicyanopyrazine compounds with a structure shown in a formula I; the mixed solvent comprises an organic solvent and water;
the structural formula of the halogenated dicyanopyrazine isWherein X is chlorine, bromine or iodine;
the structural formula of the compound II is
Preferably, the preparation method of the halogenated dicyanopyrazine comprises the following steps:
mixing diiminosuccinonitrile, halogenated diaminobenzene and trifluoroacetic acid, and performing cyclization reaction to obtain halogenated dicyanopyrazine;
the structural formula of the halogenated diaminobenzene isIn the structural formula, X is chlorine, bromine or iodine.
Preferably, the molar ratio of halogenated dicyanopyrazine to compound II is 1:2 to 3.
Preferably, the molar ratio of the halogenated dicyanopyrazine to the alkaline agent is 1:4 to 10.
Preferably, the temperature of the coupling reaction is 60-70 ℃, and the heat preservation time is 20-24 h.
The invention provides an application of the dicyanopyrazine compound prepared by the technical scheme or the preparation method of the dicyanopyrazine compound in an organic electroluminescent device.
The invention provides an organic electroluminescent device, which comprises a luminescent layer, an electrode layer and a functional layer, wherein the luminescent layer is prepared from the dicyanopyrazine compound prepared by the technical scheme or the dicyanopyrazine compound prepared by the preparation method.
Preferably, the functional layer includes one or more of a hole transport layer, a hole blocking layer, an electron transport layer, and an electron injection layer.
The invention provides application of the organic electroluminescent device in an illumination light source, a signal lamp, a sign board or a flat panel display.
The invention provides a dicyanopyrazine compound, which is prepared by introducing electronegative functional groups (diphenylamino) as electron donor groups and thiophene (pi bridge) to chemically modify 5-position and 8-position of dicyanopyrazine, wherein electron donating capacity of substituent and connection of pi bridge can influence intramolecular charge transfer effect and spatial distribution of molecular front line orbitals, so that adjustment of molecular front line molecular orbital energy level is realized, further, adjustment of luminescent color of dicyanopyrazine compound in red light region is realized, luminescent material with luminescent wavelength of near infrared emission is obtained, and near infrared emission of dicyanopyrazine compound is realized. The dicyanopyrazine compound provided by the invention can emit red light, has high luminous efficiency and has good application prospect in organic electroluminescent devices. The test results of the examples show that the dicyanopyrazine compound provided by the invention has the advantages of near infrared emission of light emitting wavelength, high fluorescence quantum yield, simple preparation method operation, high product yield, low price of preparation raw materials, low production cost and suitability for industrial production.
Drawings
Fig. 1 is a spectrum of an organic electroluminescent device prepared in application example 1.
Detailed Description
The invention provides a dicyanopyrazine compound, which has a structure shown in a formula I:
the dicyanopyrazine compound provided by the invention has a larger rigid planar skeleton, good thermal stability and higher fluorescence quantum yield, can realize near infrared light emission, and is used for preparing a near infrared electroluminescent device.
The invention provides a preparation method of dicyanopyrazine compounds, which comprises the following steps:
mixing halogenated dicyanopyrazine, a compound II, a palladium catalyst, an alkaline reagent and a mixed solvent in a protective atmosphere, and performing a coupling reaction to obtain dicyanopyrazine compounds with a structure shown in a formula I; the mixed solvent comprises an organic solvent and water;
the structural formula of the halogenated dicyanopyrazine isWherein X is chlorine, bromine or iodine;
the structural formula of the compound II is
In the present invention, all raw material components are commercially available products well known to those skilled in the art unless specified otherwise.
The preparation method provided by the invention is simple, high in yield and easy to purify.
In the present invention, the preparation method of halogenated dicyanopyrazine preferably comprises the following steps:
mixing diiminosuccinonitrile, halogenated diaminobenzene and trifluoroacetic acid, and performing cyclization reaction to obtain halogenated dicyanopyrazine;
the structural formula of the halogenated diaminobenzene isIn the structural formula, X is chlorine, bromine or iodine.
In the present invention, the diiminosuccinonitrile is preferably obtained by commercial or homemade products well known to those skilled in the art. In the present invention, the method for producing diiminosuccinonitrile preferably comprises the steps of: diaminomaleonitrile, 2, 3-dichloro-5, 6-dicyano-1, 4-benzoquinone and an organic solvent are mixed and subjected to elimination reaction to obtain diiminosuccinonitrile. In the present invention, the molar ratio of diaminomaleonitrile to 2, 3-dichloro-5, 6-dicyano-1, 4-benzoquinone is preferably 1:1 to 1.5, more preferably 1:1.2 to 1.4. In the present invention, the organic solvent preferably includes acetonitrile; the amount of the organic solvent used in the present invention is not particularly limited, and the elimination reaction can be smoothly performed. The mixing mode is not particularly limited, and the raw materials can be uniformly mixed, such as stirring and mixing; the order of mixing is preferably: the diaminomaleonitrile is dissolved in an organic solvent and then 2, 3-dichloro-5, 6-dicyano-1, 4-benzoquinone is added to mix. In the present invention, the temperature of the elimination reaction is preferably 18 to 40 ℃, more preferably room temperature; the time for the elimination reaction is preferably 30 to 70 minutes, more preferably 45 to 55 minutes; the reaction occurring during the elimination reaction is represented by formula (1):
after the elimination reaction, the present invention preferably further includes a post-treatment, which preferably includes: and (3) carrying out solid-liquid separation on the reaction liquid obtained by the elimination reaction, concentrating the obtained liquid product, and drying to obtain the diiminosuccinonitrile. The solid-liquid separation is not particularly limited, and may be carried out by a solid-liquid separation method known to those skilled in the art, such as filtration. The concentration method is not particularly limited, and any concentration method known to those skilled in the art may be used. The temperature and time of the drying are not particularly limited in the present invention, and the drying temperature well known to those skilled in the art may be used to dry the material to a constant weight.
After the diiminosuccinonitrile is obtained, the present invention preferably mixes the diiminosuccinonitrile, halogenated diaminobenzene and trifluoroacetic acid, and carries out cyclization reaction to obtain halogenated dicyanopyrazine.
In the present invention, the molar ratio of the diiminosuccinonitrile to the halogenated diaminobenzene is preferably 1 to 1.5:1, more preferably 1.1 to 1.4:1, more preferably 1.2 to 1.3:1. in the present invention, the ratio of the amount of the diiminosuccinonitrile substance to the volume of trifluoroacetic acid (TFA) is preferably 0.2 to 0.5mol:1L, more preferably 0.25 to 0.4mol:1L, more preferably 0.3 to 0.35mol:1L. The mixing mode is not particularly limited, and a mixing mode well known to those skilled in the art, such as stirring and mixing, can be adopted; the order of mixing is preferably: mixing diiminosuccinonitrile and halogenated diaminobenzene, and adding the mixture into trifluoroacetic acid in batches for mixing; the batch added in portions is preferably 2 to 3 times. In the present invention, the temperature of the cyclization reaction is preferably 10 to 40 ℃, more preferably room temperature; the cyclization reaction time is preferably 4 to 25 hours, more preferably 5 to 15 hours, and even more preferably 8 hours; the reaction occurring during the cyclization reaction is represented by formula (2):
after the cyclization reaction, the present invention preferably further includes a post-treatment comprising: adding ice water into the reaction liquid obtained by the cyclization reaction, carrying out solid-liquid separation, washing the obtained solid product with water, and purifying to obtain the halogenated dicyanopyrazine. The invention is not particularly limited to the addition amount of the ice water until the water phase is neutral. The solid-liquid separation is not particularly limited, and may be carried out by a solid-liquid separation method known to those skilled in the art, such as filtration. The concentration method is not particularly limited, and any concentration method known to those skilled in the art may be used. In the present invention, the purification is preferably silica gel column chromatography purification, and the eluent for silica gel column chromatography purification preferably comprises a mixed solvent of a large polar solvent and a small polar solvent; the large polar solvent preferably comprises one or more of dichloromethane, ethyl acetate and acetone; the small polar solvent preferably comprises one or more of petroleum ether, diethyl ether and n-hexane; the volume ratio of the large polar solvent to the small polar solvent in the mixed solvent is preferably 1:1.5 to 3, more preferably 1:2 to 2.5.
After the halogenated dicyanopyrazine is obtained, the halogenated dicyanopyrazine, the compound II, the palladium catalyst, the alkaline reagent and the mixed solvent are mixed in the protective atmosphere to carry out coupling reaction, so as to obtain the dicyanopyrazine compound with the structure shown in the formula I. In the present invention, the protective atmosphere is preferably a nitrogen atmosphere. In the present invention, the mixed solvent includes an organic solvent and water, more preferably tetrahydrofuran and water. In the present invention, the volume ratio of the organic solvent to water is preferably 40:7 to 8.
In the present invention, the molar ratio of the halogenated dicyanopyrazine to compound II is preferably 1:2 to 3, more preferably 1:2.5; the molar ratio of the halogenated dicyanopyrazine to the alkaline agent is preferably 1:4 to 10, more preferably 1:5 to 8. In the present invention, the alkaline agent preferably includes potassium carbonate or cesium carbonate. In the present invention, the molar ratio of the halogenated dicyanopyrazine to palladium catalyst is preferably 2 to 4:0.1, more preferably 3:0.1. In the present invention, the palladium catalyst is preferably tetrakis (triphenylphosphine) palladium.
In the present invention, the temperature of the coupling reaction is preferably 60 to 90 ℃, more preferably 70 to 80 ℃; the heat preservation time is preferably 12-24 hours. In the present invention, the coupling reaction is preferably carried out under oil bath conditions.
After the coupling reaction, the present invention preferably further includes a post-treatment comprising: pouring the reaction liquid obtained by the coupling reaction into water, extracting with dichloromethane, concentrating the obtained organic phase, and purifying to obtain the dicyanopyrazine compound with the structure shown in the formula I. In the present invention, the purification is preferably silica gel column chromatography purification, and the eluent for silica gel column chromatography purification preferably comprises a mixed solvent of a large polar solvent and a small polar solvent; the large polar solvent preferably comprises one or more of dichloromethane, ethyl acetate and acetone; the small polar solvent preferably comprises one or more of petroleum ether, diethyl ether and n-hexane; the volume ratio of the large polar solvent to the small polar solvent in the mixed solvent is preferably 1:1.
in a specific embodiment of the present invention, the preparation process of the dicyanopyrazine compound is as follows:
in the invention, the yield of the dicyanopyrazine compound is preferably 60-80%; the purity is preferably >99%.
The invention also provides an application of the dicyanopyrazine compound prepared by the technical scheme or the preparation method of the dicyanopyrazine compound in an organic electroluminescent device. In the present invention, the organic electroluminescent device is preferably a near infrared electroluminescent device.
In the invention, the dicyanopyrazine compound is preferably used as an undoped luminescent layer material of a near infrared electroluminescent device; the dicyanopyrazine compound is preferably used as a guest doping material of a doped light-emitting layer of a near-infrared light electroluminescent device.
The invention provides an organic electroluminescent device, which comprises a luminescent layer, an electrode layer and a functional layer, wherein the luminescent layer is prepared from the dicyanopyrazine compound prepared by the technical scheme or the dicyanopyrazine compound prepared by the preparation method.
In the present invention, the raw materials for preparing the light-emitting layer preferably further include a host material; the host material preferably comprises a small molecule host material and/or a high molecule host material; the small molecule host material preferably comprises one or more of 4,4'-N, N' -dicarbazole biphenyl (CBP), 2- (4-diphenyl) -5- (4-tert-butylphenyl) -1,3, 4-oxadiazole (PBD), 1,3, 5-tris (2-N-phenylbenzimidazolyl) benzene (TPBI) and 3- (4-diphenyl) -5- (4-tert-butylphenyl) -4- (4-ethylphenyl) -,1,2, 4-Triazole (TAZ); the polymer main body material preferably comprises one or more of polystyrene, polyphenylene, polyvinylcarbazole, polycarbazole, polyfluorene and polyfluorene derivatives; the mass ratio of the dicyanopyrazine compound to the main material is preferably 1-25: 100, more preferably 5 to 15:100, more preferably 8 to 12:100. in the invention, the number of the light-emitting layers is preferably not less than 1, more preferably 1; the thickness of each light-emitting layer is independently preferably 15 to 45nm, more preferably 20 to 30nm, and further preferably 25nm.
In the present invention, the electrode layer preferably includes an anode layer and a cathode layer; the anode layer preferably comprises an anode transparent conductive film shielding glass (ITO) layer; the thickness of the anode layer is preferably 20 to 50nm, more preferably 30 to 40nm; the cathode layer preferably comprises an aluminum layer; the thickness of the cathode layer is preferably 150 to 200nm, more preferably 180nm.
In the present invention, the functional layer preferably includes one or more layers of a hole transporting layer, a hole blocking layer, an electron transporting layer, and an electron injecting layer, more preferably a hole transporting layer, a hole blocking layer, an electron transporting layer, and an electron injecting layer, or a hole transporting layer and an electron injecting layer. In the present invention, the hole transport layer is preferably disposed between the anode layer and the light emitting layer; the hole blocking layer is preferably arranged between the hole transport layer and the light emitting layer; the electron transport layer and the electron injection layer are preferably disposed between the light emitting layer and the cathode layer.
In the present invention, the hole transport layer is preferably prepared from at least one of N, N '-bis (1-naphthyl) -N, N' -diphenyl-1, 1-biphenyl-4, 4 '-diamine (NPB), poly 3, 4-ethylenedioxythiophene/polystyrene sulfonate (PEDOT/PSS), 4, -tris (carbazol-9-yl) triphenylamine, 4' -cyclohexylbis [ N, N-bis (4-methylphenyl) aniline ] and 2- (4-diphenyl) -5- (4-t-butylphenyl) -1,3, 4-oxadiazole; the thickness of the hole transport layer is preferably 20 to 50nm, more preferably 30nm. In the present invention, the hole blocking layer is preferably prepared from at least one of 4,4',4 "-tris (9-carbazolyl) triphenylamine (TCTA) and 1,3, 5-tris (1-phenyl-1H-benzimidazol-2-yl) benzene; the thickness of the hole blocking layer is preferably 5 to 20nm, more preferably 10 to 15nm. In the present invention, the electron transport layer is preferably prepared from at least one of m-tris (phenylbenzimidazole) benzene (TPBI), 4, 7-diphenyl-1, 10-phenanthroline, and 3- (4-diphenyl) -5- (4-t-butylphenyl) -4- (4-ethylphenyl) -,1,2, 4-triazole; the thickness of the electron transport layer is preferably 20 to 50nm, more preferably 30 to 40nm. In the present invention, the electron injection layer is preferably prepared from a raw material comprising LiF; the thickness of the electron injection layer is preferably 5 to 10nm, more preferably 6nm.
In the present invention, the organic electroluminescent device is preferably an anode layer, a hole transport layer, a hole blocking layer, a light emitting layer, an electron transport layer, an electron injection layer, and a cathode layer, which are sequentially stacked, or an anode layer, a hole transport layer, a light emitting layer, an electron injection layer, and a cathode layer, which are sequentially stacked.
The invention also provides a preparation method of the organic electroluminescent device, which preferably comprises the following steps:
sequentially preparing a hole transport layer, a hole blocking layer, a light emitting layer, an electron transport layer, an electron injection layer and a cathode layer on the surface of the anode layer to obtain an organic electroluminescent device; alternatively, a hole transport layer, a light emitting layer, an electron injection layer, and a cathode layer are sequentially prepared on the surface of the anode layer.
In the present invention, the preparation method is preferably evaporation or solution coating; the electron injection layer and the cathode layer are preferably prepared by vapor deposition. In the present invention, the vapor deposition is preferably vacuum vapor deposition, and the vacuum degree of the vacuum vapor deposition is preferably 0.8X10 -5 ～1.5×10 -5 Torr, more preferably 1.2X10 -5 ～1.4×10 -5 Torr. In the present invention, the solution is coatedThe use solution preferably includes a light-emitting layer-producing raw material solution and a functional layer-producing raw material solution. In the present invention, the solvent in the light-emitting layer preparation raw material solution preferably includes one or more of toluene, xylene, and chlorobenzene; the concentration of the light-emitting layer-producing raw material solution is preferably 0.4 to 1.8g/L, more preferably 0.8 to 1.5g/L, and still more preferably 1 to 1.2g/L. In the present invention, the solvent in the functional layer preparation raw material solution preferably includes water; the solid content of the functional layer preparation raw material solution is preferably 5 to 6wt%, more preferably 5.3 to 5.7wt%, and still more preferably 5.4 to 5.6wt%.
The invention also provides application of the organic electroluminescent device in an illumination light source, a signal lamp, a sign board or a flat panel display.
The technical solutions of the present invention will be clearly and completely described in the following in connection with the embodiments of the present invention. It will be apparent that the described embodiments are only some, but not all, embodiments of the invention. 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.
Example 1
(1) Synthesis of diiminosuccinonitrile
50mL of acetonitrile is added into 10mmol of diaminomaleonitrile, after stirring and dissolving, 10 mmole of 2, 3-dichloro-5, 6-dicyano-1, 4-benzoquinone is added, after stirring for 15min at room temperature, filtration is carried out, and the obtained liquid product is concentrated and dried to constant weight, thus obtaining diiminosuccinonitrile; the resulting diiminosuccinonitrile was a brown solid, 1.01g, yield 95%.
(2) Synthesis of the Compound 5, 8-dibromo [3,4-b ] -2, 3-dicyanopyrazine (5, 8-DBrPhPD)
3.6mmol of diiminosuccinonitrile and 3mmol of 3, 6-dibromo-1, 2-phenylenediamine are mixed and added into 12mL of trifluoroacetic acid in 3 batches, the mixture is stirred for 8h at room temperature to carry out cyclization reaction, the obtained reaction solution is poured into ice water, filtration is carried out, the obtained solid product is washed with water and then purified by silica gel column chromatography (the eluent is petroleum ether/dichloromethane volume ratio=1.5/1), and 5, 8-dibromo [3,4-b ] is obtained]-2, 3-dicyanopyrazine (5, 8-DBrPhPD); the resulting 5,8-DBrPhPD was a pale yellow powder, 2.11g, 76% yield. Structural characterization data: 1 H NMR(400MHz,CDCl 3 ) Delta 7.61 (s, 2H); the mass spectrum analysis determines the molecular ion mass as follows: 337.95 (calculated: 337.96); theoretical element content (wt%) C 10 H 2 Br 2 N 4 : c35.54, H0.60, N16.58, br47.29; measured elemental content (wt%): c35.17, H0.62, N16.52, br47.69.
3mmol of prepared 5,8-DBrPhPD, 6.6mmol of compound II, 15mmol of potassium carbonate, 0.1mmol of tetra (triphenylphosphine) palladium, 40mL of tetrahydrofuran and 7.5mL of water are added into a three-mouth bottle to react for 12h under the conditions of nitrogen protection, oil bath and 70 ℃, the obtained reaction liquid product is poured into distilled water, dichloromethane is used for extraction, and the obtained organic phase is concentrated and then purified by silica gel column chromatography (the volume ratio of petroleum ether to dichloromethane is=1/1) to obtain dicyanopyrazine compounds with the structure shown in the formula I; the dicyanopyrazine compound was obtained as a red powder, 1.50g, 75% yield.
Structural characterization data: 1 H NMR(400MHz,DMSO-d 6 ) δ8.08 (s, 2H), 7.24 (td, j=7.2 hz, 8H), 7.00-7.08 (m, 12H), 6.85 (d, j=8.4 hz, 2H), 6.15 (d, j=8.2 hz 2H), 7.02-6.98 (m, 8H); the mass spectrum analysis determines the molecular ion mass as follows: 678.25 (calculated: 678.83); theoretical element content (wt%) C 42 H 26 N 6 S 2 : c74.31, H3.86, N12.38, S9.45; measured elemental content (wt%): c74.81, H3.62, N12.27, S9.30.
The dicyanopyrazine compound prepared in the embodiment emits near infrared light, the light emitting wavelength is 730nm, and the fluorescence quantum yield is 7.2%.
In this embodiment, the preparation process of the dicyanopyrazine compound is as follows:
example 2
(1) Synthesis of diiminosuccinonitrile
50mL of acetonitrile is added into 10mmol of diaminomaleonitrile, after stirring and dissolving, 10 mmole of 2, 3-dichloro-5, 6-dicyano-1, 4-benzoquinone is added, after stirring for 15min at room temperature, filtration is carried out, and the obtained liquid product is concentrated and dried to constant weight, thus obtaining diiminosuccinonitrile; the resulting diiminosuccinonitrile was a brown solid, 1.01g, yield 95%.
(2) Synthesis of the Compound 5, 8-dichloro [3,4-b ] -2, 3-dicyanopyrazine (5, 8-DClPhPD)
3.8mmol of diiminosuccinonitrile and 3mmol of 3, 6-dichloro-1, 2-phenylenediamine are mixed and added into 15mL of trifluoroacetic acid in 3 batches, the mixture is stirred for 7h at room temperature to carry out cyclization reaction, the obtained reaction solution is poured into ice water, filtration is carried out, the obtained solid product is washed with water and then purified by silica gel column chromatography (the eluent is petroleum ether/dichloromethane volume ratio=1.5/1), and 5, 8-dichloro [3,4-b ] is obtained]-2, 3-dicyanopyrazine (5, 8-dclphd); the obtained 5,8-DClPhPD was pale yellow powder, 0.53g, and the yield was 71%. Structural characterization data: 1 HNMR(400MHz,CDCl 3 ) Delta 7.55 (s, 2H); the mass spectrum analysis determines the molecular ion mass as follows: 247.90 (calculated: 247.97); theoretical element content (wt%) C 10 H 2 Cl 2 N 4 : c48.23, H0.81, N22.50, cl 28.47; measured elemental content (wt%): c48.18, H0.82, N22.60, cl 28.40.
3mmol of prepared 5,8-DClPhPD, 6.9mmol of compound II, 16mmol of potassium carbonate, 0.1mmol of tetra (triphenylphosphine) palladium, 40mL of tetrahydrofuran and 8mL of water are added into a three-mouth bottle, the mixture is reacted for 12 hours under the conditions of nitrogen protection, oil bath and 85 ℃, the obtained reaction liquid product is poured into distilled water, dichloromethane is used for extraction, the obtained organic phase is concentrated and then purified by silica gel column chromatography (the eluent is petroleum ether/dichloromethane volume ratio=1/1), and the dicyanopyrazine compound with the structure shown in the formula I is obtained; the dicyanopyrazine compound was obtained as a red powder, 1.40g, and 70% yield.
Structural characterization data: 1 HNMR(400MHz,DMSO-d 6 ) δ8.08 (s, 2H), 7.24 (td, j=7.2 hz, 8H), 7.00-7.08 (m, 12H), 6.85 (d, j=8.4 hz, 2H), 6.15 (d, j=8.2 hz 2H), 7.02-6.98 (m, 8H); the mass spectrum analysis determines the molecular ion mass as follows: 678.25 (calculated: 678.83); theoretical element content (wt%) C 42 H 26 N 6 S 2 : c74.31, H3.86, N12.38, S9.45; measured elemental content (wt%): c74.66, H3.68, N12.29, S9.37.
The dicyanopyrazine compound prepared in the embodiment emits near infrared light, the light emitting wavelength is 730nm, and the fluorescence quantum yield is 7.2%.
In this embodiment, the preparation process of the dicyanopyrazine compound is as follows:
example 3
(1) Synthesis of diiminosuccinonitrile
50mL of acetonitrile is added into 10mmol of diaminomaleonitrile, after stirring and dissolving, 10 mmole of 2, 3-dichloro-5, 6-dicyano-1, 4-benzoquinone is added, after stirring for 15min at room temperature, filtration is carried out, and the obtained liquid product is concentrated and dried to constant weight, thus obtaining diiminosuccinonitrile; the resulting diiminosuccinonitrile was a brown solid, 1.01g, yield 95%.
(2) Synthesis of the Compound 5, 8-diiodo [3,4-b ] -2, 3-dicyanopyrazine (5, 8-DIPhPD)
3.7mmol of diiodosuccinonitrile and 3mmol of 3, 6-diiodo-1, 2-phenylenediamine are mixed and added into 13mL of trifluoroacetic acid in 3 batches, the mixture is stirred for 9h at room temperature to carry out cyclization reaction, the obtained reaction solution is poured into ice water, filtration is carried out, the obtained solid product is washed with water and then purified by silica gel column chromatography (the eluent is petroleum ether/dichloromethane volume ratio=1.5/1), and 5, 8-diiodo [3,4-b ] is obtained]-2, 3-dicyanopyrazine (5, 8-DIPhPD); the resulting 5,8-DIPhPD was pale yellow powder, 1.04g, and 80% yield. Structural characterization data: 1 HNMR(400MHz,CDCl 3 ) Delta 7.88 (s, 2H); the mass spectrum analysis determines the molecular ion mass as follows: 431.61 (calculated: 431.84); theoretical element content (wt%) C 10 H 2 I 2 N 4 : c27.81, H0.47, N12.97, I58.76; measured elemental content (wt%): c27.56, H0.44, N13.11, I58.89.
3mmol of prepared 5,8-DIPhPD, 6.3mmol of compound II, 14mmol of potassium carbonate, 0.1mmol of tetra (triphenylphosphine) palladium, 40mL of tetrahydrofuran and 7mL of water are added into a three-mouth bottle, the mixture is reacted for 18h under the conditions of nitrogen protection, oil bath and 60 ℃, the obtained reaction liquid product is poured into distilled water, dichloromethane is used for extraction, the obtained organic phase is concentrated, and then silica gel column chromatography is carried out for purification (the eluent is petroleum ether/dichloromethane volume ratio=1/1), so as to obtain dicyanopyrazine compounds with the structure shown in formula I; the dicyanopyrazine compound was obtained as a red powder, 1.50g, 80% yield.
Structural characterization data: 1 HNMR(400MHz,DMSO-d 6 ) δ8.08 (s, 2H), 7.24 (td, j=7.2 hz, 8H), 7.00-7.08 (m, 12H), 6.85 (d, j=8.4 hz, 2H), 6.15 (d, j=8.2 hz 2H), 7.02-6.98 (m, 8H); the mass spectrum analysis determines the molecular ion mass as follows: 678.66 (calculated: 678.83); theoretical element content (wt%) C 42 H 26 N 6 S 2 : c74.31, H3.86, N12.38, S9.45; measured elemental content (wt%): c74.26, H3.90, N12.40, S9.44.
The dicyanopyrazine compound prepared in the embodiment emits near infrared light, the light emitting wavelength is 730nm, and the fluorescence quantum yield is 7.2%.
In this embodiment, the preparation process of the dicyanopyrazine compound is as follows:
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application example 1
An organic electroluminescent device (noted as IT 0/NPB/TCTA/dicyanopyrazine compound/TPBI/LiF/Al) was obtained by sequentially vapor-depositing a hole transport layer NPB (thickness 50 nm), a hole blocking layer TCTA (thickness 10 nm), a light emitting layer (dicyanopyrazine compound prepared in example 1, thickness 25 nm), an electron transport layer TPBI (thickness 20 nm), an electron injection layer LiF (thickness 6 nm), and an Al cathode layer (thickness 180 nm) on a glass substrate coated with an ITO anode.
The organic electroluminescent device has an on-voltage of 3.5V, a maximum current efficiency of 1.42cd/A, and a power efficiency of 1.71m/W.
FIG. 1 is a spectrum of an organic electroluminescent device prepared in application example 1, and it is apparent from FIG. 1 that the organic electroluminescent device emits near infrared light with a peak position of 720nm and a maximum brightness of 990cd/m 2 。
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (10)
1. A dicyanopyrazine compound having a structure represented by formula I:
2. the process for producing dicyanopyrazine compound of claim 1, comprising the steps of:
mixing halogenated dicyanopyrazine, a compound II, a palladium catalyst, an alkaline reagent and a mixed solvent in a protective atmosphere, and performing a coupling reaction to obtain dicyanopyrazine compounds with a structure shown in a formula I; the mixed solvent comprises an organic solvent and water;
the structural formula of the halogenated dicyanopyrazine isWherein X is chlorine, bromine or iodine;
the structural formula of the compound II is
3. The preparation method according to claim 2, characterized in that the preparation method of the halogenated dicyanopyrazine comprises the following steps:
mixing diiminosuccinonitrile, halogenated diaminobenzene and trifluoroacetic acid, and performing cyclization reaction to obtain halogenated dicyanopyrazine;
the structural formula of the halogenated diaminobenzene isIn the structural formula, X is chlorine, bromine or iodine.
4. A process according to claim 2 or 3, wherein the molar ratio of halogenated dicyanopyrazine to compound II is 1:2 to 3.
5. The preparation method according to claim 2, wherein the molar ratio of the halogenated dicyanopyrazine to the alkaline agent is 1:4 to 10.
6. The preparation method according to claim 2, wherein the coupling reaction temperature is 60-70 ℃ and the incubation time is 20-24 h.
7. The dicyanopyrazine compound of claim 1 or the application of the dicyanopyrazine compound prepared by the preparation method of any one of claims 2 to 6 in an organic electroluminescent device.
8. An organic electroluminescent device comprising a luminescent layer, an electrode layer and a functional layer, wherein the luminescent layer is prepared from the dicyanopyrazine compound according to claim 1 or the dicyanopyrazine compound prepared by the preparation method according to any one of claims 2 to 6.
9. The organic electroluminescent device according to claim 8, wherein the functional layer comprises one or more of a hole transport layer, a hole blocking layer, an electron transport layer, and an electron injection layer.
10. Use of an organic electroluminescent device as claimed in any one of claims 8 to 9 in an illumination source, a signal lamp, a sign or a flat panel display.
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| CN113200929A (en) * | 2021-04-01 | 2021-08-03 | 黑龙江大学 | Cyanoquinoxaline red-light thermal excitation delayed fluorescent material, and synthesis method and application thereof |
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| CN107602540A (en) * | 2016-12-12 | 2018-01-19 | 吉林大学 | The electroluminescent device to acceptor compound and for preparation based on dicyano pyrazine and dicyano benzo pyrazines derivatives |
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