CN113214226B - Tetraphenylpyrazine compound, polymer and electroluminescent device - Google Patents

Tetraphenylpyrazine compound, polymer and electroluminescent device Download PDF

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CN113214226B
CN113214226B CN202010371660.6A CN202010371660A CN113214226B CN 113214226 B CN113214226 B CN 113214226B CN 202010371660 A CN202010371660 A CN 202010371660A CN 113214226 B CN113214226 B CN 113214226B
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tetraphenylpyrazine
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CN113214226A (en
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周兴邦
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Guangdong Juhua Printing Display Technology Co Ltd
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Abstract

The invention relates to a tetraphenylpyrazine compound, a polymer and an electroluminescent device. The tetraphenylpyrazine compound has a structure represented by formula (I-1). The compound structure contains a crosslinking segment which can endow the material with crosslinkable curing performance; and tetraphenylpyrazine fragment, pyrazine is electron withdrawing group, is favorable to electron transmission, has large molecular torsion degree and has the characteristic of large volume, the characteristic of increasing the distance between the molecule of the electron transmission layer and the molecule of the luminescent layer, inhibiting exciton quenching and improving the efficiency and stability of the device, and a classical electron withdrawing structure, and the structure can ensure the electron transmission performance. The combination of the three structures can obtain a crosslinkable electron transport material with good performance. The electron transport material is used for solution processing, can be crosslinked and cured to obtain high thermal stability, has good electron transport performance, and can reduce the manufacturing cost of OLED and improve the degree of freedom of the preparation process.
Figure DDA0002478527250000011

Description

Tetraphenylpyrazine compound, polymer and electroluminescent device
Technical Field
The invention relates to the field of photoelectric materials, in particular to a tetraphenylpyrazine compound, a polymer and an electroluminescent device.
Background
Organic Light Emitting Diodes (OLEDs) have become the mainstream of high-end displays, such as high-end flagship mobile phones, televisions, lighting, wearable displays and the like, due to the advantages of high contrast, wide viewing angle, low energy consumption, thinness, flexibility and the like, and the market share of OLED display screens is gradually increased. At present, the OLED display screen is mainly prepared by an evaporation method, and the evaporation method can be used for preparing a device which is arranged upright or inverted, so that the preparation process has higher degree of freedom, and the defect that the price of the OLED display screen is higher than that of an LCD screen. The OLED screen can be prepared by adopting a solution method of ink jet printing, so that the cost is reduced. The preparation method of the OLED screen for ink-jet printing mainly comprises the steps of dissolving OLED organic materials by using a solvent, and then directly spraying and printing the materials on the surface of a substrate to form R (red), G (green) and B (blue) organic light-emitting layers. Compared with the evaporation technology, the inkjet printing OLED technology has obvious advantages in the aspects of manufacturing process, yield, cost and the like.
Generally suitable electron transport materials for solution processes are crosslinkable or polymeric materials, however, such materials are currently scarce. Secondly, the technology for preparing the OLED by the solution method is not mature, only the device preparation sequence of the positive position (a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, an electron injection layer and a cathode) is not as flexible as the evaporation method, and if the inverted device is required to be prepared, a cross-linkable electron transport material or a polymer electron transport material is also required. In addition, polymeric electron transport materials are less solvent resistant than crosslinkable electron transport materials. Therefore, there is a need to develop a class of crosslinkable electron transport materials.
Disclosure of Invention
Based on the above, the invention aims to provide a tetraphenylpyrazine compound which is suitable for solution processing, can be crosslinked and cured to obtain high thermal stability and has good electron transport performance.
The technical scheme is as follows:
a tetraphenylpyrazine compound has a structure shown in a formula (I-1):
Figure BDA0002478527230000021
wherein R is 1 、R 2 Is independently selected from
Figure BDA0002478527230000022
R 3 、R 4 Independently selected from electron withdrawing groups.
In one embodiment, R is 3 、R 4 Independently selected from: positively charged group, halogen atom, nitro group, trihalomethyl group,Cyano, sulfonic acid group, formyl, acyl, carboxyl, substituted electron-withdrawing aromatic ring compound, or substituted or unsubstituted electron-withdrawing non-aromatic ring compound.
In one embodiment, R is 3 、R 4 Independently selected from: a tertiary amine cation, fluorine, an electron-withdrawing aromatic ring compound having 6 to 60 substituted ring atoms, or an electron-withdrawing non-aromatic ring compound having 6 to 60 substituted or unsubstituted ring atoms.
In one embodiment, R is 3 、R 4 Independently selected from one of the following structures:
Figure BDA0002478527230000031
wherein X 1 Selected from N or CR 5 And at least one X 1 Is N;
X 2 selected from N or CR 6 ；
Y 1 And Y 2 Independently selected from: n (R) 7 )、C＝N(R 8 )、P(R 9 ) Or P (= O) R 10 ；
Y 3 Selected from the group consisting of: single bond, N (R) 7 )、C＝N(R 8 )、P(R 9 ) Or P (= O) R 10 ；
R 5 ～R 10 Each independently selected from: H. d, F, alkyl, alkoxy, amino, alkenyl, alkynyl, heteroalkyl, aryl having 6 to 30 carbon atoms, or heteroaryl having 5 to 30 ring atoms.
In one embodiment, R is 3 、R 4 Independently selected from one of the following structures:
Figure BDA0002478527230000032
wherein, X 1 Selected from N or CR 5 And at least one X 1 Is N;
X 2 selected from N or CR 6 ；
X 3 Represents CR 11 ；
Y 1 And Y 2 Independently selected from: n (R) 7 )、C＝N(R 8 )、P(R 9 ) Or P (= O) R 10 ；
R 5 ～R 11 Each independently selected from: H. an alkyl group, an aryl group having 6 to 20 carbon atoms, or a heteroaryl group having 5 to 20 ring atoms.
In one embodiment, R is 3 、R 4 Independently selected from one of the following structures:
Figure BDA0002478527230000041
wherein the content of the first and second substances,
R 12 selected from: an alkyl group having 1 to 3 carbon atoms, an aryl group having 6 to 10 carbon atoms or a heteroaryl group having 5 to 10 ring atoms, or is absent.
In one embodiment, R is 3 、R 4 Independently selected from one of the following structures:
Figure BDA0002478527230000042
in one embodiment, the tetraphenylpyrazine compound is selected from any one of the following structures:
Figure BDA0002478527230000043
Figure BDA0002478527230000051
Figure BDA0002478527230000061
Figure BDA0002478527230000071
the invention also provides a tetraphenylpyrazine polymer, and the monomer of the tetraphenylpyrazine polymer comprises the tetraphenylpyrazine compound.
The present invention also provides an electroluminescent device comprising:
a light emitting layer, an electron transport layer, and other functional layers; the other functional layer is at least one of a hole injection layer, a hole transport layer, a hole blocking layer, an electron blocking layer and an electron injection layer;
wherein at least one of a raw material of a host material of the light-emitting layer and a raw material of the electron-transporting layer includes the tetraphenylpyrazine compound described above; alternatively, the first and second electrodes may be,
at least one of the host material of the light-emitting layer and the raw material of the electron-transporting layer includes the aforementioned tetraphenylpyrazine-based polymer.
The invention principle and the beneficial effects of the invention are as follows:
the tetraphenylpyrazine compound provided by the invention comprises three parts, wherein the first part is a cross-linking segment which endows the material with cross-linking curing performance; the second part is a tetraphenylpyrazine segment, pyrazine is an electron-withdrawing group, electron transmission is facilitated, the molecular torsion degree is large, and the electronic material has the characteristic of large volume, so that the distance between molecules of an electron transmission layer and molecules of a light emitting layer is increased, exciton quenching is inhibited, the efficiency and stability of a device are improved, and particularly, the efficiency and stability of the device made of the phosphorescent material are improved; the third part is an electron-withdrawing group structure which can ensure the electron transmission performance. The three structures are combined to obtain the crosslinkable electron transmission material with good performance.
The electron transport material is used for solution processing, can be crosslinked and cured to obtain high thermal stability, has good electron transport performance, and can reduce the manufacturing cost of OLED and improve the degree of freedom of the preparation process.
Drawings
Fig. 1 is a schematic structural diagram of an OLED device.
Detailed Description
The present invention will be described in further detail with reference to specific examples. The present invention may be embodied in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
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. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
In the present invention, the Host material, matrix material, host or Matrix material have the same meaning and are interchangeable with each other.
In the present invention, "substituted" means that a hydrogen atom in a substituent is substituted by a substituent.
In the present invention, the "number of ring atoms" represents the number of atoms among atoms constituting the ring itself of a structural compound (for example, a monocyclic compound, a condensed ring compound, a crosslinked compound, a carbocyclic compound, and a heterocyclic compound) in which atoms are bonded in a ring shape. When the ring is substituted with a substituent, the atom included in the substituent is not included in the ring-forming atoms. The "number of ring atoms" described below is the same unless otherwise specified. For example, the number of ring atoms of the benzene ring is 6, the number of ring atoms of the naphthalene ring is 10, and the number of ring atoms of the thienyl group is 5.
In the present invention, the aromatic ring compound or the aryl group or the aromatic ring system or the aromatic group means a hydrocarbon group containing at least one aromatic ring, including monocyclic groups and polycyclic ring systems. Heteroaryl or heteroaromatic ring systems or heteroaromatic groups or heteroaromatic groups refer to hydrocarbon radicals (containing heteroatoms) which contain at least one heteroaromatic ring, including monocyclic groups and polycyclic ring systems. These polycyclic rings may have two or more rings in which two carbon atoms are shared by two adjacent rings, i.e., fused rings. At least one of these ring members of the polycyclic ring system is aromatic or heteroaromatic. For the purposes of the present invention, aromatic or heteroaromatic ring systems include not only aromatic or heteroaromatic systems, but also systems in which a plurality of aryl or heteroaryl groups may also be interrupted by short nonaromatic units (< 10% of non-H atoms, preferably less than 5% of non-H atoms, such as C, N or O atoms). Thus, for example, systems such as 9,9' -spirobifluorene, 9,9-diarylfluorene, triarylamines, diaryl ethers, etc., are likewise considered aromatic ring systems for the purposes of this invention.
In the present invention, the heterocyclic compound means a cyclic compound in which at least one carbon atom in the ring is substituted with a hetero atom (N, O, S).
The non-aromatic ring compound refers to a cyclic compound having no aromaticity.
Generally, the molecular structure design of the electron transport material mainly considers the introduction of electron-withdrawing groups (such as pyridine, triazine, phenanthroline, oxadiazole, benzimidazole and the like) without considering the size of the molecular volume; the bulky electron transport material can increase the distance between the molecules of the electron transport layer and the molecules of the light emitting layer, inhibit exciton quenching and improve the efficiency and stability of the device, particularly for phosphorescent materials; the invention obtains the high-performance electron transport material by introducing novel electron-withdrawing groups and a large-volume structure.
The technical scheme is as follows:
a tetraphenylpyrazine compound has a structure shown in a formula (I-1):
Figure BDA0002478527230000101
wherein R is 1 、R 2 Is independently selected from
Figure BDA0002478527230000102
R 3 、R 4 Independently selected from electron withdrawing groups.
In one embodiment, R is 3 、R 4 Independently selected from: a positively charged group, a halogen atom, a nitro group, a trihalomethyl group, a cyano group, a sulfonic acid group, a formyl group, an acyl group, a carboxyl group, a substituted electron-withdrawing aromatic ring compound, or a substituted or unsubstituted electron-withdrawing non-aromatic ring compound.
In one embodiment, R is 3 、R 4 Independently selected from: a tertiary amine cation, fluorine, an electron-withdrawing aromatic ring compound having 6 to 60 substituted ring atoms, or an electron-withdrawing non-aromatic ring compound having 6 to 60 substituted or unsubstituted ring atoms.
Preferably, said R is 3 、R 4 Independently selected from one of the following structures:
Figure BDA0002478527230000111
wherein, X 1 Selected from N or CR 5 And at least one X 1 Is N;
X 2 selected from N or CR 6 ；
Y 1 And Y 2 Independently selected from: n (R) 7 )、C＝N(R 8 )、P(R 9 ) Or P (= O) R 10 ；
Y 3 Selected from: single bond, N (R) 7 )、C＝N(R 8 )、P(R 9 ) Or P (= O) R 10 ；
R 5 ～R 10 Each independently selected from: H. d, F, alkyl, alkoxy, amino, alkenyl, alkynyl, heteroalkyl, aryl of 6 to 30 carbon atoms or heteroaryl of 5 to 30 ring atoms.
Further preferably, R is 3 、R 4 Independently selected from one of the following structures:
Figure BDA0002478527230000112
wherein, X 1 Selected from N or CR 5 And at least one X 1 Is N;
X 2 selected from N or CR 6 ；
X 3 Represents CR 11 ；
Y 1 And Y 2 Independently selected from: n (R) 7 )、C＝N(R 8 )、P(R 9 ) Or P (= O) R 10 ；
R 5 ～R 11 Each independently selected from: H. an alkyl group, an aryl group having 6 to 20 carbon atoms, or a heteroaryl group having 5 to 20 ring atoms.
Even more preferably, said R 3 、R 4 Independently selected from one of the following structures:
Figure BDA0002478527230000121
wherein, the first and the second end of the pipe are connected with each other,
R 12 selected from: an alkyl group having 1 to 3 carbon atoms, an aryl group having 6 to 10 carbon atoms or a heteroaryl group having 5 to 10 ring atoms, or is absent.
Particularly preferably, R is 3 、R 4 Independently selected from one of the following structures:
Figure DEST_PATH_FDA0002478527220000032
the tetraphenylpyrazine compound provided by the invention comprises three parts. The first part is a cross-linking segment which imparts cross-linkable curing properties to the material; the second part is a tetraphenylpyrazine segment, pyrazine is an electron-withdrawing group, electron transmission is facilitated, the molecular torsion degree is large, and the electronic transmission layer has the characteristic of large volume, so that the distance between molecules of the electron transmission layer and molecules of the light emitting layer is increased, exciton quenching is inhibited, and the efficiency and stability of the device are improved, particularly for phosphorescent materials; the third part is an electron-withdrawing group structure which can ensure the electron transmission performance. The three structures are combined to obtain the crosslinkable electron transmission material with good performance.
In some preferred embodiments, the structure of the tetraphenylpyrazine-based compounds according to the present invention is shown below, but not limited thereto:
Figure BDA0002478527230000131
Figure BDA0002478527230000141
Figure BDA0002478527230000151
the invention also provides a tetraphenylpyrazine polymer, and the monomer of the tetraphenylpyrazine polymer comprises the tetraphenylpyrazine compound.
The present invention also provides an electroluminescent device comprising:
a light emitting layer, an electron transport layer, and other functional layers; the other functional layer is at least one of a hole injection layer, a hole transport layer, a hole blocking layer, an electron blocking layer and an electron injection layer;
wherein at least one of the raw material of the host material of the light-emitting layer and the raw material of the electron transport layer comprises the tetraphenylpyrazine compound; alternatively, the first and second electrodes may be,
at least one of the host material of the light-emitting layer and the raw material of the electron transport layer includes the above tetraphenylpyrazine-based polymer.
The tetraphenylpyrazine compound comprises three parts, wherein the first part is a cross-linking segment which endows the material with cross-linking and curing properties; the second part is a tetraphenylpyrazine segment, pyrazine is an electron-withdrawing group, electron transmission is facilitated, the molecular torsion degree is large, and the electronic material has the characteristic of large volume, so that the distance between molecules of an electron transmission layer and molecules of a light emitting layer is increased, exciton quenching is inhibited, the efficiency and stability of a device are improved, and particularly, the efficiency and stability of the device made of the phosphorescent material are improved; the third part is an electron-withdrawing group structure which can ensure the electron transmission performance. The three structures are combined to obtain the crosslinkable electron transmission material with good performance.
The tetraphenylpyrazine compound is used as a raw material of the electron transport layer, or the tetraphenylpyrazine polymer is used as a material of the electron transport layer, so that high thermal stability can be obtained, good electron transport performance is achieved, the manufacturing cost of the OLED can be reduced, and the degree of freedom of the preparation process can be improved. More specifically, when the tetraphenylpyrazine compound is used as a raw material of an electron transport layer, the tetraphenylpyrazine compound can be processed by a solution method, and crosslinkable groups in the tetraphenylpyrazine compound can form a crosslinked layer which is not easy to dissolve in a conventional solvent through a crosslinking reaction, namely, the crosslinked layer can be crosslinked and cured to obtain high thermal stability, so that the manufacturing cost of the OLED can be reduced, and the degree of freedom of a preparation process can be improved.
When the above tetraphenylpyrazine-based compound is used as a raw material of a host material of a light-emitting layer, or a tetraphenylpyrazine-based polymer is used as a host material of a light-emitting layer, which is mainly used as an electron-type host material, a guest material matched with the electron-type host material may be a phosphorescent or fluorescent material, such as: ir (ppy) 3 (tris (2-phenylpyridine) iridium (III)), ir (ppy) 2 (acac) (bis (2-phenylpyridine) iridium acetylacetonate), ir (mppy) 3 (tris [2- (p-tolyl) pyridine)]Iridium (III)), ir (dmppy-pro) 2 tmd, BPTAPA, etc., can adjust the electrical balance of the light emitting region, stabilizing the device. More specifically, when the tetraphenylpyrazine compound is used as a raw material of a host material of a light-emitting layer, the end of the raw material of the host material is a crosslinkable group, the crosslinkable group can form a host material crosslinked layer which is not easily dissolved by a conventional solvent through a crosslinking reaction, the crosslinked layer can wrap a guest material like an interpenetrating network, and the functions that the host material is responsible for transmitting holes and electrons, and the guest material is responsible for emitting light are realized. The formed interpenetrating network structure is beneficial to uniform dispersion of a host material and a guest material, and the reduction of efficiency caused by quenching due to overhigh concentration of a luminophor is avoided.
In some of these embodiments, a specific type of the electroluminescent device described above may be an organic light emitting diode. The organic light emitting diode further comprises a first electrode, an electron injection layer, an electron blocking layer, a hole transport layer, a hole injection layer and a second electrode. The electron injection layer is arranged on the first electrode, the electron transport layer is arranged on the electron injection layer, the luminescent layer is arranged on the electron transport layer, the electron blocking layer is arranged on the luminescent layer, the hole transport layer is arranged on the electron blocking layer, the hole injection layer is arranged on the hole transport layer, and the second electrode is arranged on the hole injection layer.
In the present invention, the material of the hole injection layer may be made of a hole injection material that is conventional in the art, and may be PEODT: PSS (poly (3,4-ethylenedioxythiophene): poly (styrenesulfonic acid)), cuPc, HAT-CN (2,3,6,7,10,11-hexacyano-1,4,5,8,9,12-hexaazatriphenylene), woO x 、MoO x 、CrO x 、 NiO、CuO、VO x 、CuS、MoS 2 、MoSe 2 、WS 2 And WSe 2 But is not limited thereto. The thickness of the hole injection layer is 10-100 nm.
Preferably, the material of the hole injection layer is HAT-CN, and the thickness of the hole injection layer is 10nm.
In the present invention, the material of the hole transport layer can be made of a hole transport material conventional in the art, and can be TFB (poly [ (9,9-di-N-octylfluorenyl-2,7-diyl) -alt- (4,4' - (N- (4-N-butyl) phenyl) -diphenylamine)]) PVK (polyvinylcarbazole), PFB [ N, N '- (4-N-butylphenyl) -N, N' -diphenyl-p-phenylenediamine]- [9,9-di-n-octylfluorenyl-2,7-diyl]Copolymers, TPD (N, N ' -bis (3-methylphenyl) -N, N ' -diphenyl-1,1 ' -biphenyl-4,4 ' -diamine), TCTA (4,4 ', 4' -tris (carbazol-9-yl) triphenylamine), TAPC (4,4 ' -cyclohexylbis [ N, N-bis (4-methylphenyl) aniline)]) Poly-TBP, poly-TPD, NPB (N, N ' -diphenyl-N, N ' - (1-naphthyl) -1,1' -biphenyl-4,4 ' -diamine), CBP (4,4 ' -bis (9-carbazole) biphenyl), moO 3 、 WoO 3 、NiO、CuO、V 2 O 5 And CuS, but not limited thereto. The thickness of the hole transport layer is 20 to100nm。
Preferably, the material of the hole transport layer is NPB, and the thickness of the hole transport layer is 20nm.
In the present invention, the material of the electron blocking layer may be made of an electron blocking material that is conventional in the art, and may be one of TAPC (4,4 '-cyclohexylbis [ N, N-bis (4-methylphenyl) aniline ]), TPD (N, N' -bis (3-methylphenyl) -N, N '-diphenyl-1,1' -biphenyl-4,4 '-diamine), NPB (N, N' -diphenyl-N, N '- (1-naphthyl) -1,1' -biphenyl-4,4 '-diamine, and TCTA (4,4', 4 "-tris (carbazol-9-yl) triphenylamine), but is not limited thereto.
Preferably, the material of the electron blocking layer is TCTA, and the thickness of the electron blocking layer is 10nm.
In the present invention, the light emitting layer can be made of light emitting layer host material and light emitting layer guest material which are conventional in the art, and the light emitting layer host material can be DIC-TRZ (2,4-diphenyl-6-bis (12-phenylindole [2,3-a ] carbazole-11-yl) -1,3,5-triazine), CBP (4,4' -bis (9-carbazole) biphenyl), CDBP (CDBP: (9-carbazole) biphenyl)
4,4' -bis (9-carbazolyl) -2,2' -dimethylbiphenyl, AND (9,10-bis (2-naphthyl) anthracene) AND TCTA (4,4 ',4 "-tris (carbazol-9-yl) triphenylamine). The emissive layer guest material can be Ir (ppy) 3 (tris (2-phenylpyridine) iridium (III)), ir (ppy) 2 (acac) (bis (2-phenylpyridine) iridium acetylacetonate), ir (mppy) 3 (tris [2- (p-tolyl) pyridine)]Iridium (III)), ir (dmppy-pro) 2 tmd and BPTAPA, but not limited thereto. The thickness of the luminescent layer is 30-100 nm.
Preferably, the host material of the light emitting layer is DIC-TRZ and the guest material is 10wt% Ir (ppy) 3 And the thickness of the light-emitting layer is 30nm.
The preparation method of the organic light-emitting diode comprises the following steps:
(1) Firstly, an ITO substrate is cleaned in the following sequence: 5% KOH solution ultrasound for 15min, pure water ultrasound for 15min, isopropanol ultrasound for 15min, oven drying for 1h;
(2) The substrate was then transferred to a UV-ozon apparatus for surface treatment for 15min and immediately transferred to a glove box after treatment.
(3) And then spin coating is carried out to form a film: preparing an electron injection layer and an electron transport layer in sequence, and heating the electron transport layer at 200 ℃ for 30min for curing; then, evaporation film forming is carried out: and preparing a luminescent layer, a hole transport layer, a hole injection layer and a second electrode in sequence.
(4) Finally, UV curing packaging is carried out, and baking is carried out for 60min at 80 ℃.
The following is a detailed description of the embodiments.
The general synthetic route for the compounds disclosed in the present invention is shown below:
Figure BDA0002478527230000191
wherein X is F, cl or Br atom, R 1 、R 2 Is independently selected from
Figure BDA0002478527230000192
R 3 、R 4 Independently selected from electron withdrawing groups. More specifically, in the following examples, R 3 And R 4 Each independently selected from the following groups:
Figure BDA0002478527230000201
with reference to the above reaction scheme:
step 1 the preparation of intermediate II-2 or II-4 is as follows:
in a 250mL two-necked flask were sequentially added 8.5mmol of boric acid compound, 4mmol of II-1, and 0.4mmol of tetrakistriphenylphosphine palladium Pd (PPh) 3 ) 4 16mmol of potassium carbonate K 2 CO 3 Adding stirring magnetons, vacuumizing and changing nitrogen, repeating for three times to enable the interior of a reaction bottle to be in a nitrogen atmosphere, adding 120ml of mixed solvent Tetrahydrofuran (THF)/pure water (V/V = 2:1), and then carrying out reflux reaction at 100 ℃ for 24 hours; after the reaction is finished, cooling to room temperature, andthe solvent was removed by rotary evaporation, the reaction solution was extracted with dichloromethane 3 times, and the organic layer was extracted with anhydrous MgSO 4 Drying, filtering, removing solvent by rotary evaporation, separating and purifying with silica gel chromatographic column, eluting with n-hexane/dichloromethane, removing solvent by rotary evaporation, and collecting product II-2 with yield of 50-90%; (when II-3 was used in place of II-1, II-4 was obtained in a yield of 40-90%). And (3) combining a nuclear magnetic resonance hydrogen spectrum and a mass spectrum to characterize the structure of the compound.
Step 2 preparation of the final product I-1
Sequentially adding 3.8mmol II-2 and 8mmol II-4 into a 250mL two-mouth bottle, adding a stirring magneton, vacuumizing and changing nitrogen for three times to enable the two-mouth bottle to be in a nitrogen atmosphere, adding 50mL of acetic acid, and carrying out reflux reaction at 100 ℃ for 6 hours; after completion of the reaction, the reaction mixture was cooled to room temperature, and then extracted with dichloromethane 3 times, and the organic layer was extracted with anhydrous MgSO 4 Drying, filtering, removing solvent by rotary evaporation, separating and purifying with silica gel chromatographic column, eluting with n-hexane/dichloromethane, removing solvent by rotary evaporation, and collecting product I-1 with yield of 40-80%. And (3) characterizing the structure and the molecular weight of the compound by combining a nuclear magnetic resonance hydrogen spectrum and a liquid chromatography-mass spectrum.
The synthesis of the compounds E1 to E28 can be carried out according to the general synthetic route described above. In the following, the compounds E6, E12, E16 and E24 are exemplified, and it is understood that R in the structural formula is replaced correspondingly 1 、R 2 、 R 3 And R 4 Compounds E1 to E5, E7 to E11, E13 to E15, E17 to E23 and E25 to E28 can also be synthesized successfully with reference to similar synthetic routes.
Example 1: synthesis of Compound E6
In a 250mL two-necked flask were sequentially added 8.5mmol of Compound 2, 4mmol of Compound 1, and 0.4mmol of Tetratriphenylphosphine palladium Pd (PPh) 3 ) 4 16mmol of potassium carbonate K 2 CO 3 Adding stirring magnetons, vacuumizing and changing nitrogen, repeating for three times to enable the interior of a reaction bottle to be in a nitrogen atmosphere, adding 120ml of mixed solvent Tetrahydrofuran (THF)/pure water (V/V = 2:1), and then carrying out reflux reaction at 100 ℃ for 24 hours; cooling to room temperature after the reaction is finished, and reacting the solutionThe solvent was removed by rotary evaporation, followed by extraction with dichloromethane 3 times, and the organic layer was over anhydrous MgSO 4 Drying, filtering, removing solvent by rotary evaporation, separating and purifying by silica gel chromatographic column, collecting product compound 3 by rotary evaporation with n-hexane/dichloromethane as eluent, and finally vacuum drying at room temperature for 12h with the yield of 83%. 1 H NMR(500MHz,CDCl 3 ),δ(TMS,ppm):8.04(d,4H)，7.83(d,4H),7.53-7.59(m, 8H),6.72(m,2H),5.76(d,2H),5.25(d,2H)。
Figure BDA0002478527230000211
In a 250mL two-necked flask were sequentially added 8.5mmol of Compound 5, 4mmol of Compound 4, and 0.4mmol of Tetratriphenylphosphine palladium Pd (PPh) 3 ) 4 16mmol of potassium carbonate K 2 CO 3 Adding stirring magnetons, vacuumizing and changing nitrogen repeatedly for three times to enable the interior of a reaction bottle to be in a nitrogen atmosphere, adding 120ml of mixed solvent Tetrahydrofuran (THF)/pure water (V/V = 2:1), and then carrying out reflux reaction at 100 ℃ for 24 hours; cooling to room temperature after reaction, removing solvent by rotary evaporation, extracting with dichloromethane for 3 times, and collecting organic layer with anhydrous MgSO 4 Drying, filtering, removing solvent by rotary evaporation, separating and purifying by silica gel chromatographic column, collecting product compound 6 by rotary evaporation with n-hexane/dichloromethane as eluent, and vacuum drying at room temperature for 12h with 79% yield. 1 H NMR(500MHz,CDCl 3 ),δ(TMS,ppm):9.18(d,2H),8.93-8.97(m,4H), 8.55-8.62(d,6H)，8.00(d,2H),7.74(t,2H),7.41-7.47(m,8H),7.23(m,2H), 4.24(s,2H)。
Figure BDA0002478527230000221
Sequentially adding 3.8mmol of compound 3 and 8mmol of compound 6 into a 250mL two-mouth bottle, adding stirring magnetons, vacuumizing and changing nitrogen, repeating for three times to enable the two-mouth bottle to be in a nitrogen atmosphere, adding 50mL of acetic acid, and carrying out reflux reaction at 100 ℃ for 6 hours; after the reaction was completed, it was cooled to room temperature and then extracted with dichloromethane 3 timesThe organic layer was over anhydrous MgSO 4 Drying, filtering, removing solvent by rotary evaporation, separating and purifying by silica gel chromatographic column, collecting the product E6 by rotary evaporation with n-hexane/dichloromethane as eluent, and finally vacuum drying at room temperature for 12h with the yield of 71%.
Figure BDA0002478527230000222
Nuclear magnetic resonance hydrogen spectrum data: 1 H NMR(500MHz,CDCl 3 ),δ(TMS,ppm):9.18(d,2H), 8.93-8.97(m,4H),8.55(d,2H),8.01(d,2H),7.89(d,4H),7.75(t,2H),7.53-7.59(m,8H), 7.23-7.29(m,6H),6.72(m,2H),5.76(d,2H),5.25(m,2H)。
the compound, formula C, was identified using HPLC-MS 64 H 44 N 6 Detection value [ M +1 ]] + =897.40, calculated 896.36.
Thus, the target compound E6 is successfully synthesized.
Example 2: synthesis of Compound E12
In a 250mL two-necked flask were sequentially added 8.5mmol of Compound 7, 4mmol of Compound 4, and 0.4mmol of Tetratriphenylphosphine palladium Pd (PPh) 3 ) 4 16mmol of potassium carbonate K 2 CO 3 Adding stirring magnetons, vacuumizing and changing nitrogen repeatedly for three times to enable the interior of a reaction bottle to be in a nitrogen atmosphere, adding 120ml of mixed solvent Tetrahydrofuran (THF)/pure water (V/V = 2:1), and then carrying out reflux reaction at 100 ℃ for 24 hours; cooling to room temperature after reaction, removing solvent by rotary evaporation, extracting with dichloromethane for 3 times, and collecting organic layer with anhydrous MgSO 4 Drying, filtering, removing solvent by rotary evaporation, separating and purifying with silica gel chromatographic column, collecting product compound 8 by rotary evaporation with n-hexane/dichloromethane as eluent, and vacuum drying at room temperature for 12 hr to obtain 68% yield. 1 H NMR(500MHz,CDCl 3 ),δ(TMS,ppm):8.60-8.62(m,8H),8.36(m,8H), 7.47-7.50(m,16H),4.24(s,2H)。
Figure BDA0002478527230000231
Sequentially adding 3.8mmol of compound 3 and 8mmol of compound 8 into a 250mL two-mouth bottle, adding stirring magnetons, vacuumizing and changing nitrogen, repeating for three times to enable the two-mouth bottle to be in a nitrogen atmosphere, adding 50mL of acetic acid, and carrying out reflux reaction at 100 ℃ for 6 hours; after completion of the reaction, the reaction mixture was cooled to room temperature, and then extracted with dichloromethane 3 times, and the organic layer was extracted with anhydrous MgSO 4 Drying, filtering, removing solvent by rotary evaporation, separating and purifying by silica gel chromatographic column, collecting product E12 by rotary evaporation with n-hexane/dichloromethane as eluent, and vacuum drying at room temperature for 12h with a yield of 75%.
Figure BDA0002478527230000241
Nuclear magnetic resonance hydrogen spectrum data: 1 H NMR(500MHz,CDCl 3 ),δ(TMS,ppm):8.86(d,8H), 8.37(d,8H),8.02(d,4H),7.89(d,4H),7.50-7.59(m,20H),6.72(m,2H),5.76(d,2H), 5.25(d,2H)。
the compound, formula C, was identified using HPLC-MS 74 H 50 N 8 Detection value [ M +1 ]] + =1051.46, calculated 1050.42.
Thus, the target compound E12 is successfully synthesized.
Example 3: synthesis of Compound E16
In a 250mL two-necked flask were sequentially added 8.5mmol of Compound 9, 4mmol of Compound 1, and 0.4mmol of Tetratriphenylphosphine palladium Pd (PPh) 3 ) 4 16mmol of potassium carbonate K 2 CO 3 Adding stirring magnetons, vacuumizing and changing nitrogen repeatedly for three times to enable the interior of a reaction bottle to be in a nitrogen atmosphere, adding 120ml of mixed solvent Tetrahydrofuran (THF)/pure water (V/V = 2:1), and then carrying out reflux reaction at 100 ℃ for 24 hours; cooling to room temperature after reaction, removing solvent by rotary evaporation, extracting with dichloromethane for 3 times, and collecting organic layer with anhydrous MgSO 4 Drying, filtering, removing solvent by rotary evaporation, separating and purifying with silica gel chromatographic column, eluting with n-hexane/dichloromethane, collecting product compound 10 by rotary evaporation, and vacuum drying at room temperature12h, yield 87%. 1 H NMR(500MHz,CDCl 3 ),δ(TMS,ppm):8.05(d,4H),7.85(d,4H),7.56(d,4H), 6.81(d,4H)。
Figure BDA0002478527230000251
In a 250mL two-necked flask were sequentially added 8.5mmol of Compound 11, 4mmol of Compound 4, and 0.4mmol of Tetratriphenylphosphine palladium Pd (PPh) 3 ) 4 16mmol of potassium carbonate K 2 CO 3 Adding stirring magnetons, vacuumizing and changing nitrogen, repeating for three times to enable the interior of a reaction bottle to be in a nitrogen atmosphere, adding 120ml of mixed solvent Tetrahydrofuran (THF)/pure water (V/V = 2:1), and then carrying out reflux reaction at 100 ℃ for 24 hours; cooling to room temperature after reaction, removing solvent by rotary evaporation, extracting with dichloromethane for 3 times, and collecting organic layer with anhydrous MgSO 4 Drying, filtering, removing solvent by rotary evaporation, separating and purifying by silica gel chromatographic column, collecting product compound 12 by rotary evaporation with n-hexane/dichloromethane as eluent, and vacuum drying at room temperature for 12h with 73% yield. 1 H NMR(500MHz,CDCl 3 ),δ(TMS,ppm):9.24(s,2H),8.70(d,2H),8.62(s,4H), 8.42(d,2H),7.57(t,2H),7.41-7.47(m,8H),4.23(s,2H)。
Figure BDA0002478527230000252
Sequentially adding 3.8mmol of compound 10 and 8mmol of compound 12 into a 250mL two-mouth bottle, adding stirring magnetons, vacuumizing and changing nitrogen for three times, keeping the two-mouth bottle in a nitrogen atmosphere, adding 50mL of acetic acid, and carrying out reflux reaction at 100 ℃ for 6 hours; after completion of the reaction, the reaction mixture was cooled to room temperature, and then extracted with dichloromethane 3 times, and the organic layer was extracted with anhydrous MgSO 4 Drying, filtering, removing solvent by rotary evaporation, separating and purifying by silica gel chromatographic column, collecting product E16 by rotary evaporation with n-hexane/dichloromethane as eluent, and vacuum drying at room temperature for 12h to obtain 82% yield.
Figure BDA0002478527230000261
Nuclear magnetic resonance hydrogen spectrum data: 1 H NMR(500MHz,CDCl 3 ),δ(TMS,ppm):9.25(s,2H), 8.86(d,8H),8.70(d,2H),8.42(d,2H),7.89(d,4H),7.57(m,6H),7.29(d,4H),6.81(d,4H).
the compound, formula C, was identified using HPLC-MS 54 H 32 F 6 N 4 O 2 Detection value [ M +1 ]] + = 883.36, calculated 882.24.
Thus indicating the successful synthesis of the target compound E16.
Example 4: synthesis of Compound E24
In a 250mL two-necked flask were sequentially added 8.5mmol of Compound 13, 4mmol of Compound 4, and 0.4mmol of Tetratriphenylphosphine palladium Pd (PPh) 3 ) 4 16mmol of potassium carbonate K 2 CO 3 Adding stirring magnetons, vacuumizing and changing nitrogen, repeating for three times to enable the interior of a reaction bottle to be in a nitrogen atmosphere, adding 120ml of mixed solvent Tetrahydrofuran (THF)/pure water (V/V = 2:1), and then carrying out reflux reaction at 100 ℃ for 24 hours; cooling to room temperature after reaction, removing solvent by rotary evaporation, extracting with dichloromethane for 3 times, and collecting organic layer with anhydrous MgSO 4 Drying, filtering, removing solvent by rotary evaporation, separating and purifying by silica gel chromatography column, collecting product compound 14 by rotary evaporation with n-hexane/dichloromethane as eluent, and vacuum drying at room temperature for 12h to obtain 74% yield. 1 H NMR(500MHz,CDCl 3 ),δ(TMS,ppm):8.71(d,8H),8.62(s,4H), 8.00-8.04(m,14H),7.41-7.47(m,8H),4.24(s,2H)。
Figure BDA0002478527230000262
Sequentially adding 3.8mmol of compound 10 and 8mmol of compound 14 into a 250mL two-mouth bottle, adding stirring magnetons, vacuumizing and changing nitrogen, repeating for three times to enable the two-mouth bottle to be in a nitrogen atmosphere, adding 50mL of acetic acid, and carrying out reflux reaction at 100 ℃ for 6 hours; after the reaction is completed, cooling to room temperature, then using dichloro-methaneExtracting with methane for 3 times, and extracting the organic layer with anhydrous MgSO 4 Drying, filtering, removing solvent by rotary evaporation, separating and purifying by silica gel chromatographic column, collecting product E24 by rotary evaporation with n-hexane/dichloromethane as eluent, and vacuum drying at room temperature for 12h with a yield of 76%.
Figure BDA0002478527230000271
Nuclear magnetic resonance hydrogen spectrum data: 1 H NMR(500MHz,CDCl 3 ),δ(TMS,ppm):8.86(d,8H), 8.71(d,8H),8.01-8.05(m,14H),7.89(d,8H),7.57(d,4H),6.85(d,4H)。
the compound, formula C, was identified using HPLC-MS 76 H 46 F 6 N 6 O 2 Detection value [ M +1 ]] + = 1189.42, calculated 1188.36.
Thus, the target compound E24 is successfully synthesized.
Example 5: organic light emitting diode component and preparation method thereof
The present embodiment provides an organic light emitting diode device, which includes: the organic light-emitting diode comprises a first electrode, an electron injection layer, an electron transport layer, a light-emitting layer, an electron blocking layer, a hole transport layer, a hole injection layer and a second electrode.
The preparation method comprises the following steps:
an electron injection layer formed on the first electrode, an electron transport layer formed on the electron injection layer, a light emitting layer formed on the electron transport layer, an electron blocking layer formed on the light emitting layer, a hole transport layer formed on the electron blocking layer, a hole injection layer formed on the hole transport layer, and a second electrode formed on the hole injection layer.
Wherein the raw material for preparing the electron transport layer comprises the compound E12 of example 2.
The preparation method of the organic light-emitting diode component comprises the following steps:
(1) Firstly, the ITO substrate is cleaned according to the following sequence: 5 percent, KOH solution ultrasound 15min, pure water ultrasound 15min, isopropanol ultrasound 15min, oven drying 1h;
(2) Then transferring the substrate to UV-OZONE equipment for surface treatment for 15min, and immediately transferring the substrate to a glove box after the surface treatment;
(3) And then spin coating is carried out to form a film: preparing an electron injection layer and an electron transport layer in sequence, and heating the electron transport layer at 200 ℃ for 30min for curing; then, evaporation film forming is carried out: and preparing a luminescent layer, an electron blocking layer, a hole transport layer, a hole injection layer and a second electrode in sequence.
(4) Finally, UV curing packaging is carried out, and baking is carried out for 60min at 80 ℃.
An example of a multilayer organic light emitting diode device of ITO/EIL/ETL/EML/HTL/HIL/anode. Please refer to fig. 1, the structure is: ITO/ZnO (30 nm)/E12 (30 nm)/DIC-TRZ: 10wt% Ir (ppy) 3 (30nm)/T CTA(10nm)/NPB(20nm)/HAT-CN(10nm)/Al。
Here, ITO as the anode, znO as the electron injection layer, E12 as the electron transport layer, DIC-TRZ:10wt% Ir (ppy) 3 (30 nm) as the light-emitting layer, TCTA as the electron blocking layer, NPB as the hole transport layer, HAT-CN as the hole injection layer, and Al as the cathode, this exemplary device is denoted as "E12 device".
Referring to the method for manufacturing the organic light emitting diode in this embodiment, the compounds E1 to E28 are used as raw materials of the electron transport layer to manufacture the device illustrated in fig. 1, which is respectively referred to as "E1 device", "E2 device", … … "E28 device".
Comparative example 1
In this comparative example, a device having a structure shown in FIG. 1 was prepared as an "R1 device" by using the conventional TV-TmPY (having a structure represented by formula 2) as a crosslinked electron-transporting material in accordance with the method shown in example 5.
The R1 device structure is as follows: ITO/ZnO (30 nm)/TV-TmPY (30 nm)/DIC-TRZ: 10wt% the content: PPy 3 (30nm)/TCTA(10nm)/NPB(20nm)/HAT-CN(10nm)/Al。
Figure BDA0002478527230000291
And testing the maximum external quantum efficiency and the service life of the E1 device to the E28 device and the R1 device by referring to a conventional method, wherein the service life refers to that: time taken to drop from 1000nit to 95% brightness in the constant current case. See table 1 for results.
TABLE 1
Figure BDA0002478527230000292
Figure BDA0002478527230000301
As can be seen from Table 1, the maximum external quantum efficiency of the obtained OLED device is more than or equal to 20.8 percent and is higher than that of a comparative example by using the tetraphenylpyrazine compound as a raw material to form an electron transport layer; the lifetime is also longer than that of the device in comparative example 1; the tetraphenylpyrazine compound disclosed by the invention is used in an OLED device, and the photoelectric property of the OLED device can be effectively improved.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.

Claims (8)

1. A tetraphenylpyrazine compound having a structure represented by the formula (I-1):
Figure FDA0003936510370000011
wherein R is 1 、R 2 Is independently selected from
Figure FDA0003936510370000012
The R is 3 、R 4 Independently selected from one of the following structures:
Figure FDA0003936510370000013
wherein the content of the first and second substances,
Y 1 selected from: n (R) 7 )、C＝N(R 8 )、P(R 9 ) Or P (= O) R 10 ；
R 7 ～R 10 Each independently selected from: H. an aryl group having 6 to 20 carbon atoms or a heteroaryl group having 5 to 20 ring atoms;
R 12 selected from: an alkyl group having 1 to 3 carbon atoms, an aryl group having 6 to 10 carbon atoms, or a heteroaryl group having 5 to 12 ring atoms, or is absent.
2. A tetraphenylpyrazine compound having a structure represented by the formula (I-2):
Figure FDA0003936510370000021
wherein R is 1 、R 2 Is independently selected from
Figure FDA0003936510370000022
Said R is 3 、R 4 Independently selected from one of the following structures:
Figure FDA0003936510370000023
3. a tetraphenylpyrazine compound, characterized in that it is selected from any one of the following structures:
Figure FDA0003936510370000031
Figure FDA0003936510370000041
Figure FDA0003936510370000051
Figure FDA0003936510370000061
Figure FDA0003936510370000071
4. a tetraphenylpyrazine-based polymer characterized in that a monomer thereof comprises the tetraphenylpyrazine-based compound according to any one of claims 1 to 3.
5. An electroluminescent device, comprising:
a light emitting layer, an electron transport layer, and other functional layers; the other functional layer is at least one of a hole injection layer, a hole transport layer, a hole blocking layer, an electron blocking layer and an electron injection layer;
wherein at least one of a raw material of a host material of the light-emitting layer and a raw material of the electron-transporting layer comprises the tetraphenylpyrazine compound according to any one of claims 1 to 3; alternatively, the first and second electrodes may be,
at least one of a host material of the light-emitting layer and a raw material of the electron-transporting layer includes the tetraphenylpyrazine-based polymer according to claim 4.
6. The electroluminescent device according to claim 5, characterized in that the tetraphenylpyrazine compound according to any one of claims 1 to 3 is used as a raw material of the electron transport layer, or the tetraphenylpyrazine polymer according to claim 4 is used as a material of the electron transport layer.
7. The electroluminescent device according to claim 5, wherein the tetraphenylpyrazine-based compound according to any one of claims 1 to 3 is used as a raw material of the host material of the light-emitting layer, or the tetraphenylpyrazine-based polymer according to claim 4 is used as a host material of the light-emitting layer;
the guest material of the light-emitting layer is tris (2-phenylpyridine) iridium (III), bis (2-phenylpyridine) iridium acetylacetonate or tris [2- (p-tolyl) pyridine ] iridium (III).
8. The electroluminescent device of claim 5, wherein the electroluminescent device is an organic light emitting diode.
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