A diamine derivative and an organic electroluminescent device thereof

Abstract

The present invention provides a diamine derivative and an organic electroluminescent device, specifically relating to the technical field of organic electroluminescence. The deuterated diamine derivative provided by the present invention has high hole-transporting ability, increases the transport balance of holes and electrons, effectively blocks electrons from passing through the light-emitting layer, and increases the recombination probability of excitons within the light-emitting layer. At the same time, the diamine derivative also has a high HOMO energy level, reduces the energy barrier for hole injection and transport, is beneficial to hole injection and transport, and the hole-transporting layer material has the advantages of a high glass transition temperature, being not easy to crystallize, and good film-forming property. When used as a hole-transporting material in an organic electroluminescent device, it significantly improves the light-emitting efficiency of the device and extends the service life.

Description

Technical Field

[0001] The present invention relates to the technical field of organic electroluminescence, and particularly relates to a diamine derivative and an organic electroluminescent device thereof. Background Art

[0002] Organic Light-Emitting Diode (OLED). Compared with traditional liquid crystal display (LCD), OLED display technology has the advantages of self-luminescence, wide viewing angle, high resolution, low power consumption, extremely high response speed, etc., and has a wide application prospect in new-generation display and lighting products, and is a popular research field in the past ten-odd years.

[0003] OLED was discovered by the Chinese-American professor Ching W. Tang in the laboratory in 1979, and thus the research on OLED was launched. Its principle is to use ITO transparent glass electrode and metal electrode as the anode and cathode of the device respectively. Under the drive of a certain voltage, electrons and holes are respectively injected into the electron transport layer and the hole transport layer from the cathode and the anode, and then migrate to the light-emitting layer respectively, meet to form excitons to excite the light-emitting molecules, and the latter emits visible light after radiation. The organic functional layer generally includes an electron transport layer (ETL), a light-emitting layer (EML) and a hole transport layer (HTL). With the progress of society, the requirements for the device functions are continuously improved, and now various auxiliary functional layers such as an electron injection layer (ETL), an electron blocking layer (EBL), a hole injection layer (HIL), a hole blocking layer (HBL) and a capping layer (CPL) are added, and these functional layers play different roles in the device.

[0004] As an important part for transferring holes, the hole transport material has an important position in the organic electroluminescent device. Its function is to improve the injection and transport efficiency of holes, reduce the injection barrier of holes, and effectively block electrons in the light-emitting layer to achieve the maximum recombination of carriers, thereby improving the luminous efficiency and service life of the organic electroluminescent device. Therefore, it is particularly important to develop a hole transport material with high hole mobility, good film-forming property and thermal stability, appropriate HOMO energy level and easy carrier transport to achieve the high-efficiency and long-life performance of the device. However, at present, the types of hole transport materials that can meet the above excellent performance in the OLED industry are limited. Therefore, designing more and better hole transport materials is a technical problem that the OLED industry needs to continuously overcome. Summary of the Invention

[0005] In order to solve the problems in the prior art that affect the use performance of the device, the present invention provides a diamine derivative and an organic electroluminescent device thereof. When applied to the hole transport region, it can effectively improve the luminous efficiency and service life of the device.

[0006] The present invention provides a diamine derivative, and the diamine derivative has a structure shown in Formula I,

[0007]

[0008] In Formula I, the Ar 1 ~Ar 4 are the same as or different from each other, at least one of which is selected from the group shown in Formula I-1, and the rest are the same as or different from each other and are selected from the group shown in Formula I-2;

[0009]

[0010] The R a , R b , R c are the same as or different from each other and are selected from any one of hydrogen, deuterium, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C3-C6 cycloalkyl, and substituted or unsubstituted C6-C30 aryl;

[0011] The m is selected from 1, 2 or 3;

[0012] The m 1 is selected from 0, 1, 2, 3 or 4. When there are two or more R a , the two or more R a are the same as or different from each other, or two adjacent R a can be connected to each other to form a substituted or unsubstituted benzene ring, naphthalene ring or phenanthrene ring;

[0013] The m 2 is selected from 0, 1, 2, 3, 4, 5, 6 or 7. When there are two or more R b , the two or more R b are the same as or different from each other;

[0014] The m 3 is selected from 0, 1, 2, 3, 4 or 5. When there are two or more R c , the two or more R c are the same as or different from each other;

[0015] The L is selected from any one of a phenylene group substituted or unsubstituted by one or more R, a biphenylene group substituted or unsubstituted, a terphenylene group substituted or unsubstituted, a naphthylene group substituted or unsubstituted, an anthrylene group substituted or unsubstituted, a phenanthrylene group substituted or unsubstituted, a triphenylene group substituted or unsubstituted, and combinations thereof;

[0016] R is selected from any one of methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, phenyl;

[0017] The L 1 -L 4 are the same as or different from each other, and are each independently selected from a single bond, a substituted or unsubstituted phenylene, a substituted or unsubstituted biphenylene, a substituted or unsubstituted terphenylene, a substituted or unsubstituted naphthylene, a substituted or unsubstituted anthracenylene, a substituted or unsubstituted phenanthrylene, a substituted or unsubstituted triphenylene, and combinations thereof;

[0018] Provided that at least one of Ar 1 , Ar 2 , Ar 3 , Ar 4 , L 1 , L 2 , L 3 or L 4 in Formula I contains deuterium.

[0019] The present invention also provides an organic electroluminescent device, comprising an anode, an organic layer, and a cathode, wherein the organic layer is located between the anode and the cathode or outside any one of the anode and the cathode, and the organic layer contains any one or more of the diamine derivatives.

[0020] Advantageous effects: The deuterated diamine derivative of Formula I of the present invention has at least one bridging and naphthalene group in the arylamine group. Compared with the non-deuterated diamine derivative and the deuterated diamine derivative in which naphthalene is directly connected to the amine, it has excellent properties such as good hole transport ability, appropriate HOMO energy level, high glass transition temperature, and good film-forming property. Especially when the number of bridging and naphthalene groups in the arylamine increases, the electron-donating ability of the compound of Formula I is further improved. When it is used as a hole transport layer material in an organic electroluminescent device, it can reduce the energy barrier during hole transport, facilitate hole injection and transport, increase hole transport ability, increase the carrier recombination probability, and increase the exciton utilization rate, thereby improving the light emission efficiency and service life of the device. In addition, when the deuterated diamine derivative of Formula I is combined with the triarylamine derivative shown in Formula II to form a bilayer hole transport layer, it has a synergistic effect and further improves the device performance. Specific embodiments

[0021] The technical solutions of the embodiments of the present invention will be described clearly and completely below. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. All other embodiments obtained by those skilled in the art based on the embodiments of the present invention without creative efforts belong to the protection scope of the present invention.

[0022] In the compounds of the present invention, any atom not specified as a particular isotope is included as any stable isotope of that atom, and includes atoms in both their natural and non-natural isotope abundances.

[0023] In the present invention, "D" is the isotope deuterium of hydrogen.

[0024] In the present invention, "*" means the part connected to another substituent.

[0025] In the present invention, when the position of a substituent on a ring is not fixed, it means that it can be connected to any of the corresponding optional sites of the ring. For example, can represent etc. And so on.

[0026] Examples of the halogen atoms described in the present invention may include fluorine, chlorine, bromine or iodine.

[0027] The alkyl group described in the present invention refers to a monovalent group obtained by removing one hydrogen atom from an alkane molecule, which may be a straight-chain alkyl group or a branched-chain alkyl group, preferably having 1 to 12 carbon atoms, more preferably having 1 to 8 carbon atoms, and particularly preferably having 1 to 6 carbon atoms. The alkyl group may be substituted or unsubstituted. Specific examples may include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, undecyl, dodecyl, etc., but are not limited thereto.

[0028] The cycloalkyl group described in the present invention refers to a monovalent group obtained by removing one hydrogen atom from a cyclic alkane molecule, preferably having 3 to 6 carbon atoms. The cycloalkyl group may be substituted or unsubstituted. The cycloalkyl group includes cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc., but is not limited thereto.

[0029] As used herein, the term "aryl" refers to a monovalent group obtained by removing a hydrogen atom from the aromatic nucleus carbon of an aromatic compound molecule, which may be a monocyclic aryl, a polycyclic aryl or a fused-ring aryl, preferably having 6 to 30 carbon atoms, more preferably 6 to 18 carbon atoms, and particularly preferably 6 to 12 carbon atoms. The aryl may be substituted or unsubstituted. The monocyclic aryl refers to an aryl having only one aromatic ring in the molecule, such as phenyl, etc., but not limited thereto; the polycyclic aryl refers to an aryl having two or more independent aromatic rings in the molecule, such as biphenyl, terphenyl, quaterphenyl, etc., but not limited thereto; the fused-ring aryl refers to an aryl having two or more aromatic rings and fused together by sharing two adjacent carbon atoms, such as naphthyl, anthryl, phenanthryl, pyrenyl, perylenyl, etc., but not limited thereto.

[0030] As used herein, the term "arylene" refers to the general term for a divalent group remaining after removing two hydrogen atoms from the aromatic nucleus carbon of an aromatic hydrocarbon molecule, which may be a monocyclic arylene, a polycyclic arylene or a fused-ring arylene, preferably having 6 to 30 carbon atoms, more preferably having 6 to 22 carbon atoms, still more preferably having 6 to 18 carbon atoms, and most preferably having 6 to 12 carbon atoms. Regarding the above arylene, as the monocyclic arylene, it may be phenylene, etc., but not limited thereto. The arylene may be substituted or unsubstituted. As the above polycyclic arylene, it may be biphenylene, terphenylene, quaterphenylene, etc., but not limited thereto. As the above fused-ring arylene, it may be naphthylene, anthrylene, phenanthrylene, triphenylene, but not limited thereto.

[0031] As used herein, "unsubstituted" in "substituted or unsubstituted" means that the hydrogen atoms on the group are not replaced by any substituents; "substituted" means that at least one hydrogen atom on the group is replaced by a substituent, and the substitution position is not limited. When multiple hydrogens are replaced by multiple substituents, the multiple substituents may be the same or different.

[0032] In the "substituted or unsubstituted" described in the present invention, the substituents are the same as or different from each other and are selected from deuterium, cyano group, nitro group, amino group, halogen atom, substituted or unsubstituted C1-C12 alkyl group, substituted or unsubstituted C3-C12 cycloalkyl group, substituted or unsubstituted C2-C12 heterocycloalkyl group, substituted or unsubstituted C6-C30 aryl group, substituted or unsubstituted C6-C30 arylamino group, and any one of them, preferably deuterium, cyano group, halogen atom, amino group, C1-C12 alkyl group, C3-C12 cycloalkyl group, C2-C12 heterocycloalkyl group, C6-C30 aryl group, C6-C30 arylamino group. Specific examples may include deuterium, fluorine, chlorine, bromine, iodine, cyano group, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, tert-butyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, phenyl group, biphenyl group, terphenyl group, tolyl group, pentadeuterophenyl group, biphenyl group, naphthyl group, anthracenyl group, phenanthryl group, pyrenyl group, triphenylenyl group, base, perylenyl group, fluoranthenyl group, fluorenyl group, 9,9-dimethylfluorenyl group, 9,9-diphenylfluorenyl group, 9-methyl-9-phenylfluorenyl group, spirofluorenyl group, 9,9'-spirobifluorenyl group, phenylamino group, biphenylamino group, etc., but not limited thereto.

[0033] Unless otherwise specified, the term "ring" as used herein refers to a fused ring composed of an aliphatic ring having 3 to 30 carbon atoms, an aromatic ring having 6 to 30 carbon atoms, a heterocycle having 2 to 60 carbon atoms, or a combination thereof, and it includes a saturated or unsaturated ring.

[0034] The "linked to form a ring" described in the present invention means that two groups are linked to each other by a chemical bond and optionally aromatized. As exemplified below:

[0035]

[0036] In the present invention, the ring formed by linking can be an aromatic ring system, an aliphatic ring system, or a ring system formed by the fusion of both, and the ring formed by linking can be a three-membered ring, a four-membered ring, a five-membered ring, a six-membered ring, a seven-membered ring, or a fused ring, such as benzene, naphthalene, indene, cyclopentene, cyclopentane, cyclobutane, cyclohexene, cyclohexane, naphthalene, phenanthrene, or pyrene, but not limited thereto.

[0037] The present invention provides a diamine derivative, and the diamine derivative has a structure shown in Formula I,

[0038]

[0039] In Formula I, the Ar 1 ~Ar 4 are the same as or different from each other, and at least one of them is selected from the group shown in Formula I-1, and the rest are the same as or different from each other and are selected from the group shown in Formula I-2;

[0040]

[0041] The said R a and R b and R c are the same as or different from each other, and are each independently selected from hydrogen, deuterium, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C3-C6 cycloalkyl, and substituted or unsubstituted C6-C30 aryl;

[0042] The said m is selected from 1, 2 or 3;

[0043] The said m 1 is selected from 0, 1, 2, 3 or 4. When there are two or more Rs a the two or more Rs a are the same as or different from each other, or two adjacent Rs a may be connected to each other to form a substituted or unsubstituted benzene ring, naphthalene ring or phenanthrene ring;

[0044] The said m 2 is selected from 0, 1, 2, 3, 4, 5, 6 or 7. When there are two or more Rs b the two or more Rs b are the same as or different from each other;

[0045] The said m 3 is selected from 0, 1, 2, 3, 4 or 5. When there are two or more Rs c the two or more Rs c are the same as or different from each other;

[0046] The said L is selected from phenylene, biphenylene, terphenylene, naphthylene, anthracenylene, phenanthrenylene, triphenylene which are substituted or unsubstituted by one or more Rs, and any combination thereof;

[0047] The said R is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, phenyl;

[0048] The said L 1 -L 4 are the same as or different from each other, and are each independently selected from a single bond, phenylene, biphenylene, terphenylene, naphthylene, anthracenylene, phenanthrenylene, triphenylene which are substituted or unsubstituted, and any combination thereof;

[0049] Provided that, in formula I, the said Ar 1 and Ar 2, Ar 3 , Ar 4 , L 1 , L 2 , L 3 or L 4 at least one of them contains deuterium.

[0050] Preferably, the formula I-2 is selected from any one of the following groups:

[0051]

[0052] The R e is selected from hydrogen, deuterium or any one of the following groups which are substituted or unsubstituted by one or more deuteriums, C1-C12 alkyl groups: methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, phenyl, biphenyl or naphthyl;

[0053] The q 1 is selected from 0, 1, 2, 3, 4 or 5, and the q 2 is selected from 0, 1, 2, 3 or 4.

[0054] Preferably, the formula I-2 is selected from any one of the following groups:

[0055]

[0056]

[0057] The s 1 is selected from 1, 2, 3, 4 or 5, and the s 2 is selected from 0, 1, 2, 3 or 4, and the s 3 is selected from 0, 1, 2, 3, 4 or 5, and the s 4 is selected from 0, 1, 2, 3, 4, 5, 6 or 7, and the s 5 is selected from 0, 1, 2, 3, 4, 5, 6, 7, 8 or 9, and the s 6 is selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 or 11, and the s 7 is selected from 0, 1, 2 or 3.

[0058] Preferably, Ar 1 ~Ar 4 are the same as or different from each other, at least one of them is selected from the group shown in formula I-1, at least one of the remaining groups is selected from the groups containing deuterium in the aforementioned formula I-2, and the remaining are selected from the groups shown in formula I-2.

[0059] Preferably, the Ar 1 , Ar 2 , Ar 3or Ar 4 is selected from the groups represented by Formula I-1.

[0060] Preferably, the Ar 1 and Ar 2 , or the Ar 1 and Ar 4 are selected from the groups represented by Formula I-1.

[0061] Preferably, the Ar 1 , Ar 2 and Ar 4 are selected from the groups represented by Formula I-1.

[0062] Preferably, the Ar 1 , Ar 2 , Ar 3 and Ar 4 are selected from the groups represented by Formula I-1.

[0063] Preferably, the diamine derivative is selected from any one of Formula I-a to Formula I-e,

[0064]

[0065] Preferably, the Formula I-1 is selected from any one of the following groups:

[0066]

[0067] The R a , R b are the same as or different from each other and are selected from hydrogen, deuterium, or any one of the following groups which are substituted or unsubstituted by one or more deuteriums, C1-C12 alkyl groups: methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, phenyl, biphenyl, terphenyl, or naphthyl;

[0068] The n 1 is selected from 0, 1, 2, 3, or 4, the n 2 is selected from 0, 1, 2, 3, 4, 5, 6, or 7, the n 3 is selected from 0, 1, 2, 3, 4, 5, or 6, the n 4 is selected from 0, 1, or 2.

[0069] Preferably, the Formula I-1 is selected from any one of the following groups:

[0070]

[0071]

[0072] Preferably, the Formula I-1 contains at least one deuterium.

[0073] Preferably, in the formula I-1 group contains at least one deuterium atom.

[0074] Preferably, in the formula I-1 group contains at least one deuterium atom.

[0075] Preferably, in the formula I-1 group, group each contains at least one deuterium atom. Preferably, the formula I-1 is selected from any one of the following groups,

[0076]

[0077]

[0078] The R a and R b are the same as or different from each other, and are each independently selected from hydrogen, methyl, deuterated methyl, ethyl, n-propyl, isopropyl, deuterated isopropyl, n-butyl, tert-butyl, deuterated tert-butyl, cyclobutyl, cyclopentyl, cyclohexyl, phenyl, deuterated phenyl, biphenyl, naphthyl;

[0079] The p 1 is selected from 0, 1, 2 or 3, the p 2 is selected from 0, 1, 2, 3, 4, 5, 6 or 7, the p 3 is selected from 0, 1, 2, 3 or 4, the p 4 is selected from 0, 1, 2, 3, 4 or 5, p 5 is selected from 0, 1, 2, 3, 4, 5 or 6, p 6 is selected from 0, 1 or 2;

[0080] The t 1 is selected from 1, 2, 3 or 4, the t 2 is selected from 1, 2, 3, 4, 5 or 6, the t 3 is selected from 1, 2, 3, 4, 5, 6 or 7.

[0081] Preferably, at least one of the Ar 1 , Ar 2 , Ar 3 , Ar 4 is selected from the groups containing deuterium in the groups shown in the foregoing formula I-1.

[0082] Preferably, the L is selected from any one of the following groups, and their combinations,

[0083]

[0084] Preferably, the L1 -L 4 Same as or different from each other, selected from a single bond and the following groups which are unsubstituted or substituted by one or more deuterium, methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, phenyl, deuterated phenyl: phenylene, biphenylene, terphenylene, naphthylene, anthrylene, phenanthrylene, triphenylene, and any combination thereof.

[0085] Preferably, Formula I satisfies at least one of the following conditions:

[0086] i. At least one of Ar 1 , Ar 2 , Ar 3 , Ar 4 is selected from the groups containing deuterium among the groups shown in Formula I-1 above;

[0087] ii. At least one of Ar 1 , Ar 2 , Ar 3 , Ar 4 is selected from the groups containing deuterium among the groups shown in Formula I-2 above;

[0088] iii. At least one of L 1 , L 2 , L 3 , L 4 is selected from the groups containing deuterium among the groups above.

[0089] Preferably, the diamine derivative is selected from any one of the following structures

[0090]

[0091]

[0092]

[0093]

[0094]

[0095]

[0096]

[0097]

[0098]

[0099]

[0100]

[0101]

[0102]

[0103]

[0104]

[0105]

[0106] Some specific chemical structures of the diamine derivatives represented by Chemical Formula I of the present invention are listed above. However, the present invention is not limited to these listed chemical structures, and all those based on the structure shown in Chemical Formula I with substituents being the groups defined as above should be included.

[0107] The present invention also provides an organic electroluminescent device, comprising an anode, an organic layer, and a cathode. The organic layer is located between the anode and the cathode or outside any one of the anode and the cathode, and the organic layer contains any one or more of the above-mentioned diamine derivatives.

[0108] Preferably, the organic layer is located outside any one of the anode and the cathode and contains a covering layer.

[0109] Preferably, the organic layer is located between the anode and the cathode and includes at least one of a hole transport region, a light-emitting layer, and an electron transport region.

[0110] Preferably, the electron transport region of the present invention contains at least one of an electron injection layer, an electron transport layer, and a hole blocking layer.

[0111] Preferably, the electron transport region of the present invention contains at least one of an electron transport layer and a hole blocking layer.

[0112] Preferably, the electron transport region of the present invention contains a hole blocking layer.

[0113] Preferably, the light-emitting layer of the present invention contains a host material and a guest material; preferably, the host material of the present invention contains a single host material or a dual host material.

[0114] Preferably, the hole transport region of the present invention contains at least one of a hole injection layer, a hole transport layer, and an electron blocking layer.

[0115] Preferably, the hole transport region of the present invention comprises at least one of a hole injection layer and a hole transport layer. More preferably, the hole transport region of the present invention comprises a hole transport layer, and the hole transport layer comprises any one or more of the diamine derivatives of the present invention.

[0116] Preferably, the hole transport layer of the present invention comprises a first hole transport layer and a second hole transport layer.

[0117] Preferably, the first hole transport layer of the present invention is located between the hole injection layer and the second hole transport layer.

[0118] Preferably, the second hole transport layer of the present invention is located between the first hole transport layer and the light-emitting layer.

[0119] Preferably, the first hole transport layer of the present invention comprises the diamine derivative represented by Formula I of the present invention, and the second hole transport layer comprises a triarylamine derivative represented by Formula II.

[0120]

[0121] In Formula II, Ar is selected from any one of phenyl, biphenyl, terphenyl, naphthyl which is substituted or unsubstituted by one or more R', and combinations thereof;

[0122] R' is selected from deuterium or the following groups which are substituted or unsubstituted by one or more deuteriums: methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl, norbornyl, phenyl, biphenyl, naphthyl;

[0123] The L a 、L b 、L c are the same as or different from each other, and are each selected from a single bond or any one of substituted or unsubstituted C6-C18 arylene groups;

[0124] The R 1 are the same as or different from each other, and are each selected from hydrogen, deuterium, substituted or unsubstituted C1-C12 alkyl groups, substituted or unsubstituted C3-C12 cycloalkyl groups, substituted or unsubstituted C6-C30 aryl groups;

[0125] The a 1 is selected from 0, 1, 2 or 3, the a 2 is selected from 0, 1, 2, 3 or 4, the a 3 is selected from 0, 1, 2, 3, 4 or 5; when there are two or more R 1 s, two or more R 1are the same as or different from each other, or two adjacent Rs 1 may be connected to each other to form a substituted or unsubstituted ring.

[0126] Preferably, the Ar is selected from any one of the following groups shown below,

[0127]

[0128]

[0129] Preferably, the L a 、L b 、L c are the same as or different from each other, and are selected from a single bond or any one of the following groups shown below,

[0130]

[0131] Preferably, the Rs 1 are the same as or different from each other, and are selected from hydrogen, deuterium, or the following groups which are substituted or unsubstituted by one or more deuteriums: methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl, norbornyl, phenyl, biphenyl, naphthyl.

[0132] Preferably, the triarylamine derivative of formula II is selected from any one of the following structures,

[0133]

[0134]

[0135]

[0136]

[0137]

[0138]

[0139] Some specific chemical structures of the derivatives represented by formula II of the present invention are listed above, but the present invention is not limited to these listed chemical structures. All those based on the structure shown in formula II with substituents as defined above should be included.

[0140] The organic layer described in the present invention can be a single-layer structure, a double-layer structure or a multi-layer structure. At the same time, each of the organic layers can also contain multiple compounds. However, the structure of the organic electroluminescent device is not limited to this.

[0141] The organic electroluminescent device of the present invention is generally formed on a substrate. The above-mentioned substrate only needs to remain unchanged when forming electrodes and organic layers. For example, substrates such as glass, plastic, polymer film, and silicon can be used.

[0142] The anode material of the present invention preferably uses a material with a high work function to improve the hole injection efficiency. The anode materials applicable to the present invention are selected from the following: indium tin oxide (ITO), indium zinc oxide (IZO), tin oxide (SnO 2 ), zinc oxide (ZnO) or any combination thereof, magnesium (Mg), silver (Ag), aluminum (Al), aluminum-lithium (Al-Li), calcium (Ca), magnesium-indium (Mg-In), magnesium-silver (Mg-Ag) or any combination thereof. The anode can have a single-layer structure or a multi-layer structure including two or more layers. For example, the anode can have a single-layer structure of Al or a three-layer structure of ITO / Ag / ITO, but is not limited thereto.

[0143] The hole injection layer material of the present invention preferably uses a material with good hole acceptance ability. It can be selected from any one or more of the following structures: metal porphyrin, oligothiophene, arylamine derivative, perylene derivative, hexanitrile hexaazatriphenylene compound, phthalocyanine compound, polycyano conjugated organic material, quinacridone compound, anthraquinone compound, and conductive polymers based on polyaniline and polythiophene, etc., but is not limited thereto.

[0144] The hole transport layer material of the present invention preferably uses a material with a high hole mobility. It can be selected from any one or more of the following structures: carbazole derivative, triarylamine derivative, biphenyldiamine derivative, fluorene derivative, stilbene derivative, hexanitrile hexaazatriphenylene compound, quinacridone compound, anthraquinone compound, polyaniline, polythiophene, polyvinylcarbazole, etc. Examples of the hole transport layer material include the materials described below, N,N'-diphenyl-N,N'-bis(3-methylphenyl)-1,1'-biphenyl-4,4'-diamine (TPD), N,N'-diphenyl-N,N'-(1-naphthyl)-1,1'-biphenyl-4,4'-diamine (NPB), 4-[1-[4-[bis(4-methylphenyl)amino]phenyl]cyclohexyl]-N-(3-methylphenyl)-N-(4-methylphenyl)aniline (TAPC), N,N,N',N'-tetrakis(3-methylphenyl)-3,3'-dimethylbiphenyldiamine (HMTPD), etc., but is not limited thereto.

[0145] The luminescent layer material of the present invention includes a host material and a dopant material. The host material of the luminescent layer can be selected from 4,4'-bis(9-carbazolyl)biphenyl (CBP), 9,10-bis(2-naphthyl)anthracene (ADN), 4,4-bis(9-carbazolyl)biphenyl (CPB), 9,9'-(1,3-phenylene)di-9H-carbazole (mCP), 4,4',4”-tris(carbazol-9-yl)triphenylamine (TCTA), 9,10-bis(1-naphthyl)anthracene (α-AND), N,N'-di-(1-naphthyl)-N,N'-diphenyl-[1,1':4',1”:4”,1”'-quaterphenyl]-4,4”'-diamine (4PNPB), 1,3,5-tris(9-carbazolyl)benzene (TCP), etc. In addition to the above materials and their combinations, the host material of the luminescent layer may also include other known materials suitable for the luminescent layer, etc., but not limited thereto. The dopant materials of the luminescent layer of the present invention are divided into blue luminescent materials, green luminescent materials, and red luminescent materials. The dopant material of the luminescent layer can be selected from (6-(4-(diphenylamino)phenyl)-N,N-diphenylpyrene-1-amine) (DPAP-DPPA), 2,5,8,11-tetra-tert-butylperylene (TBPe), 4,4'-bis[4-(diphenylamino)styryl]biphenyl (BDAVBi), 4,4'-bis[4-(di-p-tolylamino)styryl]biphenyl (DPAVBi), beryllium bis(2-hydroxyphenylpyridine) (Bepp2), iridium bis(4,6-difluorophenylpyridine-C2,N)picolinate (FIrpic), tris(2-phenylpyridine)iridium (Ir(ppy)3), iridium bis(2-phenylpyridine)(acetylacetonate) (Ir(ppy)2(acac)), 9,10-bis[N-(p-tolyl)anilino]anthracene (TPA), 4-(dicyanomethylene)-2-methyl-6-(4-dimethylaminostyryl)-4H-pyran (DCM), tris[1-phenylisoquinoline-C2,N]iridium(III) (Ir(piq)3), iridium bis(1-phenylisoquinoline)(acetylacetonate) (Ir(piq)2(acac)), etc., but not limited thereto.

[0146] The doping ratio of the host material and the guest material in the luminescent layer of the present invention is determined according to the materials used. The amount of the dopant material is preferably selected from 0.1 to 70% by mass, more preferably 0.1 to 30% by mass, further preferably 1 to 30% by mass, still more preferably 1 to 20% by mass, and particularly preferably 1 to 10% by mass.

[0147] The hole blocking layer material described in the present invention is preferably a material that can effectively block hole transport and enable excitons to recombine in the light-emitting layer rather than in the electron transport layer. In addition to the nitrogen-containing heterocyclic derivatives provided by the present invention, it can also be selected from any one or several of the following structures: phenanthroline derivatives, rare earth derivatives, imidazole derivatives, oxazole derivatives, oxadiazole derivatives, triazole derivatives, triazine derivatives, quinoline derivatives, phenanthroline derivatives, azabenzene derivatives, anthrone derivatives, etc., but not limited thereto.

[0148] The electron transport layer material described in the present invention is preferably a material with high electron mobility. It can be selected from any one or several of the following structures: 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP), 1,3,5-tris(N-phenyl-2-benzimidazole)benzene (TPBi), tris(8-hydroxyquinoline)aluminum(III) (Alq3), 8-hydroxyquinoline-lithium (Liq), bis(2-methyl-8-hydroxyquinoline)(4-phenylphenol)aluminum(III) (BAlq), and 3-(biphenyl-4-yl)-5-(4-tert-butylphenyl)-4-phenyl-4H-1,2,4-triazole (TAZ), 4,7-diphenyl-1,10-phenanthroline (Bphen), etc., but not limited thereto.

[0149] The electron injection layer material described in the present invention is preferably a material with a relatively small potential barrier difference from the adjacent organic layer material. Specific examples can include: alkali metal compounds (such as lithium oxide, lithium fluoride, cesium carbonate, cesium fluoride, cesium 8-hydroxyquinoline, aluminum 8-hydroxyquinoline), organometallic salts (metal acetates, metal benzoates or metal stearates), molybdenum trioxide, aluminum metal, etc., but not limited thereto.

[0150] The cathode material described in the present invention is preferably a material with a low work function that can promote electron injection into the organic layer to reduce the electron injection barrier. It can be selected from any one or several of the following materials: Ag, Mg, Cu, Al, Pt, Pd, Au, Ni, Nd, Ir, Cr, Li, Ca, LiF / Ca, LiF / Al, Mo, Ti, including their compounds or their mixtures (for example, a mixture of Ag and Mg), but not limited thereto.

[0151] The cover layer described in the present invention is provided outside any one or more of the anode and the cathode to reduce the total reflection loss of light and improve the light extraction efficiency. It can be selected from any one or more of the following structures: arylamine derivatives, biscarbazole derivatives, benzimidazole derivatives, benzoxazole derivatives, benzothiazole derivatives, triazole derivatives, benzofuran derivatives, diamine derivatives, porphyrin derivatives, phthalocyanine derivatives, Alq 3 、TPBi or their mixtures, but not limited thereto.

[0152] The present invention has no special limitation on the thickness of each organic layer of the organic electroluminescent device, and the thickness commonly used in the art can be adopted.

[0153] The organic electroluminescent device described in the present invention can be manufactured by sequentially laminating the above structures. Known methods such as wet film forming methods and dry film forming methods can be used for the manufacturing method. Specific examples of wet film forming methods include various coating methods such as spin coating method, dipping method, casting method, and inkjet method. Specific examples of dry film forming methods include vacuum evaporation method, sputtering method, plasma method, ion plating method, etc., but are not limited thereto.

[0154] The organic light-emitting device described in the present invention can be widely applied to fields such as panel display, lighting source, flexible OLED, electronic paper, organic solar cell, organic photoreceptor or organic thin film transistor, sign board, signal lamp, etc.

[0155] The present invention will be more specifically explained by the following examples, but it is not intended to limit the present invention thereby. Based on this description, those of ordinary skill in the art will be able to implement the present invention and prepare other compounds and devices according to the present invention within the entire disclosed scope without creative labor.

[0156] The present invention provides a preparation method for the compounds represented by Formula I and Formula II, but the preparation method of the present invention is not limited thereto, and the specific synthesis route is as shown below:

[0157] [Synthesis route of Formula I]

[0158] Preparation of raw material a:

[0159]

[0160] Preparation of intermediate A:

[0161]

[0162] Preparation of intermediate B:

[0163]

[0164] Preparation of the compound of Formula I:

[0165]

[0166] Wherein, X a are the same as or different from each other and are each independently selected from any one of Cl, Br, and I; Ar 1 ~Ar 4 , L 1 ~L 4 are defined in the same manner as above.

[0167] [Synthesis Route of Formula II]

[0168] Preparation of starting material m':

[0169]

[0170] Preparation of the compound of Formula II:

[0171]

[0172] Wherein, X a are the same as or different from each other, and are each independently selected from any one of Cl, Br, and I; Ar, L a ~L c , R 1 , a 1 ~a 3 are defined as above.

[0173] In the present invention, the above substituents can be bonded by methods known in the art, and the types, positions or numbers of the substituents can be changed according to techniques known in the art.

[0174] Description of starting materials, reagents and characterization equipment:

[0175] In the present invention, there are no particular restrictions on the sources of the starting materials and reagents used in the following examples, and they can be commercially available products or prepared by methods well-known to those skilled in the art.

[0176] The mass spectrometry was performed using a Waters G2-Si quadrupole tandem time-of-flight high-resolution mass spectrometer from the UK, with chloroform as the solvent;

[0177] Elemental analysis was performed using a Vario EL cube type organic elemental analyzer from Elementar of Germany, with a sample mass of 5 - 10 mg.

[0178] Synthesis Example 1: Preparation of Compound 1-19

[0179]

[0180] Preparation of Intermediate A-1-19:

[0181] Under nitrogen protection, a-1-19 (22.98 g, 80 mmol), b-1-19 (16.43 g, 80 mmol), and sodium tert-butoxide (11.53 g, 120 mmol) were added to 400 ml of toluene, and Pd(dppf)Cl was added with stirring 2(0.59 g, 0.80 mmol), heat the mixed solution of the above reactants under reflux for 4 h. After the reaction is completed, cool to room temperature, add distilled water, extract with dichloromethane, let stand for liquid separation, collect the organic layer, dry it with anhydrous magnesium sulfate, filter, concentrate the filtrate by reduced pressure distillation, cool to crystallize, filter by suction, recrystallize the obtained solid with ethyl acetate to obtain intermediate A-1-19 (26.67 g, 81%), HPLC purity ≥ 99.84%. Mass spectrometry m / z: 411.2881 (theoretical value: 411.2864).

[0182] Preparation of Compound 1-19:

[0183] Under nitrogen protection, add intermediate A-1-19 (22.64 g, 55 mmol), raw material g-1-19 (5.90 g, 25 mmol), and sodium tert-butoxide (7.21 g, 75 mmol) to 100 ml of toluene. Add Pd 2 (dba) 3 (0.27 g, 0.30 mmol), BINAP (0.37 g, 0.60 mmol) to the above mixed solution of reactants, and heat the solution under reflux for 5.5 h. After the reaction is completed, cool to room temperature, add distilled water, extract with dichloromethane, let stand for liquid separation, collect the organic layer, dry it with anhydrous magnesium sulfate, filter, concentrate the filtrate by reduced pressure distillation, cool to crystallize, filter by suction, recrystallize the obtained solid with toluene to obtain compound 1-19 (16.82 g, yield 75%), HPLC purity ≥ 99.91%. Mass spectrometry m / z: 896.5868 (theoretical value: 896.5885). Theoretical elemental content (%) C 66 H 60 D 8 N 2 : C, 88.34; H, 8.54; N, 3.12. Measured elemental content (%): C, 88.36; H, 8.53; N, 3.11.

[0184] Synthesis Example 2: Preparation of Compound 1-37

[0185]

[0186] Preparation of Intermediate A-1-37:

[0187] Under nitrogen protection, add a-1-37 (22.65 g, 80 mmol), b-1-37 (13.94 g, 80 mmol), and sodium tert-butoxide (11.53 g, 120 mmol) to 400 ml of toluene. Add Pd(dppf)Cl 2(0.59 g, 0.80 mmol), heat the mixed solution of the above reactants under reflux for 4 h. After the reaction is completed, cool to room temperature, add distilled water, extract with dichloromethane, let it stand for liquid separation, collect the organic layer, dry it with anhydrous magnesium sulfate, filter, concentrate the filtrate by reduced pressure distillation, cool for crystallization, filter by suction, recrystallize the obtained solid with ethyl acetate to obtain intermediate A-1-37 (24.70 g, 82%), HPLC purity ≥ 99.73%. Mass spectrometry m / z: 376.1976 (theoretical value: 376.1988).

[0188] Preparation of intermediate B-1-37:

[0189] Under nitrogen protection, add a-1-37 (22.65 g, 80 mmol), d-1-37 (17.54 g, 80 mmol), and sodium tert-butoxide (11.53 g, 120 mmol) to 400 ml of toluene. Stir and add Pd(dppf)Cl 2 (0.59 g, 0.80 mmol), heat the mixed solution of the above reactants under reflux for 4.5 h. After the reaction is completed, cool to room temperature, add distilled water, extract with dichloromethane, let it stand for liquid separation, collect the organic layer, dry it with anhydrous magnesium sulfate, filter, concentrate the filtrate by reduced pressure distillation, cool for crystallization, filter by suction, recrystallize the obtained solid with ethyl acetate to obtain intermediate B-1-37 (27.32 g, 81%), HPLC purity ≥ 99.69%. Mass spectrometry m / z: 421.1845 (theoretical value: 421.1830).

[0190] Preparation of intermediate C-1-37:

[0191] Under nitrogen protection, add intermediate A-1-37 (24.47 g, 65 mmol), g-1-37 (12.44 g, 65 mmol), and sodium tert-butoxide (11.24 g, 117 mmol) to 300 ml of toluene. Stir and add Pd(OAc) 2 (0.18 g, 0.78 mmol), P(t-Bu) 3 (3.12 mL of 0.5 M toluene solution, 1.56 mmol), heat the mixed solution of the above reactants under reflux for 5 h. After the reaction is completed, cool to room temperature, add distilled water, extract with dichloromethane, let it stand for liquid separation, collect the organic layer, dry it with anhydrous magnesium sulfate, filter, concentrate the filtrate by reduced pressure distillation, cool for crystallization, filter by suction, recrystallize the obtained solid with toluene / ethanol = 5 / 1 to obtain intermediate C-1-37 (23.74 g, 75%), HPLC purity ≥ 99.82%. Mass spectrometry m / z: 486.1928 (theoretical value: 486.1911).

[0192] Preparation of compound 1-37:

[0193] Under nitrogen protection, intermediate C-1-37 (19.48 g, 40 mmol), B-1-37 (18.55 g, 44 mmol), and sodium tert-butoxide (7.69 g, 80 mmol) were added to 200 ml of toluene. Pd 2 (dba) 3 (0.55 g, 0.60 mmol) and BINAP (0.75 g, 1.20 mmol) were added, and the mixed solution of the above reactants was heated under reflux for 6 h. After the reaction was completed, it was cooled to room temperature, distilled water was added, extracted with dichloromethane, allowed to stand for liquid separation, the organic layer was collected, dried over anhydrous magnesium sulfate, filtered, the filtrate was concentrated by distillation under reduced pressure, cooled for crystallization, filtered by suction, and the obtained solid was recrystallized with toluene to obtain compound 1-37 (26.86 g, yield 77%), HPLC purity ≥ 99.93%. Mass spectrometry m / z: 871.3958 (theoretical value: 871.3975). Theoretical elemental content (%) C 66 H 41 D 5 N 2 : C, 90.89; H, 5.89; N, 3.21. Measured elemental content (%): C, 90.91; H, 5.86; N, 3.19.

[0194] Synthesis Example 3: Preparation of Compound 1-63

[0195]

[0196] According to the same preparation method of compound 1-37 in Synthesis Example 2, equimolar amounts of a-1-37, b-1-37, a-1-37, d-1-37, and g-1-37 were respectively replaced with equimolar amounts of a-1-63, b-1-63, c-1-63, d-1-63, and g-1-63 to obtain compound 1-63 (25.17 g), HPLC purity ≥ 99.94%. Mass spectrometry m / z: 861.4145 (theoretical value: 861.4131). Theoretical elemental content (%) C 65 H 43 D 5 N 2 : C, 90.56; H, 6.20; N, 3.25. Measured elemental content (%): C, 90.54; H, 6.18; N, 3.28.

[0197] Synthesis Example 4: Preparation of Compound 1-71

[0198]

[0199] According to the same preparation method as that of Compound 1-37 in Synthesis Example 2, equimolar amounts of a-1-37, b-1-37, a-1-37, d-1-37, and g-1-37 were respectively replaced with equimolar amounts of a-1-71, b-1-71, c-1-71, b-1-71, and g-1-71 to obtain Compound 1-71 (26.46 g), with HPLC purity ≥ 99.95%. Mass spectrometry m / z: 847.3990 (theoretical value: 847.3975). Theoretical elemental content (%) C 64 H 41 D 5 N 2 : C, 90.64; H, 6.06; N, 3.30. Measured elemental content (%): C, 90.66; H, 6.03; N, 3.29.

[0200] Synthesis Example 5: Preparation of Compound 1-76

[0201]

[0202] According to the same preparation method as that of Compound 1-19 in Synthesis Example 1, equimolar amounts of a-1-19, b-1-19, and g-1-19 were respectively replaced with equimolar amounts of a-1-76, d-1-63, and g-1-76 to obtain Compound 1-76 (17.39 g), with HPLC purity ≥ 99.95%. Mass spectrometry m / z: 902.4453 (theoretical value: 902.4445). Theoretical elemental content (%) C 68 H 38 D 10 N 2 : C, 90.43; H, 6.47; N, 3.10. Measured elemental content (%): C, 90.41; H, 6.45; N, 3.08.

[0203] Synthesis Example 6: Preparation of Compound 1-84

[0204]

[0205] According to the same preparation method as that of Compound 1-19 in Synthesis Example 1, equimolar amounts of a-1-19, b-1-19, and g-1-19 were respectively replaced with equimolar amounts of a-1-84, b-1-84, and g-1-76 to obtain Compound 1-84 (17.62 g), with HPLC purity ≥ 99.96%. Mass spectrometry m / z: 902.6156 (theoretical value: 902.6137). Theoretical elemental content (%) C 66 H 38 D 22 N 2: C, 87.75; H, 9.15; N, 3.10. Measured elemental content (%): C, 87.78; H, 9.13; N, 3.08.

[0206] Synthesis Example 7: Preparation of Compound 1-88

[0207]

[0208] According to the same preparation method as in Compound 1-19 of Synthesis Example 1, equimolar amounts of b-1-19 and g-1-19 were respectively replaced with equimolar amounts of b-1-88 and g-1-76 to obtain Compound 1-88 (17.58 g), with HPLC purity ≥ 99.93%. Mass spectrometry m / z: 912.5241 (theoretical value: 912.5259). Theoretical elemental content (%) C 68 H 52 D 8 N 2 : C, 89.43; H, 7.50; N, 3.07. Measured elemental content (%): C, 89.45; H, 7.49; N, 3.10.

[0209] Synthesis Example 8: Preparation of Compound 1-131

[0210]

[0211] According to the same preparation method as in Compound 1-19 of Synthesis Example 1, equimolar amounts of a-1-19, b-1-19, and g-1-19 were respectively replaced with equimolar amounts of c-1-71, b-1-131, and g-1-76 to obtain Compound 1-131 (18.00 g), with HPLC purity ≥ 99.97%. Mass spectrometry m / z: 910.4931 (theoretical value: 910.4947). Theoretical elemental content (%) C 68 H 30 D 18 N 2 : C, 89.63; H, 7.30; N, 3.07. Measured elemental content (%): C, 89.65; H, 7.29; N, 3.06.

[0212] Synthesis Example 9: Preparation of Compound 1-135

[0213]

[0214] Preparation of Intermediate a-1-135:

[0215] Under nitrogen protection, raw material e-1-135 (20.71 g, 100.00 mmol), raw material f-1-135 (16.36 g, 102.00 mmol), Pd(PPh 3 ) 4 (1.73 g, 1.50.00 mmol), K 2 CO 3 (27.64 g, 200.00 mmol), 300 mL of toluene, 100 mL of ethanol, and 100 mL of water were successively added to the reaction flask. The mixture was stirred, and the above reaction system was heated to reflux for 3.5 hours; after the reaction was completed, it was cooled to room temperature, and the filter cake was obtained by suction filtration. The filter cake was rinsed with ethanol, and finally the filter cake was recrystallized with ethyl acetate to obtain intermediate a-1-135 (20.63 g, yield 85%); HPLC purity ≥ 98.78%. Mass spectrometry m / z: 242.0817 (theoretical value: 242.0800).

[0216] According to the same preparation method as in Compound 1-19 of Synthesis Example 1, equimolar amounts of a-1-19, b-1-19, and g-1-19 were respectively replaced with equimolar amounts of a-1-135, b-1-135, and g-1-135 to obtain Compound 1-135 (17.89 g, yield 77%), HPLC purity ≥ 99.96%. Mass spectrometry m / z: 928.4653 (theoretical value: 928.4633). Theoretical elemental content (%) C 70 H 44 D 8 N 2 : C, 90.48; H, 6.51; N, 3.01. Measured elemental content (%): C, 90.50; H, 6.49; N, 3.02.

[0217] Synthesis Example 10: Preparation of Compound 1-191

[0218]

[0219] According to the same preparation method as intermediate a-1-135 in Synthesis Example 9, equimolar amounts of e-1-135 and f-1-135 were respectively replaced with equimolar amounts of e-1-191 and f-1-191 to obtain intermediate a-1-191 (20.64 g), HPLC purity ≥ 99.69%. Mass spectrometry m / z: 245.0979 (theoretical value: 245.0989).

[0220] According to the same preparation method as in Compound 1-37 of Synthesis Example 2, equimolar amounts of a-1-37, b-1-37, a-1-37, d-1-37, and g-1-37 were respectively replaced with equimolar amounts of a-1-191, b-1-191, c-1-191, d-1-191, and g-1-71 to obtain Compound 1-191 (25.84 g), with HPLC purity ≥ 99.93%. Mass spectrometry m / z: 849.4116 (theoretical value: 849.4100). Theoretical elemental content (%) C 64 H 39 D 7 N 2 : C, 90.42; H, 6.28; N, 3.30. Measured elemental content (%): C, 90.39; H, 6.26; N, 3.29.

[0221] Synthesis Example 11: Preparation of Compound 1-206

[0222]

[0223] According to the same preparation method as in Compound 1-19 of Synthesis Example 1, equimolar amounts of a-1-19, b-1-19, and g-1-19 were respectively replaced with equimolar amounts of a-1-37, b-1-206, and g-1-76 to obtain Compound 1-206 (17.61 g), with HPLC purity ≥ 99.98%. Mass spectrometry m / z: 902.4428 (theoretical value: 902.4445). Theoretical elemental content (%) C 68 H 38 D 10 N 2 : C, 90.43; H, 6.47; N, 3.10. Measured elemental content (%): C, 90.41; H, 6.49; N, 3.09.

[0224] Synthesis Example 12: Preparation of Compound 1-209

[0225]

[0226] According to the same preparation method as in Compound 1-19 of Synthesis Example 1, equimolar amounts of a-1-19, b-1-19, and g-1-19 were respectively replaced with equimolar amounts of a-1-37, b-1-209, and g-1-76 to obtain Compound 1-209 (17.39 g), with HPLC purity ≥ 99.95%. Mass spectrometry m / z: 902.4430 (theoretical value: 902.4445). Theoretical elemental content (%) C 68 H 38 D 10 N 2: C, 90.43; H, 6.47; N, 3.10. Measured elemental content (%): C, 90.42; H, 6.49; N, 3.11.

[0227] Synthesis Example 13: Preparation of Compound 1-212

[0228]

[0229] According to the same preparation method as in Compound 1-19 of Synthesis Example 1, equimolar amounts of a-1-19, b-1-19, and g-1-19 were respectively replaced with equimolar amounts of a-1-212, b-1-71, and g-1-76 to obtain Compound 1-212 (17.57 g), with HPLC purity ≥ 99.97%. Mass spectrometry m / z: 900.4339 (theoretical value: 900.4320). Theoretical elemental content (%) C 68 H 40 D 8 N 2 : C, 90.63; H, 6.26; N, 3.11. Measured elemental content (%): C, 90.66; H, 6.24; N, 3.09.

[0230] Synthesis Example 14: Preparation of Compound 1-218

[0231]

[0232] According to the same preparation method as in Compound 1-19 of Synthesis Example 1, equimolar amounts of a-1-19, b-1-19, and g-1-19 were respectively replaced with equimolar amounts of a-1-218, b-1-71, and g-1-76 to obtain Compound 1-218 (17.69 g), with HPLC purity ≥ 99.95%. Mass spectrometry m / z: 906.4679 (theoretical value: 906.4696). Theoretical elemental content (%) C 68 H 34 D 14 N 2 : C, 90.03; H, 6.89; N, 3.09. Measured elemental content (%): C, 90.01; H, 6.90; N, 3.11.

[0233] Synthesis Example 15: Preparation of Compound 1-221

[0234]

[0235] According to the same preparation method of Compound 1-19 in Synthesis Example 1, equimolar amounts of a-1-19, b-1-19, and g-1-19 were respectively replaced with equimolar amounts of a-1-221, b-1-191, and g-1-76 to obtain Compound 1-221 (17.24 g), with HPLC purity ≥ 99.92%. Mass spectrometry m / z: 906.4688 (theoretical value: 906.4696). Theoretical elemental content (%) C 68 H 34 D 14 N 2 : C, 90.03; H, 6.89; N, 3.09. Measured elemental content (%): C, 90.05; H, 6.91; N, 3.10.

[0236] Synthesis Example 16: Preparation of Compound 1-234

[0237]

[0238] According to the same preparation method of Compound 1-19 in Synthesis Example 1, equimolar amounts of a-1-19, b-1-19, and g-1-19 were respectively replaced with equimolar amounts of a-1-234, b-1-234, and g-1-76 to obtain Compound 1-234 (16.67 g), with HPLC purity ≥ 99.95%. Mass spectrometry m / z: 900.4336 (theoretical value: 900.4320). Theoretical elemental content (%) C 68 H 40 D 8 N 2 : C, 90.63; H, 6.26; N, 3.11. Measured elemental content (%): C, 90.64; H, 6.24; N, 3.09.

[0239] Synthesis Example 17: Preparation of Compound 1-298

[0240]

[0241] According to the same preparation method of Compound 1-37 in Synthesis Example 2, equimolar amounts of a-1-37, b-1-37, a-1-37, d-1-37, and g-1-37 were respectively replaced with equimolar amounts of a-1-71, b-1-206, c-1-298, d-1-298, and g-1-71 to obtain Compound 1-298 (27.46 g), with HPLC purity ≥ 99.93%. Mass spectrometry m / z: 902.4436 (theoretical value: 902.4445). Theoretical elemental content (%) C 68 H 38 D 10 N 2: C, 90.43; H, 6.47; N, 3.10. Measured elemental content (%): C, 90.41; H, 6.45; N, 3.08.

[0242] Synthesis Example 18: Preparation of Compound 1-331

[0243]

[0244] According to the same preparation method as in Synthesis Example 2 for Compound 1-37, equimolar amounts of a-1-37, b-1-37, a-1-37, d-1-37, g-1-37 were respectively replaced with equimolar amounts of a-1-191, b-1-63, a-1-212, d-1-331, g-1-331 to obtain Compound 1-331 (27.46 g), with HPLC purity ≥ 99.90%. Mass spectrometry m / z: 900.4338 (theoretical value: 900.4320). Theoretical elemental content (%) C 68 H 40 D 8 N 2 : C, 90.63; H, 6.26; N, 3.11. Measured elemental content (%): C, 90.61; H, 6.27; N, 3.12.

[0245] Synthesis Example 19: Preparation of Compound 1-339

[0246]

[0247] According to the same preparation method as in Synthesis Example 1 for Compound 1-19, equimolar amounts of a-1-19, b-1-19, g-1-19 were respectively replaced with equimolar amounts of a-1-37, b-1-339, g-1-339 to obtain Compound 1-339 (15.11 g), with HPLC purity ≥ 99.96%. Mass spectrometry m / z: 774.3872 (theoretical value: 774.3881). Theoretical elemental content (%) C 58 H 38 D 6 N 2 : C, 89.88; H, 6.50; N, 3.61. Measured elemental content (%): C, 89.91; H, 6.48; N, 3.60.

[0248] Synthesis Example 20: Preparation of Compound 1-384

[0249]

[0250] According to the same preparation method as that of Compound 1-37 in Synthesis Example 2, equimolar amounts of a-1-37, b-1-37, a-1-37, d-1-37, and g-1-37 were respectively replaced with equimolar amounts of a-1-384, b-1-384, c-1-384, b-1-384, and g-1-71 to obtain Compound 1-384 (27.46 g), with HPLC purity ≥ 99.93%. Mass spectrometry m / z: 847.3964 (theoretical value: 847.3975). Theoretical elemental content (%) C 64 H 41 D 5 N 2 : C, 90.64; H, 6.06; N, 3.30. Measured elemental content (%): C, 90.67; H, 6.04; N, 3.28.

[0251] Synthesis Example 21: Preparation of Compound 1-401

[0252]

[0253] According to the same preparation method as that of Intermediate a-1-135 in Synthesis Example 10, equimolar amounts of f-1-135 were respectively replaced with equimolar amounts of f-1-401 to obtain Intermediate a-1-401 (22.41 g), with HPLC purity ≥ 99.58%. Mass spectrometry m / z: 266.0849 (theoretical value: 266.0862).

[0254] According to the same preparation method as that of Compound 1-37 in Synthesis Example 2, equimolar amounts of a-1-37, b-1-37, a-1-37, d-1-37, and g-1-37 were respectively replaced with equimolar amounts of a-1-401, b-1-191, c-1-401, b-1-191, and g-1-71 to obtain Compound 1-401 (26.41 g), with HPLC purity ≥ 99.91%. Mass spectrometry m / z: 879.4555 (theoretical value: 879.4539). Theoretical elemental content (%) C 66 H 41 D 9 N 2 : C, 90.06; H, 6.75; N, 3.18. Measured elemental content (%): C, 90.08; H, 6.72; N, 3.20.

[0255] Synthesis Example 22: Preparation of Compound 1-416

[0256]

[0257] According to the same preparation method as that of Compound 1-37 in Synthesis Example 2, equimolar amounts of A-1-37, a-1-37, d-1-37, and g-1-37 were respectively replaced with equimolar amounts of A-1-206, c-1-416, b-1-206, and g-1-416 to obtain Compound 1-416 (27.57 g), with HPLC purity ≥ 99.94%. Mass spectrometry m / z: 894.4739 (theoretical value: 894.4758). Theoretical elemental content (%) C 67 H 42 D 10 N 2 : C, 89.89; H, 6.98; N, 3.13. Measured elemental content (%): C, 89.91; H, 6.95; N, 3.14.

[0258] Synthesis Example 23: Preparation of Compound 1-451

[0259]

[0260] According to the same preparation method as that of Compound 1-19 in Synthesis Example 1, equimolar amounts of a-1-19, b-1-19, and g-1-19 were respectively replaced with equimolar amounts of c-1-37, b-1-451, and g-1-451 to obtain Compound 1-451 (19.05 g), with HPLC purity ≥ 99.95%. Mass spectrometry m / z: 974.4484 (theoretical value: 974.4476). Theoretical elemental content (%) C 74 H 42 D 8 N 2 : C, 91.13; H, 5.99; N, 2.87. Measured elemental content (%): C, 91.16; H, 5.97; N, 2.85.

[0261] Synthesis Example 24: Preparation of Compound 1-454

[0262]

[0263] According to the same preparation method as that of Compound 1-37 in Synthesis Example 2, equimolar amounts of a-1-37, b-1-37, a-1-37, d-1-37, and g-1-37 were respectively replaced with equimolar amounts of a-1-454, d-1-63, c-1-454, d-1-454, and g-1-454 to obtain Compound 1-454 (23.88 g), with HPLC purity ≥ 99.93%. Mass spectrometry m / z: 795.3644 (theoretical value: 795.3662). Theoretical elemental content (%) C 60 H 37 D 5 N 2: C, 90.53; H, 5.95; N, 3.52. Measured elemental content (%): C, 90.55; H, 5.94; N, 3.51.

[0264] Synthesis Example 25: Preparation of Compound 1-461

[0265]

[0266] According to the same preparation method as in Synthesis Example 2 for Compound 1-37, equimolar amounts of a-1-37, b-1-37, g-1-37 were respectively replaced with equimolar amounts of a-1-461, d-1-63, g-1-461 to obtain Compound 1-461 (29.74 g), HPLC purity ≥ 99.94%. Mass spectrometry m / z: 977.4744 (theoretical value: 977.4757). Theoretical elemental content (%) C 74 H 51 D 5 N 2 : C, 90.85; H, 6.28; N, 2.86. Measured elemental content (%): C, 90.83; H, 6.30; N, 2.87.

[0267] Synthesis Example 26: Preparation of Compound 1-466

[0268]

[0269] According to the same preparation method as in Synthesis Example 2 for Compound 1-37, equimolar amounts of a-1-37, b-1-37, a-1-37, d-1-37, g-1-37 were respectively replaced with equimolar amounts of a-1-37, b-1-384, c-1-466, b-1-384, g-1-466 to obtain Compound 1-466 (24.18 g), HPLC purity ≥ 99.91%. Mass spectrometry m / z: 827.4148 (theoretical value: 827.4164). Theoretical elemental content (%) C 62 H 29 D 13 N 2 : C, 89.93; H, 6.69; N, 3.38. Measured elemental content (%): C, 89.89; H, 6.70; N, 3.40.

[0270] Synthesis Example 28: Preparation of Compound 2-5

[0271]

[0272] Preparation of Intermediate M-2-5:

[0273] Under nitrogen protection, m-2-5 (23.67 g, 50 mmol), d-1-72 (4.66 g, 50 mmol), sodium tert-butoxide (9.61 g, 100 mmol) were added to 300 ml of toluene, and Pd(OAc) was added under stirring. 2 (0.17g, 0.75mmol) and tri-tert-butylphosphine (3.00mL of 0.5M toluene solution, 1.50mmol), the mixed solution of the above reactants was heated to reflux for 4h. After the reaction was completed, it was cooled to room temperature, distilled water was added, extracted with dichloromethane, and the liquid was separated by standing. The organic layer was collected and dried with anhydrous magnesium sulfate, filtered, and the filtrate was concentrated by vacuum distillation. The temperature was lowered for crystallization, and suction was filtered. The obtained solid was recrystallized with toluene / ethanol = 8 / 1 to obtain intermediate M-2-5 (20.40g, 84%), HPLC purity ≧99.71%. Mass spectrum m / z: 485.2155 (theoretical value: 485.2143).

[0274] Preparation of compound 2-5:

[0275] Under nitrogen protection, intermediate M-2-5 (14.57 g, 30 mmol), m'-2-5 (14.20 g, 30 mmol), sodium tert-butoxide (5.77 g, 60 mmol) were added to 220 ml of toluene, and Pd was added under stirring. 2 (dba) 3 (0.27g, 0.30mmol) and BINAP (0.37g, 0.60mmol), the mixed solution of the above reactants was heated to reflux for 5.5h. After the reaction was completed, it was cooled to room temperature, distilled water was added, extracted with dichloromethane, and the liquid was separated by standing. The organic layer was collected and dried with anhydrous magnesium sulfate, filtered, and the filtrate was concentrated by vacuum distillation. The temperature was lowered for crystallization, and suction was filtered. The obtained solid was recrystallized from toluene to obtain compound 2-5 (19.23g, yield 73%), HPLC purity ≧99.94%. Mass spectrum m / z: 877.3717 (theoretical value: 877.3709). Theoretical element content (%) C 68 H 47 N: C, 93.01; H, 5.40; N, 1.60. Measured element content (%): C, 93.03; H, 5.38; N, 1.59.

[0276] Synthesis Example 29: Preparation of Compound 2-36

[0277]

[0278] According to the same preparation method of Compound 2-5 in Synthesis Example 28, equimolar amounts of m-2-5, d-1-72, and m'-2-5 were respectively replaced with equimolar amounts of m-2-36, b-1-479, and m-2-36 to obtain Compound 2-36 (18.73 g), with HPLC purity ≥ 99.96%. Mass spectrometry m / z: 878.3752 (theoretical value: 878.3771). Theoretical elemental content (%) C 68 H 46 DN: C, 92.90; H, 5.50; N, 1.59. Measured elemental content (%): C, 92.89; H, 5.48; N, 1.62.

[0279] Synthesis Example 30: Preparation of Compound 2-66

[0280]

[0281] Preparation of Intermediate m'-2-66:

[0282] Under nitrogen protection, m-2-66 (19.87 g, 50.00 mmol), f-2-66 (8.02 g, 50.00 mmol), Pd(PPh 3 ) 4 (0.58 g, 0.50 mmol), K 2 CO 3 (10.37 g, 75.00 mmol) and 330 mL of a mixed solution of toluene / ethanol / water (2:1:1) were successively added to the reaction flask. The mixture was stirred and the above system was refluxed for 4 hours. After the reaction was completed, it was cooled to room temperature, filtered by suction to obtain a filter cake, and the filter cake was rinsed with ethanol. Finally, the filter cake was recrystallized with ethyl acetate to obtain Intermediate m'-2-66 (17.75 g, yield 82%), with HPLC purity ≥ 99.67%. Mass spectrometry m / z: 432.1596 (theoretical value: 432.1583).

[0283] According to the same preparation method of Compound 2-5 in Synthesis Example 28, equimolar amounts of m-2-5, d-1-72, and m'-2-5 were respectively replaced with equimolar amounts of m-2-66, n-2-66, and m'-2-66 to obtain Compound 2-66 (19.25 g), with HPLC purity ≥ 99.95%. Mass spectrometry m / z: 890.4537 (theoretical value: 890.4524). Theoretical elemental content (%) C 68 H 34 D 13 N: C, 91.64; H, 6.78; N, 1.57. Measured elemental content (%): C, 91.67; H, 6.80; N, 1.55.

[0284] Synthesis Example 31: Preparation of Compound 2-82

[0285]

[0286] According to the same preparation method as that of Compound 2-5 in Synthesis Example 28, equimolar amounts of m-2-5 and m'-2-5 were respectively replaced with equimolar amounts of m-2-82 and m-2-82 to obtain Compound 2-82 (17.10 g), with HPLC purity ≥ 99.93%. Mass spectrometry m / z: 837.4327 (theoretical value: 837.4335). Theoretical elemental content (%) C 64 H 55 N: C, 91.71; H, 6.61; N, 1.67. Measured elemental content (%): C, 91.69; H, 6.59; N, 1.70.

[0287] Synthesis Example 32: Preparation of Compound 2-83

[0288]

[0289] According to the same preparation method as that of Compound 2-5 in Synthesis Example 28, equimolar amounts of m-2-5, d-1-72, and m'-2-5 were respectively replaced with equimolar amounts of m-2-83, b-1-191, and m-2-83 to obtain Compound 2-83 (18.02 g), with HPLC purity ≥ 99.95%. Mass spectrometry m / z: 857.4039 (theoretical value: 857.4022). Theoretical elemental content (%) C 66 H 51 N: C, 92.38; H, 5.99; N, 1.63. Measured elemental content (%): C, 92.36; H, 5.97; N, 1.66.

[0290] Synthesis Example 33: Preparation of Compound 2-97

[0291]

[0292] According to the same preparation method as that of Compound 2-5 in Synthesis Example 28, equimolar amounts of m-2-5, d-1-72, and m'-2-5 were respectively replaced with equimolar amounts of m-2-97, b-1-234, and m-2-97 to obtain Compound 2-97 (17.34 g), with HPLC purity ≥ 99.93%. Mass spectrometry m / z: 813.4156 (theoretical value: 813.4149). Theoretical elemental content (%) C 62 H 31 D 12 N: C, 91.47; H, 6.81; N, 1.72. Measured elemental content (%): C, 91.50; H, 6.79; N, 1.71.

[0293] Synthesis Example 34: Preparation of Compound 2-101

[0294]

[0295] According to the same preparation method of Compound 2-5 in Synthesis Example 28, equimolar amounts of m-2-5, d-1-72, and m'-2-5 were replaced with equimolar amounts of m-2-101, d-1-63, and m'-2-101, respectively, to obtain Compound 2-101 (17.34 g), with HPLC purity ≥ 99.91%. Mass spectrometry m / z: 747.4449 (theoretical value: 747.4463). Theoretical elemental content (%) C 56 H 17 D 22 N: C, 89.91; H, 8.21; N, 1.87. Measured elemental content (%): C, 89.89; H, 8.20; N, 1.90.

[0296] Synthesis Example 35: Preparation of Compound 2-111

[0297]

[0298] According to the same preparation method of Compound 2-5 in Synthesis Example 28, equimolar amounts of m-2-5, d-1-72, and m'-2-5 were replaced with equimolar amounts of m-2-66, d-1-63, and m-2-66, respectively, to obtain Compound 2-111 (16.45 g), with HPLC purity ≥ 99.96%. Mass spectrometry m / z: 730.3378 (theoretical value: 730.3396). Theoretical elemental content (%) C 56 H 34 D 5 N: C, 92.02; H, 6.07; N, 1.92. Measured elemental content (%): C, 92.05; H, 6.08; N, 1.89.

[0299] Synthesis Example 36: Preparation of Compound 2-113

[0300]

[0301] According to the same preparation method of Compound 2-5 in Synthesis Example 28, equimolar amounts of m-2-5 and m'-2-5 were replaced with equimolar amounts of m-2-66 and m-2-66, respectively, to obtain Compound 2-113 (16.77 g), with HPLC purity ≥ 99.98%. Mass spectrometry m / z: 725.3072 (theoretical value: 725.3083). Theoretical elemental content (%) C 56 H 39N: C, 92.66; H, 5.42; N, 1.93. Measured elemental content (%): C, 92.67; H, 5.40; N, 1.94.

[0302] Synthesis Example 37: Preparation of Compound 2-119

[0303]

[0304] According to the same preparation method as in Compound 2-5 of Synthesis Example 28, equimolar amounts of m-2-5, d-1-72, and m'-2-5 were respectively replaced with equimolar amounts of m-2-66, b-1-19, and m-2-66 to obtain Compound 2-119 (17.60 g), with HPLC purity ≥ 99.93%. Mass spectrometry m / z: 837.4346 (theoretical value: 837.4335). Theoretical elemental content (%) C 64 H 55 N: C, 91.71; H, 6.61; N, 1.67. Measured elemental content (%): C, 91.69; H, 6.59; N, 1.69.

[0305] Synthesis Example 38: Preparation of Compound 2-123

[0306]

[0307] According to the same preparation method as in Compound 2-5 of Synthesis Example 28, equimolar amounts of m-2-5, d-1-72, and m'-2-5 were respectively replaced with equimolar amounts of m-2-66, b-1-84, and m-2-66 to obtain Compound 2-123 (16.48 g), with HPLC purity ≥ 99.94%. Mass spectrometry m / z: 795.3874 (theoretical value: 795.3865). Theoretical elemental content (%) C 61 H 49 N: C, 92.04; H, 6.20; N, 1.76. Measured elemental content (%): C, 92.07; H, 6.18; N, 1.74.

[0308] Synthesis Example 39: Preparation of Compound 2-131

[0309]

[0310] According to the same preparation method as that of Compound 2-5 in Synthesis Example 28, equimolar amounts of m-2-5, d-1-72, and m'-2-5 were respectively replaced with equimolar amounts of m-2-131, b-1-42, and m'-2-131 to obtain Compound 2-131 (17.93 g), with HPLC purity ≥ 99.92%. Mass spectrometry m / z: 829.3729 (theoretical value: 829.3709). Theoretical elemental content (%) C 64 H 47 N: C, 92.61; H, 5.71; N, 1.69. Measured elemental content (%): C, 92.59; H, 5.69; N, 1.72.

[0311] Synthesis Example 40: Preparation of Compound 2-147

[0312]

[0313] According to the same preparation method as that of Compound 2-5 in Synthesis Example 28, equimolar amounts of m-2-5, d-1-72, and m'-2-5 were respectively replaced with equimolar amounts of m-2-66, b-1-13, and m-2-66 to obtain Compound 2-147 (17.56 g), with HPLC purity ≥ 99.94%. Mass spectrometry m / z: 801.3385 (theoretical value: 801.3396). Theoretical elemental content (%) C 62 H 43 N: C, 92.85; H, 5.40; N, 1.75. Measured elemental content (%): C, 92.84; H, 5.39; N, 1.77.

[0314] Synthesis Example 41: Preparation of Compound 2-157

[0315]

[0316] According to the same preparation method as that of Compound 2-5 in Synthesis Example 28, equimolar amounts of m-2-5, d-1-72, and m'-2-5 were respectively replaced with equimolar amounts of m-2-66, b-1-206, and m-2-66 to obtain Compound 2-157 (17.19 g), with HPLC purity ≥ 99.96%. Mass spectrometry m / z: 806.3720 (theoretical value: 806.3709). Theoretical elemental content (%) C 62 H 38 D 5 N: C, 92.27; H, 5.99; N, 1.74. Measured elemental content (%): C, 92.25; H, 5.97; N, 1.77.

[0317] Synthesis Example 42: Preparation of Compound 2-165

[0318]

[0319] According to the same preparation method as that of Compound 2-5 in Synthesis Example 28, replace equimolar amounts of m-2-5, d-1-72, and m'-2-5 with equimolar amounts of m-2-66, b-1-131, and m-2-66 respectively to obtain Compound 2-165 (17.52 g), with HPLC purity ≥ 99.94%. Mass spectrometry m / z: 810.3943 (theoretical value: 810.3960). Theoretical elemental content (%) C 62 H 34 D 9 N: C, 91.81; H, 6.46; N, 1.73. Measured elemental content (%): C, 91.80; H, 6.47; N, 1.72.

[0320] Synthesis Example 43: Preparation of Compound 2-202

[0321]

[0322] According to the same preparation method as that of Compound 2-5 in Synthesis Example 28, replace equimolar amounts of m-2-5, d-1-72, and m'-2-5 with equimolar amounts of m-2-131, b-1-72, and m-2-131 respectively to obtain Compound 2-202 (18.06 g), with HPLC purity ≥ 99.92%. Mass spectrometry m / z: 859.4165 (theoretical value: 859.4178). Theoretical elemental content (%) C 66 H 53 N: C, 92.16; H, 6.21; N, 1.63. Measured elemental content (%): C, 92.15; H, 6.19; N, 1.66.

[0323] Synthesis Example 44: Preparation of Compound 2-214

[0324]

[0325] According to the same preparation method as that of Compound 2-5 in Synthesis Example 28, replace equimolar amounts of m-2-5, d-1-72, and m'-2-5 with equimolar amounts of m-2-66, b-1-135, and m-2-131 respectively to obtain Compound 2-214 (17.08 g), with HPLC purity ≥ 99.93%. Mass spectrometry m / z: 801.3386 (theoretical value: 801.3396). Theoretical elemental content (%) C 62 H 43 N: C, 92.85; H, 5.40; N, 1.75. Measured elemental content (%): C, 92.88; H, 5.38; N, 1.73.

[0326] Synthesis Example 45: Preparation of Compound 2-215

[0327]

[0328] According to the same preparation method as that of Compound 2-5 in Synthesis Example 28, equimolar amounts of m-2-5, d-1-72, and m'-2-5 were respectively replaced with equimolar amounts of m-2-66, n-1-215, and m-2-131 to obtain Compound 2-215 (17.76 g), with HPLC purity ≥ 99.96%. Mass spectrometry m / z: 857.4040 (theoretical value: 857.4022). Theoretical elemental content (%) C 66 H 51 N: C, 92.38; H, 5.99; N, 1.63. Measured elemental content (%): C, 92.40; H, 5.98; N, 1.66.

[0329] [Device Example 1]

[0330] First, the ITO substrate was washed in distilled water 3 times and ultrasonically washed for 15 minutes. After the washing with distilled water was completed, it was ultrasonically washed in solvents such as isopropanol, acetone, and methanol in sequence, and then dried at 120 °C.

[0331] By means of vacuum evaporation, NPNPB with a thickness of 30 nm was evaporated on the already cleaned ITO substrate as a hole injection layer material; Compound 1-19 with a thickness of 70 nm was evaporated on this hole injection layer as a hole transport layer material; CDBP:Ir(piq) 2 (acac) = 98:2 (mass ratio) was evaporated as a light-emitting layer with a thickness of 40 nm; BAlq was evaporated on this light-emitting layer as a hole blocking layer with a thickness of 35 nm; Alq 3 and Liq (doping mass ratio of 1:1) were evaporated as an electron transport layer material with a thickness of 25 nm; LiF was evaporated on this electron transport layer as an electron injection layer with a thickness of 0.8 nm; then Al was evaporated on this electron injection layer as a cathode with a thickness of 130 nm; thus, an organic electroluminescent device was prepared.

[0332]

[0333]

[0334] [Device Examples 2-26]

[0335] Using Compound 1-37, Compound 1-63, Compound 1-71, Compound 1-76, Compound 1-84, Compound 1-88, Compound 1-131, Compound 1-135, Compound 1-191, Compound 1-206, Compound 1-209, Compound 1-212, Compound 1-218, Compound 1-221, Compound 1-234, Compound 1-298, Compound 1-331, Compound 1-339, Compound 1-384, Compound 1-401, Compound 1-416, Compound 1-451, Compound 1-454, Compound 1-461, and Compound 1-466 of the present invention to replace Compound 1-19 in Device Example 1 as the hole transport layer respectively, and in addition, through the same preparation method as in Device Example 1, an organic electroluminescent device is prepared.

[0336] [Comparative Device Examples 1-3]

[0337] Using Comparative Compound 1, Comparative Compound 2, Comparative Compound 3, and Comparative Compound 4 to replace Compound 1-19 in Device Example 1 as the hole transport layer respectively, and in addition, through the same preparation method as in Device Example 1, an organic electroluminescent device is prepared.

[0338] A combined IVL test system is composed of a test software, a computer, a K2400 digital source meter produced by Keithley Corporation in the United States, and a PR788 spectral scanning luminance meter of PhotoResearch Corporation in the United States to test the luminous efficiency of the organic electroluminescent device. The lifetime test is carried out using the M6000 OLED lifetime test system of McScience Corporation. The test environment is an atmospheric environment and the temperature is room temperature.

[0339] The test results of the luminous characteristics of the organic electroluminescent devices obtained in Device Examples 1-26 of the present invention and Comparative Examples 1-3 are shown in Table 1 below.

[0340]

[0341]

[0342] It can be seen from the data results in Table 1 that when the diamine derivative of the present invention is applied to the organic electroluminescent device as the hole transport layer material, compared with Comparative Examples 1-4, the luminous efficiency and service life of the device can be significantly improved. This is because the compound of the present invention has a high hole transport ability and increases the recombination probability of excitons, thereby optimizing the use performance of the device.

[0343] [Device Example 27]

[0344] First, place the ITO substrate in distilled water and wash it 3 times, followed by ultrasonic washing for 15 minutes. After the distilled water washing is completed, perform ultrasonic washing with solvents such as isopropanol, acetone, and methanol in sequence, and then dry it at 120 °C.

[0345] Using the method of vacuum evaporation, deposit a 35-nm-thick HAT-CN on the already cleaned ITO substrate as the hole injection layer material; deposit a 50-nm-thick compound 1-19 on this hole injection layer as the first hole transport layer material; deposit a 20-nm-thick compound 2-111 on this first hole transport layer as the second hole transport layer material; deposit MCP:Ir(mppy) 3 = 92:8 (mass ratio) as the light-emitting layer, with a deposition thickness of 35 nm; deposit TmPyPB on this light-emitting layer as the hole-blocking layer material, with a deposition thickness of 30 nm; deposit BTB and Liq (doping mass ratio of 1:1) on this hole-blocking layer as the electron transport layer material, with a deposition thickness of 30 nm; deposit LiF on this electron transport layer as the electron injection layer, with a deposition thickness of 1.0 nm; then deposit Al on this electron injection layer as the cathode, with a deposition thickness of 120 nm; thereby preparing an organic electroluminescent device.

[0346] [Device Example 28-52]

[0347] Replace the first hole transport layer and the second hole transport layer in Device Example 27 with the following combinations. Except for this, prepare an organic electroluminescent device by the same preparation method as in Device Example 27.

[0348] Compound 1-37 and Compound 2-215, Compound 1-63 and Compound 2-165, Compound 1-71 and Compound 2-113, Compound 1-76 and Compound 2-83, Compound 1-84 and Compound 2-123, Compound 1-88 and Compound 2-202, Compound 1-131 and Compound 2-111, Compound 1-135 and Compound 2-82, Compound 1-191 and Compound 2-147, Compound 1-206 and Compound 2-113, Compound 1-209 and Compound 2-147, Compound 1-212 and Compound 2-97, Compound 1-218 and Compound 2-157, Compound 1-221 and Compound 2-165, Compound 1-234 and Compound 2-214, Compound 1-298 and Compound 2-119, Compound 1-331 and Compound 2-36, Compound 1-339 and Compound 2-97, Compound 1-384 and Compound 2-131, Compound 1-401 and Compound 2-202, Compound 1-416 and Compound 2-101, Compound 1-451 and Compound 2-215, Compound 1-454 and Compound 2-119, Compound 1-461 and Compound 2-5, Compound 1-466 and Compound 2-83.

[0349] [Comparative Device Example 5]

[0350] First, the ITO substrate was washed in distilled water 3 times, ultrasonically washed for 15 minutes. After the distilled water washing was completed, solvents such as isopropanol, acetone, and methanol were ultrasonically washed in sequence, and then dried at 120 °C.

[0351] By using the method of vacuum evaporation, HAT-CN with a thickness of 35 nm was evaporated on the already cleaned ITO substrate as the hole injection layer material; Compound 2-5 with a thickness of 70 nm was evaporated on this hole injection layer as the hole transport layer material; MCP:Ir(mppy) 3 = 92:8 (mass ratio) was evaporated as the light-emitting layer with a thickness of 35 nm; TmPyPB was evaporated on this light-emitting layer as the hole blocking layer material with a thickness of 30 nm; BTB and Liq (doping mass ratio of 1:1) were evaporated on this hole blocking layer as the electron transport layer material with a thickness of 30 nm; LiF was evaporated on this electron transport layer as the electron injection layer with a thickness of 1.0 nm; then Al was evaporated on this electron injection layer as the cathode with a thickness of 120 nm; thus, an organic electroluminescent device was fabricated.

[0352] [Comparative Device Examples 6-9]

[0353] Replace compound 2-5 in Comparative Device Example 5 with compound 2-36, compound 2-66, compound 2-82, and compound 2-214 respectively as the hole transport layer; except for this, an organic electroluminescent device was prepared by the same preparation method as in Comparative Device Example 5.

[0354] [Reference Example 1-5]

[0355] Replace compound 2-5 in Comparative Device Example 5 with compound 1-63, compound 1-71, compound 1-76, compound 1-135, and compound 1-339 respectively as the hole transport layer; except for this, an organic electroluminescent device was prepared by the same preparation method as in Comparative Device Example 5.

[0356] The test results of the luminescence characteristics of the organic electroluminescent devices obtained in Device Examples 27-52, Comparative Examples 5-9, and Reference Examples 1-5 of the present invention are shown in Table 2 below.

[0357]

[0358]

[0359] It can be seen from the data results in Table 2 that for the organic electroluminescent devices 27-52 of the double hole transport layer materials of the present invention, compared with the single-layer organic electroluminescent comparative devices 5-9 and Reference Examples 1-5, the synergistic effect between them significantly improves the luminescence efficiency of the device and extends the service life.

[0360] It should be noted that the present invention has been specifically described with individual embodiments, but without departing from the principle of the present invention, those of ordinary skill in the art can make various improvements in form or details to the present invention, and these improvements also fall within the protection scope of the present invention.

Claims

1. A diamine derivative, characterized in that, the diamine derivative has a structure shown in Formula I, In formula I, said Ar 1 and Ar 4 are the same as or different from each other and are each independently selected from any one of the groups shown below, or said Ar 1 and Ar 2 are the same as or different from each other and are each independently selected from any one of the groups shown below, Meanwhile, Ar 1 ~Ar 4 The remaining groups in are the same as or different from each other and are each independently selected from any one of the groups shown below: wherein s2 is selected from 0, s3 is selected from 0, s5 is selected from 0, s6 is selected from 0, s7 is selected from 0; Alternatively, the Ar 1 and Ar 4 are the same as or different from each other and are each independently selected from any of the groups shown below, or the Ar 1 and Ar 2 are the same as or different from each other and are each independently selected from any of the groups shown below, Meanwhile, Ar 1 ~Ar 4 The remaining groups in are the same as or different from each other and are each independently selected from any of the groups shown below: s1a is selected from 5, s2a is selected from 0 or 4, s3a is selected from 0 or 5, and s2a and s3a are not simultaneously selected from 0; L is selected from any one of the following groups, The said L 1 -L 4 is selected from a single bond.

2. The diamine derivative according to claim 1, characterized in that, The Ar 1 and Ar 4 are the same as or different from each other and are each independently selected from any one of the groups shown below. Meanwhile, Ar 2 and Ar 3 are the same as or different from each other and are each independently selected from any one of the groups shown below. Alternatively, said Ar 1 and Ar 4 are the same as or different from each other and are each independently selected from any of the groups shown below, Meanwhile, Ar 1 ~Ar 4 The remaining groups in are the same as or different from each other and are each independently selected from any one of the groups shown below:

3. The diamine derivative according to claim 1, characterized in that, L is selected from any one of the following groups, 4. A diamine derivative, characterized in that, the diamine derivative is selected from any one of the following structures, 5. An organic electroluminescent device comprising an anode, an organic layer, and a cathode, wherein the organic layer is located between the anode and the cathode or outside any one of the anode and the cathode, characterized in that, the organic layer is located between the anode and the cathode and includes a hole transport region, and the hole transport region includes a hole transport layer, and the hole transport layer contains any one or more of the diamine derivatives described in any one of claims 1-4.

6. The organic electroluminescent device according to claim 5, wherein the organic layer includes a hole transport region, and the hole transport region includes a first hole transport layer and a second hole transport layer, characterized in that, the first hole transport layer contains the diamine derivative shown in Formula I, and the second hole transport layer contains a triarylamine derivative shown in Formula II, In Formula II, Ar is selected from any one of phenyl, biphenyl, terphenyl, and naphthyl which are substituted or unsubstituted by one or more R'; R' is selected from deuterium or the following groups which are substituted or unsubstituted by one or more deuteriums: methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl, norbornyl, phenyl, biphenyl, naphthyl; The L a , L b , L c are the same as or different from each other, and are each independently selected from a single bond or any one of substituted or unsubstituted C6-C18 arylene groups; The R 1 are the same as or different from each other and are each independently selected from any one of hydrogen, deuterium, a substituted or unsubstituted C1-C12 alkyl group, a substituted or unsubstituted C3-C12 cycloalkyl group, and a substituted or unsubstituted C6-C30 aryl group; The said a 1 is selected from 0, 1, 2 or 3, the said a 2 is selected from 0, 1, 2, 3 or 4, the said a 3 is selected from 0, 1, 2, 3, 4 or 5; when there are two or more Rs 1 two or more Rs 1 are the same as or different from each other, or two adjacent Rs 1 can be connected to each other to form a substituted or unsubstituted ring, and the ring is selected from benzene, naphthalene, indene, cyclopentene, cyclopentane, cyclobutane, cyclohexene, cyclohexane, naphthalene, phenanthrene or pyrene; The substituents in the "substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted C6-C18 arylene, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted ring" are the same or different and are selected from deuterium, cyano, nitro, amino, halogen atom, C1-C12 alkyl substituted or unsubstituted by deuterium, C3-C12 cycloalkyl substituted or unsubstituted by deuterium, C2-C12 heterocycloalkyl substituted or unsubstituted by deuterium, C6-C30 aryl substituted or unsubstituted by deuterium, and C6-C30 arylamino substituted or unsubstituted by deuterium. In the "substituted or unsubstituted C1-C12 alkyl group, substituted or unsubstituted C3-C12 cycloalkyl group", the substituents are the same as or different from each other, and are selected from any one of deuterium, amino group, halogen atom, deuterium-substituted or unsubstituted C1-C12 alkyl group, deuterium-substituted or unsubstituted C3-C12 cycloalkyl group, deuterium-substituted or unsubstituted C2-C12 heterocycloalkyl group, and deuterium-substituted or unsubstituted C6-C30 arylamino group.

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