Organic electroluminescent compound and application thereof

Abstract

The invention relates to an organic electroluminescent compound and application thereof. The organic electroluminescent compound provided by the invention has a structure as shown in formula 1. When the organic electroluminescent compound is applied to the organic electroluminescent device, especially used as a material of an electron transport layer, the luminous efficiency and stability of the device can be effectively improved, the service life of the device is prolonged, the working voltage is reduced, and the device is endowed with more excellent comprehensive performance. # imgabs0 #

Description

Technical Field

[0001] The present invention relates to the technical field of organic electroluminescent materials, and particularly relates to an organic electroluminescent compound and its application. Background Art

[0002] Since the first report of highly efficient organic light emitting diodes (OLEDs), many scholars have been committed to studying how to improve the efficiency and stability of devices. Currently, commonly used electron transport materials mainly include metal complexes, nitrogen-containing heterocyclic compounds, perfluorinated compounds, organosilicon compounds, organoboron compounds, etc. Among them, nitrogen-containing heterocyclic compounds are structures that have been studied more, with a wide variety, but in the material combinations for fabricating devices, there are more or less some defects. While improving the device efficiency, the working voltage cannot be reduced, and instead, the device lifetime is reduced. Therefore, it is still necessary to continue to develop new structures, optimize the material combinations of devices, and improve the comprehensive performance of devices. Summary of the Invention

[0003] Aiming at the problems existing in the prior art, the present invention provides an organic electroluminescent compound. Through the design of the molecular structure, it has excellent luminescent properties. When applied to an organic electroluminescent device, it can improve the device efficiency while reducing the working voltage, thereby solving the problem that the nitrogen-containing heterocyclic compounds in the prior art lead to a reduction in luminescence efficiency in the material compositions for fabricating devices.

[0004] To achieve the above object, according to one aspect of the present invention, there is provided an organic electroluminescent compound having the structure shown in Formula 1 below:

[0005]

[0006] In Formula 1, X 1 、X 2 and X 3 each independently selected from N or CR 2 , and X 1 、X 2 and X 3 at least one is N;

[0007] R 1 and R 2 each independently selected from hydrogen, or substituted or unsubstituted five-membered heteroaryl, and R 1 and R 2 are not both hydrogen at the same time;

[0008] L is selected from any one of a single bond, a substituted or unsubstituted C6-C30 arylene, and a substituted or unsubstituted C3-C30 heteroarylene;

[0009] Ar is selected from the structure shown in formula a:

[0010] Z 1 、Z 2 and Z 3 are each independently selected from N or CR 5 and at least one of Z 1 、Z 2 and Z 3 is N;

[0011] R 3 、R 4 、R 5 are each independently selected from hydrogen, deuterium, halogen, cyano, nitro, hydroxy, ester, amino, substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C1-C20 alkoxy, substituted or unsubstituted C1-C20 alkenyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C2-C20 heterocycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, substituted or unsubstituted C6-C30 arylamino, substituted or unsubstituted C3-C30 heteroarylamino, substituted or unsubstituted C6-C30 aryloxy, substituted or unsubstituted C3-C30 heteroaryloxy; R 3 、R 4 、R 5 are each independently not connected to the adjacent ring structure or connected by a chemical bond to form a ring;

[0012] R 1 、R 2 、R 3 、R 4 、R 5 in the substituents of the substitution are each independently selected from deuterium, halogen, cyano, C1-C20 alkyl, C3-C20 cycloalkyl, C6-C30 aryl, C3-C30 heteroaryl, or a combination of any one or at least two of them,

[0013] wherein the substituents of the R 1 、R 2 are not connected to the adjacent ring structure.

[0014] In the present invention, "the substituent of R 1 is not connected to the adjacent ring structure" means that the substituent of R 1 is only connected to the five-membered heteroaryl by a single bond, and the same applies to R 2 and will not be elaborated here.

[0015] In the present invention, "R 3 is not connected to the adjacent ring structure" means that R 3 is only connected to the C atom by a single bond; "R3 "Connected to the adjacent ring structure by a chemical bond to form a ring" means that R 3 In addition to being connected to a C atom by a chemical bond, it is also connected to the adjacent ring by a chemical bond, thereby forming a fused ring structure. R 4 , R 5 Similarly, it will not be elaborated here. When the same description is involved below, it has the same meaning and will not be elaborated one by one.

[0016] In the present invention, the halogens can all be fluorine, chlorine, bromine or iodine. When the same description is involved below, it has the same meaning.

[0017] In the present invention, for the expression of chemical elements, if there is no special description, it includes the concept of isotopes with the same chemical properties. For example, hydrogen (H) includes 1 H (protium), 2 H (deuterium, D), 3 H (tritium, T), etc.; carbon (C) includes 12 C, 13 C, etc.

[0018] In the present invention, if there is no special description, the heteroatoms of the heteroaryl or heterocycloalkyl are selected from N, O, S, P, B, Si or Se, preferably N, O or S.

[0019] In the present invention, the expression of the ring structure with a "-" drawn across it indicates that the connection site is at any position on the ring structure capable of forming a bond.

[0020] In the present invention, "*" all represents the connection site of the group.

[0021] In the present invention, the expression Ca-Cb represents that the group has a carbon atom number of a-b. If there is no special description, the carbon atom number does not include the carbon atom number of the substituent.

[0022] In the present invention, "each independently" means that when its subject has multiple, they can be the same or different from each other.

[0023] In the present invention, the C3-C20 can all be C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17, C18 or C19, etc.

[0024] In the present invention, C6-C30 can all be C6, C9, C10, C12, C14, C16, C18, C20, C22, C24, C26 or C28, etc.

[0025] In the present invention, the C3-C30 can each be C3, C4, C5, C6, C9, C10, C12, C14, C16, C18, C20, C22, C24, C26, or C28, etc.

[0026] In the present invention, the C1-C20 can each be C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17, C18, or C19, etc.

[0027] In the present invention, the C3-C20 can each be C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17, C18, or C19, etc.

[0028] In the present invention, the C2-C20 can each be C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17, C18, or C19, etc.

[0029] In the present invention, the C1-C20 alkyl group, preferably C1-C16 alkyl group, more preferably C1-C10 alkyl group, includes but is not limited to, for example: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, neohexyl, 2-ethylhexyl, n-octyl, n-heptyl, n-nonyl, n-decyl, etc.

[0030] In the present invention, specific examples of the C1-C20 alkoxy group can be monovalent groups obtained by connecting an oxygen atom to the above-mentioned alkyl groups.

[0031] In the present invention, the C2-C20 alkenyl group, preferably C2-C10 alkenyl group, contains at least one C═C, and includes but is not limited to, for example: vinyl, propenyl, allyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, butadienyl, pentadienyl, etc.

[0032] In the present invention, the C3-C20 cycloalkyl group, preferably C3-C10 cycloalkyl group, includes monocyclic alkyl groups or polycyclic alkyl groups. Among them, the monocyclic alkyl group refers to an alkyl group containing a single cyclic structure, and the polycyclic alkyl group refers to a structure formed by two or more cycloalkyl groups sharing one or more carbon atoms on the ring; includes but is not limited to, for example: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl, etc.

[0033] In the present invention, specific examples of the C2-C20 heterocycloalkyl group may include groups formed by replacing at least one C atom in the aforementioned cycloalkyl group with a heteroatom (such as N, O, S, etc.). Exemplarily, but not limited to: epoxy group, oxetanyl group, tetrahydrofuranyl group, tetrahydrothienyl group, pyrrolidinyl group, tetrahydropyranyl group, piperidinyl group, piperazinyl group, dioxanyl group, morpholinyl group, etc.

[0034] In the present invention, the C6-C30 aryl group, preferably a C6-C20 aryl group, includes monocyclic aryl groups and polycyclic aryl groups; the monocyclic aryl group means a group containing at least 1 phenyl group. When containing at least 2 phenyl groups, the phenyl groups are connected by a single bond. Exemplarily, but not limited to: phenyl group, biphenyl group, terphenyl group, etc.; the polycyclic aryl group means a group containing at least 2 aromatic rings, and the aromatic rings are fused to each other by sharing two adjacent carbon atoms. Exemplarily, but not limited to: naphthyl group, anthracenyl group, phenanthryl group, indenyl group, fluorenyl group and its derivatives (9,9-dimethylfluorenyl group, 9,9-diethylfluorenyl group, 9,9-dipropylfluorenyl group, 9,9-dibutylfluorenyl group, 9,9-dipentylfluorenyl group, 9,9-dihexylfluorenyl group, 9,9-diphenylfluorenyl group, 9,9-dinaphthylfluorenyl group, spirobifluorenyl group, benzofluorenyl group, etc.), fluoranthenyl group, triphenylenyl group, pyrenyl group, perylenyl group or tetracenyl group, etc.

[0035] In the present invention, the C3-C30 heteroaryl group, further preferably a C3-C20 heteroaryl group, includes monocyclic heteroaryl groups or polycyclic heteroaryl groups. The monocyclic heteroaryl group means a molecule containing at least one heteroaryl group. When the molecule contains a heteroaryl group and other groups (such as aryl groups, heteroaryl groups, etc.), the heteroaryl group and other groups are connected by a single bond. Exemplarily, but not limited to: pyridyl group, pyrimidinyl group, pyrazinyl group, pyridazinyl group, triazinyl group, furyl group, thienyl group, pyrrolyl group, etc. The polycyclic heteroaryl group means a molecule containing at least one heteroaromatic ring and an aromatic ring (heteroaromatic ring or aromatic ring), and the two are fused to each other by sharing two adjacent atoms. Exemplarily, but not limited to: quinolinyl group, isoquinolinyl group, quinoxalinyl group, quinazolinyl group, benzofuranyl group, benzothienyl group, isobenzofuranyl group, isobenzothienyl group, indolyl group, dibenzofuranyl group, benzonaphthofuranyl group (benzo[B]naphtho[2,3-D]furanyl group, benzo[B]naphtho[1,2-D]furanyl group, benzo[B]naphtho[2,1-D]furanyl group), dibenzothienyl group, benzonaphthothienyl group (benzo[B]naphtho[2,3-D]thienyl group, benzo[B]naphtho[1,2-D]thienyl group, benzo[B]naphtho[2,1-D]thienyl group), carbazolyl group and its derivatives (N-phenylcarbazolyl group, N-naphthylcarbazolyl group, benzocarbazolyl group, dibenzocarbazolyl group, indolocarbazolyl group, azacarbazolyl group, etc.), acridinyl group, phenothiazinyl group, phenoxazinyl group, hydroacridinyl group, etc.

[0036] In the present invention, the C6-C30 aryloxy group is a monovalent group formed by connecting the above-mentioned aryl groups and O, and the C3-C30 heteroaryloxy group is a monovalent group formed by connecting the above-mentioned heteroaryl groups and O.

[0037] In the present invention, a specific example of the C6-C30 arylamino group is -NH 2 The monovalent group obtained by replacing at least one hydrogen in the C3-C30 heteroarylamino group with the above-mentioned aryl group includes, but is not limited to, phenylamino, methylphenylamino, naphthylamino, anthracenylamino, phenanthrenylamino, biphenylamino, etc. A specific example of the C3-C30 heteroarylamino group is -NH 2 The monovalent group in which at least one hydrogen in the amino group is replaced by the above-mentioned heteroaryl group includes, but is not limited to, pyridylamino, pyrimidylamino, dibenzofuranylamino and the like.

[0038] According to some embodiments of the present invention, the compound has a structure represented by any one of Formula 1-1 to Formula 1-4:

[0039]

[0040] In Formula 1-1 to Formula 1-4, R 1 To R 4 , L, Z 1 To Z 3 The definition of is the same as that of formula 1.

[0041] According to some embodiments of the present invention, the compound has a structure represented by any one of Formula 1-5 to Formula 1-16:

[0042]

[0043] In Formula 1-5 to Formula 1-16, R 1 , R 2 are each independently selected from substituted or unsubstituted five-membered heteroaryl; R 3 and R 4 , L, Z 1 To Z 3 The definition of is the same as that of formula 1.

[0044] According to some embodiments of the present invention, in Formula 1-5 to Formula 1-16, R 1 , R 2 Each is independently selected from a substituted or unsubstituted five-membered heteroaryl group, wherein the heteroatom in the five-membered heteroaryl group is O or S. In some embodiments, the five-membered heteroaryl group is a thienyl group or a furyl group.

[0045] According to some embodiments of the present invention, R 1 and R 2The substituents in [x] are each independently selected from any one or a combination of two of deuterium, halogen, cyano, C1-C10 (such as C2, C3, C4, C5, C6, C7, C8, C9, etc.) alkyl, C3-C10 (such as C4, C5, C6, C7, C8, C9, etc.) cycloalkyl, C6-C20 (such as C6, C9, C10, C12, C14, C15, C16 or C18, etc.) aryl, and C3-C20 (such as C3, C4, C5, C6, C9, C10, C12, C14, C15, C16, C18, etc.) heteroaryl. In some embodiments, the substituents are selected from any one or a combination of two of deuterium, halogen, cyano, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl, phenyl, biphenyl, naphthyl, furyl, thienyl, pyridyl.

[0046] According to some embodiments of the present invention, R 1 the substituents in [x] are not connected to each other; R 2 the substituents in [x] are not connected to each other.

[0047] According to some preferred embodiments of the present invention, in Formulas 1-5 to 1-16, R 1 and R 2 are each independently selected from the structures shown in any of the following:

[0048]

[0049] According to some embodiments of the present invention, L is selected from any one of a single bond, a substituted or unsubstituted C6-C20 (such as C6, C9, C10, C12, C14, C15, C16, C18, etc.) arylene, and a substituted or unsubstituted C3-C20 (such as C3, C4, C5, C6, C9, C10, C12, C14, C15, C16, C18, etc.) heteroarylene.

[0050] In some embodiments, L is selected from a single bond, a substituted or unsubstituted C6-C20 arylene, a substituted or unsubstituted C3-C20 heteroarylene, preferably selected from a substituted or unsubstituted phenylene, a substituted or unsubstituted biphenylene, a substituted or unsubstituted naphthylene, a substituted or unsubstituted phenanthrylene, a substituted or unsubstituted anthrylene, a substituted or unsubstituted pyridylene, a substituted or unsubstituted phenylpyridylene, a substituted or unsubstituted bipyridylene, a substituted or unsubstituted phenylnaphthylene, a substituted or unsubstituted phenylanthrylene, a substituted or unsubstituted quinolinylene, a substituted or unsubstituted isoquinolinylene, a substituted or unsubstituted thiazolinylene, a substituted or unsubstituted naphthyridinylene, a substituted or unsubstituted dibenzothiophenylene, a substituted or unsubstituted dibenzofuranyl, a substituted or unsubstituted fluorenyl.

[0051] According to some embodiments of the present invention, L is selected from a single bond, or a substituted or unsubstituted structure as shown below:

[0052]

[0053] indicating the connection site;

[0055] Optionally, the substituents in L are each independently selected from deuterium, halogen, cyano, C1-C10 (such as C2, C3, C4, C5, C6, C7, C8, C9, etc.) alkyl, C3-C10 (such as C4, C5, C6, C7, C8, C9, etc.) cycloalkyl, C6-C20 (such as C6, C9, C10, C12, C14, C15, C16 or C18, etc.) aryl, C3-C20 (such as C3, C4, C5, C6, C9, C10, C12, C14, C15, C16, C18, etc.) heteroaryl, or a combination of any one or two of them. In some embodiments, the substituents in L are each independently selected from deuterium, halogen, cyano, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl, phenyl, biphenyl, naphthyl, pyridyl, or a combination of any one or two of them.

[0056] According to some embodiments of the present invention, formula a is any one of the structures of formula a-1 to formula a-7:

[0057]

[0058] In formula a-1 to formula a-7, R 3 and R 4 are defined as in formula 1.

[0059] In some preferred embodiments, R 3 and R 4Each independently selected from hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C10 (such as C2, C3, C4, C5, C6, C7, C8, C9, etc.) alkyl, substituted or unsubstituted C3-C10 (such as C4, C5, C6, C7, C8, C9, etc.) cycloalkyl, substituted or unsubstituted C2-C10 (such as C3, C4, C5, C6, C7, C8, C9, etc.) heterocycloalkyl, substituted or unsubstituted C6-C30 (such as C6, C9, C10, C12, C14, C15, C16, C18, C20, C22, C24, C26, C28, etc.) aryl, substituted or unsubstituted C3-C30 (such as C3, C4, C5, C6, C9, C10, C12, C14, C15, C16, C18, C20, C22, C24, C26, C28, etc.) heteroaryl.

[0060] In some embodiments, R 3 and R 4 Each independently selected from hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl.

[0061] In some embodiments, R 3 and R 4 Each independently selected from hydrogen, deuterium, halogen, cyano, substituted or unsubstituted groups consisting of the following: phenyl, pyridyl, indanyl, tetrahydronaphthyl, biphenyl, terphenyl, naphthyl, phenylnaphthyl naphthylphenyl binaphthyl, anthracenyl, phenanthryl, fluoranthenyl, pyrenyl, triphenylenyl, benzoxanthenyl, benzothioxanthenyl, carbazolyl, dibenzothiophenyl, dibenzothiophenyl, fluorenyl, spirobifluorenyl, benzonaphthofuranyl, benzonaphthothiophenyl, benzofluorenyl.

[0062] Optionally, R 3 and R 4 Each independently not connected to the adjacent ring structure or connected by a chemical bond to form a ring.

[0063] Optionally, the substituents of the substituted R 3 and R 4 Each independently selected from deuterium, halogen, cyano, C1-C10 alkyl, C3-C10 cycloalkyl, C6-C20 aryl, C3-C20 heteroaryl, any one or a combination of at least two. In some embodiments, R 3 and R 4The substituents described in are each independently selected from any one of deuterium, halogen, cyano, C1-C6 alkyl, deuterated C1-C6 alkyl, C6-C12 aryl-substituted C1-C6 alkyl, C3-C6 cycloalkyl, C6-C12 aryl, deuterated C6-C12 aryl, and C1-C6 alkyl-substituted C6-C12 aryl. In some embodiments, R 3 and R 4 The substituents described in are selected from deuterium, fluorine, chlorine, bromine, cyano, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, phenyl-substituted tert-butyl (e.g., ), n-pentyl, isopentyl, neopentyl, perdeuterated tert-butyl, tri-deuterated methyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl, phenyl, deuterated phenyl, biphenyl, naphthyl, 1,1,4,4-tetramethyl-1,2,3,4-tetrahydronaphthalene.

[0064] In some preferred embodiments, R 3 and R 4 are each independently selected from hydrogen, deuterium, halogen, cyano, or any of the groups shown below:

[0065]

[0066]

[0067] In some preferred embodiments, the compound has any of the structures shown below:

[0068]

[0069]

[0070]

[0071]

[0072]

[0073]

[0074]

[0075]

[0076]

[0077]

[0078]

[0079]

[0080]

[0081]

[0082]

[0083]

[0084]

[0085]

[0086]

[0087]

[0088]

[0089]

[0090] In a second aspect, the present invention provides an application of the organic electroluminescent compound in the preparation of an organic electroluminescent device.

[0091] In some embodiments, the organic electroluminescent compound is used as a light-emitting layer material and / or an electron transport material in an organic electroluminescent device.

[0092] In a third aspect, the present invention provides an organic electroluminescent device, which includes an anode, a cathode, and at least one organic layer disposed between the anode and the cathode, and the organic layer includes at least one organic electroluminescent compound as described in the first aspect.

[0093] In some embodiments, the organic layer includes a light-emitting layer, and the light-emitting layer includes at least one organic electroluminescent compound as described in the first aspect.

[0094] In some embodiments, the organic layer includes an electron transport layer, and the electron transport layer includes at least one organic electroluminescent compound as described in the first aspect.

[0095] Specifically, the present invention provides an organic electroluminescent device, which includes a substrate, and an anode, a plurality of light-emitting functional layers (organic layers), and a cathode sequentially disposed on the substrate; the light-emitting functional layers include a hole injection layer, a hole transport layer, an electron blocking layer, a light-emitting layer, and an electron transport layer; wherein, the organic layer (such as an electron transport layer or a light-emitting layer) includes at least one organic electroluminescent compound as described in the first aspect.

[0096] As a preferred embodiment, the thickness of the electron transport layer may be 10 to 50 nm, preferably 20 to 40 nm.

[0097] As a preferred embodiment, the thickness of the light-emitting layer may be 10 to 50 nm, preferably 15 to 30 nm.

[0098] Fourthly, the present invention provides a display device, which includes the organic electroluminescent device described above.

[0099] Fifthly, the present invention provides an illumination device, which includes the organic electroluminescent device described above.

[0100] The compound provided by the present invention has the structure shown in Formula I. It is a compound in which a nitrogen-containing heteroaryl group (such as triazine) and a five-membered heteroaryl group (such as thiophene or furan) are connected to a quinoline derivative. Through the synergistic effect of specific sites and specific groups, it has good thermal stability and excellent electron transport ability. When the compound is applied to an organic electroluminescent device, especially as a material for the electron transport layer, it can effectively improve the light-emitting efficiency and stability of the device, extend the lifespan of the device, reduce the working voltage, and endow the device with more excellent comprehensive performance. Detailed Embodiments

[0101] The technical solutions of the present application will be described in detail below through specific examples. The following examples are used to illustrate the present application, but not to limit the scope of the present application. Any equivalent changes or modifications made without departing from the spirit disclosed by the present application shall be included within the scope of the corresponding claims.

[0102] Devices manufactured according to the embodiments of the present application can be incorporated into various consumer products having one or more electronic component modules (or units) of the device. Some examples of these consumer products include flat panel displays, monitors, medical monitors, televisions, billboards, lights for indoor or outdoor lighting and / or signaling, head-up displays, fully or partially transparent displays, flexible displays, smart phones, tablet computers, phablets, wearable devices, smart watches, laptop computers, digital cameras, portable video cameras, viewfinders, microdisplays, 3-D displays, vehicle displays, and taillights.

[0103] The materials and structures described herein can also be used in other organic electronic devices listed above.

[0104] There is no limitation on the preparation method of the compound of the present application. Typically but not restrictively, the following compound is taken as an example, and its synthetic route and preparation method are as follows:

[0105] Synthesis Example 1. Synthesis of Compound A-1-3

[0106]

[0107] Under nitrogen protection, raw material M1-1 (8.70 g), raw material M1-2 (5.78 g), K 2 CO 3 (3.32 g), Pd(PPh 3 ) 4 (0.23 g), water (10 mL) and 1,4-dioxane (100 mL) were added to the reaction flask, and the temperature was raised to 80 °C and reacted for 5 h. After the reaction was completed, it was cooled to room temperature, extracted with dichloromethane and water, and the organic phase was concentrated and then washed with ethanol and filtered to obtain compound A-1-3 (7.44 g, yield 71.8%).

[0108] MS (m / e) of compound A-1-3: 518.01; 1 HNMR (400 MHz, CDCl 3 ): δ 8.91 (d, 1H), 8.46 - 8.36 (m, 5H),

[0109] 8.18 (t, 1H), 8.11 (d, 1H), 7.94 - 7.88 (m, 2H), 7.79 (dd, 1H), 7.74 - 7.68 (m, 2H), 7.55 - 7.43 (m, 7H), 7.38 (dd, 1H), 7.12 (dd, 1H).

[0110] Synthesis Example 2, Synthesis of Compound B-2-29

[0111]

[0112] Under nitrogen protection, raw material M2-1 (37.71 g), raw material M2-2 (22.12 g), K 2 CO 3 (16.58 g), Pd(PPh 3 ) 4 (1.16 g), water (20 mL) and 1,4-dioxane (200 mL) were added to the reaction flask, and the temperature was raised to 100 °C and reacted for 7 h. After the reaction was completed, it was cooled to room temperature, extracted with dichloromethane and water, and the organic phase was concentrated and then washed with ethanol and filtered to obtain intermediate S2-1 (32.75 g, yield 75.1%).

[0113]

[0114] Under nitrogen protection, raw material M2-4 (28.81 g), raw material M2-5 (14.59 g), K 2 CO 3(16.58 g), Pd(PPh 3 ) 4 (1.16 g), water (20 mL) and 1,4 - dioxane (200 mL), heated to 80 °C and reacted for 4 h. After the reaction, it was cooled to room temperature, extracted with dichloromethane and water, and the organic phase was concentrated, washed with ethanol and filtered to obtain intermediate S2 - 2 (16.85 g, yield 73.6%).

[0115] Under nitrogen protection, intermediate S2 - 2 (11.45 g), raw material M2 - 7 (19.01 g), K 2 CO 3 (8.29 g), Pd(PPh 3 ) 4 (0.58 g), water (15 mL) and 1,4 - dioxane (150 mL), heated to 100 °C and reacted for 7 h. After the reaction, it was cooled to room temperature, extracted with dichloromethane and water, and the organic phase was concentrated, washed with ethanol and filtered to obtain intermediate S2 - 3 (15.77 g, yield 70.5%).

[0116]

[0117] Under nitrogen protection, intermediate S2 - 1 (8.72 g), intermediate S2 - 3 (8.94 g), K 2 CO 3 (3.32 g), Pd(PPh 3 ) 4 (0.23 g), water (10 mL) and 1,4 - dioxane (100 mL), heated to 80 °C and reacted for 5 h. After the reaction, it was cooled to room temperature, extracted with dichloromethane and water, and the organic phase was concentrated, washed with ethanol and filtered to obtain compound B - 2 - 29 (10.45 g, yield 72.4%).

[0118] MS (m / e) of compound B - 2 - 29: 721.76; 1 HNMR (400 MHz, CDCl 3 ): δ 8.97 (d, 1H), 8.82 (t, 1H), 8.47 - 8.33 (m, 5H), 8.16 - 8.00 (m, 6H), 7.77 - 7.56 (m, 8H), 7.48 - 7.34 (m, 8H), 6.94 (dd, 1H), 6.75 (dd, 1H).

[0119] Synthesis Example 3, Synthesis of Compound C - 3 - 3

[0120]

[0121] Under nitrogen protection, add raw material M3-1 (28.81 g), raw material M3-2 (23.39 g), K 2 CO 3 (16.58 g), Pd(PPh 3 ) 4 (1.16 g), water (20 mL) and 1,4-dioxane (200 mL) into the reaction flask, and heat to 90 °C for reaction for 4 h. After the reaction is completed, cool to room temperature, extract with dichloromethane and water, concentrate the organic phase, wash with ethanol and filter to obtain intermediate S3-1 (24.17 g, yield 76.5%).

[0122]

[0123] Under nitrogen protection, add raw material M3-3 (42.02 g), raw material M3-4 (31.88 g), K 2 CO 3 (16.58 g), Pd(PPh 3 ) 4 (1.16 g), water (20 mL), 1,4-dioxane (200 mL) into the reaction flask, and heat to 90 °C for reaction for 4 h. After the reaction is completed, cool to room temperature, extract with dichloromethane and water, concentrate the organic phase, wash with ethanol and filter to obtain intermediate S3-2 (23.28 g, yield 71.2%).

[0124] Under nitrogen protection, add intermediate S3-2 (16.35 g), bis(pinacolato)diboron (15.24 g), potassium acetate (7.85 g), 1,1'-bis(diphenylphosphino)ferrocene dichloropalladium (5.48 g) and dioxane (1000 mL) into the reaction flask, and heat to 90 °C for reaction for 6 h. After the reaction is completed, cool to room temperature, extract with dichloromethane and water, separate the organic phase and concentrate to obtain intermediate S3-3 (17.35 g, yield 82.8%).

[0125]

[0126] Under nitrogen protection, add intermediate S3-3 (12.57 g), intermediate S3-1 (9.48 g), K 2 CO 3 (4.98 g), Pd(PPh 3 ) 4 (0.35 g), water (10 mL) and 1,4-dioxane (100 mL) into the reaction flask, and heat to 80 °C for reaction for 5 h. After the reaction is completed, cool to room temperature, extract with dichloromethane and water, concentrate the organic phase, wash with ethanol and filter to obtain intermediate S3-4 (11.55 g, yield 72.8%).

[0127] Under nitrogen protection, add intermediate S3-4 (10.58 g), bis(pinacolato)diboron (7.62 g), potassium acetate (3.93 g), 1,1'-bis(diphenylphosphino)ferrocene dichloropalladium (2.93 g) and dioxane (800 mL) into the reaction flask, and heat to 90 °C for reaction for 6 h. After the reaction is completed, cool to room temperature, extract with dichloromethane and water, separate the organic phase and concentrate to obtain intermediate S3-5 (10.08 g, yield 81.2%).

[0128]

[0129] Under nitrogen protection, add intermediate S3-5 (6.21 g), raw material M3-5 (2.90 g), K 2 CO 3 (1.66 g), Pd(PPh 3 ) 4 (0.12 g), water (10 mL) and 1,4-dioxane (100 mL) into the reaction flask, heat to 80 °C and react for 4 h. After the reaction is completed, cool to room temperature, extract with dichloromethane and water, concentrate the organic phase, wash with ethanol and filter to obtain compound C-3-3 (5.64 g, yield 75.3%).

[0130] MS (m / e) of compound C-3-3: 749.44; 1 HNMR (400 MHz, CDCl 3 ): δ 8.22 - 8.17 (m, 2H), 8.15 - 7.93 (m, 11H), 7.91 - 7.78 (m, 3H), 7.69 (d, 1H), 7.65 - 7.45 (m, 12H), 7.22 - 7.13 (m, 2H).

[0131] The present invention exemplarily provides examples of synthesizing the compounds of the present invention by Suzuki reaction of some intermediates with triazine raw materials. For compounds without specific synthesis methods, they can all be synthesized by the above Suzuki method, only by replacing the raw materials, which will not be elaborated here, or those skilled in the art can also prepare them by other methods in the prior art.

[0132] The above organic compounds of the present invention are particularly suitable for the electron transport layer in OLED devices. The application effects of the organic compounds of the present invention as electron transport materials in OLED devices are described in detail below through specific examples.

[0133] Device Example 1

[0134] First, clean the glass substrate, which has A thick indium tin oxide (ITO) anode was then treated with UV ozone and oxygen plasma. After treatment, the substrate was dried in a nitrogen-filled glove box to remove moisture, and then the substrate was mounted on a substrate holder and loaded into a vacuum chamber.

[0135] At a vacuum of about 10 -7 Torr, thermal evaporation was sequentially carried out on the ITO anode at a rate of . At the same time, the co-evaporation of compound HT1 and NDP-9 (weight ratio 96:4) was used as the hole injection layer (HIL), with a thickness of Compounds HT1 and HT2 were used as the hole transport layer (HTL), with thicknesses of and Compound BH and compound BD as a dopant (weight ratio 96:4) were co-evaporated as the emitting layer (EML), with a thickness of In the present invention, compound A-1-3 and lithium 8-hydroxyquinoline (Liq) were co-evaporated (weight ratio 50:50) as the electron transport layer (ETL), with a thickness of Finally, Yb with a thickness of was evaporated as the electron injection layer (EIL), and Ag with a thickness of was evaporated as the cathode. Then the device was transferred back to the glove box and encapsulated with a glass cover to complete the device.

[0136] Device Examples 2 to Device Example 13, Device Comparative Examples 1 to Device Comparative Example 2

[0137] An organic electroluminescent device, which is different from Device Example 1 only in that the compounds shown in Table 1 are used in the electron transport layer, and other layers, thicknesses, materials, and preparation methods are the same as those in Device Example 1.

[0138] The material structure used in the device is as follows:

[0139]

[0140] The performance of the above-prepared devices was detected. The working voltage (V), current efficiency (cd / A), and LT95 @ 50 mA / cm 2 of the device at a current density, and the specific data of the lifetime (h) at 2 are shown in Table 1. In Table 1, the current efficiency or LT95 lifetime test value of Device Comparative Example 1 was recorded as 1, and the ratio (relative current efficiency or relative lifetime) of the current efficiency or LT95 lifetime test value of other devices to the current efficiency or LT95 lifetime test value of Device Comparative Example 1 was calculated.

[0141] Table 1

[0142]

[0143]

[0144] The data in Table 1 show that, compared with Device Comparative Examples 1 and 2 of the present invention, for the device using the compound provided by the present invention as the electron transport material, the voltage is significantly reduced, the efficiency is improved, and the lifespan is extended to some extent.

[0145] It should be understood that the various embodiments described herein are only examples and are not intended to limit the scope of the present application. Thus, as will be apparent to those skilled in the art, the claimed present application may include variations of the specific and preferred embodiments described herein. Many of the materials and structures described herein may be replaced with other materials and structures without departing from the spirit of the present application. It should be understood that the various theories as to why the present application works are not intended to be limiting.

Claims

1. An organic electroluminescent compound having a structure shown in Formula 1: in, X1, X2 and X3 are each independently selected from N or CR2, and at least one of X1, X2 and X3 is N; R1 and R2 are each independently selected from hydrogen, or a substituted or unsubstituted five-membered heteroaryl group, and R1 and R2 are not hydrogen at the same time; L is selected from any one of a single bond, a substituted or unsubstituted C6-C30 arylene group, and a substituted or unsubstituted C3-C30 heteroarylene group; Ar is selected from the structure shown in formula a: Z1, Z2 and Z3 are each independently selected from N or CR5, and at least one of Z1, Z2 and Z3 is N; R3, R4, and R5 are each independently selected from any one of hydrogen, deuterium, halogen, cyano, nitro, hydroxyl, ester, amino, substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C1-C20 alkoxy, substituted or unsubstituted C2-C20 alkenyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C2-C20 heterocycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, substituted or unsubstituted C6-C30 arylamino, substituted or unsubstituted C3-C30 heteroarylamino, substituted or unsubstituted C6-C30 aryloxy, and substituted or unsubstituted C3-C30 heteroaryloxy; R3, R4, and R5 are each independently not connected to adjacent ring structures or are connected to form a ring by chemical bonds; The substituents substituted in R1, R2, R3, R4 and R5 are each independently selected from any one or a combination of at least two of deuterium, halogen, cyano, C1-C20 alkyl, C3-C20 cycloalkyl, C6-C30 aryl, C3-C30 heteroaryl, Wherein, the substituents in R1 and R2 are not connected to the adjacent ring structures.

2. The organic electroluminescent compound according to claim 1, characterized in that The compound has a structure represented by any one of Formula 1-1 to Formula 1-4: In Formulae 1-1 to 1-4, the definitions of R1 to R4, L, and Z1 to Z3 are the same as those in Formula 1.

3. The organic electroluminescent compound according to claim 1 or 2, characterized in that: The compound has a structure represented by any one of Formula 1-5 to Formula 1-16: In Formulae 1-5 to 1-16, R3 to R4, L, and Z1 to Z3 are defined the same as in Formula 1; R1 and R2 are each independently selected from a substituted or unsubstituted five-membered heteroaryl group.

4. The organic electroluminescent compound according to claim 3, characterized in that R1 and R2 are each independently selected from a substituted or unsubstituted five-membered heteroaryl group, wherein the heteroatom in the five-membered heteroaryl group is O or S, and preferably, the five-membered heteroaryl group is a thienyl group or a furyl group; Optionally, the substituents substituted in R1 and R2 are each independently selected from any one or a combination of two of deuterium, halogen, cyano, C1-C10 alkyl, C3-C10 cycloalkyl, C6-C20 aryl, C3-C20 heteroaryl, preferably selected from any one or a combination of two of deuterium, halogen, cyano, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl, phenyl, biphenyl, naphthyl, furanyl, thienyl, pyridyl; Preferably, R1 and R2 are each independently selected from any of the following structures:

5. The organic electroluminescent compound according to any one of claims 1 to 4, characterized in that: L is selected from any one of a single bond, a substituted or unsubstituted C6-C20 arylene group, and a substituted or unsubstituted C3-C20 heteroarylene group, and is preferably selected from any one of a substituted or unsubstituted phenylene group, a substituted or unsubstituted biphenylene group, a substituted or unsubstituted naphthylene group, a substituted or unsubstituted phenanthrylene group, a substituted or unsubstituted anthrylene group, a substituted or unsubstituted pyridylene group, a substituted or unsubstituted phenylene pyridylene group, a substituted or unsubstituted bipyridylene group, a substituted or unsubstituted phenylene naphthyl group, a substituted or unsubstituted phenylene anthracenyl group, a substituted or unsubstituted quinolylene group, a substituted or unsubstituted isoquinolylene group, a substituted or unsubstituted thiazolinyl group, a substituted or unsubstituted naphthyridinylene group, a substituted or unsubstituted dibenzothiophenylene group, a substituted or unsubstituted dibenzofuranyl group, and a substituted or unsubstituted fluorenyl group; Preferably, L is selected from a single bond, or a substituted or unsubstituted structure as shown below: Optionally, the substituents substituted in L are each independently selected from any one or a combination of two of deuterium, halogen, cyano, C1-C10 alkyl, C3-C10 cycloalkyl, C6-C20 aryl, C3-C20 heteroaryl, preferably selected from any one or a combination of two of deuterium, halogen, cyano, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl, phenyl, biphenyl, naphthyl, pyridyl.

6. The organic electroluminescent compound according to any one of claims 1 to 5, characterized in that: Formula a is any structure of formula a-1 to formula a-7: In formula a-1 to formula a-7, R3 and R4 have the same definitions as in formula 1; Preferably, R3 and R4 are each independently selected from any one of hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C2-C10 heterocycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, preferably selected from any one of hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, more preferably selected from any one of hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl. The group consisting of the following groups which are substituted or unsubstituted: phenyl, pyridyl, indanyl, tetrahydronaphthyl, biphenyl, terphenyl, naphthyl, phenylnaphthyl, naphthylphenyl, binaphthyl, anthracenyl, phenanthrenyl, fluoranthene, pyrene, triphenylene, benzoxanthracene, benzothioanthracene, carbazolyl, N-phenylcarbazolyl, dibenzothiophenyl, dibenzothiophenyl, fluorenyl, spirobifluorenyl, benzonaphthofuranyl, benzonaphthothiophenyl, benzofluorenyl; wherein R3 and R4 are each independently not connected to the adjacent ring structure or are connected to form a ring by a chemical bond, Optionally, the substituents substituted in R3 and R4 are each independently selected from any one of deuterium, halogen, cyano, C1-C10 alkyl, C3-C10 cycloalkyl, C6-C20 aryl, C3-C20 heteroaryl or a combination of at least two thereof, preferably selected from deuterium, halogen, cyano, C1-C6 alkyl, deuterated C1-C6 alkyl, C6-C12 aryl substituted C1-C6 alkyl, C3-C6 cycloalkyl, C6-C12 aryl, deuterated C6-C12 aryl , any one of C6-C12 aryl substituted by C1-C6 alkyl; more preferably any one selected from deuterium, fluorine, chlorine, bromine, cyano, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, perdeuterated tert-butyl, trideuterated methyl, tert-butyl substituted by phenyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl, phenyl, deuterated phenyl, biphenyl, naphthyl, 1,1,4,4-tetramethyl-1,2,3,4-tetrahydronaphthalene; More preferably, R3 and R4 are each independently selected from hydrogen, deuterium, halogen, cyano or any of the following groups:

7. The organic electroluminescent compound according to any one of claims 1 to 6, characterized in that: The organic electroluminescent compound is selected from the group consisting of the following compounds:

8. Use of the organic electroluminescent compound according to any one of claims 1 to 7 in the preparation of an organic electroluminescent device, Preferably, the organic electroluminescent compound is used as a light-emitting layer material and / or an electron transport material in an organic electroluminescent device.

9. An organic electroluminescent device, comprising: An anode, a cathode, and at least one organic layer disposed between the anode and the cathode, wherein the organic layer comprises the organic electroluminescent compound according to any one of claims 1 to 7; Preferably, the organic layer comprises a light-emitting layer, and the light-emitting layer comprises the organic electroluminescent compound; Preferably, the organic layer comprises an electron transport layer, and the electron transport layer comprises the organic electroluminescent compound.

10. A display / illumination device, comprising the organic electroluminescent compound according to any one of claims 1 to 7 or the organic electroluminescent device according to claim 9.

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