Metal complex and organic electroluminescent device

Abstract

The invention relates to a metal complex and an organic electroluminescent device. The metal complex provided by the invention has a structure as shown in a formula (I). When the metal complex disclosed by the invention is used in an OLED (Organic Light Emitting Diode), an organic electroluminescent device with dark blue phosphorescence in electroluminescence and improved luminous efficiency can be obtained, the thermal stability of the luminescent device is good, and the metal complex has a wide application prospect in the fields of OLED display and illuminating lamps. # imgabs0 #

Description

Technical Field

[0001] The present invention belongs to the technical field of luminescent materials, and particularly relates to a metal complex and an organic electroluminescent device. Background Art

[0002] OLED (organic light-emitting diode) utilizes an organic thin film, which emits light when a voltage is applied to the device. OLED is becoming an increasingly concerned technology for applications such as flat panel displays, lighting, and backlighting.

[0003] One application of phosphorescent emission molecules is full-color displays. Industry standards for such displays require pixels suitable for emitting specific colors. Specifically, these standards require saturated red, green, and blue pixels. Currently, red and green phosphorescent materials with a luminous efficiency of 100% are used in OLEDs of various sizes, and so far, no blue phosphorescent material has been commercialized. There are many dissipation pathways for triplet excitons of phosphorescent materials, such as non-radiative transitions, delayed fluorescence, triplet-triplet annihilation, quenching by oxygen and water vapor, etc., which seriously affect the improvement of phosphorescent performance. Crystal engineering can utilize strong intermolecular interactions to effectively inhibit non-radiative transitions of triplet excitons, and due to its dense molecular packing, it can reduce the quenching of triplet excitons by oxygen, water vapor, etc., which is an effective way to achieve high-efficiency room-temperature phosphorescence. However, in the crystal aggregate state, intermolecular π-π stacking easily leads to triplet-triplet annihilation, dissipating a large amount of triplet excitons and affecting the improvement of phosphorescent efficiency; and π-π stacking will increase the intermolecular conjugation degree and cause a red shift in luminescence, making it difficult to achieve blue phosphorescence. How to construct long-life and high-efficiency blue phosphorescence is one of the challenges in the field of organic phosphorescent materials. Summary of the Invention

[0004] In order to solve the above problems existing in the prior art, the present invention provides a metal complex and its application. When the metal complex is used in an OLED, especially in the blue light emission region, it exhibits an enhanced phosphorescence quantum yield and is suitable as an emitter material in OLED applications.

[0005] In a first aspect, the present invention provides a metal complex, characterized in that the general formula of formula (I) is:

[0006]

[0007] Wherein, ring A and ring B are each independently selected from an aromatic ring of C 6 ~C 60 or a heteroaromatic ring of C 2 ~C 60 ;

[0008] M represents a metal element with an atomic weight greater than 40;

[0009] X 1 ~X 6 are each independently selected from C, N, or B;

[0010] X 7 ~X 14 are each independently selected from CR 3 or N;

[0011] Z 1 、Z 2 are each independently selected from CR 4 、SiR 4 、GeR 4 、B or N;

[0012] L 1 is selected from a single bond, O, S, S=O, SO 2 、Se、NR 5 、PR 5 、R 5 P=O、CR 5 R 6 、C=O、SiR 5 R 6 、GeR 5 R 6 or BR 5 ;

[0013] R 1 、R 2 each represent mono-substituted or poly-substituted to saturated substitution, or unsubstituted;

[0014] R 1 ~R 6 are each independently selected from hydrogen, or a group selected from the group consisting of: deuterium, a halogen atom, a nitrile group, an acyl group, a carboxyl group, an ether group, an ester group, an isonitrile group, a sulfur group, a selenoalkyl group, a sulfinyl group, a sulfonyl group, a phosphino group, a substituted or unsubstituted C 1 ~C 40 linear alkyl group, a substituted or unsubstituted C 1 ~C 40 linear heteroalkyl group, a substituted or unsubstituted C 3 ~C 40 branched or cyclic alkyl group, a substituted or unsubstituted C 1 ~C 40 alkoxy group, a substituted or unsubstituted C 6 ~C 60 arylalkyl group, a substituted or unsubstituted C 6 ~C 60 aryloxy group, a substituted or unsubstituted C 6 ~C 60 arylamino group, a substituted or unsubstituted C 3 ~C40 Silanyl, substituted or unsubstituted C 2 ~C 40 alkenyl, substituted or unsubstituted C 4 ~C 40 cycloalkenyl, substituted or unsubstituted C 2 ~C 40 heteroalkenyl, substituted or unsubstituted C 2 ~C 40 alkynyl, substituted or unsubstituted C 6 ~C 60 aryl, substituted or unsubstituted C 2 ~C 60 heteroaryl and combinations thereof, any two or more adjacent R 1 ~R 6 may optionally be joined or fused to form a substituted or unsubstituted ring.

[0015] In some embodiments, the ring A is selected from C 2 ~C 60 heteroaromatic rings.

[0016] In some embodiments, the ring B is selected from C 6 ~C 60 aromatic rings or C 2 ~C 60 heteroaromatic rings.

[0017] In some embodiments, the ring A is selected from C 2 ~C 20 heteroaromatic rings. In some embodiments, the ring B is selected from C 6 ~C 20 aromatic rings or C 2 ~C 20 heteroaromatic rings.

[0018] In some embodiments, L 1 is selected from a single bond, O, S, NR 5 or CR 5 R 6 .

[0019] In some embodiments, the metal complex is selected from the group consisting of:

[0020]

[0021]

[0022]

[0023]

[0024]

[0025] Wherein, each Y is independently selected from O, S or NR 5 ;

[0026] R is selected from hydrogen, deuterium, fluorine, cyano group, substituted or unsubstituted C 1 ~C 40 linear alkyl, substituted or unsubstituted C 1 ~C 40 linear heteroalkyl, substituted or unsubstituted C 3 ~C 40 branched or cyclic alkyl, substituted or unsubstituted C 1 ~C 40 alkoxy, substituted or unsubstituted C 6 ~C 60 arylalkyl, substituted or unsubstituted C 6 ~C 60 aryloxy, substituted or unsubstituted C 6 ~C 60 arylamino, substituted or unsubstituted C 3 ~C 40 silyl, substituted or unsubstituted C 2 ~C 40 alkenyl, substituted or unsubstituted C 4 ~C 40 cycloalkenyl, substituted or unsubstituted C 2 ~C 40 heteroalkenyl, substituted or unsubstituted C 2 ~C 40 alkynyl, substituted or unsubstituted C 6 ~C 60 aryl, substituted or unsubstituted C 2 ~C 60 heteroaryl and their combinations;

[0027] M is selected from Ir, Pt, Pd, Ru, Rh, Os, Au, Cu, Ni, Co, Ga or Ge;

[0028] R 1 ~R 6 has the same definition as that in formula (I).

[0029] In some embodiments, the R is selected from hydrogen, deuterium, fluorine, cyano group, substituted or unsubstituted C 1 ~C 20 linear alkyl, substituted or unsubstituted C 1 ~C 40 linear heteroalkyl, substituted or unsubstituted C 3 ~C 20 branched or cyclic alkyl, substituted or unsubstituted C 7 ~C30 Arylalkyl, substituted or unsubstituted C 2 ~C 20 Alkenyl, substituted or unsubstituted C 4 ~C 20 Cycloalkenyl, substituted or unsubstituted C 2 ~C 20 Heteroalkenyl, substituted or unsubstituted C 2 ~C 20 Alkynyl, substituted or unsubstituted C 6 ~C 30 Aryl, substituted or unsubstituted C 2 ~C 30 Heteroaryl and combinations thereof.

[0030] In some embodiments, M is selected from Pt or Pd. In some embodiments, the metal M is Pt.

[0031] In some embodiments, Y are each independently selected from O or S.

[0032] In some embodiments, R 1 ~R 6 are each independently selected from hydrogen, or the group consisting of: deuterium, fluorine, cyano, substituted or unsubstituted C 1 ~C 20 linear alkyl, substituted or unsubstituted C 1 ~C 20 linear heteroalkyl, substituted or unsubstituted C 3 ~C 20 branched or cyclic alkyl, substituted or unsubstituted C 1 ~C 20 alkoxy, substituted or unsubstituted C 7 ~C 30 arylalkyl, substituted or unsubstituted C 6 ~C 30 aryloxy, substituted or unsubstituted C 6 ~C 30 arylamino, substituted or unsubstituted C 3 ~C 20 silyl, substituted or unsubstituted C 2 ~C 20 alkenyl, substituted or unsubstituted C 4 ~C 20 cycloalkenyl, substituted or unsubstituted C 2 ~C 20 heteroalkenyl, substituted or unsubstituted C 2 ~C 20 alkynyl, substituted or unsubstituted C 6 ~C 30 aryl, substituted or unsubstituted C2 ~C 30 Heteroaryl and combinations thereof; any two or more adjacent R 1 ~R 6 may optionally be joined or cyclized to form a substituted or unsubstituted ring.

[0033] In some embodiments of the present invention, the L 1 is selected from a single bond, O, S, NR 5 or CR 5 R 6 .

[0034] In some embodiments of the present invention, each Y is O or NR 5 .

[0035] In some embodiments of the present invention, the R 1 ~R 6 are each independently selected from the group consisting of a hydrogen atom, a deuterium atom, fluorine, a nitrile group, an isonitrile group, R A1 ~R A30 , R B1 ~R B195 , R C1 ~R C80 .

[0036] In some embodiments, the structure represented by the R A1 ~R A30 is as shown below:

[0037]

[0038] Optionally, the hydrogen atoms in each substituent (R A1 ~R A30 ) can be partially or completely replaced by deuterium atoms.

[0039] In some embodiments, the structure represented by the R B1 ~R B195 is as shown below:

[0040]

[0041]

[0042]

[0043]

[0044]

[0045] Optionally, the hydrogen atoms in each substituent (R B1 ~R B195) The hydrogen atoms therein can be partially or completely replaced by deuterium atoms. In some embodiments, the R C1 ~R C80 The structures are shown as follows:

[0046]

[0047]

[0048]

[0049] Optionally, the hydrogen atoms in each substituent (R C1 ~R C80 ) can be partially or completely replaced by deuterium atoms.

[0050] In some embodiments, X 9 、X 10 、X 11 and X 12 each independently selected from CR 3a or N, and R 3a is selected from hydrogen, deuterium, halogen, a straight-chain alkyl group having 1 to 6 carbon atoms or a branched-chain alkyl group or cycloalkyl group having 3 to 6 carbon atoms.

[0051] In some embodiments, is selected from phenyl, pyridyl.

[0052] According to an embodiment of the present invention, the metal complex is selected from the group consisting of:

[0053]

[0054]

[0055]

[0056]

[0057]

[0058]

[0059]

[0060] Optionally, some or all of the hydrogen atoms in the above structures can be replaced by deuterium atoms.

[0061] In a second aspect, the present invention provides an application of the metal complex described in the first aspect in an organic electroluminescent device.

[0062] 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 at least one of the organic layers contains the metal complex described in the first aspect.

[0063] In some embodiments, the organic electroluminescent device according to the present invention may further include a light-emitting layer, and the light-emitting layer contains the metal complex as described in the first aspect.

[0064] According to some embodiments of the present invention, the light-emitting layer in the organic electroluminescent device emits blue light.

[0065] In some embodiments, the light-emitting layer includes an organic electroluminescent material, and the organic electroluminescent material contains the metal complex represented by formula (I) disclosed herein. Preferably, the organic electroluminescent material may further contain other compounds, such as a fluorescent emitter, a delayed fluorescent emitter, and combinations thereof.

[0066] In some embodiments, the light-emitting layer includes a host material and a dopant material, and the dopant material includes the metal complex of the present invention. In some embodiments, the host material may include one or more; when the host compounds are in multiple combinations, it includes at least one n-type host compound and at least one p-type host compound.

[0067] In some embodiments, the light-emitting layer in the organic electroluminescent device contains the organic electroluminescent material of the present invention. Further, the organic electroluminescent material contains the metal complex disclosed in the present invention.

[0068] In some embodiments, at least one of the host materials is selected from the group consisting of phenyl, naphthyl, pyridyl, quinolinyl, isoquinolinyl, quinazolinyl, quinoxalinyl, phenanthryl, azaphenanthryl, pyrimidinyl, triazine, triphenylene, carbazolyl, indolocarbazolyl, dibenzothienyl, dibenzofuranyl, fluorenyl, silylfluorenyl, dibenzoselenophenyl, 5,9-dioxa-13b-boranaphtho[3,2,1-de]anthracenyl, aza-triphenylene, aza-carbazolyl, aza-indolocarbazolyl, aza-dibenzothienyl, aza-dibenzofuranyl, aza-dibenzoselenophenyl, and aza-(5,9-diaza-13b-boranaphtho[3,2,1-de]anthracene)yl, or a combination derived from these systems.

[0069] The organic layer described in the present invention may be a light-emitting layer, and the metal complex as described herein may be an emissive dopant compound or a non-emissive dopant compound.

[0070] In some embodiments, the dopant material is 0.1% to 100% of the mass of the light-emitting layer.

[0071] In some embodiments, the doping material is 1% to 50% of the mass of the light-emitting layer.

[0072] In some embodiments, the doping material is 1% to 30% of the mass of the light-emitting layer.

[0073] In some embodiments, the host material is selected from the group consisting of the following structures:

[0074]

[0075] According to one embodiment of the present invention, the organic electroluminescent device further includes a hole injection layer, which can be a single-material functional layer or a functional layer containing multiple materials. Among them, the most common multiple materials are hole transport materials doped with a certain proportion of p-type conductive doping materials. Common p-type doping materials include:

[0076]

[0077] The materials described herein as being suitable for specific layers in an organic light-emitting device can be used in combination with a variety of other materials present in the device. For example, the emissive doping compounds disclosed herein can be used in combination with a wide variety of hosts, transport layers, blocking layers, injection layers, electrodes, and other layers that may be present. The materials described or mentioned below are non-limiting examples of materials that can be used in combination with the compounds disclosed herein, and those skilled in the art can readily consult the literature to identify other materials that can be used in combination.

[0078] These methods are generally known to those of ordinary skill in the art, and they can apply them to organic electroluminescent devices containing the compounds according to the present invention without creative effort.

[0079] In a fourth aspect, the present invention provides a consumer product including the organic electroluminescent device described above.

[0080] The consumer product of the present invention can be one of the following products: flat panel display, computer monitor, medical monitor, television, billboard, lamp for internal or external lighting and / or signaling, head-up display, fully transparent or partially transparent display, flexible display, laser printer, telephone, cellular phone, tablet computer, phablet, personal digital assistant (PDA), wearable device, laptop computer, digital camera, video camera, viewfinder, microdisplay with a diagonal less than 2 inches, 3-D display, virtual reality or augmented reality display, vehicle, video wall comprising a plurality of tiled together displays, theater or stadium screen, light therapy device, and sign.

[0081] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0082] (1) When the metal complex of the present invention is used in an OLED, especially in the blue light emission region, it exhibits enhanced phosphorescence quantum yield, good luminescence stability, and high luminescence efficiency. And in OLED applications, it is suitable as an emissive dopant. The metal complex of the present invention can obtain an organic electroluminescent device with blue phosphorescent electroluminescence and improved luminescence efficiency, and the luminescent device has good thermal stability. The consumer product of the present invention can obtain an electronic device with blue phosphorescent electroluminescence and improved luminescence efficiency by containing the organic electroluminescent device of the present invention;

[0083] (2) The metal complex of the present invention regulates its photophysical properties by adjusting the structure of the ligands around the metal center and controlling the structure of the substituents on the ligands, and has the advantages of narrow emission spectrum, high stability, and high efficiency, and has broad application prospects in many fields such as OLED displays and lighting lamps. Description of the Drawings

[0084] In order to more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the following will briefly introduce the drawings required for the description of the embodiments or the prior art. Obviously, the drawings in the following description are only some embodiments of the present invention. For those of ordinary skill in the art, other drawings can be obtained based on these drawings without creative efforts.

[0085] Figure 1 Schematic diagram showing the organic light-emitting device 100.

[0086] The device 100 includes a substrate 101, an anode 102, a hole injection layer 103, a hole transport layer 104, an electron blocking layer 105, a light-emitting layer 106, a hole blocking layer 107, an electron transport layer 108, an electron injection layer 109, a cathode 110, and a capping layer (CPL) 111.

[0087] Figure 2 Schematic diagram showing the organic light-emitting device 200 with two light-emitting layers.

[0088] The device includes a substrate 201, an anode 202, a hole injection layer 203, a hole transport layer 204, a first light-emitting layer 205, an electron transport layer 206, a charge generation layer 207, a hole injection layer 208, a hole transport layer 209, a second light-emitting layer 210, an electron transport layer 211, an electron injection layer 212, and a cathode 213. Detailed Embodiments

[0089] To make the objectives, technical solutions and advantages of the present invention clearer, the technical solutions of the present invention will be described in detail below. Apparently, the described embodiments are only a part of the embodiments of the present invention, rather than all of them. All other implementation manners obtained by those of ordinary skill in the art based on the embodiments of the present invention without any creative efforts fall within the scope protected by the present invention.

[0090] In the substituted or unsubstituted ring formed by the binding of adjacent groups to each other in the present invention, the "ring" refers to a substituted or unsubstituted hydrocarbon ring or a substituted or unsubstituted heterocyclic ring. The term "joining" to form a ring refers to a fused ring, and a fused ring refers to a fused aliphatic ring, a fused aromatic ring, a fused aliphatic heterocyclic ring, a fused aromatic heterocyclic ring, or a form formed by their combination. The term "fused" ring refers to two aromatic rings joined together by a shared single bond or double bond. As non-limiting examples, for instance, two benzene rings are fused to form a naphthalene ring, a benzene ring and a furan ring are fused to form benzofuran, two benzene rings and a furan ring are fused to form dibenzofuran, etc.

[0091] The "aryl" or "aromatic ring" of the present invention refers to and includes a monocyclic aromatic hydrocarbon group and a polycyclic aromatic ring system. The polycycle can have two or more rings in which two carbons are shared by two adjacent rings (the rings are "fused"), where at least one of the rings is an aromatic hydrocarbon group. For example, the other rings can be cycloalkyl, cycloalkenyl, aryl, heterocyclic, and / or heteroaryl. The preferred aryl or aromatic ring is an aryl group containing 6 to 30 carbon atoms, preferably 6 to 20 carbon atoms, more preferably 6 to 12 carbon atoms. Particularly preferred are aryl groups having six, ten, or twelve carbon atoms. Suitable aryl groups include phenyl, biphenyl, terphenyl, triphenylene, tetraphenylene, naphthyl, anthracenyl, phenalenyl, phenanthrenyl, fluorenyl, pyrenyl, perylenyl, yl, and azulyl, preferably phenyl, biphenyl, terphenyl, triphenylene, fluorenyl, and naphthyl. Additionally, the aryl group can be optionally substituted.

[0092] As used herein, "heteroaryl" or "heteroaromatic ring" refers to a monocyclic aromatic group and a polycyclic aromatic ring system containing at least one heteroatom. Heteroatoms include, but are not limited to, oxygen, sulfur, nitrogen, phosphorus, boron, silicon, or selenium. In many cases, oxygen, sulfur, or nitrogen is the preferred heteroatom. The monocyclic heteroaromatic system is preferably a monocyclic ring having 5 or 6 ring atoms, and the ring may have one to six heteroatoms. The heteropolycyclic system may have two or more rings in which two atoms are shared by two adjacent rings (the rings are "fused"), where at least one of the rings is heteroaryl, for example, the other rings may be cycloalkyl, cycloalkenyl, aryl, heterocyclic, and / or heteroaryl. The heteropolycyclic aromatic ring system may have one to six heteroatoms on each ring of the polycyclic aromatic ring system. Preferred heteroaryl groups are heteroaryl groups containing three to thirty carbon atoms, preferably three to twenty carbon atoms, more preferably three to twelve carbon atoms. Suitable heteroaryl groups include dibenzothienyl, dibenzofuranyl, dibenzoselenophenyl, furyl, thienyl, benzofuranyl, benzothienyl, benzoselenophenyl, carbazolyl, indolocarbazolyl, pyridylindolyl, pyrrolodipyridyl, pyrazolyl, imidazolyl, triazolyl, oxazolyl, thiazolyl, oxadiazolyl, oxatriazolyl, dioxazolyl, thiadiazolyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, oxazinyl, oxathiazinyl, oxadiazinyl, indolyl, benzimidazolyl, indazolyl, indoxazinyl, benzoxazolyl, benzisoxazolyl, benzothiazolyl, quinolinyl, isoquinolinyl, cinnolinyl, quinazolinyl, quinoxalinyl, naphthyridinyl, phthalazinyl, pteridinyl, xanthenyl, acridinyl, phenazinyl, phenothiazinyl, phenoxazinyl, benzofuranopyridyl, furanodipyridyl, benzothiophenopyridyl, thiophenodipyridyl, benzoselenophenopyridyl, selenophenodipyridyl, 1,2-azaborolyl, 1,3-azaborolyl, 1,4-azaborolyl, borazonyl, and their nitrogen analogs, preferably dibenzothienyl, dibenzofuranyl, dibenzoselenophenyl, carbazolyl, indolocarbazolyl, imidazolyl, pyridyl, triazinyl, benzimidazolyl, 1,2-azaborolyl, 1,3-azaborolyl, 1,4-azaborolyl, borazonyl, and their nitrogen analogs. Additionally, the heteroaryl group may be optionally substituted.

[0093] As used herein, "aryl" or "heteroaryl" refers particularly to a group derived from: phenyl, naphthyl, anthracenyl, benzanthracenyl, phenanthryl, pyrenyl, a group selected from the group consisting of a base, a perylene group, a fluoranthene group, a tetracenyl group, a pentacenyl group, a benzopyrenyl group, a biphenyl group, a diphenyl group, a terphenyl group, a triphenyl group, a quaterphenyl group, a fluorenyl group, a spirobifluorenyl group, a dihydrophenanthrenyl group, a triphenylene group, a dihydropyrenyl group, a tetrahydropyrenyl group, a cis- or trans-indeno[1,2-b]fluorene group, a cis- or trans-indeno[1,2-b]carbazole group, a cis- or trans-indolo[2,3-b]carbazole group, a trindene group, an isotrindene group, a spirotrindene group, a spiroisotrindene group, a furyl group, a benzofuryl group, an isobenzofuryl group, a dibenzofuryl group, a thienyl group, a benzothienyl group, an isobenzothienyl group, a dibenzothienyl group, a pyrrolyl group, an indolyl group, an isoindolyl group, a carbazolyl group, a pyridyl group, a quinolinyl group, an isoquinolinyl group, an acridinyl group, a phenanthridinyl group, a benzo[5,6]quinolinyl group, a benzo[6,7]quinolinyl group, a benzo[7,8]quinolinyl group, a phenothiazinyl group, a phenoxazinyl group, a pyrazolyl group, a benzopyrazolyl group, an indazolyl group, an imidazolyl group, a benzimidazolyl group, a naphthimidazolyl group, a phenanthrimidazolyl group, a pyridinimidazolyl group, a pyrazinimidazolyl group, a quinoxalinimidazolyl group, an oxazolyl group, a benzoxazolyl group, a naphthoxazolyl group, an anthroxazolyl group, a phenanthroxazolyl group, an isoxazolyl group, a 1,2-thiazolyl group, a 1,3-thiazolyl group, a benzothiazolyl group, a pyridazinyl group, a hexaazatriphenylene group, a benzopyridazinyl group, a pyrimidinyl group, a benzopyrimidinyl group, a quinoxalinyl group, a 1,5-diazaanthracenyl group, a 2,7-diazapyrenyl group, a 2,3-diazapyrenyl group, a 1,6-diazapyrenyl group, a 1,8-diazapyrenyl group, a 4,5-diazapyrenyl group, a 4,5,9,10-tetraazaperylene group, a pyrazinyl group, a phenazinyl group, a phenoxazinyl group, a phenothiazinyl group, a fluoranthene ring group, a naphthyridinyl group, an azacarbazolyl group, a benzocarbazolyl group, a carbazolyl group, a phenanthrolinyl group, a 1,2,3-triazolyl group, a 1,2,4-triazolyl group, a benzotriazolyl group, a 1,2,3-oxadiazolyl group, a 1,2,4-oxadiazolyl group, a 1,2,5-oxadiazolyl group, a 1,3,4-oxadiazolyl group, a 1,2,3-thiadiazolyl group, a 1,2,4-thiadiazolyl group, a 1,2,5-thiadiazolyl group, a 1,3,4-thiadiazolyl group, a 1,3,5-triazinyl group, a 1,2,4-triazinyl group, a 1,2,3-triazinyl group, a tetrazolyl group, a 1,2,4,5-tetrazinyl group, a 1,2,3,4-tetrazinyl group, a 1,2,3,5-tetrazinyl group, a purinyl group, a pteridinyl group, an indolizinyl group, a quinazolinyl group, a benzothiadiazolyl group, a 1,3,2-diazaborolyl group, a 1,3,2-benzo[d][1,3,2]diazaborolyl group, or a group derived from a combination of these systems.

[0094] As used in the present invention, "alkyl" includes straight-chain and branched-chain alkyl groups. The alkyl group can be an alkyl group having 1 to 40 carbon atoms, preferably an alkyl group having 1 to 20 carbon atoms, and more preferably an alkyl group having 1 to 12 carbon atoms. Examples of alkyl groups include methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, neopentyl, 1-methylpentyl, 2-methylpentyl, 1-pentylhexyl, 1-butylpentyl, 1-heptyloctyl, 3-methylpentyl. Among the above, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, neopentyl and n-hexyl are preferred. Additionally, the alkyl group can be optionally substituted.

[0095] "Cycloalkyl" refers to a cyclic alkyl group, including monocyclic, polycyclic and spiroalkyl groups. The cycloalkyl group can be a cycloalkyl group having 3 to 40 ring carbon atoms, preferably a cycloalkyl group having 4 to 20 carbon atoms. Examples of cycloalkyl groups include cyclobutyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, 4,4-dimethylcyclohexyl, 1-adamantyl, 2-adamantyl, 1-norbornyl, 2-norbornyl, etc. Among the above, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, 4,4-dimethylcyclohexyl are preferred. Additionally, the cycloalkyl group can be optionally substituted.

[0096] "Heterocycloalkyl" in the sense of the present invention refers to a cycloalkyl group in which a single hydrogen atom or -CH 2 - group can be substituted by an oxygen, sulfur, halogen atom, nitrogen, phosphorus, boron, silicon or selenium atom, preferably a group substituted by oxygen, sulfur or nitrogen. Additionally, the heteroalkyl or heterocycloalkyl group can be optionally substituted.

[0097] "Alkenyl" encompasses straight-chain, branched-chain and cyclic olefin groups. The alkenyl group can be an alkenyl group containing 2 to 40 carbon atoms, preferably an alkenyl group having 2 to 20 carbon atoms. Examples of alkenyl groups include vinyl, propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1,3-butadienyl, 1-methylethenyl, styryl, 2,2-diphenylethenyl, 1,2-diphenylethenyl, 1-methylallyl, 1,1-dimethylallyl, 2-methylallyl, 1-phenylallyl, 2-phenylallyl, 3-phenylallyl, 3,3-diphenylallyl, 1,2-dimethylallyl, 1-phenyl-1-butenyl, 3-phenyl-1-butenyl, cyclopentenyl, cyclopentadienyl, cyclohexenyl, cycloheptenyl, cycloheptatrienyl, cyclooctenyl, cyclooctatetraenyl and norbornenyl. Additionally, the alkenyl group can be optionally substituted.

[0098] "Alkynyl" encompasses straight-chain alkynyl groups. The alkynyl group can be an alkynyl group containing 2 to 40 carbon atoms, preferably an alkynyl group having 2 to 20 carbon atoms. Examples of alkynyl groups include ethynyl, propynyl, propargyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-pentynyl, 2-pentynyl, 3,3-dimethyl-1-butynyl, 3-ethyl-3-methyl-1-pentynyl, 3,3-diisopropyl-1-pentynyl, phenyl ethynyl, phenyl propynyl, etc. Among the above, ethynyl, propynyl, propargyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-pentynyl, and phenyl ethynyl are preferred. Additionally, the alkynyl group can be optionally substituted.

[0099] "Cycloalkenyl" refers to a cyclic olefin group, including monocyclic, polycyclic, and spiro cycloalkenyl groups. Preferred cycloalkenyl groups are those containing 3 to 15 ring carbon atoms, which can be cyclobutenyl, cyclopentenyl, cyclohexenyl, cycloheptenyl, etc.; in addition, one or more hydrogen atoms can also be replaced by deuterium atoms, halogen atoms, or nitrile groups.

[0100] "Heteroalkenyl" or "heterocycloalkenyl" in the sense of the present invention refers to an alkenyl or cycloalkenyl group in which at least one carbon atom is replaced by a heteroatom. Optionally, the at least one heteroatom is selected from oxygen, sulfur, nitrogen, phosphorus, boron, silicon, or selenium, preferably oxygen, sulfur, or nitrogen. Preferred alkenyl and cycloalkenyl groups are those containing 3 to 15 carbon atoms. Additionally, heteroalkenyl and heterocycloalkenyl groups can be optionally substituted.

[0101] "Heteroalkyl" is formed by replacing one or more carbons in an alkyl chain with a heteroatom selected from the group consisting of nitrogen atoms, oxygen atoms, sulfur atoms, selenium atoms, phosphorus atoms, silicon atoms, germanium atoms, and boron atoms. The heteroalkyl can be a heteroalkyl having 1 to 40 carbon atoms, preferably a heteroalkyl having 1 to 20 carbon atoms, and more preferably a heteroalkyl having 1 to 12 carbon atoms. Examples of heteroalkyl groups include methoxymethyl, ethoxymethyl, ethoxyethyl, methylthiomethyl, ethylthiomethyl, ethylthioethyl, methoxymethoxymethyl, ethoxymethoxymethyl, ethoxyethoxyethyl, hydroxymethyl, hydroxyethyl, hydroxypropyl, mercaptomethyl, mercaptoethyl, mercaptopropyl, aminomethyl, aminoethyl, aminopropyl, dimethylaminomethyl, trimethylgermylmethyl, trimethylgermylethyl, trimethylgermylisopropyl, dimethylethylgermylmethyl, dimethylisopropylgermylmethyl, tert-butyldimethylgermylmethyl, triethylgermylmethyl, triethylgermylethyl, triisopropylgermylmethyl, triisopropylgermylethyl, trimethylsilylmethyl, trimethylsilylethyl, trimethylsilylisopropyl, triisopropylsilylmethyl, triisopropylsilylethyl. Additionally, the heteroalkyl can be optionally substituted.

[0102] In the present invention, "alkoxy" is represented by -O-alkyl, -O-cycloalkyl, -O-heteroalkyl or -O-heteroalkenyl. Examples and preferred examples of alkyl, cycloalkyl, heteroalkyl and heteroalkenyl are the same as those described above. The alkoxy may be an alkoxy having 1 to 40 carbon atoms, preferably an alkoxy having 1 to 20 carbon atoms. Examples of alkoxy include methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, cyclopropyloxy, cyclobutyloxy, cyclopentyloxy, cyclohexyloxy, tetrahydrofuryloxy, tetrahydropyranyloxy, methoxypropyloxy, ethoxyethyloxy, methoxymethyloxy and ethoxymethyloxy. Additionally, the alkoxy may be optionally substituted.

[0103] "Selenoalkyl" is represented by -Se-alkyl, -Se-cycloalkyl, -Se-heteroalkyl or -Se-heteroalkenyl. Examples and preferred examples of alkyl, cycloalkyl, heteroalkyl and heteroalkenyl are the same as those described above. The selenoalkyl may be a selenoalkyl having 1 to 40 carbon atoms, preferably a selenoalkyl having 1 to 20 carbon atoms. Examples of selenoalkyl include methylseleno, ethylseleno, propylseleno, butylseleno, pentylseleno, hexylseleno, cyclopropylseleno, cyclobutylseleno, cyclopentylseleno, cyclohexylseleno, tetrahydrofurylseleno, tetrahydropyranylseleno, methoxypropylseleno, ethoxyethylseleno, methoxymethylseleno and ethoxymethylseleno, etc. Additionally, the selenoalkyl may be optionally substituted.

[0104] "Acyl" in the present invention refers to a substituted carbonyl (COR x ). "Carboxyl" or "carboxylic acid group" in the present invention refers to a substituted carboxyl (R x COOH). "Ester group" in the present invention refers to a substituted oxycarbonyl (-OCOR x or CO 2 R x ). "Ether group" in the present invention refers to an -OR x group. "Thio group" or "thioether" in this text is used interchangeably and refers to an -SR x group. "Sulfinyl" in the present invention refers to an -SOR x group. "Sulfonyl" in the present invention refers to an -SO 2 R x group. "Phosphino" in the present invention refers to a -PR x 3 group, where each R x may be the same or different.

[0105] Each of the above R x , preferably, is selected from the group consisting of alkyl, cycloalkyl, aryl and heteroaryl.

[0106] The aryloxy group is represented by -O-aryl or -O-heteroaryl. Examples and preferred examples of the aryl and heteroaryl groups are the same as those described above. The aryloxy group may be an aryloxy group having 6 to 60 carbon atoms, preferably an aryloxy group having 6 to 20 carbon atoms. Examples of the aryloxy group include phenoxy and biphenyloxy. Additionally, the aryloxy group may be optionally substituted.

[0107] The arylphosphino group used in the present invention refers to a diarylphosphino group substituted by an aryl group having 6 to 60 carbon atoms. As non-limiting examples of the arylphosphino group, there are diphenylphosphino, bis(4-trimethylsilylphenyl)phosphino, and the like. The aryloxyphosphino group is a diarylphosphino group in which the phosphorus atom is oxidized to the highest valence state.

[0108] The arylamino group or arylamine group used in the present invention refers to an amino group substituted by an aryl group having 6 to 60 carbon atoms. As non-limiting examples of the arylamino group, there are diphenylamino, carbazolyl, and the like.

[0109] In the present invention, "halogen", "halo", "halo atom", and "halo group" are used interchangeably and refer to fluorine, chlorine, bromine, or iodine.

[0110] Arylalkyl or aryl-alkyl may be used interchangeably and encompasses an alkyl group substituted by an aryl group. The arylalkyl group may be an arylalkyl group having 7 to 60 carbon atoms, preferably an arylalkyl group having 7 to 40 carbon atoms, and more preferably an arylalkyl group having 7 to 20 carbon atoms. Examples of the arylalkyl group include benzyl, 1-phenylethyl, 2-phenylethyl, 1-phenylisopropyl, 2-phenylisopropyl, phenyl tert-butyl, α-naphthylmethyl, 1-α-naphthyl-ethyl, 2-α-naphthylethyl, 1-α-naphthylisopropyl, 2-α-naphthylisopropyl, β-naphthylmethyl, 1-β-naphthyl-ethyl, 2-β-naphthyl-ethyl, 1-β-naphthylisopropyl, 2-β-naphthylisopropyl, p-methylbenzyl, m-methylbenzyl, o-methylbenzyl, p-chlorobenzyl, m-chlorobenzyl, o-chlorobenzyl, p-bromobenzyl, m-bromobenzyl, o-bromobenzyl, p-iodobenzyl, m-iodobenzyl, o-iodobenzyl, p-hydroxybenzyl, m-hydroxybenzyl, o-hydroxybenzyl, p-aminobenzyl, m-aminobenzyl, o-aminobenzyl, p-nitrobenzyl, m-nitrobenzyl, o-nitrobenzyl, p-cyanobenzyl, m-cyanobenzyl, o-cyanobenzyl, 1-hydroxy-2-phenylisopropyl, and 1-chloro-2-phenylisopropyl. Among the above, benzyl, p-cyanobenzyl, m-cyanobenzyl, o-cyanobenzyl, 1-phenylethyl, 2-phenylethyl, 1-phenylisopropyl, and 2-phenylisopropyl are preferred. Additionally, the arylalkyl group may be optionally substituted.

[0111] Alkylsilyl or silyl encompasses alkyl-substituted silicon groups. It may be an alkylsilyl having 3 to 40 carbon atoms, preferably an alkylsilyl having 3 to 20 carbon atoms. Examples of alkylsilyl include trimethylsilyl, triethylsilyl, methyldiethylsilyl, ethyldimethylsilyl, tripropylsilyl, tributylsilyl, triisopropylsilyl, methyldiisopropylsilyl, dimethylisopropylsilyl, tri-tert-butylsilyl, triisobutylsilyl, dimethyltert-butylsilyl, methylditert-butylsilyl. In addition, the alkylsilyl may be optionally substituted.

[0112] The arylsilyl group encompasses at least one aryl-substituted silicon group. The arylsilyl group can be an arylsilyl group having 6 to 60 carbon atoms, preferably an arylsilyl group having 8 to 40 carbon atoms. Examples of the arylsilyl group include triphenylsilyl, phenyldiphenylsilyl, diphenylbiphenylsilyl, phenyldiethylsilyl, diphenylethylsilyl, phenyldimethylsilyl, diphenylmethylsilyl, phenyldiisopropylsilyl, diphenylisopropylsilyl, diphenylbutylsilyl, diphenylisobutylsilyl, and diphenyltert-butylsilyl. In addition, the arylsilyl group can be optionally substituted.

[0113] Alkylgermanyl encompasses alkyl-substituted germanium. The alkylgermanyl may be an alkylgermanyl having 3 to 40 carbon atoms, preferably an alkylgermanyl having 3 to 20 carbon atoms. Examples of alkylgermanyl include trimethylgermanyl, triethylgermanyl, methyldiethylgermanyl, ethyldimethylgermanyl, tripropylgermanyl, tributylgermanyl, triisopropylgermanyl, methyldiisopropylgermanyl, dimethylisopropylgermanyl, tri-tert-butylgermanyl, triisobutylgermanyl, dimethyltert-butylgermanyl, methyldi-tert-butylgermanyl. In addition, the alkylgermanyl may be optionally substituted.

[0114] Arylgermanyl encompasses germanium groups substituted with at least one aryl or heteroaryl group. Arylgermanyl may be an arylgermanyl having 6 to 60 carbon atoms, preferably an arylgermanyl having 8 to 40 carbon atoms. Examples of arylgermanyl include triphenylgermanyl, phenyldiphenylgermanyl, diphenylbiphenylgermanyl, phenyldiethylgermanyl, diphenylethylgermanyl, phenyldimethylgermanyl, diphenylmethylgermanyl, phenyldiisopropylgermanyl, diphenylisopropylgermanyl, diphenylbutylgermanyl, diphenylisobutylgermanyl, diphenyltert-butylgermanyl. In addition, arylgermanyl may be optionally substituted.

[0115] In the present disclosure, the term "aza" in azadibenzofuran, azadibenzothiophene, etc. refers to one or at least two CH groups in the corresponding aromatic fragment are replaced by nitrogen atoms. For example, azatriphenylene includes dibenzo [f, h] quinoxaline, dibenzo [f, h] quinoline and other analogs with two or more nitrogens in the ring system. Other nitrogen analogs of the above-mentioned aza derivatives can be easily thought of by those of ordinary skill in the art, and all such analogs are determined to be included in the terms described herein.

[0116] In many cases, the general substituents are selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxyl, ether, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, and phosphino.

[0117] As used herein, the term "substituted or unsubstituted" means being substituted or unsubstituted by one or more substituents selected from hydrogen, deuterium, halogen atom, hydroxyl, nitrile, nitro, amino, amidino, hydrazino, hydrazono, carboxyl or its carboxylate, sulfonic acid group or its sulfonate, phosphoric acid group or its phosphate, C 1 -C 40 alkyl, C 2 -C 40 alkenyl, C 2 -C 40 alkynyl, C 1 -C 40 alkoxy, C 3 -C 40 cycloalkyl, C 3 -C 40 cycloalkenyl, C 6 -C 60 aryl, C 6 -C 60 aryloxy, C 6 -C 60 arylthioether group and C 2 -C 60 heteroaryl, or being substituted or unsubstituted by a substituent formed by linking two or more of the above-exemplified substituents.

[0118] As used herein, "in combination" or "group" means that one or more members of the applicable list are combined to form a known or chemically stable arrangement that a person of ordinary skill in the art can envision from the applicable list. For example, an alkyl and deuterium can be combined to form a partially or fully deuterated alkyl; a halogen and an alkyl can be combined to form a haloalkyl substituent such as difluoromethyl, trifluoromethyl, etc.; and a halogen, an alkyl, and an aryl can be combined to form a haloaralkyl.

[0119] In one example, the term "substituted" includes combinations of two to four of the listed groups.

[0120] In another instance, the term "substituted" includes combinations of two to three groups. In yet another instance, the term "substituted" includes combinations of two groups. Preferred combinations of substituents are combinations containing up to fifty atoms that are not hydrogen or deuterium, or combinations comprising up to forty atoms that are not hydrogen or deuterium, or combinations comprising up to thirty atoms that are not hydrogen or deuterium. In many cases, preferred combinations of substituents will comprise up to twenty atoms that are not hydrogen or deuterium in combination.

[0121] In the compounds mentioned in the present disclosure, unless explicitly defined, for example, adjacent substituents can optionally be linked to form a ring, adjacent substituents in the compounds cannot be linked to form a ring. In the compounds mentioned in the present disclosure, adjacent substituents can optionally be linked to form a ring, which includes both the case where adjacent substituents can be linked to form a ring and the case where adjacent substituents are not linked to form a ring. When adjacent substituents can optionally be linked to form a ring, the resulting ring can be a monocyclic or polycyclic ring (including spiro rings, bridged rings, fused rings, etc.), and an alicyclic ring, heteroalicyclic ring, aromatic ring or heteroaromatic ring. In this expression, adjacent substituents can refer to substituents bonded to the same atom, substituents bonded to carbon atoms directly bonded to each other, or substituents bonded to carbon atoms further away. Preferably, adjacent substituents refer to substituents bonded to the same carbon atom and substituents bonded to carbon atoms directly bonded to each other.

[0122] "EQE" in the present invention refers to the external quantum efficiency of the device, that is, the ratio of the number of photons emitted by the device to the number of electrons injected into the device.

[0123] The organic electroluminescent device described in the present invention comprises at least one organic layer, which is disposed between the anode and the cathode and is electrically connected to the anode and the cathode. Figure 1 A schematic diagram of the organic light-emitting device 100 is shown. The illustration is not necessarily drawn to scale. The device 100 may comprise a substrate 101, an anode 102, a hole injection layer 103, a hole transport layer 104, an electron blocking layer 105, a light-emitting layer 106, a hole blocking layer 107, an electron transport layer 108, an electron injection layer 109, a cathode 110, and a capping layer (CPL) 111. The device 100 can be fabricated by sequentially depositing the described layers.

[0124] Figure 2Schematic diagram showing an organic light-emitting device 200 having two light-emitting layers. The device includes a substrate 201, an anode 202, a hole injection layer 203, a hole transport layer 204, a first light-emitting layer 205, an electron transport layer 206, a charge generation layer 207, a hole injection layer 208, a hole transport layer 209, a second light-emitting layer 210, an electron transport layer 211, an electron injection layer 212, and a cathode 213. The device 200 can be fabricated by sequentially depositing the described layers. Since the most common OLED devices have a single monochromatic light-emitting layer or light-emitting layers of three primary colors, while the device 200 has two light-emitting layers of the same light color, the emission peak shapes of the first light-emitting layer and the second light-emitting layer can be overlapping or cross-overlapping or non-overlapping. In the corresponding layers of the device 200, materials similar to those described with respect to the device 100 can be used. Figure 2 Provide an example of how some layers can be added to the structure of the device 100.

[0125] Although many of the examples provided herein describe the various layers as including a single material, it will be understood that combinations of materials can be used, such as mixtures of a matrix and a dopant, or more generally, mixtures. Also, the layers can have various sub-layers. The names given to the individual layers herein are not intended to be strictly limiting. For example, in the device 200, the hole transport layer 204 transports holes and injects holes into the light-emitting layer 205, and can be described as a hole transport layer or an electron blocking layer. In one embodiment, an OLED can be described as having an organic layer disposed between the cathode and the anode. This organic layer can include a single layer or can further include multiple layers of different organic materials as described, for example Figure 1 and Figure 2 as described.

[0126] Structures and materials not specifically described can also be used, such as PLEDs containing polymeric materials. As another example, an OLED having a single organic layer or multiple stacks can be used. The OLED structure can deviate from Figure 1 and Figure 2 the simple layered structure illustrated therein. For example, the substrate can include angled reflective surfaces to improve light coupling.

[0127] Unless otherwise specified, any of the layers of the various embodiments can be deposited by any suitable method. For organic layers, preferred methods include thermal evaporation, organic vapor deposition methods, or the application of one or more layers by sublimation with a carrier gas, where, at 10 -5The material is applied at a pressure between millibars and 1 bar. A particular example of the method is an organic vapor jet printing method, in which the material is applied directly through a nozzle and is thus structured. Other suitable deposition methods include, for example, spin coating or by means of any desired printing method such as screen printing, flexographic printing, lithographic printing, thermal imaging, thermal transfer, inkjet printing or nozzle printing to produce one or more layers. Soluble compounds are obtained, for example, by appropriate substitution. These methods are also particularly suitable for oligomers, dendrimers and polymers. Also feasible are hybrid methods, in which, for example, one or more layers are applied from a solution and one or more additional layers are applied by vapor deposition.

[0128] The device manufactured according to an embodiment of the present invention may further optionally include a barrier layer. One use of the barrier layer is to protect the electrodes and the organic layers from damage due to exposure to harmful substances in the environment, including moisture, vapors and / or gases, etc. The barrier layer can be deposited on the substrate, on the electrodes, under the substrate, under the electrodes or beside the substrate, electrodes, or on any other part of the device, including the edges. The barrier layer can include a single layer or multiple layers. The barrier layer can be formed by various known chemical vapor deposition techniques and can include compositions having a single phase as well as compositions having multiple phases. Any suitable material or combination of materials can be used for the barrier layer. The barrier layer can incorporate inorganic or organic compounds or both. Preferably, the barrier layer includes a mixture of a polymeric material and a non-polymeric material. In order to be considered a mixture, the aforementioned polymeric and non-polymeric materials constituting the barrier layer should be deposited under the same conditions and / or simultaneously. The weight ratio of the polymeric material to the non-polymeric material can be in the range of 95 / 5 to 5 / 95. In one example, the mixture of the polymeric material and the non-polymeric material consists essentially of polymeric silicon and inorganic silicon.

[0129] In any of the compounds mentioned above used in each layer of the OLED device described above, the hydrogen atoms can be partially or completely deuterated. Thus, any specifically listed substituents, such as (but not limited to) methyl, ethyl, isopropyl, tert-butyl, phenyl, pyridyl, etc. can be in their non-deuterated, partially deuterated and fully deuterated forms. Similarly, substituent classes (such as (but not limited to) alkyl, aryl, cycloalkyl, heteroaryl, etc.) can also be in their non-deuterated, partially deuterated and fully deuterated forms.

[0130] The materials and structures described herein can be applied to devices other than OLEDs. For example, other optoelectronic devices such as organic solar cells and organic photodetectors can use the materials and structures.

[0131] Furthermore, organic devices such as organic transistors can use the materials and structures.

[0132] In the following embodiments of the present invention, conventional preparation methods are used unless otherwise specified. The raw materials used can be obtained from public commercial sources unless otherwise specified, and the percentages are all mass percentages unless otherwise specified. In order to more clearly illustrate the present invention, the technical solution of the present invention is described below in conjunction with some specific embodiments:

[0133] In the embodiment of material synthesis, unless otherwise stated, all reactions are carried out under nitrogen protection. All reaction solvents are anhydrous and used as they are from commercial sources. The synthetic product uses one or more conventional equipment in the art (including but not limited to nuclear magnetic resonance, liquid chromatograph, liquid chromatography mass spectrometer, gas chromatography mass spectrometer, differential scanning calorimeter, fluorescence spectrophotometer, electrochemical workstation, sublimator, etc.), and the structure is confirmed and the characteristics are tested by methods well known to those skilled in the art. In the embodiment of the device, the characteristics of the device are also tested by methods well known to those skilled in the art using conventional equipment in the art (including but not limited to evaporation machine, optical test system, life test system, ellipsometer, etc.). Since those skilled in the art are aware of the relevant contents such as the use of the above-mentioned equipment and the test method, the inherent data of the sample can be obtained with certainty and without being affected, so the above-mentioned relevant contents will not be elaborated in this patent.

[0134] In the embodiments of the present invention, the performance testing conditions of the prepared electroluminescent device are as follows:

[0135] Current-voltage: Tested using a digital source meter Keithley 2420;

[0136] Power efficiency: tested using NEWPORT 1931-C;

[0137] Brightness: Tested using a brightness meter Minolta CS-1000A.

[0138] Example 1

[0139] Preparation of metal complex P7:

[0140] Step 1: Preparation of compound Int-1

[0141]

[0142] Under nitrogen protection, 20.0 mmol of compound S1, 2.0 mmol of copper(I) iodide, 22.0 mmol of 2-bromo-4-tert-butylpyridine S2, 4.0 mmol of 1-methylimidazole and 40.0 mmol of lithium tert-butoxide were mixed, 100 mL of xylene was added, the temperature was raised to reflux, and the mixture was stirred and reacted for 48 hours. The temperature was lowered to room temperature, 50 mL of water was added, the mixture was stirred and reacted for 10 minutes, the organic phase was separated, dried, and filtered. The filtrate was concentrated to dryness under reduced pressure, separated and purified by silica gel column chromatography to obtain compound Int-1, a yellow solid, with a yield of 90%.

[0143] Step 2: Preparation of compound Int-2

[0144]

[0145] 20.0 mmol of compound Int-1 and 100 mL of ethyl acetate were mixed, and then 0.2 g of 5% palladium / carbon was added. Hydrogen was introduced at room temperature and atmospheric pressure, and the mixture was stirred and reacted for 8 hours. It was filtered, 30.0 mmol of triethylamine was added to the filtrate, the temperature was lowered to 0 °C, 24.0 mmol of acetyl chloride was added dropwise, and the mixture was stirred and reacted for 1 hour. 50 mL of water was added, the mixture was stirred for 10 minutes, the organic phase was separated, the aqueous phase was extracted with ethyl acetate, the organic phases were combined, dried, and filtered. The filtrate was concentrated to dryness, separated and purified by silica gel column chromatography to obtain compound Int-2, a yellow solid, with a yield of 92%.

[0146] Step 3: Preparation of compound Int-3

[0147]

[0148] 37.0 mmol of compound Int-2 prepared in the previous step was dissolved in 100 mL of glacial acetic acid, the temperature was raised to 60 °C, and a solution of 37.0 mmol of fuming nitric acid in 15 mL of glacial acetic acid was added dropwise, and the mixture was stirred and reacted for 10 hours. It was cooled to room temperature, concentrated to dryness under reduced pressure, 150 mL of ethyl acetate was added and stirred for 30 minutes, washed three times with saturated sodium carbonate aqueous solution, the organic phase was dried, and filtered. The filtrate was concentrated to dryness under reduced pressure, separated and purified by silica gel column chromatography to obtain compound Int-3, a yellow solid, with a yield of 86%.

[0149] Step 4: Preparation of compound Int-4

[0150]

[0151] Dissolve 32.0 mmol of the compound Int-3 prepared in the previous step and 160.0 mmol of sodium hydroxide in 150 mL of ethanol, heat to reflux, and stir the reaction for 5 hours. Cool to room temperature, concentrate to dryness under reduced pressure, add 150 mL of ethyl acetate, stir for 30 minutes, wash three times with water, dry the organic phase, and filter. Concentrate the filtrate to dryness under reduced pressure to obtain the compound Int-4, a yellow solid, which is used directly in the next step without purification, with a yield of 82%.

[0152] Step 5: Preparation of Compound Int-5

[0153]

[0154] Mix 20.0 mmol of the compound Int-4 and 100 mL of ethyl acetate, then add 0.2 g of 5% palladium / carbon, and introduce hydrogen at room temperature and atmospheric pressure, stir the reaction for 8 hours. Filter, concentrate the filtrate to dryness, to obtain the compound Int-5, a yellow solid, which is used directly in the next step without purification, with a yield of 100%.

[0155] Step 6: Preparation of Compound Int-6

[0156]

[0157] Under nitrogen protection, mix 20.0 mmol of the compound Int-5, 21.0 mmol of 4-chlorocatechol, and 100 mL of liquid paraffin, heat to 175 - 180 °C, and stir the reaction for 48 hours. Cool to room temperature, filter, wash the filter cake with petroleum ether and water, dry in vacuo, dissolve in dichloromethane, filter through a short silica-aluminum column, concentrate the filtrate to dryness under reduced pressure to obtain the compound Int-6, a yellow solid, with a yield of 58%.

[0158] Step 7: Preparation of Compound Int-7

[0159]

[0160] Under nitrogen protection, mix 20.0 mmol of the compound Int-6, 60.0 mmol of sodium tert-butoxide, 21.0 mmol of o-diiodobenzene, and 2.0 mmol of copper(I) iodide, add 80 mL of dry DMSO, heat to 120 °C and stir the reaction for 2 hours. Cool to room temperature, pour the reaction solution into 200 mL of ice-water solution, stir the reaction for 30 minutes, and filter. Wash the filter cake with water, and purify the solid by silica column chromatography to obtain the compound Int-7, a yellow solid, with a yield of 52%.

[0161] Step 8: Preparation of Compound Int-8

[0162]

[0163] Under nitrogen protection, 20.0 mmol of compound Int-7, 22.0 mmol of compound S3, 30.0 mmol of sodium tert-butoxide and 2.0 mmol of copper(I) iodide were mixed, and then 0.1 mmol of Pd 2 (dba) 3 、0.2 mmol of Xantphos and 80 mL of dry toluene were added. The temperature was raised to 110 °C and the mixture was stirred and reacted for 15 hours. After cooling to room temperature, 50 mL of water was added, and the mixture was stirred for 30 minutes. The organic phase was separated, and the aqueous phase was extracted with ethyl acetate. The organic phase was dried and filtered. The filtrate was filtered through a short basic alumina column, eluted with ethyl acetate, and concentrated to dryness under reduced pressure to obtain compound Int-8, a brown solid, with a yield of 80%.

[0164] Step 9: Preparation of compound Int-9

[0165]

[0166] Under nitrogen protection, 20.0 mmol of compound Int-8 prepared in the previous step, 1.0 mol of triethyl orthoformate and 40.0 mmol of ammonium hexafluorophosphate were mixed. The temperature was raised to 90 °C and the mixture was stirred and reacted for 18 hours. After cooling to room temperature, the mixture was concentrated under reduced pressure to a remaining volume of about 20 mL, 150 mL of n-hexane was added, and the mixture was stirred and filtered. The filter cake was washed with ether and dried in vacuo to obtain compound Int-9, a gray solid, with a yield of 75%.

[0167] Step 10: Preparation of compound P7

[0168]

[0169] Under nitrogen protection, 14.0 mmol of compound Int-9 prepared in the previous step, 7.0 mmol of silver oxide and 80 mL of 1,2-dichloroethane were mixed, and the mixture was stirred and reacted at room temperature for 18 hours. After concentration to dryness under reduced pressure, 14.0 mmol of Pt(COD)Cl 2 and 80 mL of o-dichlorobenzene were added, and the mixture was stirred and heated to reflux for 3 days. After cooling to room temperature, the mixture was concentrated to dryness under reduced pressure, dispersed in dichloromethane, and filtered. The filtrate was concentrated to dryness under reduced pressure and separated and purified by silica gel column chromatography to obtain compound P7, with a yield of 40%.

[0170] 1HNMR (δ, DMSO-d6): 8.51 - 8.50 (1H, d); 8.32 - 8.30 (1H, m); 7.86 - 7.84 (1H, m); 7.54 (1H, s); 7.40 - 7.36 (1H, m); 7.32 - 7.28 (1H, m); 7.21 - 7.19 (1H, d); 7.14 - 7.05 (6H, m); 7.03 - 6.97 (4H, m); 6.95 - 6.87 (3H, m); 6.65 - 6.63 (1H, d); 1.40 (18H, s); 1.31 (9H, s). HRMS: 976.3624 [M + H].

[0171] Example 2

[0172] Preparation of metal complex P3:

[0173] First step: Preparation of compound Int-10

[0174]

[0175] Under nitrogen protection, 21.0 mmol of compound nt-7, 20.0 mmol of compound S4, 30.0 mmol of sodium tert-butoxide and 2.0 mmol of cuprous iodide were mixed, and then 0.1 mmol of Pd 2 (dba) 3 , 0.2 mmol of 10% tri-tert-butylphosphine toluene solution and 80 mL of dry toluene were added. The temperature was raised to 110 °C and stirred for reaction for 15 hours. After cooling to room temperature, 50 mL of water was added, stirred for 30 minutes, the organic phase was separated, the aqueous phase was extracted with ethyl acetate, the organic phase was dried and filtered. The filtrate was filtered through a short silica gel column, eluted with ethyl acetate, and concentrated to dryness under reduced pressure to obtain compound Int-10, a yellow solid, yield: 87%.

[0176] Second step: Preparation of compound P3

[0177]

[0178] Under nitrogen protection, 15.0 mmol of compound Int-10 was dissolved in 100 mL of glacial acetic acid, 16.5 mmol of K 2 PtCl 4 and 1.5 mmol of tetrabutylammonium bromide were added, and the mixture was stirred and heated to reflux for reaction for 48 hours. After cooling to room temperature, it was concentrated to dryness under reduced pressure, dispersed in dichloromethane and filtered. The filtrate was concentrated to dryness under reduced pressure and separated and purified by silica gel column to obtain compound P3, yield: 38%.

[0179] 1HNMR (δ, DMSO-d6): 9.07 (1H, s); 8.51 - 8.50 (1H, d); 8.32 - 8.29 (1H, m); 8.21 - 8.18 (1H, m); 8.10 - 8.07 (1H, m); 7.94 - 7.92 (1H, m); 7.70 - 7.68 (2H, d); 7.58 - 7.54 (1H, m); 7.48 - 7.43 (3H, m); 7.40 - 7.36 (1H, m); 7.21 - 7.19 (1H, d); 7.16 - 7.11 (3H, m); 7.08 - 7.05 (2H, m); 1.35 (9H, s). HRMS: 788.2036 [M + H].

[0180] Example 3

[0181] Preparation of metal complex P16:

[0182] First step: Preparation of compound Int-11

[0183]

[0184] Under nitrogen protection, 20.0 mmol of phthalic anhydride, 40.0 mmol of anhydrous aluminum chloride and 80 mL of 1,2-dichloroethane were mixed, cooled to 0 °C, and then 40.0 mmol of compound S5 was added. The mixture was stirred and reacted for 10 hours. The temperature was raised to room temperature, and the mixture was stirred and reacted for 15 hours. 100 mL of ice water and 40 mL of concentrated hydrochloric acid were added, and the mixture was stirred for 30 minutes and then filtered. The filter cake was washed with water to obtain compound Int-11, a yellow solid, with a yield of 76%.

[0185] Second step: Preparation of compound Int-12

[0186]

[0187] Under nitrogen protection, 20.0 mmol of the compound Int-11 prepared in the previous step and 50 mL of polyphosphoric acid were mixed, heated to 90 °C and stirred for 24 hours. The temperature was lowered to room temperature, 150 mL of ice water was added, and the mixture was stirred and filtered. The filter cake was washed with water and purified by silica gel column to obtain compound Int-12, a yellow solid, with a yield of 65%.

[0188] Third step: Preparation of compound Int-13

[0189]

[0190] Under nitrogen protection, 20.0 mmol of the compound Int-12 prepared in the previous step was dissolved in 50 mL of dry THF, cooled to 0 °C, and 60.0 mmol of 1.0 M methylmagnesium bromide THF solution was added dropwise, followed by stirring for 2 hours. The reaction mixture was warmed to room temperature, 50 mL of 1 M dilute hydrochloric acid was added, the organic phase was separated, the aqueous phase was extracted with ethyl acetate, the organic phase was dried and filtered. The filtrate was concentrated under reduced pressure to dryness, and 80 mL of dry THF was added to the residue for later use.

[0191] Under nitrogen protection, 80.0 mmol of titanium trichloride was dissolved in 80 mL of dry THF, cooled to 0 °C, and 40.0 mmol of lithium aluminum hydride was added in portions, followed by stirring for 30 minutes. The previously prepared THF solution was added dropwise, the reaction mixture was warmed to room temperature and stirred for 2 hours. The temperature was raised to reflux and stirred for 3 hours. The reaction mixture was cooled to room temperature, 150 mL of 2 M dilute hydrochloric acid was added, the organic phase was separated, the aqueous phase was extracted with ethyl acetate, the organic phase was dried and filtered. The filtrate was concentrated under reduced pressure to dryness and purified by silica gel column chromatography to obtain compound Int-13, a yellow solid, yield: 90%.

[0192] Step 4: Preparation of compound Int-14

[0193]

[0194] Under nitrogen protection, 0.28 mol of compound Int-13 and 0.67 mol of isoamyl nitrite were dissolved in 300 mL of THF, the temperature was raised to reflux, and 0.62 mol of 2-amino-5-bromobenzoic acid dissolved in 200 mL of THF solution was slowly added dropwise, followed by stirring for 4 hours. The reaction mixture was concentrated under reduced pressure to dryness, 400 mL of xylene and 0.84 mol of maleic anhydride were added, the temperature was raised to reflux and reacted for 2 hours, cooled to room temperature, concentrated under reduced pressure to dryness, and purified by silica gel column chromatography to obtain compound Int-14, a yellow solid, yield: 46%.

[0195] Step 5: Preparation of compound Int-15

[0196]

[0197] Referring to the synthesis method in the eighth step of Example 1, only replacing the compound Int-7 in the eighth step of Example 1 with compound Int-14, compound Int-15 was prepared, a brown solid, yield 84%.

[0198] Step 6: Preparation of compound Int-16

[0199]

[0200] Referring to the synthesis method of the ninth step in Example 1, only replace the compound Int-8 in the ninth step of Example 1 with the compound Int-15 to prepare the compound Int-16, a brown solid, with a yield of 82%.

[0201] Step 7: Preparation of Compound P16

[0202]

[0203] Under nitrogen protection, 14.0 mmol of the compound Int-16 prepared in the previous step, 14.0 mmol of Pt(COD)Cl 2 and 500 mL of 2-methyltetrahydrofuran were mixed, then 42.0 mmol of anhydrous sodium acetate and 50 mL of toluene were added, and the mixture was stirred and heated to reflux for 3 days. It was cooled to room temperature, concentrated to dryness under reduced pressure, dispersed in dichloromethane, and filtered. The filtrate was concentrated to dryness under reduced pressure and purified by silica gel column chromatography to obtain the compound P16, a yellow solid, with a yield of 35%.

[0204] 1 HNMR (δ, DMSO-d6): 8.53 - 8.52 (1H, d); 8.35 - 8.33 (1H, m); 8.06 (1H, s); 7.93 - 7.90 (1H, m); 7.36 - 7.33 (2H, m); 7.31 - 7.29 (1H, d); 7.26 - 7.20 (4H, m); 7.16 - 7.11 (3H, m); 7.09 - 7.05 (3H, m); 7.01 - 6.98 (1H, d); 6.91 - 6.86 (3H, m); 2.35 (3H, s); 2.30 (3H, s); 1.42 (18H, s); 1.31 (9H, s). HRMS: 1002.4008 [M + H].

[0205] Example 4

[0206] Preparation of Metal Complex P73:

[0207] Step 1: Preparation of Compound Int-17

[0208]

[0209] Referring to the synthesis method of the third step in Example 3, only replace the methylmagnesium bromide in the third step of Example 3 with phenylmagnesium bromide to prepare the compound Int-17, a yellow solid, with a yield of 92%.

[0210] Step 2: Preparation of Compound Int-18

[0211]

[0212] Referring to the synthesis method in the fourth step of Example 3, only replace the compound Int-13 in the fourth step of Example 3 with the compound Int-17 to prepare the compound Int-18, a yellow solid, with a yield of 34%.

[0213] Step 3: Preparation of compound Int-19

[0214]

[0215] Referring to the synthesis method in the eighth step of Example 1, only replace the compound Int-7 in the eighth step of Example 1 with the compound Int-18 to prepare the compound Int-19, a brown solid, with a yield of 82%.

[0216] Step 4: Preparation of compound Int-20

[0217]

[0218] Referring to the synthesis method in the ninth step of Example 1, only replace the compound Int-8 in the ninth step of Example 1 with the compound Int-19 to prepare the compound Int-20, a brown solid, with a yield of 80%.

[0219] Step 5: Preparation of compound P73

[0220]

[0221] Referring to the synthesis method in the seventh step of Example 3, only replace the compound Int-16 in the seventh step of Example 3 with the compound Int-20 to prepare the compound P73, a yellow solid, with a yield of 44%.

[0222] 1 HNMR (δ, DMSO-d6): 8.53 - 8.51 (1H, d); 8.01 - 7.99 (1H, m); 7.96 - 7.94 (1H, m); 7.48 - 7.43 (2H, m); 7.34 - 7.26 (5H, m); 7.21 - 7.19 (1H, d); 7.11 - 7.05 (5H, m); 7.01 - 6.93 (6H, m); 6.91 - 6.80 (8H, m); 6.76 - 6.74 (1H, d); 1.37 (18H, s); 1.31 (9H, s). HRMS: 1126.4313 [M + H].

[0223] Example 5

[0224] Preparation of metal complex P84:

[0225] Step 1: Preparation of compound Int-21

[0226]

[0227] Under nitrogen protection, 30.0 mmol of 2-bromo-9,10-diphenylanthracene and 33.0 mmol of isoamyl nitrite were dissolved in 100 mL of dichloromethane. The temperature was raised to reflux, and a solution of 33.0 mmol of 2-amino-5-chlorobenzoic acid in 100 mL of acetone was slowly added dropwise. The mixture was stirred for 4 hours. It was concentrated to dryness under reduced pressure, 200 mL of xylene and 45.0 mmol of maleic anhydride were added, and the temperature was raised to reflux for 24 hours. Then it was cooled to room temperature and concentrated to dryness under reduced pressure. It was separated and purified by silica gel column chromatography to obtain compound Int-21, a yellow solid, with a yield of 33%.

[0228] Step 2: Preparation of compound Int-22

[0229]

[0230] Under nitrogen protection, 20.0 mmol of compound Int-21, 20.0 mmol of carboline, 80.0 mmol of anhydrous potassium carbonate and 2.0 mmol of cuprous iodide were mixed. Then 120 mL of toluene and 10.0 mmol of N,N'-dimethylethylenediamine were added. The temperature was raised to reflux and the mixture was stirred for 24 hours. It was cooled to room temperature, filtered, and the filtrate was concentrated to dryness under reduced pressure. It was separated and purified by silica gel column chromatography to obtain compound Int-22, a yellow solid, with a yield of 89%.

[0231] Step 3: Preparation of compound Int-23

[0232]

[0233] Under nitrogen protection, 21.0 mmol of compound Int-22, 20.0 mmol of compound S5, 30.0 mmol of sodium tert-butoxide and 2.0 mmol of cuprous iodide were mixed. Then 0.1 mmol of Pd 2 (dba) 3 CHCl 3 , 0.2 mmol of 10% tri-tert-butylphosphine toluene solution and 80 mL of dry toluene were added. The temperature was raised to 110 °C and the mixture was stirred for 15 hours. It was cooled to room temperature, 50 mL of water was added, and the mixture was stirred for 30 minutes. The organic phase was separated, the aqueous phase was extracted with ethyl acetate, and the organic phase was dried and filtered. The filtrate was filtered through a short silica gel column, eluted with ethyl acetate, and concentrated to dryness under reduced pressure to obtain compound Int-23, a brown solid, with a yield of 82%.

[0234] Step 4: Preparation of compound Int-24

[0235]

[0236] Referring to the synthesis method of the ninth step in Example 1, only replace the compound Int-8 in the ninth step of Example 1 with the compound Int-23 to prepare the compound Int-24, a yellow solid, with a yield of 84%.

[0237] Step 5: Preparation of Compound P84

[0238]

[0239] Referring to the synthesis method of the seventh step in Example 3, only replace the compound Int-16 in the seventh step of Example 3 with the compound Int-24 to prepare the compound P84, a yellow solid, with a yield of 32%.

[0240] 1 HNMR (δ, DMSO-d6): 8.49 - 8.47 (1H, m); 8.37 - 8.35 (1H, m); 8.12 - 8.10 (1H, m); 7.91 - 7.88 (1H, m); 7.64 - 7.61 (1H, m); 7.52 - 7.50 (1H, d); 7.44 - 7.28 (8H, m); 7.23 - 7.19 (1H, m); 7.11 - 7.03 (7H, m); 7.01 - 6.92 (4H, m); 6.90 - 6.84 (3H, m); 6.75 - 6.72 (1H, m); 6.42 - 6.41 (1H, m); 1.43 (18H, s). HRMS: 1071.3648 [M + H].

[0241] Example 6

[0242] Preparation of Metal Complex P110:

[0243] Step 1: Preparation of Compound Int-25

[0244]

[0245] Referring to the synthesis method of the third step in Example 3, replace the methylmagnesium bromide in the third step of Example 3 with phenylmagnesium bromide, and replace the compound Int-12 with the compound Int-12' (prepared according to the synthesis method of Example 3) to prepare the compound Int-25, a yellow solid, with a yield of 88%.

[0246] Step 2: Preparation of Compound Int-26

[0247]

[0248] Referring to the synthesis method of the fourth step in Example 3, only replace the compound Int-13 in the fourth step of Example 3 with the compound Int-25 to prepare the compounds Int-26 and Int-26’, yellow solid, yield 42%.

[0249] Step 3: Preparation of Compound Int-27

[0250]

[0251] Referring to the synthesis method of the eighth step in Example 1, only replace the compound Int-7 in the eighth step of Example 1 with the compound Int-26 to prepare the compound Int-27, brown solid, yield 86%.

[0252] Step 4: Preparation of Compound Int-28

[0253]

[0254] Referring to the synthesis method of the ninth step in Example 1, only replace the compound Int-8 in the ninth step of Example 1 with the compound Int-27 to prepare the compound Int-28, brown solid, yield 87%.

[0255] Step 5: Preparation of Compound P110

[0256]

[0257] Under nitrogen protection, 14.0 mmol of the compound Int-28 prepared in the previous step, 14.0 mmol of Pt(COD)Cl 2 and 250 mL of 1,4-dioxane were mixed, then 42.0 mmol of anhydrous sodium acetate was added, and the mixture was stirred and heated to reflux for 3 days. Cooled to room temperature, concentrated under reduced pressure to dryness, dispersed in dichloromethane, filtered, the filtrate was concentrated under reduced pressure to dryness, and purified by silica gel column chromatography to obtain the compound P110, yellow solid, yield: 53%.

[0258] 1 HNMR (δ, DMSO-d6): 8.51~8.50 (1H, d); 8.45~8.41 (2H, m); 8.01 (1H, s); 7.86~7.84 (1H, m); 7.46~7.44 (1H, m); 7.41~7.39 (1H, d); 7.36~7.33 (1H, m); 7.25~7.17 (6H, m); 7.15~7.09 (5H, m); 7.06~6.98 (6H, m); 6.96~6.90 (4H, m); 6.86~6.83 (1H, m); 1.35 (18H, s); 1.31 (9H, s). HRMS: 1127.4274 [M+H.

[0259] Example 7

[0260] Refer to the similar synthesis method of the above examples to prepare the compounds: P1, P2, P4 - P6, P8 - P15, P17 - P72, P74 - P83, P85 - P109, P111.

[0261] Preparation of Organic Electroluminescent Device

[0262] Ultrasonically treat the glass substrate with the patterned ITO electrode in a cleaning agent for 30 minutes, rinse it in deionized water, ultrasonically treat it in an acetone / ethanol mixed solvent for 30 minutes, bake it in a clean environment until completely dry, irradiate it with an ultraviolet light cleaning machine for 10 minutes, and bombard the surface with a low-energy cation beam.

[0263] Place the above-treated ITO glass substrate in a vacuum chamber, evacuate to less than 1×10 -5 Pa, deposit metallic silver as the anode on the above ITO film, and the deposited film thickness is Continue to deposit the compound HATCN as the hole injection layer, and the deposited film thickness is Continue to deposit the compound HTM as the hole transport layer on the above hole injection layer film, and the deposited film thickness is

[0264] Deposit the compound BPrime as the electron blocking layer on the above hole transport layer, and the deposited film thickness is

[0265] Deposit the metal complex of the present invention, compound H1, and compound H2 as the organic light-emitting layer of the device on the above electron blocking layer. Among them, compound H1 and compound H2 are the host materials, and the mass ratio of compound H1 to compound H2 is 1:1. The metal complex of the present invention is the doping material, and the doping concentration is 12%, and the deposited film thickness is

[0266] Deposit a layer of compound DPO as the hole blocking layer of the device on the above organic light-emitting layer, and the deposited film thickness is

[0267] Deposit a layer of LiQ and compound ET018 as the electron transport layer of the device on the above hole blocking layer. Among them, LiQ is 50% of the mass of compound ET018, and the deposited film thickness is

[0268] Deposit a layer of LiF as the electron injection layer of the device on the above electron transport layer, and the deposited film thickness is

[0269] On top of the above-mentioned electron injection layer, magnesium and silver are evaporated as the cathode layer of the device, where the mass ratio of magnesium to silver is 1:10, and the evaporation film thickness is

[0270] Finally, a compound HTM is evaporated on top of the cathode layer as a capping layer, and the evaporation film thickness is To fabricate the organic electroluminescent device of the present invention, as shown in the attached Figure 1 device 100.

[0271] Application of Comparative Example 1

[0272] The metal complex of the above-mentioned organic electroluminescent device is replaced with the compound BD012, and other steps are the same as above to fabricate Comparative Element 1.

[0273] The structural formulas of the aforementioned compounds HATCN, HTM, BPrime, H1, H2, BD012, DPO, and ET018 are as follows:

[0274]

[0275] Application Example 1

[0276] Following the same steps as for the preparation of the above-mentioned organic electroluminescent device, the metal complexes P1 - P111 prepared in the examples of the present invention are used to replace the metal complex of the above-mentioned organic electroluminescent device to fabricate the organic electroluminescent device of the present invention. A digital source meter and a luminance meter are used to measure the driving voltage, current efficiency, and the lifetime of the light-emitting device. Specifically, the voltage is increased at a rate of 0.1 V per second, and the voltage when the current density of the organic electroluminescent device reaches 10 mA / cm 2 is measured as the driving voltage, and the luminance at this time is also measured; the ratio of the luminance to the current density is the current efficiency. The LT95% lifetime test is as follows: Using a luminance meter at a luminance of 1000 cd / m 2 and maintaining a constant current, the time when the luminance attenuation of the organic electroluminescent device reaches 950 cd / m 2 is measured, and the unit is hours. The test results are summarized in Table 1, and the * data is normalized with respect to Comparative Element 1.

[0277] Table 1

[0278]

[0279]

[0280]

[0281] As can be seen from Table 1, compared with Comparative Element 1, the organic electroluminescent device prepared with the metal complex of the present invention has a lower driving voltage, a higher luminous efficiency and an excellent lifespan, and is an organic electroluminescent material with excellent performance.

[0282] Compared with the metal complex BD012 of Comparative Element 1, in the charge transfer process of the hexadentate metal ligand of C^Pt^C in the metal complex of the present invention, the anchoring effect of the parent nucleus such as triptycene is utilized to enhance the charge transfer rate, improve the stability and quantum efficiency of the ligand. Therefore, the metal complex of the present disclosure has a higher efficiency, a relatively lower driving voltage and an outstanding element lifespan performance than BD012.

[0283] As described above, only representative examples of the specific embodiments of the present invention are given, but the protection scope of the present invention is not limited thereto. Any person skilled in the art within the technical scope disclosed by the present invention can easily think of changes or substitutions, which should be covered within the protection scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.

Claims

1. A metal complex having a structure shown in formula (I): in, Ring A and Ring B are each independently selected from C6 to C 60 Aromatic ring or C2~C 60 Heteroaromatic rings; M represents a metal element with an atomic weight greater than 40; X 1 ~X 6 Each is independently selected from C, N or B; X 7 ~X 14 Each independently selected from CR 3 or N; Z 1 , Z 2 Each independently selected from CR 4 、SiR 4 ,GeR 4 , B or N; L 1 Selected from single bond, O, S, S=O, SO2, Se, NR 5 , PR 5 , R 5 P=O、CR 5 R 6 、C=O、SiR 5 R 6 ,GeR 5 R 6 or BR 5 ; R 1 , R 2 Each represents a single substitution or multiple substitution to saturated substitution, or no substitution; R 1 ~R 6 Each is independently selected from hydrogen, or selected from the group consisting of the following groups: deuterium, halogen atoms, nitrile groups, acyl groups, carboxyl groups, ether groups, ester groups, isonitrile groups, sulfides, selenoyl groups, sulfinyl groups, sulfonyl groups, phosphino groups, substituted or unsubstituted C1-C 40 Straight chain alkyl, substituted or unsubstituted C1~C 40 Straight chain heteroalkyl, substituted or unsubstituted C3~C 40 Branched or cyclic alkyl, substituted or unsubstituted C1~C 40 Alkoxy, substituted or unsubstituted C6~C 60 Arylalkyl, substituted or unsubstituted C6~C 60 Aryloxy, substituted or unsubstituted C6~C 60 Aromatic amino, substituted or unsubstituted C3~C 40 Silane, substituted or unsubstituted C2~C 40 Alkenyl, substituted or unsubstituted C4~C 40 Cycloalkenyl, substituted or unsubstituted C2~C 40 Heteroalkenyl, substituted or unsubstituted C2~C 40 Alkynyl, substituted or unsubstituted C6~C 60 Aryl, substituted or unsubstituted C2~C 60 Heteroaryl and combinations thereof, any adjacent two or more R 1 ~R 6 They may be arbitrarily joined or fused to form a substituted or unsubstituted ring.

2. The metal complex according to claim 1, characterized in that Ring A is selected from C2~C 20 The heteroaromatic ring, ring B is selected from C6~C 20 Aromatic ring or C2~C 20 Heteroaromatic ring; L 1 Selected from single bond, O, S, NR 5 or CR 5 R 6 ; Preferably, the metal complex is selected from the group consisting of: Wherein, Y is independently selected from O, S or NR 5 ; R is selected from hydrogen, deuterium, fluorine, nitrile, substituted or unsubstituted C1-C 40 Straight chain alkyl, substituted or unsubstituted C1~C 40 Straight chain heteroalkyl, substituted or unsubstituted C3~C 40 Branched or cyclic alkyl, substituted or unsubstituted C1~C 40 Alkoxy, substituted or unsubstituted C6~C 60 Arylalkyl, substituted or unsubstituted C6~C 60 Aryloxy, substituted or unsubstituted C6~C 60 Aromatic amino, substituted or unsubstituted C3~C 40 Silane, substituted or unsubstituted C2~C 40 Alkenyl, substituted or unsubstituted C4~C 40 Cycloalkenyl, substituted or unsubstituted C2~C 40 Heteroalkenyl, substituted or unsubstituted C2~C 40 Alkynyl, substituted or unsubstituted C6~C 60 Aryl, substituted or unsubstituted C2~C 60 Heteroaryl and combinations thereof; The metal M is selected from Ir, Pt, Pd, Ru, Rh, Os, Au, Cu, Ni, Co, Ga or Ge; R 1 ~R 6 The definition of is the same as that of formula (I).

3. The metal complex according to claim 1 or 2, characterized in that The metal M is selected from Pt or Pd; Y is each independently selected from O or S; R 1 ~R 6 are independently selected from hydrogen, or from the group consisting of deuterium, fluorine, nitrile, substituted or unsubstituted C1-C 40 Straight chain alkyl, substituted or unsubstituted C1~C 20 Straight chain heteroalkyl, substituted or unsubstituted C3~C 20 Branched or cyclic alkyl, substituted or unsubstituted C1~C 20 Alkoxy, substituted or unsubstituted C6~C 30 Arylalkyl, substituted or unsubstituted C6~C 30 Aryloxy, substituted or unsubstituted C6~C 30 Aromatic amino, substituted or unsubstituted C3~C 20 Silane, substituted or unsubstituted C2~C 20 Alkenyl, substituted or unsubstituted C4~C 20 Cycloalkenyl, substituted or unsubstituted C2~C 20 Heteroalkenyl, substituted or unsubstituted C2~C 20 Alkynyl, substituted or unsubstituted C6~C 30 Aryl, substituted or unsubstituted C2~C 30 Heteroaryl and combinations thereof; any adjacent two or more R 1 ~R 6 They may be optionally joined or cyclized to form substituted or unsubstituted rings.

4. The metal complex according to any one of claims 1 to 3, characterized in that The metal M is Pt or Pd; R 1 ~R 6 are each independently selected from a hydrogen atom, a deuterium atom, a fluorine atom, a nitrile group, an isonitrile group, R A1 ~R A30 , R B1 ~R B195 , R C1 ~R C80 The group composed of; Among them, R A1 ~R A30 The structural formula shown is as follows: R B1 ~R B195 The structure shown is as follows: R C1 ~R C80 The structure shown is as follows: Optionally, R 1 ~R 6 The hydrogen atoms in the ions can be partially or completely replaced by deuterium atoms.

5. The metal complex according to any one of claims 1 to 4, characterized in that X 9 , X 10 , X 11 and X 12 Each independently selected from CR 3a or N, R 3a Selected from hydrogen, deuterium, halogen, C1-C6 straight chain alkyl or C3-C6 branched chain alkyl or cycloalkyl.

6. The metal complex according to any one of claims 1 to 5, characterized in that The metal complex is selected from the group consisting of: Alternatively, some or all of the hydrogen atoms in the above structures may be replaced by deuterium atoms.

7. 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 metal complex according to any one of claims 1 to 6.

8. The organic electroluminescent device according to claim 7, characterized in that: The organic layer comprises a light-emitting layer, the light-emitting layer comprises a main material and a doping material, and the doping material comprises the metal complex according to any one of claims 1 to 6; Preferably, the host material is selected from the group consisting of triphenylene, carbazole, indolecarbazole, dibenzothiophene, dibenzofuran, fluorene, dibenzoselenophene, 5,9-dioxa-13b-boronaphtho[3,2,1-de]anthrene, aza-triphenylene, aza-carbazole, aza-indolecarbazole, aza-dibenzothiophene, aza-dibenzofuran, aza-dibenzoselenophene and aza-(5,9-diaza-13b-boronaphtho[3,2,1-de]anthrene) or a combination derived from these systems.

9. The organic electroluminescent device according to claim 8, characterized in that: The main material is selected from the group consisting of the following structures:

10. The organic electroluminescent device according to claim 8 or 9, characterized in that: The doping material accounts for 0.1% to 100% of the mass of the light-emitting layer.

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