Metal complex, organic electroluminescent element and consumer product

Abstract

The invention discloses a metal complex, an organic electroluminescent element and a consumer product. The metal complex provided by the invention comprises a ligand LA with a structure shown in the following formula. When the metal complex is applied to the organic electroluminescent element, very excellent element performance can be obtained, and particularly, the service life of the element is prolonged, and the efficiency of the element is improved. Wide application prospects are realized in various fields such as OLED (Organic Light Emitting Diode) display and illumination. # imgabs0 #

Description

Technical Field

[0001] The present invention belongs to the technical field of luminescent materials, and in particular relates to a metal complex, an organic electroluminescent element and a consumer product. Background Art

[0002] Currently, optoelectronic devices using organic materials are becoming increasingly popular, and many of the materials used to manufacture such devices are relatively inexpensive, so organic optoelectronic devices have the potential to offer cost advantages over inorganic devices. In addition, the inherent properties of organic materials (e.g., their flexibility) can make them more suitable for specific applications, such as fabrication on flexible substrates. Examples of organic optoelectronic devices include organic light-emitting diodes / devices (OLEDs), organic phototransistors, organic photovoltaic cells, and organic photodetectors. For OLEDs, organic materials can offer performance advantages over conventional materials.

[0003] OLEDs utilize organic thin films that emit light when a voltage is applied across the device. OLEDs are becoming an increasingly attractive technology for applications such as flat panel displays, lighting, and backlighting.

[0004] One application of phosphorescent emitting molecules is full-color displays. Industry standards for such displays require pixels that are suitable for emitting specific colors. Specifically, these standards require saturated red, green, and blue pixels. Alternatively, OLEDs can be designed to emit white light. In conventional liquid crystal displays, absorption filters are used to filter the emission from a white backlight to produce red, green, and blue emissions. The same technology can also be used for OLEDs. White OLEDs can be single-emission layer (EML) devices or stacked structures. Color can be measured using CIE coordinates, which are well known in the art. The luminescent materials in the prior art have poor luminescent stability and low luminous efficiency.

[0005] In view of the above reasons, the present invention is proposed. Summary of the Invention

[0006] To address the above problems in the prior art, the present invention provides a metal complex, an organic electroluminescent device, and a consumer product containing the metal complex. When used in an OLED, particularly in the green emission region, the metal complex exhibits enhanced phosphorescence quantum yield.

[0007] In a first aspect, the present invention provides a metal complex comprising a ligand represented by formula LA:

[0008]

[0009] Among them, X 1 ~X 4 Each independently selected from N or CR1 ;X 5 ~X 7 Each independently selected from N or CR 2 ;X 8 ~X 11 Each independently selected from N or CR 3 ;

[0010] R 1 ~R 3 is selected, at each occurrence, identically or differently, from hydrogen, or from the group consisting of: deuterium, a halogen atom, a nitrile group, an acyl group, a carboxylic acid group, an ether group, an ester group, an isonitrile group, a sulfide group, a selenoyl group, a sulfinyl group, a sulfonyl group, a phosphine group, a 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 C3~C 40 Branched or cyclic heteroalkyl, substituted or unsubstituted C1~C 40 Straight chain alkoxy, substituted or unsubstituted C3~C 40 Branched or cyclic alkoxy, substituted or unsubstituted C6~C 60 Arylalkyl, substituted or unsubstituted C6~C 60 Aryloxy, substituted or unsubstituted C6~C 60 Arylamine, 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 A group consisting of heteroaryl groups, any two or more adjacent R 1 ~R 3 They may be optionally joined or fused to form a substituted or unsubstituted ring, and optionally, the substituent in the case of substitution is selected from deuterium, a halogen atom, a nitrile group, a hydroxyl group, a C1-C6 straight-chain alkyl group, a C3-C6 branched-chain alkyl group, a C1-C6 straight-chain alkoxy group or a C3-C6 branched-chain alkoxy group;

[0011] The ligand LA is coordinated by the metal M to form a five-membered chelate ring;

[0012] M can coordinate with other ligands; and the ligand LA can be connected with other ligands to form a tridentate, tetradentate, pentadentate or hexadentate ligand; the M is selected from one of Os, Ir, Pd, Pt, Cu, Ag and Au.

[0013] In some embodiments, the M is selected from Ir, Pd, or Pt.

[0014] In some embodiments, the metal complex has the chemical formula M(LA) m (LB) n (LC) r , wherein M, at each occurrence, is identically or differently selected from Pt or Ir;

[0015] LA, LB and LC are the first ligand, the second ligand and the third ligand coordinated to the metal M, respectively, and LC and LB are the same or different; LA, LB and LC may be optionally linked to form a multidentate ligand;

[0016] m is 1, 2 or 3, n is 0, 1 or 2, r is 0, 1 or 2, and m+n+r equals the oxidation state of the metal M.

[0017] In some embodiments, when m is greater than or equal to 2, the multiple LAs are the same or different. In some embodiments, when n is equal to 2, the two LBs are the same or different. In some embodiments, when r is equal to 2, the two LCs are the same or different.

[0018] In some embodiments, the LB and LC are identically or differently selected from any one of the following structures at each occurrence:

[0019]

[0020] Among them, Y 1 ~Y 11 Each independently selected from N or CR 14 , T 1 Selected from BR 12 NR 12 PR 12 ,O,S,Se,C=O,S=O,SO2,CR 12 R 13 、SiR 12 R 13 and GeR 12 R 13 One of them, R 12 and R 13 They can be arbitrarily joined or fused to form a ring;

[0021] R 11 、R 12 、R 13 、R 14 are independently selected from hydrogen, or from the group consisting of deuterium, fluorine, nitrile, substituted or unsubstituted C1-C 40Straight chain alkyl, substituted or unsubstituted C1~C 40 Straight chain heteroalkyl, substituted or unsubstituted C3~C 40 Branched or cyclic alkyl, substituted or unsubstituted C3~C 40 Branched or cyclic heteroalkyl, substituted or unsubstituted C3~C 40 Silane, substituted or unsubstituted C6~C 60 Aryl, substituted or unsubstituted C2~C 60 The group consisting of heteroaryl groups, optionally, the substituents during the above substitution are selected from deuterium, halogen atoms, nitrile groups, hydroxyl groups, C1-C6 straight-chain alkyl groups, C3-C6 branched-chain alkyl groups, C1-C6 straight-chain alkoxy groups or C3-C6 branched-chain alkoxy groups.

[0022] In some embodiments, the metal complex has the chemical formula Ir(LA) m (LB) n , m is selected from 1, 2 or 3, n is selected from 0, 1 or 2, and m+n=3; when n is 2, the two LBs are the same or different; when m is 2 or 3, the multiple LAs are the same or different, wherein LA and LB have the definitions described in the present invention.

[0023] In some embodiments, the metal complex has the chemical formula of Ir(LA)(LB)2, Ir(LA)2(LB) or Ir(LA)3, wherein LA and LB have the definitions described herein.

[0024] In some embodiments, LB is selected from the group consisting of LB1-LB432:

[0025]

[0026]

[0027]

[0028]

[0029]

[0030]

[0031]

[0032]

[0033]

[0034]

[0035]

[0036]

[0037] Optionally, some or all of the hydrogen atoms in LB may be replaced by deuterium atoms. In some embodiments, the metal complex comprises a ligand LA represented by the following formula:

[0038]

[0039]

[0040]

[0041]

[0042] Wherein, a is 0, 1, 2, 3 or 4, b is 0, 1, 2 or 3, and c is 0, 1, 2, 3 or 4;

[0043] Each R 1 、R 2 and R 3 The same or different, each independently selected from hydrogen, deuterium, nitrile, halogen, C1-C6 alkyl, C6-C12 aryl, C3-C15 nitrogen heteroaryl, C3-C8 cycloalkyl, optionally, two or more adjacent R 1 The carbon atoms connected thereto combine to form a C3-C8 cycloalkyl, C6-C12 aryl, or C3-C15 nitrogen heteroaryl; optionally, two or more adjacent R 2 The carbon atoms connected thereto combine to form a C3-C8 cycloalkyl, C6-C12 aryl, or C3-C15 nitrogen heteroaryl; optionally, two or more adjacent R 3 The carbon atom connected thereto combines to form a C3-C8 cycloalkyl group, a C6-C20 aryl group, or a C3-C15 nitrogen heteroaryl group;

[0044] wherein the C1-C6 alkyl, C6-C12 aryl, C3-C15 nitrogen heteroaryl, C3-C8 cycloalkyl is optionally substituted by one or more substituents selected from hydrogen, deuterium, nitrile, halogen atom, C1-C4 alkyl;

[0045] Preferably, each R 1 、R 2 and R 3are the same or different and are independently selected from hydrogen, deuterium, a nitrile group, a halogen atom, a C1-C6 alkyl group without substituents, a halogenated C1-C6 alkyl group, a deuterated C1-C6 alkyl group, a C6-C12 aryl group without substituents, a C6-C10 aryl group substituted by a C1-C4 alkyl group, a C6-C12 aryl group substituted by a C1-C4 deuterated alkyl group, a C3-C15 azaaryl group without substituents, a C3-C15 azaaryl group substituted by a C1-C4 alkyl group, a C3-C15 azaaryl group substituted by a C1-C4 deuterated alkyl group, a C3-C8 cycloalkyl group without substituents, and a deuterated C3-C8 cycloalkyl group. Alternatively, R 1 The carbon atom connected thereto forms a benzene ring, a naphthalene ring or a pyridine ring. Optionally, R 2 The carbon atom connected thereto forms a benzene ring, a naphthalene ring or a pyridine ring. Optionally, R 3 The carbon atoms connected to it combine to form a benzene ring, a naphthalene ring or a pyridine ring;

[0046] Each group of Z1 and Z2 is independently selected from CH or N;

[0047] T 2 Selected from BR 4 NR 4 PR 4 、O、S、Se、CR 4 R 5 、SiR 4 R 5 and GeR 4 R 5 One of them, R 4 and R 5 They can be arbitrarily joined or fused to form a ring;

[0048] R 4 、R 5 Each independently selected from hydrogen, deuterium, a nitrile group, a halogen atom, a C1-C6 alkyl group without a substituent, a halogenated C1-C6 alkyl group, a C6-C10 aryl group without a substituent, a C1-C4 alkyl-substituted C6-C10 aryl group, a C3-C20 nitrogen heteroaryl group without a substituent, a C3-C8 cycloalkyl group without a substituent, and the adjacent R 4 and R 5 The carbon atom connected thereto combines to form a C3-C8 cycloalkyl group or a C6-C2 aryl group.

[0049] In some embodiments, T 2 is selected from O, S or Se; preferably, T 2 It is O.

[0050] In some embodiments, the metal complex has a structure shown in formula (I):

[0051]

[0052] wherein m is selected from 1, 2 or 3, n is selected from 0, 1 or 2, and m+n=3; when n is 2, the two LBs are the same or different; when m is 2 or 3, the multiple LAs are the same or different; X 1 ~X 11 The meaning of has the definition of the present invention;

[0053] R a ~R h is selected, at each occurrence, identically or differently, from hydrogen, or from the group consisting of: deuterium, a halogen atom, a nitrile group, an acyl group, a carboxylic acid group, an ether group, an ester group, an isonitrile group, a sulfide group, a selenoyl group, a sulfinyl group, a sulfonyl group, a phosphine group, a 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 C3~C 40 Branched or cyclic heteroalkyl, substituted or unsubstituted C1~C 40 Straight chain alkoxy, substituted or unsubstituted C3~C 40 Branched or cyclic alkoxy, substituted or unsubstituted C6~C 60 Arylalkyl, substituted or unsubstituted C6~C 60 Aryloxy, substituted or unsubstituted C6~C 60 Arylamine, 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 The group consisting of heteroaryl groups, any two or more adjacent substituents may be optionally joined or fused to form a substituted or unsubstituted ring, and optionally, the substituents in the case of substitution are selected from deuterium, halogen atoms, nitrile groups, hydroxyl groups, C1-C6 straight-chain alkyl groups, C3-C6 branched-chain alkyl groups, C1-C6 straight-chain alkoxy groups or C3-C6 branched-chain alkoxy groups.

[0054] In some embodiments, the X 1 ~X 4 CR 1 .

[0055] In some embodiments, the X 5 N, X 6 、X 7 CR2 , X 8 ~X 11 CR 3 .

[0056] In some embodiments, the X 5 N, X 6 、X 7 CR 2 , X 8 ~X 11 At least one of them is N.

[0057] In some embodiments, the X 6 N, X 5 、X 7 CR 2 , X 8 ~X 11 CR 3 .

[0058] In some embodiments, the X 6 N, X 5 、X 7 CR 2 , X 8 ~X 11 At least one of them is N.

[0059] In some embodiments, the X 7 N, X 5 、X 6 CR 2 , X 8 ~X 11 CR 3 .

[0060] In some embodiments, the X 7 N, X 5 、X 6 CR 2 , X 8 ~X 11 At least one of them is N.

[0061] In some embodiments, the R 1 ~R 3 、R 11 、R 12 、R 13 、R 14 、R a ~R h Each independently selected from hydrogen, deuterium, fluorine, nitrile, R A1 ~R A55 、R B1 ~R B45 、RC1 ~R C295 Groups composed of.

[0062] In some embodiments, R 1 、R 2 and R 3 Selected from the group consisting of hydrogen, deuterium, fluorine, chlorine, bromine, nitrile, methyl, ethyl, n-propyl, isopropyl, deuterated isopropyl (e.g. ), n-butyl, isobutyl, tert-butyl, deuterated dimethylbutyl (e.g. ), trifluoromethyl, trideuteromethyl, phenyl, biphenyl, methyl-substituted phenyl, trideuteromethyl-substituted phenyl, isopropyl-substituted phenyl, tert-butyl-substituted phenyl, deuterated isopropyl and tert-butyl-substituted phenyl (e.g. ), pyridyl, trideuteromethyl-substituted pyridyl, cyclopentyl, deuterated cyclopentyl (e.g. ), cyclohexyl, deuterated cyclohexyl (e.g. ), carbazolyl, methyl-substituted carbazolyl, tert-butyl-substituted carbazolyl.

[0063] In some embodiments, two adjacent R 1 The carbon atoms connected to it combine to form a benzene ring Naphthalene ring or pyridine ring The dotted lines indicate the fusion positions.

[0064] In some embodiments, two adjacent R 2 The carbon atoms connected to it combine to form a benzene ring Naphthalene ring or pyridine ring The dotted lines indicate the fusion positions.

[0065] In some embodiments, two adjacent R 3 The carbon atoms connected to it combine to form a benzene ring Naphthalene ring or pyridine ring The dotted lines indicate the fusion positions.

[0066] In some embodiments, the R 4 and R 5 Each independently selected from hydrogen, deuterium, fluorine, nitrile, R A1 ~R A55 、R B1 ~R B45 、R C1 ~R C295 the groups formed;

[0067] In some embodiments, R 4 and R 5Selected from the following groups: hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, phenyl, methyl-substituted phenyl, or adjacent R 4 and R 5 The carbon atom connected to it combines to form cyclopentyl, cyclohexyl, and spirofluorenyl.

[0068] In the present invention, the R A1 ~R A55 The structural formula is as follows:

[0069]

[0070]

[0071] R C1 ~R C295 The structural formula is as follows:

[0072]

[0073]

[0074]

[0075]

[0076]

[0077]

[0078] R A1 -R A55 、R B1 -R B45 and R C1 -R C295 Some or all of the hydrogen atoms in the ion can be replaced by deuterium atoms.

[0079] In some embodiments, the T 1 Selected from O.

[0080] In some embodiments, the T 1 Selected from S.

[0081] In some embodiments, the T 1 Selected from NR 12 , the R 12 Choose from R A1 ~R A55 、R B1 ~R B45 、R C1 ~R C208 、R C218 ~R C230 、RC243 ~R C295 Groups composed of.

[0082] In some embodiments, the T 2 Selected from O.

[0083] In some embodiments, the T 2 Selected from S.

[0084] In some embodiments, the T 2 Selected from C(CH3)2.

[0085] In some embodiments, the LA is selected from the group consisting of:

[0086]

[0087]

[0088]

[0089]

[0090]

[0091]

[0092]

[0093] Alternatively, some or all of the hydrogen atoms in LA1-LA188 may be replaced by deuterium atoms.

[0094] Furthermore, the chemical formula of the metal complex is Ir(LAi)2(LBj), Ir(LAi)(LBj)2, or Ir(LAi)3;

[0095] Wherein, i is an integer from 1 to 188, j is an integer from 1 to 432, and LA1 to LA188 and LB1 to LB432 have the same meanings as above.

[0096] The organic electroluminescent material of the present invention includes one or more of the metal complexes of the present invention. The organic electroluminescent material of the present invention may be formed solely of one or more of the metal complexes of the present invention, or may contain other materials in addition to the metal complexes of the present invention.

[0097] By incorporating the metal complex of the present invention into the organic electroluminescent material of the present invention, an organic electroluminescent material with green, yellow or red electroluminescence and high luminous efficiency can be obtained. In addition, the organic electroluminescent material of the present invention is an organic electroluminescent material with good thermal stability.

[0098] In a second aspect, the present invention provides an organic electroluminescent element comprising a first electrode, a second electrode and an organic layer disposed between the first electrode and the second electrode, wherein the organic layer comprises the metal complex.

[0099] In some embodiments, the organic layer includes a hole injection layer, a hole transport layer, an electron blocking layer, a light-emitting layer, a hole blocking layer, and an electron transport layer. The light-emitting layer includes a host material and a doping material. The doping material includes a metal complex.

[0100] In some embodiments, the host material mainly includes the group consisting of the following compounds: triphenylene, carbazole, dibenzothiophene, dibenzofuran, dibenzoselenophene, azatriphenylene, azacarbazole, azadibenzothiophene, azadibenzofuran and azadibenzoselenophene, indolecarbazole, 5,9-dioxa-13b-boronaphtho[3,2,1-de]anthracene, azaindolecarbazole and aza-(5,9-dioxa-13b-boronaphtho[3,2,1-de]anthracene) and derivatives or combinations thereof.

[0101] Optionally, any substituent in the host material is a non-fused substituent independently selected from the group consisting of: C n H 2n+1 , OC n H 2n+1 、OAr 1 、N(C n H 2n+1 )2、N(Ar 1 )(Ar 2 ), CH=CH-C n H 2n+1 、C≡CC n H 2n+1 、Ar 1 、Ar 1 -Ar 2 、C n H 2n -Ar 1 or no substituent, wherein n is an integer from 1 to 10; and wherein Ar 1 with Ar 2 Independently selected from the group consisting of benzene, biphenyl, naphthalene, triphenylene, carbazole, and heteroaromatic analogs thereof.

[0102] In some embodiments, the host material is selected from any one compound, two compounds, or a combination of multiple compounds shown below:

[0103] In some embodiments, the mass ratio of the host material to the doping material is 99:1 to 1:99.

[0104] In some embodiments, the mass percentage of the doping material in the light-emitting layer is 1% to 50%, and preferably the mass percentage of the doping material in the light-emitting layer is 1% to 10%.

[0105] In the organic electroluminescent device of the present invention, one layer may be a layer containing the metal complex of the present invention, or the metal complex of the present invention may be contained in two or more layers.

[0106] The organic layer can be a light emitting layer (emissive layer) and the metal complex as described herein can be an emissive dopant or a non-emissive dopant.

[0107] In a third aspect, the present invention provides a consumer product comprising the above-mentioned organic electroluminescent element.

[0108] The consumer product of the present invention is one or more of the following: a flat panel display, a computer monitor, a medical monitor, a television, a sign, a light for interior or exterior lighting and / or signaling, a head-up display, a fully or partially transparent display, a flexible display, a laser printer, a telephone, a cellular telephone, a tablet computer, a phablet, a personal digital assistant (PDA), a wearable device, a laptop computer, a digital camera, a video camera, a viewfinder, a microdisplay having a diagonal of less than 2 inches, a 3-D display, a virtual reality or augmented reality display, a vehicle, a video wall comprising multiple displays tiled together, a theater or stadium screen, a light therapy device, and a sign.

[0109] Compared with the prior art, the present invention has the following beneficial effects:

[0110] The metal complex of the present invention, when used as a luminescent material, can produce a green phosphorescent material with high luminescence efficiency. The organic electroluminescent element prepared therefrom emits green phosphorescence with high luminescence efficiency and good thermal stability. The consumer product of the present invention, by incorporating the organic electroluminescent element of the present invention, can produce green phosphorescent electroluminescence with high luminescence efficiency. BRIEF DESCRIPTION OF THE DRAWINGS

[0111] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the following briefly introduces the drawings required for use in the embodiments or the description of the prior art. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying any creative work.

[0112] Figure 1A schematic diagram of an organic electroluminescent device 100 is shown. The device 100 may include 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, an electron transport layer 108, an electron injection layer 109, a cathode 110, and a capping layer (CPL) 111.

[0113] Figure 2 A schematic diagram of an organic electroluminescent device 200 is shown. The device 200 is an example of the device 100 with a hole blocking layer 107 added.

[0114] Figure 3 Schematic diagram of an organic electroluminescent device 300 showing two light-emitting layers. Device 300 includes a substrate 101, an anode 102, a hole injection layer 103, a hole transport layer 104, a first light-emitting layer 1061, an electron transport layer 108, a charge generation layer 1022, a hole injection layer 103, a hole transport layer 104, a second light-emitting layer 1063, an electron transport layer 108, an electron injection layer 109, a cathode 110, and a capping layer 111. In device 300, the emission peaks of the first and second light-emitting layers can overlap, cross-overlap, or be non-overlapping. DETAILED DESCRIPTION

[0115] To make the objectives, technical solutions, and advantages of the present invention more apparent, the technical solutions of the present invention will be described in detail below. Obviously, the embodiments described are only some of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other implementations obtained by those of ordinary skill in the art without inventive effort are within the scope of protection of the present invention.

[0116] In the organic electroluminescent device of the present invention, the composition of layers other than the layer containing the metal complex of the present invention is not limited in any way, and those skilled in the art can determine the composition of other layers of the organic electroluminescent device as needed based on common technical knowledge in the field.

[0117] "Halogen", "halogen", "halogen atom", and "halo" herein are used interchangeably and refer to fluorine, chlorine, bromine, or iodine. "Acyl" herein refers to a substituted carbonyl (COR). "Ester" herein refers to a substituted oxycarbonyl (-OCOR or C02R). "Ether" herein refers to an -OR group. "Thio" or "thioether" herein are used interchangeably and refer to an -SR group. "Sulfinyl" herein refers to a -SOR group. "Sulfonyl" herein refers to a -S02R group. "Phosphino" herein refers to a -PR3 group, wherein each R may be the same or different. "Silyl" herein refers to a -SiR3 group, wherein each R may be the same or different. Each of the above R is preferably selected from the group consisting of an alkyl group, a cycloalkyl group, an aryl group, and a heteroaryl group.

[0118] According to the present invention, “alkyl”, “alkenyl” or “alkynyl” is preferably taken to mean methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, 2-methylbutyl, n-pentyl, sec-pentyl, neopentyl, cyclopentyl, n-hexyl, neohexyl, cyclohexyl, n-heptyl, cycloheptyl, n-octyl, cyclooctyl, 2-ethylhexyl, cyclohexenyl, heptenyl, cycloheptenyl, octenyl, cyclooctenyl, ethynyl, propynyl, butynyl, pentynyl, hexynyl, heptynyl or octynyl.

[0119] The “alkoxy group” of the present invention is preferably an alkoxy group having 1 to 40 carbon atoms, which is considered to be methoxy, trifluoromethoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentoxy, sec-pentoxy, 2-methylbutoxy, n-hexyloxy, cyclohexyloxy, n-heptyloxy, cycloheptyloxy, n-octyloxy, cyclooctyloxy, 2-ethylhexyloxy, pentafluoroethoxy and 2,2,2-trifluoroethoxy.

[0120] The term "cycloalkyl" or "cycloalkenyl" as used herein refers to and includes monocyclic, polycyclic, and spiroalkyl groups. Preferred cycloalkyl groups are those containing 3 to 15 ring carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, cycloheptyl, cycloheptenyl, bicyclo[3.1.1]heptyl, spiro[4.5]decyl, spiro[5.5]undecyl, and adamantyl, wherein one or more -CH2- groups may be replaced by the aforementioned groups; in addition, one or more hydrogen atoms may be replaced by a deuterium atom, a halogen atom, or a nitrile group.

[0121] In the present invention, "heteroalkyl" or "heterocycloalkyl" refers to an alkyl or cycloalkyl group, preferably an alkyl or cycloalkyl group having 1 to 40 carbon atoms, and refers to a group in which individual hydrogen atoms or -CH2- groups may be replaced by oxygen, sulfur, a halogen atom, nitrogen, phosphorus, boron, silicon or selenium, preferably by oxygen, sulfur or nitrogen. In addition, the heteroalkyl or heterocycloalkyl group may be optionally substituted.

[0122] As used herein, "heteroalkenyl" or "heterocycloalkenyl" 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. In addition, heteroalkenyl and heterocycloalkenyl groups may be optionally substituted.

[0123] The present invention uses "aralkyl" or "arylalkyl" interchangeably and refers to an alkyl group substituted with an aryl group. In addition, the aralkyl group may be optionally substituted.

[0124] The "aryl" of the present invention refers to and includes monocyclic aromatic hydrocarbon groups and polycyclic aromatic ring systems. Polycyclic rings may have two or more rings in which two carbon atoms are shared by two adjacent rings (the rings are "fused"), wherein at least one of the rings is an aromatic hydrocarbon group, for example, the other rings may be cycloalkyl, cycloalkenyl, aryl, heterocycle and / or heteroaryl. Preferred aryl groups are those containing 6 to 30 carbon atoms, preferably 6 to 20 carbon atoms, more preferably 6 to 12 carbon atoms. Especially preferred are aryl groups having six carbon atoms, ten carbon atoms or twelve carbon atoms. Suitable aryl groups include phenyl, biphenyl, terphenyl, triphenylene, tetraphenylene, naphthalene, anthracene, phenanthren, fluorene, pyrene, perylene, and azulene, preferably phenyl, biphenyl, terphenyl, triphenylene, fluorene and naphthalene. In addition, the aryl group may be optionally substituted.

[0125] "Heteroaryl" herein refers to monocyclic aromatic groups and polycyclic aromatic ring systems that include 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 are preferred heteroatoms. Monocyclic heteroaromatic systems are preferably monocyclic rings having 5 or 6 ring atoms, and the rings may have from one to six heteroatoms. Heteropolycyclic ring systems may have two or more rings in which two atoms are shared by two adjacent rings (the rings are "fused"), wherein at least one of the rings is a heteroaryl group, for example, the other rings may be cycloalkyl, cycloalkenyl, aryl, heterocycle, and / or heteroaryl groups. Heteropolycyclic aromatic ring systems may have from one to six heteroatoms on each ring of the polycyclic aromatic ring system. Preferred heteroaryl groups are those containing from three to thirty carbon atoms, preferably from three to twenty carbon atoms, and more preferably from three to twelve carbon atoms. Suitable heteroaryl groups include dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridylindole, pyrrolodipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indazole, indoxazine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazole In some embodiments, the heteroaryl group may be substituted with 1,2-azaborine, 1,3-azaborine, 1,4-azaborine, borazine and aza analogs thereof. In some embodiments, the heteroaryl group may be substituted with 1,2-azaborine, 1,3-azaborine, 1,4-azaborine, borazine and aza analogs thereof. In some embodiments, the heteroaryl group may be substituted with 1,2-azaborine, 1,3-azaborine, 1,4-azaborine, borazine and aza analogs thereof. In some embodiments, the heteroaryl group may be substituted with 1,2-azaborine, 1,3-azaborine, 1,4-azaborine, borazine and aza analogs thereof. In some embodiments, the heteroaryl group may be substituted with 1,2-azaborine, 1,3-azaborine, 1,4-azaborine, borazine and aza analogs thereof.

[0126] In the present invention, the term "substituted or unsubstituted" means a group selected from hydrogen, deuterium, a halogen atom, a hydroxyl group, a nitrile group, a nitro group, an amino group, an amidine group, a hydrazine group, a hydrazone group, a carboxyl group or a carboxylate thereof, a sulfonic acid group or a sulfonate thereof, a phosphoric acid group or a phosphate thereof, a C1-C 40 Alkyl, C2-C 40 Alkenyl, C2-C 40 Alkynyl, C1-C 40 Alkoxy, C3-C 40 Cycloalkyl, C3-C 40 Cycloalkenyl, C6-C 60 Aryl, C6-C 60 Aryloxy, C6-C 60 Aryl sulfide group and C2-C 60The heteroaryl group may be substituted or unsubstituted with one or more substituents, or may be substituted or unsubstituted with a substituent formed by linking two or more of the substituents exemplified above.

[0127] As used herein, "a combination thereof" or "a group thereof" means that one or more members of an applicable list are combined to form a known or chemically stable arrangement that one of ordinary skill in the art can conceive from the applicable list. For example, an alkyl group and a deuterium group can be combined to form a partially or fully deuterated alkyl group; a halogen group and an alkyl group can be combined to form a haloalkyl substituent, such as a trifluoromethyl group; and a halogen group, an alkyl group, and an aryl group can be combined to form a haloaralkyl group.

[0128] In one example, the term substitution comprises a combination of two to four listed groups. In another example, the term substitution comprises a combination of two to three groups. In yet another example, the term substitution comprises a combination of two groups. The preferred combination of substituents is a combination containing up to fifty atoms that are not hydrogen or deuterium, or comprises a combination of up to forty atoms that are not hydrogen or deuterium, or comprises a combination of up to thirty atoms that are not hydrogen or deuterium. In many cases, the preferred combination of substituents will comprise up to twenty atoms that are not hydrogen or deuterium.

[0129] The names given to the various layers herein are not intended to be strictly limiting. For example, Figure 3 In the embodiment, the hole transport layer 104 transports holes and injects holes into the first organic light emitting layer 1061 and can be described as a hole transport layer, a hole injection layer, an electron blocking layer or an enhancement layer. In one embodiment, the OLED can be described as having an organic layer disposed between a cathode and an anode. This organic layer can include a single layer or can further include, for example, Figure 1 、 Figure 2 or Figure 3 Multiple layers of different organic materials are described.

[0130] Structures and materials not specifically described may also be used, such as PLEDs comprising polymeric materials. As another example, an OLED having a single organic layer or a stack of multiple layers may be used. The OLED structure may be separated from Figure 1 、 Figure 2 and Figure 3 For example, the substrate may include angled reflective surfaces to improve light coupling.

[0131] The elements manufactured according to embodiments of the present invention may further optionally include a barrier layer. One purpose of the barrier layer is to protect the electrodes and organic layers from damage due to exposure to harmful substances in the environment, including moisture, vapor and / or gas. The barrier layer can be deposited on the substrate, the electrode, under the substrate, the electrode, or next to the substrate, the electrode, or on any other part of the device, including the edge. The barrier layer may include a single layer or multiple layers. The barrier layer can be formed by various known chemical vapor deposition techniques and may include compositions with a single phase as well as compositions with multiple phases. Any suitable material or combination of materials can be used for the barrier layer. The barrier layer may incorporate inorganic or organic compounds or both. Preferably, the barrier layer includes a mixture of polymeric material and non-polymeric material. In order to be considered a mixture, the aforementioned polymer and non-polymeric materials that constitute the barrier layer should be deposited under the same conditions and / or at the same time. The weight ratio of polymeric material to non-polymeric material may be in the range of 95 / 5 to 5 / 95. In one example, the mixture of polymeric material and non-polymeric material essentially consists of polymeric silicon and inorganic silicon.

[0132] In any of the above-mentioned compounds used in each layer of the OLED device, the hydrogen atoms may be partially or fully deuterated. Thus, any of the specifically listed substituents, such as (but not limited to) methyl, phenyl, pyridyl, etc., may be in their non-deuterated, partially deuterated, and fully deuterated forms. Similarly, substituent groups (such as (but not limited to) alkyl, aryl, cycloalkyl, heteroaryl, etc.) may also be in their non-deuterated, partially deuterated, and fully deuterated forms.

[0133] 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. Furthermore, organic devices such as organic transistors can use the materials and structures.

[0134] These processes are generally known to those skilled in the art and they can apply them without inventive step to organic electroluminescent devices comprising the compounds according to the invention.

[0135] According to one embodiment, novel ligands for metal complexes are disclosed. The inventors have discovered that the introduction of these ligands unexpectedly narrows the emission spectrum, lowers the sublimation temperature, and improves the luminous efficiency of the device.

[0136] In the embodiments of the present invention, the performance testing conditions of the prepared electroluminescent device are as follows: brightness and chromaticity coordinates: measured using a spectrum scanner PhotoResearch PR-715; current density and turn-on voltage: measured using a digital source meter Keithley 2420; power efficiency: measured using a NEWPORT 1931-C.

[0137] Example 1

[0138] Preparation of metal complex Ir(LA73)(LB105)2:

[0139] Step 1: Preparation of compound 73

[0140]

[0141] Under nitrogen protection, 20.0mmol of compound sub-1 (CAS: 1701428-62-7) and 40.0mmol of pyridine were dissolved in 50mL of dichloromethane, cooled to 0°C, and then 22.0mmol of compound sub-2 was added, and the temperature was raised to room temperature, and the reaction was stirred for 2 hours. 50mL of water was added, the organic phase was separated, dried, and filtered. The filtrate was concentrated and dried under reduced pressure, the residue was mixed with 100mL of toluene, and 2.0mmol of p-toluenesulfonic acid was added, the temperature was raised to reflux, and the reaction was stirred for 12 hours. The water generated by the reaction was separated by a water separator, cooled to room temperature, concentrated and dried under reduced pressure, and separated and purified by silica gel column to obtain compound 73 as a light yellow solid with a yield of 86%.

[0142] Step 2: Preparation of compound Int-1

[0143]

[0144] Under nitrogen, 52.9 mmol of compound 105 and 26.0 mmol of IrCl3·3H2O were dispersed in 150 mL of ethylene glycol ethyl ether and 50 mL of water and refluxed for 24 hours. The mixture was cooled to room temperature, filtered, and the filter cake was washed with water and ethanol, then dried under vacuum to obtain a yellow solid. The resulting yellow solid was dissolved in 250 mL of dichloromethane and 25 mL of methanol, and 30.0 mmol of silver trifluoromethanesulfonate was added. The mixture was stirred for 24 hours. The mixture was filtered, concentrated to dryness under reduced pressure, and the solid was washed with methanol and ether, then dried under vacuum at 55°C for 15 hours to obtain compound Int-1 as an orange solid in a 76% yield.

[0145] Step 3: Preparation of metal complex Ir(LA73)(LB105)2

[0146]

[0147] Under nitrogen, 4.3 mmol of compound 73, 2.4 mmol of intermediate Int-1, and 7.2 mmol of anhydrous potassium acetate were dispersed in 50 mL of ethylene glycol ethyl ether and 50 mL of DMF. The mixture was heated to 140°C and stirred for 5 hours. After cooling to room temperature, the mixture was directly irradiated with a UV lamp (254 nm) for 12 hours for transposition isomerization. The mixture was concentrated and dried under reduced pressure, and then purified on a silica gel column using toluene-petroleum ether as the eluent to obtain the metal complex Ir(LA73)(LB105)2 as a yellow solid in a yield of 55%. MS (ESI): 1115.4927 [M + ]. 1 HNMR(δ, CDCl3): 8.42(2H,s); 8.33(1H,s); 8.16~8.14(1H,d); 7.98~7.96(1H,d); 7.94~7.92(1H,d); 7.83~7.82(1H,d); 7.78(1H,s); 7.74~7.69(4H,m); 7.64~7.62 (1H,d); 7.54~7.52(2H,d); 7.48~7.43(3H,m); 7.41~7.38(1H,m); 7.33~7.31(2H, d); 7.26~7.24(2H,d); 7.18~7.16(2H,m); 7.14(2H,s); 1.45(9H,m); 1.33(9H,m).

[0148] Example 2

[0149] Preparation of metal complex Ir(LA127)(LB367)2:

[0150] Step 1: Preparation of compound 127

[0151]

[0152] Referring to the synthesis method of the first step of Example 1, only the compound sub-1 in the first step of Example 1 was replaced by compound sub-3, and the compound sub-2 was replaced by compound sub-4 to obtain compound 127 as a yellow solid in a yield of 64%.

[0153] Step 2: Preparation of compound Int-2

[0154]

[0155] Referring to the synthesis method of the second step of Example 1, only the compound 105 in the second step of Example 1 was replaced by compound 367 to obtain compound Int-2 as an orange solid in a yield of 78%.

[0156] Step 3: Preparation of metal complex Ir(LA127)(LB367)2

[0157]

[0158] Under nitrogen, 4.5 mmol of compound 127 and 2.0 mmol of intermediate Int-2 were dispersed in 100 mL of DMF. 6.0 mmol of anhydrous potassium acetate was added, and the mixture was heated to 140°C and stirred for 2 days. After cooling to room temperature, the mixture was irradiated with a 254 nm UV lamp for 12 hours for transposition isomerization. The mixture was concentrated and dried under reduced pressure, and then purified on a silica gel column using toluene-n-hexane as the eluent to obtain the metal complex Ir(LA127)(LB367)2 as a yellow solid in a 48% yield. MS (ESI): 955.4054 [M+H]. 1 HNMR (δ, CDCl3): 8.39~8.37(2H,d); 8.28~8.25(3H,m); 8.12(2H,s); 8.09~8.07(1H,d); 7.71(1H,s); 7.59~7. 56(2H,dd); 7.46~7.43(3H,m); 7.40~7.34(4H,m); 7.31~7.26(3H,m); 7.11(1H,s); 1.42(9H,s); 1.31(18H,s).

[0159] Example 3

[0160] Preparation of metal complex Ir(LA174)(LB367)2:

[0161] Step 1: Preparation of compound Int-3

[0162]

[0163] Under nitrogen, 24.0 mmol of 2-methyl-4-pyridineboronic acid, 20.0 mmol of 3-bromo-2-nitroaniline, and 50.0 mmol of hydrated potassium phosphate were dispersed in 50 mL of toluene and 30 mL of ethanol. 0.2 mmol of Pd(PPh3)4 and 20 mL of water were added, and the mixture was heated and refluxed for 15 hours. After cooling to room temperature, 50 mL of water was added, and the organic phase was separated. The aqueous phase was extracted with ethyl acetate, the organic phase was dried, filtered, and the filtrate was concentrated under reduced pressure to dryness and recrystallized from methanol to obtain compound Int-3 as a dark yellow solid in a yield of 72%.

[0164] Step 2: Preparation of compound Int-4

[0165]

[0166] Under nitrogen protection, 20.0mmol of compound Int-3 and 0.1mol of triphenylphosphine were dispersed in 50mL of o-dichlorobenzene and heated to reflux for 5 hours. Cooled to room temperature, 150mL of toluene and 0.1mol of anhydrous magnesium chloride were added, heated to reflux for 1 hour, cooled to room temperature, and filtered. The filtrate was concentrated and dried under reduced pressure, the residue was dissolved with 50mL of anhydrous THF, cooled to 0°C, 22.0mmol of lithium aluminum hydride was added in batches, warmed to room temperature, stirred for 1 hour, 2.5mL of 15% sodium hydroxide aqueous solution was added dropwise, filtered, and the filtrate was concentrated and dried under reduced pressure to obtain compound Int-4 as a yellow solid with a yield of 54%.

[0167] Step 3: Preparation of compound LA174'

[0168]

[0169] Referring to the synthesis method of the first step of Example 1, only the compound sub-1 in the first step of Example 1 was replaced by compound Int-4, and the compound sub-2 was replaced by benzoyl chloride to obtain compound 174' as a yellow solid in 85% yield.

[0170] Step 4: Preparation of Compound 174

[0171]

[0172] Under nitrogen, 10.0 mmol of compound 174' was mixed with 10 mL of DMSO-D6, and 0.5 mmol of potassium tert-butoxide was added. The mixture was stirred for 3 hours. The reaction solution was poured into 100 mL of ice water and filtered. The filter cake was washed with water and purified using a silica gel column to obtain compound 174 as a yellow solid in a 96% yield with a deuterated fraction of 98%.

[0173] Step 5: Preparation of metal complex Ir(LA174)(LB367)2

[0174]

[0175] Referring to the synthesis method of the third step of Example 2, except that compound 127 in the third step of Example 2 was replaced by compound 174, the metal complex Ir(LA174)(LB367)2 was obtained as a yellow solid in a yield of 54%. MS (ESI): 899.3424 [M+H]. 1HNMR (δ, CDCl3): 8.64(1H,s); 8.33~8.31(2H,d); 8.25~8.22(3H,m); 8.08(2H,s); 7.62~7.58(2H,m); 7.54~7.50 (3H,m); 7.46(1H,s); 7.42~7.41(2H,d); 7.38~7.34(2H,m); 7.26~7.22(2H,m); 7.19~7.15(3H,m); 1.44(18H,s).

[0176] Example 4

[0177] Referring to a synthetic method similar to that of Example 1 and Example 3, a compound represented by the formula Ir(LAi)(LBj)2 was prepared, wherein i is an integer from 1 to 188, j is an integer from 1 to 432, and the ligands LA1 to LA188 and LB1 to LB432 have the same structure as described above.

[0178] Example 5

[0179] Preparation of metal complex Ir(LA1)2(LB397):

[0180] Step 1: Preparation of compound 1

[0181]

[0182] Referring to the synthesis method of the first step of Example 1, only the compound sub-1 in the first step of Example 1 was replaced by 1-aminocarbazole and the compound sub-2 was replaced by benzoyl chloride to obtain compound 1 as a yellow solid in a yield of 86%.

[0183] Step 2: Preparation of compound Int-5

[0184]

[0185] Referring to the preparation method of the second step of Example 1, only compound 105 in the second step of Example 1 was replaced by compound 1, and the mass amount of the compound was changed according to the molar amount. Other experimental parameters were adjusted accordingly according to actual needs to prepare compound Int-5, a brown solid, with a yield of 73%.

[0186] Step 3: Preparation of metal complex Ir(LA1)2(LB397)

[0187]

[0188] 5.6 mmol of compound 397 (CAS: 2170167-51-6) and 2.5 mmol of intermediate Int-5 were dispersed in 50 mL of ethylene glycol ethyl ether and 50 mL of DMF. Under nitrogen, the mixture was heated to 120°C with stirring for 7 days. After cooling to room temperature, the mixture was irradiated with a UV lamp (254 nm) for 2 hours to induce transposition isomerization. The mixture was concentrated to dryness under reduced pressure and purified on a silica gel column using dichloromethane-petroleum ether as the eluent to obtain the metal complex Ir(LA1)2 (LB397) as a yellow solid in a 58% yield. MS (ESI): 992.3147 [M+H]. 1 HNMR (δ, CDCl3): 8.52(1H,s); 8.26(1H,s); 8.17(2H,s); 8.00~7.98(2H,d); 7.82~7.80(1H,d); 7.76~7.74(1H,d); 7.61~7.58(3H,m); 7.56~7 .53(3H,m); 7.51~7.47(2H,m); 7.45~7.40(4H,m); 7.38~7.35(2H,m); 7.32(1H,s); 7.25~7.20(3H,m); 7.18~7.15(4H,m); 7.08~7.05(2H,m).

[0189] Example 6

[0190] Referring to a similar synthesis method as in Example 5, a compound represented by the formula Ir(LAi)2(LBj) was prepared, wherein i is an integer from 1 to 188, j is an integer from 1 to 432, and LA1 to LA188 and LB1 to LB432 have the same meanings as above.

[0191] Example 7

[0192] Preparation of metal complex Ir(LA3)3:

[0193] Step 1: Preparation of compound Int-6

[0194]

[0195] 11.0 mmol of compound 3 (prepared according to the synthetic methods of Examples 1 to 5 above) and 5.0 mmol of IrCl3·3H2O were dispersed in 90 mL of ethylene glycol ethyl ether and 30 mL of water. The mixture was heated and refluxed under nitrogen for 24 hours. The mixture was cooled to room temperature, filtered, and the filter cake was washed with water and ethanol and dried under vacuum at 55°C for 12 hours to obtain compound Int-6 as a brown solid in a 63% yield.

[0196] Step 2: Preparation of metal complex Ir(LA3)3

[0197]

[0198] 5.0 mmol of the intermediate Int-6 prepared in the first step, 10.0 mmol of silver trifluoromethanesulfonate, and 15.0 mmol of compound 3 were dispersed in 50 mL of ethylene glycol ether and stirred under reflux under nitrogen for 48 hours. The mixture was cooled to room temperature and filtered. The filter cake was dissolved in dichloromethane, dried, and irradiated with a UV lamp (254 nm) for 1 hour for transposition isomerization. The mixture was separated and purified on a silica gel column to obtain compound Ir(LA3)3 as a yellow solid in a yield of 52%. MS (ESI): 1046.3442 [M + ]. 1 HNMR(δ, CDCl3): 8.17(3H,s); 8.12~8.10(3H,d); 7.84(3H,s); 7.61~7.59(3H,m); 7.56 ~7.53(3H,dd); 7.51~7.47(3H,m); 7.39~7.33(3H,m); 7.23~7.15(6H,m); 6.94(3H,s).

[0199] Example 8

[0200] Referring to the synthesis method of Example 7, the experimental parameters and conditions were appropriately adjusted to prepare the metal complex Ir(LAi)3, where i is an integer from 1 to 188, and LA1 to LA188 have the same meaning as above.

[0201] Example 9 Preparation of organic electroluminescent element

[0202] OLED components (such as Figure 1 The preparation method of the invention is as follows:

[0203] The glass substrate coated with the ITO conductive layer was ultrasonically treated in a cleaning agent for 30 minutes, rinsed in deionized water, ultrasonically treated in an acetone / ethanol mixed solvent for 30 minutes, baked in a clean environment until completely dry, irradiated with an ultraviolet light cleaner for 10 minutes, and bombarded with a low-energy cation beam.

[0204] Place the treated ITO glass substrate in a vacuum chamber and evacuate to a temperature less than 1×10 -5 Pa, silver is evaporated on the above ITO film as the anode, and the thickness of the evaporated film is Continue to evaporate the compound HATCN as the hole injection layer, and the thickness of the evaporated film is The hole injection layer is further evaporated to form a hole transport layer. The thickness of the evaporated film is

[0205] The compound EBM is evaporated on the hole transport layer as an electron blocking layer with a film thickness of

[0206] Compound H1 and the metal complex of the present invention are evaporated on the electron blocking layer as a light-emitting layer, wherein the metal complex prepared by the present invention is a doping material, the doping mass is 5% of compound H1, and the evaporated film thickness is

[0207] On the organic light-emitting layer, a layer of LiQ and compound ETM is further evaporated as the electron transport layer of the element, wherein LiQ is 50% of the mass of ETM and the thickness of the evaporated film is

[0208] A layer of LiF is continuously evaporated on the above electron transport layer as the electron injection layer of the device, and the thickness of the evaporated film is

[0209] On the electron injection layer, magnesium and silver are evaporated as the cathode of the device, wherein the mass ratio of magnesium to silver is 1:10 and the thickness of the evaporated film is

[0210] Finally, the compound HTM is evaporated on the cathode layer as a capping layer with a thickness of The organic electroluminescent element of the present invention is produced.

[0211] Comparative Example 1

[0212] Comparative element 1 was prepared by using the compound shown in GD-1 instead of the metal complex of the present invention in Example 9 and following the same other steps as in Example 9.

[0213] The structural formulas of the aforementioned compounds HATCN, HTM, EBM, H1, LiQ, GD-1, and ETM are shown below:

[0214]

[0215] The driving voltage and current efficiency of the organic electroluminescent element manufactured above, as well as the life of the element, were measured using a digital source meter and a luminance meter. Specifically, the voltage was increased at a rate of 0.1 V per second, and the current density of the organic electroluminescent element was measured when it reached 10 mA / cm 2 The voltage at which the current density is measured is the driving voltage, and the brightness at this time is measured at the same time; the ratio of brightness to current density is the current efficiency. The LT98% life test is as follows: Use a luminance meter at 1000cd / m 2 Under the brightness, the current is kept constant and the brightness decay of the organic electroluminescent element is measured to be 980cd / m 2The time is expressed in hours. The metal complex of the present invention is exemplified by Ir(LAi)(LBj)2, where i is an integer from 1 to 188, the ligands LA1 to LA188 have the same meaning as described above, and the ligand LB is represented by LB367. The experimental results are summarized in Table 1. *The data are normalized compared to Comparative Element 1.

[0216] Table 1

[0217]

[0218]

[0219]

[0220]

[0221]

[0222] As can be seen from Table 1, the metal complex of the present invention, as a doping material for the light-emitting layer, has a lower driving voltage than that of Comparative Example 1, especially has a significant advantage in current efficiency over Comparative Example 1, and the LT98% life of the device is also very ideal.

[0223] The main difference between the comparative compound GD-1 and the metal complex of the present invention is that compound GD-1 improves quantum efficiency by extending the polarization direction of the metal-to-ligand charge transfer (MLCT) reaction in the Ir^N^C substituent. The ligand LA of the present invention, by incorporating a group in the polarization direction of Ir^N, elevates the LUMO energy level, thereby increasing the MLCT transfer rate, shortening the phosphorescence lifetime, and reducing energy transfer losses. Consequently, the metal complex of the present invention exhibits excellent stability, enhanced luminescence efficiency, and significantly increased luminescence lifetime, making it a high-performance luminescent material.

[0224] The above description is merely a specific embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any modifications or substitutions that can be easily conceived by a person skilled in the art within the technical scope disclosed in the present invention should be included in the scope of protection of the present invention. Therefore, the scope of protection of the present invention should be based on the scope of protection of the claims.

Claims

1. A metal complex, characterized in that The metal complex comprises a ligand LA shown in the following formula: in, X 1 ~X 4 Each independently selected from N or CR 1 ; X 5 ~X 7 Each independently selected from N or CR 2 ; X 8 ~X 11 Each independently selected from N or CR 3 ; R 1 ~R 3 is selected, at each occurrence, identically or differently, from hydrogen, or from the group consisting of: deuterium, a halogen atom, a nitrile group, an acyl group, a carboxylic acid group, an ether group, an ester group, an isonitrile group, a sulfide group, a selenoyl group, a sulfinyl group, a sulfonyl group, a phosphine group, a 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 C3~C 40 Branched or cyclic heteroalkyl, substituted or unsubstituted C1~C 40 Straight chain alkoxy, substituted or unsubstituted C3~C 40 Branched or cyclic alkoxy, substituted or unsubstituted C6~C 60 Arylalkyl, substituted or unsubstituted C6~C 60 Aryloxy, substituted or unsubstituted C6~C 60 Arylamine, 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 A group consisting of heteroaryl groups, any two or more adjacent R 1 ~R 3 may be optionally joined or fused to form a substituted or unsubstituted ring, Optionally, the substituent in the above substitution is selected from deuterium, a halogen atom, a nitrile group, a hydroxyl group, a C1-C6 straight-chain alkyl group, a C3-C6 branched-chain alkyl group, a C1-C6 straight-chain alkoxy group or a C3-C6 branched-chain alkoxy group; The ligand LA is coordinated by the metal M to form a five-membered chelate ring; M is capable of coordinating with other ligands; and the ligand LA is capable of connecting with other ligands to form a tridentate, tetradentate, pentadentate or hexadentate ligand; The M is selected from one of Os, Ir, Pd, Pt, Cu, Ag and Au.

2. The metal complex according to claim 1, characterized in that The chemical formula of the metal complex is M(LA) m (LB) n (LC) r , wherein M, at each occurrence, is identically or differently selected from Pt or Ir; LA, LB and LC are the first ligand, the second ligand and the third ligand coordinated to the metal M, respectively, and LC and LB are the same or different; LA, LB and LC may be optionally linked to form a multidentate ligand; m is 1, 2 or 3, n is 0, 1 or 2, r is 0, 1 or 2, and m+n+r is equal to the oxidation state of the metal M, when m is greater than or equal to 2, the multiple LAs are the same or different; when n is equal to 2, the two LBs are the same or different; when r is equal to 2, the two LCs are the same or different; The LB and LC are selected from any one of the following structures at each occurrence, either identically or differently: Among them, Y 1 ~Y 11 Each independently selected from N or CR 14 , T 1 Selected from BR 12 NR 12 PR 12 ,O,S,Se,C=O,S=O,SO2,CR 12 R 13 、SiR 12 R 13 and GeR 12 R 13 One of them, R 12 and R 13 They can be arbitrarily joined or fused to form a ring; R 11 、R 12 、R 13 、R 14 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 40 Straight chain heteroalkyl, substituted or unsubstituted C3~C 40 Branched or cyclic alkyl, substituted or unsubstituted C3~C 40 Branched or cyclic heteroalkyl, substituted or unsubstituted C3~C 40 Silane, substituted or unsubstituted C6~C 60 Aryl, substituted or unsubstituted C2~C 60 The group consisting of heteroaryl groups, Optionally, the substituent in the above substitution is selected from deuterium, a halogen atom, a nitrile group, a hydroxyl group, a C1-C6 straight-chain alkyl group, a C3-C6 branched-chain alkyl group, a C1-C6 straight-chain alkoxy group or a C3-C6 branched-chain alkoxy group.

3. The metal complex according to claim 1 or 2, characterized in that The chemical formula of the metal complex is Ir(LA) m (LB) n , m is selected from 1, 2 or 3, n is selected from 0, 1 or 2, and m+n=3; when n is 2, the two LBs are the same or different; when m is 2 or 3, the multiple LAs are the same or different; preferably, the chemical formula of the metal complex is Ir(LA)(LB)2, Ir(LA)2(LB) or Ir(LA)3, and the definitions of LA and LB are the same as those in claim 2.

4. The metal complex according to any one of claims 1 to 3, characterized in that LB is selected from the group consisting of LB1-LB432: Alternatively, some or all of the hydrogen atoms in LB may be replaced by deuterium atoms.

5. The metal complex according to claim 1 or 2, characterized in that The metal complex has a structure shown in formula (I): wherein m is selected from 1, 2 or 3, n is selected from 0, 1 or 2, and m+n=3; when n is 2, the two LBs are the same or different; when m is 2 or 3, the multiple LAs are the same or different; X 1 ~X 11 The same definition as in claim 1; R a ~R h is selected, at each occurrence, identically or differently, from hydrogen, or from the group consisting of: deuterium, a halogen atom, a nitrile group, an acyl group, a carboxylic acid group, an ether group, an ester group, an isonitrile group, a sulfide group, a selenoyl group, a sulfinyl group, a sulfonyl group, a phosphine group, a 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 C3~C 40 Branched or cyclic heteroalkyl, substituted or unsubstituted C1~C 40 Straight chain alkoxy, substituted or unsubstituted C3~C 40 Branched or cyclic alkoxy, substituted or unsubstituted C6~C 60 Arylalkyl, substituted or unsubstituted C6~C 60 Aryloxy, substituted or unsubstituted C6~C 60 Arylamine, 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 The group consisting of heteroaryl groups, any two or more adjacent substituents may be optionally joined or fused to form a substituted or unsubstituted ring; optionally, the substituents in the above substitution are selected from deuterium, halogen atoms, nitrile groups, hydroxyl groups, C1-C6 straight-chain alkyl groups, C3-C6 branched-chain alkyl groups, C1-C6 straight-chain alkoxy groups or C3-C6 branched-chain alkoxy groups.

6. The metal complex according to any one of claims 1 to 5, characterized in that The R 1 ~R 3 、R 11 、R 12 、R 13 、R 14 、R a ~R h Each independently selected from hydrogen, deuterium, fluorine, nitrile, R A1 ~R A55 、R B1 ~R B45 、R C1 ~R C295 the groups formed; Among them, the R A1 ~R A55 The structural formula is as follows: R B1 ~R B45 The structural formula is as follows: R C1 ~R C295 The structural formula is as follows: Optionally, R A1 -R A55 、R B1 -R B45 and R C1 -R C295 Some or all of the hydrogen atoms in the ion can be replaced by deuterium atoms.

7. The metal complex according to any one of claims 1 to 6, characterized in that The metal complex includes a ligand LA shown in the following formula: Wherein, a is 0, 1, 2, 3 or 4, b is 0, 1, 2 or 3, and c is 0, 1, 2, 3 or 4; Each R 1 、R 2 and R 3 The same or different, each independently selected from hydrogen, deuterium, nitrile, halogen, C1-C6 alkyl, C6-C12 aryl, C3-C15 nitrogen heteroaryl, C3-C8 cycloalkyl, optionally, two or more adjacent R 1 The carbon atoms connected thereto combine to form a C3-C8 cycloalkyl, C6-C12 aryl, or C3-C15 nitrogen heteroaryl; optionally, two or more adjacent R 2 The carbon atoms connected thereto combine to form a C3-C8 cycloalkyl, C6-C12 aryl, or C3-C15 nitrogen heteroaryl; optionally, two or more adjacent R 3 The carbon atom connected thereto combines to form a C3-C8 cycloalkyl group, a C6-C20 aryl group, or a C3-C15 nitrogen heteroaryl group; wherein the C1-C6 alkyl, C6-C12 aryl, C3-C15 nitrogen heteroaryl, C3-C8 cycloalkyl is optionally substituted by one or more substituents selected from hydrogen, deuterium, nitrile, halogen atom, C1-C4 alkyl; Preferably, each R 1 、R 2 and R 3 are the same or different and are independently selected from hydrogen, deuterium, a nitrile group, a halogen atom, a C1-C6 alkyl group without substituents, a halogenated C1-C6 alkyl group, a deuterated C1-C6 alkyl group, a C6-C12 aryl group without substituents, a C6-C10 aryl group substituted by a C1-C4 alkyl group, a C6-C12 aryl group substituted by a C1-C4 deuterated alkyl group, a C3-C15 azaaryl group without substituents, a C3-C15 azaaryl group substituted by a C1-C4 alkyl group, a C3-C15 azaaryl group substituted by a C1-C4 deuterated alkyl group, a C3-C8 cycloalkyl group without substituents, and a deuterated C3-C8 cycloalkyl group. Alternatively, R 1 The carbon atom connected thereto forms a benzene ring, a naphthalene ring or a pyridine ring; optionally, R 2 The carbon atom connected thereto forms a benzene ring, a naphthalene ring or a pyridine ring; optionally, R 3 The carbon atoms connected to it combine to form a benzene ring, a naphthalene ring or a pyridine ring; Each group of Z1 and Z2 is independently selected from CH or N; T 2 Selected from BR 4 NR 4 PR 4 、O、S、Se、CR 4 R 5 、SiR 4 R 5 and GeR 4 R 5 One of them, R 4 and R 5 They can be arbitrarily joined or fused to form a ring; R 4 、R 5 Each independently selected from hydrogen, deuterium, a nitrile group, a halogen atom, a C1-C6 alkyl group without a substituent, a halogenated C1-C6 alkyl group, a C6-C10 aryl group without a substituent, a C1-C4 alkyl-substituted C6-C10 aryl group, a C3-C20 nitrogen heteroaryl group without a substituent, a C3-C8 cycloalkyl group without a substituent, and the adjacent R 4 and R 5 The carbon atom connected thereto combines to form a C3-C8 cycloalkyl group or a C6-C2 aryl group.

8. The metal complex according to any one of claims 1 to 7, characterized in that The LA is selected from the group consisting of the following structures: Alternatively, some or all of the hydrogen atoms in LA1-LA188 may be replaced by deuterium atoms.

9. An organic electroluminescent element comprising a first electrode, a second electrode, and an organic layer disposed between the first electrode and the second electrode, wherein: The organic layer comprises the metal complex according to any one of claims 1 to 8.

10. The organic electroluminescent element according to claim 9, wherein The organic layer includes a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting layer, a hole blocking layer, and an electron transport layer; The light-emitting layer comprises a host material and a doping material, wherein the doping material comprises the metal complex according to any one of claims 1 to 8; Preferably, the host material comprises a group consisting of the following compounds: triphenylene, carbazole, dibenzothiophene, dibenzofuran, dibenzoselenophene, nitrogen triphenylene, azacarbazole, azadibenzothiophene, azadibenzofuran and azadibenzoselenophene, and derivatives or combinations thereof; Preferably, the mass ratio of the host material to the doping material is 99:1-1:99.

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