Metal Complex, Organic Electroluminescent Element Containing the Same, and Consumer Product

Abstract

The present invention relates to a metal complex, an organic electroluminescent device comprising the same, and a consumer product. The metal complex described in the present invention can be used as a luminescent material to obtain a green phosphorescent material with high luminous efficiency, and the prepared luminescent material has good thermal stability; the organic electroluminescent device described in the present invention emits green phosphorescence and has the advantages of narrow emission spectrum, high stability and high efficiency; an electronic device can obtain a consumer product with green electroluminescence and high luminous efficiency by containing the organic electroluminescent device of the present invention.

Description

Technical Field

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

[0002] Currently, optoelectronic devices using organic materials have become increasingly popular, and many of the materials used to fabricate such devices are relatively inexpensive. Therefore, organic optoelectronic devices have the potential for cost advantages over inorganic devices. Additionally, the inherent properties of organic materials (such as 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 have performance advantages over conventional materials.

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

[0004] One application of phosphorescent emissive 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. 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 technique can also be used for OLEDs. White OLEDs can be single-emissive layer (EML) devices or stacked structures. Color can be measured using CIE coordinates well-known in the art. The luminescent materials in the prior art have poor luminescent stability and low luminescent efficiency.

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

[0006] In order to solve the above problems existing in the prior art, the present invention provides a metal complex, an organic electroluminescent device comprising the same, and a consumer product. When the metal complex of the present invention is used in an OLED, especially when used in the green emission region, it exhibits an enhanced phosphorescent quantum yield.

[0007] The first object of the present invention is to provide a metal complex with stable electroluminescence and high luminescent efficiency.

[0008] The second object of the present invention is to provide an organic electroluminescent device made of the metal complex.

[0009] The third object of the present invention is to provide a consumer product made of the organic electroluminescent device.

[0010] To achieve the above object, the present invention adopts the following technical solution:

[0011] A metal complex, wherein the metal complex comprises a ligand represented by formula (LA):

[0012]

[0013] wherein W is selected from O, S or NR 7 ;

[0014] X 1 、X 2 、X 3 、X 4 are each independently selected from N or CR 8

[0015] R 1 ~R 8 are the same or different each time they appear and are selected from the group consisting of hydrogen, deuterium, halogen atoms, C1-C 40 alkyl, C3-C 40 cycloalkyl, C1-C 40 heteroalkyl, C3-C 40 heterocycloalkyl, C6-C 60 arylalkyl, C1-C 40 alkoxy, C6-C 60 aryloxy, C3-C 40 silyl, C2-C 40 alkenyl, C5-C 40 cycloalkenyl, C3-C 40 heteroalkenyl, C2-C 40 alkynyl, C6-C 60 aryl, C2-C 60 heteroaryl, C1-C 40 acyl, carboxyl, amino, ether, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl and phosphino; R 5 is substituted with one or more to saturation, R 6 is one or two, and any two or more adjacent substituents may optionally be joined or fused together to form a substituted or unsubstituted five-membered ring, six-membered ring or polycyclic ring;

[0016] m and n are each independently selected from 0, 1 or 2, and m + n ≥ 2;

[0017] The metal complex is formed by coordinating the ligand represented by formula (LA) with metal M via a dotted line to form a five-membered chelate ring;

[0018] The metal complex further comprises other ligands, and the ligand represented by formula (LA) is connected to other ligands to form a tridentate, tetradentate, pentadentate or hexadentate ligand;

[0019] The metal M is selected from one of Os, Ir, Pd, Pt, Cu, Ag and Au, and preferably, the metal M is selected from one of Ir, Pd or Pt.

[0020] Furthermore, the formula (LA) includes one of the structures represented by the following LAI to LAIV:

[0021]

[0022] Wherein, R 1 ~R 6 、W、X 1 ~X 4 have the same meanings as defined above.

[0023] Furthermore, the chemical formula of the metal complex is M(LA) p (LB) q , LB is a bidentate ligand, p is 1, 2 or 3, q is 0, 1 or 2, and p + q is equal to the oxidation state of the metal M; preferably, LB is selected from one of the following structures:

[0024]

[0025]

[0026] Wherein, Y 1 ~Y 16 each independently selected from N or CR 10 , T 1 is selected from BR 12 , NR 13 , pR 14 , O, S, Se, C=O, S=O, SO2, CR 12 R 13 , SiR 12 R 13 and GeR 12 R 13 in one of them, R 12 and R 13 can be joined or fused arbitrarily to form a ring; T 2 is selected from N, B, SiR 12 , P or P=O;

[0027] Each R 10 , R 11 , R 12 , R 13 , R 14 、R15 , R 16 Each independently selected from the group consisting of hydrogen, deuterium, halogen atom, C1-C 40 alkyl chain, C3-C 40 cycloalkyl, C1-C 40 heteroalkyl, C3-C 40 heterocycloalkyl, C6-C 60 arylalkyl, C1-C 40 alkoxy, C6-C 60 aryloxy, amino, C3-C 40 silyl, C2-C 40 alkenyl, C5-C 40 cycloalkenyl, C3-C 40 heteroalkenyl, C2-C 40 alkynyl, C6-C 60 aryl, C2-C 60 heteroaryl, C1-C 40 acyl group, carboxyl group, ether, ester group, nitrile group, isonitrile group, sulfide group, sulfinyl group, sulfonyl group and phosphine group; and any two or more adjacent substituents are optionally joined or fused together to form a substituted or unsubstituted five-membered ring, six-membered ring or polycyclic ring.

[0028] Regarding the oxidation state of metal M, when M is Ir, the oxidation state of Ir can be 3, and when M is Pt, the oxidation state of Pt can be 2.

[0029] "Halogen", "halogen atom", "halogen group" in the sense of the present invention can be used interchangeably and refer to fluorine, chlorine, bromine or iodine.

[0030] "Acyl group" in the sense of the present invention refers to a substituted carbonyl group (COR).

[0031] "Ester or ester group" in the sense of the present invention refers to a substituted oxycarbonyl group (-OCOR or CO2R).

[0032] "Ether or ether group" in the sense of the present invention refers to the -OR group.

[0033] "Sulfide group" or "sulfide" described herein can be used interchangeably and refers to the -SR group.

[0034] "Sulfinyl group" in the sense of the present invention refers to the -SOR group.

[0035] "Sulfonyl group" in the sense of the present invention refers to the -SO2R group.

[0036] "Phosphine group" in the sense of the present invention refers to the -PR3 group, where each R can be the same or different.

[0037] "Silalkyl" in the sense of the present invention refers to a -SiR3 group, where each R can be the same or different.

[0038] Each of the above Rs is preferably selected from the group consisting of alkyl, cycloalkyl, aryl, and heteroaryl.

[0039] "Alkyl", "alkenyl" or "alkynyl" in the sense of the present invention are preferably considered to refer to the following groups: 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.

[0040] "Alkoxy" in the sense of the present invention preferably refers to alkoxy groups having 1 to 40 carbon atoms, which are considered to be methoxy, trifluoromethoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentyloxy, sec-pentyloxy, 2-methylbutoxy, n-hexyloxy, cyclohexyloxy, n-heptyloxy, cycloheptyloxy, n-octyloxy, cyclooctyloxy, 2-ethylhexyloxy, pentafluoroethoxy and 2,2,2-trifluoroethoxy.

[0041] Generally, "cycloalkyl" and "cycloalkenyl" according to the present invention refer to and include monocyclic, polycyclic and spiroalkyls. Preferred cycloalkyls and cycloalkenyls are cycloalkyls containing 3 to 15 ring carbon atoms, which can be cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, cycloheptyl, cycloheptenyl, bicyclo[3.1.1]heptyl, spiro[4.5]decyl, spiro[5.5]undecyl, adamantyl, etc., where one or more -CH2- groups can be replaced by O, S or N; in addition, one or more hydrogen atoms can also be replaced by deuterium atoms, halogen atoms or nitrile groups.

[0042] "Heteroalkyl" or "heterocycloalkyl" in the sense of the present invention refer to alkyl or cycloalkyl, preferably alkyl or cycloalkyl having 1 to 40 carbon atoms, which refer to groups in which individual hydrogen atoms or -CH2- groups can be replaced by oxygen, sulfur, halogen atoms, nitrogen, phosphorus, boron, silicon or selenium, preferably groups replaced by oxygen, sulfur or nitrogen. Additionally, heteroalkyl or heterocycloalkyl can be optionally substituted.

[0043] "Heteroalkenyl" or "heterocycloalkenyl" in the sense of the present invention refers to an alkenyl or cycloalkenyl 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 alkenyls and cycloalkenyls are those containing 3 to 15 carbon atoms. Additionally, heteroalkenyl and heterocycloalkenyl can be optionally substituted.

[0044] "Aralkyl" or "arylalkyl" in the sense of the present invention is used interchangeably and means an alkyl group substituted by an aryl group. Additionally, the aralkyl group may be optionally substituted.

[0045] "Aryl" according to the present invention means and includes monocyclic aromatic hydrocarbon groups and polycyclic aromatic ring systems. The polycycle may 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 may be cycloalkyl, cycloalkenyl, aryl, heterocyclic, and / or heteroaryl. Preferred aryl groups are aryl groups 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, naphthalene, anthracene, chrysene, phenanthrene, fluorene, pyrene, perylene, and azulene, preferably phenyl, biphenyl, terphenyl, triphenylene, fluorene, and naphthalene. Additionally, the aryl group may be optionally substituted.

[0046] "Heteroaryl" in the sense of the present invention means and includes monocyclic aromatic groups and polycyclic aromatic ring systems 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 are preferred heteroatoms. The monocyclic heteroaromatic system is preferably a monocyclic ring having 5 or 6 ring atoms, and the ring can have one to six heteroatoms. The hetero polycyclic system can 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 can be cycloalkyl, cycloalkenyl, aryl, heterocycle and / or heteroaryl. The hetero polycyclic aromatic ring system can have one to six heteroatoms on each ring of the polycyclic aromatic ring system. Preferred heteroaryl is heteroaryl containing three to thirty carbon atoms, preferably three to twenty carbon atoms, more preferably three to twelve carbon atoms. Suitable heteroaryl 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, quinazoline, quinoxaline, naphthyridine, phthalazine, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzofuranopyridine, furanodipyridine, benzothiophenopyridine, thiophenodipyridine, benzoselenophenopyridine, selenophenodipyridine, 1,2-azaborole, 1,3-azaborole, 1,4-azaborole, borazene and their nitrogen analogs, preferably dibenzothiophene, dibenzofuran, dibenzoselenophene, carbazole, indolocarbazole, imidazole, pyridine, triazine, benzimidazole, 1,2-azaborole, 1,3-azaborole, 1,4-azaborole, borazene and their nitrogen analogs. Additionally, the heteroaryl can be optionally substituted.

[0047] In many cases, typical 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, carboxylic acid group, ether group, ester group, nitrile group, isonitrile group, thio group, sulfinyl group, sulfonyl group and phosphino group.

[0048] 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, alkyl and deuterium can be combined to form a partially or fully deuterated alkyl; halogen and alkyl can be combined to form a haloalkyl substituent, such as trifluoromethyl, etc.; and halogen, alkyl and aryl can be combined to form a haloaralkyl.

[0049] In one instance, the term substitution includes combinations of two to four of the listed groups.

[0050] In another instance, the term substitution includes combinations of two to three groups. In yet another instance, the term substitution includes combinations of two groups. Preferred combinations of substituents are combinations containing up to fifty atoms that are not hydrogen or deuterium, or combinations including up to forty atoms that are not hydrogen or deuterium, or combinations including up to thirty atoms that are not hydrogen or deuterium. In many cases, the preferred combination of substituents will include up to twenty atoms that are not hydrogen or deuterium.

[0051] Further, said R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 8 each independently selects from the group consisting of a hydrogen atom, a deuterium atom, a fluorine atom, a nitrile group, R A1 ~R A55 、R B1 ~R B45 、R C1 ~R C295 when each appears;

[0052] wherein, R A1 ~R A55 has the following structural formula:

[0053]

[0054]

[0055] R B1 ~R B45 has the following structural formula:

[0056]

[0057]

[0058] R C1 ~R C295 has the following structural formula:

[0059]

[0060]

[0061]

[0062]

[0063]

[0064]

[0065]

[0066] Further, the chemical formula of the metal complex is Ir(LA)(LB)2, Ir(LA)2(LB), or Ir(LA)3; wherein, LB is selected from the group consisting of LB1 to LB432, and the specific structures of LB1 to LB432 are shown as follows:

[0067]

[0068]

[0069]

[0070]

[0071]

[0072]

[0073]

[0074]

[0075]

[0076]

[0077]

[0078]

[0079]

[0080] Further, M is selected from one of Ir, Pd or Pt.

[0081] Further, the formula (LA) includes one of LA1 to LA208, and the specific structures of LA1 to LA208 are shown as follows:

[0082]

[0083]

[0084]

[0085]

[0086]

[0087]

[0088] Among them, the hydrogen atoms in the structural formula may be partially or completely replaced by deuterium atoms.

[0089] Furthermore, the chemical formula of the metal complex is Ir(LAi)(LBj)2, Ir(LAi)2(LBj) or Ir(LAi)3, where i is an integer from 1 to 208 and j is an integer from 1 to 432;

[0090] The structures of LA1-LA208 and LB1-LB432 are as shown above.

[0091] 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 only by one or more of the metal complexes of the present invention, or may contain other materials other than the metal complexes of the present invention.

[0092] By containing the aforementioned metal complex of the present invention in the organic electroluminescent material of the present invention, an organic electroluminescent material with green 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.

[0093] An organic electroluminescent device includes a first electrode, a second electrode, and an organic layer disposed between the first electrode and the second electrode, and the organic layer includes the metal complex.

[0094] Furthermore, the organic layer further includes a host material, and the host material includes the following chemical groups: a group consisting of triphenylene, carbazole, dibenzothiophene, dibenzofuran, dibenzoselenophene, nitrogen triphenylene, azacarbazole, azadibenzothiophene, azadibenzofuran, and azadibenzoselenophene.

[0095] Any substituent in the host is independently a non-fused substituent 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≡CCn H 2n+1 、 Ar 1 、 Ar 1 -Ar 2 、 C n H 2n -Ar 1 or unsubstituted, where n is an integer from 1 to 10; and where Ar 1 and Ar 2 are independently selected from the group consisting of benzene, biphenyl, naphthalene, triphenylene, carbazole, and their heteroaromatic analogs.

[0096] 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.

[0097] The organic layer may be a light-emitting layer and the metal complex as described herein may be an emissive dopant or a non-emissive dopant.

[0098] A consumer product made from the organic electroluminescent device described above.

[0099] The consumer product described in the present invention may 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 of 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.

[0100] Compared with the prior art, the beneficial effects of the present invention are:

[0101] The metal complex described in the present invention forms a ligand with a large steric hindrance structure by connecting pyridine, quinoline or isoquinoline with a heterocyclic ring of seven-membered ring or more containing heteroatoms such as O or S, effectively blocking the energy loss caused by the free rotation of the single bond conjugation between pyridine and aryl, and improving the quantum efficiency. It not only has good thermal stability, but also has an increased conjugated area, improved molecular film-forming and exciton transport properties, and a reduced sublimation temperature of the material. When used as a luminescent material, a green phosphorescent material with high luminescence efficiency can be obtained; an electronic device containing the organic electroluminescent device of the present invention can obtain a consumer product with a narrow emission spectrum, high stability and high efficiency. Description of the Drawings

[0102] 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, without creative efforts, other drawings can be obtained based on these drawings.

[0103] Figure 1 is a schematic diagram of an organic electroluminescent element of the present invention;

[0104] Figure 2 is a schematic diagram of an inverted organic electroluminescent element of the present invention;

[0105] Reference numerals

[0106] 110 - Substrate, 115 - Anode layer, 120 - Hole injection layer, 125 - Hole transport layer, 130 - Electron blocking layer, 135 - Organic light - emitting layer, 140 - Hole blocking layer, 145 - Electron transport layer, 150 - Electron injection layer, 155 - Protective layer, 160 - Cathode layer, 162 - First conductive layer, 164 - Second conductive layer, 170 - Capping layer. Detailed implementation manners

[0107] In the organic electroluminescent element of the present invention, there is no limitation on the constitution of the layers other than the layer containing the metal complex of the present invention. Those skilled in the art can determine the constitution of other layers of the organic electroluminescent element according to the common general knowledge in the art as needed.

[0108] Among them, Figure 1 on the substrate 110, there are successively an anode layer 115, a hole injection layer 120, a hole transport layer 125, an electron blocking layer 130, an organic light - emitting layer 135, a hole blocking layer 140, an electron transport layer 145, an electron injection layer 150, a protective layer 155, a cathode layer 160 and a packaging layer 170. The organic light - emitting layer mentioned above contains the metal complex of the present invention. When the organic electroluminescent device of the present invention is connected to an external power supply and a voltage is applied, the metal complex in the organic light - emitting layer 135 electroluminesces, and the wavelength range of the emitted light is 520 - 650 nm. The cathode layer 160 is a composite cathode having a first conductive layer 162 and a second conductive layer 164. This device can be manufactured by sequentially depositing the said layers.

[0109] Figure 2It includes a substrate 110, a cathode layer 160, an organic light-emitting layer 135, a hole transport layer 125, and an anode layer 115. This device can be manufactured by depositing each layer in sequence. Since the most common OLED configuration has a cathode disposed above the anode, while this device has a cathode layer 160 disposed under the anode layer 115, this device can be referred to as an inverted type. Materials similar to those described for this device can be used in the corresponding layers of this device. Figure 2 Provide an example of how some layers can be omitted from Figure 1 the structure of the device.

[0110] Figure 1 and Figure 2 The simple layered structure illustrated in is provided as a non-limiting example, and it should be understood that embodiments of the present invention can be used in combination with a wide variety of other structures. The specific materials and structures described are exemplary in nature, and other materials and structures can be used. Functional OLEDs can be achieved by combining the various layers described in different ways based on design, performance, and cost factors, or several layers can be completely omitted. Other layers not specifically described can also be included. Materials different from those specifically described can be used. Although many of the examples provided herein describe the various layers as including a single material, it can be understood that combinations of materials can be used, such as a mixture of a matrix and a dopant, or more generally, mixtures. And, the layers can have various sub-layers. The names given to the individual layers herein are not intended to be strictly restrictive. For example, Figure 2 in, the hole transport layer 125 transports holes and injects the holes into the organic light-emitting layer 135, and can be described as a hole transport layer or a hole injection layer. In one embodiment, the 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 in examples Figure 1 and Figure 2 .

[0111] Structures and materials not specifically described can also be used, such as PLEDs containing polymer materials. As another example, OLEDs with 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 in. For example, the substrate can include an angled reflective surface to improve light coupling.

[0112] Unless otherwise specified, any suitable method can be used to deposit any of the layers of the various embodiments. For organic layers, the preferred methods include thermal evaporation, organic vapor deposition methods, or applying one or more layers by sublimation with a carrier gas, where, at 10 - 5The material is applied under 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. Additionally feasible are hybrid methods, in which, for example, one or more layers are applied from solution and one or more additional layers are applied by vapor deposition.

[0113] 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 organic layers from damage due to exposure to harmful substances in the environment, including moisture, vapors and / or gases, etc. The barrier layer may be deposited on the substrate, on the electrodes, under the substrate, under the electrodes, beside the substrate, beside the electrodes, or on any other part of the device, including the edges. The barrier layer may include a single layer or multiple layers. The barrier layer may be formed by various known chemical vapor deposition techniques and may include compositions having a single phase as well as compositions having multiple phases. Any suitable material or combination of materials may 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 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 may 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.

[0114] In any of the compounds mentioned above used in each layer of the above OLED device, the hydrogen atoms may be partially or fully deuterated. Thus, any 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 classes (such as (but not limited to) alkyl, aryl, cycloalkyl, heteroaryl, etc.) may also be in their non-deuterated, partially deuterated and fully deuterated forms.

[0115] The materials and structures described herein may be applied to devices other than OLEDs. For example, other optoelectronic devices such as organic solar cells and organic photodetectors may use the materials and structures. Further, organic devices such as organic transistors may use the materials and structures.

[0116] These methods are generally known to those of ordinary skill in the art, and they can be applied to organic electroluminescent devices containing the compounds according to the present invention without creative work.

[0117] According to one embodiment, novel ligands of metal complexes are disclosed. The inventors have found that the introduction of these ligands unexpectedly narrows the emission spectrum, reduces the sublimation temperature, and improves the luminous efficiency of the device.

[0118] As a method for preparing the organic electroluminescent element of the present invention, the following preparation methods can be cited, but it is not limited thereto, and those skilled in the art can make various changes based on the common general knowledge in the art. The aforementioned preparation method includes the following steps:

[0119] Cleaning step: Cleaning a glass substrate with ITO using a cleaning agent, deionized water, an organic solvent, etc.;

[0120] Step of forming a hole injection layer: Evaporating a hole injection layer forming material containing the metal complex of the present invention on the aforementioned anode layer by vacuum evaporation to form a hole injection layer containing the metal complex of the present invention on the aforementioned substrate;

[0121] Step of forming a hole transport layer: Forming a hole transport layer on the aforementioned hole injection layer by vacuum evaporation;

[0122] Step of forming an organic light-emitting layer: Forming an organic light-emitting layer containing the metal complex of the present invention on the aforementioned hole transport layer by vacuum evaporation of an organic light-emitting layer forming material containing the material of the present invention on the aforementioned hole transport layer;

[0123] Step of forming an electron transport layer: Forming an electron transport layer containing the metal complex of the present invention on the aforementioned organic light-emitting layer by vacuum evaporation of an electron transport layer forming material containing the metal complex of the present invention on the aforementioned organic light-emitting layer;

[0124] Step of forming a cathode layer: Evaporating, sputtering, or spin-coating a cathode forming material on the aforementioned electron transport layer to form a cathode layer.

[0125] In the examples of the present invention, the performance detection conditions of the prepared electroluminescent devices are as follows:

[0126] Luminance and chromaticity coordinates: Measured using a spectral scanner PhotoResearch PR-715;

[0127] Current density and turn-on voltage: Measured using a digital source meter Keithley 2420;

[0128] Power efficiency: Measured using NEWPORT 1931-C;

[0129] Lifetime test: Use the LTS-1004AC lifetime test device.

[0130] Example 1

[0131] General preparation method of metal complex: Ir(LAi)(LBj)2, where i is an integer from 1 to 208 and j is an integer from 1 to 432, includes the following steps;

[0132] First step: Preparation of trifluoromethanesulfonate of bis-LBj iridium complex:

[0133]

[0134] 10.0 mmol of compound LBj and 4.5 mmol of IrCl3·3H2O are dispersed in 60 mL of ethylene glycol monoethyl ether and 20 mL of water. Under nitrogen protection, the temperature is raised to reflux for 24 hours, cooled to room temperature, filtered, the filter cake is washed with water and ethanol, and dried in vacuum to obtain a yellow solid. The obtained yellow solid is dissolved in 100 mL of dichloromethane and 10 mL of methanol, 5.0 mmol of silver trifluoromethanesulfonate is added, and the mixture is stirred and reacted for 24 hours, filtered, and the filtrate is concentrated to dryness under reduced pressure to obtain trifluoromethanesulfonate of bis-LBj iridium complex.

[0135] Second step: Preparation of metal complex Ir(LAi)(LBj)2

[0136]

[0137] 4.8 mmol of compound LAi and 2.3 mmol of trifluoromethanesulfonate of bis-LBj iridium complex prepared in the first step are dispersed in 50 mL of ethylene glycol monoethyl ether and 50 mL of DMF. Under nitrogen protection, the temperature is raised to 100 °C and stirred for 7 days, cooled to room temperature, concentrated to dryness under reduced pressure, and separated and purified by silica gel column chromatography, eluted with dichloromethane - n-hexane to obtain metal complex Ir(LAi)(LBj)2, where LA1 - LA208 and LB1 - LB432 are the same as defined above.

[0138] Referring to the general preparation method of the above metal complex: Ir(LAi)(LBj)2, only the preparation of metal complex Ir(LA2)(LB105)2 is taken as an example for more detailed description:

[0139] First step: Preparation of compound Iht-1

[0140]

[0141] 10.0 g of compound LB105 and 9.5 g of IrCl3·3H2O were dispersed in 150 mL of ethylene glycol monoethyl ether and 50 mL of water. Under nitrogen protection, the temperature was raised to reflux for 24 hours, cooled to room temperature, filtered, the filter cake was washed with water and ethanol, and dried in vacuo to obtain 14.8 g of a yellow solid. The obtained yellow solid was dissolved in 250 mL of dichloromethane and 25 mL of methanol, 6.5 g of silver trifluoromethanesulfonate was added, and the mixture was stirred and reacted for 24 hours, filtered, and the filtrate was concentrated to dryness under reduced pressure to obtain compound Iht-1, yield: 83%.

[0142] Step 2: Preparation of metal complex Ir(LA2)(LB105)2

[0143]

[0144] 4.8 mmol of compound LA2 and 2.3 mmol of intermediate Int-1 were dispersed in 50 mL of ethylene glycol monoethyl ether and 50 mL of DMF. Under nitrogen protection, the temperature was raised to 100 °C and stirred for 7 days, cooled to room temperature, concentrated to dryness under reduced pressure, and purified by silica gel column chromatography, eluted with dichloromethane - n-hexane to obtain metal complex Ir(LA2)(LB105)2, a dark yellow solid, yield: 49%, HRMS(TOF): m / z = 846.3664[M + H] + 。

[0145] Example 2

[0146] General preparation method of metal complex: Ir(LAi)2(LBj), where i is an integer from 1 to 208 and j is an integer from 1 to 432, includes the following steps;

[0147] Step 1: Preparation of trifluoromethanesulfonate of bis-LAi iridium complex:

[0148]

[0149] Referring to the synthesis method of Step 1 in Example 1, only replacing LBj in Step 1 of Example 1 with LAi, prepare the intermediate compound trifluoromethanesulfonate of bis-LAi iridium complex.

[0150] Step 2: Preparation of metal complex: Ir(LAi)2(LBj)

[0151]

[0152] Referring to the synthesis method of Step 2 in Example 1, only replacing LAi in Step 2 of Example 1 with LBj and replacing the trifluoromethanesulfonate of bis-LBj iridium complex with the trifluoromethanesulfonate of bis-LAi iridium complex, prepare the metal complex Ir(LAi)2(LBj).

[0153] LA1 to LA208 and LB1 to LB432 are the same as defined above.

[0154] Referring to the general preparation method of the above metal complex: Ir(LAi)2(LBj), only the preparation of the metal complex Ir(LA30)2(LB90) is described in more detail as an example;

[0155] Step 1: Preparation of compound Int-2

[0156]

[0157] 10.0 mmol of compound LA30 and 4.5 mmol of IrCl3·3H2O are dispersed in 60 mL of ethylene glycol monoethyl ether and 20 mL of water. Under nitrogen protection, the temperature is raised to reflux for 24 hours, cooled to room temperature, filtered, the filter cake is washed with water and ethanol, and dried in vacuo to obtain a yellow solid. The obtained yellow solid is dissolved in 50 mL of dichloromethane and 5 mL of methanol, 20.0 mmol of silver trifluoromethanesulfonate is added, and the mixture is stirred and reacted for 24 hours, filtered, and the filtrate is concentrated to dryness under reduced pressure to obtain compound Int-2, a yellow solid, yield: 86%.

[0158] Step 2: Preparation of metal complex Ir(LA30)2(LB90)

[0159]

[0160] 5.0 mmol of compound LB90 and 2.5 mmol of intermediate Int-2 are dispersed in 15 mL of ethylene glycol monoethyl ether and 15 mL of DMF. Under nitrogen protection, the temperature is raised to 100 °C and stirred for 7 days, cooled to room temperature, the reaction solution is poured into 250 mL of ice water, extracted with dichloromethane, the organic phase is collected, dried, filtered, the filtrate is concentrated to dryness under reduced pressure, and purified by silica gel column chromatography, eluted with dichloromethane - n-hexane to obtain metal complex Ir(LA30)2(LB90), a dark yellow solid, yield: 48%, HRMS(TOF): m / z = 917.3298 [M+H] + 。

[0161] Example 3

[0162] General preparation method of metal complex Ir(LAi)3, where i is an integer from 1 to 208, includes the following steps:

[0163] Step 1: Preparation of LAi iridium chloride bridge complex:

[0164]

[0165] 9.5 mmol of compound LAi and 4.5 mmol of IrCl3·3H2O were dispersed in 60 mL of ethylene glycol monoethyl ether and 20 mL of water. Under nitrogen protection, the mixture was heated to reflux for 24 hours, cooled to room temperature, filtered, and the filter cake was washed with water and ethanol and then dried under vacuum to obtain the LAi iridium chloride bridge complex.

[0166] Step 2: Preparation of metal complex: Ir(LAi)3,

[0167]

[0168] 5.0 mmol of the LAi iridium chloride bridge complex prepared in the first step, 10.0 mmol of silver trifluoromethanesulfonate, and 12.0 mmol of LAi were dispersed in 20 mL of ethylene glycol monoethyl ether. Under nitrogen protection, the mixture was heated to reflux with stirring for 24 hours, cooled to room temperature, filtered, and the filter cake was dissolved in dichloromethane and purified by silica gel column chromatography to obtain the metal complex Ir(LAi)3.

[0169] The LA1 - LA208 are the same as defined above.

[0170] Referring to the general preparation method of the above metal complex: Ir(LAi)3, only the preparation of the metal complex Ir(LA161)3 is described in more detail as an example;

[0171] Step 1: Preparation of compound Int - 3

[0172]

[0173] 9.5 mmol of compound LA161 and 4.5 mmol of IrCl3·3H2O were dispersed in 60 mL of ethylene glycol monoethyl ether and 20 mL of water. Under nitrogen protection, the mixture was heated to reflux for 24 hours, cooled to room temperature, filtered, and the filter cake was washed with water and ethanol and then dried under vacuum to obtain compound Int - 3, a yellow solid, yield: 76%.

[0174] Second step: Preparation of metal complex Ir(LA161)3

[0175]

[0176] 5.0 mmol of Int - 3 prepared in the first step, 10.0 mmol of silver trifluoromethanesulfonate, and 12.0 mmol of LA161 were dispersed in 20 mL of ethylene glycol monoethyl ether. Under nitrogen protection, the mixture was heated to reflux with stirring for 24 hours, cooled to room temperature, filtered, and the filter cake was dissolved in dichloromethane and purified by silica gel column chromatography to obtain the metal complex Ir(LA161)3, a yellow solid, yield: 42%, HRMS(TOF): m / z = 1022.3621[M + H] +。

[0177] Example 4

[0178] Preparation of organic electroluminescent device:

[0179] (1) The glass substrate coated with 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 cleaning machine for 10 minutes, and bombarded with a low-energy cation beam on the surface;

[0180] (2) The above-treated ITO glass substrate was placed in a vacuum chamber, and the vacuum was pumped to 1×10 -5 ~9×10 -3 Pa. On the above anode layer film, compound HATCN was further evaporated as a hole injection layer, and the evaporation film thickness was On the above hole injection layer film, HTM was further evaporated as a hole transport layer, and the evaporation film thickness was

[0181] (3) On the above hole transport layer, EBM was evaporated as an electron blocking layer, and the evaporation film thickness was

[0182] (4) On the above electron blocking layer, an organic light-emitting layer was evaporated. The light-emitting layer contained H1 as a host and 3% by mass of the metal complex prepared in the present invention as a doping material, and the evaporation film thickness was

[0183] (5) On the above organic light-emitting layer, a layer of LiQ and ETM was further evaporated as the electron transport layer of the device, where LiQ was 50% of the mass of ETM, and the evaporation film thickness was

[0184] (6) On the above light-emitting layer, a layer of LiF was further evaporated as the electron injection layer of the device, and the evaporation film thickness was

[0185] (7) On the above electron injection layer, metallic aluminum was evaporated as the cathode layer of the device, and the evaporation film thickness was

[0186] Comparative Example 1

[0187] The compound shown in GD-1 was used to replace the metal complex in Example 4, and the other steps were the same as those in Example 4 to fabricate Comparative Element 1.

[0188] Comparative Example 2

[0189] The compound shown in GD-2 was used to replace the metal complex in Example 4, and the other steps were the same as those in Example 4 to fabricate Comparative Element 2.

[0190] The structural formulas of the aforementioned HATCN, HTM, EBM, H1, LiQ, GD-1, GD-2, and ETM are as follows:

[0191]

[0192] According to the same method as in Example 4, an organic electroluminescent device was fabricated using the metal complex of the present invention as a doping material for the organic light-emitting layer. The structure and performance data are summarized in Table 1. Only the complex Ir(LA1-LA208)(LB105)2 is taken as an example in the table. *The data are normalized with respect to Comparative Element 1.

[0193] Table 1

[0194]

[0195]

[0196]

[0197]

[0198]

[0199] As can be seen from Table 1, when the metal complex of the present invention is used as a doping material for the light-emitting layer, the driving voltage is lower than that of Comparative Example 1. In particular, the external quantum efficiency and LT95% lifetime are significantly improved compared with Comparative Example 1 and Comparative Example 2, showing great advantages. Therefore, the metal complex of the present invention is a light-emitting layer material with excellent performance.

[0200] Only the performance of some metal complexes is listed in Table 1 above. The inventor also conducted the above tests on other metal complexes, and the results were basically the same. Due to space limitations, they are not listed one by one.

[0201] 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. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without creative efforts fall within the scope of protection of the present invention.

[0202] The above is only the specific implementation manner of the present invention, but the scope of protection 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 all be covered by the scope of protection of the present invention. Therefore, the scope of protection of the present invention should be subject to the scope of protection of the claims.

Claims

1. A metal complex, characterized in that, The chemical formula of the metal complex is Ir(LA)(LB)2, where LB is selected from LB105, and the specific structure of LB105 is shown as follows: ; The described formula LA is selected from one of LA1 to LA208, and the specific structures of LA1 to LA208 are shown as follows:

2. An organic electroluminescent element, comprising a first electrode, a second electrode, and an organic layer disposed between the first electrode and the second electrode, characterized in that, The organic layer includes the metal complex described in claim 1.

3. The organic electroluminescent element according to claim 2, wherein, The organic layer further includes a host material, and the host material includes the following chemical groups: a group consisting of triphenylene, carbazole, dibenzothiophene, dibenzofuran, dibenzoselenophene, azatriphenylene, azacarbazole, azadibenzothiophene, azadibenzofuran, and azadibenzoselenophene.

4. A consumer product made of the organic electroluminescent device described in claim 2 or 3.

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