Platinum complex of carbonyl-nitrogen-containing [3, 2, 1-de] acridine-5, 9-diketone quinothionine derivative, preparation method of platinum complex, and organic electroluminescent device of carbonyl-nitrogen-containing [3, 2, 1-de] acridine-5, 9-diketone quinothionine derivative

Abstract

The invention relates to a metal platinum complex of carbonyl-nitrogen-containing [3, 2, 1-de] acridine-5, 9-diketoquinoline derivatives, a preparation method thereof and an organic electroluminescent device, the structure of the metal platinum complex comprises a main ligand and an auxiliary ligand, the main ligand is the carbonyl-nitrogen-containing [3, 2, 1-de] acridine-5, 9-diketoquinoline derivatives, the auxiliary ligand is the carbonyl-nitrogen-containing [3, 2, 1-de] acridine-5, 9-diketoquinoline derivatives, and the auxiliary ligand is the carbonyl-nitrogen-containing [3, 2, 1-de] acridine-5, 9-diketoquinoline derivatives. The structure of the 2, 9-diketoquinothionine derivative contains an aza-aromatic ring or an aza-aromatic ring derivative, and the auxiliary ligand is acetylacetone, an acetylacetone derivative, benzoic acid or a benzoic acid derivative. The metal platinum complex provided by the invention has the characteristics of high photoluminescence quantum yield, short excited state life and narrow band emission, and can regulate and control the luminescence color, efficiency and electron transmission performance, thereby enhancing the stability of the platinum complex; therefore, the organic light-emitting device has the advantages of low starting voltage, high external quantum efficiency, low efficiency rolling and narrow band emission.

Description

Technical Field

[0001] The present application relates to the field of organic electroluminescent materials, and in particular to a metal platinum complex of a [3,2,1-de]acridine-5,9-dionequinolinone derivative containing carbonyl nitrogen, a preparation method thereof, and an organic electroluminescent device. Background Art

[0002] With the continuous development of modern display technology, organic electroluminescence (OLED) technology has become a key development direction in the display field due to its significant advantages such as self-luminescence, high contrast, wide viewing angle, fast response, low power consumption, and flexible display. In OLED devices, the performance of the luminescent material directly determines key parameters such as device luminous efficiency, brightness, lifespan, and color purity.

[0003] Among numerous luminescent materials, platinum complexes have attracted considerable attention as novel luminescent materials. However, existing phosphorescent platinum complexes still have limitations in terms of color purity, luminous efficiency, and stability, restricting their widespread application in high-performance OLED devices. Summary of the Invention

[0004] In view of this, in order to solve at least one of the above technical problems, the present application provides a novel metal platinum complex of a [3,2,1-de]acridine-5,9-dionequinolinone derivative containing carbonyl nitrogen.

[0005] In addition, the present application also provides a method for preparing the aforementioned metal platinum complex and an organic electroluminescent device using the metal platinum complex.

[0006] In the first aspect, an embodiment of the present application provides a metal platinum complex of a [3,2,1-de]acridine-5,9-dionequinocinoid derivative containing carbonyl nitrogen, wherein the structure of the metal platinum complex comprises a primary ligand and an auxiliary ligand, wherein the primary ligand is a [3,2,1-de]acridine-5,9-dionequinocinoid derivative containing carbonyl nitrogen, and the structure of the [3,2,1-de]acridine-5,9-dionequinocinoid derivative contains an nitrogen heteroaromatic ring or an nitrogen heteroaromatic ring derivative, and the auxiliary ligand is acetylacetone, an acetylacetone derivative, benzoic acid, or a benzoic acid derivative.

[0007] In a second aspect, an embodiment of the present application also provides a method for preparing a metal platinum complex of a [3,2,1-de]acridine-5,9-dionequinocin derivative containing carbonyl nitrogen, the preparation method comprising: synthesizing a main ligand, wherein the main ligand is a [3,2,1-de]acridine-5,9-dionequinocin derivative containing carbonyl nitrogen, and the structure of the [3,2,1-de]acridine-5,9-dionequinocin derivative contains an nitrogen heteroaromatic ring or an nitrogen heteroaromatic ring derivative; the main ligand and a platinum source are reacted in an ethylene glycol diethyl ether solution to obtain a metal platinum complex precursor; and the metal platinum complex precursor and an auxiliary ligand are reacted in an ethylene glycol diethyl ether solution, wherein the auxiliary ligand is acetylacetone, an acetylacetone derivative, benzoic acid or a benzoic acid derivative to obtain the metal platinum complex.

[0008] In a third aspect, an embodiment of the present application further provides an organic electroluminescent device, which includes: an anode, a cathode, and an organic light-emitting layer arranged between the anode and the cathode, wherein the organic light-emitting layer contains the metal platinum complex as described above.

[0009] Compared to the prior art, the metal platinum complexes provided in the embodiments of the present application, by introducing nitrogen heteroaromatic rings or nitrogen heteroaromatic ring derivatives, can effectively regulate the luminescence color, efficiency, and electron transport properties of the metal platinum complexes, improve the stability of the metal platinum complexes, and suppress efficiency roll-off, thereby making the metal platinum complexes have a high photoluminescence quantum yield and a short excited state lifetime, and have the characteristics of narrow-band emission. Organic electroluminescent devices (OLEDs) using this metal platinum complex have excellent performance, low starting voltage, high external quantum efficiency, low efficiency roll-off, and narrow-band emission characteristics, and have high application value in the field of OLED display and lighting. BRIEF DESCRIPTION OF THE DRAWINGS

[0010] Figure 1 This is a single crystal structure diagram of the metal platinum complex Pt-81 provided in one embodiment of the present application.

[0011] Figure 2 This is the absorption and emission spectra of the metal platinum complex Pt-5 in toluene provided in one embodiment of the present application.

[0012] Figure 3 This is the emission spectrum of the metal platinum complex Pt-5 in different solvents provided in one embodiment of the present application.

[0013] Figure 4 Schematic diagram of the structures of various transport layer and host layer materials used in preparing organic electroluminescent devices using metal platinum complexes provided in one embodiment of the present application.

[0014] Figure 5This is a graph showing the current density-voltage-brightness curves of the organic electroluminescent devices of the metal platinum complexes Pt-1, Pt-5, Pt-7, and Pt-12 provided in the examples of the present application. DETAILED DESCRIPTION

[0015] The embodiments of the present application are described in detail below. The embodiments described below with reference to the accompanying drawings are exemplary and are only used to explain the present application, and should not be understood as limiting the present application; it should be noted that, unless otherwise defined, all technical and scientific terms used herein have the same meaning as those commonly understood by those skilled in the art to which the present application belongs; the embodiments of the present application and the features in the embodiments can be combined with each other unless there is a conflict; many specific details are set forth in the following description to facilitate a full understanding of the present application, and the embodiments described are only part of the embodiments of the present application, not all of the embodiments.

[0016] In the various embodiments of the present application, the following descriptions are merely exemplary and are for the purpose of description and are not intended to limit the present application. Various processes and methods not described in detail are conventional methods well known in the art.

[0017] The term "halogen" herein refers to F, Cl, Br, and I.

[0018] The terms "alkyl", "alkoxy", "haloalkyl" and any substituent containing the "alkyl" portion of the present application include branched or straight-chain alkyl groups optionally with at least one substituent, optionally interrupted by at least one heteroatom, preferably C1-C40 alkyl, C1-C20 alkyl, more preferably C1-C8 alkyl, and particularly preferably C1-C6 alkyl, such as methyl, ethyl, propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, pentyl, isopentyl, hexyl, n-hexyl, isohexyl, heptyl, isoheptyl, octyl, isooctyl, etc. In addition, the alkyl group is optionally substituted with one or more substituents, preferably halogen, more preferably F, C1-C20 haloalkyl, C1-C8 haloalkyl, C1-C4 haloalkyl, and most preferably CF3, perfluoroethyl, trifluoroethyl, perfluoropropyl, and perfluorobutyl.

[0019] The term "alkenyl" in this application includes branched or straight-chain alkenyl groups optionally with at least one substituent and optionally interrupted by at least one heteroatom, preferably C2-C40 alkenyl groups, C1-C20 alkenyl groups, more preferably C2-C8 alkenyl groups, and particularly preferably C2-C6 alkenyl groups, for example: ethenyl, propenyl, butenyl, pentenyl, etc.

[0020] The term "alkynyl" in the present application includes branched or straight-chain alkynyl groups optionally with at least one substituent and optionally interrupted by at least one heteroatom, preferably C2-C40 alkynyl, C2-C20 alkynyl, more preferably C2-C8 alkynyl, and particularly preferably C2-C6 alkynyl, for example: ethynyl, propynyl, butynyl, pentynyl, etc.

[0021] The term "cycloalkyl" in this application includes substituted or unsubstituted saturated cycloalkyl groups, which may contain a monocyclic ring of 4-8, preferably 56 ring atoms, or a polycyclic ring system of 6-40, preferably 6-20, 6-13, more preferably 9-13 ring atoms. Specific examples include: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, 1-adamantyl, 2-adamantyl, 1-norbornyl, 2-norbornyl, bicyclo[2.2.1]heptyl, bicyclo[2,2,2]octyl, etc.

[0022] The term "heterocycloalkyl" in the present application refers to a cycloalkyl group containing 1 to 4 heteroatoms selected from N, O, and S as cycloalkyl backbone atoms and carbon atoms as the remaining cycloalkyl backbone atoms. The heterocycloalkyl group can be a 3-, 4-, 5-, 6-, 7-, or 8-membered monocyclic heterocycloalkyl group or a polycyclic system having 6-40, preferably 6-20, 6-13, and more preferably 9-13 ring atoms, for example: morpholinyl, thiomorpholinyl, etc.

[0023] The term "aryl" as used herein refers to an organic group derived from an aromatic hydrocarbon by removing a hydrogen atom, and may comprise a single ring of 4-8, preferably 5-6, ring atoms or a fused ring system of 6-40, preferably 6-20, 6-13, more preferably 9-13 ring atoms. Examples include phenyl, naphthyl, diphenyl, anthracenyl, tetrahydronaphthyl, indenyl, fluorenyl, phenanthrenyl, triphenylenyl, pyrenyl, pyrenyl, naphthacene, fluoranthenyl, and the like.

[0024] The term "heteroaryl" herein refers to an aryl group containing 1 to 4 heteroatoms selected from N, O, S, and P as aromatic ring backbone atoms and carbon atoms as the remaining aromatic ring backbone atoms. The heteroaryl group may be a 5-, 6-, 7-, or 8-membered monocyclic heteroaryl group or a polycyclic heteroaryl group fused to one or more benzene rings, which may be partially saturated. The polycyclic heteroaryl group may contain 6-40, preferably 6-20, and more preferably 9-13 ring atoms. For example: monocyclic heteroaryl groups such as furyl, thienyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, thiadiazolyl, isothiazolyl, oxazolyl, isoxazolyl, oxadiazolyl, triazinyl, tetrazinyl, triazolyl, 1,2,3-triazolyl, 1,2,4-triazolyl, tetrazolyl, furazolyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, etc.; polycyclic heteroaryl groups such as benzofuranyl, benzothienyl, isobenzofuranyl, benzimidazolyl, benzothiazolyl, benzisothiazolyl, benzisoxazolyl, benzoxazolyl, isoindolyl, indolyl, indazolyl, benzothiadiazolyl, quinolyl, isoquinolyl, quinazolinyl, quinolizinyl, quinoxalyl, carbazolyl, phenanthridinyl, benzodioxolyl, etc.

[0025] The term "carboxyl" herein refers to "Ra-COO-", wherein Ra refers to alkyl, alkenyl, alkynyl, cycloalkyl, heterocycloalkyl, aryl, or heteroaryl, and each group is as defined above.

[0026] The term "substituted" herein refers to being optionally substituted with at least one substituent, for example, monosubstituted, disubstituted, trisubstituted, tetrasubstituted, pentasubstituted, and the like.

[0027] An embodiment of the present application provides a metal platinum complex of a [3,2,1-de]acridine-5,9-dionequinocinoid derivative containing carbonyl nitrogen (C=O / N). The structure of the metal platinum complex contains a main ligand and an auxiliary ligand, wherein the main ligand is a [3,2,1-de]acridine-5,9-dionequinocinoid derivative containing carbonyl nitrogen, and the structure of the [3,2,1-de]acridine-5,9-dionequinocinoid derivative contains an azoaromatic ring or an azoaromatic ring derivative, and the auxiliary ligand is acetylacetone, an acetylacetone derivative, benzoic acid, or a benzoic acid derivative.

[0028] The introduction of nitrogen-heteroaromatic rings or their derivatives into the structure of [3,2,1-de]acridine-5,9-dionequinolinoid derivatives imparts excellent electron affinity due to the presence of the nitrogen atom, offering significant advantages in terms of hole blocking, electron transport, and thermal stability. Furthermore, the nitrogen-heteroaromatic rings or their derivatives extend the conjugation length of the primary ligand molecule, which is beneficial for improving the thermal stability and luminescence properties of the platinum complex. Furthermore, the nitrogen-heteroaromatic rings or their derivatives are easily modifiable, which facilitates the regulation of the luminescence color of the platinum complex. Therefore, the introduction of nitrogen-heteroaromatic rings or their derivatives effectively increases the rigidity of the platinum complex and can effectively regulate its luminescence color, efficiency, and electron transport properties, improving its stability and suppressing efficiency roll-off, thereby enabling the platinum complex to exhibit high photoluminescence quantum yields, short excited-state lifetimes, and excellent narrow-band emission characteristics. This metal platinum complex can be used as a phosphorescent material in organic electroluminescent devices, which can significantly improve the device's luminous efficiency, color purity, stability and other performance, and achieve high-brightness, low-power green light emission.

[0029] In some embodiments, the metal platinum complex has a general structural formula as shown in Formula (I) or Formula (II):

[0030]

[0031] Wherein, R in formula (I) and formula (II) m Independently selected from hydrogen, halogen, -CF3, -CN, -OR 1 、-Si(R 1 )2、-N(R 1 )2、-SR 1 (R 1 )2、-C(O)R 1 、-C(O)OR 1 、-C(O)NR 1 、-SOR 1 、-SO2R 1 、-SO2R 1 、-P(O)(R 1 )2、-P(O)(OR 1 )R 1 、-P(O)(OR 1 )2, substituted or unsubstituted C1-C40 alkyl, substituted or unsubstituted C2-C40 alkenyl, substituted or unsubstituted C2-C40 alkynyl, substituted or unsubstituted C3-C40 cycloalkyl, substituted or unsubstituted C3-C40 heterocycloalkyl, substituted or unsubstituted C6-C40 aryl, or substituted or unsubstituted C6-C40 heteroaryl;

[0032] R1 to R in formula (I) 11 and R1 to R in formula (II) 15 are independently selected from hydrogen, halogen, -CF3, -CN, -OR 2 、-Si(R 2 )2、-N(R 2 )2、-SR(R 2 )2、-C(O)R 2 、-C(O)OR 2 、-C(O)NR 2 、-SOR 2 、-SO2R 2 、-SO2R 2 、-P(O)(R 2 )2、-P(O)(OR 2 )R 2 、-P(O)(OR 2 )2, substituted or unsubstituted C1-C40 alkyl, substituted or unsubstituted C2-C40 alkenyl, substituted or unsubstituted C2-C40 alkynyl, substituted or unsubstituted C3-C40 cycloalkyl, substituted or unsubstituted C3-C40 heterocycloalkyl, substituted or unsubstituted C6-C40 aryl, or substituted or unsubstituted C6-C40 heteroaryl; R 1 are independently selected from hydrogen, -CN, halogen, C1-C40 alkyl, C2-C40 alkenyl, C2-C40 alkynyl or C1-C40 haloalkyl, and multiple R 2 Can be the same or different;

[0033] Ring V is selected from a C2-C20 nitrogen heteroaromatic ring or a C2-C20 nitrogen heteroaromatic ring derivative;

[0034] The Ar ring is selected from a C6-C20 aromatic ring or a condensed aromatic ring, and n is an integer greater than or equal to 0.

[0035] The V ring is the nitrogen heteroaromatic ring or nitrogen heteroaromatic ring derivative introduced above, and the ring skeleton of the V ring contains at least one nitrogen atom, and the number of carbon atoms is in the range of 2 to 20.

[0036] In some embodiments, the V ring contains an O heteroatom and / or an S heteroatom, and the number of O heteroatoms or S heteroatoms can be one or more. The O heteroatoms and S heteroatoms can reduce molecular stacking and reduce non-radiative transitions through steric hindrance, thereby further improving the luminescence efficiency of the metal platinum complex; they can also further enhance the stability of the metal platinum complex through strong coordination with metal platinum; in addition, the O heteroatoms and S heteroatoms can further regulate the luminescence color of the metal platinum complex.

[0037] In some embodiments, any position in the V ring can be substituted by one or more first substituents, wherein the first substituents are independently selected from hydrogen (H), methyl (-CH3), methoxy (-OCH3), tert-butyl (-tBu), trifluoromethyl (-CF3), trimethylsilyl (-Si(CH3)3) or triphenylsilyl (-SiPh3).

[0038] Exemplarily, the V-ring may have one of the following structures:

[0039]

[0040] In some embodiments, when R1-R 11 and R1-R in formula (II) 15 When containing a second substituent, the second substituent is independently selected from halogen, -CN, -OR 3 、-N(R 3 )2、-Si(R 3 )2, C1-C40 alkyl, C2-C40 alkenyl, C2-C40 alkynyl, C3-C40 cycloalkyl, C3-C40 heterocycloalkyl, C6-C40 aryl or C6-C40 heteroaryl; wherein, R 3 are independently selected from hydrogen, -CN, halogen, C1-C40 alkyl, C2-C40 alkenyl, C2-C40 alkynyl or C1-C40 haloalkyl. 3 The second substituent can regulate the metal platinum complex from multiple dimensions such as electronic effect regulation, steric hindrance regulation or structural rigidity, so as to further improve the luminescent properties of the metal platinum complex.

[0041] In some embodiments, R1-R 11 or R1-R in formula (II) 15 Any two adjacent groups can also undergo a cross-linking reaction and form a ring with the ring atoms connected to the two groups. Further, the formed ring can be independently selected from a substituted or unsubstituted 5-7 membered aryl group, a substituted or unsubstituted 5-7 membered heteroaryl group, a substituted or unsubstituted 8-10 membered fused bicyclic aryl group, a substituted or unsubstituted 8-10 membered fused bicyclic heteroaryl group, a substituted or unsubstituted 11-14 membered fused tricyclic aryl group, or a substituted or unsubstituted 11-14 membered fused tricyclic heteroaryl group.

[0042] Furthermore, when the formed ring contains a third substituent, the third substituent can be independently selected from halogen, -CF3, -CN, -OR 4 、-Si(R 4 )2、-N(R 4 )2、-SR(R 4)2、-C(O)R 4 、-C(O)OR 4 、-C(O)NR 4 、-SOR 4 、-SO2R 4 、-SO2R 4 、-P(O)(R 4 )2、-P(O)(OR 4 )R 4 、-P(O)(OR 4 )2, C1-C40 alkyl, C2-C40 alkenyl, C2-C40 alkynyl, C3-C40 cycloalkyl, C3-C40 heterocycloalkyl, C6-C40 aryl, C6-C40 heteroaryl, wherein R 4 independently selected from hydrogen, -CN, halogen, C1-C40 alkyl, C2-C40 alkenyl, C2-C40 alkynyl, C3-C40 cycloalkyl, C3-C40 heterocycloalkyl, C6-C40 aryl, C6-C40 heteroaryl, multiple R in the same group 4 Can be the same or different.

[0043] Furthermore, any position of the C1-C40 alkyl, C2-C40 alkenyl, C2-C40 alkynyl, C3-C40 cycloalkyl, C3-C40 heterocycloalkyl, C6-C40 aryl, or C6-C40 heteroaryl in the third substituent may be substituted by one or more fourth substituents, and the fourth substituents are independently selected from halogen, -CN, -OR 5 、-N(R 5 )2、-Si(R 5 )2, C1-C40 alkyl, C2-C40 alkenyl, C2-C40 alkynyl, C3-C40 cycloalkyl, C3-C40 heterocycloalkyl, C6-C40 aryl, C6-C40 heteroaryl, wherein R 5 are independently selected from hydrogen, -CN, halogen, C1-C40 alkyl, C2-C40 alkenyl, C2-C40 alkynyl, C1-C40 haloalkyl, multiple R 5 Can be the same or different.

[0044] In some embodiments, R in Formula (I) and Formula (II) m It can further be independently selected from hydrogen, a substituted or unsubstituted C1-C4 alkyl group, a substituted or unsubstituted C6-C30 aryl group, or a substituted or unsubstituted C6-C30 heteroaryl group, wherein the heteroatom in the C6-C30 heteroaryl group is at least one of an N atom, an O atom and an S atom.

[0045] In some embodiments, when R mWhen the fifth substituent is contained, the fifth substituent is independently selected from halogen, -CN, -OR 6 、-N(R 6 )2、-Si(R 6 )2, C1-C40 alkyl, C2-C40 alkenyl, C2-C40 alkynyl, C3-C40 cycloalkyl, C3-C40 heterocycloalkyl, C6-C40 aryl or C6-C40 heteroaryl, wherein R 6 Independently selected from C1-C40 alkyl, C2-C40 alkenyl, C2-C40 alkynyl, C3-C40 cycloalkyl, C3-C40 heterocycloalkyl, C6-C40 aryl, and C6-C40 heteroaryl.

[0046] In some embodiments, any position in the Ar ring can be substituted by one or more sixth substituents, wherein the sixth substituent is independently selected from hydrogen (H), methyl (-CH3), methoxy (-OCH3), tert-butyl (-tBu), trifluoromethyl (-CF3), trimethylsilyl (-Si(CH3)3) or triphenylsilyl (-SiPh3).

[0047] Illustratively, the Ar ring may have one of the following structures:

[0048]

[0049] Illustratively, the metal platinum complex may have one of the following structures:

[0050]

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[0096]

[0097] Compared with the prior art, the metal platinum complex provided in this application can effectively regulate the luminescence color, efficiency and electron transport performance of the metal platinum complex due to the introduction of nitrogen heteroaromatic rings or nitrogen heteroaromatic ring derivatives, and improve the stability of the metal platinum complex and suppress efficiency roll-off, so that the metal platinum complex has a higher photoluminescence quantum yield and a short excited state lifetime, and has the characteristics of narrow-band emission.

[0098] The present application also provides a method for preparing a metal platinum complex of a [3,2,1-de]acridine-5,9-dione quinolinoid derivative containing carbonyl nitrogen, which specifically comprises the following steps:

[0099] Step S1, synthesizing a main ligand, wherein the main ligand is a [3,2,1-de]acridine-5,9-dione quinolinium derivative containing carbonyl nitrogen, and the structure of the [3,2,1-de]acridine-5,9-dione quinolinium derivative contains an azo aromatic ring or an azo aromatic ring derivative.

[0100] The synthesis of the main ligand in this step includes the reaction of iodo[3,2,1-de]acridine-5,9-dione quinolinone derivatives with nitrogen heteroaromatic rings and their derivatives under alkaline conditions, so as to introduce nitrogen heteroaromatic rings or nitrogen heteroaromatic ring derivatives into the structure of [3,2,1-de]acridine-5,9-dione quinolinone derivatives. The synthesis method of the main ligand may exemplarily include: (1) aromatic coupling reaction of 4-iodoaniline and 2-iodobenzoic acid methyl ester under alkaline conditions by copper catalysis to obtain 2-[(4-iodophenyl)[2-(methoxycarbonyl)phenyl]amino]benzoic acid methyl ester; (2) demethylation of the ester group in 2-[(4-iodophenyl)[2-(methoxycarbonyl)phenyl]amino]benzoic acid methyl ester under alkaline conditions to generate carboxylic acid, and the addition of 2-iodoaniline to the carboxylic acid. Add sulfuryl chloride and dimethylformamide to react, and then add aluminum chloride to generate iodo[3,2,1-de]acridine-5,9-dione quinolinium derivatives; (3) iodo[3,2,1-de]acridine-5,9-dione quinolinium derivatives react with nitrogen heteroaromatic rings and their derivatives under alkaline conditions to introduce nitrogen heteroaromatic rings or nitrogen heteroaromatic ring derivatives into the structure of [3,2,1-de]acridine-5,9-dione quinolinium derivatives. Step S2: The primary ligand and the platinum source react in an ethylene glycol ether solution to obtain a metal platinum complex precursor.

[0101] Specifically, under nitrogen conditions, the main ligand synthesized in step S1 and a platinum source (such as potassium chloroplatinite K2PtCl4) are dissolved in an ethylene glycol ether solution in a molar ratio of 1:1. The volume ratio of ethylene glycol ether to water in the ethylene glycol ether solution can be 3:1. The reaction is refluxed at 130°C for 24 hours. After the reaction is completed, the temperature is lowered to room temperature, and the precipitate is collected by filtration to obtain a metal platinum complex precursor.

[0102] Step S3: a metal platinum complex precursor and an auxiliary ligand react in an ethylene glycol ether solution, wherein the auxiliary ligand is acetylacetone, acetylacetone derivatives, benzoic acid or benzoic acid derivatives, to obtain a metal platinum complex.

[0103] Specifically, a metal platinum complex precursor and an auxiliary ligand are dissolved in an ethylene glycol ether solution to react, and stirred for 6 hours under a nitrogen atmosphere at 100° C. to obtain a metal platinum complex.

[0104] In some embodiments, the metal platinum complex can also be purified by column chromatography and sublimation reaction under vacuum conditions to obtain a high-purity metal platinum complex to meet the requirements of organic electroluminescent device (OLED) light-emitting materials.

[0105] The present application also provides an organic electroluminescent device, comprising: an anode, a cathode, and an organic light-emitting layer disposed between the anode and the cathode, wherein the organic light-emitting layer contains the aforementioned metal platinum complex.

[0106] In some embodiments, the anode generally serves as a positive electrode in an organic electroluminescent device, and is generally made of a material with high transparency and conductivity, such as indium tin oxide.

[0107] In some embodiments, the cathode generally serves as a negative electrode in an organic electroluminescent device, and common cathode materials include metals such as aluminum, silver, calcium, and lithium.

[0108] In some embodiments, the organic light-emitting layer further includes a host material, and the platinum complex is doped in the organic light-emitting layer at a concentration of 1 wt% to 30 wt%, thereby improving luminous efficiency and color purity. The platinum complex can be doped in the organic light-emitting layer at a concentration of 1 wt%, 5 wt%, 10 wt%, 15 wt%, 20 wt%, 25 wt%, 30 wt%, or any value within a range consisting of any two of these values. The platinum complex can further be doped in the organic light-emitting layer at a concentration of 5 wt% to 20 wt%.

[0109] In some embodiments, the organic electroluminescent device may be an organic light-emitting diode device, which may include, from bottom to top, a substrate, an anode, a hole injection layer, a hole transport layer, an electron blocking layer, the organic light-emitting layer, a hole blocking layer, an electron transport layer, an electron injection layer, and a cathode. The introduction of the electron blocking layer and the hole blocking layer effectively limits the recombination of excitons within the organic light-emitting layer, thereby improving device efficiency.

[0110] Furthermore, the performance of the device can be further improved by selecting and matching the materials in the organic electroluminescent device. Figure 4 Various types of transport layer and main layer materials can be selected. For example, choosing appropriate hole injection layer (HAT-CN), hole transport layer material (TAPC), main material (TCTA or DMIC-TRZ) and electron transport layer material (PO-T2T or TmPyPB) can optimize the injection and transport balance of carriers.

[0111] In some embodiments, an organic electroluminescent device may be applied to a display device, which includes the organic electroluminescent device.

[0112] In some embodiments, the organic electroluminescent device may also be applied to a lighting device, wherein the lighting device includes the organic electroluminescent device.

[0113] It is understood that the organic electroluminescent device can emit light within a wavelength range unique to the metal platinum complex (from ultraviolet light to near-infrared light). For example, the metal platinum complex can be used as a luminescent material to prepare a blue-green light-emitting OLED device. In addition, the organic electroluminescent device can also achieve mixed light emission through specific device preparation processes, such as stacking multiple organic light-emitting layers or doping other light-emitting materials into the organic light-emitting layers, wherein at least one organic light-emitting layer contains the metal platinum complex of the present application.

[0114] Compared with the existing technology, the organic electroluminescent device provided in this application has excellent performance due to the application of the aforementioned metal platinum complex, and has low starting voltage, high external quantum efficiency, low efficiency roll-off and narrow band emission characteristics, and has high application value in the field of OLED display and lighting.

[0115] The above-mentioned metal platinum complex, its preparation method, and organic electroluminescent device are further described below through specific examples.

[0116] Example 1

[0117] Provided is a metal platinum complex Pt-81 of a [3,2,1-de]acridine-5,9-dione quinoline derivative containing carbonyl nitrogen, comprising a primary ligand and an auxiliary ligand. The primary ligand is a [3,2,1-de]acridine-5,9-dione quinoline derivative containing carbonyl nitrogen, the [3,2,1-de]acridine-5,9-dione quinoline derivative containing a nitrogen heteroaromatic ring, and the auxiliary ligand is acetylacetone. The metal platinum complex has the following structural formula:

[0118] The specific preparation method comprises the following steps, and the synthetic route is:

[0119]

[0120] Step S1, synthesizing the main ligand, the main ligand is a [3,2,1-de]acridine-5,9-dione quinolinium derivative containing carbonyl nitrogen. The synthesis route of the main ligand is as follows:

[0121] (1) Synthesis of methyl 2-[(4-iodophenyl)[2-(methoxycarbonyl)phenyl]amino]benzoate:

[0122]

[0123] 4-iodoaniline (4.89 ml, 53.7 mmol), 2-iodobenzoic acid methyl ester (23.7 ml, 161 mmol), potassium carbonate (K2CO3) (15.6 g, 113 mmol), copper (Cu) (0.68 g, 10.7 mmol), cuprous iodide (CuI) (0.51 g, 2.69 mmol) and dibutyl ether (50 ml) were added to the reaction vessel. Then, under an argon atmosphere, the mixture was stirred at reflux for 48 hours to promote the reaction. After the reaction was complete, the crude product was purified by column chromatography using a solvent system of n-hexane and ethyl acetate in a ratio of 4:1. The purified product was recrystallized from ethanol to obtain 2-[(4-iodophenyl)[2-(methoxycarbonyl)phenyl]amino]benzoic acid methyl ester (15.7 g, 81% productive rate) as a white solid. 1 H NMR (400MHz, CDCl3) δ7.71 (dd, J=7.7, 1.7Hz, 2H), 7.49 (ddd, J=8.1, 7.4, 1.7Hz ,2H),7.46-7.42(m,2H),7.27-7.21(m,4H),6.52-6.48(m,2H),3.46(s,6H).13C NMR (126MHz, CD2Cl2) δ167.29,148.56,145.65,137.60,132.81,130.96,129. 08,128.20,124.70,121.85,83.12,53.89,53.68,53.46,53.25,53.03,51.75.

[0124] (2) Synthesis of iodo[3,2,1-de]acridine-5,9-dionequinolinium:

[0125]

[0126] Methyl 2-[(4-iodophenyl)[2-(methoxycarbonyl)phenyl]amino]benzoate (1.8 g, 5 mmol) and sodium hydroxide (1 g, 25 mmol) were added to a 20 ml ethanol / water (1:1) mixed solvent system. The mixture was heated under reflux for 12 hours, then cooled to room temperature and the pH was carefully adjusted to 2-3 with dilute hydrochloric acid to induce precipitation of the diacid as a solid. The precipitate was isolated by vacuum filtration and washed with copious amounts of water to remove residual salt and hydrochloric acid, and finally dried under vacuum to obtain the intermediate product.

[0127] Under a nitrogen atmosphere, the dried intermediate product was dispersed in 60 ml of dichloromethane. Sulfuryl chloride (0.7 ml, 10.0 mmol) and a small amount of dimethylformamide (DMF) were added sequentially. The reaction mixture was maintained under reflux for 3 hours and then cooled to room temperature. Then, under a nitrogen atmosphere, aluminum chloride (6.7 g, 50 mmol) was slowly added to the cooled mixture, noting that this process would produce an exothermic reaction. The mixture was refluxed again for 12 hours, and then the reaction was terminated by carefully adding water and stirring vigorously (this process would also be exothermic). The reaction mixture was extracted with dichloromethane (50 ml each time, 3 times in total), the organic layer was separated, and concentrated under reduced pressure. The concentrated product was washed with n-hexane and recrystallized from boiling tetrahydrofuran (THF). Finally, the crystals obtained were collected by filtration to obtain the target product as a yellow solid with an output of 1.69 g and a yield of 80%. 1 H NMR (400MHz, CDCl3) δ8.93–8.84(m,3H),8.56(dd,J=8.0,1.6Hz,1H),8.17(dd,J=8.6,0.9Hz,1H),8.08 (dd,J=9.0,2.1Hz,1H),7.99(d,J=9.0Hz,1H),7.88-7.78(m,2H),7.64(ddd,J=8.0,7.1,1.0Hz,1H).13C NMR (101MHz, CDCl3) δ142.31,139.59,139.00,136.73,134.95,134.76,134.23,128.28,126.47,12 4.73,122.31,120.47,118.47,115.64,112.81,109.98,89.83.HRMS[M+H]+Calculated:423.9834(C 20 H 11 INO2); Found:423.9822.

[0128] (3) Synthesis of pyridyl[3,2,1-de]acridine-5,9-dionequinolinol (primary ligand):

[0129]

[0130] In a reaction vessel, iodo[3,2,1-de]acridine-5,9-dionequinoctane (10 mmol), 2-pyridineboronic acid (12 mmol), and potassium carbonate (K2CO3, 20 mmol) were added in sequence. Subsequently, a mixed solvent of water (40 mL) and tetrahydrofuran (THF, 250 mL) was added. Nitrogen was bubbled for 5 minutes to replace the air in the reaction system to ensure that the reaction was carried out in an oxygen-free environment. Under a continuous high nitrogen flow, the catalyst Pd(PPh3)4 (0.5 mmol) was added. The reaction mixture was heated to reflux and stirred under this condition for 24 hours. After the reaction was completed, it was cooled to room temperature and then extracted with dichloromethane and water. The organic layers were combined and concentrated under reduced pressure. Finally, the crude product was purified by column chromatography to obtain 0.94 g of the yellow solid precursor ligand pyridyl[3,2,1-de]acridine-5,9-dionequinoctane with a yield of 25%. 1 H NMR (400MHz, CDCl3) δ9.01 (d, 1H), 8.79-73 (m, J=8.0, 1.6Hz, 3H), 8.53-8.50 (ddd, J=8.6, 0.9Hz, 2H), 8.26-8.16 (d, J=9.0, 2.1Hz, 1H) , 7.99-7.96(d,J=9.0Hz,1H), 7.87-7.85(dt,1H), 7.73-7.65(m,J=8.0,7.1,1.0Hz,2H), 7.54-7.50(ddd,1H), 7.33-7.30(ddd,1H).13C NMR (101MHz, CDCl3) δ142.31,139.59,139.00,136.73,134.95,134.76,134.23,128.28,126.47,12 4.73,122.31,120.47,118.47,115.64,112.81,109.98,89.83.HRMS[M+H]+Calculated:375.1128(C 25 H 14 N2O2); Found: 375.1136.

[0131] Step S2: The primary ligand and the platinum source react in an ethylene glycol ether solution to obtain a metal platinum complex precursor:

[0132]

[0133] A platinum source, K2PtC14 (1 mmol), and the primary ligand, pyridyl[3,2,1-de]acridine-5,9-dionequinoctane (2.2 mmol), were added to a reaction flask. A mixture of ethylene glycol diethyl ether and water (20 mL / 5 mL) was added under nitrogen. The reaction was refluxed at 130°C for 24 hours. After the reaction was complete, the temperature was lowered to room temperature and filtered to obtain the platinum complex precursor, the chloroplatinum complex [Pt(L),(u-C1)]2, in an 85% yield.

[0134] Step S3: The metal platinum complex precursor and the auxiliary ligand acetylacetone react in an ethylene glycol ether solution to obtain the metal platinum complex Pt-81:

[0135]

[0136] The above-mentioned metal platinum complex precursor, i.e., the chlorobridged platinum complex [Pt(L), (u-Cl)]2 and the auxiliary ligand acetylacetone (acac) (0.60 mmol) were dissolved in ethylene glycol ethyl ether (15 ml) and stirred under a nitrogen atmosphere at 10°C for 6 h. After cooling, the solvent was removed under reduced pressure. The crude product was purified by column chromatography on silica gel (PE / DCM=8 / 1, v / v) to obtain the final product, the metal platinum complex, as a yellow solid in a yield of 20.54%. 1 H NMR (400MHz, Chloroform-d) δ9.08 (d, J = 5.7 Hz, 1H), 8.75 (ddd, J = 10.2, 7.8, 1. 7Hz,2H),8.58(s,1H),8.48(dd,J=7.9,1.7Hz,1H),8.43-8.31(m,2H),8.02–7.8 9(m,2H),7.64(q,J=7.6,7.0Hz,2H),7.45(t,J=7.5Hz,1H),7.29(d,J=2.0Hz,1 H),5.85(s,1H),1.30(s,9H),1.10(s,9H).HRMS[M+H]+Calculated:751.2010(C 36 H 32 PtN2O4), Found: 751.2026.

[0137] The organic electroluminescent device includes: a substrate, an anode, a hole injection material, a hole transport layer, an electron blocking layer, an organic light-emitting layer, a hole blocking layer, an electron transport layer, an electron injection material and a cathode. Among them, the substrate is glass, the anode is indium tin oxide (ITO), the hole injection layer is 2,3,6,7,10,11-hexacyano-1,4,5,8,9,12-hexaazatriphenylene (HAT-CN), the hole layer is 4,4'-cyclohexylbis[N,N-di(4-methylphenyl)aniline (TAPC), the electron blocking layer is 4,4',4"-tris(carbazol-9-yl)triphenylamine (TCTA), the hole blocking layer is 2,4,6-tris[3-(diphenylphosphinoyl)phenyl]-1,3,5-triazole (PO- T2T), the electron transport layer adopts 1,3,5-tris[(3-pyridyl)-3-phenyl]benzene (TmPyPb), the electron injection material is Liq, the cathode is metal Al, the organic light-emitting layer includes a host material and a light-emitting material, the host material is 5-(3-(4,6-diphenyl-1,3,5-triazine-2-yl)phenyl)-7,7-dimethyl-5,7-dihydroindole[2,1-b]carbazole (DMIC-Trz), the light-emitting material is the metal platinum complex prepared above, and the mass fraction of the metal platinum complex is 5wt%.

[0138] Other metal platinum complexes and organic electroluminescent devices were prepared by referring to the preparation method in Example 1 above to obtain metal platinum complexes ranging from Pt-1 to Pt-940 and their corresponding organic electroluminescent devices. The synthesis process of each metal platinum complex follows the same steps, but is appropriately adjusted according to different ligand structures and reaction conditions to ensure the diversity and functionality of the synthesis. The molecular formulas, mass spectrometry analysis and elemental analysis results of all synthesized metal platinum complexes are summarized in Table 1. The performance of the above-mentioned metal platinum complexes in organic electroluminescent devices is shown in Table 2.

[0139] Table 1

[0140]

[0141]

[0142]

[0143]

[0144]

[0145]

[0146]

[0147]

[0148]

[0149]

[0150]

[0151]

[0152]

[0153]

[0154]

[0155] Table 2

[0156]

[0157]

[0158]

[0159]

[0160]

[0161]

[0162]

[0163]

[0164] The above test results show that:

[0165] Combine Figures 1 to 5 , and Table 2, the metal platinum complex phosphorescent material Pt1-Pt940 provided in this application has excellent narrow-band green light emission characteristics due to the optimization of the structure of [3,2,1-de] acridine-5,9-dione quinolinone by introducing nitrogen heteroaromatic rings and their derivatives. Its spectral half-maximum width is less than 40nm, and the luminescence peak wavelength is in the range of 500nm to 540nm, and it has a high photoluminescence quantum efficiency (PLQY) and good thermal stability. The metal platinum complex provided in this application can be used as a luminescent material in the organic light-emitting layer of an organic electroluminescent device, thereby achieving the purpose of regulating the efficiency and life of the device. It can be seen from the results in Table 2 that the organic electroluminescent device has a low turn-on voltage, high current efficiency, brightness and external quantum efficiency, indicating that the metal platinum complex provided in this application performs well in device performance.

[0166] In summary, the [3,2,1-de]acridine-5,9-dionequinolinium provided in this application introduces nitrogen-heteroaromatic rings and its derivatives into metal platinum complexes, which have the effect of regulating the luminescent color, efficiency, and electron transport properties of the material, increasing material stability, improving device efficiency, and reducing efficiency roll-off. The metal platinum complexes in this application have the characteristics of high photoluminescence quantum yield, short excited state lifetime, and narrow-band emission. OLED devices prepared using the metal platinum complexes of this application exhibit excellent performance, with low starting voltage, high external quantum efficiency, low efficiency roll-off, and narrow-band emission, and have high application value in the field of OLED lighting and display.

[0167] It will be understood that the above embodiments are merely exemplary embodiments for illustrating the principles of the present invention, and the present invention is not limited thereto. Those skilled in the art will appreciate that various modifications and improvements can be made without departing from the spirit and substance of the present invention, and such modifications and improvements are also considered to be within the scope of protection of the present invention.

Claims

1. A metal platinum complex of a [3,2,1-de]acridine-5,9-dionequinolinoid derivative containing carbonyl nitrogen, characterized in that: The structure of the metal platinum complex contains a main ligand and an auxiliary ligand, wherein the main ligand is a [3,2,1-de]acridine-5,9-dione quinoline derivative containing carbonyl nitrogen, the structure of the [3,2,1-de]acridine-5,9-dione quinoline derivative contains an nitrogen heteroaromatic ring or an nitrogen heteroaromatic ring derivative, and the auxiliary ligand is acetylacetone, an acetylacetone derivative, benzoic acid or a benzoic acid derivative.

2. The metal platinum complex according to claim 1, wherein the metal platinum complex has the general structural formula shown in formula (I) or formula (II): in, R in the formula (I) and the formula (II) m Independently selected from hydrogen, halogen, -CF3, -CN, -OR 1 、-Si(R 1 )2、-N(R 1 )2、-SR 1 (R 1 )2、-C(O)R 1 、-C(O)OR 1 、-C(O)NR 1 、-SOR 1 、-SO2R 1 、-SO2R 1 、-P(O)(R 1 )2、-P(O)(OR 1 )R 1 、-P(O)(OR 1 )2, substituted or unsubstituted C1-C40 alkyl, substituted or unsubstituted C2-C40 alkenyl, substituted or unsubstituted C2-C40 alkynyl, substituted or unsubstituted C3-C40 cycloalkyl, substituted or unsubstituted C3-C40 heterocycloalkyl, substituted or unsubstituted C6-C40 aryl, or substituted or unsubstituted C6-C40 heteroaryl; R 1 are independently selected from hydrogen, -CN, halogen, C1-C40 alkyl, C2-C40 alkenyl, C2-C40 alkynyl or C1-C40 haloalkyl, and multiple R 1 Can be the same or different; The V ring in the formula (I) and the formula (II) is independently selected from a C2-C20 nitrogen heteroaromatic ring or a nitrogen heteroaromatic ring derivative; The Ar rings in the formula (I) and the formula (II) are independently selected from C6-C20 aromatic rings or fused aromatic rings, and n is an integer greater than or equal to 0; R1 to R in the formula (I) 11 and R1 to R in the formula (II) 15 are independently selected from hydrogen, halogen, -CF3, -CN, -OR 2 、-Si(R 2 )2、-N(R 2 )2、-SR 2 (R 2 )2、-C(O)R 2 、-C(O)OR 2 、-C(O)NR 2 、-SOR 2 、-SO2R 2 、-SO2R 2 、-P(O)(R 2 )2、-P(O)(OR 2 )R 2 、-P(O)(OR 2 )2, substituted or unsubstituted C1-C40 alkyl, substituted or unsubstituted C2-C40 alkenyl, substituted or unsubstituted C2-C40 alkynyl, substituted or unsubstituted C3-C40 cycloalkyl, substituted or unsubstituted C3-C40 heterocycloalkyl, substituted or unsubstituted C6-C40 aryl, or substituted or unsubstituted C6-C40 heteroaryl; R 1 are independently selected from hydrogen, -CN, halogen, C1-C40 alkyl, C2-C40 alkenyl, C2-C40 alkynyl or C1-C40 haloalkyl, and multiple R 1 Can be the same or different.

3. The metal platinum complex according to claim 2, characterized in that R1 to R in the formula (I) 11 or R1 to R in the formula (II) 15 Any two adjacent groups in the formula (I) may undergo a cross-linking reaction and form a ring with the ring atoms connecting the two groups.

4. The metal platinum complex according to claim 3, characterized in that R1 to R in the formula (I) 11 or R1 to R in the formula (II) 15 Any two adjacent groups in the group may undergo a cross-linking reaction and form a ring with the ring atoms connected to the two groups, and the formed ring is independently selected from a substituted or unsubstituted 5-7 membered aryl group, a substituted or unsubstituted 5-7 membered heteroaryl group, a substituted or unsubstituted 8-10 membered fused bicyclic aryl group, a substituted or unsubstituted 8-10 membered fused bicyclic heteroaryl group, a substituted or unsubstituted 11-14 membered fused tricyclic aryl group, or a substituted or unsubstituted 11-14 membered fused tricyclic heteroaryl group.

5. The metal platinum complex according to claim 2 or claim 3, characterized in that The V ring contains an O heteroatom and / or a S heteroatom, and the number of the O heteroatom or the S heteroatom is one or more.

6. The metal platinum complex according to claim 2 or claim 3, characterized in that The V-ring has one of the following structures:

7. The metal platinum complex according to claim 2 or claim 3, characterized in that The Ar ring has one of the following structures:

8. The metal platinum complex according to claim 2 or claim 3, characterized in that The metal platinum complex has one of the following structures:

9. A method for preparing a metal platinum complex of a [3,2,1-de]acridine-5,9-dione quinolinoid derivative containing carbonyl nitrogen, characterized in that: include: Synthesizing a main ligand, wherein the main ligand is a [3,2,1-de]acridine-5,9-dione quinolinium derivative containing carbonyl nitrogen, and the [3,2,1-de]acridine-5,9-dione quinolinium derivative contains an azo aromatic ring or an azo aromatic ring derivative in its structure; The primary ligand and the platinum source react in an ethylene glycol diethyl ether solution to obtain a metal platinum complex precursor; and The metal platinum complex precursor and the auxiliary ligand react in an ethylene glycol ether solution, wherein the auxiliary ligand is acetylacetone, acetylacetone derivatives, benzoic acid or benzoic acid derivatives, to obtain the metal platinum complex.

10. An organic electroluminescent device, characterized in that: include: An anode, a cathode, and an organic light-emitting layer disposed between the anode and the cathode, wherein the organic light-emitting layer contains the metal platinum complex according to claim 1 to claim 8.

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