JP7308357B2 - Heterotrinuclear metal organic alkyne complex, method for producing the same, and use thereof - Google Patents

Description

Detailed description of the invention

The present invention is the prior application number 201910877419.8 filed with the State Intellectual Property Office of China on September 17, 2019, and the invention title is "Heterotrinuclear metal organic alkyne complex and its preparation and use" Claim priority of the application. The entire text of that application is incorporated herein by reference.

〔Technical field〕
The present invention belongs to the technical field of light-emitting materials and organic light-emitting diodes, specifically phosphorescent Pt ₂ M (M=Au(I), Ag(I), Cu(I)) heterotrinuclear metal organic alkyne complexes , its method of synthesis and its use as a phosphorescent material in organic light-emitting diodes.

[Background technology]
Organic light-emitting diodes (OLEDs) are thin-film light-emitting devices that generally contain multiple organic thin-film interlayers, such as light-emitting layers, between their cathodes and anodes to emit electrical energy under the action of low drive voltages (3-12V). Since it can be converted into light energy, that is, it can be electroluminescent, it is expected to be widely used in flat panel display and lighting fields. The core of organic light-emitting diodes is light-emitting thin film materials, and the breakthrough in light-emitting materials is also the key to achieving high electroluminescence-efficiency displays and the spread of lighting. there is Conventional commercial luminescent materials for OLEDs are mainly phosphorescent cyclic metallized iridium (III) complexes, whose energy utilization efficiency reaches 100%, but with high price and imperfect chromaticity (blue Due to the shortage of phosphorescent materials), there are difficult problems such as lack of iridium resources. Therefore, it is of great practical significance to develop a novel low-cost light-emitting material that has a new structure, a simple manufacturing method, and a high synthetic yield.

[Outline of the invention]
In order to solve the above problems, the present invention provides a phosphorescent Pt ₂ M (M=Au(I), Ag(I), Cu(I)) heterotrinuclear metal organic alkyne complex, a method for producing the same, and an organic light-emitting diode. its use as a highly efficient phosphorescent material in

The above objects of the present invention are achieved by the following technical solutions.

A Pt ₂ M heterotrinuclear metal-organoalkyne complex, the structure of which is shown in formula (I) below:
[Pt ₂ M(μ−dpmp) ₂ (μ−C≡C−R′−C≡C)(C≡CR) ₂ ] ⁺ _m A ^m− (I)
wherein μ represents a bridge; dpmp is bis(diphenylphosphinomethyl)phenylphosphine;
M is selected from Au(I), Ag(I), or Cu(I);
R are homologous or different and are independently selected from alkyl groups, aryl groups and heteroaryl groups; any of said alkyl groups, aryl groups and heteroaryl groups may be substituted by one or more substituents; Often said substituents are selected from alkyl groups, alkenyl groups, alkynyl groups, alkoxy groups, amino groups, halogens, haloalkyl groups, aryl groups, heteroaryl groups;
R' is selected from an alkylene group, an arylene group, and a heteroarylene group; any of the alkylene group, the arylene group, and the heteroarylene group may be substituted with one or more substituents, and the substituents may be an alkyl group or an alkenyl group; , alkynyl groups, alkoxy groups, amino groups, halogens, haloalkyl groups, aryl groups, heteroaryl groups;
A ^m- is a monovalent or divalent anion, where m is 1 or 2;

In an embodiment of the invention, the monovalent or divalent anion is ClO ₄ ⁻ , PF ₆ ⁻ , SbF ₆ ⁻ , BF ₄ ⁻ , B(C ₆ H ₅ ) ₄ ⁻ , CF ₃ SO ₃ ⁻ , or It is selected from SiF ₆ ^2- and the like.

In an embodiment of the present invention, the stereostructure of the heterotrinuclear metal-organoalkyne complex represented by formula (I) above is as follows:

。

.

In an embodiment of the present invention, said R is preferably an aryl group, carbazolyl group, phenothiazinyl group, quinazolinyl group, aryl-substituted carbazolyl group, diarylaminophenyl group; said aryl group, carbazolyl group, phenothiazinyl group, quinazolinyl groups, aryl-substituted carbazolyl groups, diarylaminophenyl groups are optionally substituted by one or more substituents; said substituents being selected from alkyl groups, alkoxy groups, amino groups, halogens, haloalkyl groups, aryl groups ;
In an embodiment of the present invention, R′ is an arylene group, a nitrogen-containing heteroarylene group (e.g., carbazolylene group), an oxygen-containing heteroarylene group (e.g., dibenzofuranylene group), a sulfur-containing heteroarylene group (e.g., dibenzothienylene group). , a sulfur- and nitrogen-containing heteroarylene group (e.g., a phenothiadinylene group), and the like, and the arylene group, nitrogen-containing heteroarylene group, oxygen-containing heteroarylene group, sulfur-containing heteroarylene group, and sulfur- and nitrogen-containing heteroarylene group are optional. optionally substituted by one or more substituents; said substituents being selected from alkyl groups, alkoxy groups, amino groups, halogens, haloalkyl groups, aryl groups;
More preferably, said R is a phenyl group, an alkyl-substituted phenyl group, a phenyl-substituted carbazolyl group, or a haloalkylphenyl group, an alkoxy-substituted phenyl group, an alkyl-substituted phenothiazinyl group; said R' is an alkyl-substituted carbazolylene group, dibenzofuranylene. a dibenzothienylene group.

By way of example, the heterotrinuclear metal-organoalkyne complexes of formula (I) above are selected from, but not limited to, the following structures:

。

.

The present invention also provides a method for preparing a heterotrinuclear metal-organoalkyne complex of formula (I), comprising the steps of:
reacting dpmp with an ionic complex containing M in a solvent to give intermediate M(dpmp) ₂ ;
Next, the intermediate and Pt ₂ (PPh ₃ ) ₄ (μ-C≡CR′-C≡C)(C≡CR) ₂ are reacted in a solvent to form a heterotrinuclear metal compound represented by formula (I). obtaining an organic alkyne complex;
Here, the ion-bonded complex containing M is [Au(tht) ₂ ] ⁺ _m (A ^m− ), [Ag(tht)] ⁺ _m (A ^m− ), or [Cu(MeCN) ₄ ] ⁺ _m (A ^m− );
Said PPh ₃ represents triphenylphosphine, tht is tetrahydrothiophene, MeCN is acetonitrile and said dpmp, A ^m− , R, R′, M are as defined above.

In an embodiment of the invention, said solvent is preferably a halogenated hydrocarbon solvent, for example dichloromethane.

In an embodiment of the present invention, the molar ratio between dpmp, an ionic complex containing M and Pt ₂ (PPh ₃ ) ₄ (μ-C≡CR′C≡C)(C≡CR) ₂ is 1. 5-2.5:1-1.5:1-1.5, preferably the molar ratio is 2:1:1.

In an embodiment of the invention said reaction is carried out at room temperature.

In an embodiment of the present invention, the reaction time is preferably 12-16 hours;
In an embodiment of the present invention, the production method further comprises separating and purifying the obtained intermediates and/or products using silica gel column chromatography after the completion of the reaction.

The present invention also provides the use of the heterotrinuclear metal-organoalkyne complexes of formula (I) for manufacturing organic light-emitting diodes.

The present invention also provides an organic light-emitting diode comprising a light-emitting layer, said light-emitting layer comprising a heterotrinuclear metal-organoalkyne complex represented by formula (I) above.

In an embodiment of the present invention, in said light-emitting layer, the heterotrinuclear metal-organoalkyne complex of formula (I) comprises 3-20% (weight percent) of all materials in the light-emitting layer of the organic light-emitting diode, preferably It accounts for 5-10%, more preferably 6%.

In embodiments of the present invention, the structure of the organic light emitting diode may be various structures known in the prior art. Preferably, it includes a glass substrate, an anode, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer and a cathode layer.

the anode may be indium tin oxide (ITO);
The hole injection layer or hole transport layer is PEDOT:PSS (PEDOT:PSS = poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonic acid)), or m-PEDOT:PSS [PEDOT:PSS ( 0.8 wt%): PSS-Na (15 mg/mL, dissolved in H _O )];
The light-emitting layer comprises a heterotrinuclear metal organic alkyne complex represented by formula (I), TCTA (tris(4-(9-carbazole)phenyl)amine), mCP(1,3-bis( 9-carbazolyl)benzene), CBP (4,4'-bis(9-carbazole)-1,1'-biphenyl), or 2,6-DCZPPY (2,6-bis(3-(9-carbazole)phenyl ) pyridine) and OXD-7 (1,3-bis(5-(4-(tert-butyl)phenyl)-1,3,4-oxadiazol-2-yl) having electron transport properties ) benzene);
The electron transport layer is TPBi (1,3,5-tris(1-phenyl-1H-benzo[d]imidazol-2-yl)benzene), BmPyPb (3,3'',5,5''-tetrakis( 3-pyridinyl)-1,1′:3′,1″-terphenyl), BCP (2,9-dimethyl-4,7-diphenyl-1,10-phenanthrene), or at least OXD-7 may be one;
The electron injection layer is LiF; the cathode is Al.

In an embodiment of the present invention, the organic light emitting diode structure is shown in formula (I) of ITO/m-PEDOT:PSS (20 nm)/62% mCP:32% OXD-7:6% wt It is preferably a heterotrinuclear metal organic alkyne complex (50 nm)/BmPyPb (50 nm)/LiF (1 nm)/Al (100 nm), in which ITO is an indium tin oxide conductive film, m -PEDOT:PSS is modified poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonic acid), mCP is (1,3-bis(9-carbazolyl)benzene), OXD-7 is 1,3-bis(5-(4-(tert-butyl)phenyl)-1,3,4-oxadiazol-2-yl)benzene and BmPyPb is 3,3″,5,5′ '-Tetrakis(3-pyridinyl)-1,1':3',1''-terphenyl.

The present invention also provides a method for manufacturing said organic light emitting diode, comprising:
1) Fabricating the hole injection layer of the organic light emitting diode using solution method;
2) preparing a light-emitting layer doped with a heterotrinuclear metal-organoalkyne complex of formula (I) using a solution method;
3) Next, an electron-transporting layer, an electron-injecting layer, and a cathode layer are fabricated in this order using a vacuum thermal evaporation method.

In one preferred embodiment, the method first utilizes water-soluble m-PEDOT:PSS to fabricate a hole injection layer, and then mCP with hole-transporting properties and OXD with electron-transporting properties. -7 as a mixed host material, doping the heterotrinuclear metal-organoalkyne complex shown in formula (I) to fabricate a light-emitting layer, and then utilizing a vacuum thermal evaporation method to form a BmPyPb electron-transporting layer, LiF and fabricating an electron injection layer and an Al cathode layer in that order.

In an embodiment of the present invention, in the method, the m-PEDOT:PSS hole-injection layer and the mCP:OXD-7-doped light-emitting layer respectively utilize solution spin-coating to fabricate thin films, and the BmPyPb electron-transport layer And the LiF electron injection layer is formed into a thin film using a vacuum thermal evaporation method.

The organic light-emitting diodes produced by the heterotrinuclear metal-organoalkyne complexes represented by formula (I) have excellent properties and high electro-optical conversion efficiency.

The present invention also provides applications of said organic light emitting diodes in the fields of flat panel displays and everyday lighting.

The present invention has the following advantages over the prior art.

1) The heterotrinuclear metal-organoalkyne complex represented by the formula (I) of the present invention emits strong phosphorescence in solution, solid and thin film, and emits yellow light;
2) In the present invention, for the first time, an organic light-emitting device is assembled using a phosphorescent Pt ₂ M heterotrinuclear metal-organoalkyne complex as a light-emitting material. Organic light-emitting diodes prepared with the heterotrinuclear organic alkyne complexes of the present invention as light-emitting layer dopants have high electroluminescence efficiency and external quantum efficiency (EQE) higher than 12.5%;
3) In the present invention, the improved m-PEDOT:PSS is used to fabricate the hole injection layer, and the electroluminescence efficiency of the device is obviously improved.

(Term definitions and explanations):
Unless defined otherwise, all technical terms used herein have the same meaning as understood by one of ordinary skill in the art to which the claimed subject matter belongs. It should be noted that the above summary and the following detailed description are used for illustration and interpretation only, and do not limit the subject matter of the present application. In this application, "or" and "or" are used to refer to "and/or" unless stated otherwise. Also, versions of the term "comprise," such as "contains," etc., are not used in a limiting sense.

The term "alkyl group" refers to a straight or branched chain alkyl group having 1 to 12, preferably 1 to 10 carbon atoms, said alkyl group being, for example, methyl, ethyl, propyl. , isopropyl group, butyl group, isobutyl group, tert-butyl group, sec-butyl group, pentyl group and neopentyl group.

The term “alkenyl group” is understood to denote a straight-chain or branched monovalent hydrocarbon group preferably containing one or more double bonds and having from 2 to 12 carbon atoms, preferably is a “C _2-10 alkenyl group”. A “C _2-10 alkenyl group” preferably contains one or more double bonds and has 2, 3, 4, 5, 6, 7, 8, 9 or 10 carbon atoms, especially 2 or 3 is understood to denote a straight or branched chain monovalent hydrocarbon group having 1 carbon atom (“C _2-3 alkenyl group”), provided that said alkenyl group contains two or more double bonds In some cases, the double bonds may be separate or conjugated to each other. The alkenyl group is, for example, ethenyl group, allyl group, (E)-2-methylethenyl group, (Z)-2-methylethenyl group, (E)-but-2-enyl group, (Z)-but-2- enyl group, (E)-but-1-enyl group, (Z)-but-1-enyl group, pent-4-enyl group, (E)-pent-3-enyl group, (Z)-pent-3 -enyl group, (E) -pent-2-enyl group, (Z) -pent-2-enyl group, (E) -pent-1-enyl group, (Z) -pent-1-enyl group, hexa- 5-enyl group, (E)-hex-4-enyl group, (Z)-hex-4-enyl group, (E)-hex-3-enyl group, (Z)-hex-3-enyl group, ( E)-hex-2-enyl group, (Z)-hex-2-enyl group, (E)-hex-1-enyl group, (Z)-hex-1-enyl group, isopropenyl group, 2-methylprop -2-enyl group, 1-methylprop-2-enyl group, 2-methylprop-1-enyl group, (E)-1-methylprop-1-enyl group, (Z)-1-methylprop-1-enyl group be.

The term “alkynyl group” is understood to denote a straight or branched chain monovalent hydrocarbon group containing one or more triple bonds and having 2 to 12 carbon atoms, preferably “C ₂ - _C10 alkynyl group”. The term “C _2-10 alkynyl group” preferably contains one or more triple bonds and has 2, 3, ₄ , 5, 6, 7, 8, 9 or 10 carbon atoms, especially 2 or 3 It is understood to denote a straight-chain or branched monovalent hydrocarbon radical having 1 carbon _atom (“C _2-3 -alkynyl radical”). The alkynyl group is, for example, ethynyl group, prop-1-ynyl group, prop-2-ynyl group, but-1-ynyl group, but-2-ynyl group, but-3-ynyl group, pent-1-ynyl group. group, pent-2-ynyl group, pent-3-ynyl group, pent-4-ynyl group, hex-1-ynyl group, hex-2-ynyl group, hex-3-ynyl group, hex-4-ynyl group , hex-5-ynyl group, 1-methylprop-2-ynyl group, 2-methylbut-3-ynyl group, 1-methylbut-3-ynyl group, 1-methylbut-2-ynyl group, 3-methylbut-1- It is an inyl group.

The term “aryl group” is understood to denote an aromatic or partially aromatic monocyclic, bicyclic or tricyclic cyclic hydrocarbon preferably having from 5 to 20 carbon atoms. and preferably a “C _6-14 aryl group”. The term “C _6-14 aryl group” preferably refers to a monovalent aromatic or partially aromatic understood to denote a monocyclic, bicyclic or tricyclic cyclic hydrocarbon (“C _6-14 aryl group”), in particular a ring having 6 carbon atoms (“C ₆ aryl group” ), such as a phenyl group, or a biphenyl group, or a ring having 9 carbon atoms (a “ _C9 aryl group”, such as an indanyl or indenyl group), or a ring having 10 carbon atoms (a “ _C10 aryl group"), such as a tetrahydronaphthyl group, a dihydronaphthyl group or a naphthyl group, or a ring having 13 carbon atoms (a " _C13 aryl group"), such as a fluorenyl group, or having 14 carbon atoms A ring (“ _C14 aryl group”), for example an anthryl group.

The term “heteroaryl group” refers to 5 to 20 ring atoms, 5 to 14 ring atoms, or 5 to 12 ring atoms, or 5 to 10 ring atoms, or 5 to 6 ring atoms. It is understood as monocyclic, bicyclic and tricyclic ring systems containing atoms, at least one ring system being aromatic and at least one ring system containing one or more heteroatoms (e.g. N, O, S, Se, etc.), each ring system comprising a ring of 5-7 atoms, and one or more points of attachment being attached to the remainder of the molecule. Said heteroaryl group is optionally substituted with one or more substituents according to the invention. In some embodiments, the 5-10 atom heteroaryl group contains 1, 2, 3, or 4 heteroatoms independently selected from O, S, Se, and N. Also, in some embodiments, the 5-6 atom heteroaryl group includes 1, 2, 3, or 4 heteroatoms independently selected from O, S, Se, and N.

Examples of monocyclic heteroaryl groups are thienyl, furanyl, pyrrolyl, oxazolyl, thiazolyl, imidazolyl, pyrazolyl, isoxazolyl, isothiazolyl, oxadiazolyl, triazolyl, thiadiazolyl, thia-4H- pyrazolyl group, etc., and benzo derivatives thereof (e.g., benzofuranyl group, benzothienyl group, benzoxazolyl group, benzoisoxazolyl group, benzimidazolyl group, benzotriazolyl group, indazolyl group, indolyl group, isoindolyl group, etc.) ); or pyridinyl groups, pyridazinyl groups, pyrimidinyl groups, pyrazinyl groups, triazinyl groups, etc., and benzo derivatives thereof (e.g., quinolinyl groups, quinazolinyl groups, isoquinolinyl groups, etc.); or azocinyl groups, indolizinyl groups, purinyl groups, etc.; benzo derivatives thereof; including but not limited to.

The term "alkoxy group" refers to an alkyl-O- group, where alkyl group is as defined above. Similarly, the definition of alkyl groups applies to groups containing alkyl groups, such as "haloalkyl groups."

[Brief description of the drawing]
FIG. 1 is a structural schematic diagram of an electroluminescence device of Example 13 and a chemical structure of an organic material constituting a part of the component.

[Mode for carrying out the invention]
In order to make the purpose, technical solution and beneficial effects of the present invention clearer, the present invention will be described in more detail below with reference to drawings and examples. It should be noted that the examples provided herein are intended to interpret the invention rather than limit it.

In the examples below, dpmp represents the bis(diphenylphosphinomethyl)phenylphosphine group, decz represents the 3,6-ditert-butyl-carbazolyl-1,8-diethynyl group, debf represents dibenzofuranyl-4 , represents a 6-diethynyl group, debt represents a dibenzothienyl-4,6-diethynyl group, Ph represents a phenyl group, tht represents tetrahydrothiophene, 9-Ph-carb-3 represents 9-phenyl-carbazole- 3-yl, Ph-(OMe) ₂ -2,4 represents a 2,4-dimethoxyphenyl group, 10-Me-PTZ-3 represents 10-methyl-phenothiazin-3-yl, PPh ₃ represents represents triphenylphosphine, MeCN is acetonitrile and _ClO4 is perchlorate ion.

In the examples below, decz-2H represents the corresponding compound corresponding to the group decz in question, as well as other compounds such as debf-2H.

Example 1: Preparation of Pt ₂ complex Pt ₂ (PPh ₃ ) ₄ (μ-decz)(C≡CPh) ₂ Pt(PPh ₃ ) ₂ (C≡CPh)Cl (180 mg, 0.21 mmol), cuprous iodide (1 mg) and triethylamine (1 mL) were added and reacted at 50 degrees Celsius for 18 hours. A yellow clear solution was obtained. After concentrating the reaction mixture, the product was purified by silica gel column chromatography, and the pale yellow product was recovered using petroleum ether-dichloromethane (2:1) as an eluent, with a yield of 78%. there were. Elemental _{analysis : C112H93NP4Pt2 .} Calculated values: C68.39, H4.77. Measurements: C68.14, H4.82. High resolution mass spectrum m/z (%): 1967.5549 (100) [M+H] ⁺ (calcd 1967.5627). Proton nuclear magnetic resonance (400 MHz, CD ₂ Cl ₂ , ppm): 7.85-7.77 (m, 24H), 7.60 (m, 2H), 7.32 (t, 24H, J = 7.36 ), 7.24 (t, 12H, J = 7.32), 6.94-6.88 (m, 6H), 6.73-6.70 (m, 2H), 6.69 (s, 1H ), 6.30-6.22 (m, 4H), 1.29 (s, 18H). Phosphorus isotope nuclear magnetic resonance (162 MHz, CD ₂ Cl ₂ , ppm): 17.9 (J _Pt-P =2641 Hz). Infrared spectrum (KBr, cm ⁻¹ ): 2109 m (C≡C).

Example 2: Preparation of Pt ₂ complex Pt ₂ (PPh ₃ ) ₄ (μ-decz)(C≡C-(9-Ph-carb-3)) ₂ The preparation method is basically the same as that of Example 1. and using Pt(PPh ₃ ) ₂ (C≡C-(9-Ph-carb-3)Cl instead of Pt(PPh ₃ ) ₂ (C≡CPh)Cl, the yield was 72%. Elemental analysis: _{C136H107N3P4Pt2} Calculated values _: C71.10, _H4.69 Measured values _: C70.99, H4.81 High-resolution mass spectrum m _/ z (%): 2297 .6781(100) [M+H] ⁺ (calcd 2297.6793) Proton nuclear magnetic resonance (CD ₂ Cl ₂ , ppm): 7.95-7.80 (m, 24H), 7.64-7.53 (m, 6H), 7.51-7.39 (m, 12H), 7.39-7.32 (m, 24H), 7.31-7.21 (m, 12H), 6.97 (d , 2H, J = 8.48), 6.85 (s, 1H), 6.74 (s, 2H), 6.33 (d, 2H, J = 8.44), 1.29 (s, 18H Phosphorus isotope nuclear magnetic resonance (162 MHz, CD ₂ Cl ₂ , ppm): 18.0 (J _Pt-P =2645 Hz) Infrared spectrum (KBr, cm ⁻¹ ): 2117 (w).

Example 3: Preparation of Pt ₂ complex Pt ₂ (PPh ₃ ) ₄ (μ-debf)(C≡CPh) ₂ -2H was used and the yield was 70%. Elemental _{analysis : C104H76OP4Pt2 .} Calculated values: C67.31, H4.13. Measurements: C67.21, H4.08. High resolution mass spectrum m/z (%): 1854.4132 (100) [M+H] ⁺ (calcd 1854.4140). Proton nuclear magnetic resonance (CD ₂ Cl ₂ , ppm): 7.72-7.68 (m, 26H), 7.61-7.57 (m, 4H), 7.36-7.32 (m, 26H ), 7.27-7.24 (m, 14H), 6.97-6.92 (t, 2H, J = 8.38), 6.53-6.51 (d, 2H, J = 8) , 6.46-6.45 (d, 2H, J=8.38). Phosphorus isotope nuclear magnetic resonance (162 MHz, CD ₂ Cl ₂ , ppm): 17.77 (J _Pt-P =2134 Hz). Infrared spectrum (KBr, cm ⁻¹ ): 2110 (w).

Example 4: Preparation of Pt ₂ complex Pt ₂ (PPh ₃ ) ₄ (μ-debf)(C≡CPh-(OMe) ₂ -2,4) ₂ and debf-2H instead of decz-2H and Pt(PPh ₃ ) ₂ (C≡CPh-(OMe) ₂ -2,4)Cl instead of Pt(PPh ₃ ) ₂ (C≡CPh)Cl. used and the yield was 81%. _{Elemental analysis : C108H84O5P4Pt2 .} Calculated values: C65.65, H4.29. Measurements: C65.79, H4.20. High resolution mass spectrum m/z (%): 1974.4532 (100) [M+H] ⁺ (calcd 1974.4553). Proton nuclear magnetic resonance (CD ₂ Cl ₂ , ppm): 7.74-7.69 (m, 24H), 7.62-7.60 (d, 2H, J=8.30), 7.40-7 .36 (m, 24H), 7.29-7.23 (m, 10H), 6.97-6.93 (t, 2H, J = 7.68), 6.53-6.49 (d, 2H, J=9), 6.13-6.11 (d, 2H, J=8), 3.61 (s, 12H). Phosphorus isotope nuclear magnetic resonance (162 MHz, CD ₂ Cl ₂ , ppm): 19.21 (J _Pt-P =1634 Hz). Infrared spectrum (KBr, cm ⁻¹ ): 2102 (w).

Example 5: Preparation of Pt ₂ complex Pt ₂ (PPh ₃ ) ₄ (μ-debt)(C≡C-(10-Me-PTZ-3) ₂ and debt-2H instead of decz-2H and Pt(PPh ₃ ) ₂ (C≡C-(10-Me-PTZ-3)Cl instead of Pt(PPh ₃ ) ₂ (C≡CPh)Cl. Used, yield 69% Elemental analysis: _{C118H86N2P4Pt2S3} Calculated: _C66.16 , _H4.05 Found _{: C66.09} , _H4.10 . High-resolution mass spectrum m/z (%): 2140.4225 (100) [M+H] ⁺ (calculated 2140.4210) Proton nuclear magnetic resonance (CD ₂ Cl ₂ , ppm): 7.70-7.65 ( m, 26H), 7.54-7.51 (m, 40H), 7.18-7.14 (d, 2H, J=8), 7.09-7.08 (d, 2H, J=4 ), 6.93-6.84 (m, 4H), 6.49-6.47 (d, 2H, J=6.8), 5.91-5.89 (d, 2H, J=8. 2), 5.54-5.53 (d, 2H, J=2), 3.15 (s, 6H) Phosphorus isotope nuclear magnetic resonance (162 MHz, CD ₂ Cl ₂ , ppm): 19.64 ( J _Pt-P =1334 Hz) Infrared spectrum (KBr, cm ⁻¹ ): 2111 (w).

Example 6: Preparation of Pt ₂ Au complex [Pt ₂ Au(μ-dpmp) ₂ (μ-decz)(C≡CC ₆ H ₅ ) ₂ ](ClO ₄ ) complex (1) dpmp (50.6 mg, 0 [Au(tht) ₂ ](ClO ₄ ) (23.6 mg, 0.05 mmol) was added to 20 mL of a dichloromethane solution in which (.1 mmol) was dissolved and stirred for 5 minutes. Pt ₂ (PPh ₃ ) ₄ (μ-decz)(C≡CPh) ₂ (98.4 mg, 0.05 mmol) prepared in Example 1 was added and stirred at room temperature for 12 hours to form a yellow clear solution. got After concentrating the reaction solution, the product was purified using silica gel column chromatography, and the yellow product was recovered using dichloromethane-acetone (10:1) as an eluent, the yield was 73%. . _{Elemental analysis : C104H91AuClNO4P6Pt2 .} Calculated values: C53.08, H4.12. Measurements: C53.21, H4.02. High resolution mass spectrum m/z (%): 2127.4519 (100) [M-ClO ₄ ] ⁺ (calcd 2127.4542). Proton nuclear magnetic resonance (400 MHz, CD ₂ Cl ₂ , ppm): 8.66 (s, 1H), 7.93-7.82 (m, 4H), 7.81 (s, 2H), 7.81 -7.67 (m, 16H), 7.28-7.14 (m, 16H), 7.10-6.96 (m, 12H), 6.91 (t, 4H, J = 7.49) , 6.77 (t, 4H, J = 7.44), 6.52 (s, 2H), 6.24 (d, 4H, J = 7.24), 4.55-4.37 (m, 4H), 4.00-3.88 (m, 4H), 1.35 (s, 18H). Phosphorus isotope nuclear magnetic resonance (162 MHz, CD ₂ Cl ₂ , ppm): 20.12 (m, 1P, J _PP =29.5 Hz,), 3.34 (m, 2P, J _PP =29 .7 Hz, J _Pt−P =2694 Hz). Infrared spectrum (KBr, cm ⁻¹ ): 2105 w (C≡C), 1098 s (ClO ₄ ).

Example 7: Preparation of Pt ₂ Au Complex [Pt ₂ Au(μ-dpmp) ₂ (μ-decz)(C≡C-(9-Ph-carb-3)) ₂ ](ClO ₄ ) Complex (2) The production method is basically the same as that of Example 6, and instead of Pt ₂ (PPh ₃ ) ₄ (μ-decz)(C≡CPh) ₂ Pt ₂ (PPh ₃ ) ₄ (μ-decz)( C≡C-(9-Ph-carb-3)) ₂ was used and the yield was 68%. _{Elemental analysis : C128H105AuClN3O4P6Pt2 . _} Calculated values: C60.11, H4.14. Measurements: C59.96, H4.29. High resolution mass spectrum m/z (%): 2457.5667 (100) [M-ClO ₄ ] ⁺ (calcd 2457.5699). Proton nuclear magnetic resonance (400 MHz, CD ₂ Cl ₂ , ppm): 8.78 (s, 1H), 8.02-7.88 (m, 4H), 7.88-7.73 (m, 16H), 7.70 (d, 2H, J = 7.60), 7.62-7.49 (m, 8H), 7.48-7.30 (m, 12H), 7.30-7.17 (m , 16H), 7.15-7.05 (m, 8H), 6.97-6.90 (m, 2H), 6.89-6.77 (m, 4H), 6.61 (s, 2H) ), 6.58 (s, 2H), 6.24 (d, 2H, J = 8.44), 4.63-4.39 (m, 4H), 4.09-3.89 (m, 4H ), 1.37(s, 18H). Phosphorus isotope nuclear magnetic resonance (162 MHz, CD ₂ Cl ₂ , ppm): 19.5 (m, 1P, J _PP =29.3 Hz), 3.96 (m, 2P, J _PP =28. 8 Hz, J _Pt−P =2711 Hz). Infrared spectrum (KBr, cm ⁻¹ ): 2107 w (C≡C), 1099 s (ClO ₄ ).

Example 8: Preparation of Pt ₂ Au complex [Pt ₂ Au(μ-dpmp) ₂ (μ-debf)(C≡CC ₆ H ₅ ) ₂ ](ClO ₄ ) complex (3) method, using Pt ₂ (PPh ₃ ) ₄ (μ-debf)(C≡CPh) ₂ instead of Pt ₂ (PPh ₃ ) ₄ (μ-decz)(C≡CPh) ₂ and the yield was 76%. _{Elemental analysis : C96H74AuClO5P6Pt2 .} Calculated values: C54.49, H3.52. Measurements: C54.56, H3.60. High resolution mass spectrum m/z (%): 2015.3114 (100) [M-ClO ₄ ] ⁺ (calcd 2015.3121). Proton nuclear magnetic resonance (400 MHz, CD ₂ Cl ₂ , ppm): 7.88-7.85 (m, 8H), 7.75-7.66 (m, 14H), 7.25-7.22 (m , 10H), 7.17-7.07 (m, 8H), 7.03-7.00 (t, 2H, J = 8.44), 6.95-6.92 (t, 4H, J = 8), 6.89-6.85 (m, 4H), 6.62-6.60 (d, 2H, J = 8.44), 6.27-6.26 (d, 2H, J = 4 ), 4.44-4.34 (m, 4H), 3.87-3.77 (m, 4H). Phosphorus isotope nuclear magnetic resonance (162 MHz, CD ₂ Cl ₂ , ppm): 19.67 (m, 1P, J _PP =26.3 Hz), 4.52 (m, 2P, J _PP =27. 7 Hz, J _Pt-P =1336 Hz). Infrared spectrum (KBr, cm ⁻¹ ): 2106 w (C≡C), 1135 s (ClO ₄ ).

Example 9: Preparation of Pt ₂ Au Complex [Pt ₂ Au(μ-dpmp) ₂ (μ-debf)(C≡CPh-(OMe) ₂ -2,4) ₂ ](ClO ₄ ) Complex (4) Preparation The method is basically the same as that of Example ₆ , _{except Pt 2} (PPh ₃ ) ₄ (μ-debf)( _C ≡CPh-(OMe) ₂ -2,4) ₂ was used and the yield was 67%. _{Elemental analysis : C100H82AuClO9P6Pt2 .} Calculated values: C53.71, H3.70. Measurements: C53.66, H3.66. High resolution mass spectrum m/z (%): 2135.3524 (100) [M-ClO ₄ ] ⁺ (calcd 2015.3551). Proton nuclear magnetic resonance (400 MHz, CD ₂ Cl ₂ , ppm): 7.93-7.89 (m, 4H), 7.81-7.77 (m, 8H), 7.75-7.73 (d , 2H, J=8), 7.67-7.62 (m, 8H), 7.21-7.19 (m, 14H), 7.14-7.01 (m, 12H), 6.77 -6.73 (t, 4H, J = 4.44), 6.43-6.38 (m, 6H), 6.01-5.99 (d, 4H, J = 8), 4.79- 4.76 (m, 4H), 3.73-3.71 (m, 4H), 3.60 (s, 12H). Phosphorus isotope nuclear magnetic resonance (162 MHz, CD ₂ Cl ₂ , ppm): 17.05 (m, 1P, J _PP =16.3 Hz), 1.35 (m, 2P, J _PP =29. 16 Hz, J _{Pt -P} = 1335 Hz). Infrared spectrum (KBr, cm ⁻¹ ): 2108 w (C≡C), 1158 s (ClO ₄ ).

Example 10 Preparation of Pt ₂ Au Complex [Pt ₂ Au(μ-dpmp) ₂ (μ-debt)(C≡C-(10-Me-PTZ-3](ClO ₄ ) Complex (5) It is basically the same as the method of Example 6, and instead of Pt ₂ (PPh ₃ ) ₄ (μ-decz)(C≡CPh) ₂ , Pt ₂ (PPh ₃ ) ₄ (μ-debt)(C≡C -(10-Me-PTZ-3) ₂ was used and the yield was 62% Elemental analysis: C ₁₁₀ H ₈₄ AuN ₂ ClO ₄ P ₆ Pt ₂ S ₃ Calculated: C54.99, H3 .52 Measured: C55.06, H3.50 High resolution mass spectrum m/z (%): 2301.3214 (100) [M-ClO ₄ ] ⁺ (calculated 2301.3208) Proton nuclear magnetic resonance (400 MHz, CD ₂ Cl ₂ , ppm): 7.70-7.65 (m, 26H), 7.48-7.46 (m, 4H), 7.35-7.33 (m, 30H), 7.12-7.11 (t, 2H, J=3), 7.06-7.05 (d, 2H, J=8), 6.99-6.95 (t, 2H, J=8. 2), 6.89-6.81 (m, 4H), 4.69-4.60 (m, 4H), 3.93-3.81 (m, 4H), 3.65 (s, 6H) Phosphorus isotope nuclear magnetic resonance (162 MHz, CD ₂ Cl ₂ , ppm): 19.06 (m, 1P, J _PP =13.5 Hz), 3.26 (m, 2P, J _PP =27 .26 Hz, J _Pt-P =1453 Hz) Infrared spectrum (KBr, cm ⁻¹ ): 2109 w (C≡C), 1103 s (ClO ₄ ).

Example 11: Preparation of Pt ₂ Cu complex [Pt ₂ Cu(μ-dpmp) ₂ (μ-decz)(C≡CC ₆ H ₅ ) ₂ ](ClO ₄ ) complex (6) method, using [Cu(MeCN) ₄ ](ClO ₄ ) instead of [Au(tht) ₂ ](ClO ₄ ). Yield was 72%. _{Elemental analysis : C104H91ClCuNO4P6Pt2 .} Calculated values: C59.66, H4.38. Measurements: C59.28, H4.55. High resolution mass spectrum m/z (%): 1993.4160 (100) [M-ClO ₄ ] ⁺ (calcd 1993.4172). Proton nuclear magnetic resonance (400 MHz, CD ₂ Cl ₂ , ppm): 8.73 (s, 1H), 7.90-7.83 (m, 4H), 7.82-7.78 (m, 2H) , 7.70-7.57 (m, 16H), 7.28-7.22 (m, 4H), 7.19-7.03 (m, 22H), 6.95 (t, 4H, J= 7.48), 6.86-6.75 (m, 8H), 6.64-6.60 (m, 2H), 5.94-5.87 (m, 2H), 4.20-3. 96 (m, 4H), 3.78-3.56 (m, 4H), 1.35 (s, 18H). Phosphorus isotope nuclear magnetic resonance (162 MHz, CD ₂ Cl ₂ , ppm): 9.6 (m, 2P, J _P-P = 37.3 Hz, J _Pt-P = 2550 Hz), -13.2 (m, 1P, J _PP =34.6 Hz). Infrared spectrum (KBr, cm ⁻¹ ): 2102 w (C≡C), 1099 s
( _ClO4 ).

Example 12: Photoluminescence performance test of complexes (1)-(6) Excitation spectra, emission spectra, emission lifetimes and luminescence in different states of complexes (1)-(6) prepared in the example in a fluorescence spectrometer Edinburgh FLS920 The quantum yield was tested respectively. The emission quantum yield of the samples was measured using an integrating sphere with a diameter of 142 mm. See Table 1 for details of the results.

Example 13: Production and performance test of electroluminescent devices with complexes (1) to (5) Phosphorescent complexes (1) to (5) produced in Examples 6 to 10, respectively, were used as light-emitting materials and mCP at 6% weight percent (63%): OXD-7 (32%) mixed host material doped organic light-emitting diode was fabricated with light-emitting layer, device structure was ITO/m-PEDOT:PSS (20 nm)/62% mCP: 32% OXD-7:6% wt complex (50 nm)/Bmpypb (50 nm)/LiF (1 nm)/Al (100 nm).

The ITO substrates were first cleaned using glass cleaner, acetone, isopropanol, and deionized water, respectively, and then treated with UV-ozone for 15 minutes. PSS-Na aqueous solution (15 mg/mL) and PEDOT:PSS were mixed at 5:1 (volume ratio), filtered, spin-coated on ITO at 4000 rpm in a spin coater, and dried at 120°C for 15 minutes. A hole transport layer with a thickness of 20 nm was obtained. A post-filter concentration of 5 mg/mL of 62% mCP:32% OXD-7:6% complex (weight percent) in dichloromethane was then applied at 2100 rpm using a spin coater. The thin film was spin-coated to form a light-emitting layer with a thickness of 50 nm. Subsequently, the ITO substrate was placed in a vacuum chamber with a degree of vacuum of 4×10 ⁻⁴ Pa or more, and a BmPyPb electron transport layer with a thickness of 50 nm, a LiF electron injection layer with a thickness of 1 nm, and an Al with a thickness of 100 nm were formed on the cathode of the device. were thermally evaporated in this order.

Light-emitting diode device performance tests were conducted in a dry air environment under room temperature. Electroluminescent performance parameters are electroluminescent wavelength (λ _EL ), turn-on voltage (V _on ), maximum luminance (L _max ), maximum current efficiency (CE _max ), maximum power efficiency (PE _max ), maximum external quantum efficiency (EQE _max ), summarized in Table 2.

Embodiments of the present invention have been described above. However, the invention is not limited to the above embodiments. Modifications, equivalent replacements, improvements, etc. made without departing from the spirit of the present invention are all included in the scope of the present invention.

FIG. 13 is a structural schematic diagram of an electroluminescence device of Example 13 and a chemical structure of an organic material constituting a part of the component.

Claims (11)

A Pt ₂ M heterotrinuclear metal-organoalkyne complex characterized in that the structure is as shown in formula (I) below:
[Pt ₂ M(μ−dpmp) ₂ (μ−C≡C−R′−C≡C)(C≡CR) ₂ ] ⁺ _m A ^m− (I)
wherein μ represents a bridge; dpmp is bis(diphenylphosphinomethyl)phenylphosphine;
M is selected from Au(I), Ag(I), or Cu(I);
R are homologous or different and are independently selected from alkyl groups, aryl groups and heteroaryl groups; any of said alkyl groups, aryl groups and heteroaryl groups may be substituted by one or more substituents; Often said substituents are selected from alkyl groups, alkenyl groups, alkynyl groups, alkoxy groups, amino groups, halogens, haloalkyl groups, aryl groups, heteroaryl groups;
R' is selected from an alkylene group, an arylene group, and a heteroarylene group; any of the alkylene group, the arylene group, and the heteroarylene group may be substituted with one or more substituents, and the substituents may be an alkyl group or an alkenyl group; , alkynyl groups, alkoxy groups, amino groups, halogens, haloalkyl groups, aryl groups, heteroaryl groups;
A ^m- is a monovalent or divalent anion, where m is 1 or 2; (1) the monovalent or divalent anion is ClO ₄ ⁻ , PF ₆ ⁻ , SbF ₆ ⁻ , BF ₄ ⁻ , B(C ₆ H ₅ ) ₄ ⁻ , CF ₃ SO ₃ ⁻ , or SiF ₆ ²⁻ selected from;
(2) The three-dimensional structure of the heterotrinuclear metal organic alkyne complex represented by the formula (I) is as follows;

(3) R is an aryl group, carbazolyl group, phenothiazinyl group, quinazolinyl group, aryl-substituted carbazolyl group, or diarylaminophenyl group; groups, or diarylaminophenyl groups are optionally substituted by one or more substituents; said substituents being selected from alkyl groups, alkoxy groups, amino groups, halogens, haloalkyl groups, or aryl groups; or
(4) R′ is an arylene group, a nitrogen-containing heteroarylene group , an oxygen-containing heteroarylene group , a sulfur-containing heteroarylene group , or a sulfur and nitrogen-containing heteroarylene group, and the arylene group, nitrogen-containing heteroarylene group, oxygen-containing heteroarylene group, A sulfur-containing heteroarylene group or a sulfur and nitrogen-containing heteroarylene group is optionally substituted with one or more substituents; said substituents being selected from alkyl groups, alkoxy groups, amino groups, halogens, haloalkyl groups, aryl groups. The complex according to claim 1, characterized in that it is The nitrogen-containing heteroarylene group is a carbazolylene group, the oxygen-containing heteroarylene group is a dibenzofuranylene group, the sulfur-containing heteroarylene group is a dibenzothienylene group, and the sulfur and nitrogen-containing heteroarylene group is a phenol. 3. A complex according to claim 2, characterized in that it is a thiazinylene group. R is a phenyl group, an alkyl-substituted phenyl group, a phenyl-substituted carbazolyl group , a haloalkylphenyl group, an alkoxy-substituted phenyl group, or an alkyl-substituted phenothiazinyl group; or a dibenzothienylene group, according to any one of claims 1 to 3 . The complex according to any one of claims 1 to 4 , characterized in that the heterotrinuclear metal organic alkyne complex of formula (I) is selected from the following structures:

. A method for preparing a complex according to any one of claims 1 to 5 , characterized in that it comprises the following steps:
reacting dpmp with an ionic complex containing M in a solvent to give intermediate M(dpmp) ₂ ;
Next, M(dpmp) ₂ and Pt ₂ (PPh ₃ ) ₄ (μ-C≡CR′-C≡C)(C≡CR) ₂ are reacted in a solvent to form a heterodimer of formula (I). obtaining a trinuclear metal-organoalkyne complex;
Here, the ion-bonded complex containing M is [Au(tht) ₂ ] ⁺ _m (A ^m− ), [Ag(tht)] ⁺ _m (A ^m− ), or [Cu(MeCN) ₄ ] ⁺ _m (A ^m− );
said PPh ₃ represents triphenylphosphine, tht is tetrahydrothiophene, MeCN is acetonitrile and said dpmp, A ^m− , R, R′, M are as defined in any one of claims 1 to 5 That's right. The molar ratio of dpmp, the ionically bonded complex containing M, and Pt ₂ (PPh ₃ ) ₄ (μ-C≡CR′C≡C)(C≡CR) ₂ is 1.5-2.5:1. The production method according to claim 6 , characterized in that the ratio is ~1.5:1~1.5. Use of the complexes according to any one of claims 1-5 for the production of organic light-emitting diodes. An organic light-emitting diode comprising a light-emitting layer, characterized in that said light-emitting layer comprises a complex according to any one of claims 1-5. 1) fabricating a hole injection layer of an organic light emitting diode using a solution method;
2) preparing a light-emitting layer doped with a complex according to any one of claims 1 to 5 using a solution method;
3) then fabricating an electron-transporting layer, an electron-injecting layer and a cathode layer in this order using vacuum thermal evaporation. Use of the organic light emitting diode according to claim 9 in the field of flat panel displays or everyday lighting.

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