HK1237786A - A phosphorescent ptag2 complex, processes for its preparation and uses thereof - Google Patents

Description

Phosphorescent PtAg2Complexes, preparation method and application thereof

Technical Field

The invention belongs to the field of organic electroluminescence, and can be applied to the fields of color flat panel display and illumination. In particular to PtAg₂The (meso-/rac-dpmppe) heterotrimeric metal organic alkyne complex is used for preparing organic light-emitting diodes.

Background

The organic electroluminescence is a light emitting phenomenon that an Organic Light Emitting Diode (OLED) directly converts electric energy into light energy under the action of 3-12V low direct current voltage, and has very wide application in the fields of panel display and illumination. Compared with the traditional lighting and display technology, the organic electroluminescence has the advantages of full-color display, wide viewing angle, high definition, quick response, low power consumption, low temperature resistance and the like; and the organic light-emitting device has the excellent characteristics of simple structure, ultralight weight, ultra-thin property, flexibility, foldability and the like.

The core of the organic light emitting diode is a light emitting thin film material, most of phosphorescent materials used by current commercial organic electroluminescent devices are electrically neutral ring metal iridium (III) complexes, and the complexes are doped in an organic main material to form a light emitting layer, so that the most advantage is that the ideal thin film light emitting layer can be manufactured by vacuum thermal evaporation conveniently. However, the equipment required for vacuum evaporation is expensive, and especially the process for preparing the organic doped luminescent thin film layer is complex, which greatly limits the industrial development and commercial application of the organic light emitting diode in large-area full-color display. In order to break through the technical bottleneck, the selection of the ionic phosphorescent metal organic compound with high quantum efficiency as the luminescent material is a feasible alternative way. Compared with the charge neutral compound, the ionic phosphorescent metal complex is simpler and cheaper to prepare, has better stability, is easy to dissolve in an organic solvent, is suitable for large-area solution spin coating or ink-jet printing film forming, and can greatly reduce the preparation cost of devices.

Disclosure of Invention

The invention aims to provide ionic phosphorescent PtAg with meso- (meso-) or rac-) structure₂Complexes, and a preparation method and application thereof.

Another object of the present invention is to provide an organic light emitting diode comprising the above ionic phosphorescent metal complex.

The object of the invention is achieved by:

an ionic phosphorescent metal complex with a racemic structure, which has a structure shown as the following formula (I) or formula (II):

[PtAg₂{rac-(PPh₂CH₂PPhCH₂-)₂}(C≡CR)₂(PR'₃)₂]²⁺A^n- _2/n； (I)

or

[PtAg₂{meso-(PPh₂CH₂PPhCH₂-)₂}(C≡CR)₂(PR'₃)(μ-X)]⁺ _mA^m-(II)

Wherein the content of the first and second substances,

r, which may be the same or different, is independently selected from: alkyl, aryl, heteroaryl, heteroarylaryl,

r', which may be the same or different, is independently selected from: alkyl, aryl, heteroaryl;

the alkyl, aryl and heteroaryl can be substituted by one or more substituents selected from alkyl, alkenyl, alkynyl, alkoxy, amino, halogen, haloalkyl and aryl;

x is selected from halogen;

A^m-、A^n-is a monovalent or divalent anion, m or n is 1, 2, the anion is, for example, ClO₄ ^-、PF₆ ^-、SbF₆ ^-、BF₄ ^-、SiF₆ ^2-And the like. Mu represents a bridge.

According to the invention, the phosphorescent metal complex of formula (I) or formula (II) has the following three-dimensional structure:

in the present invention, the alkyl group means a linear or branched alkyl group having 1 to 10, preferably 1 to 6 carbon atoms, for example, methyl, ethyl, propyl, butyl, isobutyl, tert-butyl, etc.

The alkenyl group represents a linear or branched alkenyl group having 2 to 6 carbon atoms, for example, ethylene, propylene, butene, etc.

The alkynyl group represents a linear or branched alkynyl group having 2 to 6 carbon atoms, for example, acetylene, propyne, butyne and the like.

The aryl group means a monocyclic, polycyclic aromatic group having 6 to 20 carbon atoms, and representative aryl groups include: phenyl, naphthyl, and the like.

Said heteroaryl refers to a monocyclic or polycyclic heteroaromatic group having 1 to 20 carbon atoms and containing at least 1, preferably 1 to 4 heteroatoms selected from N, S, O, representative heteroaryl groups include: pyrrolyl, pyridyl, pyrimidinyl, imidazolyl, thiazolyl, oxazolyl, oxadiazolyl, carbazolyl, quinolinyl, quinazolinyl, indolyl, phenothiazinyl, and the like.

According to the invention, A is^m-Or A^n-Preferably ClO₄ ^-、PF₆ ^-、SiF₆ ^2-And m/n is 1 or 2.

According to the invention, R is preferably an aryl group, a carbazolyl group, a phenothiazinyl group, a carbazolylalkyl group. The aryl, carbazolyl, phenothiazinyl group may be optionally substituted with one or more substituents selected from the group consisting of alkyl, alkoxy, amino, halo, haloalkyl, aryl; preferably, R' is aryl, a nitrogen-containing heterocycle (e.g., carbazolyl), which may be optionally substituted with one or more substituents selected from the group consisting of alkyl, alkoxy, amino, halo, haloalkyl, aryl. Further preferably, R is phenyl, alkyl-phenyl, haloalkyl-phenyl, carbazolyl, alkyl-carbazolyl, phenyl-carbazolyl, phenothiazinyl, alkyl-phenothiazinyl; r' is phenyl, alkyl phenyl, carbazolyl, alkyl-carbazolyl or phenyl-carbazolyl.

According to the present invention, the specific structure of the ionic phosphorescent metal complex is preferably as follows:

the invention also provides a preparation method of the phosphorescent complex of the formula (I), which comprises the following steps: 1) mixing rac- (PPh)₂CH₂PPhCH₂-)₂And Pt (PPh)₃)₂(C≡CR)₂Reacting in a solvent to obtain an intermediate; 2) then the intermediate obtained in the step 1) is reacted with [ Ag (tht ]](A^n-) And PR'₃Reacting in a solvent to obtain the phosphorescent complex of the formula (I). Wherein the tht (tetrahydrothiophene) is tetrahydrothiophene, and A is^n-R, R', X are as defined above.

The invention also provides a preparation method of the phosphorescent complex of the formula (II), which comprises the following steps: A) mixing meso- (PPh)₂CH₂PPhCH₂-)₂And Pt (PPh)₃)₂(C≡CR)₂Reacting in a solvent to obtain an intermediate; B) prepared from PR'₃、ⁿBu₄NX、[Ag(tht)](A^m-) Andreacting the intermediate obtained in the step A) in a solvent to obtain the phosphorescent complex shown in the formula (II). Wherein the tht (tetrahydrothiophene) is tetrahydrothiophene, and A is^m-R, R', X are as defined above.

According to the invention, in step 1), step a), the solvent is preferably a halogenated hydrocarbon, for example dichloromethane. Preferably, the intermediate obtained from the reaction is concentrated and recrystallized.

According to the invention, in step 2), step B), the solvent is preferably a halogenated hydrocarbon, for example dichloromethane. Preferably, PR 'is firstly performed in the step B)'₃AndⁿBu₄NX, mixing the mixed solution with [ Ag (tht) ]](A^m-) Adding to a solution in which the intermediate obtained in step A) above is dissolved.

According to the invention, in the process, rac- (PPh)₂CH₂PPhCH₂-)₂：Pt(PPh₃)₂(C≡CR)₂：[Ag(tht)](A^n-):PR'₃The molar ratio of (a) is 1-1.5: 2-3, preferably 1:1:2: 2; meso- (PPh)₂CH₂PPhCH₂-)₂：Pt(PPh₃)₂(C≡CR)₂：[Ag(tht)](A^m-):ⁿBu₄NX:PR'₃The molar ratio of (a) is 1-1.5: 2-3: 1-1.5, and preferably 1:1:2:1: 1.

According to the invention, the reactions are all carried out at room temperature. Preferably, after the reaction is completed, the reaction product is separated and purified by silica gel column chromatography.

The phosphorescence complex of formula (I) or formula (II) has strong phosphorescence emission in solid and thin film, and the phosphorescence quantum yield is higher than 50% in the thin film; and the emitted light color distribution is wide, from sky blue to orange red. Therefore, the organic light emitting diode can be used as a light emitting layer doping body for preparing an organic light emitting diode.

The invention also provides the use of the phosphorescent complex for an organic light-emitting diode.

Furthermore, the invention also provides an organic light-emitting diode which comprises a light-emitting layer, wherein the light-emitting layer contains the phosphorescent complex shown in the formula (I) or the formula (II).

According to the present invention, in the light emitting layer, the phosphorescent complex of formula (I) of the present invention preferably accounts for 3 to 20% (weight percent) of all materials, more preferably 5 to 10%, and further preferably, the phosphorescent complex of formula (I) of the present invention is doped into the host material as a light emitting layer in a weight percent of 6%; the phosphorescent complex of formula (II) of the present invention preferably accounts for 5-25% (wt%) of all materials, more preferably 8-15%, and further preferably, the phosphorescent complex of formula (II) of the present invention is doped into the host material as a light emitting layer in a weight percentage of 10%.

According to the present invention, the structure of the organic light emitting diode may be various structures known in the art. Preferably, the method comprises the following steps: an anode layer, a hole injection layer, optionally a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, a cathode layer. The organic light emitting diode further includes a substrate (e.g., a glass substrate). The anode may be indium tin oxide and the hole injection layer may be PEDOT: PSS (PEDOT: PSS ═ poly (3, 4-ethylenedioxythiophene) -poly (styrenesulfonic acid)). The hole transport layer may be CuSCN, CuI, CuBr. The light-emitting layer contains the phosphorescent complex of the present invention, and a substance having a hole-transporting property and/or a substance having an electron-transporting property. The substance having a hole-transporting property may be one or more of 2,6-DCZPPY (2, 6-bis (3- (9-carbazole) phenyl) pyridine), mCP (1, 3-bis (9-carbazolyl) benzene), CBP (4,4 '-bis (9-carbazole) -1,1' -biphenyl), or TCTA (tris (4- (9-carbazole) phenyl) amine). The substance having electron transport properties may be OXD-7(1, 3-bis (5- (4- (tert-butyl) phenyl) -1,3, 4-oxadiazol-2-yl) benzene); the electron transport layer may be one or more of BmPyPB (3,3 ", 5, 5" -tetrakis (3-pyridyl) -1,1':3',1 "-terphenyl), TPBi (1,3, 5-tris (1-phenyl-1H-benzo [ d ] imidazol-2-yl) benzene), BCP (2, 9-dimethyl-4, 7-diphenyl-1, 10-phenanthroline), or OXD-7; the electron injection layer is LiF, and the cathode is Al.

According to the invention, the device structure containing the phosphorescent complex of formula (I) is preferably: ITO/PEDOT PSS (50nm)/CuSCN (30 nm)/70.5% 2, 6-DCZPy 23.5% OXD-7: 6% wt Complex of formula (I) (50nm)/BmPy PB (50nm)/LiF (1nm)/Al (100nm), or ITO/PEDOT PSS (50 nm)/70.5% OmCP 23.5% OXD-7: 6% wt Complex of formula (I) (50nm)/BmPy PB (50nm)/LiF (1nm)/Al (100 nm); the device structure containing the phosphorescent complex of formula (II) is preferably: ITO/PEDOT PSS (50nm)/CuSCN (30 nm)/90% 2, 6-DCZPy 10% wt of the complex of formula (II) according to the invention (50nm)/BmPy (50nm)/LiF (1nm)/Al (100nm), or ITO/PEDOT PSS (50 nm)/90% mCP 10% wt of the complex of formula (II) according to the invention (50nm)/BmPy (50nm)/LiF (1nm)/Al (100 nm). Wherein ITO is indium tin oxide conductive film, PEDOT is PSS is poly (3, 4-ethylenedioxythiophene) -poly (styrenesulfonic acid), 2,6-DCZPPY is (2, 6-bis (3- (9-carbazolyl) phenyl) pyridine), 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, BmPb is (3, 3', 5,5 ' -tetra (3-pyridyl) -1,1':3', 1' -terphenyl).

The present invention also provides a method of preparing the organic light emitting diode, comprising: 1) preparing a hole injection layer in the organic light-emitting diode on the anode by adopting a solution method; 2) optionally preparing a hole transport layer in the organic light emitting diode by adopting a solution method; 3) preparing a luminescent layer doped with the phosphorescent complex by a solution method; 4) and preparing the electron transport layer, the electron injection layer and the cathode layer by sequentially utilizing a vacuum thermal evaporation method.

In a preferred embodiment, for the phosphorescent complex of formula (I), the method comprises: firstly, preparing a hole injection layer by using water-soluble PEDOT (PSS); secondly, preparing a hole transport layer by using a diethyl sulfide solution of cuprous thiocyanate; then 2, 6-DCZPy with hole transport property and OXD-7 with electron transport property are used as mixed main materials to be doped with the phosphorescence complex with the formula (I) to prepare a luminescent layer; preparing a Bmpypb electron transport layer, a LiF electron injection layer and an Al cathode layer by using a vacuum thermal evaporation method in sequence; for the phosphorescent complex of formula (II), the method comprises: firstly, preparing a hole injection layer by using water-soluble PEDOT (PSS); secondly, preparing a hole transport layer by using a diethyl sulfide solution of cuprous thiocyanate; doping 2,6-DCZPPY with hole transport property and the phosphorescence complex with the formula (II) to prepare a luminescent layer; and then preparing the Bmpypb electron transport layer, the LiF electron injection layer and the Al cathode layer by using a vacuum thermal evaporation method in sequence.

According to the invention, in the method, the ratio of PEDOT to PSS hole injection layer, 2,6-DCZPPY: the OXD-7 or 2, 6-DCZPyP doped luminescent layer is respectively prepared into a film by a solution spin coating method, and the BmPyPB electron transport layer and the LiF electron injection layer are prepared into the film by a vacuum thermal evaporation method.

The organic light-emitting diode prepared from the phosphorescent complex has excellent performance and higher electric-optical conversion efficiency.

The invention further provides the application of the organic light-emitting diode, which can be used in the fields of flat panel display and daily illumination.

Compared with the prior art, the invention has the following advantages:

1) the phosphorescence complex of the invention has strong phosphorescence emission in solid and thin film, and the phosphorescence quantum efficiency of the thin film is higher than 50% and even up to 90%;

2) the invention utilizes the phosphorescent Pt-Ag dissimilar metal complex as the luminescent material to assemble the organic luminescent device for the first time, and the organic light-emitting diode prepared by using the phosphorescent complex as the luminescent layer dopant has high electroluminescent external quantum conversion efficiency;

3) the hole injection layer and the light-emitting layer of the organic light-emitting diode are prepared by an orthogonal solution method, so that the preparation cost of the device can be greatly reduced;

4) the ligand of the phosphorescence complex has different configurations of internal/racemic, the electroluminescence changes from sky blue to orange red, and the luminous efficiency of each color is higher.

Description of the drawings:

fig. 1 is a schematic view of a device structure and a chemical structure diagram of an organic material.

The specific implementation mode is as follows:

in order to make the objects, technical solutions and technical effects of the present invention more clear, the present invention is further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the embodiments described in this specification are only for the purpose of illustrating the present invention and are not to be construed as limiting the present invention.

In the following examples dpmppe stands for (PPh)₂CH₂PPhCH₂-)₂Carb represents carbazolyl, PhBu^t-4 represents 4-tert-butyl-phenyl, 9-Ph-carb-3 represents 9-phenyl-carbazol-3-yl, 9-Et-carb-3 represents 9-ethylcarbazol-3-yl, PhCF₃-4 represents 4-trifluoromethyl-phenyl, 9- (4-Ph) -carb represents 9- (4-phenyl) -carbazolyl, 10-Et-PTZ-3 represents 10-ethylphenothiazin-3-yl, tht is tetrahydrothiophene.

Example 1: complex [ PtAg₂(rac-dpmppe)(C≡CC₆H₄Bu^t-4)₂{PhP(9-Ph-carb-3)₂}₂](ClO₄)₂Preparation of (rac-1)

To 20mL of Pt (PPh)₃)₂(C≡CC₆H₄Bu^t-4)₂(80.6mg,0.078mmol) in dichloromethane was added rac-dpmppe (50mg,0.078 mmol). After stirring for 30 minutes, the mixture was concentrated, and 20mL of n-hexane was added to precipitate a pale yellow solid as an intermediate in a yield of 90% (80.8 mg). To 20mL of a methylene chloride solution in which the above intermediate was dissolved, Ag (tht) ClO was added₄(41.4mg,0.14mmol) and PhP (9-Ph-carb-3)₂(82.9mg,0.14mmol), and the reaction mixture was stirred at room temperature for 1 hour and turned pale green. Purifying the product by silica gel column chromatography using CH₂Cl₂MeCN (8:1) collects the light green product as eluent. Yield: 70 percent. Elemental analysis (C)₁₄₈H₁₂₂Ag₂Cl₂N₄O₈P₆Pt) Calculations C, 64.59; h, 4.47; n,2.04, measurement C, 64.40; h, 4.55; n,1.96 electrospray mass spectrum M/z (%): 1276.2909(100) [ M-2 ClO%₄]²⁺Nuclear magnetic resonance hydrogen spectroscopy (CDCl)₃,ppm):8.20-8.14(dd,4H,J₁＝16Hz，J₂＝12Hz),8.08-8.04(dd,4H,J₁＝12Hz,J₂8Hz),7.73-7.59(m,12H),7.53-7.35(m,36H),7.27-7.11(m,20H),6.95-6.88(m,12H),6.69-6.67(d,4H, J ═ 8Hz),6.59-6.57(d,4H, J ═ 8Hz),4.29(m,2H),3.02-2.93(3,2H),2.63-2.46(m,2H),0.97(s,18H),0.54(m,2H), nuclear magnetic resonance phosphorus spectrum (CDCl)₃,ppm):46.0(d,2P,J_P-P＝78Hz,J_Pt-P＝2448Hz),13.8(m,2P,J_P-Ag＝526Hz),1.8(m,2P,J_P-Ag＝526Hz,J_P-PInfrared spectrum (KBr, cm) ·^-1):2081w(C≡C),1099s(ClO₄ ^-)。

Example 2: complex [ PtAg₂(rac-dpmppe){(C≡C-4)C₆H₄-carb-9}₂(PPh₃)₂](ClO₄)₂Preparation of (rac-2)

The preparation method is basically the same as that in example 1, except that Pt (PPh) is used₃)₂{(C≡C-4)C₆H₄-carb-9}₂Substitution of Pt (PPh)₃)₂(C≡CC₆H₄Bu^t-4)₂，PPh₃Alternative PhP (9-Ph-carb-3)₂. The yield was 71%. Elemental analysis (C)₁₁₆H₉₂Ag₂Cl₂N₂O₈P₆Pt) Calculations C, 60.33; h, 4.02; n,1.21, measurement C, 60.12; h, 4.02; n,1.15 electrospray mass spectrum M/z (%) 1055.1713 (100%, [ M-2ClO ]₄]²⁺) Nuclear magnetic resonanceHydrogen spectrum (CDCl3, ppm):8.21-8.13(m,8H),7.59-7.54(m,14H),7.48-7.14(m,18H),7.34-7.24(m,22H),7.20-7.12(m,14H),7.02-6.98(m,4H),6.86-6.85(d,4H, J ═ 7Hz),4.59(m,2H),3.15-3.06(m,2H),2.73-2.59(m,2H),0.61(m,2H). Nuclear magnetic resonance phosphorus Spectrum (CDCl) in the form of particles₃,ppm):47.0(d,2P,J_P-P＝76Hz,J_Pt-P＝2375Hz),11.8(m,2P,J_P-Ag＝506Hz),3.4(m,2P,J_P-Ag＝410Hz,J_P-PIr spectrum (KBr, cm) ·^-1):2091w(C≡C),1099s(ClO₄ ^-).

Example 3: complex [ PtAg₂(rac-dpmppe){C≡C-(9-Ph-carb-3)}₂(PPh₃)₂](ClO₄)₂Preparation of (rac-3)

The preparation method is basically the same as that in example 1, except that Pt (PPh) is used₃)₂(C≡C-(9-Ph-carb-3))₂Substitution of Pt (PPh)₃)₂(C≡CC₆H₄Bu^t-4)₂，PPh₃Alternative PhP (9-Ph-carb-3)₂. The yield was 71%. Elemental analysis (C)₁₁₆H₉₂Ag₂Cl₂N₂O₈P₆Pt) Calculations C, 60.33; h, 4.02; n,1.21, measurement C, 60.10; h, 4.05; n,1.16 electrospray mass spectrum M/z (%) 1055.1717 (100%, [ M-2ClO ]₄]²⁺) Nuclear magnetic resonance hydrogen spectroscopy (CDCl)₃,ppm):8.17-8.12(dd,4H,J₁＝12Hz,J₂8Hz),7.67-7.63(t,4H, J-8 Hz),7.54-7.46(m,22H),7.43-7.40(m,8H),7.37-7.31(m,10H),7.29-7.18(m,10H),7.13-7.03(m,20H),6.95-6.92(m,4H),6.83-6.81(d,2H),4.45(m,2H),3.18-3.09(m,2H),2.69-2.50(m,2H),0.59(m,2H), nuclear magnetic resonance phosphorus spectrum (CDCl)₃,ppm):46.3(d,2P,J_P-P＝75Hz,J_Pt-P＝2384Hz),11.9(m,2P,J_P-Ag＝510Hz),2.4(m,2P,J_P-Ag＝398Hz,J_P-P51 Hz.) infrared spectrum (KBr, cm)^-1):2075w(C≡C),1093s(ClO₄ ^-).

Example 4: complexes

[PtAg₂(rac-dpmppe)(C≡C-(9-Ph-carb-3))₂{P(9-Et-carb-3)₃}₂](ClO₄)₂(rac-4) preparation.

The preparation method is basically the same as that in example 1, except that Pt (PPh) is used₃)₂{C≡C-(9-Ph-carb-3)}₂Substitution of Pt (PPh)₃)₂(C≡CC₆H₄-Bu^t-4)₂，P(9-Et-carb-3)₃Alternative PhP (9-Ph-carb-3)₂. The yield was 71%. Elemental analysis (C)₁₆₄H₁₃₄Ag₂Cl₂N₈O₈P₆Pt) Calculations C, 65.39; h, 4.48; n,3.72, measurement C, 65.14; h, 4.53; n,3.53 electrospray mass spectrum M/z (%): 1406.8446[ M-2ClO₄]²⁺Nuclear magnetic resonance hydrogen spectroscopy (CDCl)₃,ppm):8.27-8.22(dd,4H,J₁＝12Hz,J₂＝8Hz),8.20-8.17(d,6H,J＝12Hz),8.04-7.99(dd,6H,J₁＝12Hz,J₂8Hz),7.71(s,2H),7.50-7.40(m,16H),7.37-7.32(m,12H),7.27-7.25(m,10H),7.17-7.14(m,6H),7.07-7.03(t,2H, J ═ 7Hz),7.0-6.90(m,12H),6.88-6.77(m,16H),6.73-6.66(m,4H),4.4(m,2H),3.88-3.83(q,12H, J ═ 7Hz),3.27-3.18(m,2H),2.62-2.44(m,2H),1.0-0.97(d,18H, J ═ 7Hz),0.72(m,2H), phosphorus nuclear magnetic resonance spectrum (cl), 0.72(m,2H)₃,ppm):46.5(d,2P,J_P-P＝78Hz,J_Pt-P＝2380Hz),15.3(m,2P,J_P-Ag＝534Hz),0.8(m,2P,J_P-Ag＝378Hz,J_P-P53Hz) infrared spectrum (KBr, cm)^-1):2081w(C≡C),1093s(ClO₄ ^-)。

Example 5: complexes

[PtAg₂(rac-dpmppe){C≡C-(9-Et-carb-3)}₂{P(9-Et-carb-3)₃}₂](ClO₄)₂(rac-5) preparation.

The preparation method is basically the same as that in the example 1,using only Pt (PPh)₃)₂{C≡C-(9-Et-carb-3)}₂Substitution of Pt (PPh)₃)₂(C≡CC₆H₄Bu^t-4)₂，P(9-Et-carb-3)₃Alternative PhP (9-Ph-carb-3)₂. The yield is 72%. Elemental analysis (C)₁₅₆H₁₃₄Ag₂Cl₂N₈O₈P₆Pt) Calculations C, 64.25; h, 4.63; n,3.84, measurement C, 64.02; h, 4.65; n,3.58 electrospray mass spectrum M/z (%): 1358.3459 (100%) [ M-2ClO ]₄]²⁺Nuclear magnetic resonance hydrogen spectroscopy (CDCl)₃8.25-8.16(m,8H),8.01(m,6H),7.73-7.68(m,10H),7.44-7.27(m,28H),7.18-7.02(m,10H),6.94-6.82(m,22H),6.70-6.64(m,4H),4.33(m,2H),4.05-3.99(q,4H, J ═ 7Hz),3.85-3.79(q,12H, J ═ 7Hz),3.26-3.22(m,2H),2.64-2.51(m,2H),1.29-1.15(t,6H, J ═ 7Hz),1.11-0.97(t,18H, J ═ 7Hz),0.71(m,2H), phosphorus (cl) (CDCl), etc₃,ppm):46.2(d,2P,J_P-P＝78Hz,J_Pt-P＝2376Hz),15.3(m,2P,J_P-Ag＝524Hz),0.6(m,2P,J_P-Ag＝369Hz,J_P-P52Hz) infrared spectrum (KBr, cm)^-1)(KBr,cm^-1):2073w(C≡C),1093s(ClO₄ ^-)。

Example 6: complex [ PtAg₂(rac-dpmppe){C≡C-(10-Et-PTZ-3)}₂{P(9-Et-carb-3)₃}₂](ClO₄)₂(rac-6).

The preparation method is basically the same as that in example 1, except that Pt (PPh) is used₃)₂{C≡C-(10-Et-PTZ-3)}₂Substitution of Pt (PPh)₃)₂(C≡CC₆H₄Bu^t-4)₂，P(9-Et-carb-3)₃Alternative PhP (9-Ph-carb-3)₂. The yield was 73%. Elemental analysis (C)₁₅₆H₁₃₄Ag₂Cl₂N₈O₈P₆PtS₂) Calculated value C, 62.86; h, 4.53; n,3.76. measurement C, 62.62; h, 4.57; n,3.59 electrospray mass spectrum M/z (%): 1390.8150 (100%) [ M-2ClO ]₄]²⁺Nuclear magnetic resonance hydrogen spectroscopy (CDCl)₃8.16-8.13(m,8H),8.01-7.96(dd,6H, J ═ 8Hz),7.58-7.55(m,6H),7.42-7.38(m,12H),7.34-7.30(m,8H),7.15-6.99(m,22H),6.90-6.86(m,14H),6.69-6.67(d,2H, J ═ 8Hz),6.54-6.52(d,2H, J ═ 8Hz),6.35-6.32(m,4H),5.92-5.90(d,2H, J ═ 8Hz),4.23(m,2H),4.05-3.99(q,12H, J ═ 7Hz),3.45-3.39(q,4H, 7J ═ 8Hz), 3.7.06-3.7H, 7J ═ 1.59 (m, 1H, 6H, 8Hz, 2H) nuclear magnetic resonance phosphorus spectrum (CDCl)₃,ppm):46.5(d,2P,J_P-P＝78Hz,J_Pt-P＝2376Hz),15.2(m,2P,J_P-Ag＝536Hz),1.5(m,2P,J_P-Ag＝381Hz,J_P-P54Hz) infrared spectrum (KBr, cm)^-1):2081w(C≡C),1093s(ClO₄ ^-)。

Example 7: complex [ PtAg₂(meso-dpmppe)(C≡CC₆H₄CF₃-4)₂(PPh₃)Cl](ClO₄) (meso-7) preparation.

To 20mL of Pt (PPh)₃)₂(C≡CC₆H₄CF₃-4)₂To a solution of (82.5mg,0.078mmol) in dichloromethane was added meso-dpmppe (50mg,0.078 mmol). After stirring for 30 minutes, the mixture was concentrated, and 20mL of n-hexane was added to precipitate a pale yellow solid as an intermediate in a yield of 90% (82.4 mg). Mixing PPh first₃(18.3mg,0.07mmol) andⁿBu₄NCl (19.5mg,0.07mmol), mixing the mixed solution with Ag (tht) ClO₄(41.4mg,0.14mmol) was added to a dichloromethane solution in which the above intermediate was dissolved, and the reaction solution was stirred at room temperature for 1 hour and then turned pale blue. Purifying the product by silica gel column chromatography using CH₂Cl₂MeCN (15:1) as eluent collected the yellow product. Yield: 75 percent. Elemental analysis (C)₇₆H₆₁Ag₂Cl₂F₆O₄P₅Pt) calculated as C, 51.03; h,3.44 measured C, 51.21; h,3.60. electrospray mass spectrometry m/z (%): 1688.0808 (100%, [ M-ClO ]₄]⁺) Nuclear magnetic resonance hydrogen spectroscopy (CDCl)₃,ppm):8.03-7.96(m,8H),7.59-7.36(m,22H),7.33-7.29(t,4H, J ═ 7Hz),7.25-7.17(m,11H),6.92-6.89(m,4H),6.65-6.62(m,4H),3.86(m,2H),3.37(m,2H),2.28-2.11(m,4H), nuclear magnetic resonance phospho-spectrum (CDCl)₃,ppm):47.6(dd,2P,J_P-P＝30Hz,J_Pt-P＝2412Hz),7.6(m,1P,J_P-Ag＝579Hz),-8.9(m,2P,J_P-Ag＝422Hz,J_P-P59Hz) infrared spectrum (KBr, cm)^-1):2092w(C≡C),1104s(ClO₄ ^-).

Example 8: complex [ PtAg₂(meso-dpmppe)(C≡CC₆H₄Bu^t-4)₂(PPh₃)Cl](ClO₄) (meso-8) preparation.

The preparation method is basically the same as that in example 7, except that Pt (PPh) is used₃)₂(C≡CC₆H₄Bu^t-4)₂Substitution of Pt (PPh)₃)₂(C≡CC₆H₄CF₃-4)₂. The yield was 74%. Elemental analysis (C)₈₂H₇₉Ag₂Cl₂O₄P₅Pt) calculated as C, 55.80; h,4.51 measured C, 56.02; h,4.74 electrospray mass spectrometry m/z (%): 1665.2304 (100%, [ M-ClO ]₄]⁺) Nuclear magnetic resonance hydrogen spectroscopy (CDCl)₃Ppm) 8.03-7.97(m,8H),7.53-7.50(m,7H),7.41-7.31(m,20H),7.24-7.16(m,12H),6.71-6.59(m,8H),3.81(m,2H),3.46(m,2H),2.18-2.01(m,4H),1.45(s,18H). Nuclear magnetic resonance phosphorus Spectroscopy (CDCl)₃,ppm):47.1(q,2P,J_P-P＝30Hz,J_Pt-P＝2409Hz),7.2(m,1P,J_P-Ag＝565Hz),-9.5(m,2P,J_P-Ag＝417Hz,J_P-P58Hz) infrared spectrum (KBr, cm)^-1):2092w(C≡C),1093s(ClO₄ ^-).

Example 9: complex [ PtAg₂(meso-dpmppe)(C≡CC₆H₄Bu^t-4)₂{P(9-Et-carb-3)₃}Cl](ClO₄) (meso-9) preparation.

The preparation method is basically the same as that in example 7, except that Pt (PPh) is used₃)₂(C≡CC₆H₄Bu^t-4)₂Substitution of Pt (PPh)₃)₂(C≡CC₆H₄CF₃-4)₂，P(9-Et-carb-3)₃Substitution of PPh₃. The yield was 74%. Elemental analysis (C)₁₀₆H₁₀₀Ag₂Cl₂N₃O₄P₅Pt) Calculations C, 60.15; h, 4.76; n,1.99, measurement C, 60.32; h, 4.73; n,1.88 electrospray mass spectrometry m/z (%): 2016.4011 (100%, [ M-ClO ]₄]⁺) Nuclear magnetic resonance hydrogen spectroscopy (CDCl)₃,ppm):8.48-8.45(d,2H,J＝12Hz),8.08-8.04(dd,4H,J₁＝12Hz,J₂8Hz),7.94-7.92(d,2H, J-8 Hz),7.89(m,4H),7.53-7.41(m,26H),7.25-7.15(m,13H),6.61-6.59(m,4H),6.40-6.38(m,4H),4.41-4.37(q,6H, J-7 Hz),3.76(m,2H),3.49(m,2H),2.24-2.05(m,4H),1.49-1.47(t,9H, J-7 Hz),0.76(s,18H), nuclear magnetic resonance phosphorus spectrum (CDCl)₃,ppm):47.5(q,2P,J_P-P＝29Hz,J_Pt-P＝2394Hz),10.4(m,1P,J_P-Ag＝601Hz),-9.3(m,2P,J_P-Ag＝417Hz,J_P-P56Hz) infrared spectrum (KBr, cm)^-1):2110w(C≡C),1093s(ClO₄ ^-).

Example 10: complex [ PtAg₂(meso-dpmppe)(C≡CC₆H₄Bu^t-4)₂{P(9-Et-carb-3)₃}I](ClO₄) (meso-10) preparation.

The preparation method is basically the same as that in example 7, except that Pt (PPh) is used₃)₂(C≡CC₆H₄Bu^t-4)₂Substitution of Pt (PPh)₃)₂(C≡CC₆H₄CF₃-4)₂，P(9-Et-carb-3)₃Substitution of PPh₃，ⁿBu₄NI substitutionⁿBu₄NCl. The yield is 72%. Elemental analysis (C)₁₀₆H₁₀₀Ag₂ClIN₃O₄P₅Pt) Calculations C, 57.66; h, 4.56; n,1.90, measurement C, 57.57; h, 4.60; n,1.83 electrospray mass spectrum M/z (%) 2108.3387 (100%, [ M-ClO ]₄]⁺) Nuclear magnetic resonance hydrogen spectroscopy (CDCl)₃,ppm):8.51-8.48(d,2H,J＝12Hz),8.11-8.07(dd,4H,J₁＝12Hz,J₂8Hz),7.98-7.96(d,2H, J-8 Hz),7.82(m,4H),7.54-7.40(m,26H),7.29-7.16(m,13H),6.54-6.52(m,4H),6.37-6.35(m,4H),4.39-4.35(q,6H, J-7 Hz),3.71(m,2H),3.52(m,2H),2.25-2.05(m,4H),1.49-1.47(t,9H, J-7 Hz),0.72(s,18H), nuclear magnetic resonance phosphorus spectrum (CDCl)₃,ppm):48.5(q,2P,J_P-P＝30Hz,J_Pt-P＝2391Hz),9.0(m,1P,J_P-Ag＝547Hz),-11.7(m,2P,J_P-Ag＝386Hz,J_P-P59Hz) infrared spectrum (KBr, cm)^-1):2104w(C≡C),1093s(ClO₄ ^-)。

Example 11: complex [ PtAg₂(meso-dpmppe)(C≡C-(10-Et-PTZ-3))₂{P(9-Et-carb-3)₃}(μ-I)](ClO₄) (meso-11) preparation.

The preparation method is basically the same as that in example 7, except that Pt (PPh) is used₃)₂{C≡C-(10-Et-PTZ-3)}₂Substitution of Pt (PPh)₃)₂(C≡CC₆H₄CF₃-4)₂，P(9-Et-carb-3)₃Substitution of PPh₃，ⁿBu₄NI substitutionⁿBu₄NCl. Yield: 75 percent. Elemental analysis (C)₁₁₄H₉₈Ag₂ClIN₅O₄P₅PtS₂) Calculated value C, 57.19; h, 4.13; n,2.93, measurement C, 57.42; h, 4.33; n,2.84 electrospray mass spectrum M/z (%) 2294.2671 (100%, [ M-ClO ]₄]⁺) Nuclear magnetic resonance hydrogen spectroscopy (CDCl)₃,ppm):8.54-8.51(d,2H,J＝12Hz),8.09-8.04(dd,4H,J₁＝12Hz,J₂＝8Hz),7.95-7.93(d,2H,J＝8Hz),7.80(m,4H),7.59-7.29(m,29H),7.18-7.01(m,12H),6.75(m,4H),6.51-6.49(d,2H,J＝8Hz),6.41-6.39(d,2H,J＝8Hz),6.22(s,2H),5.63-5.61(d,2H,J＝8Hz),4.45-4.27(q,6H,J＝7Hz),3.71(m,2H),3.46(m,2H) 3.14-3.08(q,4H, J ═ 6Hz),2.28-2.03(m,4H),1.44-1.40(t,9H, J ═ 7Hz),0.86-0.81(t,6H, J ═ 6Hz)₃,ppm):48.6(q,2P,J_P-P＝29Hz,J_Pt-P＝2391Hz),9.1(m,1P,J_P-Ag＝548Hz),-11.4(m,2P,J_P-Ag＝384Hz,J_P-P60Hz) infrared spectrum (KBr, cm)^-1):2101w(C≡C),1094s(ClO₄ ^-)。

Example 12: measurement of photoluminescent Property

The complexes rac-1, rac-4, rac-5, rac-6 prepared in examples 1, 4, 5, 6 were tested on an Edinburgh FLS920 fluorescence spectrometer for excitation spectrum, emission spectrum, luminescence lifetime and luminescence quantum yield, respectively, in solid powder and 70.5% 2,6-DCZPP Y: 23.5% OXD-7: 6% complex rac-1, 4, 5, or 6 (by weight) thin film and in solid powder and 90% 2,6-DCZPP Y: 10% complex meso-11 (by weight) thin film, complex meso-11 prepared in example 11. The luminescence quantum yield of the solid powder sample was measured using an integrating sphere having a diameter of 142 mm.

The solid state emission wavelength and quantum yield of the complex rac-1, rac-4, rac-5, rac-6, or meso-11 were 500nm and 15.1% (rac-1), 566nm and 37.1% (rac-4), 580nm and 30.4% (rac-5), 662nm and 1.7% (rac-6), 600nm and 8.1% (meso-11), respectively;

complexes rac-1, rac-4, rac-5, or rac-6 emission wavelengths and quantum yields in 70.5% 2,6-DCZPP 23.5% OXD-7: 6% films of complexes rac-1, 4, 5, or 6 of the invention (by weight) were 487nm and 52.2% (rac-1), 527nm and 90.5% (rac-4), 535nm and 77.0% (rac-5), 616nm and 56.8% (rac-6), respectively; the emission wavelength and quantum yield of the complex meso-11 in a 90% 2,6-DCZPPY: 10% film of the complex meso-11 of the present invention (by weight) were 570nm and 52.2% (meso-11), respectively.

Example 13: preparation of organic light-emitting diode device and electroluminescent performance test

An organic light emitting diode was prepared by doping 6% by weight of phosphorescent complexes rac-1, rac-4, rac-5 or rac-6 prepared in examples 1, 4, 5 and 6, respectively, as light emitting materials into a 2, 6-DCZPy (70.5%) oxD-7 (23.5%) mixed host material as a light emitting layer, and the device structure was: ITO/PEDOT PSS (50nm)/CuSCN (30 nm)/70.5% 2,6-DCZPPY 23.5% OXD-7: 6% complex of the invention rac-1, 4, 5, or 6(50nm)/Bmpypb (50nm)/LiF (1nm)/Al (100 nm); the phosphorescent complex meso-11 prepared in example 11 is a light emitting material doped into a 2,6-DCZPPY (90%) host material in a weight percentage of 10% to prepare an organic light emitting diode as a light emitting layer, and the device structure is as follows: ITO/PEDOT PSS (50nm)/CuSCN (30 nm)/90% 2,6-DCZPPY 10% meso-11(50nm)/Bmpypb (50nm)/LiF (1nm)/Al (100nm) of the complex of the invention.

Firstly, respectively cleaning an ITO substrate by using deionized water, acetone and isopropanol, then treating for 15 minutes by using UV-ozone, spin-coating filtered PEDOT: PSS aqueous solution on the ITO substrate at the rotating speed of 4800 r/min on a spin coater, drying for 20 minutes at 140 ℃ to obtain a hole injection layer with the thickness of 50nm, then spin-coating CuSCN diethyl sulfide solution (10mg/mL) on the PEDOT: PSS hole injection layer at the rotating speed of 4800 r/min, drying for 30 minutes at 120 ℃ to obtain a hole transport layer with the thickness of 30nm, then using the spin coater to filter 70.5 mg/mL of 70.5% 2,6-DCZPP with the concentration of 5.5mg/mL, 23.5% XD-7: 6% of the complex rac-1, rac-4, rac-5 or rac-6 (weight percentage) or 5.5mg/mL of 90% 2,6-DCZP with the concentration of 5.5mg/mL, 10% of the complex meso-11 (weight percentage) of the complex of the invention, and then placing the filtered PEDOT: PSS aqueous solution on the substrate at the rotating speed of not less than 2100 minutes to form a light emitting layer, and then spin-coating the film^{- 4}And in a vacuum cavity of Pa, thermally evaporating 50 nm-thick Bmpypb, 1 nm-thick LiF electron injection layer and 100 nm-thick Al as device cathodes.

The performance test of the light-emitting diode device is carried out in a room-temperature dry air environment. The electroluminescent property parameter comprises electroluminescent wavelength (lambda)_EL) Starting voltage (V)_on) Maximum luminance (L)_max) Maximum Current Efficiency (CE)_max) Maximum Power Efficiency (PE)_max) Maximum External Quantum Efficiency (EQE)_max) Are shown in Table 1.

TABLE 1 Performance data for the inventive phosphorescent complexes rac-1, rac-4, rac-5, rac-6, or meso-11 electroluminescent devices

^a)Luminance of 1cd/m²The lighting voltage of the lighting circuit is set to be,^b)the maximum brightness of the light emitted from the light source,^c)the efficiency of the maximum current is set to be,^d)the efficiency of the maximum power is improved,^e)maximum external quantum efficiency, CIE, chromaticity coordinates.

Claims (10)

1. An ionic phosphorescent metal complex with a racemic structure, which has a structure shown as the following formula (I) or formula (II):

[PtAg₂{rac-(PPh₂CH₂PPhCH₂-)₂}(C≡CR)₂(PR'₃)₂]²⁺A^n- _2/n； (I)

or

[PtAg₂{meso-(PPh₂CH₂PPhCH₂-)₂}(C≡CR)₂(PR'₃)(μ-X)]⁺ _mA^m-(II)

Wherein the content of the first and second substances,

r, which may be the same or different, is independently selected from: alkyl, aryl, heteroaryl, heteroarylaryl,

r', which may be the same or different, is independently selected from: alkyl, aryl, heteroaryl;

the alkyl, aryl and heteroaryl can be substituted by one or more substituents selected from alkyl, alkenyl, alkynyl, alkoxy, amino, halogen, haloalkyl and aryl;

x is selected from halogen;

A^m-、A^n-is a monovalent or divalent anion, m or n is 1, 2, the anion is, for example, ClO₄ ^-、PF₆ ^-、SbF₆ ^-、BF₄ ^-、SiF₆ ^2-Etc., μ represents a bridge.

2. The phosphorescent metal complex of claim 1, wherein the formula (I) or formula (II) phosphorescent metal complex has a steric structure as follows:

。

3. the phosphorescent metal complex of claim 1 or 2, wherein R is preferably an aryl group, a carbazolyl group, a phenothiazinyl group, a carbazolylalkyl group; the aryl, carbazolyl, phenothiazinyl group may be optionally substituted with one or more substituents selected from the group consisting of alkyl, alkoxy, amino, halo, haloalkyl, aryl; preferably, R' is aryl, a nitrogen-containing heterocycle (e.g., carbazolyl), which may be optionally substituted with one or more substituents selected from the group consisting of alkyl, alkoxy, amino, halo, haloalkyl, aryl; further preferably, R is phenyl, alkyl-phenyl, haloalkyl-phenyl, carbazolyl, alkyl-carbazolyl, phenyl-carbazolyl, phenothiazinyl, alkyl-phenothiazinyl; r' is phenyl, alkyl phenyl, carbazolyl, alkyl-carbazolyl, phenyl-carbazolyl;

further preferably, the metal complex is specifically 11 complexes as follows:

。

4. the method for preparing a phosphorescent metal complex of any one of claims 1 to 3, wherein the method for preparing the phosphorescent metal complex of formula (I) comprises the steps of: 1) mixing rac- (PPh)₂CH₂PPhCH₂-)₂And Pt (PPh)₃)₂(C≡CR)₂Reacting in a solvent to obtain an intermediate; 2) then the intermediate obtained in the step 1) is reacted with [ Ag (tht ]](A^n-) And PR'₃Reacting in a solvent to obtain the phosphorescent complex shown in the formula (I); wherein the tht (tetrahydrothiophene) is tetrahydrothiophene, and A is^n-R, R', X are as defined in any one of claims 1 to 3;

alternatively, the first and second electrodes may be,

the preparation method of the phosphorescent complex of the formula (II) comprises the following steps: A) mixing meso- (PPh)₂CH₂PPhCH₂-)₂And Pt (PPh)₃)₂(C≡CR)₂Reacting in a solvent to obtain an intermediate; B) prepared from PR'₃、ⁿBu₄NX、[Ag(tht)](A^m-) Reacting with the intermediate obtained in the step A) in a solvent to obtain the phosphorescent complex shown in the formula (II); wherein the tht (tetrahydrothiophene) is tetrahydrothiophene, and A is^m-R, R', X are as defined in any one of claims 1 to 3;

preferably, in the step 1) and the step A), the solvent is halogenated hydrocarbon, such as dichloromethane;

preferably, in step 2) and step B), the solvent is preferably a halogenated hydrocarbon, such as dichloromethane.

5. Use of a phosphorescent metal complex as claimed in any of claims 1 to 3 for an organic light-emitting diode.

6. An organic light-emitting diode comprising a light-emitting layer, wherein the light-emitting layer contains the phosphorescent complex of formula (I) or formula (II) according to any one of claims 1 to 3;

preferably, in the light-emitting layer, the phosphorescent complex of formula (I) according to any one of claims 1 to 3 is preferably 3 to 20% (by weight), more preferably 5 to 10%, of all the materials, and further preferably, the phosphorescent complex of formula (I) is doped into the host material as a light-emitting layer at a weight percentage of 6%; the phosphorescent complex of formula (II) according to any one of claims 1 to 3 is preferably 5 to 25% by weight, more preferably 8 to 15% by weight, of all materials, and further preferably the phosphorescent complex of formula (II) is doped into a host material as a light emitting layer at a weight percentage of 10%.

7. The organic light emitting diode of claim 6, wherein the organic light emitting diode further comprises: an anode layer, a hole injection layer, optionally a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, a cathode layer.

8. The organic light emitting diode of claim 7, wherein the anode may be indium tin oxide and the hole injection layer may be PEDOT: PSS (PEDOT: PSS ═ poly (3, 4-ethylenedioxythiophene) -poly (styrenesulfonic acid)); the hole transport layer can be CuSCN, CuI or CuBr; the light-emitting layer contains the phosphorescent complex compound according to any one of claims 1 to 3, and a substance having a hole-transporting property and/or a substance having an electron-transporting property; wherein the substance having hole transport property may be one or more of 2,6-DCZPPY (2, 6-bis (3- (9-carbazole) phenyl) pyridine), mCP (1, 3-bis (9-carbazolyl) benzene), CBP (4,4 '-bis (9-carbazole) -1,1' -biphenyl), or TCTA (tris (4- (9-carbazole) phenyl) amine); the substance having electron transport properties may be OXD-7(1, 3-bis (5- (4- (tert-butyl) phenyl) -1,3, 4-oxadiazol-2-yl) benzene); the electron transport layer may be one or more of BmPyPB (3,3 ", 5, 5" -tetrakis (3-pyridyl) -1,1':3',1 "-terphenyl), TPBi (1,3, 5-tris (1-phenyl-1H-benzo [ d ] imidazol-2-yl) benzene), BCP (2, 9-dimethyl-4, 7-diphenyl-1, 10-phenanthroline), or OXD-7; the electron injection layer is LiF, and the cathode is Al.

Preferably, the structure of the device containing the phosphorescent complex of formula (I) is as follows: ITO/PEDOT PSS (50nm)/CuSCN (30 nm)/70.5% 2, 6-DCZPy 23.5% OXD-7: 6% wt Complex of formula (I) (50nm)/BmPy PB (50nm)/LiF (1nm)/Al (100nm), or ITO/PEDOT PSS (50 nm)/70.5% OmCP 23.5% OXD-7: 6% wt Complex of formula (I) (50nm)/BmPy PB (50nm)/LiF (1nm)/Al (100 nm);

preferably, the device structure containing the phosphorescent complex of formula (II) is: ITO/PEDOT PSS (50nm)/CuSCN (30 nm)/90% 2, 6-DCZPy 10% wt of the complex of formula (II) according to the invention (50nm)/BmPy (50nm)/LiF (1nm)/Al (100nm), or ITO/PEDOT PSS (50 nm)/90% mCP 10% wt of the complex of formula (II) according to the invention (50nm)/BmPy (50nm)/LiF (1nm)/Al (100 nm).

Wherein ITO is an indium tin oxide conductive film, PEDOT: PSS is poly (3, 4-ethylenedioxythiophene) -poly (styrenesulfonic acid), 2,6-DCZPPY is (2, 6-bis (3- (9-carbazolyl) phenyl) pyridine), 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, BmPb is (3, 3', 5,5 ' -tetra (3-pyridyl) -1,1':3', 1' -terphenyl).

9. A method of manufacturing an organic light emitting diode according to any one of claims 6 to 8, comprising: 1) preparing a hole injection layer in the organic light-emitting diode on the anode by adopting a solution method; 2) optionally preparing a hole transport layer in the organic light emitting diode by adopting a solution method; 3) preparing a luminescent layer doped with the phosphorescent complex by a solution method; 4) and preparing the electron transport layer, the electron injection layer and the cathode layer by sequentially utilizing a vacuum thermal evaporation method.

10. Use of the organic light emitting diode according to any one of claims 6 to 8 in the field of flat panel displays and daily lighting.