HK1237786B - A phosphorescent ptag2 complex, processes for its preparation and uses thereof - Google Patents

Description

A phosphorescent PtAg2 complex and its preparation method and use

Technical Field

The present invention belongs to the field of organic electroluminescence and can be applied to the fields of color flat panel display and lighting. Specifically, it relates to a PtAg ₂ (meso-/rac-dpmppe) heterotrinuclear metal organic alkyne complex for preparing organic light-emitting diodes.

Background Art

Organic electroluminescence (OLED) is a light-emitting diode (OLED) that converts electrical energy directly into light energy when powered by a low DC voltage of 3-12V. It has a wide range of applications in flat-panel displays and lighting. Compared with traditional lighting and display technologies, OLED offers numerous advantages, including full-color display, wide viewing angles, high definition, fast response, low power consumption, and low-temperature resistance. Furthermore, OLED devices offer advantages such as simple structure, ultra-light weight, ultra-thinness, flexibility, and foldability.

The core of organic light-emitting diodes is the light-emitting thin film material. Currently, the majority of phosphorescent materials used in commercial organic electroluminescent devices are electrically neutral cyclometallated iridium (III) complexes, which are doped into organic host materials to form the light-emitting layer. Their biggest advantage is that they are easy to prepare by vacuum thermal evaporation to form an ideal thin film light-emitting layer. However, the equipment required for vacuum evaporation is expensive, and in particular, the process for preparing organic doped light-emitting thin film layers is complicated, which greatly limits the industrial development and commercial application of organic light-emitting diodes in large-area full-color displays. In order to break through this technical bottleneck, choosing ionic phosphorescent metal organic compounds with high quantum efficiency as light-emitting materials is a feasible alternative. Compared with electrically neutral compounds, ionic phosphorescent metal complexes are simpler and cheaper to prepare, have better stability, and are easily soluble in organic solvents. They are suitable for large-area solution spin coating or inkjet printing to form films, which can significantly reduce the cost of device preparation.

Summary of the Invention

The purpose of the present invention is to provide an ionic phosphorescent _PtAg2 complex with meso- or rac-phase, and a preparation method and use thereof.

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

The purpose of the present invention is achieved by the following methods:

An ionic phosphorescent metal complex having a racemic structure, the structure of which is shown in the following formula (I) or formula (II):

[PtAg ₂ {rac-(PPh ₂ CH ₂ PPhCH ₂ -) ₂ }(C≡CR) ₂ (PR' ₃ ) ₂ ] ²⁺ A ^n- _2/n ; (I)

or

[PtAg ₂ {meso-(PPh ₂ CH ₂ PPhCH ₂ -) ₂ }(C≡CR) ₂ (PR' ₃ )(μ-X)] ⁺ _m A ^m- (II)

in,

R may be the same or different and independently selected from: alkyl, aryl, heteroaryl, heteroarylaryl,

R' may be the same or different and independently selected from: alkyl, aryl, heteroaryl;

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

X is selected from halogen;

A ^m- and ^An- are monovalent or divalent anions, m or n is 1 or 2, and the anions are, for example, ClO ₄ ^- , PF ₆ ^- , SbF ₆ ^- , BF ₄ ^- , SiF ₆ ^{2- ,} etc. μ represents a bridge.

According to the present invention, the stereostructure of the phosphorescent metal complex of formula (I) or formula (II) is as follows:

In the present invention, the alkyl group refers to a straight-chain or branched alkyl group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, such as methyl, ethyl, propyl, butyl, isobutyl, tert-butyl, etc.

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

The alkynyl group represents a straight chain or branched chain alkynyl group having 2 to 6 carbon atoms, for example, acetylene, propyne, butyne, etc.

The aryl group refers to a monocyclic or polycyclic aromatic group having 6 to 20 carbon atoms. Representative aryl groups include phenyl, naphthyl, and the like.

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

According to the present invention, the A ^m- or A ^n- is preferably ClO ₄ ^- , PF ₆ ^- , SiF ₆ ^2- or the like, and m/n is 1 or 2.

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

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

The present invention also provides a method for preparing the _{phosphorescent} complex of formula (I), comprising the following steps _: 1) reacting rac-( _{PPh2CH2PPhCH2-} ) ₂ and Pt( _PPh3 ) ₂ (C≡CR) ₂ in a solvent to obtain an intermediate; and 2) reacting the intermediate obtained in step 1) with [Ag(tht)]( ^An- ) and _PR'3 in a solvent to obtain the phosphorescent complex of formula (I). Wherein, tht (tetrahydrothiophene) is tetrahydrothiophene, and ^An- , R, R', and X are as defined above.

The present invention also provides a method for preparing the _{phosphorescent} complex of formula (II), comprising the following steps: A) reacting _meso- ( _{PPh2CH2PPhCH2-} ) ₂ and Pt( _PPh3 ) ₂ (C≡CR) ₂ in a solvent to obtain an intermediate; _and B) reacting the intermediate obtained in step A) with _PR'3 , ^nBu4NX , and [Ag(tht)]( ^Am- ) in a solvent to obtain the phosphorescent complex of formula (II). Wherein, tht (tetrahydrothiophene) is tetrahydrothiophene, and ^Am- , R, R', and X are as defined above.

According to the present invention, in step 1) and step A), the solvent is preferably a halogenated hydrocarbon, such as dichloromethane. Preferably, the intermediate obtained by the reaction is concentrated and recrystallized.

According to the present invention, in step 2) and step B _{), the solvent is preferably a halogenated hydrocarbon, such as dichloromethane. Preferably, in step B), PR'3 and nBu4NX are} ^first mixed, and then the mixed solution and [Ag(tht)]( ^Am- ) are added to the solution containing the intermediate obtained in step A).

According to the present invention, in the method, the molar ratio of rac-(PPh ₂ CH ₂ PPhCH ₂ -) ₂ : Pt(PPh ₃ ) ₂ (C≡CR) ₂ : [Ag(tht)](A ^n- ): PR' ₃ is 1-1.5:1-1.5:2-3:2-3, preferably 1:1:2: 2; the molar ratio of meso-(PPh ₂ CH ₂ PPhCH ₂ -) ₂ : Pt(PPh ₃ ) ₂ (C≡CR) ₂ : [Ag(tht)](A ^m- ): ⁿ Bu ₄ NX: PR' ₃ is 1-1.5:1-1.5:2-3:1-1.5:1-1.5, preferably 1:1:2:1:1.

According to the present invention, the reaction is carried out at room temperature. Preferably, after the reaction is completed, silica gel column chromatography is used for separation and purification.

The phosphorescent complexes of formula (I) or (II) described herein exhibit strong phosphorescence emission in both solid and thin film forms, with a phosphorescence quantum yield exceeding 50% in thin film. Furthermore, the emitted light has a wide color distribution, ranging from sky blue to orange-red. Therefore, they can be used as dopants in the light-emitting layer of organic light-emitting diodes.

The present invention also provides use of the phosphorescent complex in an organic light emitting diode.

Furthermore, the present invention also provides 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) of the present invention.

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

According to the present invention, the structure of the organic light-emitting diode can be various structures known in the prior art. Preferably, it includes: an anode layer, a hole injection layer, optionally a hole transport layer, a light-emitting layer, an electron transport layer, an electron injection layer, and a cathode layer. The organic light-emitting diode further includes a substrate (such as a glass substrate). The anode can be indium tin oxide, and the hole injection layer can 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 described in the present invention, as well as a substance having hole transport properties and/or a substance having electron transport properties. Among them, the substance having hole transport properties can be one or more of 2,6-DCZPPY (2,6-bis(3-(9-carbazolyl)phenyl)pyridine), mCP (1,3-bis(9-carbazolyl)benzene), CBP (4,4'-bis(9-carbazolyl)-1,1'-biphenyl), or TCTA (tris(4-(9-carbazolyl)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 present invention, the structure of the device containing the phosphorescent complex of formula (I) is preferably: ITO/PEDOT: PSS (50nm)/CuSCN (30nm)/70.5% 2,6-DCZPPY: 23.5% OXD-7: 6% wt of the complex of formula (I) of the present invention (50nm)/BmPyPB (50nm)/LiF (1nm)/Al (100nm), or ITO/PEDOT: PSS (50nm)/70.5% mCP: 23.5% OXD-7: 6% wt of the complex of formula (I) of the present invention (50nm)/BmPyPB (50nm)/LiF (1nm)/Al (100nm); the structure of the device containing the phosphorescent complex of formula (II) is preferably: ITO/PEDOT: PSS (50nm)/CuSCN (30nm)/ 90% 2,6-DCZPPY: 10% wt complex of formula (II) of the present invention (50 nm)/BmPyPB (50 nm)/LiF (1 nm)/Al (100 nm), or ITO/PEDOT:PSS (50 nm)/90% mCP: 10% wt complex of formula (II) of the present invention (50 nm)/BmPyPB (50 nm)/LiF (1 nm)/Al (100 nm). Among them, 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, and BmPyPB is (3,3",5,5"-tetrakis(3-pyridyl)-1,1':3',1"-terphenyl).

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

In a preferred embodiment, for the phosphorescent complex of formula (I), the method comprises: first, preparing a hole injection layer using water-soluble PEDOT:PSS; second, preparing a hole transport layer using a diethyl sulfide solution of cuprous thiocyanate; then, using 2,6-DCZPPY having hole transport properties and OXD-7 having electron transport properties as a mixed host material, and doping with the phosphorescent complex of formula (I) of the present invention to prepare a light-emitting layer; then, sequentially preparing a Bmpypb electron transport layer, a LiF electron injection layer, and an Al cathode layer by vacuum thermal evaporation; for the phosphorescent complex of formula (II), the method comprises: first, preparing a hole injection layer using water-soluble PEDOT:PSS; second, preparing a hole transport layer using a diethyl sulfide solution of cuprous thiocyanate; then, doping 2,6-DCZPPY having hole transport properties with the phosphorescent complex of formula (II) of the present invention to prepare a light-emitting layer; then, sequentially preparing a Bmpypb electron transport layer, a LiF electron injection layer, and an Al cathode layer by vacuum thermal evaporation.

According to the present invention, in the method, the PEDOT:PSS hole injection layer and the 2,6-DCZPPY:OXD-7 or 2,6-DCZPPY doped light-emitting layer are prepared by solution spin coating, and the BmPyPB electron transport layer and the LiF electron injection layer are prepared by vacuum thermal evaporation.

The organic light-emitting diode prepared from the phosphorescent complex of the present invention has excellent performance and high electro-optical conversion efficiency.

The present invention further provides uses of the organic light emitting diode, which can be used in the fields of flat panel display and daily lighting.

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

1) The phosphorescent complex of the present invention has strong phosphorescent emission in both solid and thin films, and the phosphorescent quantum efficiency of the thin film is higher than 50% and even as high as 90%;

2) The present invention is the first to utilize a phosphorescent Pt-Ag heterometallic complex as a luminescent material to assemble an organic light-emitting device. The organic light-emitting diode prepared using the phosphorescent complex of the present invention as a dopant for the luminescent layer has a high electroluminescence external quantum conversion efficiency;

3) The present invention utilizes an orthogonal solution method to prepare the hole injection layer and the light-emitting layer of the organic light-emitting diode, which can significantly reduce the device preparation cost;

4) The ligands of the phosphorescent complexes of the present invention have different configurations of endo/racemic, and the electroluminescence changes from sky blue to orange-red, and the luminous efficiency of each color is high.

Description of the drawings:

Figure 1 is a schematic diagram of the device structure and the chemical structure of the organic material.

Specific implementation method:

In order to make the invention purpose, technical scheme and technical effect of the present invention clearer, 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 explaining the present invention, rather than limiting the present invention.

In the following examples, dpmppe represents (PPh ₂ CH ₂ PPhCH ₂ -) ₂ , carb represents carbazolyl, PhBut ^- 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, PhCF ₃ -4 represents 4-trifluoromethyl-phenyl, 9-(4-Ph)-carb represents 9-(4-phenyl)-carbazolyl, 10-Et-PTZ-3 represents 10-ethylphenothiazin-3-yl, and tht represents tetrahydrothiophene.

Example 1: Preparation of complex [PtAg ₂ (rac-dpmppe)(C≡CC ₆ H ₄ Bu ^t -4) ₂ {PhP(9-Ph-carb-3) ₂ } ₂ ](ClO ₄ ) ₂ (rac-1)

To a 20 mL solution of Pt(PPh ₃ ) ₂ (C≡CC ₆ H ₄ Bu ^t -4) ₂ (80.6 mg, 0.078 mmol) dissolved in dichloromethane was added rac-dpmppe (50 mg, 0.078 mmol). After stirring for 30 minutes, the mixture was concentrated and 20 mL of n-hexane was added to precipitate a pale yellow solid, the intermediate, with a yield of 90% (80.8 mg). To a 20 mL solution of the intermediate dissolved in dichloromethane were added Ag(tht)ClO ₄ (41.4 mg, 0.14 mmol) and PhP(9-Ph-carb-3) ₂ (82.9 mg, 0.14 mmol). The reaction mixture stirred at room temperature for 1 hour, and the color turned light green. The product was purified by silica gel column chromatography using CH ₂ Cl ₂ -MeCN (8:1) as the eluent, collecting the light green product. Yield: 70%. Elemental analysis (C ₁₄₈ H ₁₂₂ Ag ₂ Cl ₂ N ₄ O ₈ P ₆ Pt) calculated value: C, 64.59; H, 4.47; N, 2.04. Measured value: C, 64.40; H, 4.55; N, 1.96. Electrospray mass spectrum m/z (%): 1276.2909 (100) [M-2ClO ₄ ] ²⁺ . Nuclear magnetic resonance spectrum (CDCl ₃ , ppm): 8.20-8.14 (dd, 4H, J ₁ =16 Hz, J ₂ =12 Hz), 8.08-8.04 (dd, 4H, J ₁ =12 Hz, J ₂ =8 Hz), 7.73-7.59 (m, 12H), δ 5.87-5.71 (m, 2H), 4.70-4.99 (m, 3H), 3.39-3.63 (m, 2H), 2.63-2.46 (m, 2H), 1.23-1.96 (m, 3H), 2.76-2.84 (m, 3H), 1.22-1.63 (m, 3H), 1.47-1.69 (m, _3H ), 3.10-3.31 (m, 3H), 1.22-1.63 (m, 3H), 1.21-1.63 _{(m, 3H), 1.20-1.63 (m, 3H), 1.21-1.63} (m, 3H ₎ , _{1.21-1.63 (} m, _3H) , =52Hz)..Infrared spectrum (KBr, cm ^-1 ): 2081w (C≡C), 1099s (ClO ₄ ^- ).

Example 2: Preparation of complex [PtAg ₂ (rac-dpmppe){(C≡C-4)C ₆ H ₄ -carb-9} ₂ (PPh ₃ ) ₂ ](ClO ₄ ) ₂ (rac-2)

The preparation method is basically the same as that in Example 1, except that Pt(PPh ₃ ) ₂ {(C≡C-4)C ₆ H ₄ -carb-9} ₂ is used instead of Pt(PPh ₃ ) ₂ (C≡CC ₆ H ₄ Bu ^t -4) ₂ , and PPh ₃ is used instead of PhP(9-Ph-carb-3) ₂ . Yield: 71%. Elemental analysis (C ₁₁₆ H ₉₂ Ag ₂ Cl ₂ N ₂ O ₈ P ₆ Pt) calculated values: C, 60.33; H, 4.02; N, 1.21. Measured values: C, 60.12; H, 4.02; N, 1.15. Electrospray mass spectrum m/z (%): 1055.1713 (100%, [M-2ClO ₄ ] ²⁺ ). Nuclear magnetic resonance spectroscopy (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, δ = 1.47 (m, 14H), 7.02-6.98 (m, 4H), 6.86-6.85 (d, 4H, J = 7 Hz), 4.59 (m, 2H), 3.15-3.06 (m, 2H), 2.73-2.59 (m, 2H), 0.61 (m, 2H). Phosphorus nuclear magnetic resonance spectrum (CDCl ₃ , ppm): 47.0 (d, 2P, J _PP = 76 Hz, J _Pt-P = 2375 Hz), 11.8 (m, 2P, J _P-Ag = 506 Hz), 3.4 (m, 2P, J _P-Ag = 410 Hz, J _PP = 45 Hz). Infrared spectrum (KBr, cm ^-1 ): 2091 w (C≡C), 1099 s (ClO ₄ ^- ).

Example 3: Preparation of the complex [PtAg ₂ (rac-dpmppe){C≡C-(9-Ph-carb-3)} ₂ (PPh ₃ ) ₂ ](ClO ₄ ) ₂ (rac-3)

The preparation method is basically the same as that in Example 1, except that Pt(PPh ₃ ) ₂ (C≡C-(9-Ph-carb-3)) ₂ is used instead of Pt(PPh ₃ ) ₂ (C≡CC ₆ H ₄ Bu ^t -4) ₂ , and PPh ₃ is used instead of PhP(9-Ph-carb-3) ₂ . Yield: 71%. Elemental analysis (C ₁₁₆ H ₉₂ Ag ₂ Cl ₂ N ₂ O ₈ P ₆ Pt) calculated values: C, 60.33; H, 4.02; N, 1.21. Measured values: C, 60.10; H, 4.05; N, 1.16. Electrospray mass spectrum m/z (%): 1055.1717 (100%, [M-2ClO ₄ ] ²⁺ ). Nuclear magnetic resonance spectrum (CDCl ₃ , ppm): 8.17-8.12 (dd, 4H, J ₁ =12 Hz, J ₂ =8 Hz), 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). Phosphorus NMR (CDCl ₃ , ppm): 46.3 (d, 2P, J _PP =75 Hz, J _Pt-P =2384 Hz), 11.9 (m, 2P, J _P-Ag =510 Hz), 2.4 (m, 2P, J _P-Ag =398 Hz, J _PP =51 Hz). Infrared spectrum (KBr, cm ^-1 ): 2075 w (C≡C), 1093 s (ClO ₄ ^- ).

Example 4: Complex

Preparation of [PtAg ₂ (rac-dpmppe)(C≡C-(9-Ph-carb-3)) ₂ {P(9-Et-carb-3) ₃ } ₂ ](ClO ₄ ) ₂ (rac-4).

The preparation method was basically the same as that in Example 1, except that Pt(PPh ₃ ) ₂ {C≡C-(9-Ph-carb-3)} ₂ was used instead of Pt(PPh ₃ ) ₂ (C≡CC ₆ H ₄ -But ^- 4) ₂ , and P(9-Et-carb-3) ₃ was used instead of PhP(9-Ph-carb-3) ₂ . Yield: 71%. Elemental analysis (C ₁₆₄ H ₁₃₄ Ag ₂ Cl ₂ N ₈ O ₈ P ₆ Pt) calculated values: C, 65.39; H, 4.48; N, 3.72. Measured values: C, 65.14; H, 4.53; N, 3.53. Electrospray mass spectrum m/z (%): 1406.8446 [M-2ClO ₄ ] ²⁺ . H NMR (CDCl ₃ , ppm): 8.27-8.22 (dd, 4H, J ₁ =12 Hz, J ₂ =8 Hz), 8.20-8.17 (d, 6H, J =12 Hz), 8.04-7.99 (dd, 6H, J ₁ =12 Hz, J ₂ =8Hz), 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) _. , ppm): 46.5 (d, 2P, J _PP ＝78 Hz, J _Pt-P ＝2380 Hz), 15.3 (m, 2P, J _P-Ag ＝534 Hz), 0.8 (m, 2P, J _P-Ag ＝378 Hz, J _PP ＝53 Hz). Infrared spectrum (KBr, cm ^-1 ): 2081w (C≡C), 1093s (ClO ₄ ^- ).

Example 5: Complex

Preparation of [PtAg ₂ (rac-dpmppe){C≡C-(9-Et-carb-3)} ₂ {P(9-Et-carb-3) ₃ } ₂ ](ClO ₄ ) ₂ (rac-5).

The preparation method is basically the same as that in Example 1, except that Pt(PPh ₃ ) ₂ {C≡C-(9-Et-carb-3)} ₂ is used instead of Pt(PPh ₃ ) ₂ (C≡CC ₆ H ₄ Bu ^t -4) ₂ , and P(9-Et-carb-3) ₃ is used instead of PhP(9-Ph-carb-3) ₂ . Yield: 72%. Elemental analysis (C ₁₅₆ H ₁₃₄ Ag ₂ Cl ₂ N ₈ O ₈ P ₆ Pt) calculated values: C, 64.25; H, 4.63; N, 3.84. Measured values: C, 64.02; H, 4.65; N, 3.58. Electrospray mass spectrum m/z (%): 1358.3459 (100%) [M-2ClO ₄ ] ²⁺ . Nuclear magnetic resonance spectrum (CDCl ₃ , ppm): 8.25-8.16(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). Nuclear magnetic resonance phosphorus spectrum (CDCl ₃ , ppm): 46.2 (d, 2P, J _PP =78 Hz, J _Pt-P =2376 Hz), 15.3 (m, 2P, J _P-Ag =524 Hz), 0.6 ( ^m , 2P, J _P-Ag =369 Hz, J _PP =52 Hz). Infrared spectrum (KBr, cm ^-1 ): 2073w (C≡C), 1093s (ClO ₄ ^- ).

Example 6: Preparation of the complex [PtAg ₂ (rac-dpmppe){C≡C-(10-Et-PTZ-3)} ₂ {P(9-Et-carb-3) ₃ } ₂ ](ClO ₄ ) ₂ (rac-6).

The preparation method is basically the same as that in Example 1, except that Pt(PPh ₃ ) ₂ {C≡C-(10-Et-PTZ-3)} ₂ is used instead of Pt(PPh ₃ ) ₂ (C≡CC ₆ H ₄ Bu ^t -4) ₂ , and P(9-Et-carb-3) ₃ is used instead of PhP(9-Ph-carb-3) ₂ . Yield: 73%. Elemental analysis (C ₁₅₆ H ₁₃₄ Ag ₂ Cl ₂ N ₈ O ₈ P ₆ PtS ₂ ) calculated values: C, 62.86; H, 4.53; N, 3.76. Measured values: C, 62.62; H, 4.57; N, 3.59. Electrospray mass spectrum m/z (%): 1390.8150 (100%) [M-2ClO ₄ ] ²⁺ . Nuclear magnetic resonance spectrum (CDCl ₃ , ppm): 8.16-8.13 (m, 8H), 8.01-7.96 (dd, 6H, J=8 Hz), 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＝8 Hz),4.23(m,2H),4.05-3.99(q,12H,J＝7Hz),3.45-3.39(q,4H,J＝7Hz), 3.06-2.97(m,2H),2.64-2.45(m,2H),1.18-1.14(t,18H,J=7Hz),1.06-1.02(t,6H, J＝7 Hz), 0.59 (m, 2H). Phosphorus nuclear magnetic resonance spectrum (CDCl ₃ , ppm): 46.5 (d, 2P, J _PP ＝78 Hz, J _Pt-P ＝2376 Hz), 15.2 (m, 2P, J _P-Ag ＝536 Hz), 1.5 (m, 2P, J _P-Ag ＝381 Hz, J _PP ＝54 Hz). Infrared spectrum (KBr, cm ^-1 ): 2081w (C≡C), 1093s (ClO ₄ ^- ).

Example 7: Preparation of the complex [PtAg ₂ (meso-dpmppe)(C≡CC ₆ H ₄ CF ₃ -4) ₂ (PPh ₃ )Cl](ClO ₄ ) (meso-7).

Meso-dpmppe (50 mg, 0.078 mmol) was added to a 20 mL dichloromethane solution of Pt( _PPh₃ ) _₂ ( _{C≡CC₆H₄CF₃ - 4} ) _₂ (82.5 mg, 0.078 mmol). After stirring for 30 minutes, the mixture was concentrated and 20 mL _of n-hexane was added to precipitate a pale yellow solid, the intermediate, in a 90% yield (82.4 mg). _PPh₃ (18.3 mg, 0.07 mmol) and ^nBu₄NCI (19.5 mg, 0.07 mmol) were mixed. This mixture and Ag(tht) _ClO₄ (41.4 mg, 0.14 mmol) were added to the dichloromethane solution containing the intermediate. The reaction mixture was stirred at room temperature for 1 hour, turning light blue. The product was purified by silica gel column chromatography using _{CH₂Cl₂ -} MeCN (15:1) as the eluent to collect the yellow solid. Yield: 75%. Elemental analysis ( _{C76H61Ag2Cl2F6O4P5Pt} ) calculated: C, 51.03; H, _3.44 . Found: C, 51.21; H, 3.60. Electrospray mass spectrometry _m /z ( _{% ) :} 1688.0808 (100%, [M- _{ClO4 ]} ⁺ ). H NMR ( _CDCl3 , ppm): 8.03-7.96 (m, 8H), 7.59-7.36 (m, 22H), 7.33-7.29 (t, 4H, J=7 Hz), 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 phosphorus spectrum (CDCl ₃ , ppm): 47.6 (dd, 2P, J _PP ＝30 Hz, J _Pt-P ＝2412 Hz), 7.6 (m, 1P, J _P-Ag ＝579 Hz), -8.9 (m, 2P, J _P-Ag ＝422 Hz, J _PP ＝59 Hz). Infrared spectrum (KBr, cm ^-1 ): 2092 w (C≡C), 1104 s (ClO ₄ ^- ).

Example 8: Preparation of the complex [PtAg ₂ (meso-dpmppe)(C≡CC ₆ H ₄ Bu ^t -4) ₂ (PPh ₃ )Cl](ClO ₄ ) (meso-8).

The preparation method is basically the same as that in Example 7, except that Pt(PPh ₃ ) ₂ (C≡CC ₆ H ₄ Bu ^t -4) ₂ is used instead of Pt(PPh ₃ ) ₂ (C≡CC ₆ H ₄ CF ₃ -4) _2. Yield: 74%. Elemental analysis (C ₈₂ H ₇₉ Ag ₂ Cl ₂ O ₄ P ₅ Pt) calculated value: C, 55.80; H, 4.51. Measured value: C, 56.02; H, 4.74. Electrospray mass spectrum m/z (%): 1665.2304 (100%, [M-ClO ₄ ] ⁺ ). Nuclear magnetic resonance spectroscopy (CDCl ₃ , ppm): 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 spectrum (CDCl ₃ , ppm): 47.1 (q, 2P, J _PP = 30 Hz, J _Pt-P = 2409 Hz), 7.2 (m, 1P, J _P-Ag = 565 Hz), -9.5 (m, 2P, J _P-Ag = 417 Hz, J _PP = 58 Hz). Infrared spectrum (KBr, cm ^-1 ): 2092 w (C≡C), 1093 s (ClO ₄ ^- ).

Example 9: Preparation of the complex [PtAg ₂ (meso-dpmppe)(C≡CC ₆ H ₄ ^But -4) ₂ {P(9-Et-carb-3) ₃ }Cl](ClO ₄ )(meso-9).

The preparation method is basically the same as that in Example 7, except that Pt(PPh ₃ ) ₂ (C≡CC ₆ H ₄ ^But -4) ₂ is used instead of Pt(PPh ₃ ) ₂ (C≡CC ₆ H ₄ CF ₃ -4) ₂ and P(9-Et-carb-3) ₃ is used instead of PPh ₃ . Yield: 74%. Elemental analysis (C ₁₀₆ H ₁₀₀ Ag ₂ Cl ₂ N ₃ O ₄ P ₅ Pt) calculated values: C, 60.15; H, 4.76; N, 1.99. Measured values: C, 60.32; H, 4.73; N, 1.88. Electrospray mass spectrum m/z (%): 2016.4011 (100%, [M-ClO ₄ ] ⁺ ). Nuclear magnetic resonance spectrum (CDCl ₃ , ppm): 8.48-8.45 (d, 2H, J = 12 Hz), 8.08-8.04 (dd, 4H, J ₁ = 12 Hz, J ₂ = 8 Hz), 7.94-7.92 (d, 2H, J = 8 Hz), 7.89 (m, 4H), 7.53-7.41 (m, 26H), δ 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). Phosphorus nuclear magnetic resonance spectrum (CDCl ₃ , ppm): 47.5 (q, 2P, J _PP = 29 Hz, J _Pt-P = 2394 Hz), 10.4 (m, 1P, J _P-Ag = 601 Hz), -9.3 (m, 2P, J _P-Ag = 417 Hz, J _PP = 56 Hz). Infrared spectrum (KBr, cm ^-1 ):2110w(C≡C),1093s(ClO ₄ ^- ).

Example 10: Preparation of the complex [PtAg ₂ (meso-dpmppe)(C≡CC ₆ H ₄ Bu ^t -4) ₂ {P(9-Et-carb-3) ₃ }I](ClO ₄ )(meso-10).

The preparation method is basically the same as that in Example 7, except that Pt( _PPh3 ) ₂ ( _C≡CC6H4But ^- ₄ ) ₂ is used instead of Pt( _PPh3 ) ₂ ( _{C≡CC6H4CF3-4} ) ₂ , P( ₉ -Et-carb _- 3) ₃ is used instead of _PPh3 , ^and _nBu4NI is used instead of ^nBu4NCI . Yield: ₇₂ %. Elemental analysis (C ₁₀₆ H ₁₀₀ Ag ₂ ClIN ₃ O ₄ P ₅ Pt) calculated values: C, 57.66; H, 4.56; N, 1.90. Measured values: C, 57.57; H, 4.60; N, 1.83. Electrospray mass spectrum m/z (%): 2108.3387 (100%, [M-ClO ₄ ] ⁺ ). Nuclear magnetic resonance spectroscopy (CDCl ₃ , ppm): 8.51-8.48 (d, 2H, J = 12 Hz), 8.11-8.07 (dd, 4H, J ₁ = 12 Hz, J ₂ = 8 Hz), 7.98-7.96 (d, 2H, J = 8 Hz), 7.82 (m, 4H), δ 5.87-5.71 (m, 2H), 2.49-2.63 (m, 1H), 4.73-4.96 (m, 2H), 2.30-2.66 (m, 1H), 2.79-2.86 (m, 2H), 1.30-1.31 ₍ m, _1H ), 2.76-2.99 (m, 2H), _1.64-1.60 (m, 1H), 1.49-1.61 (m, 2H ₎ , 1.47-1.63 ₍ m, 18H ₎ . =59 Hz). Infrared spectrum (KBr, cm ^-1 ): 2104w (C≡C), 1093s (ClO ₄ ^- ).

Example 11: Preparation of the complex [PtAg ₂ (meso-dpmppe)(C≡C-(10-Et-PTZ-3)) ₂ {P(9-Et-carb-3) ₃ }(μ-I)](ClO ₄ )(meso-11).

The preparation method is basically the same as that in Example 7, except that Pt(PPh ₃ ) ₂ {C≡C-(10-Et-PTZ-3)} ₂ is used instead of Pt(PPh ₃ ) ₂ (C≡CC ₆ H ₄ CF ₃ -4) ₂ , P(9-Et-carb-3) ₃ is used instead of PPh ₃ , ^{and n} Bu ₄ NI is used instead of ⁿ Bu ₄ NCl. Yield: 75%. Elemental analysis (C ₁₁₄ H ₉₈ Ag ₂ ClIN ₅ O ₄ P ₅ PtS ₂ ) calculated values: C, 57.19; H, 4.13; N, 2.93. Measured values: C, 57.42; H, 4.33; N, 2.84. Electrospray mass spectrum m/z (%): 2294.2671 (100%, [M-ClO ₄ ] ⁺ ). H NMR (CDCl ₃ , ppm): 8.54-8.51 (d, 2H, J=12 Hz), 8.09-8.04 (dd, 4H, J _{1 =12 Hz, J 2 =} 8 Hz), 7.95-7.93 (d, 2H, J=8 Hz), 7.80 (m, 4H), 7.59-7.29 (m, 29H), 7.18-7.01 (m, 3H). 3H), 4.76-4.90 (m, 2H), 3.54-3.72 (m, 2H), 3.30-3.79 (m, 4H), 2.39-2.83 (m, 5H), 1.43-1.63 (t, 9H, J=7 Hz), 1.26-1.47 (t, 6H, J=6 Hz). 3.71 (m, 2H), 3.46 (m, 2H), 3.14-3.08 (q, 4H, J=6 Hz), 2.28-2.03 (m, 4H), 1.44-1.40 (t, 9H, J=7 Hz), 0.86-0.81 (t, _6H , _J =6 _Hz ). =2391 Hz), 9.1 (m, 1P, JP _-Ag = 548 Hz), -11.4 (m, 2P, JP _-Ag = 384 Hz, _JPP = 60 Hz). Infrared spectrum (KBr, cm ^-1 ): 2101 w (C≡C), 1094 s ( _ClO4- ⁾ .

Example 12: Photoluminescence performance test

The excitation spectra, emission spectra, luminescence lifetime, and quantum yield of the complexes rac-1, rac-4, rac-5, and rac-6 prepared in Examples 1, 4, 5, and 6, respectively, in solid powders and thin films containing 70.5% 2,6-DCZPPY:23.5% OXD-7:6% of the present complexes rac-1, 4, 5, or 6 (by weight), and the complex meso-11 prepared in Example 11, respectively, in solid powders and thin films containing 90% 2,6-DCZPPY:10% of the present complex meso-11 (by weight), were measured on an Edinburgh FLS920 fluorescence spectrometer. The quantum yield of the solid powder samples was measured using an integrating sphere with a diameter of 142 mm.

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

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

Example 13: Preparation of organic light-emitting diode devices and electroluminescence performance testing

The phosphorescent complexes rac-1, rac-4, rac-5, or rac-6 prepared in Examples 1, 4, 5, and 6 were used as luminescent materials and doped at a weight percentage of 6% into a mixed host material of 2,6-DCZPPY (70.5%):OXD-7 (23.5%) as the luminescent layer to prepare an organic light-emitting diode. The device structure was: ITO/PEDOT:PSS (50nm)/CuSCN (30nm)/70.5% 2,6-DCZPPY:23.5% OXD-7:6% complexes rac-1, 4, 5, or 6 (50nm)/Bmpypb (50nm)/LiF (1 nm)/Al (100 nm); the phosphorescent complex meso-11 prepared in Example 11 was used as a luminescent material and doped into a 2,6-DCZPPY (90%) main material at a weight percentage of 10% as a light-emitting layer to prepare an organic light-emitting diode, and the device structure was: ITO/PEDOT:PSS (50 nm)/CuSCN (30 nm)/90% 2,6-DCZPPY:10% of the complex of the present invention meso-11 (50 nm)/Bmpypb (50 nm)/LiF (1 nm)/Al (100 nm).

The ITO substrate was first cleaned with deionized water, acetone, and isopropyl alcohol, followed by UV-ozone treatment for 15 minutes. The filtered PEDOT:PSS aqueous solution was spin-coated onto the ITO substrate at 4800 rpm and dried at 140°C for 20 minutes to create a 50 nm thick hole injection layer. A 10 mg/mL solution of CuSCN in diethyl sulfide was then spin-coated onto the PEDOT:PSS hole injection layer at 4800 rpm and dried at 120°C for 30 minutes to create a 30 nm thick hole transport layer. Next, a filtered solution of 5.5 mg/mL of 70.5% 2,6-DCZPPY: 23.5% XD-7: 6% of the present invention's complexes rac-1, rac-4, rac-5, or rac-6 (by weight), or 5.5 mg/mL of 90% 2,6-DCZPPY: 10% of the present invention's complex meso-11 (by weight) in dichloromethane was spin-coated onto the PEDOT:PSS film at 2100 rpm to form a 50 nm thick light-emitting layer. Subsequently, the ITO substrate was placed in a vacuum chamber maintained at a vacuum level of no less than 4× ^10⁻⁴ Pa, and a 50 nm thick layer of Bmpypb, a 1 nm thick LiF electron injection layer, and a 100 nm thick layer of Al were thermally evaporated to form the device cathode.

Light-emitting diode device performance testing was conducted in a dry air environment at room temperature. Electroluminescent performance parameters, including electroluminescence wavelength (λ _EL ), turn-on voltage (V _on ), maximum brightness (L _max ), maximum current efficiency (CE _max ), maximum power efficiency (PE _max ), and maximum external quantum efficiency (EQE _max ), are listed in Table 1.

Table 1. Performance data of electroluminescent devices of the phosphorescent complexes rac-1, rac-4, rac-5, rac-6, or meso-11 of the present invention

^a) Turn-on voltage at a luminance of 1 cd/ ^m² , ^b) Maximum luminance, ^c) Maximum current efficiency, ^d) Maximum power efficiency, ^e) Maximum external quantum efficiency, and CIE chromaticity coordinates.

Claims (17)

1. A racemic ionic phosphorescent metal complex, wherein the stereostructure of the ionic phosphorescent metal complex is shown below: in, R is aryl, carbazolyl, phenothiazinyl, or carbazolylaryl; the aryl, carbazolyl, or phenothiazinyl group may be optionally substituted by one or more substituents selected from alkyl, alkoxy, amino, halogen, haloalkyl, or aryl groups. R' is an aryl or nitrogen-containing heterocycle, which may be optionally substituted by one or more substituents selected from alkyl, alkoxy, amino, halogen, haloalkyl, and aryl groups. X is selected from halogens; A m- and A n-  are monovalent or divalent anions, where m or n is 1 or 2, and the anions are ClO 4-  , PF 6-  , SbF 6- , BF 4-  , or SiF 62-  . The alkyl group refers to a straight-chain or branched alkyl group having 1-10 carbon atoms; The aryl group refers to a monocyclic or polycyclic aromatic group having 6-20 carbon atoms; The ionic phosphorescent metal complex is either racemic or meso. 2. The ionic phosphorescent metal complex according to claim 1, wherein R is phenyl, alkyl-phenyl, haloalkyl-phenyl, carbazolyl-phenyl, carbazolyl, alkyl-carbazolyl, phenyl-carbazolyl, phenthiazinyl, or alkyl-phenthiazinyl; and R' is phenyl, alkylphenyl, carbazolyl, alkyl-carbazolyl, or phenyl-carbazolyl. 3. The ionic phosphorescent metal complex according to claim 1, wherein the ionic phosphorescent metal complex comprises the following 11 complexes: The aforementioned ionic phosphorescent metal complexes are either racemic or meso. 4. A method for preparing the ionic phosphorescent metal complex according to any one of claims 1-3, wherein the method for preparing the ionic phosphorescent metal complex of formula (I) comprises the following steps: 1) Reaction of rac-(PPh 2 CH 2 PPhCH 2 -) 2 and Pt(PPh 3 ) 2 (C≡CR) 2 in a solvent yields an intermediate; 2) The intermediate obtained in step 1) is then reacted with [Ag(tht)](A n- ) and PR' 3 in a solvent to obtain the ionic phosphorescent metal complex of formula (I); Wherein, tht is tetrahydrothiophene, and An- , R, R', and X are as defined in any one of claims 1-3; or, The preparation method of the ionic phosphorescent metal complex of formula (II) includes the following steps: A) React meso-( PPh₂CH₂PPhCH₂- ) ₂ and Pt( PPh₃ ) ₂ (C≡CR) ₂ in a solvent to obtain an intermediate; B) React PR' 3 , n Bu 4 NX, [Ag(tht)](A m- ) with the intermediate obtained in step A) in a solvent to obtain the ionic phosphorescent metal complex of formula (II); Wherein, tht is tetrahydrothiophene, and A m- , R, R', X are as defined in any one of claims 1-3. 5. The method for preparing ionic phosphorescent metal complexes according to claim 4, wherein, in step 1) and step A), the solvent is a haloalkane; and in step 2) and step B), the solvent is a haloalkane. 6. The method for preparing ionic phosphorescent metal complexes according to claim 5, wherein the halohydrocarbon is dichloromethane. 7. Use of the ionic phosphorescent metal complex according to any one of claims 1-3 in organic light-emitting diodes. 8. An organic light-emitting diode, comprising a light-emitting layer, wherein the light-emitting layer contains an ionic phosphorescent metal complex of formula (I) or formula (II) as described in any one of claims 1-3. 9. The organic light-emitting diode according to claim 8, wherein, in the light-emitting layer, the ionic phosphorescent metal complex of formula (I) according to any one of claims 1-3 accounts for 3-20% by weight of all materials; and the ionic phosphorescent metal complex of formula (II) according to any one of claims 1-3 accounts for 5-25% by weight of all materials. 10. The organic light-emitting diode according to claim 9, wherein, in the light-emitting layer, the ionic phosphorescent metal complex of formula (I) according to any one of claims 1-3 accounts for 5-10% by weight of all materials; and the ionic phosphorescent metal complex of formula (II) according to any one of claims 1-3 accounts for 8-15% by weight of all materials. 11. The organic light-emitting diode according to claim 10, wherein the ionic phosphorescent metal complex of formula (I) is doped into the host material at a weight percentage of 6% as a light-emitting layer; and the ionic phosphorescent metal complex of formula (II) is doped into the host material at a weight percentage of 10% as a light-emitting layer. 12. The organic light-emitting diode according to any one of claims 8-11, wherein the organic light-emitting diode further comprises: an anode layer, a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, an electron injection layer, and a cathode layer; or, the organic light-emitting diode further comprises: an anode layer, a hole injection layer, a light-emitting layer, an electron transport layer, an electron injection layer, and a cathode layer. 13. The organic light-emitting diode according to claim 12, wherein the anode is indium tin oxide, the hole injection layer is poly(3,4-ethylenedioxythiophene)-poly(styrene sulfonic acid); the hole transport layer is CuSCN, CuI, or CuBr; the light-emitting layer contains the ionic phosphorescent metal complex according to any one of claims 1-3, and a substance having hole transport properties and/or a substance having electron transport properties; wherein the substance having hole transport properties is 2,6-bis(3-(9-carbazole)phenyl)pyridine, 1,3-bis(9-carbazole)benzene, or 4,4'-bis(9-carbazole). The electron transport layer is one or more of 1,1'-biphenyl or tris(4-(9-carbazole)phenyl)amine; the electron transport layer is 1,3-bis(5-(4-(tert-butyl)phenyl)-1,3,4-oxadiazol-2-yl)benzene; the electron transport layer is one or more of 3,3”,5,5”-tetra(3-pyridyl)-1,1':3',1”-terphenyl, 1,3,5-tris(1-phenyl-1H-benzo[d]imidazol-2-yl)benzene, 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline or OXD-7; the electron injection layer is LiF; and the cathode is Al. 14. The organic light-emitting diode according to claim 13, wherein the device structure containing the ionic phosphorescent metal complex of formula (I) is: ITO/PEDOT:PSS/CuSCN/70.5wt% 2,6-DCZPPY:23.5wt% OXD-7:6wt% of the complex of formula (I) according to any one of claims 1-3/BmPyPB/LiF/Al, or ITO/PEDOT:PSS/70.5wt% mCP:23.5wt% OXD-7:6wt% of the complex of formula (I) according to any one of claims 1-3/BmPyPB/LiF/Al; Among them, ITO is indium tin oxide conductive film, PEDOT:PSS is poly(3,4-ethylenedioxythiophene)-poly(styrene sulfonic 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, and BmPyPB is 3,3”,5,5”-tetra(3-pyridinyl)-1,1':3',1”-terphenyl. 15. The organic light-emitting diode according to claim 13, wherein the device structure containing the ionic phosphorescent metal complex of formula (II) is: ITO/PEDOT:PSS/CuSCN/90wt% 2,6-DCZPPY:10wt% of the complex of formula (II) according to any one of claims 1-3/BmPyPB/LiF/Al, or ITO/PEDOT:PSS/90wt% mCP:10wt% of the complex of formula (II) according to any one of claims 1-3/BmPyPB/LiF/Al; Among them, ITO is indium tin oxide conductive film, PEDOT:PSS is poly(3,4-ethylenedioxythiophene)-poly(styrene sulfonic acid), 2,6-DCZPPY is 2,6-bis(3-(9-carbazolyl)phenyl)pyridine, mCP is 1,3-bis(9-carbazolyl)benzene, and BmPyPB is 3,3”,5,5”-tetra(3-pyridyl)-1,1':3',1”-terphenyl. 16. A method for fabricating an organic light-emitting diode according to any one of claims 8-15, comprising: 1) A hole injection layer in an organic light-emitting diode is prepared on the anode using a solution method; 2) The hole transport layer in the organic light-emitting diode is optionally prepared using a solution method; 3) A light-emitting layer doped with the ionic phosphorescent metal complex according to any one of claims 1-3 is prepared by solution method; 4) Then, the electron transport layer, electron injection layer, and cathode layer are prepared sequentially using vacuum thermal evaporation. 17. Use of the organic light-emitting diode according to any one of claims 8-15, for use in flat panel displays and everyday lighting applications.