A metal complex and an organic electroluminescent device

Abstract

This invention relates to the field of electronic materials technology, specifically to a metal complex and an organic electroluminescent device. The metal complex provided by this invention has the following structure, which enables the organic electroluminescent device containing the metal complex to have high external quantum efficiency and long device lifetime.

Description

Technical Field

[0001] This invention relates to the field of electronic materials technology, specifically to a metal complex and an organic electroluminescent device. Background Technology

[0002] Organic light-emitting diodes (OLEDs) convert electrical energy into light energy and feature low driving voltage, low power consumption, flexibility, short response time, and wide operating temperature range. They hold great promise for applications in industrial lighting, smartphone displays, and large-screen television displays. Therefore, the emergence of OLEDs has generated significant interest in both industry and academia, and they are considered the dominant lighting and flat-panel display technology of the future. OLED devices generally consist of two electrodes (anode and cathode) and several organic layers, such as a hole injection layer, a hole and electron transport layer, and an emissive layer (EML) between the two electrodes. Under external voltage injection, oppositely charged charge carriers of holes and electrons are injected from the anode and cathode, and ultimately recombine within the emissive layer to generate photons. The emissive layer not only largely determines the device's performance but also its fabrication methods; therefore, it is the most critical component of all OLED components.

[0003] Over the past three decades, luminescent materials have developed rapidly, evolving from traditional fluorescent, phosphorescent, and triplet-triplet annihilation (TTA) materials to the third-generation thermally activated delayed fluorescence (TADF) materials. According to spin statistical distribution, when an OLED device is excited by an electric field, a 1:3 ratio of singlet and triplet excitons is generated within the emitting layer. The different exciton utilization rates of different luminescent materials lead to variations in OLED device efficiency. For example, first-generation fluorescent materials, which can only utilize singlet excitons, have a theoretical upper limit of only 25% for internal quantum efficiency (exciton utilization) and a maximum external quantum efficiency (the ratio of photons emitted by the emitting layer to the injected charge) of only 5%. Second-generation OLED materials employ phosphorescent complexes containing the extremely rare noble metal iridium. Because they can utilize both singlet and triplet excitons simultaneously, the theoretical internal quantum efficiency of phosphorescent OLEDs can reach 100%. However, the high cost and heavy metal pollution associated with noble metal phosphorescent materials have significantly hindered the development of new phosphorescent materials.

[0004] TADF materials can trap triplet excitons by upconverting them to singlet excitons via reverse system-reinforced crosstalk (RISC), achieving a theoretical internal quantum efficiency of 100%. Compared to organometallic phosphorescent complexes, organic TADF luminescent materials offer greater freedom in chemical design and exhibit higher long-term stability and sustainability. Their potential for high efficiency, high design versatility, and environmental friendliness makes TADF materials a promising candidate for third-generation OLED devices.

[0005] TADF materials can be divided into pure organic materials and metal complex materials. Pure organic TADF materials typically have a long emission lifetime, but the efficiency of the devices rolls off significantly at high brightness. This long emission lifetime is also considered a key reason for the poor stability of OLED devices.

[0006] However, existing linear carbene-metal-amine complexes have limited ligand types and suffer from low device lifetime and efficiency, posing challenges in practical applications. Platinum(II) complexes are widely used in phosphorescent OLED devices, but platinum(II) complex TADF materials are rarely studied. This is mainly due to the large spin-orbit coupling constant of metallic platinum(II), leading to phosphorescence emission as the dominant emission. On the other hand, some palladium(II) complex OLED devices exhibit excellent performance; however, there are very few reports on palladium(II) complex OLED materials, whether phosphorescent or TADF, highlighting the urgent need to design novel palladium(II) complex OLED systems. Summary of the Invention

[0007] Therefore, the technical problem to be solved by this invention is to overcome the shortcomings of existing linear carbene-metal-amine complex TADF materials, which have low performance and result in low device lifetime and external quantum efficiency of the prepared organic electroluminescent devices. Thus, this invention provides a metal complex and an organic electroluminescent device.

[0008] The solution adopted in this invention is as follows:

[0009] This invention provides a metal complex having the following structure:

[0010]

[0011] Wherein, M is selected from platinum or palladium, and the oxidation state of M is +2;

[0012] Rings A, B, and C are each independently selected from substituted or unsubstituted C6-C. 48 Aromatic ring, substituted or unsubstituted C4-C 48 The heteroaryrheic ring; rings A and B are connected by single bonds or by forming a fused ring; rings B and C are connected by single bonds or by forming a fused ring; rings A, B, and C are coordinated to the metal M center as monovalent tridentate ligands;

[0013] R 1 -R 7 Whether the same or different, each is independently selected from hydrogen, substituted or unsubstituted C1-C. 40 Alkyl, substituted or unsubstituted C6-C 48 Aryl, substituted or unsubstituted C3-C 48 Mixed aromatics;

[0014] Ra represents substituted or unsubstituted C6-C. 48 Aryl or substituted or unsubstituted C6-C 48 Mixed aromatic compounds.

[0015] Preferred, substituted C6-C 48 Aromatic rings, substituted C4-C 48 heterocyclic aromatic rings, substituted C1-C 40 Alkyl, substituted C6-C 48 Aryl, substituted C3-C 48 The substituents of the heteroaryl group are selected from deuterium, halogen, cyano, C1-C6 alkyl, C3-C 30 cycloalkyl, C6-C 30 aryl, C3-C 30 It is one of the heteroaryl groups.

[0016] In this invention, the oxidation state of M is +2.

[0017] Preferred, R 1 R 3 R 4 R 6 and R 7 For hydrogen, R 2 and R 5 Whether identical or different, each is independently selected from substituted or unsubstituted C1-C. 40 Alkyl, substituted or unsubstituted C6-C 48 Aryl, substituted or unsubstituted C3-C 48 Mixed aromatic compounds.

[0018] Preferably, the substituted C1-C 40 Alkyl, substituted C6-C 48 aryl, substituted C3-C 48 The heteroaryl group is optionally substituented by one or more R groups. b Replace; each R b Independently selected from hydrogen, halogen, cyano, C1-C 10 Alkyl, C6-C 30 Aryl.

[0019] Preferably, the C1-C 40The alkyl group is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and tert-butyl;

[0020] The C1-C 10 The alkyl group is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and tert-butyl;

[0021] The C6-C 48 The aryl group is selected from phenyl, naphthyl, and anthracene;

[0022] The C6-C 30 The aryl group is selected from phenyl, naphthyl, and anthracene.

[0023] Preferably, it is characterized in that,

[0024] The tridentate ligand formed by rings A, B, and C has any of the following structures:

[0025]

[0026] Preferably, Ra has any of the following structures:

[0027]

[0028] Preferably, the metal complex has any of the following structures:

[0029]

[0030]

[0031]

[0032]

[0033]

[0034]

[0035]

[0036]

[0037]

[0038]

[0039]

[0040]

[0041]

[0042]

[0043]

[0044] The present invention also provides a method for preparing the above-described metal complex, comprising the following steps:

[0045] Step 1: The tridentate ligand reacts with potassium chloroplatinate or palladium dichloride to generate tridentate ligand M metal chloride E;

[0046] Step 2: Compound A and pinacol diboronic acid ester are coupled via Suzuki coupling reaction to obtain compound arylboronic acid ester B, and then compound B and C are coupled via Suzuki coupling reaction to obtain ligand D;

[0047] Alternatively, compound N can be obtained by reacting compound C with pinacolborane, and then ligand D can be obtained by reacting compound N with A via a Suzuki coupling reaction.

[0048] Step 3: Ligand D undergoes a coordination reaction with the tridentate ligand M and metal chloride E to obtain the metal complex (compound of general formula 1).

[0049] The synthetic route for the metal complexes described in this invention is as follows:

[0050] Step 1

[0051]

[0052] The present invention also provides an organic electroluminescent device, the organic electroluminescent device comprising a first electrode, a second electrode, and a light-emitting layer located between the first electrode and the second electrode, the light-emitting layer comprising any one or a combination of at least two of the metal complexes described above.

[0053] Preferably, the light-emitting layer comprises the metal complex and organic functional material described above, wherein the metal complex accounts for 0.01%-100% by mass percentage, and the organic functional material accounts for 0-99.9%.

[0054] It should be noted that the application of the metal complexes described in this invention is not limited to the device configuration, and the film thickness or constituent materials of each layer can be appropriately modified according to the basic properties of the specific compound structure based on this invention.

[0055] The method for fabricating the organic device described in this invention is a conventional method in the art. Optionally, the fabrication of the organic electroluminescent device includes the following steps: using a glass substrate coated with ITO as a transparent support substrate, and sequentially depositing organic layers and metal electrodes on the ITO film of the transparent support substrate.

[0056] The present invention also provides the application of the above-described organic electroluminescent devices in electronic devices.

[0057] The beneficial effects of this invention are:

[0058] This invention provides a metal complex with the structure of Formula 1, containing a tridentate ligand-metal-secondary amine structure that exhibits excellent TADF performance. Through the unique molecular structure and transition mechanism, and by introducing aryl, heteroaryl, or electron-withdrawing heteroaryl groups at the 1st substitution site Ra of carbazole, an intramolecular non-covalent interaction can be formed between Ra and the tridentate ligand, improving the stability of the metal complex and enhancing the charge transfer process within and between ligands. This suppresses the geometric distortion of the metal complex and, consequently, the nonradiative transition process, resulting in organic electroluminescent devices with high external quantum efficiency and long device lifetime, with an external quantum efficiency as high as 35.6%.

[0059] Furthermore, the tridentate ligand used in the metal complex provided by this invention can be obtained in high yield through simple organic synthesis, and the raw material cost is low, which is of great significance for the mass production process of luminescent materials. Attached Figure Description

[0060] In order to more clearly illustrate the specific embodiments of the present invention or the technical solutions in the prior art, the following briefly introduces the drawings required for use in the specific embodiments or the description of the prior art. Obviously, the drawings described below are some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying any creative work.

[0061] Figure 1 The diagram shows the structure of the organic electroluminescent device in embodiments 1-11 of this invention.

[0062] Figure 2 This is a crystal structure diagram of PtNCN1-12 prepared in Example 3 of the present invention;

[0063] Figure 3 Thermogravimetric analysis curve of PtNCN1-12 prepared in Example 3 of this invention;

[0064] Figure 4 The absorption spectrum of PdCCC1-B5 prepared in Example 30 of this invention in toluene solution;

[0065] Figure 5 The absorption spectrum of PdCCC1-5 prepared in Example 28 of this invention in toluene solution;

[0066] Figure 6The absorption spectrum of PdCCC1-3 prepared in Example 26 of this invention in toluene solution;

[0067] Figure 7 The emission spectrum of PdCCC1-B5 prepared in Example 30 of this invention in toluene solution;

[0068] Figure 8 The emission spectrum of PdCCC1-5 prepared in Example 28 of this invention in toluene solution;

[0069] Figure 9 The emission spectrum of PdCCC1-3 prepared in Example 26 of this invention in toluene solution;

[0070] Figure 10 The absorption spectrum of PtNCN1-5 prepared in Example 7 of this invention in toluene solution;

[0071] Figure 11 The absorption spectrum of PtNCN1-3 prepared in Example 8 of this invention in toluene solution;

[0072] Figure 12 The absorption spectrum of PtNCN1-16 prepared in Example 11 of this invention in toluene solution;

[0073] Figure 13 The absorption spectrum of PtNCN1-12 prepared in Example 3 of this invention in toluene solution;

[0074] Figure 14 The absorption spectrum of PtNCN1-20 prepared in Example 21 of this invention in toluene solution;

[0075] Figure 15 The absorption spectrum of PtNCN1-21 prepared in Example 22 of this invention in toluene solution;

[0076] Figure 16 The absorption spectrum of PtNCN3-16 prepared in Example 16 of this invention in toluene solution;

[0077] Figure 17 The absorption spectrum of PtNCN3-22 prepared in Example 23 of this invention in toluene solution;

[0078] Figure 18 The absorption spectrum of PtNCN3-23 prepared in Example 24 of this invention in toluene solution;

[0079] Figure 19The absorption spectrum of PtNCN3-24 prepared in Example 25 of this invention in toluene solution;

[0080] Figure 20 The emission spectrum of PtNCN1-5 prepared in Example 7 of this invention in tetrahydrofuran solution;

[0081] Figure 21 The emission spectrum of PtNCN1-3 prepared in Example 8 of this invention in tetrahydrofuran solution;

[0082] Figure 22 The emission spectrum of PtNCN1-12 prepared in Example 3 of this invention in toluene solution;

[0083] Figure 23 The emission spectrum of PtNCN1-5 prepared in Example 7 of this invention in a polymethyl methacrylate film;

[0084] Figure 24 The emission spectrum of PtNCN1-3 prepared in Example 8 of this invention in a polymethyl methacrylate film;

[0085] Figure 25 The emission spectrum of PtNCN1-16 prepared in Example 11 of this invention in a polymethyl methacrylate film;

[0086] Figure 26 The emission spectrum of PtNCN1-12 prepared in Example 3 of this invention in a polymethyl methacrylate film;

[0087] Figure 27 The emission spectrum of PtNCN1-20 prepared in Example 21 of this invention in a polymethyl methacrylate film;

[0088] Figure 28 The emission spectrum of PtNCN1-21 prepared in Example 22 of this invention in a polymethyl methacrylate film;

[0089] Figure 29 The emission spectrum of PtNCN3-22 prepared in Example 23 of this invention in a polymethyl methacrylate film;

[0090] Figure 30 The emission spectrum of PtNCN3-23 prepared in Example 24 of this invention in a polymethyl methacrylate film;

[0091] Figure 31 The emission spectrum of PtNCN3-24 prepared in Example 25 of this invention in a polymethyl methacrylate film;

[0092] Figure 32 The emission spectrum of PdCCC1-12 prepared in Example 27 of this invention in a polymethyl methacrylate film;

[0093] Figure 33 The emission spectrum of PdCCC1-3 prepared in Example 26 of this invention in a polymethyl methacrylate film;

[0094] Figure 34 This is a lifetime decay curve of PtNCN1-5 prepared in Example 7 of the present invention in a polymethyl methacrylate film;

[0095] Figure 35 This is a lifetime decay curve of PtNCN1-3 prepared in Example 8 of the present invention in a polymethyl methacrylate film;

[0096] Figure 36 This is a lifetime decay curve of PtNCN1-16 prepared in Example 11 of the present invention in a polymethyl methacrylate film;

[0097] Figure 37 This is a lifetime decay curve of PtNCN1-12 prepared in Example 3 of the present invention in a polymethyl methacrylate film;

[0098] Figure 38 This is a lifetime decay curve of PtNCN1-20 prepared in Example 21 of the present invention in a polymethyl methacrylate film;

[0099] Figure 39 This is a lifetime decay curve of PtNCN1-21 prepared in Example 21 of the present invention in a polymethyl methacrylate film;

[0100] Figure 40 This is a lifetime decay curve of PtNCN3-16 prepared in Example 16 of the present invention in a polymethyl methacrylate film;

[0101] Figure 41 This is a lifetime decay curve of PtNCN3-22 prepared in Example 23 of the present invention in a polymethyl methacrylate film;

[0102] Figure 42 This is a lifetime decay curve of PtNCN3-23 prepared in Example 24 of the present invention in a polymethyl methacrylate film;

[0103] Figure 43 This is a lifetime decay curve of PtNCN3-24 prepared in Example 25 of the present invention in a polymethyl methacrylate film;

[0104] Figure 44 This is a lifetime decay curve of PdCCC1-12 prepared in Example 27 of the present invention in a polymethyl methacrylate film;

[0105] Figure 45 This is a lifetime decay curve of PdCCC1-3 prepared in Example 26 of the present invention in a polymethyl methacrylate film;

[0106] Figure 46 The electroluminescence patterns of the devices in Examples 1-4 of this invention based on compound PtNCN1-12 are shown.

[0107] Figure 47 The electroluminescence quantum efficiency diagrams of the devices in Examples 1-4 of this invention based on compound PtNCN1-12 are shown.

[0108] Figure 48 The electroluminescence patterns of devices in Examples 5-7 of this invention based on compound PdCCC1-12 are shown.

[0109] Figure 49 The electroluminescence quantum efficiency diagrams of devices in Examples 5-7 of this invention based on compound PdCCC1-12 are shown.

[0110] Figure 50 The brightness of the device in Example 12 of this invention, based on compound PdCCC1-12, changes over time;

[0111] Figure 51 Electroluminescence patterns of devices in Examples 8-9 of this invention based on compound PdCCC1-5;

[0112] Figure 52 The electroluminescence quantum efficiency diagrams of the devices in Examples 8-9 of this invention based on compound PdCCC1-5 are shown.

[0113] Figure 53 The electroluminescence patterns of devices in Examples 10-11 of the present invention based on compound PdCCC1-3 are shown.

[0114] Figure 54 Electroluminescence quantum efficiency diagrams of devices in Examples 10-11 of the present invention based on compound PdCCC1-3; Reference numerals:

[0115] 1-Anode layer, 2-Hole injection layer, 3-First hole transport layer, 4-Second hole transport layer, 5-Electron blocking layer, 6-Light emitting layer, 7-First electron transport layer, 8-Second electron transport layer, 9-Electron injection layer, 10-Cathode layer, 100-Glass substrate. Detailed Implementation

[0116] The following embodiments are provided to better understand the present invention and are not limited to the preferred embodiments described. They do not constitute a limitation on the content and scope of protection of the present invention. Any product that is the same as or similar to the present invention, derived by any person under the guidance of the present invention or by combining the features of the present invention with other prior art, falls within the protection scope of the present invention.

[0117] For experiments not specifically described in the examples, the procedures or conditions should be followed according to the conventional experimental procedures described in the literature in this field. Reagents or instruments whose manufacturers are not specified are all commercially available conventional reagent products.

[0118] The method for preparing the metal complex in this embodiment includes the following steps:

[0119] Step 1: The tridentate ligand reacts with potassium chloroplatinate to generate tridentate ligand M metal chloride E;

[0120] Step 2: Compound A and pinacol diboronic acid ester are coupled via Suzuki coupling reaction to obtain compound arylboronic acid ester B, and then compound B and C are coupled via Suzuki coupling reaction to obtain ligand D;

[0121] Alternatively, compound N can be obtained by reacting compound C with pinacolborane, and then ligand D can be obtained by reacting compound N with A via a Suzuki coupling reaction.

[0122] Step 3: Ligand D undergoes a coordination reaction with the tridentate ligand M and metal chloride E to obtain the metal complex (compound of general formula I).

[0123] The synthetic route for the metal complex in this embodiment is shown below:

[0124] Step 1

[0125]

[0126] Example 1

[0127] This embodiment provides a method for preparing the tridentate ligand intermediate and its tridentate ligand M metal chloride required for subsequent preparation of metal complexes, as detailed below:

[0128] 1) Preparation of the tridentate ligand intermediate CNN

[0129] Its synthesis path is shown below:

[0130]

[0131] Phenylated acid (244 mg, 2 mmol), 6-bromo-2,2-bipyridine (383 mg, 1.63 mmol), Na₂CO₃ (864 mg, 8.15 mmol), and tetra(triphenylphosphine)palladium (95 mg, 0.0815 mmol) were dissolved in 30 mL of ultra-dry tetrahydrofuran solution and 10 mL of deoxygenated water. The mixture was stirred and slowly heated to 108 °C. The reaction was allowed to proceed overnight. The mixture was extracted with dichloromethane and water, purified by vacuum distillation, and column chromatography (eluent: petroleum ether: dichloromethane = 10:1) to give a colorless solid intermediate CNN (yield 98%).

[0132] 2) Preparation of the tridentate ligand intermediate NCN1

[0133] Its synthesis path is shown below:

[0134]

[0135] 1,3-Diphenylboronic acid (166 mg, 1 mmol), 1-bromopyridine (258 mg, 1.63 mmol), Na₂CO₃ (864 mg, 8.15 mmol), and tetra(triphenylphosphine)palladium (95 mg, 0.0815 mmol) were dissolved in 30 mL of ultra-dry tetrahydrofuran solution and 10 mL of deoxygenated water. The mixture was stirred and slowly heated to 108 °C. The reaction was allowed to proceed overnight. The mixture was extracted with dichloromethane and water, purified by vacuum distillation, and then by column chromatography (eluent: petroleum ether:dichloromethane = 10:1) to give a colorless solid intermediate NCN1 (yield 88%). 1 HNMR(400MHz, CDCl3)δ8.71(d,J=4.4Hz,2H),8.64(s,1H),8.05(d,J=7.6Hz,2H),7.81 (d,J=7.5Hz,2H),7.72(t,J=7.6Hz,2H),7.57(t,J=7.8Hz,1H),7.21(t,J=5.6Hz,2H); 13 CNMR(101MHz, CDCl3)δ157.1,149.7,139.9,136.8,129.2,127.5,125.5,122.3,120.7ppm; EI-MS:m / zcalcdforC 16 H 12 N2[M] + :232.10; found:232.27.

[0136] 3) Preparation of the tridentate ligand intermediate NCN2

[0137] Its synthesis path is shown below:

[0138]

[0139] 2-Pyridineboronic acid (234 mg, 1.9 mmol), its monobrominated derivative (421 mg, 1.63 mmol), Na₂CO₃ (864 mg, 8.15 mmol), and tetra(triphenylphosphine)palladium (95 mg, 0.0815 mmol) were dissolved in 30 mL of ultra-dry tetrahydrofuran solution and 10 mL of deoxygenated water. The mixture was stirred and slowly heated to 108 °C. The reaction was allowed to proceed overnight. The mixture was extracted with dichloromethane and water, purified by vacuum distillation, and column chromatography (eluent: petroleum ether: dichloromethane = 10:1) to give a colorless solid intermediate NCN₂ (yield 78%).

[0140] 4) Preparation of the tridentate ligand intermediate NCN3

[0141] Its synthesis path is shown below:

[0142]

[0143] 2-(3-bromobenzene)-pyridine (234 mg, 1 mmol), pyrazole (102 mg, 1.5 mmol), K₂CO₃ (830 mg, 6 mmol), 1,2-cyclohexanediamine (46 mg, 0.4 mmol), and cuprous iodide (19 mg, 0.1 mmol) were dissolved in 30 mL of DMF, stirred, and slowly heated to 130 °C. The reaction was allowed to proceed overnight. The mixture was extracted with dichloromethane and water, purified by vacuum distillation, and column chromatography (eluent: petroleum ether: dichloromethane = 2:1) to give a colorless solid intermediate NCN₃ (yield 88%). 1 HNMR(500MHz, CDCl3)δ8.73(d,J=4.6Hz,1H),8.38(t,J=1.9Hz,1H),8.07(d,J=2.4Hz,1 H), 8.03 (s, 1H), 7.93 (d, J = 7.8Hz, 1H), 7.80 (m, 4H), 7.58 (t, J = 7.9Hz, 1H), 7.29 (m, 1H).

[0144] 5) Preparation of the tridentate ligand intermediate CCC1

[0145] Its synthesis path is shown below:

[0146]

[0147] 1,3-Diiodobenzene (330 mg, 1 mmol), imidazole (102 mg, 1.5 mmol), K2CO3 (830 mg, 6 mmol), cuprous iodide (19 mg, 0.1 mmol), and L-proline (58 mg, 0.5 mmol) were dissolved in 30 mL of ultradry DMSO solution, stirred, and slowly heated to 140 °C. The reaction was carried out for 48 h, followed by extraction with dichloromethane and water, vacuum distillation, and purification by column chromatography (eluent: petroleum ether: dichloromethane = 2:1) to give colorless solid intermediate 1 (yield 80%).

[0148] Intermediate 1 (210 mg, 1 mmol) and n-butyl bromide (1370 mg, 10 mmol) were dissolved in 30 mL of acetonitrile solution, stirred, and slowly heated to 80 °C. The reaction was carried out for 72 h, filtered, and distilled under reduced pressure to give colorless solid intermediate CCC1 (yield 60%). 1 HNMR (300MHz, CD2Cl2): d11.56(s,2H),9.04(t,J=2.0Hz,1H),8.91(t,J=1.8Hz,2H),8.24(dd,J=8.3,2.0Hz,2H),7.72(t,J=8 .3Hz,1H),7.60(t,J=1.8Hz,2H),4.45(t,J=7.3Hz,4H),2.02(tt,J=7.5Hz,4H),1.43(qt,J=7.5Hz,4H),1.00(t,J=7.3Hz,6H). 13 CNMR (126MHz, CD2Cl2):d137.0,136.5,133.0,123.4,122.8,122.4,115.5,51.0,32.4,20.1,13.8.

[0149] 6) Preparation of tridentate ligand metal chloride ClPtCNN

[0150] Its synthesis path is shown below:

[0151]

[0152] CNN ligand (232 mg, 1 mmol) and potassium chloroplatinate (415 mg, 1 mmol) were dissolved in 20 mL of glacial acetic acid, stirred, and slowly heated to 120 °C. After reacting for 72 hours, the mixture was filtered, washed with water, and dried to obtain a colorless solid intermediate ClPtCNN (yield 65%).

[0153] 7) Preparation of tridentate ligand metal chloride ClPtNCN1

[0154] Its synthesis path is shown below:

[0155]

[0156] NCN1 ligand (232 mg, 1 mmol) and potassium chloroplatinate (415 mg, 1 mmol) were dissolved in 20 mL of glacial acetic acid. The mixture was stirred, slowly heated to 120 °C, and reacted for 72 hours. After filtration, the solution was washed with water and dried to obtain a colorless solid intermediate, ClPtNCN1 (yield 69%). 1 HNMR(300MHz,DMSO-d6)δ9.07(dd,J=5.5,0.9Hz,2H),8.17(td,J=7.7,1.6Hz,2H),8.07(brd, J=7.6Hz,2H),7.70(d,J=7.7Hz,2H),7.52(ddd,J=7.4,5.8,1.6Hz,2H),7.23(t,J=7.7Hz,1H); 13 CNMR(75MHz,DMSO-d6)δ166.73,161.19,151.41,140.65,140.60,125.09,124.28,123.28,120.62.

[0157] 8) Preparation of tridentate ligand metal chloride ClPtNCN2

[0158] Its synthesis path is shown below:

[0159]

[0160] NCN2 ligand (256 mg, 1 mmol) and potassium chloroplatinate (415 mg, 1 mmol) were dissolved in 20 mL of glacial acetic acid, stirred, and slowly heated to 120 °C. After reacting for 72 hours, the mixture was filtered, washed with water, and dried to obtain a colorless solid intermediate ClPtNCN2 (yield 75%).

[0161] 9) Preparation of tridentate ligand metal chloride ClPtNCN3

[0162] Its synthesis path is shown below:

[0163]

[0164] NCN3 ligand (221 mg, 1 mmol) and potassium chloroplatinate (415 mg, 1 mmol) were dissolved in 20 mL of glacial acetic acid. The mixture was stirred, and the temperature was slowly raised to 120 °C. After reacting for 72 hours, the mixture was filtered, washed with water, and dried to obtain a colorless solid intermediate, ClPtNCN3 (70% yield). 1HNMR(500MHz, CDCl3)δ9.35(t,J=10.3Hz,1H),8.07(dd,J=10.2,2.6Hz,2H),7.99(td,J=7.8,1.5Hz,1H),7 .73(d,J=7.7Hz,1H),7.38(d,J=7.7Hz,1H),7.34(m,1H),7.28(m,4H),7.15(d,J=7.8Hz,1H),6.68(m,1+H).

[0165] 10) Preparation of tridentate ligand metal chloride ClPtCCCl

[0166] Its synthesis path is shown below:

[0167]

[0168] CCC1 ligand (324 mg, 1 mmol), potassium chloroplatinate (830 mg, 2 mmol), and silver oxide (552 mg, 2.38 mmol) were dissolved in 20 mL of DMSO. The mixture was stirred in the dark and the temperature was slowly raised to 156 °C. After reacting for 72 hours, the crude product was suspended in dichloromethane and filtered. The filtrate was washed with water, and the organic phase was dried over magnesium sulfate. The organic phase was rotary evaporated, and acetonitrile was added, followed by another rotary evaporation to give a yellow solid intermediate, ClPtCCC1 (70% yield).

[0169] 11) Preparation of tridentate ligand metal chloride ClPdCNN

[0170] Its synthesis path is shown below:

[0171]

[0172] CNN ligand (232 mg, 1 mmol) and palladium dichloride (177 mg, 1 mmol) were dissolved in 20 mL of glacial acetic acid, stirred, and slowly heated to 120 °C. After reacting for 72 hours, the mixture was filtered, washed with water, and dried to obtain a colorless solid intermediate ClPdCNN (yield 75%).

[0173] 12) Preparation of tridentate ligand metal chloride ClPdNCN1

[0174] Its synthesis path is shown below:

[0175]

[0176] The NCN1 ligand (232 mg, 1 mmol) and palladium dichloride (177 mg, 1 mmol) were dissolved in 20 mL of glacial acetic acid, stirred, and slowly heated to 120 °C. After reacting for 72 hours, the mixture was filtered, washed with water, and dried to obtain a colorless solid intermediate ClPdNCN1 (yield 69%).

[0177] 13) Preparation of tridentate ligand metal chloride ClPdNCN2

[0178] Its synthesis path is shown below:

[0179]

[0180] The NCN2 ligand (256 mg, 1 mmol) and palladium dichloride (177 mg, 1 mmol) were dissolved in 20 mL of glacial acetic acid, stirred, and slowly heated to 120 °C. After reacting for 72 hours, the mixture was filtered, washed with water, and dried to obtain a colorless solid intermediate ClPdNCN2 (yield 75%).

[0181] 14) Preparation of tridentate ligand metal chloride ClPdNCN3

[0182] Its synthesis path is shown below:

[0183]

[0184] NCN3 ligand (221 mg, 1 mmol) and palladium dichloride (177 mg, 1 mmol) were dissolved in 20 mL of glacial acetic acid, stirred, and slowly heated to 120 °C. After reacting for 72 hours, the mixture was filtered, washed with water, and dried to obtain a colorless solid intermediate ClPdNCN3 (yield 70%).

[0185] 15) Preparation of tridentate ligand metal chloride ClPdCCCl

[0186] Its synthesis path is shown below:

[0187]

[0188] CCC1 ligand (485 mg, 1 mmol), palladium dichloride (177 mg, 2 mmol), and sodium acetate (320 mg, 4 mmol) were dissolved in 20 mL of DMAc (N,N-dimethylacetamide). The mixture was stirred and slowly heated to 140 °C. After reacting for three days, the crude product was suspended in dichloromethane and filtered. The filtrate was washed with water, and the organic phase was dried over magnesium sulfate. The organic phase was rotary evaporated, acetonitrile was added, followed by further rotary evaporation, and finally purified by column chromatography to obtain the final product (yield 36%). 1HNMR (500MHz, CDCl3) δ7.32(d,J=1.9Hz,2H),7.13(t,J=7.8Hz,1H),6.91(d,J=1.9Hz,2H),6.89(s,1H) ,6.87(s,1H),4.76(t,J=7.4Hz,4H),1.88(m,4H),1.47(dq,J=14.9,7.4Hz,4H),0.96(t,J=7.4Hz,6H).

[0189] Example 2

[0190] This embodiment provides a method for preparing the intermediate compound required for the subsequent preparation of the metal complex, as detailed below:

[0191] 1) Preparation of intermediate 1

[0192] Its synthesis path is shown below:

[0193]

[0194] Its preparation method specifically includes the following steps:

[0195] 2-(4-bromophenyl)-4,6-diphenyl-1,3,5-triazine (3 g, 7.73 mmol), pinacol diboronate (4.9 g, 19.3 mmol), [1,1'-bis(diphenylphosphino)ferrocene]palladium dichloride (565 mg, 0.773 mmol), and potassium acetate (4.55 g, 46.358 mmol) were dissolved in 100 mL of ultradry 1,4-dioxane solvent and refluxed at 108 °C for 12 hours. The reaction solution was filtered through diatomaceous earth, and the filtrate was purified by vacuum distillation and column chromatography to give a white solid intermediate 1 (yield 95%).

[0196] 2) Preparation of intermediate 2

[0197] Its synthesis path is shown below:

[0198]

[0199] Its preparation method specifically includes the following steps:

[0200] 2-(4-bromophenyl)-4,6-diphenyl-1,3,5-pyrimidine (3 g, 7.726 mmol), pinacol diboronate (4.9 g, 19.3 mmol), [1,1'-bis(diphenylphosphino)ferrocene]palladium dichloride (565 mg, 0.773 mmol), and potassium acetate (4.55 g, 46.358 mmol) were dissolved in 100 mL of ultradry 1,4-dioxane solvent and refluxed at 108 °C for 12 hours. The reaction solution was filtered through diatomaceous earth, and the filtrate was purified by vacuum distillation and column chromatography to give a white solid intermediate 2 (yield 90%).

[0201] 3) Preparation of intermediate 3

[0202] Its synthesis path is shown below:

[0203]

[0204] Its preparation method specifically includes the following steps:

[0205] 3,6-Di-tert-butyl-9H-carbazole (13.97 g, 50 mmol) was added to 300 mL of chloroform solution, cooled to 0 °C in an ice bath, stirred, and 30 mL of chloroform solution containing NBS (7.079 g, 60 mmol) was added dropwise. The mixture was wrapped in aluminum foil and reacted for 8 h. The solvent was removed by vacuum distillation, and the mixture was purified by dichloromethane / petroleum ether column chromatography to give a white solid intermediate 3 (yield 90%). 1H NMR (400 MHz, CDCl3): δ 8.06 (d, J = 1.6 Hz, 1H), 8.05 (s, 1H), 8.03 (d, J = 1.4 Hz, 1H), 7.61 (d, J = 1.5 Hz, 1H), 7.52 (dd, J = 8.6, 1.8 Hz, 1H), 7.40 (d, J = 8.5 Hz, 1H), 1.47 (d, J = 3.6 Hz, 18H).

[0206] 4) Preparation of intermediate 4

[0207] Its synthesis path is shown below:

[0208]

[0209] Its preparation method specifically includes the following steps:

[0210] Intermediate 3 (358 mg, 1 mmol), pinacol borane (0.8 mL, 5 mmol), [bis(triphenylphosphino)]palladium dichloride (70.2 mg, 0.1 mmol), and triethylamine (1.49 mL) were dissolved in 10 mL of ultra-dry 1,4-dioxane solvent and refluxed overnight at 108 °C. The reaction solution was filtered through diatomaceous earth, and the filtrate was purified by vacuum distillation and column chromatography (eluent: petroleum ether: dichloromethane = 20:1) to obtain a white solid intermediate. Solid 4 (yield 95%), 1H NMR (400MHz, CDCl3): δ 8.96 (s, 1H), 8.22 (d, J = 2.0 Hz, 1H), 8.08 (d, J = 1.6 Hz, 1H), 7.89 (d, J = 2.0 Hz, 1H), 7.47 (dd, J = 8.5, 1.9 Hz, 1H), 7.40 (d, J = 8.5 Hz, 1H), 1.50–1.41 (m, 30H).

[0211] 5) Preparation of intermediate 5

[0212] Its synthesis path is shown below:

[0213]

[0214] Its preparation method specifically includes the following steps:

[0215] Intermediate 3 (700 mg, 1.955 mmol), intermediate 1 (708 mg, 1.63 mmol), K₂CO₃ (1.126 g, 8.15 mmol), and tetrakis(triphenylphosphine)palladium (95 mg, 0.0815 mmol) were dissolved in 30 mL of ultra-dry tetrahydrofuran solution and 10 mL of deoxygenated water. The mixture was stirred and slowly heated to 108 °C. The reaction was allowed to proceed overnight. The mixture was extracted with dichloromethane and water, purified by vacuum distillation, and column chromatography (eluent: petroleum ether:dichloromethane = 20:1) to give intermediate 5, a yellow-green solid (yield 98%). The product emitted a sky-blue light under a 365 nm UV lamp. 1 HNMR (500MHz, CDCl3) δ8.98-8.95(m,2H),8.84-8.82(m,4H),8.21(s,1H),8.13(dd,J=5.5Hz,J=1.5Hz,2H),7.94- 7.92(m,2H),7.64-7.58(m,7H),7.50(dd,J=8.5Hz,J=2.0Hz,1H),7.36(d,J=8.5Hz,1H),1.53(s,9H),1.47(s,9H).

[0216] 6) Preparation of intermediate 6

[0217] Its synthesis path is shown below:

[0218]

[0219] Its preparation method specifically includes the following steps:

[0220] Intermediate 3 (700 mg, 1.955 mmol), intermediate 2 (708 mg, 1.63 mmol), K2CO3 (1.126 g, 8.15 mmol), and tetra(triphenylphosphine)palladium (95 mg, 0.0815 mmol) were dissolved in 30 mL of ultra-dry tetrahydrofuran solution and 10 mL of deoxygenated water. The mixture was stirred and slowly heated to 108 °C. The reaction was carried out overnight. The mixture was extracted with dichloromethane and water, purified by vacuum distillation, and column chromatography (eluent: petroleum ether: dichloromethane = 20:1) to give green solid intermediate 6 (yield 88%). The product emitted sky blue light under a 365 nm UV lamp. 1 HNMR (500MHz, CDCl3) δ8.79-8.77(m,2H),8.50-8.48(m,2H),8.35-8.33(m,2H),8.18(s,1H),8.13(t,J=2.5Hz,2H),8.11(s, 1H),7.92-7.91(m,2H),7.62-7.54(m,7H),7.49(dd,J=8.5Hz,J=1.5Hz,1H),7.35(d,J=8.5Hz,1H),1.52(s,9H),1.47(s,9H).

[0221] 7) Preparation of intermediate 7

[0222] Its synthesis path is shown below:

[0223]

[0224] Its preparation method specifically includes the following steps:

[0225] Intermediate 4 (791 mg, 1.955 mmol), intermediate 1-1 (665 mg, 1.63 mmol), K2CO3 (1.126 g, 8.15 mmol), and tetra(triphenylphosphine)palladium (95 mg, 0.0815 mmol) were dissolved in 30 mL of ultra-dry tetrahydrofuran solution and 10 mL of deoxygenated water. The mixture was stirred and slowly heated to 108 °C. The reaction was carried out overnight. The mixture was extracted with dichloromethane and water, purified by vacuum distillation, and column chromatography (eluent: petroleum ether: dichloromethane = 5:1) to give intermediate 7 as a yellow solid (yield 75%).

[0226] 8) Preparation of intermediate 8

[0227] Its synthesis path is shown below:

[0228]

[0229] Its preparation method specifically includes the following steps:

[0230] Intermediate 4 (791 mg, 1.955 mmol), intermediates 1-2 (300 mg, 1.63 mmol), K₂CO₃ (1.126 g, 8.15 mmol), and tetrakis(triphenylphosphine)palladium (95 mg, 0.0815 mmol) were dissolved in 30 mL of ultra-dry tetrahydrofuran solution and 10 mL of deoxygenated water. The mixture was stirred and slowly heated to 108 °C. The reaction was carried out overnight. The mixture was extracted with dichloromethane and water. The extract was distilled under reduced pressure and purified by column chromatography (eluent: petroleum ether: dichloromethane = 2:1) to give intermediate 8 as a yellow solid (60% yield). 1 HNMR(500MHz, CDCl3)δ8.46(m,1H),8.36(d,J=8.0Hz1H),8.23(m,1H),8.18 (s,1H),7.84(t,J=2.5Hz,4H),7.62-7.50(m,2H),1.43(s,9H),1.32(s,9H).

[0231] 9) Preparation of intermediate 9

[0232] Its synthesis path is shown below:

[0233]

[0234] Its preparation method specifically includes the following steps:

[0235] Intermediate 4 (791 mg, 1.955 mmol), intermediates 1-3 (340 mg, 1.63 mmol), K₂CO₃ (1.126 g, 8.15 mmol), and tetrakis(triphenylphosphine)palladium (95 mg, 0.0815 mmol) were dissolved in 30 mL of ultra-dry tetrahydrofuran solution and 10 mL of deoxygenated water. The mixture was stirred and slowly heated to 108 °C. The reaction was allowed to proceed overnight. The mixture was extracted with dichloromethane and water, purified by vacuum distillation, and column chromatography (eluent: petroleum ether:dichloromethane = 5:1) to give a white solid intermediate 9 (60% yield). 1 HNMR (500MHz, CDCl3) δ9.21 (d, J = 8.5Hz, 2H), 8.58 (d, J = 8.0Hz1H), 8.33 (m, 1H), 8.18 (s, 1H), 7.66-7.55 (m, 2H), 1.50 (s, 9H), 1.44 (s, 9H).

[0236] 10) Preparation of intermediate 10

[0237] Its synthesis path is shown below:

[0238]

[0239] Its preparation method specifically includes the following steps:

[0240] Intermediate 4 (791 mg, 1.955 mmol), intermediates 1-4 (470 mg, 1.63 mmol), K2CO3 (1.126 g, 8.15 mmol), and tetrakis(triphenylphosphine)palladium (95 mg, 0.0815 mmol) were dissolved in 30 mL of ultra-dry tetrahydrofuran solution and 10 mL of deoxygenated water. The mixture was stirred and slowly heated to 108 °C. The reaction was allowed to proceed overnight. The mixture was extracted with dichloromethane and water, purified by vacuum distillation, and column chromatography (eluent: petroleum ether: dichloromethane = 10:1) to give a white product (yield 75%).

[0241] The product obtained in the previous step (970 mg, 2 mmol) and 1,2-phenylenediamine (216 mg, 2 mmol) were then added to a two-necked reaction flask. 20 mL of n-butanol was injected under a nitrogen atmosphere, and the reaction was refluxed at 120 °C for 12 hours. After the reaction was complete, the solvent was evaporated, and the product was purified by column chromatography to obtain a deep yellow product 10 (98% yield). 1 H NMR(500MHz, CDCl3)δ9.53(d,J=8.0Hz,1H),9.47-9.45(m,1H),8.86(d,J=1.5Hz,1H), 8.60-8.58(m,1H),8.42-8.37(m,3H),8.20(dd,J=10.0Hz,J=1.5Hz,2H),8.06(dd,J=8. 5Hz,J=1.5Hz,1H),7.93-7.89(m,2H),7.82-7.78(m,2H),7.69(d,J=2.0Hz,J=1.5Hz,1 H), 7.53 (dd, J = 8.5Hz, J = 2.0Hz, 1H), 7.42 (d, J = 5.5Hz, 1H), 1.59 (s, 10H), 1.51 (s, 9H).

[0242] 11) Preparation of intermediate 11

[0243] Its synthesis path is shown below:

[0244]

[0245] Its preparation method specifically includes the following steps:

[0246] Intermediate 4 (791 mg, 1.955 mmol), intermediates 1-5 (538 mg, 1.63 mmol), K2CO3 (1.126 g, 8.15 mmol), and tetra(triphenylphosphine)palladium (95 mg, 0.0815 mmol) were dissolved in 30 mL of ultra-dry tetrahydrofuran solution and 10 mL of deoxygenated water. The mixture was stirred and slowly heated to 108 °C. The reaction was carried out overnight. The mixture was extracted with dichloromethane and water, purified by vacuum distillation, and column chromatography (eluent: petroleum ether: dichloromethane = 7:1) to give intermediate 11 as a yellow solid (yield 77%). 1 H NMR (500MHz, DMSO-d6) δ11.70(s,1H),9.66(d,J=8.0Hz,1H),9.50-9.42(m,2H),8.80(d,J=1.5Hz,1H),8.20(dd,J=10.0Hz,J=1.5Hz, 2H), 8.06 (dd, J=8.5Hz, J=1.5Hz, 2H), 7.91 (m, 2H), 7.53 (dd, J=8.5Hz, J=2.0Hz, 1H), 7.42 (d, J=5.5Hz, 1H), 1.60 (s, 9H), 1.51 (s, 9H).

[0247] 12) Preparation of intermediate 12

[0248] Its synthesis path is shown below:

[0249]

[0250] Its preparation method specifically includes the following steps:

[0251] Intermediate 4 (791 mg, 1.955 mmol), intermediates 1-6 (586 mg, 1.63 mmol), K₂CO₃ (1.126 g, 8.15 mmol), and tetra(triphenylphosphine)palladium (95 mg, 0.0815 mmol) were dissolved in 30 mL of ultra-dry tetrahydrofuran solution and 10 mL of deoxygenated water. The mixture was stirred and slowly heated to 108 °C. The reaction was allowed to proceed overnight. The mixture was extracted with dichloromethane and water, purified by vacuum distillation, and column chromatography (eluent: petroleum ether:dichloromethane = 15:1) to give intermediate 12 as a yellow solid (yield 50%). 1HNMR(500MHz, CDCl3)δ9.02(d,J=8.0Hz,1H),8.95(m,1H),8.80(d,J=1.5Hz,1H ),8.60(m,1H),8.22(m,3H),8.10(dd,J=10.0Hz,J=1.5Hz,2H),7.96(dd,J=8.5 Hz,J=1.5Hz,1H),7.80(m,2H),7.72(m,2H),7.60(d,J=2.0Hz,J=1.5Hz,1H),7. 43(dd,J=8.5Hz,J=2.0Hz,1H),7.03(d,J=5.5Hz,1H),1.66(s,9H),1.55(s,9H).

[0252] 13) Preparation of intermediate 13

[0253] Its synthesis path is shown below:

[0254]

[0255] Its preparation method specifically includes the following steps:

[0256] Intermediate 4 (791 mg, 1.955 mmol), intermediates 1-7 (570 mg, 1.63 mmol), K₂CO₃ (1.126 g, 8.15 mmol), and tetrakis(triphenylphosphine)palladium (95 mg, 0.0815 mmol) were dissolved in 30 mL of ultra-dry tetrahydrofuran solution and 10 mL of deoxygenated water. The mixture was stirred and slowly heated to 108 °C. The reaction was allowed to proceed overnight. The mixture was extracted with dichloromethane and water, purified by vacuum distillation, and column chromatography (eluent: petroleum ether:dichloromethane = 8:1) to give a pale yellow solid intermediate 13 (yield 53%). 1 HNMR (500MHz, CDCl3) δ (ppm): 8.71 (dd, J=8.0, 2.0Hz, 2H), 8.38 (s, 1H), 8.17 (dd, J=12.5, 2.0Hz, 2H), 7.74 (t, J=7. 8Hz,2H),7.67(s,1H),7.60-7.58(m,4H),7.51(dd,J=8.5,2.0Hz,1H),7.46–7.36(m,3H),1.56(s,9H),1.50(s,9H). 13CNMR(500MHz, CDCl3)δ(ppm):160.73,158.15,146.84,143.08,142.69,138.21,135.87,134.76,133.85,124.29,124.07 ,123.97,123.64,123.54,123.10,122.53,118.61,116.64,116.47,113.91,110.42,108.39,35.02,34.90,32.27,32.20.

[0257] 14) Preparation of intermediate 14

[0258] Its synthesis path is shown below:

[0259]

[0260] Its preparation method specifically includes the following steps:

[0261] Intermediate 4 (791 mg, 1.955 mmol), intermediates 1-8 (467 mg, 1.63 mmol), K2CO3 (1.126 g, 8.15 mmol), and tetra(triphenylphosphine)palladium (95 mg, 0.0815 mmol) were dissolved in 30 mL of ultra-dry tetrahydrofuran solution and 10 mL of deoxygenated water. The mixture was stirred and slowly heated to 108 °C. The reaction was carried out overnight. The mixture was extracted with dichloromethane and water, purified by vacuum distillation, and column chromatography (eluent: petroleum ether: dichloromethane = 5:1) to give intermediate 14 as a yellow solid (yield 88%). 1 HNMR(500MHz,DMSO-d6)δ10.07(s,1H),9.28(d,J=8.5Hz,2H),9.00(d,J=8.0Hz2H),8.88(t, J=8.0Hz,1.5Hz1H),8.33(m,4H),8.18(s,1H),7.66-7.55(m,2H),1.50(s,9H),1.44(s,9H).

[0262] 15) Preparation of intermediate 15

[0263] Its synthesis path is shown below:

[0264]

[0265] Its preparation method specifically includes the following steps:

[0266] Carbazole (8.35 g, 50 mmol) was added to 300 ml of chloroform solution, cooled to 0 °C in an ice bath, stirred, and 30 ml of chloroform solution containing NBS (7.079 g, 60 mmol) was added dropwise. The mixture was wrapped in aluminum foil and reacted for 8 h. The solvent was removed by vacuum distillation, and the mixture was purified by dichloromethane / petroleum ether column chromatography to give a white solid intermediate 15 (yield 90%).

[0267] 16) Preparation of intermediate 16

[0268] Its synthesis path is shown below:

[0269]

[0270] Its preparation method specifically includes the following steps:

[0271] Intermediate 15 (250 mg, 1 mmol), pinacol borane (0.8 mL, 5 mmol), [bis(triphenylphosphino)]palladium dichloride (70.2 mg, 0.1 mmol), and triethylamine (1.49 mL) were dissolved in 10 mL of ultradry 1,4-dioxane solvent and refluxed at 108 °C overnight. The reaction solution was filtered through diatomaceous earth, and the filtrate was purified by vacuum distillation and column chromatography (eluent: petroleum ether) to give a white solid intermediate 16 (yield 30%).

[0272] 17) Preparation of intermediate 17

[0273] Its synthesis path is shown below:

[0274]

[0275] Its preparation method specifically includes the following steps:

[0276] Intermediate 15 (500 mg, 1.955 mmol), intermediate 1 (708 mg, 1.63 mmol), K₂CO₃ (1.126 g, 8.15 mmol), and tetrakis(triphenylphosphine)palladium (95 mg, 0.0815 mmol) were dissolved in 30 mL of ultra-dry tetrahydrofuran solution and 10 mL of deoxygenated water. The mixture was stirred and slowly heated to 108 °C. The reaction was allowed to proceed overnight. The mixture was extracted with dichloromethane and water, purified by vacuum distillation, and column chromatography (eluent: petroleum ether:dichloromethane = 15:1) to give a light green solid intermediate 17 (yield 78%). 1 HNMR (500MHz, CDCl3) δ8.97 (m, 2H), 8.86 (m, 4H), 8.21 (s, 1H), 8.15 (dd, J = 5.5Hz, J = 1.5H z, 4H), 7.92 (m, 2H), 7.60 (m, 7H), 7.40 (dd, J = 8.5Hz, J = 2.0Hz, 1H), 7.36 (d, J = 8.5Hz, 1H).

[0277] 18) Preparation of intermediate 18

[0278] Its synthesis path is shown below:

[0279]

[0280] Its preparation method specifically includes the following steps:

[0281] Intermediate 16 (596 mg, 1.955 mmol), intermediates 1-7 (570 mg, 1.63 mmol), K₂CO₃ (1.126 g, 8.15 mmol), and tetrakis(triphenylphosphine)palladium (95 mg, 0.0815 mmol) were dissolved in 30 mL of ultra-dry tetrahydrofuran solution and 10 mL of deoxygenated water. The mixture was stirred and slowly heated to 108 °C. The reaction was allowed to proceed overnight. The mixture was extracted with dichloromethane and water, purified by vacuum distillation, and column chromatography (eluent: petroleum ether:dichloromethane = 5:1) to give intermediate 18 as a yellow solid (yield 67%). 1 HNMR(500MHz, CDCl3)δ(ppm):8.77(dd,J=8.0,2.0Hz,2H),8.35(s,1H),8.10(dd,J=12.5,2.0Hz ,2H),7.67(t,J=7.8Hz,2H),7.66(s,1H),7.52(m,6H),7.41(dd,J=8.5,2.0Hz,1H),7.30(m,3H).

[0282] 19) Preparation of intermediate 19

[0283] Its synthesis path is shown below:

[0284]

[0285] Its preparation method specifically includes the following steps:

[0286] Carbazole (20g, 50mmol) was added to 300ml of chloroform solution, cooled to 0℃ in an ice bath, stirred, and 30ml of chloroform solution containing NBS (7.079g, 60mmol) was added dropwise. The mixture was wrapped in aluminum foil and reacted for 8h. The solvent was removed by vacuum distillation, and the mixture was purified by dichloromethane / petroleum ether column chromatography (50:1) to give a white solid intermediate 19 (yield 90%).

[0287] 20) Preparation of intermediate 20

[0288] Its synthesis path is shown below:

[0289]

[0290] Its preparation method specifically includes the following steps:

[0291] Intermediate 19 (482 mg, 1 mmol), pinacol borane (0.8 mL, 5 mmol), [bis(triphenylphosphino)]palladium dichloride (70.2 mg, 0.1 mmol), and triethylamine (1.49 mL) were dissolved in 10 mL of ultradry 1,4-dioxane solvent and refluxed at 108 °C overnight. The reaction solution was filtered through diatomaceous earth, and the filtrate was purified by vacuum distillation and column chromatography (eluent: petroleum ether: dichloromethane = 20:1) to give a white solid intermediate 20 (yield 80%).

[0292] 21) Preparation of intermediate 21

[0293] Its synthesis path is shown below:

[0294]

[0295] Its preparation method specifically includes the following steps:

[0296] Intermediate 19 (800 mg, 1.955 mmol), intermediate 1 (708 mg, 1.63 mmol), K₂CO₃ (1.126 g, 8.15 mmol), and tetrakis(triphenylphosphine)palladium (95 mg, 0.0815 mmol) were dissolved in 30 mL of ultra-dry tetrahydrofuran solution and 10 mL of deoxygenated water. The mixture was stirred and slowly heated to 108 °C. The reaction was allowed to proceed overnight. The mixture was extracted with dichloromethane and water, purified by vacuum distillation, and column chromatography (eluent: petroleum ether:dichloromethane = 15:1) to give a light green solid intermediate 21 (yield 78%). 1 HNMR(500MHz, CDCl3)δ8.80(m,2H),8.49(m,2H),8.34(m,2H),8.20(s,1H),8.15(t,J=2.5Hz,2H),8.11(s,1H),7.92-7.91(m,4H) ,7.62-7.54(m,7H),7.49(dd,J=8.5Hz,J=1.5Hz,2H),7.35(d,J=8.5Hz,2H),2.92(s,6H),2.88(s,6H),2.48(s,3H),2.35(s,3H).

[0297] 22) Preparation of intermediate 22

[0298] Its synthesis path is shown below:

[0299]

[0300] Its preparation method specifically includes the following steps:

[0301] Intermediate 20 (1060 mg, 1.955 mmol), intermediates 1-7 (570 mg, 1.63 mmol), K₂CO₃ (1.126 g, 8.15 mmol), and tetrakis(triphenylphosphine)palladium (95 mg, 0.0815 mmol) were dissolved in 30 mL of ultra-dry tetrahydrofuran solution and 10 mL of deoxygenated water. The mixture was stirred and slowly heated to 108 °C. The reaction was allowed to proceed overnight. The mixture was extracted with dichloromethane and water, purified by vacuum distillation, and column chromatography (eluent: petroleum ether:dichloromethane = 5:1) to give intermediate 22 as a yellow solid (67% yield). 1 HNMR (500MHz, CDCl3) δ (ppm): 8.98 (dd, J=8.0, 2.0Hz, 2H), 8.55 (s, 1H), 8.37 (dd, J=12.5, 2.0Hz, 2H), 7.88 (t, J=7.8Hz, 2H ),7.80(s,1H),7.66(m,6H),7.58(dd,J=8.5,2.0Hz,1H),7.45(m,5H),2.89(s,6H),2.8.(s,6H),2.40(s,3H),2.29(s,3H).

[0302] 23) Preparation of intermediate 23

[0303] Its synthesis path is shown below:

[0304]

[0305] Its preparation method specifically includes the following steps:

[0306] Intermediate 3 (700 mg, 1.955 mmol), intermediates 1-9 (199 mg, 1.63 mmol), K₂CO₃ (1.126 g, 8.15 mmol), and tetra(triphenylphosphine)palladium (95 mg, 0.0815 mmol) were dissolved in 30 mL of ultra-dry tetrahydrofuran solution and 10 mL of deoxygenated water. The mixture was stirred and slowly heated to 108 °C. The reaction was allowed to proceed overnight. The mixture was extracted with dichloromethane and water, purified by vacuum distillation, and column chromatography (eluent: petroleum ether:dichloromethane = 20:1) to give a white solid intermediate 23 (yield 74%). The product emitted a sky-blue light under a 365 nm UV lamp. 1 HNMR (500MHz, DMSO) δ10.81 (s, 1H, NH), 8.17 (s, 2H), 7.73 (m, 2H), 7.58 (t, J = 7.5Hz, 2H), 7.43 (m, 4H), 1.45 (s, 9H), 1.41 (s, 9H).

[0307] 24) Preparation of intermediate 24

[0308] Its synthesis path is shown below:

[0309]

[0310] Its preparation method specifically includes the following steps:

[0311] Intermediate 3 (700 mg, 1.955 mmol), intermediate 1-10 (603 mg, 1.63 mmol), K₂CO₃ (1.126 g, 8.15 mmol), and tetra(triphenylphosphine)palladium (95 mg, 0.0815 mmol) were dissolved in 30 mL of ultra-dry tetrahydrofuran solution and 10 mL of deoxygenated water. The mixture was stirred and slowly heated to 108 °C. The reaction was allowed to proceed overnight. The mixture was extracted with dichloromethane and water, purified by vacuum distillation, and column chromatography (eluent: petroleum ether:dichloromethane = 20:1) to give a white solid intermediate 24 (yield 66%). The product emitted a sky-blue light under a 365 nm UV lamp. 1 HNMR(500MHz, CDCl3)δ8.23(s,1H),8.19(d,J=7.5Hz,2H),8.14(d,J=2.0Hz,2H),7.94(m,2H),7.76(m,2H),7.58(d,J=2.0Hz,1H), 7.56(d,J=8.0Hz,2H),7.50(dd,J=8.5Hz,J=2.0Hz,1H),7.46(m,2H),7.39(d,J=8.0Hz,1H),7.33(m,2H),1.53(s,9H),1.48(s,9H).

[0312] 25) Preparation of intermediate 25

[0313] Its synthesis path is shown below:

[0314]

[0315] Its preparation method specifically includes the following steps:

[0316] Intermediate 3 (700 mg, 1.955 mmol), intermediate 1-11 (668 mg, 1.63 mmol), K₂CO₃ (1.126 g, 8.15 mmol), and tetra(triphenylphosphine)palladium (95 mg, 0.0815 mmol) were dissolved in 30 mL of ultra-dry tetrahydrofuran solution and 10 mL of deoxygenated water. The mixture was stirred and slowly heated to 108 °C. The reaction was allowed to proceed overnight. The mixture was extracted with dichloromethane and water, purified by vacuum distillation, and column chromatography (eluent: petroleum ether:dichloromethane = 20:1) to give a white solid intermediate 25 (yield 61%). The product emitted a sky-blue light under a 365 nm UV lamp. 1HNMR (500MHz, CDCl3) δ8.25(s,1H,NH),8.13(d,J=1.5Hz,2H),7.96(d,J=8.5Hz,2H),7.59(d,J=2.0Hz,1H),7.50(m,5H),7.40(d,J= 8.5Hz, 1H), 7.03 (m, 2H), 6.96 (td, J = 7.5Hz, J = 1.0Hz, 2H), 6.45 (dd, J = 8.5Hz, J = 1.0Hz, 2H), 1.73 (s, 6H), 1.53 (s, 9H), 1.48 (s, 9H).

[0317] 26) Preparation of intermediate 26

[0318] Its synthesis path is shown below:

[0319]

[0320] Its preparation method specifically includes the following steps:

[0321] Intermediate 3 (700 mg, 1.955 mmol), intermediates 1-12 (630 mg, 1.63 mmol), K₂CO₃ (1.126 g, 8.15 mmol), and tetrakis(triphenylphosphine)palladium (95 mg, 0.0815 mmol) were dissolved in 30 mL of ultra-dry tetrahydrofuran solution and 10 mL of deoxygenated water. The mixture was stirred and slowly heated to 108 °C. The reaction was allowed to proceed overnight. The mixture was extracted with dichloromethane and water, purified by vacuum distillation, and column chromatography (eluent: petroleum ether:dichloromethane = 20:1) to give a white solid intermediate 26 (yield 77%). The product emitted a sky-blue light under a 365 nm UV lamp. 1 HNMR (400MHz, Acetone) δ10.23(s,1H,NH),8.28(dd,J=10.4Hz,J=2.0Hz,2H),8.08(m,2H),7.64(d,J=1.6Hz,1H),7.5 7(m,2H),7.50(dd,J=8.4Hz,J=2.0Hz,1H),7.44(d,J=8.4Hz,1H),6.71(m,6H),6.08(m,2H),1.52(s,9H),1.45(s,9H).

[0322] 27) Preparation of intermediate 27

[0323] Its synthesis path is shown below:

[0324]

[0325] Its preparation method specifically includes the following steps:

[0326] Intermediate 4 (791 mg, 1.955 mmol), intermediates 1-13 (570 mg, 1.63 mmol), K2CO3 (1.126 g, 8.15 mmol), and tetra(triphenylphosphine)palladium (95 mg, 0.0815 mmol) were dissolved in 30 mL of ultra-dry tetrahydrofuran solution and 10 mL of deoxygenated water. The mixture was stirred and slowly heated to 108 °C. The reaction was carried out overnight. The mixture was extracted with dichloromethane and water, and purified by column chromatography under reduced pressure (eluent: petroleum ether: dichloromethane = 8:1) to give a light yellow solid intermediate 27 (yield 53%). 1H NMR (500 MHz, DMSO) δ 10.86 (s, 1H, NH), 8.16 (s, 2H), 7.43 (m, 5H), 7.03 (m, 8H), 1.44 (s, 9H), 1.41 (s, 9H).

[0327] 28) Preparation of intermediate 28

[0328] Its synthesis path is shown below:

[0329]

[0330] Its preparation method specifically includes the following steps:

[0331] Intermediate 16 (586 mg, 1.955 mmol), intermediates 1-4 (470 mg, 1.63 mmol), K2CO3 (1.126 g, 8.15 mmol), and tetra(triphenylphosphine)palladium (95 mg, 0.0815 mmol) were dissolved in 30 mL of ultra-dry tetrahydrofuran solution and 10 mL of deoxygenated water. The mixture was stirred and slowly heated to 108 °C. The reaction was carried out overnight, extracted with dichloromethane and water, purified by vacuum distillation and column chromatography (eluent: petroleum ether: dichloromethane = 10:1) to give a white product (yield 80%).

[0332] The product obtained in the previous step (970 mg, 2 mmol) and 1,2-phenylenediamine (216 mg, 2 mmol) were then added to a two-necked reaction flask. 20 mL of n-butanol was injected under a nitrogen atmosphere, and the reaction was refluxed at 120 °C for 12 hours. After the reaction was complete, the solvent was evaporated, and the product was purified by column chromatography to obtain a deep yellow product 28 (90% yield). 1H NMR(600MHz,Chloroform-d)δ9.56(d,J=8.1Hz,1H),9.48–9.44(m,1H),8.87(d, J=1.6Hz,1H),8.63–8.60(m,1H),8.52(s,1H),8.42–8.35(m,2H),8.18(dd,J=7.7 ,5.9Hz,2H),8.07(dd,J=8.2,1.6Hz,1H),7.93–7.86(m,2H),7.84–7.77(m,2H),7 .66(dd,J=7.2,1.1Hz,1H),7.51–7.41(m,3H),7.30(ddd,J=8.0,6.5,1.5Hz,1H).

[0333] Example 3

[0334] This embodiment provides a method for preparing the metal complex PtNCN1-12, and its synthetic route is shown below:

[0335]

[0336] Its preparation method specifically includes the following steps:

[0337] Intermediate 10 (190 mg, 0.3413 mmol) and potassium tert-butoxide (46 mg, 0.409 mmol) were dissolved in 20 mL of ultra-dry tetrahydrofuran solution and stirred at room temperature for 1 h. Then, intermediate ClPtNCN1 (157 mg, 0.3413 mmol) was added, and the reaction was allowed to proceed overnight at room temperature. The reaction solution was filtered through diatomaceous earth, and the filtrate was distilled under reduced pressure, washed with cold n-pentane, and then recrystallized with dichloromethane:n-hexane in a ratio of 1:100 to obtain a red powder, which is the metal complex PtNCN1-12 (yield 75%). 1 HNMR (400MHz, CDCl3) δ9.18 (dd, J=8.0Hz, J=1.2Hz, 1H), 8.48 (m, 2H), 8.36 (m, 3H) ,8.30(m,1H),8.22(s,1H),7.92(m,2H),7.70(m,2H),7.65(d,J=8.8Hz,2H),7.54 (m,2H),7.46(d,J=2.4Hz,1H),7.33(dd,J=8.4Hz,J=2.0Hz,1H),7.15(m,2H),6.9 4(t,J=5.6Hz,3H),6.35(m,3H),5.97(t,J=7.6Hz,1H),1.60(s,9H),1.52(s,9H). 13CNMR (126MHz, CDCl3) δ167.45,166.11,151.80,149.42,148.07,144.81,142.43,142.21, 142.13,141.69,138.11,137.78,137.58,132.26,131.05,130.16,129.71,129.43,129.37 ,129.18,129.10,127.87,126.95,126.64,126.08,125.68,125.50,124.90,124.44,122.80,121.86,121.68,121.39,118.73,115.34,115.28,114.16,34.69,34.61,32.47,32.39.

[0338] Example 4

[0339] This embodiment provides a method for preparing the metal complex PtNCN2-12, and its synthetic route is shown below:

[0340]

[0341] Its preparation method specifically includes the following steps:

[0342] Intermediate 10 (190 mg, 0.3413 mmol) and potassium tert-butoxide (46 mg, 0.409 mmol) were dissolved in 20 mL of ultra-dry tetrahydrofuran solution and stirred at room temperature for 1 h. Then, intermediate ClPtNCN2 (482 mg, 0.3413 mmol) was added and the reaction was allowed to proceed overnight at room temperature. The reaction solution was filtered through diatomaceous earth, and the filtrate was distilled under reduced pressure, washed with cold n-pentane, and then recrystallized with dichloromethane:n-hexane in a ratio of 1:100 to obtain the red powder complex PtNCN2-12 (yield 70%).

[0343] Example 5

[0344] This embodiment provides a method for preparing the metal complex PtNCN3-12, and its synthetic route is shown below:

[0345]

[0346] Its preparation method specifically includes the following steps:

[0347] Intermediate 10 (190 mg, 0.3413 mmol) and potassium tert-butoxide (46 mg, 0.409 mmol) were dissolved in 20 mL of ultra-dry tetrahydrofuran solution and stirred at room temperature for 1 h. Then, intermediate ClPtNCN3 (450 mg, 0.3413 mmol) was added and the reaction was allowed to proceed overnight at room temperature. The reaction solution was filtered through diatomaceous earth, and the filtrate was distilled under reduced pressure, washed with cold n-pentane, and then recrystallized with dichloromethane:n-hexane in a ratio of 1:100 to obtain the red powder complex PtNCN3-12 (yield 65%).

[0348] Example 6

[0349] This embodiment provides a method for preparing the metal complex PtCCC1-12, and its synthetic route is shown below:

[0350]

[0351] Its preparation method specifically includes the following steps:

[0352] Intermediate 10 (190 mg, 0.3413 mmol) and potassium tert-butoxide (46 mg, 0.409 mmol) were dissolved in 20 mL of ultra-dry tetrahydrofuran solution and stirred at room temperature for 1 h. Then, intermediate ClPtCCC1 (553 mg, 0.3413 mmol) was added and the mixture was reacted overnight at room temperature. The reaction solution was filtered through diatomaceous earth, and the filtrate was distilled under reduced pressure, washed with cold n-pentane, and then recrystallized with dichloromethane:n-hexane in a ratio of 1:100 to obtain the red powder complex PtCCC1-12 (yield 63%).

[0353] Example 7

[0354] This embodiment provides a method for preparing the metal complex PtNCN1-5, and its synthetic route is shown below:

[0355]

[0356] Its preparation method specifically includes the following steps:

[0357] Intermediate 6 (200 mg, 0.3413 mmol) and potassium tert-butoxide (46 mg, 0.409 mmol) were dissolved in 20 mL of ultra-dry tetrahydrofuran solution and stirred at room temperature for 1 h. Then, intermediate ClPtNCN1 (157 mg, 0.3413 mmol) was added, and the reaction was allowed to proceed overnight at room temperature. The reaction solution was filtered through diatomaceous earth, and the filtrate was distilled under reduced pressure, washed with cold n-pentane, and recrystallized with dichloromethane:n-hexane in a ratio of 1:100 to obtain a yellow powder complex PtNCN1-5 (yield 55%). 1HNMR (500MHz, CDCl3) δ8.66 (dd, J=7.7, 1.8Hz, 2H), 8.30 (dd, J=9.7, 1.9Hz, 2H), 8.22 (dd ,J=7.8,1.5Hz,2H),7.93(dd,J=12.7,6.6Hz,2H),7.85(td,J=7.8,1.5Hz,2H),7.69(d,J= 8.5Hz,1H),7.60(m,7H),7.52(d,J=7.7Hz,2H),7.45(d,J=8.1Hz,2H),7.33(m,5H),7.05 (d, J=7.7Hz, 2H), 6.94 (t, J=6.6Hz, 2H), 6.64 (t, J=7.7Hz, 1H), 1.54 (s, 9H), 1.49 (s, 9H).

[0358] Example 8

[0359] This embodiment provides a method for preparing the metal complex PtNCN1-3, and its synthetic route is shown below:

[0360]

[0361] Its preparation method specifically includes the following steps:

[0362] Intermediate 5 (201 mg, 0.3413 mmol) and potassium tert-butoxide (46 mg, 0.409 mmol) were dissolved in 20 mL of ultra-dry tetrahydrofuran solution and stirred at room temperature for 1 h. Then, intermediate ClPtNCN1 (157 mg, 0.3413 mmol) was added and the mixture was reacted overnight at room temperature. The reaction solution was filtered through diatomaceous earth, and the filtrate was distilled under reduced pressure, washed with cold n-pentane, and then recrystallized with dichloromethane:n-hexane in a ratio of 1:100 to obtain the orange powder complex PtNCN1-3 (yield 75%). 1 HNMR(500MHz, CDCl3)δ8.70(dd,J=8.2,1.3Hz,4H),8.30(dd,J=8.6,1.9Hz,2H),7.88(m,6H),7.65(m,7H),7.48(d,J=7.7Hz,2H),7.33(dd,J=8.6,2.0 Hz,2H),7.31(d,J=2.0Hz,2H),7.26(m,1H),6.94(ddd,J=7.2,5.7,1.3Hz,2 H), 6.88 (d, J = 7.7Hz, 2H), 6.48 (t, J = 7.6Hz, 1H), 1.54 (s, 9H), 1.49 (s, 9H).

[0363] Example 9

[0364] This embodiment provides a method for preparing the metal complex PtNCN1-1, and its synthetic route is shown below:

[0365]

[0366] Its preparation method specifically includes the following steps:

[0367] Intermediate 8 (130 mg, 0.3413 mmol) and potassium tert-butoxide (46 mg, 0.409 mmol) were dissolved in 20 mL of ultra-dry tetrahydrofuran solution and stirred at room temperature for 1 h. Then, intermediate ClPtNCN1 (157 mg, 0.3413 mmol) was added and the mixture was reacted overnight at room temperature. The reaction solution was filtered through diatomaceous earth, and the filtrate was distilled under reduced pressure, washed with cold n-pentane, and then recrystallized with dichloromethane:n-hexane in a ratio of 1:100 to obtain the yellow-green powder complex PtNCN1-1 (yield 71%).

[0368] Example 10

[0369] This embodiment provides a method for preparing the metal complex PtNCN1-7, and its synthetic route is shown below:

[0370]

[0371] Its preparation method specifically includes the following steps:

[0372] Intermediate 9 (165 mg, 0.3413 mmol) and potassium tert-butoxide (46 mg, 0.409 mmol) were dissolved in 20 mL of ultra-dry tetrahydrofuran solution and stirred at room temperature for 1 h. Then, intermediate ClPtNCN1 (157 mg, 0.3413 mmol) was added and the mixture was reacted overnight at room temperature. The reaction solution was filtered through diatomaceous earth, and the filtrate was distilled under reduced pressure, washed with cold n-pentane, and then recrystallized with dichloromethane:n-hexane in a ratio of 1:100 to obtain the orange powder complex PtNCN1-7 (yield 63%).

[0373] Example 11

[0374] This embodiment provides a method for preparing the metal complex PtNCN1-16, and its synthetic route is shown below:

[0375]

[0376] Its preparation method specifically includes the following steps:

[0377] Intermediate 7 (206 mg, 0.3413 mmol) and potassium tert-butoxide (46 mg, 0.409 mmol) were dissolved in 20 mL of ultra-dry tetrahydrofuran solution and stirred at room temperature for 1 h. Then, intermediate ClPtNCN1 (157 mg, 0.3413 mmol) was added and the mixture was reacted overnight at room temperature. The reaction solution was filtered through diatomaceous earth, and the filtrate was distilled under reduced pressure, washed with cold n-pentane, and then recrystallized with dichloromethane:n-hexane in a ratio of 1:100 to obtain the red powder complex PtNCN1-16 (yield 80%).

[0378] Example 12

[0379] This embodiment provides a method for preparing the metal complex PtNCN1-A8, and its synthetic route is shown below:

[0380]

[0381] Its preparation method specifically includes the following steps:

[0382] Intermediate 22 (230 mg, 0.3413 mmol) and potassium tert-butoxide (46 mg, 0.409 mmol) were dissolved in 20 mL of ultra-dry tetrahydrofuran solution and stirred at room temperature for 1 h. Then, intermediate ClPtNCN1 (157 mg, 0.3413 mmol) was added and the mixture was reacted overnight at room temperature. The reaction solution was filtered through diatomaceous earth, and the filtrate was distilled under reduced pressure, washed with cold n-pentane, and then recrystallized with dichloromethane:n-hexane in a ratio of 1:100 to obtain the yellow powder complex PtNCN1-A8 (yield 70%).

[0383] Example 13

[0384] This embodiment provides a method for preparing the metal complex PtCNN1-18, and its synthesis route is shown below:

[0385]

[0386] Its preparation method specifically includes the following steps:

[0387] Intermediate 11 (180 mg, 0.3413 mmol) and potassium tert-butoxide (46 mg, 0.409 mmol) were dissolved in 20 mL of ultra-dry tetrahydrofuran solution and stirred at room temperature for 1 h. Then, intermediate ClPtCNN (157 mg, 0.3413 mmol) was added and the mixture was reacted overnight at room temperature. The reaction solution was filtered through diatomaceous earth, and the filtrate was distilled under reduced pressure and washed with cold n-pentane to obtain the red powder complex PtCNN1-5 (yield 75%).

[0388] Example 14

[0389] This embodiment provides a method for preparing the metal complex PtNCN1-14, and its synthetic route is shown below:

[0390]

[0391] Its preparation method specifically includes the following steps:

[0392] Intermediate 12 (190 mg, 0.3413 mmol) and potassium tert-butoxide (46 mg, 0.409 mmol) were dissolved in 20 mL of ultra-dry tetrahydrofuran solution and stirred at room temperature for 1 h. Then, intermediate ClPtNCN1 (157 mg, 0.3413 mmol) was added and the mixture was reacted overnight at room temperature. The reaction solution was filtered through diatomaceous earth, and the filtrate was distilled under reduced pressure, washed with cold n-pentane, and then recrystallized with dichloromethane:n-hexane in a ratio of 1:100 to obtain an orange-red powder complex PtNCN1-14 (yield 67%).

[0393] Example 15

[0394] This embodiment provides a method for preparing the metal complex PtNCN1-17, and its synthetic route is shown below:

[0395]

[0396] Its preparation method specifically includes the following steps:

[0397] Intermediate 13 (186 mg, 0.3413 mmol) and potassium tert-butoxide (46 mg, 0.409 mmol) were dissolved in 20 mL of ultra-dry tetrahydrofuran solution and stirred at room temperature for 1 h. Then, intermediate ClPtNCN1 (157 mg, 0.3413 mmol) was added and the reaction was carried out overnight at room temperature. The reaction solution was filtered through diatomaceous earth, the filtrate was distilled under reduced pressure, washed with cold n-pentane, and then recrystallized with dichloromethane:n-hexane in a ratio of 1:100 to obtain the yellow-green powder complex PtNCN1-17 (yield 63%).

[0398] Example 16

[0399] This embodiment provides a method for preparing the metal complex PtNCN3-16, and its synthetic route is shown below:

[0400]

[0401] Its preparation method specifically includes the following steps:

[0402] Intermediate 7 (206 mg, 0.3413 mmol) and potassium tert-butoxide (46 mg, 0.409 mmol) were dissolved in 20 mL of ultra-dry tetrahydrofuran solution and stirred at room temperature for 1 h. Then, intermediate ClPtNCN3 (154 mg, 0.3413 mmol) was added and the reaction was carried out overnight at room temperature. The reaction solution was filtered through diatomaceous earth, and the filtrate was distilled under reduced pressure, washed with cold n-pentane, and then recrystallized with dichloromethane:n-hexane in a ratio of 1:100 to obtain an orange-red powder complex PtNCN3-16 (yield 61%).

[0403] Example 17

[0404] This embodiment provides a method for preparing the metal complex PtNCN1-B2, and its synthetic route is shown below:

[0405]

[0406] Its preparation method specifically includes the following steps:

[0407] Intermediate 17 (165 mg, 0.3413 mmol) and potassium tert-butoxide (46 mg, 0.409 mmol) were dissolved in 20 mL of ultra-dry tetrahydrofuran solution and stirred at room temperature for 1 h. Then, intermediate ClPtNCN1 (157 mg, 0.3413 mmol) was added and the mixture was reacted overnight at room temperature. The reaction solution was filtered through diatomaceous earth, and the filtrate was distilled under reduced pressure, washed with cold n-pentane, and then recrystallized with dichloromethane:n-hexane in a ratio of 1:100 to obtain an orange-red powder complex PtNCN1-B2 (yield 70%).

[0408] Example 18

[0409] This embodiment provides a method for preparing the metal complex PtNCN1-B8, and its synthetic route is shown below:

[0410]

[0411] Its preparation method specifically includes the following steps:

[0412] Intermediate 18 (150 mg, 0.3413 mmol) and potassium tert-butoxide (46 mg, 0.409 mmol) were dissolved in 20 mL of ultra-dry tetrahydrofuran solution and stirred at room temperature for 1 h. Then, intermediate ClPtNCN1 (157 mg, 0.3413 mmol) was added and the mixture was reacted overnight at room temperature. The reaction solution was filtered through diatomaceous earth, and the filtrate was distilled under reduced pressure, washed with cold n-pentane, and then recrystallized with dichloromethane:n-hexane in a ratio of 1:100 to obtain an orange-red powder complex PtNCN1-B8 (yield 60%).

[0413] Example 19

[0414] This embodiment provides a method for preparing the metal complex PtNCN1-A2, and its synthetic route is shown below:

[0415]

[0416] Its preparation method specifically includes the following steps:

[0417] Intermediate 21 (242 mg, 0.3413 mmol) and potassium tert-butoxide (46 mg, 0.409 mmol) were dissolved in 20 mL of ultra-dry tetrahydrofuran solution and stirred at room temperature for 1 h. Then, intermediate ClPtNCN1 (157 mg, 0.3413 mmol) was added and the mixture was reacted overnight at room temperature. The reaction solution was filtered through diatomaceous earth, and the filtrate was distilled under reduced pressure, washed with cold n-pentane, and then recrystallized with dichloromethane:n-hexane in a ratio of 1:100 to obtain an orange-red powder complex PtNCN1-A2 (yield 70%).

[0418] Example 20

[0419] This embodiment provides a method for preparing the metal complex PtNCN1-19, and its synthetic route is shown below:

[0420]

[0421] Its preparation method specifically includes the following steps:

[0422] Dissolve tert-butylcarbazole (95 mg, 0.3413 mmol) and potassium tert-butoxide (46 mg, 0.409 mmol) in 20 mL of ultra-dry tetrahydrofuran solution, stir at room temperature for 1 h, then add intermediate ClPtNCN1 (157 mg, 0.3413 mmol), react overnight at room temperature, filter the reaction solution through diatomaceous earth, distill the filtrate under reduced pressure, wash with cold n-pentane, and recrystallize with dichloromethane:n-hexane in a 1:100 ratio to give a yellow-green powder complex PtNCN1-19 (yield 63%). ¹H NMR (600 nm) MHz, CDCl3) δ8.30 (d, J=1.8Hz, 2H), 8.10 (dd, J=5.7, 0.9Hz, 2H), 7.89 (td, J=7.8, 1.6Hz, 2H), 7.77 (d, J=7.9Hz, 2H), 7.70 (d, J = 8.5Hz, 2H), 7.61 (d, J = 7.7Hz, 2H), 7.35 (m, 4H), 6.96 (ddd, J = 7.3, 5.7, 1.4Hz, 2H), 1.60 (s, 18H).

[0423] Example 21

[0424] This embodiment provides a method for preparing the metal complex PtNCN1-20, and its synthetic route is shown below:

[0425]

[0426] Its preparation method specifically includes the following steps:

[0427] Intermediate 23 (120 mg, 0.3413 mmol) and potassium tert-butoxide (46 mg, 0.409 mmol) were dissolved in 20 mL of ultra-dry tetrahydrofuran solution and stirred at room temperature for 1 h. Then, intermediate ClPtNCN1 (157 mg, 0.3413 mmol) was added and the mixture was reacted overnight at room temperature. The reaction solution was filtered through diatomaceous earth, and the filtrate was distilled under reduced pressure, washed with cold n-pentane, and then recrystallized with dichloromethane:n-hexane in a ratio of 1:100 to obtain an orange-red powder complex PtNCN1-20 (yield 53%). 1 HNMR (400MHz, CDCl3) δ8.30(s,2H),7.97(d,J=5.4Hz,2H),7.84(td,J=7.9,1.3Hz,2H),7.70(d,J=8.5Hz,2H),7.62(d,J=7.7Hz,2H),7.45(d,J= 7.7Hz,2H),7.32(dd,J=8.5,1.9Hz,2H),7.25(m,2H),7.21(d,J=7.8Hz,1H),6.90(dd,J=9.5,3.5Hz,2H),6.59(m,3H),1.53(s,9H),1.51(s,9H).

[0428] Example 22

[0429] This embodiment provides a method for preparing the metal complex PtNCN1-21, and its synthetic route is shown below:

[0430]

[0431] Its preparation method specifically includes the following steps:

[0432] Intermediate 24 (177 mg, 0.3413 mmol) and potassium tert-butoxide (46 mg, 0.409 mmol) were dissolved in 20 mL of ultra-dry tetrahydrofuran solution and stirred at room temperature for 1 h. Then, intermediate ClPtNCN1 (157 mg, 0.3413 mmol) was added and the reaction was carried out overnight at room temperature. The reaction solution was filtered through diatomaceous earth, and the filtrate was distilled under reduced pressure, washed with cold n-pentane, and then recrystallized with dichloromethane:n-hexane in a ratio of 1:100 to obtain an orange-red powder complex PtNCN1-21 (yield 66%). 1HNMR (400MHz, CDCl3) δ8.34(dd,J=14.2,1.8Hz,2H),8.16(d,J=5.7Hz,2H),8.05(dd,J=6.2,2.3Hz,2H),7.83(m,2H),7.71(d,J=8.5Hz,1H),7.65(dd,J=7 .7,6.0Hz,4H),7.51(d,J=7.7Hz,2H),7.36(d,J=2.0Hz,1H),7.32(dd,J=8.7 ,2.1Hz,2H),7.22(m,4),6.98(m,4H),6.83(m,2H),1.58(s,9H),1.51(s,9H).

[0433] Example 23

[0434] This embodiment provides a method for preparing the metal complex PtNCN3-22, and its synthetic route is shown below:

[0435]

[0436] Its preparation method specifically includes the following steps:

[0437] Intermediate 25 (192 mg, 0.3413 mmol) and potassium tert-butoxide (46 mg, 0.409 mmol) were dissolved in 20 mL of ultra-dry tetrahydrofuran solution and stirred at room temperature for 1 h. Then, intermediate ClPtNCN1 (157 mg, 0.3413 mmol) was added and the mixture was reacted overnight at room temperature. The reaction solution was filtered through diatomaceous earth, and the filtrate was distilled under reduced pressure, washed with cold n-pentane, and then recrystallized with dichloromethane:n-hexane in a ratio of 1:100 to obtain an orange-red powder complex PtNCN3-22 (yield 76%).

[0438] Example 24

[0439] This embodiment provides a method for preparing the metal complex PtNCN3-23, and its synthetic route is shown below:

[0440]

[0441] Its preparation method specifically includes the following steps:

[0442] Intermediate 26 (192 mg, 0.3413 mmol) and potassium tert-butoxide (46 mg, 0.409 mmol) were dissolved in 20 mL of ultra-dry tetrahydrofuran solution and stirred at room temperature for 1 h. Then, intermediate ClPtNCN1 (157 mg, 0.3413 mmol) was added and the mixture was reacted overnight at room temperature. The reaction solution was filtered through diatomaceous earth, and the filtrate was distilled under reduced pressure, washed with cold n-pentane, and then recrystallized with dichloromethane:n-hexane in a ratio of 1:100 to obtain an orange-red powder complex PtNCN3-23 (yield 73%).

[0443] Example 25

[0444] This embodiment provides a method for preparing the metal complex PtNCN3-24, and its synthetic route is shown below:

[0445]

[0446] Its preparation method specifically includes the following steps:

[0447] Intermediate 27 (188 mg, 0.3413 mmol) and potassium tert-butoxide (46 mg, 0.409 mmol) were dissolved in 20 mL of ultra-dry tetrahydrofuran solution and stirred at room temperature for 1 h. Then, intermediate ClPtNCN1 (157 mg, 0.3413 mmol) was added and the mixture was reacted overnight at room temperature. The reaction solution was filtered through diatomaceous earth, and the filtrate was distilled under reduced pressure, washed with cold n-pentane, and then recrystallized with dichloromethane:n-hexane in a ratio of 1:100 to obtain an orange-red powder complex PtNCN3-24 (yield 80%).

[0448] Example 26

[0449] This embodiment provides a method for preparing the metal complex PdCCC1-3, and its synthetic route is shown below:

[0450]

[0451] Its preparation method specifically includes the following steps:

[0452] Intermediate 10 (200 mg, 0.3413 mmol) and potassium tert-butoxide (46 mg, 0.409 mmol) were dissolved in 20 mL of ultra-dry tetrahydrofuran solution and stirred at room temperature for 1 h. Then, intermediate ClPdCCC1 (160 mg, 0.3413 mmol) was added, and the reaction was allowed to proceed overnight at room temperature. The reaction solution was filtered through diatomaceous earth, and the filtrate was distilled under reduced pressure, washed with cold n-pentane, and then recrystallized with dichloromethane:n-hexane in a ratio of 1:100 to obtain an orange powder complex PdCCC1-3 (yield 70%). 1HNMR (600MHz, CDCl3) δ8.75 (d, J = 8.1 Hz, 4H), 8.21 (s, 1H), 8.15 (s, 1H), 8.02 (d, J = 7. 9Hz,2H),7.67(m,6H),7.57(d,J=8.4Hz,1H),7.43(d,J=7.9Hz,2H),7.31(s,1H),7.28 (m,2H),6.79(s,2H),6.38(m,1H),6.31(d,J=7.8Hz,2H),3.31(m,2H),3.10(m,2H),1. 55(s,9H),1.48(s,9H),1.18(m,4H),0.52(m,2H),0.44(t,J=7.1Hz,6H),0.26(m,2H).

[0453] Example 27

[0454] This embodiment provides a method for preparing the metal complex PdCCC1-12, and its synthetic route is shown below:

[0455]

[0456] Its preparation method specifically includes the following steps:

[0457] Intermediate 10 (190 mg, 0.3413 mmol) and potassium tert-butoxide (46 mg, 0.409 mmol) were dissolved in 20 mL of ultra-dry tetrahydrofuran solution and stirred at room temperature for 1 h. Then, intermediate ClPdCCC1 (160 mg, 0.3413 mmol) was added, and the reaction was allowed to proceed overnight at room temperature. The reaction solution was filtered through diatomaceous earth, and the filtrate was distilled under reduced pressure, washed with cold n-pentane, and then recrystallized with dichloromethane:n-hexane in a ratio of 1:100 to give the red powder complex PdCCC1-12 (yield 63%). 1HNMR(400MHz, CDCl3)δ9.17(dd,J=8.0,J=1.0Hz,1H),8.62(d,J=8.0Hz,1H),8.53(s,1H),8.35-8.31(m,1 H),8.29-8.25(m,1H),8.23(s,1H),8.14(d,J=1.7Hz,1H),7.87(dq,J=6.7,J=3.3Hz,2H),7.69(d,J=8.1Hz ,1H),7.55(t,J=7.2Hz,1H),7.33(m,4H),7.11-7.0(m,1H),6.72(s,2H),6.62(d,J=1.6Hz,2H),5.83(t,J= 7.8Hz,1H),5.67(d,J=7.7Hz,2H),3.29-3.15(m,4H),1.55(s,9H),1.45(s,9H),1.18(s,4H),0.39(m,6H). 13 CNMR (126MHz, CDCl3) δ145.10,142.68,142.40,142.07,141.67,132.31,130 .82,130.08,129.53,129.46,129.33,129.27,129.16,129.03,127.24,126. 39,125.76,124.25,123.12,122.08,119.50,118.56,114.54,113.86,108.02,107.89,106.43,49.35,33.95,32.18,32.06,19.19,13.90,13.84,13.54.

[0458] Example 28

[0459] This embodiment provides a method for preparing the metal complex PdCCC1-5, and its synthetic route is shown below:

[0460]

[0461] Its preparation method specifically includes the following steps:

[0462] Intermediate 10 (200 mg, 0.3413 mmol) and potassium tert-butoxide (46 mg, 0.409 mmol) were dissolved in 20 mL of ultra-dry tetrahydrofuran solution and stirred at room temperature for 1 h. Then, intermediate ClPdCCC1 (160 mg, 0.3413 mmol) was added and the reaction was carried out overnight at room temperature. The reaction solution was filtered through diatomaceous earth, the filtrate was distilled under reduced pressure, washed with cold n-pentane, and then recrystallized with dichloromethane:n-hexane in a ratio of 1:100 to obtain the orange powder complex PdCCC1-5 (yield 72%).

[0463] Example 29

[0464] This embodiment provides a method for preparing the metal complex PdCCC1-17, and its synthetic route is shown below:

[0465]

[0466] Its preparation method specifically includes the following steps:

[0467] Intermediate 13 (186 mg, 0.3413 mmol) and potassium tert-butoxide (46 mg, 0.409 mmol) were dissolved in 20 mL of ultra-dry tetrahydrofuran solution and stirred at room temperature for 1 h. Then, intermediate ClPdCCC1 (160 mg, 0.3413 mmol) was added, and the reaction was allowed to proceed overnight at room temperature. The reaction solution was filtered through diatomaceous earth, and the filtrate was distilled under reduced pressure, washed with cold n-pentane, and recrystallized with dichloromethane:n-hexane in a ratio of 1:100 to obtain the orange powder complex PdCCC1-17 (yield 72%). 1 HNMR(600MHz,Chloroform-d)δ8.51(dd,J=7.7,1.7Hz,2H),8.20(d,J=2.0Hz,1H),8.12(d,J=2.0Hz,1H),7.62(ddd,J=8 .4,6.9,1.6Hz,2H),7.51(d,J=8.5Hz,1H),7.33–7.31(m,2H),7.23(dd,J=8.5,1.9Hz,1H),7.19(d,J=7.9Hz,2H),7.05(s ,2H),6.79(d,J=1.8Hz,2H),6.72(d,J=1.8Hz,2H),6.29(t,J=7.8Hz,1H),5.83(d,J=7.8Hz,2H),3.31–3.25(m,2H),3.19 –3.13(m,2H),1.52(s,9H),1.44(s,9H),1.23–1.13(m,4H),0.50–0.44(m,2H),0.38(t,J=7.2Hz,6H),0.24–0.17(m,2H).

[0468] Example 30

[0469] This embodiment provides a method for preparing the metal complex PdCCC1-B5, and its synthetic route is shown below:

[0470]

[0471] Its preparation method specifically includes the following steps:

[0472] Intermediate 28 (152 mg, 0.3413 mmol) and potassium tert-butoxide (46 mg, 0.409 mmol) were dissolved in 20 mL of ultra-dry tetrahydrofuran solution and stirred at room temperature for 1 h. Then, intermediate ClPdCCC1 (160 mg, 0.3413 mmol) was added, and the reaction was allowed to proceed overnight at room temperature. The reaction solution was filtered through diatomaceous earth, and the filtrate was distilled under reduced pressure, washed with cold n-pentane, and then recrystallized with dichloromethane:n-hexane in a ratio of 1:100 to obtain an orange powder complex PdCCC1-B5 (yield 76%). 1 HNMR(600MHz,Chloroform-d)δ9.17(d,J=8.0Hz,1H),8.64(d,J=8.0Hz,1H),8.51(s,1H),8.34(dd,J=6.0,3.8Hz,1H),8.26(d, J=3.6Hz,2H),8.18(d,J=7.8Hz,1H),7.88(dd,J=6.4,3.4Hz,2H),7.66(d,J=8.1Hz,1H),7.61(d,J=8.1Hz,1H),7.56(t,J=7.4H z,1H),7.40–7.33(m,3H),7.19(t,J=7.2Hz,1H),7.16–7.12(m,1H),7.01–6.96(m,1H),6.72(s,2H),6.64(s,2H),5.86(t,J=7. 7Hz,1H),5.67(s,2H),3.22(s,4H),1.16(s,4H),0.47(dq,J=14.4,7.7,7.1Hz,2H),0.35(s,6H),0.26(dt,J=12.8,7.1Hz,2H).

[0473] Device Example 1

[0474] This embodiment provides an organic electroluminescent device, such as... Figure 1 As shown, the structure includes, from bottom to top, an anode layer 1, a hole injection layer 2, a first hole transport layer 3, a second hole transport layer 4, an electron blocking layer 5, a light-emitting layer 6, a first electron transport layer 7, a second electron transport layer 8, an electron injection layer 9, and a cathode layer 10 disposed on a glass substrate 100.

[0475] The materials used to manufacture the organic electroluminescent device are as follows:

[0476]

[0477] The anode layer 1 is made of ITO (indium tin oxide); the hole injection layer 2 is made of 1,2-hexaazabenzophenanthrene (HAT-CN); the first hole transport layer 3 is made of 4,4'-cyclohexylbis[N,N-di(4-methylphenyl)aniline] (TAPC); the second hole transport layer 4 is made of tris(4-carbazolyl-9-ylphenyl)amine (TCTA); the electron blocking layer 5 is made of 3,3'-bis(9H-carbazolyl-9-yl)-1,1'-biphenyl; 3,3'-bis(9H-carbazolyl-9-yl)-1,1'-biphenyl (mCBP); and the light-emitting layer 6 is formed by co-doping of the host material and the guest material, wherein the host material is 5-(3-(4,6-diphenyl-1,3,5-triazin-2-yl)phenyl)- 7,7-Dimethyl-5,7-dihydroindo[2,1-b]carbazole (DMIC-TRZ), the guest material is the metal complex X of this invention, wherein X is PtNCN1-12, and the doping amount of the guest material accounts for 1% of the total mass of the host material and the guest material; the material of the first electron transport layer 7 is 2,4,6-tris[3-(diphenylphosphino)phenyl]-1,3,5-triazole (PO-T2T); the material of the second electron transport layer 8 is (1-(4-(10-([1,1'-biphenyl]-4-yl)anthracene-9-yl)phenyl)-2-ethyl-1H-benzo[d]-imidazolium) (ANT-BIZ); the material of the electron injection layer 9 is Liq (lithium 8-hydroxyquinoline); the material of the cathode layer 10 is metallic Al.

[0478] The device structure is as follows: ITO / hole injection layer (HAT-CN) (5nm thick) / first hole transport layer (TAPC) (40nm thick) / second hole transport layer (TCTA) (10nm thick) / electron blocking layer (mCBP) (10nm thick) / light emitting layer (DMIC-TRZ:X) (40nm thick) / first electron transport layer (PO-T2T) (20nm thick) / second electron transport layer (ANT-BIZ) (30nm thick) / electron injection layer (Liq) (1.2nm thick) / Al (100nm thick). Wherein, X is PtNCN1-12.

[0479] Device Example 2

[0480] This embodiment provides an organic electroluminescent device, which differs from the organic electroluminescent device provided in embodiment 1 in that the doping amount of the guest material PtNCN1-12 in the light-emitting layer accounts for 3% of the total mass of the host material and the guest material.

[0481] Device Example 3

[0482] This embodiment provides an organic electroluminescent device, which differs from the organic electroluminescent device provided in embodiment 1 in that the doping amount of the guest material PtNCN1-12 in the light-emitting layer accounts for 5% of the total mass of the host material and the guest material.

[0483] Device Example 4

[0484] This embodiment provides an organic electroluminescent device, which differs from the organic electroluminescent device provided in embodiment 1 in that the doping amount of the guest material PtNCN1-12 in the light-emitting layer accounts for 10% of the total mass of the host material and the guest material.

[0485] Device Example 5

[0486] This embodiment provides an organic electroluminescent device, which differs from the organic electroluminescent device provided in embodiment 1 in that: the guest material X in the light-emitting layer is PdCCC1-12, and the doping amount of PdCCC1-12 accounts for 1% of the total mass of the host material and the guest material.

[0487] Device Example 6

[0488] This embodiment provides an organic electroluminescent device, which differs from the organic electroluminescent device provided in embodiment 1 in that: the guest material X in the light-emitting layer is PdCCC1-12, and the doping amount of PdCCC1-12 accounts for 3% of the total mass of the host material and the guest material.

[0489] Device Example 7

[0490] This embodiment provides an organic electroluminescent device, which differs from the organic electroluminescent device provided in embodiment 1 in that: the guest material X in the light-emitting layer is PdCCC1-12, and the doping amount of PdCCC1-12 accounts for 5% of the total mass of the host material and the guest material.

[0491] Device Example 8

[0492] This embodiment provides an organic electroluminescent device, which differs from the organic electroluminescent device provided in embodiment 1 in that: the guest material X in the light-emitting layer is PdCCC1-5, and the doping amount of PdCCC1-5 accounts for 1% of the total mass of the host material and the guest material.

[0493] Device Example 9

[0494] This embodiment provides an organic electroluminescent device, which differs from the organic electroluminescent device provided in embodiment 1 in that: the guest material X in the light-emitting layer is PdCCC1-5, and the doping amount of PdCCC1-5 accounts for 3% of the total mass of the host material and the guest material.

[0495] Device Example 10

[0496] This embodiment provides an organic electroluminescent device, which differs from the organic electroluminescent device provided in embodiment 1 in that: the guest material X in the light-emitting layer is PdCCC1-3, and the doping amount of PdCCC1-3 accounts for 1% of the total mass of the host material and the guest material.

[0497] Device Example 11

[0498] This embodiment provides an organic electroluminescent device, which differs from the organic electroluminescent device provided in embodiment 1 in that: the guest material X in the light-emitting layer is PdCCC1-3, and the doping amount of PdCCC1-3 accounts for 3% of the total mass of the host material and the guest material.

[0499] Device Example 12

[0500] This embodiment provides an organic electroluminescent device, comprising, from bottom to top, an anode layer, a hole injection layer, a hole transport layer, an electron blocking layer, a light-emitting layer, an electron transport layer, an electron injection layer, and a cathode layer disposed on a glass substrate;

[0501] The materials used to manufacture the organic electroluminescent device are as follows:

[0502]

[0503] The anode layer is made of ITO (indium tin oxide); the hole injection layer is made of 1,2-hexaazabenzophenanthrene (HAT-CN); the hole transport layer is made of N4,N4,N4',N4'-tetra(4-biphenyl)-biphenyl-4,4'-diamine (TBBD); the electron blocking layer is made of N-([1,1'-biphenyl]-2-yl)-N-(9,9-dimethyl-9H-fluorene-2-yl)-9,9'-spirodi[fluorene]-2-amine (o-SFAF); and the luminescent layer is formed by co-doping of the host and guest materials, wherein the host material is 5-(3-(4,6-diphenyl- The host material is 1,3,5-triazine-2-yl)phenyl)-7,7-dimethyl-5,7-dihydroindo[2,1-b]carbazole (DMIC-TRZ). The guest material is the metal complex PdCCC1-12 of this invention, and the doping amount of the guest material accounts for 1% of the total mass of the host material and the guest material. The electron transport layer material is (1-(4-(10-([1,1'-biphenyl]-4-yl)anthracene-9-yl)phenyl)-2-ethyl-1H-benzo[d]-imidazolium) (ANT-BIZ). The electron injection layer material is Liq (lithium 8-hydroxyquinoline). The cathode layer material is metallic Al.

[0504] The device structure consists of ITO / hole injection layer (HAT-CN) (5nm thick) / hole transport layer (TBBD) (30nm thick) / electron blocking layer (o-SFAF) (15nm thick) / light emitting layer (DMIC-TRZ:PdCCC1-12) (45nm thick) / electron transport layer (ANT-BIZ) (40nm thick) / electron injection layer (Liq) (2nm thick) / Al (100nm thick).

[0505] Testing and characterization of metal complexes:

[0506] The 1H NMR spectrum of the metal complex PtNCN1-12 was analyzed, and its crystal structure is as follows: Figure 2 As shown; thermal stability analysis of the metal complex PtNCN1-12 was performed. Figure 3 Thermogravimetric analysis curves of PtNCN1-12.

[0507] The absorption and emission spectra of the metal complex solution of this invention were tested, wherein the solution was a toluene solution or a tetrahydrofuran solution, and the concentration of the metal complex in the toluene solution was 1 × 10⁻⁶. -5 molL -1 The concentration of the metal complex in tetrahydrofuran solution is 1×10⁻⁶. -5 molL -1 ; Figure 4 The absorption spectrum of PdCCC1-B5 in toluene solution; Figure 5 The absorption spectrum of PdCCC1-5 in toluene solution is shown. Figure 6 The absorption spectrum of PdCCC1-3 in toluene solution is shown. Figure 7 The emission spectrum of PdCCC1-B5 in toluene solution; Figure 8 The emission spectrum of PdCCC1-5 in toluene solution; Figure 9 The emission spectrum of PdCCC1-3 in toluene solution; Figure 10 The absorption spectrum of PtNCN1-5 in toluene solution is shown. Figure 11 The absorption spectrum of PtNCN1-3 in toluene solution is shown. Figure 12 The absorption spectrum of PtNCN1-16 in toluene solution; Figure 13 The absorption spectrum of PtNCN1-12 in toluene solution; Figure 14 The absorption spectrum of PtNCN1-20 in toluene solution; Figure 15 The absorption spectrum of PtNCN1-21 in toluene solution; Figure 16 The absorption spectrum of PtNCN3-16 in toluene solution; Figure 17 The absorption spectrum of PtNCN3-22 in toluene solution; Figure 18 The absorption spectrum of PtNCN3-23 in toluene solution; Figure 19 The absorption spectrum of PtNCN3-24 in toluene solution; Figure 20 The emission spectrum of PtNCN1-5 in tetrahydrofuran solution; Figure 21 The emission spectrum of PtNCN1-3 in tetrahydrofuran solution; Figure 22 The emission spectrum of PtNCN1-12 in toluene solution is shown.

[0508] The emission spectrum and lifetime of the metal complex of the present invention in polymethyl methacrylate film were tested. The doping concentration of the metal complex in the polymethyl methacrylate film was 5 wt%. Figure 23 The emission spectrum of PtNCN1-5 in polymethyl methacrylate film; Figure 24 The emission spectrum of PtNCN1-3 in polymethyl methacrylate film; Figure 25 The emission spectrum of PtNCN1-16 in polymethyl methacrylate film; Figure 26 The emission spectrum of PtNCN1-12 in polymethyl methacrylate film; Figure 27 The emission spectrum of PtNCN1-20 in polymethyl methacrylate film; Figure 28 The emission spectrum of PtNCN1-21 in polymethyl methacrylate film; Figure 29 The emission spectrum of PtNCN3-22 in polymethyl methacrylate film; Figure 30 The emission spectrum of PtNCN3-23 in polymethyl methacrylate film; Figure 31 The emission spectrum of PtNCN3-24 in polymethyl methacrylate film; Figure 32 The emission spectrum of PdCCC1-12 in polymethyl methacrylate film; Figure 33 The emission spectrum of PdCCC1-3 in polymethyl methacrylate film; Figure 34 The lifetime decay curve of PtNCN1-5 in polymethyl methacrylate film; Figure 35 The lifetime decay curve of PtNCN1-3 in polymethyl methacrylate film; Figure 36 The lifetime decay curve of PtNCN1-16 in polymethyl methacrylate film; Figure 37 The lifetime decay curve of PtNCN1-12 in polymethyl methacrylate film; Figure 38 The lifetime decay curve of PtNCN1-20 in polymethyl methacrylate film; Figure 39 The lifetime decay curve of PtNCN1-21 in polymethyl methacrylate film; Figure 40The lifetime decay curve of PtNCN3-16 in polymethyl methacrylate film; Figure 41 The lifetime decay curve of PtNCN3-22 in polymethyl methacrylate film; Figure 42 The lifetime decay curve of PtNCN3-23 in polymethyl methacrylate film; Figure 43 The lifetime decay curve of PtNCN3-24 in polymethyl methacrylate film; Figure 44 The lifetime decay curve of PdCCC1-12 in polymethyl methacrylate film; Figure 45 This is a lifetime decay curve of PdCCC1-3 in polymethyl methacrylate film.

[0509] Test Example 1

[0510] The organic electroluminescent devices provided in Device Examples 1-4 were tested. PtNCN-12 was selected as the guest material. The current-luminosity-voltage characteristics of the devices were measured using a Keithley source measurement system (Keithley 2400 Sourcemeter, Keithley 2000 Currentmeter) with calibrated silicon photodiodes. All tests were performed at room temperature and atmospheric conditions. The test results are shown in Table 1 and... Figures 46-47 ,in Figure 46 The electroluminescence patterns of the devices in Examples 1-4 of this invention are based on the compound PtNCN1-12. Figure 47 The electroluminescence quantum efficiency diagrams for embodiments 1-4 of the present invention based on compound PtNCN1-12 are shown.

[0511] Table 1 Device performance test results

[0512]

[0513]

[0514] [a] Maximum luminance; [b] Current efficiency; [c] Lumen efficiency; [d] External quantum efficiency; [e] CIE coordinates (1000 cdm) -2 )

[0515] like Figures 46-47 As shown, the present invention uses PtNCN1-12 as the guest material and prepares a doped OLED with a doping concentration of 1%, achieving a maximum luminous intensity of 136834 cd / m². -2 The maximum current efficiency is 61.2 cd A. -1 The maximum luminous efficacy is 60.7 lm W. -1 The maximum external quantum efficiency is as high as 35.6%, with a brightness of 1000 cd / m². -2The lower CIE coordinates are (0.58, 0.42).

[0516] Test Example 2

[0517] The organic electroluminescent devices provided in Device Examples 5-7 were tested. PdCCC1-12 was selected as the guest material. The current-luminosity-voltage characteristics of the devices were measured using a Keithley source measurement system (Keithley 2400 Sourcemeter, Keithley 2000 Currentmeter) with calibrated silicon photodiodes. All tests were performed at room temperature and atmospheric conditions. The test results are shown in Table 2 and Appendix. Figures 48-49 ,in, Figure 48 The electroluminescence patterns of the devices in Examples 5-7 of this invention are based on the compound PdCCC1-12. Figure 49 The electroluminescence quantum efficiency diagrams for devices in Examples 5-7 of this invention based on compound PdCCC1-12 are shown.

[0518] Table 2 Device performance test results

[0519]

[0520] [a] Maximum luminance; [b] Current efficiency; [c] Lumen efficiency; [d] External quantum efficiency; [e] CIE coordinates (1000 cdm) -2 )

[0521] like Figures 48-49 As shown, the present invention uses PdCCC1-12 as the guest material and prepares a doped OLED with a doping concentration of 1%, achieving a maximum luminous intensity of 92000 cdm. -2 The maximum current efficiency is 29.6 cd A. -1 The maximum luminous efficacy is 27.5 lm W. -1 The maximum external quantum efficiency is as high as 30.1%, with a brightness of 1000 cd / m². -2 The lower CIE coordinates are (0.63, 0.37).

[0522] Test Example 3

[0523] The organic electroluminescent device provided in Device Example 12 was subjected to stability testing. PdCCC1-12 was selected as the guest material. The device was sealed in a nitrogen-filled glove box with a glass lid using UV-cured adhesive. After being removed from the glove box, the brightness of the working device was measured at a constant current density using an OLED lifetime testing system (FS-MP64, Suzhou FSTAR Scientific Instruments Co., Ltd., China). All tests were performed at room temperature and atmospheric conditions. Figure 50This invention uses PdCCC1-12 as the guest material and prepares a doped OLED with a doping concentration of 1%, achieving an initial brightness of 1000 cdm. -2 LT 95 (LT 95 The time it takes for brightness to decrease by 5% (defined as the time required for brightness to decay by 5%) is 232 hours, with an initial brightness of 1000 cdm. -2 LT 90 (LT 90 The time it takes for brightness to decrease by 50% is defined as 1000 hours.

[0524] Test Example 4

[0525] The organic electroluminescent devices provided in Device Examples 8-9 were tested, with PdCCC1-5 selected as the guest material. The current-luminosity-voltage characteristics of the devices were measured using a Keithley source measurement system (Keithley 2400 Sourcemeter, Keithley 2000 Currentmeter) equipped with calibrated silicon photodiodes. All tests were performed at room temperature and in atmospheric conditions. The test results are shown in Table 3 and Appendix. Figures 51-52 , Figure 51 The electroluminescence patterns of the devices in Examples 8-9 of this invention are based on compound PdCCC1-5. Figure 52 The electroluminescence quantum efficiency diagrams for devices in Examples 8-9 of this invention based on compound PdCCC1-5 are shown.

[0526] Table 3 Device Performance Test Results

[0527]

[0528] [a] Maximum luminance; [b] Current efficiency; [c] Lumen efficiency; [d] External quantum efficiency; [e] CIE coordinates (1000 cdm) -2 )

[0529] like Figures 51-52 As shown, the present invention uses PdCCC1-5 as the guest material and prepares a doped OLED with a doping concentration of 1%, achieving a maximum luminous intensity of 40550 cdm. -2 The maximum current efficiency is 65.8 cdA. -1 The maximum luminous efficacy is 73.8 lmW. -1 The maximum external quantum efficiency is as high as 21.5%, at a brightness of 1000 cdm. -2 The lower CIE coordinates are (0.42, 0.53).

[0530] Test Example 5

[0531] The organic electroluminescent devices provided in Device Examples 10-11 were tested, with PdCCC1-3 selected as the guest material. The current-luminosity-voltage characteristics of the devices were measured using a Keithley source measurement system (Keithley 2400 Sourcemeter, Keithley 2000 Currentmeter) equipped with calibrated silicon photodiodes. All tests were performed at room temperature and in atmospheric conditions. The test results are shown in Table 4 and Appendix. Figures 53-54 , Figure 53 The electroluminescence patterns of devices in Examples 10-11 of this invention are based on compound PdCCCl-3. Figure 54 The electroluminescence quantum efficiency diagrams for device embodiments 10-11 of the present invention based on compound PdCCC1-3 are shown.

[0532] Table 4 Device Performance Test Results

[0533]

[0534] [a] Maximum luminance; [b] Current efficiency; [c] Lumen efficiency; [d] External quantum efficiency; [e] CIE coordinates (1000 cdm) -2 )

[0535] like Figures 53-54 This invention uses PdCCC1-3 as the guest material and prepares a doped OLED with a doping concentration of 1%, achieving a maximum luminous intensity of 150-300 cdm. -2 The maximum current efficiency is 79.1 cdA. -1 The maximum luminous efficacy is 76.4 lmW. -1 The maximum external quantum efficiency is as high as 28.8%, at a brightness of 1000 cdm. -2 The lower CIE coordinates are (0.49, 0.50).

[0536] In summary, the "V"-shaped molecular structure containing a tripentate ligand-metal-secondary amine-acceptor in this invention exhibits excellent TADF performance. Through unique molecular design, an additional acceptor unit is introduced onto the metal ligand to construct multiple excited states, thereby weakening the charge transfer transition from metal to complex during molecular excitation transitions and enhancing the charge transfer processes within and between ligands. The excited-state properties of the metal complex in this invention can effectively suppress the excited-state structural distortion of the metal complex, thereby suppressing non-radiative transition processes. This results in organic electroluminescent devices with an external quantum efficiency as high as 35.6% and a long device lifetime.

[0537] Obviously, the above embodiments are merely illustrative examples for clear explanation and are not intended to limit the implementation. Those skilled in the art will recognize that other variations or modifications can be made based on the above description. It is neither necessary nor possible to exhaustively list all possible implementations here. However, obvious variations or modifications derived therefrom are still within the scope of protection of this invention.

Claims

1. A metal complex, characterized in that, It has the following structure: Wherein, M is selected from platinum or palladium; Rings A, B, and C coordinate with the center of metal M as monovalent tridentate ligands; the tridentate ligands formed by rings A, B, and C have any of the following structures: Ra has any of the following structures: R 1 -R 7 Whether the same or different, each is independently selected from hydrogen, substituted or unsubstituted C1-C. 40 Alkyl, substituted or unsubstituted C6-C 48 Aryl, substituted or unsubstituted C3-C 48 Mixed aromatics; Wherein, the substituted C1-C 40 Alkyl, substituted C6-C 48 aryl, substituted C3-C 48 The heteroaryl group is optionally substituented by one or more R groups. b Replace; each R b Independently selected from hydrogen, halogen, cyano, C1-C 10 Alkyl, C6-C 30 Aryl.

2. The metal complex according to claim 1, characterized in that, R 1 R 3 R 4 R 6 , and R 7 For hydrogen, R 2 and R 5 Whether identical or different, each is independently selected from substituted or unsubstituted C1-C40 alkyl groups, substituted or unsubstituted C6-C... 48 Aryl, substituted or unsubstituted C3-C 48 Mixed aromatics; Wherein, the substituted C1-C 40 Alkyl, substituted C6-C 48 aryl, substituted C3-C 48 The heteroaryl group is optionally substituented by one or more R groups. b Replace; each R b Independently selected from hydrogen, halogen, cyano, C1-C 10 Alkyl, C6-C 30 Aryl.

3. The metal complex according to claim 1 or 2, characterized in that, The C1-C 40 The alkyl group is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and tert-butyl; The C1-C 10 The alkyl group is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and tert-butyl; The C6-C 48 The aryl group is selected from phenyl, naphthyl, and anthracene; The C6-C 30 The aryl group is selected from phenyl, naphthyl, and anthracene.

4. The metal complex according to claim 1, characterized in that, The metal complex has any of the following structures:

5. An organic electroluminescent device, characterized in that, The organic electroluminescent device includes a first electrode, a second electrode, and a light-emitting layer located between the first electrode and the second electrode, wherein the light-emitting layer includes any one or a combination of at least two of the metal complexes described in any one of claims 1-4.

6. The organic electroluminescent device according to claim 5, characterized in that, The light-emitting layer comprises the metal complex and organic functional material as described in any one of claims 1-4, wherein the metal complex accounts for 0.01%-100% by mass percentage, and the organic functional material accounts for 0-99.9%.

7. The application of the organic electroluminescent device according to claim 5 or 6 in electronic devices.

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