Luminescent complex material and application thereof

Abstract

The invention belongs to the field of organic light-emitting materials, and particularly relates to a light-emitting complex material and application thereof. The luminescent complex material provided by the invention has the following advantages: the molecules contain electron-withdrawing groups or atoms with larger electronegativity, and the molecules are anchored by utilizing the interaction between the electron-withdrawing groups or the atoms with larger electronegativity and hydrogen atoms in the molecules, so that the rigidity is enhanced, the vibration of the molecules is inhibited, and the photoelectric conversion efficiency is improved. Therefore, the light-emitting half-peak width is reduced, and the molecular stability is improved. The invention also provides an application of the luminescent complex material, and the performance of an OLED device based on the luminescent complex material as an object is obviously improved, for example, the luminescent efficiency is improved, the half-peak width is reduced, and the stability of the device is improved.

Description

Technical Field

[0001] The invention belongs to the field of organic luminescent materials, and in particular relates to a luminescent complex material and application thereof. Background Art

[0002] In the 1960s, Pope et al. of New York University observed weak blue light by applying a voltage of 400V on an anthracene single crystal, which was the first report of organic electroluminescence. 20 years later, researchers invented vacuum evaporation technology to prepare anthracene thin films, and observed blue light with an external quantum efficiency (EQE) of 0.03% at a driving voltage of 30V. The organic electroluminescent devices studied in the early stage had the disadvantages of low carrier injection efficiency, poor film quality, and high device operating voltage, and their practical application value was not great. It was not until 1987 that CW Tang et al. used octahydroxyquinoline aluminum as the light-emitting layer, aromatic amine compounds as the hole transport layer, and aluminum-magnesium alloy as the cathode to obtain a sandwich-type green light device with high luminous efficiency. Since then, the research on OLED has become a research hotspot in the field of organic optoelectronics. The driving force for the ultimate popularization and application of OLED technology lies in its simple process, low energy consumption, low cost, fast response speed, and the ability to realize flexible display and large-area display.

[0003] In the field of OLED materials, phosphorescent OLED light-emitting layer doping materials have developed rapidly and matured. They are mainly based on some heavy metal organic complexes, such as iridium, platinum (II), europium, osmium, etc. Phosphorescent materials can make full use of the energy of singlet and triplet excitons in the process of luminescence, so theoretically their quantum efficiency can reach 100%, and they are luminescent materials that are studied more in the industry and academia. At present, the mainstream OLED red and green light emitting materials use iridium complexes, while blue light phosphorescent complexes have not been successfully applied to the OLED display industry. Compared with iridium complexes, platinum (II) complexes also have the advantages of heavy atom effect, d orbital participation in excited states (MLCT & MMLCT), high photoluminescence efficiency (PLQY), narrow half-peak width, high stability and easy regulation of molecular orientation, and are a potential substitute for iridium complexes.

[0004] In recent years, phosphorescent OLED materials based on platinum (II) have been gradually developed and achieved good research results. Unlike the common iridium (III) that forms an octahedral coordination structure, platinum (II) is tetradentate, and therefore generally forms a planar structured complex, whose ligands are mainly divided into bidentate, tridentate and tetradentate ligands. Compared with bidentate and tridentate ligands, tetradentate platinum (II) complexes do not contain auxiliary ligands, so the chelating effect is enhanced and they usually have good stability. In addition, tetradentate platinum (II) complexes generally have strong rigidity, which is conducive to obtaining a narrow emission spectrum and high luminous efficiency, and is conducive to meeting the needs of the ultra-high-definition display industry.

[0005] At present, devices based on blue light platinum (II) complex phosphorescent materials usually have a large half-width, resulting in insufficient purity of the luminescent color; in addition, the stability of platinum (II) complex phosphorescent material devices is not sufficient to achieve commercial application.

[0006] Therefore, the prior art still needs to be improved and developed. Summary of the invention

[0007] In view of the deficiencies of the above-mentioned technologies, the purpose of the present invention is to provide a luminescent complex material and its application, aiming to solve the problems of insufficient luminescent color purity and insufficient device stability in existing OLED devices.

[0008] To this end, the present invention provides a new design idea for luminescent materials, utilizing intramolecular interactions to enhance the rigidity and stability of platinum (II) complex phosphorescent materials, thereby reducing the luminescent half-width and improving the color purity and stability of OLED devices.

[0009] The present invention adopts the following technical solution:

[0010] The present invention provides a luminescent complex material, wherein the general structural formula of the luminescent complex material is as shown in Formula 1:

[0011]

[0012] Wherein, M is transition metal platinum or palladium;

[0013] Y a , Y b , X a , X b and X c Each independently is C or N, Y a and Y b One of them is N, and Y a and Y b The other one is C;

[0014] Ring A 5 to exist or not to exist;

[0015] When Ring A 5 When present, ring A 5 is a C5-C30 carbocyclic group or a C1-C30 heterocyclic group, wherein Y c and Y d Each is C; when ring A 5 When it does not exist, Y c and Y d Each is C;

[0016] Ring A 1 is a pyrazole ring or an imidazole ring;

[0017] Ring A2 , Ring A 3 and Ring A 4 Each is independently a C5-C30 carbocyclic group or a C1-C30 heterocyclic group;

[0018] T 1 , T 2 Each is independently selected from -S- or -Se- or -O- or -N- or -C-;

[0019] A 6 to exist or not to exist;

[0020] When A 6 When present, A 6 is a C5-C30 carbocyclic group or a C1-C30 heterocyclic group or a C=C double bond or a C=N double bond;

[0021] R a , R b , R c , R d and RA are each independently selected from hydrogen, deuterium, -F, -Cl, -Br, -I, -SF 5 , hydroxyl, cyano, trifluoromethyl, nitro, amidino, hydrazine, hydrazone, carboxylic acid group or its salt, sulfonic acid group or its salt, phosphoric acid group or its salt, substituted or unsubstituted C1-C60 alkyl, substituted or unsubstituted C2-C60 alkenyl, substituted or unsubstituted C2-C60 alkynyl, substituted or unsubstituted C1-C60 alkoxy, substituted or unsubstituted C1-C60 alkylthio, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C1-C10 heterocycloalkyl, substituted or unsubstituted C3-C10 cycloalkenyl, substituted or unsubstituted C1-C10 heterocycloalkenyl, substituted or unsubstituted C The invention may also be a C6-C60 aryl group, a substituted or unsubstituted C7-C60 alkylaryl group, a substituted or unsubstituted C7-C60 arylalkyl group, a substituted or unsubstituted C6-C60 aryloxy group, a substituted or unsubstituted C6-C60 arylthio group, a substituted or unsubstituted C1-C60 heteroaryl group, a substituted or unsubstituted C2-C60 alkylheteroaryl group, a substituted or unsubstituted C2-C60 heteroarylalkyl group, a substituted or unsubstituted C1-C60 heteroaryloxy group, a substituted or unsubstituted C1-C60 heteroarylthio group, a substituted or unsubstituted monovalent non-aromatic condensed polycyclic group, or a substituted or unsubstituted monovalent non-aromatic condensed heteropolycyclic group.

[0022] Optionally, A 1 , A 2 , A 3 , A 4 , A 5 , A 6 Can be independently selected from one of the following structures:

[0023]

[0024] Among them, X 1 is CR4 or N; Y is selected from CR5R6, SiR7R8, NR9, C(═O), S or O; R4, R5, R6, R7, R8, R9 are each independently H or D, or a linear alkyl, alkoxy or thioalkoxy group having 1 to 20 C atoms, or a branched or cyclic alkyl, alkoxy, thioalkoxy or silyl group having 3 to 20 C atoms, or a substituted keto group having 1 to 20 C atoms, or an alkoxycarbonyl group having 2 to 20 C atoms, or an aryloxycarbonyl group having 7 to 20 C atoms, or A cyano group, a carbamoyl group, a haloformyl group, a formyl group, an isocyano group, an isocyanate group, a thiocyanate group, an isothiocyanate group, a hydroxyl group, a nitro group, a CF3 group, Cl, Br, F, or a substituted or unsubstituted aromatic or heteroaromatic ring system having 5 to 40 ring atoms, or an aryloxy or heteroaryloxy group having 5 to 40 ring atoms, or a combination of these groups, wherein one or more groups R4, R5, R6, R7, R8, R9 form a monocyclic or polycyclic aliphatic or aromatic ring with each other and / or with the ring bonded to the structural group.

[0025] Optionally, R a , R b , R c and R d Each independently selected from one of the following structures: F, Cl, Br, I, CF 3 , CBr 3 , CCl 3 , CI 3 、CN、OH、OCH 3 ,SH,SCH 3 、O=CO-、-N(CH 3 ) 2 , CHO.

[0026] Optionally, M is selected from transition metals platinum or palladium, more preferably platinum.

[0027] Optionally, the luminescent complex material may include but is not limited to any one of the following structures:

[0028]

[0029]

[0030]

[0031]

[0032]

[0033] The present invention provides an application of the above-mentioned luminescent complex material in an OLED device.

[0034] The present invention provides an OLED device, comprising a light-emitting layer, wherein the light-emitting layer comprises a host material and a guest material, wherein the guest material is the light-emitting complex material of the present invention.

[0035] Beneficial effects:

[0036] The present invention provides the above-mentioned luminescent complex material, which has the following advantages: the molecules all contain electron-withdrawing groups (such as trifluoromethyl, cyano, etc.) or atoms with high electronegativity (such as fluorine atoms, etc.), and the electron-withdrawing groups or atoms with high electronegativity interact with hydrogen atoms in the molecules (such as hydrogen bonds, etc.) to anchor the molecules, enhance rigidity, and inhibit molecular vibration, thereby reducing the luminescence half-peak width and improving the stability of the molecules.

[0037] The present invention also provides an application of the above-mentioned luminescent complex material. The performance of an OLED device based on the above-mentioned luminescent complex material as the guest is significantly improved. For example, the OLED device prepared based on Examples 1-10 as the guest has an improved luminous efficiency, a reduced half-peak width, and an increased device stability compared with the comparative example. BRIEF DESCRIPTION OF THE DRAWINGS

[0038] In order to more clearly illustrate the specific implementation methods of the present invention or the technical solutions in the prior art, the drawings required for use in the specific implementation methods or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are some implementation methods of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

[0039] Figure 1 is a photoluminescence spectrum of the luminescent complex material of Example 1 in a dichloromethane solution;

[0040] Figure 2 is a photoluminescence spectrum of the luminescent complex material of Example 2 in a dichloromethane solution;

[0041] Figure 3 is a photoluminescence spectrum of the luminescent complex material of Example 3 in a dichloromethane solution;

[0042] Figure 4 is a photoluminescence spectrum of the luminescent complex material of Example 4 in a dichloromethane solution;

[0043] Figure 5is a photoluminescence spectrum of the luminescent complex material of Example 5 in a dichloromethane solution;

[0044] Figure 6 is a photoluminescence spectrum of the luminescent complex material of Example 6 in a dichloromethane solution;

[0045] Figure 7 is a photoluminescence spectrum of the luminescent complex material of Example 7 in a dichloromethane solution;

[0046] Figure 8 is a photoluminescence spectrum of the luminescent complex material of Example 8 in a dichloromethane solution;

[0047] Fig. 9 is a photoluminescence spectrum of the luminescent complex material of Example 9 in a dichloromethane solution;

[0048] Fig.10 is a photoluminescence spectrum of the luminescent complex material of Example 10 in a dichloromethane solution;

[0049] Fig.11 The photoluminescence spectrum of the luminescent complex material of the comparative example in a dichloromethane solution is shown in FIG. DETAILED DESCRIPTION

[0050] The following examples are provided for a better understanding of the present invention, but are not intended to limit the best mode of implementation, nor to limit the content and protection scope of the present invention. Any product identical or similar to the present invention obtained by anyone under the inspiration of the present invention or by combining the features of the present invention with other prior arts shall fall within the protection scope of the present invention.

[0051] If no specific experimental steps or conditions are specified in the examples, the experiments can be carried out according to the conventional experimental steps or conditions described in the literature in the art.

[0052] The following specific examples are further explanations of the present invention. The examples cited cannot list all the embodiments of the present invention. Only some of the embodiments are used as examples for explanation. The specific examples are as follows:

[0053] Example 1

[0054] This embodiment provides a method for preparing a luminescent complex material, and the preparation process is as follows:

[0055]

[0056] Synthesis of 1-(3-bromo-5-(trifluoromethyl)phenyl)-1H-benzo[d]imidazole (Compound 2)

[0057] Under nitrogen atmosphere, 1-bromo-3-iodo-5-(trifluoromethyl)benzene (10.5 g, 30.0 mmol, 1.0 eq), 1H-benzo[d]imidazole (3.54 g, 30.0 mmol, 1.0 eq), CuI (0.29 g, 1.5 mmol, 5.0% mol), K 2 CO 3 (8.28 g, 60.0 mmol, 2.0 eq) and L-proline (0.345 g, 3.0 mmol, 10% mol) were added to DMSO (80 mL), stirred at 120 ° C for 2 d, and then cooled to ambient temperature. The mixture was diluted with a large amount of ethyl acetate, filtered, and the solid was washed with ethyl acetate. The filtrate was washed three times with water, dried over sodium sulfate, and then filtered, and the filtrate was concentrated under reduced pressure. The residue was purified by silica gel column chromatography, first using hexane and then using hexane / ethyl acetate (10: 1-3: 1) as eluent to obtain a light brown solid as the target compound 2 (7.35 g, 72%). 1 H NMR (400 MHz, CDCl 3 ): δ(ppm)8.49(m,1H),8.05(m,1H),7.91(s,1H),7.88(s,1H),7.85-7.78(m,1H),7.76(s,1H),7.40(m,1H).

[0058] Synthesis of 2-(3-(1H-benzo[d]imidazol-1-yl)-5-(trifluoromethyl)phenoxy)-9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazole (Compound 3)

[0059] Compound 2 (1.70 g, 5.00 mol, 1.2 eq), 9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazole-2-ol (1.31 g, 4.15 mmol, 1.0 eq), CuI (80 mg, 0.420 mmol, 10 mol%), picolinic acid (102 mg, 8.31 mmol, 20 mol%) and K 3 PO 4 (2.65 g, 12.5 mmol, 3.0 eq) were added into a clean three-necked flask in sequence. The reaction system was evacuated and filled with N 2, repeat the operation 2 or more times. Then add DMSO (30 mL) under nitrogen atmosphere, place in an oil bath heated at 120 ° C and stir. After 18 hours, the resulting mixture was cooled to room temperature and diluted with a large amount of ethyl acetate. The mixture was then filtered through a diatomaceous earth pad and washed with ethyl acetate. The filtrate was washed three times with water, dried over anhydrous sodium sulfate, and filtered. The filtrate was concentrated under reduced pressure, and the residue was purified by silica gel column chromatography (eluent: petroleum ether / ethyl acetate = 4:1-1:1) to obtain 1.80 g of white solid as the target compound 3, with a yield of 75%. 1 H NMR (400 MHz, CDCl 3 ): δ(ppm)8.59(d,J=5.2Hz,1H),8.22(s,1H),8.15(d,J=8.4Hz,1H),8.11(d ,J=7.6Hz,1H),7.88(d,J=7.2Hz,1H),7.72(d,J=8.4Hz,1H),7.67(d,J=2.0H z,1H),7.60(d,J=1.2Hz,1H),7.55(d,J=6.0Hz,1H),7.48-7.44(m,2H),7.3 7-7.33(m,5H),7.31(dd,J=5.2Hz,1H),7.10(dd,J=8.4Hz,1H),1.38(s,9H).

[0060] Pt-CF 3 Synthesis of -1(1)

[0061] 1,3-di-tert-butyl-5-iodobenzene (3.16 g, 10.0 mmol, 2.2 eq), mesitylene (0.400 g, 15.0 mmol, 3.3 eq) and 3-chloroperoxybenzoic acid (m-CPBA 85%) (3.04 g, 15.0 mmol, 3.3 eq) were added. Then, methanesulfonic acid (7.0 mL, 79.6 mmol) was slowly added dropwise to the reaction solution at room temperature. The resulting mixture was stirred for 2 hours and then added with excess K 2 CO 3 The solutions were mixed, the organic phase was separated, and the K 2 CO 3 The organic layer was washed with a solution of trifluoromethanesulfonic acid to remove organic acids. The organic layer was separated again and washed with Na 2 SO 4 Dry and filter. Rotate and evaporate until the solvent is completely removed, add a small amount of hexane, then filter and dry the residue. The crude product (3,5-di-tert-butylphenyl)(mesityl)iodonium trifluoromethanesulfonate is directly used for the next step. Mix it with compound 3 (2.62 g, 4.54 mmol, 1 mmol) and Cu(AcO) 2(41 mg, 0.227 mmol, 5% mol) was mixed in 30 mL of dimethylformamide (DMF), and the reaction mixture was refluxed at 100 ° C for 1 hour. The solvent was removed under reduced pressure, and the crude product was subjected to silica gel column chromatography (eluent: dichloromethane: acetone) to obtain compound 4 (3.75 g, 90%). All of it was added to a 250 mL flask, mixed with dichloro(1,5-cyclooctadiene)-platinum(II) (1.53 g, 4.09 mmol) and sodium acetate (1.38 g, 16.4 mmol), and then 120 mL of DMF was added. After reflux at 150 ° C for 15 hours under a nitrogen atmosphere, all solvents were removed by rotary evaporation, and then washed with CH 2 Cl 2 The resulting mixture was dissolved. The combined organic phases were washed with water and MgSO 4 The residue was purified by silica gel column chromatography (eluent: dichloromethane and hexane) to obtain the target compound Pt-CF as a light yellow solid. 3 -1(1) (1.87 g, 48%). 1 H NMR (400 MHz, CDCl 3 ): δ(ppm)8.71(d,J=6.0Hz,1H),8.18(d,J=8.0Hz,1H),8.06(dd,J=6.0Hz,1H),7.88(d,J=8.0Hz,1H),7.81(m,1H),7. 70(d,J=7.6Hz,1H),7.67(m,1H),7.59-7.54(m,3H),7.38-7.36(m,3H),5.95(s,1H),1.18-1.14(m,18H),1.07(s,9H).

[0062] Example 2

[0063] This embodiment provides a method for preparing a luminescent complex material, and the preparation process is as follows:

[0064]

[0065] Synthesis of 4-Fluoro-2'-nitro-2-(trifluoromethyl)-1,1'-biphenyl (Compound 7)

[0066] A 250 mL two-necked flask was charged with 1-bromo-2-nitrobenzene (10.3 g, 50 mmol, 1.0 eq), 4-fluoro-2-(trifluoromethyl)phenylboronic acid (11.4 g, 55 mmol, 1.1 eq), Pd 2 (dba) 3(230 mg, 0.25 mmol, 0.5% mol), S-Phos (410 mg, 1.00 mmol, 2.0% mol), ethanol (20 mL), toluene (70 mL) and 2 mol / L K 2 CO 3 (40 mL, 80 mmol, 1.6 eq). The reaction mixture was stirred at 90 °C for 12 h. The resulting mixture was diluted with ethyl acetate, washed with water and brine, and then washed with anhydrous Na 2 SO 4 The residue was concentrated with an evaporator and purified by silica gel column chromatography (eluent: dichloromethane and hexane) to obtain the target compound 7 as a slightly yellow solid. 1 H NMR (400 MHz, CDCl 3 ): δ (ppm) 8.15 (dd, J = 8.0Hz, 1H), 7.67 (t, J = 7.6Hz, 1H), 7.60 (t, J = 8.0Hz, 1H), 7.47 (dd, J = 8.8Hz, 1H), 7.35 (d, J = 7.2Hz, 1H), 7.33-7.25 (m, 2H).

[0067] Synthesis of 2-fluoro-4-(trifluoromethyl)-9H-carbazole (Compound 8)

[0068] 4-Fluoro-2'-nitro-2-(trifluoromethyl)-1,1'-biphenyl (5.70 g, 20.0 mmol, 1.0 eq), DPPE (8.76 g, 22.0 mmol, 1.1 eq) and 1,2-dichlorobenzene (10 mL) were mixed in a 100 mL round bottle, and then the reaction bottle was immersed in an oil bath at 130°C under a nitrogen atmosphere. After stirring for 5 hours, it was cooled to room temperature, and the residue was subjected to column chromatography on silica gel using petroleum ether / ethyl acetate as an eluent to obtain a white solid as the target compound 8. 1 HNMR (400MHz, CDCl 3 ): δ (ppm) 8.32 (s, 1H), 8.26 (d, J = 8.4Hz, 1H), 7.50-7.45 (m, 2H), 7.32 (t, J = 2.4Hz, 1H), 7.30 (d, J = 7.2Hz, 1H), 7.28 (t, J = 2.0Hz, 1H).

[0069] Synthesis of 9-(4-(tert-butyl)pyridin-2-yl)-2-fluoro-4-(trifluoromethyl)-9H-carbazole (Compound 9)

[0070] Compound 8 (6.00 g, 23.7 mmol, 1.0 eq), 2-bromo-4-(tert-butyl)pyridine (5.33 g, 24.9 mmol, 1.05), copper iodide (0.450 g, 2.37 mmol, 10% mol), 1-methylimidazole (0.398 g, 4.74 mmol, 20% mol) and K 2 CO 3 (9.81 g, 71.1 mmol, 3.0 eq) was added to a two-necked flask and dissolved in 1,4-dioxane (50 mL), and stirred at 110 ° C for 12 h. Afterwards, the product was quenched with water, extracted with EA / water, and washed with brine. After further purification by column chromatography using ethyl acetate: hexane (1:9) as the eluent, a white powder was obtained as the target compound 9 (8.69 g, yield 95%). 1 HNMR (400MHz, CDCl 3 ): δ(ppm)8.65(d,J=5.2Hz,1H),8.33(d,J=8.0Hz,1H),7.69(dd,J=9.2Hz,1H),7.65( d,J=8.4Hz,1H),7.57(s,1H),7.49(t,J=8.0Hz,1H),7.40-7.35(m,3H),1.42(s,9H).

[0071] Synthesis of 9-(4-(tert-butyl)pyridin-2-yl)-4-(trifluoromethyl)-9H-carbazole-2-ol (Compound 10)

[0072] In a two-necked flask, compound 9 (3.86 g, 10.0 mmol) was dissolved in DMSO (50 mL), mixed with KOH solution (40%, 5 mL, 22 mmol), and the reaction mixture was stirred at 120 ° C for 6 hours. After cooling, it was poured into a large amount of water, and then the pH value was adjusted to 2-3 with HCl, extracted with ethyl acetate, and washed with brine. After further purification by column chromatography using EA: hexane (1: 2) eluent, a white powder was obtained as the target compound 10 (3.45 g, yield 89%). 1 H NMR (400 MHz, CDCl 3 ): δ(ppm)8.61(d,J=5.6Hz,1H),8.25(d,J=7.6Hz,1H),7.58(s,1H),7.57(d,J=5.6Hz,1H),7.41(t,J=7.2Hz,1H ),7.39(s,1H),7.37(dd,J=5.2Hz,1H),7.32(t,J=7.6Hz,1H),7.11(d,J=2.4Hz,1H),1.68(s,1H),1.40(s,9H).

[0073] Synthesis of 2-(3-(1H-benzo[d]imidazol-1-yl)phenoxy)-9-(4-(tert-butyl)pyridin-2-yl)-4-(trifluoromethyl)-9H-carbazole (Compound 11)

[0074] Compound 10 (2.30 g, 6.00 mmol, 1.0 eq), 1-(3-bromophenyl)-1H-benzo[d]imidazole (1.96 g, 7.20 mmol, 1.2 eq), CuI (114 mg, 0.600 mmol, 10 mol%), 2-pyridinecarboxylic acid (148 mg, 1.20 mmol, 20 mol%) and K 3 PO 4 (3.82 g, 18.0 mmol, 3.0 equiv) were added into a dry three-necked flask in sequence. The reaction system was evacuated and filled with N 2 , repeat the operation 2 or more times. Then DMSO (30 mL) was added under a nitrogen atmosphere and placed in an oil bath heated at 120 ° C and stirred. After 18 hours, the resulting mixture was cooled to room temperature and diluted with a large amount of ethyl acetate. The mixture was then filtered through a diatomaceous earth pad and washed with ethyl acetate. The filtrate was washed three times with water, dried over anhydrous sodium sulfate, and filtered. The filtrate was concentrated under reduced pressure, and the residue was purified by silica gel column chromatography (eluent: petroleum ether / ethyl acetate = 4: 1-1: 1) to obtain 2.80 g of white solid as the target compound 11, with a yield of 81%. 1 H NMR (500 MHz, CDCl 3 ): δ(ppm)8.60(d,J=5.5Hz,1H),8.35(d,J=8.0Hz,1H),8.33-8.20(m,1H),7.90- 7.88(m,1H),7.75(s,1H),7.66(d,J=8.5Hz,1H),7.65-7.60(m,1H),7.56(s,1H) ,7.55-7.52(m,1H),7.50(t,J=7.5Hz,2H),7.42(s,1H),7.39(d,J=7.5Hz,1H),7 .37-7.32(m,3H),7.27(d,J=7.5Hz,1H),7.24(s,1H),7.14(m,1H),1.37(s,9H).

[0075] Pt-CF 3 Synthesis of -2(2)

[0076] (3,5-di-tert-butylphenyl)(mesityl)iodonium trifluoromethanesulfonate (4.20 g, 7.2 mmol, 1.8 eq), compound 11 (2.30 g, 4.00 mmol, 1.0 eq) and Cu(AcO) were mixed.2 (36 mg, 0.200 mmol, 5.0% mol) was mixed in 30 mL of dimethylformamide (DMF), and the reaction mixture was refluxed at 100 ° C for 1 hour. The solvent was removed under reduced pressure, and the crude product was subjected to silica gel column chromatography (eluent: dichloromethane: acetone) to obtain compound 12 (3.22 g, 3.52 mmol). All of it was added to a 250 mL flask, mixed with dichloro(1,5-cyclooctadiene)-platinum(II) (1.32 g, 3.52 mmol, 1.00 eq) and sodium acetate (1.18 g, 14.1 mmol, 4.00 eq), and then 120 mL of DMF was added. After reflux at 150 ° C for 15 hours under a nitrogen atmosphere, all solvents were removed by rotary evaporation, and then washed with CH 2 Cl 2 The resulting mixture was dissolved. The combined organic phases were washed with water and MgSO 4 The residue was purified by silica gel column chromatography (eluent: dichloromethane and hexane) to obtain the target compound Pt-CF as a light yellow solid. 3 -2(2) (1.52 g, 45%). 1 H NMR (400MHz, CD 2 Cl 2 ): δ(ppm)8.65(d,J=6.4Hz,1H),8.27(d,J=8.0Hz,1H),8.21(d,J=8.4Hz,1H),7.73(d,J=8.0Hz,1H),7.69-7.65(m,2H),7.56-7.50(m ,3H),7.45-7.39(m,3H),7.37-7.35(m,2H),7.18-7.13(m,1H),7.07(d,J=8.4Hz,1H),5.85(s,1H),1.50-1.10(m,18H),0.97(s,9H).

[0077] Example 3

[0078] This embodiment provides a method for preparing a luminescent complex material, and the preparation process is as follows:

[0079]

[0080] Synthesis of 2-(3-(1H-benzo[d]imidazol-1-yl)-5-(trifluoromethyl)phenoxy)-9-(4-(tert-butyl)pyridin-2-yl)-4-(trifluoromethane)-9H-carbazole (Compound 13)

[0081] Compound 10 (2.11 g, 5.50 mmol, 1.0 eq), 1-(3-bromo-5-(trifluoromethyl)phenyl)-1H-benzo[d]imidazole (2.25 g, 6.60 mmol, 1.2 eq), CuI (114 mg, 0.600 mmol, 10 mol%), picolinic acid (148 mg, 1.20 mmol, 20 mol%) and K 3 PO 4 (3.50 g, 16.5 mmol, 3.0 eq) were added into a dry three-necked flask in sequence. The reaction system was evacuated and filled with N 2 , repeat the operation more than 2 times. Then DMSO (40mL) was added under a nitrogen atmosphere and placed in an oil bath heated at 120°C and stirred. After 18 hours, the reaction was completed by TLC monitoring. The resulting mixture was cooled to room temperature and diluted with a large amount of ethyl acetate. The mixture was then filtered through a diatomaceous earth pad and washed with ethyl acetate. The filtrate was washed three times with water, dried over anhydrous sodium sulfate, and filtered. The filtered material was concentrated under reduced pressure, and the residue was purified by silica gel column chromatography (eluent: petroleum ether / ethyl acetate = 4:1-1:1) to obtain 3.02g of white powder as the target compound 13, with a yield of 84%. 1 H NMR (400 MHz, CDCl 3 ): δ(ppm)8.60(d,J=5.2Hz,1H),8.37(d,J=8.0Hz,1H),8.27(s,1H),7.90(s,1H),7.81(d,J=2.0Hz,1H),7.78(s,1H),7.6 5(d,J=8.4Hz,1H),7.58(s,1H),7.57-7.55(m,1H),7.54-7.50(m,2H),7.44-7.40(m,3H),7.38-7.36(m,3H),1.38(s,9H).

[0082] Pt-2CF 3 (3) Synthesis

[0083] (3,5-di-tert-butylphenyl)(mesityl)iodonium trifluoromethanesulfonate (4.20 g, 7.2 mmol, 1.8 eq), compound 13 (2.58 g, 4.00 mmol, 1.0 eq) and Cu(AcO) were mixed. 2(36 mg, 0.200 mmol, 5.0% mol) was mixed in 30 mL of dimethylformamide (DMF), and the reaction mixture was refluxed at 100 ° C for 1 hour. The solvent was removed under reduced pressure, and the crude product was subjected to silica gel column chromatography (eluent: dichloromethane: acetone) to obtain compound 14 (3.34 g, 3.40 mmol). All of it was added to a 250 mL flask, mixed with dichloro(1,5-cyclooctadiene)-platinum(II) (1.27 g, 3.40 mmol, 1.00 equiv) and sodium acetate (1.12 g, 13.6 mmol, 4.00 equiv), and then 120 mL of DMF was added. After reflux at 150 ° C for 15 hours under a nitrogen atmosphere, all solvents were removed by rotary evaporation, and then washed with CH 2 Cl 2 The resulting mixture was dissolved. The combined organic phases were washed with water and MgSO 4 The residue was purified by silica gel column chromatography (eluent: dichloromethane and hexane) to obtain the desired slightly yellow solid as the target compound Pt-2CF 3 (3) (1.63 g, yield 47%). 1 H NMR (400 MHz, CDCl 3 ): δ(ppm)8.61(d,J=6.4Hz,1H),8.31(d,J=7.2Hz,1H),8.13(d,J=8.4Hz,1H),7.75(s,1H),7.67-7.66(m,2H),7.59(d,J=5.2 Hz,1H),7.55(d,J=7.2Hz,1H),7.54-7.45(m,1H),7.43-7.34(m,6H),5.79(d,J=5.6Hz,1H),1.54-1.00(m,18H),0.94(s,9H).

[0084] Example 4

[0085] This embodiment provides a method for preparing a luminescent complex material, and the preparation process is as follows:

[0086]

[0087] Synthesis of 4-methoxy-2-nitro-2'-(trifluoromethyl)-1,1'-biphenyl (Compound 17)

[0088] A 250 mL two-necked flask was charged with 4-bromo-3-nitroanisole (11.6 g, 50 mmol, 1.0 eq), 2-trifluoromethylphenylboronic acid (10.4 g, 55 mmol, 1.1 eq), Pd 2 (dba) 3(230 mg, 0.25 mmol, 0.5% mol), S-Phos (410 mg, 1.00 mmol, 2.0% mol), ethanol (20 mL), toluene (70 mL) and 2.0 mol / L K 2 CO 3 (40 mL, 80 mmol, 1.6 eq). The reaction mixture was stirred at 90 °C for 12 h. The resulting mixture was diluted with ethyl acetate, washed with water and brine, and then washed with anhydrous Na 2 SO 4 The residue was concentrated with an evaporator and purified by silica gel column chromatography (eluent: dichloromethane and hexane) to obtain the target compound 17 (10.8 g, 73%) as a slightly yellow solid. 1 H NMR (400 MHz, CDCl 3 ): δ(ppm)7.77(dd,J=8.4,1.6Hz,1H),7.62(m,1H),7.59-7.51(m,2H),7.44( m,1H),6.83(dd,J=8.0,2.4Hz,1H),6.77(dd,J=8.0,2.4Hz,1H),3.75(s,3H).

[0089] Synthesis of 2-methoxy-5-(trifluoromethyl)-9H-carbazole (Compound 18)

[0090] 4-Fluoro-2'-nitro-2-(trifluoromethyl)-1,1'-biphenyl (5.94 g, 20.0 mmol, 1.0 eq), DPPE (8.76 g, 22.0 mmol, 1.1 eq) and 1,2-dichlorobenzene (10 mL) were mixed in a 100 mL round bottle, and then the bottle was immersed in an oil bath at 130° C. under a nitrogen atmosphere. After stirring for 5 hours, the reactant was cooled, and the residue was subjected to column chromatography on silica gel using petroleum ether / ethyl acetate as an eluent to obtain a white solid as the target compound 18 (2.70 g, yield 51%). 1 HNMR (400MHz, CDCl 3 ): δ (ppm) 9.79 (s, 1H), 7.92 (d, J = 8.4Hz, 1H), 7.40 (dd, J = 7.6, 1.2Hz, 1H), 7.36 (dd, J = 10.4, 1.2Hz, 1H), 7.10 (dd, J=10.4, 7.6Hz, 1H), 6.99 (d, J=2.2Hz, 1H), 6.79 (dd, J=8.4, 2.4Hz, 1H), 3.87 (s, 3H).

[0091] Synthesis of 9-(4-(tert-butyl)pyridin-2-yl)-2-methoxy-5-(trifluoromethyl)-9H-carbazole (Compound 19)

[0092] Compound 18 (6.28 g, 23.7 mmol, 1.0 eq), 2-bromo-4-(tert-butyl)pyridine (5.33 g, 24.9 mmol, 1.05 eq), CuI (0.450 g, 2.37 mmol, 10% mol), 1-methylimidazole (0.398 g, 4.74 mmol, 20% mol) and K 2 CO 3 (9.81 g, 71.1 mmol, 3.0 eq) was added to a two-necked flask and dissolved in 1,4-dioxane (50 mL), and stirred at 100 ° C for 12 h. Afterwards, the product was quenched with water, extracted with EA / water, and washed with brine. After further purification by column chromatography using ethyl acetate: hexane (1:9) as the eluent, a white powder was obtained as the target compound 19 (8.77 g, yield 93%). 1 H NMR (400 MHz, CDCl 3 ): δ(ppm)8.64(d,J=2.8Hz,1H),7.92(d,J=8.0Hz,1H),7.68(m,1H),7.63(m,1H),7.40(d, J=1.9Hz,1H),7.11(m,1H),6.99(d,J=2.4Hz,1H),6.90(m,1H),6.79(m,1H),3.87(s,3H).

[0093] Synthesis of 9-(4-(tert-butyl)pyridin-2-yl)-5-(trifluoromethyl)-9H-carbazole-2-ol (Compound 20)

[0094] Compound 19 (3.44 g, 8.64 mmol, 1.0 eq) and anhydrous DCM (30 mL) were added to a 100 mL two-necked bottle. Boron tribromide (2.9 mL, 30.2 mmol, 3.5 eq) was slowly added dropwise during stirring. The reaction was allowed to react at room temperature for 1 h. The reaction solution was poured into ice water and an appropriate amount of NaHCO was added. 3 Adjust the pH to 8-9. Separate the organic phase and use anhydrous Na 2 SO 4 The residue was dried and filtered. The solvent was removed by distillation under reduced pressure, and the residue was subjected to column chromatography on silica gel using petroleum ether / ethyl acetate as eluent to obtain a white solid as the target compound 20 (2.39 g, yield 72%). 1 H NMR (400 MHz, CDCl 3): δ(ppm)8.64(d,J=2.8Hz,1H),7.75(d,J=8.3Hz,1H),7.68(m,1H),7.63(m,1H),7.40(d, J=2.0Hz,1H),7.11(m,1H),6.90(m,1H),6.84(d,J=2.4Hz,1H),6.67(m,1H),4.70(s,1H).

[0095] Synthesis of 2-(3-(1H-benzo[d]imidazol-1-yl)phenoxy)-9-(4-(tert-butyl)pyridin-2-yl)-5-(trifluoromethyl)-9H-carbazole (Compound 21)

[0096] Compound 20 (1.96 g, 5.12 mmol, 1.0 eq), 1-(3-bromophenyl)-1H-benzo[d]imidazole (1.68 g, 6.14 mmol, 1.2 eq), CuI (146 mg, 0.768 mmol, 15 mol%), 2-picolinic acid (189 mg, 1.54 mmol, 30 mol%) and K 3 PO 4 (3.26 g, 15.4 mmol, 3.0 eq) were added sequentially into a dry 100 mL three-necked flask. The reaction system was evacuated and filled with N 2 , repeat the operation more than 2 times. Then DMSO (30mL) was added under a nitrogen atmosphere and placed in an oil bath heated at 120°C and stirred. After 18 hours, the reaction was completed as monitored by TLC. The resulting mixture was cooled to room temperature and diluted with a large amount of ethyl acetate. The mixture was then filtered through a diatomaceous earth pad and washed with ethyl acetate. The filtrate was washed three times with water, dried over anhydrous sodium sulfate, and filtered. The filtrate was concentrated under reduced pressure, and the residue was purified by silica gel column chromatography (eluent: petroleum ether / ethyl acetate = 4:1-1:1) to obtain a white powder as the target compound 21 (2.42 g, 82%). 1 H NMR (400 MHz, CDCl 3 ): δ(ppm)8.64(d,J=3.2Hz,1H),8.58-8.51(m,1H),8.08(s,1H),7.87-7.81(m,1H),7.63(dd,J=6.0,1.1Hz,1H),7.54-7.50(m,1H) ,7.42-7.24(m,5H),7.15(t,J=2.2Hz,1H),7.10(m,1H),7.04(m,2H),6.87(d,J=2.0Hz,1H),6.73(m,1H),2.90(m,1H),1.28(s,9H).

[0097] Pt-CF3 Synthesis of -3(4)

[0098] (3,5-di-tert-butylphenyl)(mesityl)iodonium trifluoromethanesulfonate (2.52 g, 4.32 mmol, 1.8 eq), compound 21 (1.38 g, 2.40 mmol, 1.0 eq) and Cu(AcO) were mixed. 2 (22 mg, 0.120 mmol, 5.0% mol) was mixed in 30 mL of dimethylformamide (DMF), and the reaction mixture was refluxed at 100 ° C for 1 hour. The solvent was removed under reduced pressure, and the crude product was subjected to silica gel column chromatography (eluent: dichloromethane: acetone) to obtain compound 22 (2.02 g, 2.21 mmol). All of it was added to a 100 mL flask, mixed with dichloro(1,5-cyclooctadiene)-platinum(II) (0.827 g, 2.21 mmol, 1.00 eq) and sodium acetate (0.725 g, 8.84 mmol, 4.00 eq), and 50 mL of DMF was added. After reflux at 150 ° C for 15 hours under a nitrogen atmosphere, all solvents were removed by rotary evaporation, and then washed with CH 2 Cl 2 The resulting mixture was dissolved. The combined organic phases were washed with water and MgSO 4 The residue was purified by silica gel column chromatography (eluent: dichloromethane and hexane) to obtain the desired slightly yellow solid as the target compound Pt-CF 3 -3(4) (0.963 g, yield 47%). 1 H NMR (400 MHz, CDCl 3 ): δ(ppm)9.09(d,J=7.6Hz,1H),8.55(m,2H),8.12(m,1H),7.88(d,J=7.7Hz,1H),7.67(t,J=2.1Hz,1H),7.63(m,1H),7.40(d,J=2.0H z,1H),7.32(m,2H),7.30-7.24(m,3H),7.15-7.08(m,2H),6.95-6.90(m,2H),5.81(d,J=5.6Hz,1H),1.54-1.00(m,18H),0.94(s,9H).

[0099] Example 5

[0100] This embodiment provides a method for preparing a luminescent complex material, and the preparation process is as follows:

[0101]

[0102] Synthesis of 2-Fluoro-4-methoxy-2'-nitro-1,1'-biphenyl (Compound 25)

[0103] A 250 mL two-necked flask was charged with 2-fluoro-4-methoxyphenylboronic acid (Compound 23) (6.8 g, 40 mmol, 1.0 eq), 2-trifluoromethylphenylboronic acid (Compound 24) (10.4 g, 44 mmol, 1.1 eq), Pd 2 (dba) 3 (183 mg, 0.20 mmol, 0.5% mol), S-Phos (328 mg, 0.800 mmol, 2.0% mol), ethanol (20 mL), toluene (70 mL) and 2 mol / L K 2 CO 3 (36 mL, 72 mmol, 1.8 eq). The reaction mixture was stirred at 90 °C for 12 h. The resulting mixture was diluted with ethyl acetate, washed with water and brine, and then washed with anhydrous Na 2 SO 4 The residue was concentrated with an evaporator and purified by silica gel column chromatography (eluent: dichloromethane and hexane) to obtain the target compound 25 (8.40 g, yield 85%) as a slightly yellow solid. 1 HNMR (400MHz, CDCl 3 ): δ(ppm)7.77(m,1H),7.62(m,1H),7.59-7.51(m,2H),7.44(m,1H),6.83(dd,J=8.0,2.4Hz,1H),6.77(dd,J=8.0,2.4Hz,1H),3.75(s,3H).

[0104] Synthesis of 4-fluoro-2-methoxy-9H-carbazole (Compound 26)

[0105] Compound 25 (4.95 g, 20.0 mmol, 1.0 eq), DPPE (8.76 g, 22.0 mmol, 1.1 eq) and 1,2-dichlorobenzene (10 mL) were mixed in a 100 mL round bottle, and then the bottle was immersed in an oil bath at 130° C. under a nitrogen atmosphere. After stirring for 5 hours, the reactant was cooled, and the residue was subjected to column chromatography on silica gel using petroleum ether / ethyl acetate as an eluent to obtain a white solid as the target compound 26 (2.36 g, yield 55%). 1 H NMR (400 MHz, CDCl 3 ): δ(ppm)9.79(s,1H),8.01(m,1H),7.44–7.37(m,2H),7.30(m,1H),6.75(d,J=2.0Hz,1H),6.33(m,1H),3.81(s,3H).

[0106] Synthesis of 9-(4-(tert-butyl)pyridin-2-yl)-4-fluoro-2-methoxy-9H-carbazole (Compound 27)

[0107] Compound 26 (1.94 g, 9.00 mmol, 1.0 eq), 2-bromo-4-tert-butylpyridine (2.36 g, 10.8 mmol, 1.2 eq), CuI (0.170 g, 0.900 mmol, 10% mol), 1-methylimidazole (0.148 g, 1.80 mmol, 20% mol) and K 2 CO 3 (3.73 g, 27.0 mmol, 3.0 eq) was added to a two-necked flask and dissolved in 1,4-dioxane (50 mL), and stirred at 100 ° C for 12 h. After that, the product was quenched with water, extracted with ethyl acetate / water, and washed with brine. After further purification by column chromatography using ethyl acetate: hexane (1:4) as the eluent, a white solid was obtained as the target compound 27 (2.88 g, yield 92%). 1 H NMR (400 MHz, CDCl 3 ): δ(ppm)8.64(d,J=2.8Hz,1H),8.01(dd,J=7.2,1.6Hz,1H),7.68(m,1H),7.63(m,1H), 7.40(s,1H),7.33(m,1H),7.19(m,1H),6.76(d,J=2.0Hz,1H),6.33(m,1H),3.81(s,3H).

[0108] Synthesis of 9-(4-(tert-butyl)pyridin-2-yl)-4-fluoro-9H-carbazole-2-ol (Compound 28)

[0109] Compound 27 (2.00 g, 6.94 mmol, 1.0 eq) and anhydrous DCM (30 mL) were added to a 100 mL two-necked flask. Boron tribromide (2.3 mL, 24.3 mmol, 3.5 eq) was slowly added dropwise during stirring. The reaction was allowed to react at room temperature for 1 h. The reaction solution was poured into ice water and an appropriate amount of NaHCO was added. 3 Adjust the pH to 8-9. Separate the organic phase and use anhydrous Na 2 SO 4 The residue was dried and filtered. The solvent was removed by distillation under reduced pressure, and the residue was subjected to column chromatography on silica gel using petroleum ether / ethyl acetate as eluent to obtain a white solid as the target compound 28 (1.68 g, yield 72%). 1 H NMR (400 MHz, CDCl 3): δ(ppm)8.64(d,J=2.8Hz,1H),8.01(m,1H),7.68(dd,J=2.8,2.0Hz,1H),7.63(m,1H),7.40(s, 1H),7.33(m,1H),7.19(m,1H),6.61(d,J=2.0Hz,1H),6.35(s,1H),6.18(dd,J=8.0,2.0Hz,1H).

[0110] Synthesis of 2-(3-(1H-benzo[d]imidazol-1-yl)phenoxy)-9-(4-(tert-butyl)pyridin-2-yl)-4-fluoro-9H-carbazole (Compound 29)

[0111] Compound 28 (1.50 g, 4.49 mmol, 1.0 eq), 1-(3-bromophenyl)-1H-benzo[d]imidazole (1.47 g, 5.39 mmol, 1.2 eq), CuI (102 mg, 0.539 mmol, 12 mol%), 2-pyridinecarboxylic acid (132 mg, 1.08 mmol, 24 mol%) and K 3 PO 4 (1.86 g, 13.5 mmol, 3.0 eq) were added sequentially into a dry 100 mL three-necked flask. The reaction system was evacuated and filled with N 2 , repeat the operation more than 2 times. Then DMSO (30mL) was added under a nitrogen atmosphere and placed in an oil bath heated at 120°C and stirred. After 18 hours, the reaction was completed by TLC monitoring. The resulting mixture was cooled to room temperature and diluted with a large amount of ethyl acetate. The mixture was then filtered through a diatomaceous earth pad and washed with ethyl acetate. The filtrate was washed three times with water, dried over anhydrous sodium sulfate, and filtered. The filtrate was concentrated under reduced pressure, and the residue was purified by silica gel column chromatography (eluent: petroleum ether / ethyl acetate = 4:1-1:1) to obtain a white powder as the target compound 29 (1.98 g, yield 84%). 1 HNMR (400MHz, CDCl 3 ): δ (ppm) 8.64 (d, J = 2.8Hz, 1H), 8.58-8.52 (m, 1H), 8.08 (s, 1H), 8.01 (m ,1H),7.87-7.81(m,1H),7.68(dd,J=2.8,1.6Hz,1H),7.65-7.61(m,1H), 7.40(s,1H),7.37-7.29(m,3H),7.27(dd,J=7.2,6.4Hz,1H),7.19(m,1H) ,7.15(t,J=2.0Hz,1H),7.04(m,2H),6.80(d,J=2.0Hz,1H),6.37(m,1H).

[0112] Synthesis of Pt-F(5)

[0113] (3,5-di-tert-butylphenyl)(mesityl)iodonium trifluoromethanesulfonate (2.10 g, 3.6 mmol, 1.8 eq), compound 29 (1.05 g, 2.00 mmol, 1.0 eq) and Cu(AcO) were mixed. 2 (18 mg, 0.200 mmol, 5.0% mol) was mixed in 30 mL of dimethylformamide (DMF), and the reaction mixture was refluxed at 100 ° C for 1 hour. The solvent was removed under reduced pressure, and the crude product was subjected to silica gel column chromatography (eluent: dichloromethane: acetone) to obtain compound 30 (1.50 g, 1.85 mmol). All of it was added to a 250 mL flask, mixed with dichloro(1,5-cyclooctadiene)-platinum(II) (0.692 g, 1.85 mmol, 1.00 eq) and sodium acetate (0.608 g, 7.40 mmol, 4.00 eq), and then 50 mL of DMF was added. After reflux at 150 ° C for 15 hours under a nitrogen atmosphere, all solvents were removed by rotary evaporation, and then washed with CH 2 Cl 2 The resulting mixture was dissolved. The combined organic phases were washed with water and MgSO 4 The residue was purified by silica gel column chromatography (eluent: dichloromethane and hexane) to obtain the target compound Pt-F (5) (0.709 g, yield 45%) as a pale yellow solid. 1 H NMR (400 MHz, CDCl 3 ): δ(ppm)9.09(d,J=7.6Hz,1H),8.55(m,2H),8.12(m,1H),8.01(m,1H),7.66-7.58(m,2H),7.50(t,J=2.2Hz,1H),7.40(d,J=2.0Hz,1H),7 .36-7.30(m,4H),7.30-7.24(m,1H),7.19(m,1H),7.17-7.09(m,2H),6.92(m,1H),5.77(d,J=5.6Hz,1H),1.56-1.02(m,18H),0.95(s,9H).

[0114] Example 6

[0115] This embodiment provides a method for preparing a luminescent complex material, and the preparation process is as follows:

[0116]

[0117] Synthesis of Compound 3-(1H-benzimidazol-1-yl)-5-bromobenzonitrile (Compound 2)

[0118] Under nitrogen atmosphere, 3-bromo-5-iodobenzonitrile (9.2 g, 30.0 mmol, 1.0 eq), 1H-benzo[d]imidazole (3.54 g, 30.0 mmol, 1.0 eq), CuI (0.29 g, 1.5 mmol, 5.0% mol), K 2 CO 3 (8.28 g, 60.0 mmol, 2.0 eq) and L-proline (0.345 g, 3.0 mmol, 10% mol) were added to DMSO (80 mL), stirred at 120 ° C for 2 d, and then cooled to ambient temperature. The mixture was diluted with a large amount of ethyl acetate, filtered, and the solid was washed with ethyl acetate. The filtrate was washed three times with water, dried over sodium sulfate, then filtered, and the filtrate was concentrated under reduced pressure. The residue was purified by silica gel column chromatography, first using hexane and then using hexane / ethyl acetate (10: 1-3: 1) as eluent to obtain a light brown solid as the target compound 2 (6.26 g, yield 70%). 1 H NMR (400 MHz, CDCl 3 )δ8.09(s,1H),7.94(t,J=1.8Hz,1H),7.87(dd,J=6.0,2.8Hz,2H),7.81–7.75(m,1H),7.51(dd,J=5.9,3.2Hz,1H),7.44–7.32(m,2H).

[0119] Synthesis of 3-(1H-benzimidazol-1-yl)-5-[9-[4-(tert-butyl)-2-pyridyl]-9H-carbazol-2-yl]oxy]-benzonitrile (Compound 3)

[0120] Compound 2 (1.49 g, 5.00 mol, 1.2 eq), 9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazole-2-ol (1.31 g, 4.15 mmol, 1.0 eq), CuI (80 mg, 0.420 mmol, 10% mol), 2-picolinic acid (102 mg, 8.31 mmol, 20% mol) and K 3 PO 4 (2.65 g, 12.5 mmol, 3.0 eq) were added into a clean flask in sequence. The reaction system was evacuated and filled with N 2, repeat the operation 2 or more times. Then add DMSO (30 mL) under a nitrogen atmosphere and stir in an oil bath heated at 120 ° C. After 18 hours, the resulting mixture was cooled to room temperature and diluted with a large amount of ethyl acetate. The mixture was then filtered through diatomaceous earth and washed with ethyl acetate. The filtrate was washed three times with water, dried over anhydrous sodium sulfate, and filtered. The filtrate was concentrated under reduced pressure, and the residue was purified by silica gel column chromatography (eluent: petroleum ether / ethyl acetate = 4:1-1:1) to obtain 1.53 g of white solid as the target compound 3, with a yield of 69%. 1 HNMR (500MHz, CDCl 3 )δ8.59(d,J=5.3Hz,1H),8.16(d,J=8.4Hz,1H),8.14–8.07(m,2H),7.90–7.83(m,1H),7.72(d,J=8.3Hz,1H),7.68(d,J=2.0Hz,1H) ,7.62(s,1H),7.57–7.51(m,1H),7.51–7.42(m,3H),7.34(ddd,J=16.2,7.5,4.6Hz,5H),7.08(dd,J=8.4,2.0Hz,1H),1.39(s,9H).

[0121] Synthesis of Pt-CN-1(85)

[0122] 1,3-di-tert-butyl-5-iodobenzene (3.16 g, 10.0 mmol, 2.2 eq), mesitylene (0.400 g, 15.0 mmol, 3.3 eq) and 3-chloroperoxybenzoic acid (m-CPBA 85%) (3.04 g, 15.0 mmol, 3.3 eq) were added. Then, methanesulfonic acid (7.0 mL, 79.6 mmol) was slowly added dropwise to the reaction solution at room temperature. The resulting mixture was stirred for 2 hours and then added with excess K 2 CO 3 The solutions were mixed, the organic phase was separated, and the K 2 CO 3 The organic layer was washed with a solution of trifluoromethanesulfonic acid to remove organic acids. The organic layer was separated again and washed with Na 2 SO 4 Dry and filter. Rotate and evaporate until the solvent is completely removed, add a small amount of hexane, then filter and dry the residue. The crude product (3,5-di-tert-butylphenyl)(mesityl)iodonium trifluoromethanesulfonate is directly used for the next step reaction. Mix it with compound 3 (2.42 g, 4.54 mmol, 1 mmol) and Cu(AcO) 2(41 mg, 0.227 mmol, 5% mol) was mixed in 30 mL of dimethylformamide (DMF), and the reaction mixture was refluxed at 100 ° C for 1 hour. The solvent was removed under reduced pressure, and the crude product was subjected to silica gel column chromatography (eluent: dichloromethane: acetone) to obtain compound 4 (3.17 g, yield 80%). All of it was added to a 250 mL flask, mixed with dichloro(1,5-cyclooctadiene)-platinum(II) (1.53 g, 4.09 mmol) and sodium acetate (1.38 g, 16.4 mmol), and then 120 mL of DMF was added. After reflux at 150 ° C for 15 hours under a nitrogen atmosphere, all solvents were removed by rotary evaporation, and then washed with CH 2 Cl 2 The resulting mixture was dissolved. The combined organic phases were washed with water and MgSO 4 The residue was dried, filtered and concentrated. The residue was purified by silica gel column chromatography (eluent: dichloromethane and hexane) to obtain the target compound Pt-CN-1(85) (1.53 g, yield 46%) as a pale yellow solid. 1 HNMR (600MHz, CDCl 3 )δ8.66(d,J=6.2Hz,1H),8.12(d,J=8.2Hz,1H),8.00(dd,J=5.6,3.1Hz,1H),7.84(d,J=8.2Hz,1H),7.65(t,J=7.7Hz,1H) ,7.57(dd,J=5.5,3.0Hz,1H),7.55–7.39(m,5H),7.39–7.26(m,6H),5.46(s,1H),1.25(s,9H),0.97(s,9H),0.78(s,9H).

[0123] Example 7

[0124] This embodiment provides a method for preparing a luminescent complex material, and the preparation process is as follows:

[0125]

[0126] Synthesis of 4-(1H-benzimidazol-1-yl)-2-bromobenzonitrile (Compound 2)

[0127] Under nitrogen atmosphere, 2-bromo-4-iodobenzonitrile (9.2 g, 30.0 mmol, 1.0 eq), 1H-benzo[d]imidazole (3.54 g, 30.0 mmol, 1.0 eq), CuI (0.29 g, 1.5 mmol, 5.0% mol), K 2 CO 3(8.28 g, 60.0 mmol, 2.0 eq) and L-proline (0.345 g, 3.0 mmol, 10% mol) were added to DMSO (80 mL), stirred at 120 ° C for 2 d, and then cooled to ambient temperature. The mixture was diluted with a large amount of ethyl acetate, filtered, and the solid was washed with ethyl acetate. The filtrate was washed three times with water, dried over sodium sulfate, then filtered, and the filtrate was concentrated under reduced pressure. The residue was purified by silica gel column chromatography, first using hexane and then using hexane / ethyl acetate (10: 1-3: 1) as eluent to obtain a light brown solid as the target compound 2 (6.35 g, yield 71%). 1 H NMR (500 MHz, CDCl 3 )δ8.13(d,J=6.3Hz,1H),7.91(d,J=1.4Hz,1H),7.87(t,J=7.0Hz,2H),7.63(dd,J=8.3,1.5Hz,1H),7.60–7.52(m,1H),7.46–7.32(m,2H).

[0128] Synthesis of 4-(1H-benzimidazol-1-yl)-2-[9-[4-(tert-butyl)-2-pyridyl]-9H-carbazol-2-yl]oxy]-benzonitrile (Compound 3)

[0129] Compound 2 (1.49 g, 5.00 mol, 1.2 eq), 9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazole-2-ol (1.31 g, 4.15 mmol, 1.0 eq), CuI (80 mg, 0.420 mmol, 10 mol%), 2-pyridinecarboxylic acid (102 mg, 8.31 mmol, 20 mol%) and K 3 PO 4 (2.65 g, 12.5 mmol, 3.0 eq) were added into a clean three-necked flask in sequence. The reaction system was evacuated and filled with N 2 , repeat the operation 2 or more times. Then add DMSO (30 mL) under nitrogen atmosphere, place in an oil bath heated at 120 ° C and stir. After 18 hours, the resulting mixture was cooled to room temperature and diluted with a large amount of ethyl acetate. The mixture was then filtered through diatomaceous earth and washed with ethyl acetate. The filtrate was washed three times with water, dried over anhydrous sodium sulfate, and filtered. The filtrate was concentrated under reduced pressure, and the residue was purified by silica gel column chromatography (eluent: petroleum ether / ethyl acetate = 4:1-1:1) to obtain 1.66 g of white solid as the target compound 3, with a yield of 75%. 1 HNMR (500MHz, CDCl 3)δ8.56(d,J=5.3Hz,1H),8.13(d,J=8.4Hz,1H),8.09(d,J=7.7Hz,1H),7.99(s,1H),7.77(dd,J=14.5,8.0Hz,3H),7.68(d,J=8.2Hz,1H), 7.60(s,1H),7.47–7.40(m,2H),7.34–7.28(m,2H),7.22(dd,J=17.0,8.0Hz,3H),7.12(dd,J=8.4,1.9Hz,1H),7.09(s,1H),1.37(s,9H).

[0130] Synthesis of Pt-CN-2(86)

[0131] 1,3-di-tert-butyl-5-iodobenzene (3.16 g, 10.0 mmol, 2.2 eq), mesitylene (0.400 g, 15.0 mmol, 3.3 eq) and 3-chloroperoxybenzoic acid (m-CPBA 85%) (3.04 g, 15.0 mmol, 3.3 eq) were added. Then, methanesulfonic acid (7.0 mL, 79.6 mmol) was slowly added dropwise to the reaction solution at room temperature. The resulting mixture was stirred for 2 hours and then added with excess K 2 CO 3 The solutions were mixed, the organic phase was separated, and the K 2 CO 3 The organic layer was washed with a solution of trifluoromethanesulfonic acid to remove organic acids. The organic layer was separated again and washed with Na 2 SO 4 Dry and filter. Rotate and evaporate until the solvent is completely removed, add a small amount of hexane, then filter and dry the residue. The crude product (3,5-di-tert-butylphenyl)(mesityl)iodonium trifluoromethanesulfonate is directly used for the next step reaction. Mix it with compound 3 (2.42 g, 4.54 mmol, 1 mmol) and Cu(AcO) 2 (41 mg, 0.227 mmol, 5% mol) was mixed in 30 mL of dimethylformamide (DMF), and the reaction mixture was refluxed at 100 ° C for 1 hour. The solvent was removed under reduced pressure, and the crude product was subjected to silica gel column chromatography (eluent: dichloromethane: acetone) to obtain compound 4 (3.09 g, yield 78%). All of it was added to a 250 mL flask, mixed with dichloro (1,5-cyclooctadiene) -platinum (II) (1.53 g, 4.09 mmol) and sodium acetate (1.38 g, 16.4 mmol), and then 120 mL of DMF was added. After reflux at 150 ° C for 15 hours under a nitrogen atmosphere, all solvents were removed by rotary evaporation, and then washed with CH 2 Cl 2The resulting mixture was dissolved. The combined organic phases were washed with water and MgSO 4 The residue was dried, filtered and concentrated. The residue was purified by silica gel column chromatography (eluent: dichloromethane and hexane) to obtain the target compound Pt-CN-2(86) (1.46 g, yield 45%) as a pale yellow solid. 1 H NMR (500 MHz, CDCl 3 )δ8.50(d,J=6.2Hz,1H),8.05(d,J=8.2Hz,1H),8.01–7.95(m,1H),7.82( d,J=8.2Hz,2H),7.62–7.51(m,2H),7.47(dd,J=7.6,4.2Hz,3H),7.40(d,J =8.0Hz,1H),7.29(d,J=9.4Hz,2H),7.24(d,J=6.4Hz,2H),7.21(s,1H),6 .98(d,J=7.6Hz,1H),4.98(s,1H),1.56(s,9H),0.90(s,9H),0.65(s,9H).

[0132] Example 8

[0133] This embodiment provides a method for preparing a luminescent complex material, and the preparation process is as follows:

[0134]

[0135] Synthesis of 4-fluoro-2′-nitro[1,1′-biphenyl]-2-cyano (Compound 7)

[0136] A 250 mL two-necked flask was charged with 1-bromo-2-nitrobenzene (10.3 g, 50 mmol, 1.0 eq), 2-cyano-4-fluorophenylboronic acid (9.1 g, 55 mmol, 1.1 eq), Pd 2 (dba) 3 (230 mg, 0.25 mmol, 0.5% mol), S-Phos (410 mg, 1.00 mmol, 2.0% mol), ethanol (20 mL), toluene (70 mL) and 2 mol / L K 2 CO 3 (40 mL, 80 mmol, 1.6 eq). The reaction mixture was stirred at 90 °C for 12 h. The resulting mixture was diluted with ethyl acetate, washed with water and brine, and then washed with anhydrous Na 2 SO 4 The residue was concentrated with an evaporator and purified by silica gel column chromatography (eluent: dichloromethane and hexane) to obtain the target compound 7 as a slightly yellow solid. 1 H NMR (400 MHz, CDCl3 )δ8.11(d,J=8.1Hz,1H),7.71(s,1H),7.61(s,1H),7.45(d,J=7.6Hz,1H),7.25(dd,J=5.7,2.7Hz,2H),7.18(d,J=2.5Hz,1H).

[0137] Synthesis of 2-fluoro-4-(cyano)-9H-carbazole (Compound 8)

[0138] 4-Fluoro-2′-nitro[1,1′-biphenyl]-2-cyano (4.84 g, 20.0 mmol, 1.0 eq), DPPE (8.76 g, 22.0 mmol, 1.1 eq) and 1,2-dichlorobenzene (10 mL) were mixed in a 100 mL round bottle, and then the reaction bottle was immersed in an oil bath at 130° C. under a nitrogen atmosphere. After stirring for 5 hours, it was cooled to room temperature, and the residue was subjected to column chromatography on silica gel using petroleum ether / ethyl acetate as the eluent to obtain a white solid as the target compound 8. 1 HNMR (400MHz, CDCl 3 )δ8.45(d,J=7.9Hz,1H),8.33(s,1H),7.47–7.40(m,2H),7.33–7.27(m,1H),7.19–7.02(m,2H).

[0139] Synthesis of 9-(4-(tert-butyl)pyridin-2-yl)-2-fluoro-4-(cyano)-9H-carbazole (Compound 9)

[0140] Compound 8 (4.98 g, 23.7 mmol, 1.0 eq), 2-bromo-4-(tert-butyl)pyridine (5.33 g, 24.9 mmol, 1.05 eq), copper iodide (0.450 g, 2.37 mmol, 10% mol), 1-methylimidazole (0.398 g, 4.74 mmol, 20% mol) and K 2 CO 3 (9.81 g, 71.1 mmol, 3.0 eq) was added to a two-necked flask and dissolved in 1,4-dioxane (50 mL), and stirred at 100 ° C for 12 h. Afterwards, the product was quenched with water, extracted with EA / water, and washed with brine. After further purification by column chromatography using ethyl acetate: hexane (1:9) as the eluent, a white powder was obtained as the target compound 9 (6.67 g, yield 82%). 1 H NMR (500 MHz, CDCl 3)δ8.63(d,J=5.3Hz,1H),8.55(d,J=7.8Hz,1H),7.68(d,J=8.3Hz,1H),7.61(d,J=1.3Hz,1H),7 .56(d,J=2.2Hz,1H),7.50–7.43(m,1H),7.39–7.33(m,2H),7.15(d,J=2.2Hz,1H),1.42(s,9H).

[0141] Synthesis of 9-(4-(tert-butyl)pyridin-2-yl)-4-(cyano)-9H-carbazole-2-ol (Compound 10)

[0142] In a two-necked flask, compound 9 (3.43 g, 10.0 mmol) was dissolved in DMSO (50 mL), mixed with KOH solution (40%, 5 mL, 22 mmol), and the reaction mixture was stirred at 120 ° C for 6 hours. After cooling, it was poured into a large amount of water, and then the pH value was adjusted to 2-3 with HCl, extracted with ethyl acetate, and washed with brine. After further purification by column chromatography using EA: hexane (1: 2) eluent, a white powder was obtained as the target compound 10 (2.39 g, yield 70%). 1 H NMR (400MHz, DMSO) δ10.36(s,1H),8.65(d,J=5.3Hz,1H),8.34(d,J=7.7Hz,1H),7.74–7.64(m,2H),7 .56(dd,J=5.3,1.7Hz,1H),7.53–7.47(m,1H),7.45–7.36(m,2H),7.20(d,J=2.0Hz,1H),1.38(s,9H).

[0143] Synthesis of 2-(3-(1H-benzo[d]imidazol-1-yl)-5-(cyano)phenoxy)-9-(4-(tert-butyl)pyridin-2-yl)-4-(cyano)-9H-carbazole (Compound 11)

[0144] Compound 10 (2.05 g, 6.00 mmol, 1.0 eq), 3-(1H-benzimidazol-1-yl)-5-bromobenzonitrile (2.15 g, 7.20 mmol, 1.2 eq), CuI (114 mg, 0.600 mmol, 10 mol%), 2-pyridinecarboxylic acid (148 mg, 1.20 mmol, 20 mol%) and K 3 PO 4 (3.82 g, 18.0 mmol, 3.0 equiv) were added into a dry three-necked flask in sequence. The reaction system was evacuated and filled with N 2, repeat the operation 2 or more times. Then DMSO (30 mL) was added under a nitrogen atmosphere and placed in an oil bath heated at 120 ° C and stirred. After 18 hours, the resulting mixture was cooled to room temperature and diluted with a large amount of ethyl acetate. The mixture was then filtered through diatomaceous earth and washed with ethyl acetate. The filtrate was washed three times with water, dried over anhydrous sodium sulfate, and filtered. The filtrate was concentrated under reduced pressure, and the residue was purified by silica gel column chromatography (eluent: petroleum ether / ethyl acetate = 4: 1-1: 1) to obtain 2.68 g of white solid as the target compound 11, with a yield of 80%. 1 H NMR (500 MHz, CDCl 3 )δ8.52(s,1H),8.34(d,J=2.9Hz,1H),8.23–8.18(m,1H),8.03(dd,J=7.1,1.5Hz,1H),7.80(dd,J=6.7,1.4Hz,1H),7.6 9–7.64(m,1H),7.57(t,J=2.2Hz,1H),7.52(td,J=6.9,1.5Hz,1H),7.45–7.37(m,2H),7.37–7.19(m,7H),1.36(s,9H).

[0145] Synthesis of Pt-2CN(101)

[0146] (3,5-di-tert-butylphenyl)(mesityl)iodonium trifluoromethanesulfonate (4.20 g, 7.2 mmol, 1.8 eq), compound 11 (2.23 g, 4.00 mmol, 1.0 eq) and Cu(AcO) were mixed. 2 (36 mg, 0.200 mmol, 5.0% mol) was mixed in 30 mL of dimethylformamide (DMF), and the reaction mixture was refluxed at 100 ° C for 1 hour. The solvent was removed under reduced pressure, and the crude product was subjected to silica gel column chromatography (eluent: dichloromethane: acetone) to obtain compound 12 (3.16 g, yield 3.52 mmol). All of it was added to a 250 mL flask, mixed with dichloro(1,5-cyclooctadiene)-platinum(II) (1.32 g, 3.52 mmol, 1.00 eq) and sodium acetate (1.18 g, 14.1 mmol, 4.00 eq), and then 120 mL of DMF was added. After reflux at 150 ° C for 15 hours under a nitrogen atmosphere, all solvents were removed by rotary evaporation, and then washed with CH 2 Cl 2 The resulting mixture was dissolved. The combined organic phases were washed with water and MgSO 4 The residue was dried, filtered and concentrated. The residue was purified by silica gel column chromatography (eluent: dichloromethane and hexane) to obtain the target compound Pt-2CN (101) (1.49 g, yield 45%) as a pale yellow solid.1 H NMR (500 MHz, CDCl 3 )δ9.06(d,J=7.9Hz,1H),8.21–8.16(m,1H),7.86(d,J=2.3Hz,1H),7.72(dd,J=6.1,1.6Hz,1H),7.67(dd,J=7.7,2.2Hz,1H),7.53(d,J=2.2 Hz,1H),7.45–7.39(m,2H),7.39–7.30(m,5H),7.30–7.26(m,1H),7.25–7.19(m,1H),7.12(s,2H),6.96(s,1H),6.46(s,1H),1.36(s,27H).

[0147] Example 9

[0148] This embodiment provides a method for preparing a luminescent complex material, and the preparation process is as follows:

[0149]

[0150] Synthesis of 2-(3-(1H-benzo[d]imidazol-1-yl)phenoxy)-9-(4-(tert-butyl)pyridin-2-yl)-4-(cyano)-9H-carbazole (Compound 13)

[0151] Compound 10 (1.88 g, 5.50 mmol, 1.0 eq), 1-(3-bromophenyl)-1H-benzo[d]imidazole (1.80 g, 6.60 mmol, 1.2 eq), CuI (114 mg, 0.600 mmol, 10 mol%), 2-pyridinecarboxylic acid (148 mg, 1.20 mmol, 20 mol%) and K 3 PO 4 (3.50 g, 16.5 mmol, 3.0 eq) were added into a dry three-necked flask in sequence. The reaction system was evacuated and filled with N 2 , repeat the operation more than 2 times. Then DMSO (40mL) was added under a nitrogen atmosphere and placed in an oil bath heated at 120°C and stirred. After 18 hours, the reaction was completed by TLC monitoring. The resulting mixture was cooled to room temperature and diluted with a large amount of ethyl acetate. The mixture was then filtered through diatomaceous earth and washed with ethyl acetate. The filtrate was washed three times with water, dried over anhydrous sodium sulfate, and filtered. The filtered material was concentrated under reduced pressure, and the residue was purified by silica gel column chromatography (eluent: petroleum ether / ethyl acetate = 4:1-1:1) to obtain 2.41g of white powder as the target compound 13, with a yield of 82%. 1 H NMR (500 MHz, CDCl 3)δ8.64(d,J=7.9Hz,1H),8.59(d,J=5.3Hz,1H),8.12(s,1H),7.90–7.82(m,2H),7.70(d,J=8.3Hz,1H),7.56(dt,J=16.2,6.2Hz,4H) ,7.43(t,J=7.5Hz,1H),7.33(dddd,J=16.6,12.5,7.2,1.7Hz,5H),7.25(t,J=2.1Hz,1H),7.11(dd,J=8.3,1.9Hz,1H),1.38(s,9H).

[0152] Synthesis of Pt-CN-3(105)

[0153] (3,5-di-tert-butylphenyl)(mesityl)iodonium trifluoromethanesulfonate (4.20 g, 7.2 mmol, 1.8 eq), compound 13 (2.13 g, 4.00 mmol, 1.0 eq) and Cu(AcO) were mixed. 2 (36 mg, 0.200 mmol, 5.0% mol) was mixed in 30 mL of dimethylformamide (DMF), and the reaction mixture was refluxed at 100 ° C for 1 hour. The solvent was removed under reduced pressure, and the crude product was subjected to silica gel column chromatography (eluent: dichloromethane: acetone) to obtain compound 14 (2.91 g, 3.40 mmol). All of it was added to a 250 mL flask, mixed with dichloro(1,5-cyclooctadiene)-platinum(II) (1.27 g, 3.40 mmol, 1.00 equiv) and sodium acetate (1.12 g, 13.6 mmol, 4.00 equiv), and then 120 mL of DMF was added. After reflux at 150 ° C for 15 hours under a nitrogen atmosphere, all solvents were removed by rotary evaporation, and then washed with CH 2 Cl 2 The resulting mixture was dissolved. The combined organic phases were washed with water and MgSO 4 Dry, filter and concentrate. The residue was purified by silica gel column chromatography (eluent: dichloromethane and hexane) to give the desired target compound Pt-CN-3(105) (1.43 g, yield 46%) as a slightly yellow solid. 1 H NMR (500 MHz, CDCl 3)δ8.69–8.51(m,2H),8.15(d,J=8.2Hz,1H),7.70(s,1H),7.61(d,J=7.8Hz,1H),7.52(t,J=7.2Hz,3H),7.47–7.30 (m,6H),7.28(s,1H),7.03(dd,J=25.2,7.7Hz,2H),5.54(d,J=4.9Hz,1H),1.26(s,9H),0.99(s,9H),0.83(s,9H).

[0154] Example 10

[0155] This embodiment provides a method for preparing a luminescent complex material, and the preparation process is as follows:

[0156]

[0157] Synthesis of Pt-CN-4(106)

[0158] 1-(tert-butyl)-3-iodobenzene (2.60 g, 10.0 mmol, 2.2 eq), mesitylene (0.400 g, 15.0 mmol, 3.3 eq) and 3-chloroperoxybenzoic acid (m-CPBA 85%) (3.04 g, 15.0 mmol, 3.3 eq) were added. Then, methanesulfonic acid (7.0 mL, 79.6 mmol) was slowly added dropwise to the reaction solution at room temperature. The resulting mixture was stirred for 2 hours and then added with excess K 2 CO 3 The solutions were mixed, the organic phase was separated, and the K 2 CO 3 The organic layer was washed with a solution of trifluoromethanesulfonic acid to remove organic acids. The organic layer was separated again and washed with Na 2 SO 4 Dry and filter. Rotate and evaporate until the solvent is completely removed, add a small amount of hexane, and then filter and dry the residue. The crude product (3-di-tert-butylphenyl) (mesitylene) iodonium trifluoromethanesulfonate is directly used for the next step reaction. It is mixed with compound 3 (2.42 g, 4.54 mmol, 1 mmol) and Cu(AcO) 2(41 mg, 0.227 mmol, 5% mol) was mixed in 30 mL of dimethylformamide (DMF), and the reaction mixture was refluxed at 100 ° C for 1 hour. The solvent was removed under reduced pressure, and the crude product was subjected to silica gel column chromatography (eluent: dichloromethane: acetone) to obtain compound 4 (3.00 g, yield 81%). All of it was added to a 250 mL flask, mixed with dichloro (1,5-cyclooctadiene) - platinum (II) (1.53 g, 4.09 mmol) and sodium acetate (1.38 g, 16.4 mmol), and then 120 mL of DMF was added. After reflux at 150 ° C for 15 hours under a nitrogen atmosphere, all solvents were removed by rotary evaporation, and then washed with CH 2 Cl 2 The resulting mixture was dissolved. The combined organic phases were washed with water and MgSO 4 The residue was dried, filtered and concentrated. The residue was purified by silica gel column chromatography (eluent: dichloromethane and hexane) to obtain the target compound Pt-CN-4(106) (1.52 g, yield 48%) as a pale yellow solid. 1 H NMR (500 MHz, CDCl 3 )δ8.62(d,J=6.6Hz,1H),8.08(d,J=8.3Hz,1H),8.03(d,J=6.2Hz,1H),7.86(d,J=8.2H z,1H),7.69–7.54(m,4H),7.52–7.30(m,10H),5.71(s,1H),1.07(s,9H),0.92(s,9H).

[0159] Test Example 1

[0160] The weight loss curves of each example in a nitrogen atmosphere and the photoluminescence spectra in a dichloromethane solution were measured. The results are as follows: Figure 1-Figure 11 As shown in Table 1:

[0161] Table 1. Physical property data of each example

[0162]

[0163]

[0164] From the data in Table 1, it can be seen that the luminescent complex materials of each embodiment are suitable for blue light doping, and the decomposition temperature at 5% weight loss is higher than 400 degrees Celsius, indicating that the luminescent complex materials of the embodiment have good thermal stability. And compared with the comparative example, the luminescent half-peak width of the embodiment is reduced.

[0165] The structural formula of the luminescent complex material of the comparative example is:

[0166]

[0167] The structural formula of the luminescent complex material of the embodiment is:

[0168]

[0169] Test Example 2

[0170] The electroluminescent properties of the electroluminescent devices based on Examples 1-10 and Comparative Examples are measured to illustrate the application of the luminescent complex material of the present invention in the electroluminescent device. The structure of the electroluminescent device is: ITO / HAT-CN (5nm) / TBBD (15nm) / o-SFAF (15nm) / SiCzCz (15nm) / SiCzCz:SiTrzCz2:emitter (25nm) / SiTrzCz2 (20nm) / ANT-BIZ (30nm) / Liq (2nm) / Al, wherein ITO is the substrate, HAT-CN is the hole injection layer, TBBD and o-SFAF are the hole transport layer, ANT-BIZ is the electron transport layer, SiCzCz:SiTrzCz2 is the blending host, and the emitter is the luminescent complex material of Examples 1-10 and Comparative Examples, respectively. The structural formula of the structure except the luminescent complex material of the present invention is shown below, and the results are shown in Table 2 below.

[0171]

[0172] Table 2. Characterization results of devices in various embodiments and comparative embodiments

[0173]

[0174] From the data in Table 2, it can be seen that the OLED devices prepared based on Examples 1-10 as the guest have improved luminous efficiency, reduced half-peak width, and increased device stability compared with the comparative examples.

Claims

1. A luminescent complex material, characterized in that: Its general structure is shown in Formula 1: Wherein, M is transition metal platinum or palladium; Y a , Y b , X a , X b and X c Each independently represents C or N, Y a and Y b One of them is N, and Y a and Y b The other one is C; Ring A5 is present or absent; When ring A5 is present, ring A5 is a C5-C30 carbocyclic group or a C1-C30 heterocyclic group, wherein Y c and Y d Each is C; when ring A5 is absent, Y c and Y d Each is C; Ring A1 is a pyrazole ring or an imidazole ring; Ring A2, Ring A3 and Ring A4 are each independently a C5-C30 carbocyclic group or a C1-C30 heterocyclic group; T1 and T2 are each independently selected from -S- or -Se- or -O- or -N- or -C-; A6 exists or does not exist; When A6 is present, A6 is a C5-C30 carbocyclic group or a C1-C30 heterocyclic group or a C=C double bond or a C=N double bond; R a , R b , R c , R d and RA are each independently selected from hydrogen, deuterium, -F, -Cl, -Br, -I, -SF5, hydroxyl, cyano, trifluoromethyl, nitro, amidino, hydrazine, hydrazone, carboxylic acid group or its salt, sulfonic acid group or its salt, phosphoric acid group or its salt, substituted or unsubstituted C1-C60 alkyl, substituted or unsubstituted C2-C60 alkenyl, substituted or unsubstituted C2-C60 alkynyl, substituted or unsubstituted C1-C60 alkoxy, substituted or unsubstituted C1-C60 alkylthio, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C1-C10 heterocycloalkyl, substituted or unsubstituted C3-C10 cycloalkenyl, substituted or unsubstituted C1-C60 a C10 heterocycloalkenyl group, a substituted or unsubstituted C6-C60 aryl group, a substituted or unsubstituted C7-C60 alkylaryl group, a substituted or unsubstituted C7-C60 arylalkyl group, a substituted or unsubstituted C6-C60 aryloxy group, a substituted or unsubstituted C6-C60 arylthio group, a substituted or unsubstituted C1-C60 heteroaryl group, a substituted or unsubstituted C2-C60 alkylheteroaryl group, a substituted or unsubstituted C2-C60 heteroarylalkyl group, a substituted or unsubstituted C1-C60 heteroaryloxy group, a substituted or unsubstituted C1-C60 heteroarylthio group, a substituted or unsubstituted monovalent non-aromatic fused polycyclic group, and a substituted or unsubstituted monovalent non-aromatic fused heteropolycyclic group.

2. The luminescent complex material according to claim 1, characterized in that: A1, A2, A3, A4, A5, and A6 are each independently selected from one of the following structures: wherein X1 is CR4 or N; Y is selected from CR5R6, SiR7R8, NR9, C(=O), S or O; R4, R5, R6, R7, R8, R9 are each independently H or D, or a linear alkyl, alkoxy or thioalkoxy group having 1 to 20 C atoms, or a branched or cyclic alkyl, alkoxy, thioalkoxy or silyl group having 3 to 20 C atoms, or a substituted keto group having 1 to 20 C atoms, or an alkoxycarbonyl group having 2 to 20 C atoms, or an aryloxycarbonyl group having 7 to 20 C atoms R4, R5, R6, R7, R8, R9 are preferably selected from the group consisting of a 1, 2, 4, 5, 6, 7, 8, 9, 10, 12, 14, 16, 17, 18, 19, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 100, 101, 102, 103, 104, 105, 106, 107, 108, 111, 112, 113, 114, 115, 116, 117, 118, 119, 120, 121, 122, 123, 124, 131, 3. The luminescent complex material according to claim 1, characterized in that: R a , R b , R c and R d Each independently selected from one of the following structures: F, Cl, Br, I, CF3, CBr3, CCl3, CI 3、 CN, OH, OCH3, SH, SCH3, O=CO-, -N(CH3)2, CHO.

4. The luminescent complex material according to claim 1, characterized in that: M is transition metal platinum.

5. The luminescent complex material according to claim 1, characterized in that: The luminescent complex material is selected from any one of the following structures:

6. Use of the luminescent complex material according to any one of claims 1 to 5 in an OLED device.

7. An OLED device, comprising a light-emitting layer, wherein the light-emitting layer comprises a host material and a guest material, characterized in that: The guest material is the luminescent complex material according to any one of claims 1 to 5.

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