WO2019056515A1 - Multi-substituted quinoline-coordinated iridium-hybridized compound, preparation method therefor and application thereof - Google Patents

Abstract

A multi-substituted quinolone-coordinated iridium-hybridized compound and a preparation method therefor, as well as an application of the compound in electroluminescent materials. Ligand modification of the compound comprises second position-substituted 3,5 di-substituted (RdRd), fourth position-substituted (Re) and 3, 4, 5 trisubstituted (RdReRd) phenyl; the specific synthesis route of the multi-substituted quinoline-coordinated iridium-hybridized compound is as follows: by means of an amine transesterification reaction, a Skraup ring condensation reaction under the catalysis of acid and a hydroxyhalogenation reaction, multi-substituted quinoline is formed, and then a ligand is obtained by means of a Suzuki coupling reaction.

Description

Polysubstituted substituted quinoline coordination compound and preparation method and application thereof Technical field

The invention belongs to the technical field of electronic materials, and particularly relates to a polysubstituted quinoline coordinated doping compound and a preparation method thereof, and an application of the compound in an electroluminescent material.

Background technique

Photoelectric devices utilizing organic luminescent materials are becoming more and more popular, and they are popular for a number of reasons: organic luminescent materials are relatively inexpensive, and thus organic optoelectronic devices have potential cost advantages over inorganic devices. In addition, the inherent properties of organic materials, such as their flexibility, make them ideal for special applications such as processing on flexible substrates. Organic optoelectronic devices include organic light emitting diodes (OLEDs), organic transistors, organic solar cells, and organic photodetectors. For OLEDs, organic luminescent materials have performance advantages over traditional materials. For example, the wavelength at which the organic light-emitting layer emits light can usually be easily adjusted with a suitable dopant.

The energy conversion mode of the organic light-emitting material is to directly convert electrical energy into light energy, and the organic light-emitting material can be closer to the requirement of light adaptability than the inorganic light-emitting material. Displays and illuminators based on organic light emitting diode (OLED) technology have a flexible form factor and add a number of artistic elements to the electronic device. The earliest organic electroluminescent device was developed by Eastman Kodak, using an aromatic amine organic small molecule as a hole transport layer and 8-hydroxyquinoline aluminum as a light-emitting layer ("Organic electroluminescent diodes" Tang, Vanslyke et al, Appl Phys Lett, Volume 51, pp. 913-915, 1987). Such devices using organic molecules as the core luminescent materials are called organic light-emitting diodes (OLEDs), and can be applied to new fields of display and illumination, and have many advantages and potentials. The light-emitting device prepared by the organic material has the advantages of high quantum efficiency, high brightness, high luminous efficiency, etc.; the light-emitting device prepared from the organic light-emitting material has the advantages of lightness, thinness and softness, and can be specially prepared into a flexible device which is another light-emitting material. The advantages that cannot be compared. According to the classification of core electroluminescent materials, conventional OLEDs can be classified into fluorescent OLEDs and phosphorescent OLEDs. Compared with fluorescent OLEDs (the theoretical luminous efficiency is up to 25%), phosphorescent OLEDs (theoretical luminous efficiency 100%) have become the mainstream of OLED technology research and development due to their higher luminous efficiency.

The decay of excitons from the singlet excited state to the ground state produces fast luminescence, ie fluorescence. The decay of the excitons from the triplet excited state to the ground state produces light, ie phosphorescence. Since the strong spin-orbit coupling (ISC) of heavy metal atoms can very effectively enhance the electron spin state cross-change between the singlet excited state and the triplet excited state, phosphorescent metal complexes such as platinum complexes have been shown. They harvest both single and triplet excited states and the potential to achieve 100% internal quantum efficiency. Therefore, the phosphorescent metal complex is a good candidate for the dopant of the organic light-emitting device (OLED) luminescent layer, which is obtained in both academic and industrial fields. A lot of attention. And in the past decade, people have achieved some results on the road to high-margin commercialization. For example, OLED has been applied in advanced displays for smartphones, televisions and digital cameras.

The ruthenium (III) complex is a widely used phosphorescent material, such as a green light complex: fac-triphenylpyridinium oxime, ie fac-tri(2-phenylpyridinato)iridiums(III)[Ir(ppy) ₃ Red light-emitting material: bis(2-(2'-benzothienyl)pyridine-N,C ^3' ) (acetylacetone) ruthenium, ie bis[2-(2'-benzothienyl)pyridinato-N, C ^{3 '} ] (acetylacetonato) iridium (III) [Btp ₂ Ir (acac)]; blue luminescent material: bis (4,6-difluorophenylpyridine-N, C2) pyridine formyl hydrazine, ie bis[( 4,6-difluorophenyl)pyridinato-N,C ² ](picolinato)iridium(III)(FIrpic)("100% phosphorescence quantum efficiency of Ir(III) complexes in organic semiconductor films Yuichiro Kawamura,Kenichi Goushi", Jason Brooks, etc. , Appl Phys Lett, Vol. 86, 2005). Although the above organic light-emitting materials have been commercialized in the manufacture of OLED panels and lighting fixtures, these materials still have a lot of room for improvement, such as reducing the cost of material preparation processes, improving the basic photoelectric performance of materials, improving the quality of the final product application, and reducing the device process. The cost of matching materials and improving the overall resistance and weather resistance of the materials after device integration.

In the prior art, (US20120181511) discloses the synthesis of 5-position monosubstituted quinoline ligands and their Ir complexes and their use in organic optoelectronic devices; (US2016093808) discloses 4- or 5-position monosubstituted quinolines. Synthesis of ligands and their Ir complexes and their use in organic optoelectronic devices; (WO2016072780) discloses the synthesis of 4,6-substituted substituted quinoline ligands and their Ir complexes and their use in organic optoelectronic devices, The synthetic route of the molecular structure of the red light material used in the ligand synthesis method is based on malonic acid (carotic acid), and a key intermediate of dihalogen substitution is obtained by Skraup synthesis. This intermediate was obtained by a two-step suzuki coupling to obtain a final red light material by coordination. Each step of this path has a lot of competitive side reactions, which need to be carefully separated by column chromatography, and the efficiency is very low. The actual yield of ligands reported in the literature is about 10%. Moreover, the reaction involves introducing a reaction of alkyl suzuki coupling, which is harsh and costly. Based on the above factors, the material manpower and material cost prepared by the known industrial route are very high, the purification difficulty is extremely large, and a large amount of waste residue and waste liquid are generated.

The invention discloses a polysubstituted quinoline coordinated doping compound and a preparation method thereof, and the application of the compound in electroluminescent materials and related optoelectronic physical properties. The preparation route and method involved therein have the advantages of versatility, high efficiency and suitable mass production cost in preparing the doped complex compound coordinated by the polysubstituted quinoline (quinoline 3, 4, 6 position). The heterocyclic compound formed by complexing a polysubstituted quinoline ligand of a polysubstituted phenyl group with Ir can greatly increase the fluorescence quantum efficiency (PLQE) of the luminescent material molecule. Based on the spectral characteristics of these molecules and the function of compound modification, it is clear that such molecules can be used to prepare high quality OLED related devices and applications.

Summary of the invention

The technical problem to be solved by the present invention is to disclose a polysubstituted quinoline coordinated doped compound and a preparation method thereof, and the use of the compound in electroluminescent materials.

In order to solve the above technical problems, the technical scheme adopted by the present invention is to provide a polysubstituted quinoline coordinated doping compound having the following molecular structural formula:

R ^a , R ^b , R ^c R ^e represents a hydrogen atom, a halogen atom, a (C1-C6) alkyl substituent or an aryl substituent (the related substituent may be substituted, substituted with (C1-C6) alkyl or Aryl substitution). R ^d represents a hydrogen atom or a (C1-C6)alkyl substituent. R ^f , R ^h represents a (C1-C6)alkyl substituent and an aryl substituent (the related substituent may be deuterated, substituted with (C1-C6)alkyl or substituted with aryl).

The (C1-C6)alkyl group means a straight or branched alkyl group having 1 to 6 carbon atoms, and such an alkyl group includes a methyl group, an ethyl group, a n-propyl group, an isopropyl group, an n-butyl group, Isobutyl, tert-butyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1,2-dimethylpropyl, 2,3-dimethyl Propyl and 1-ethylpropyl, cyclopentyl, cyclohexyl, 2-methyl-3-pentyl, 3,3-dimethyl-2-butyl.

The molecular structure formula of the polysubstituted quinoline-coordinated hydrazine compound can be divided into the following six structures, which are respectively named as molecular formula II, molecular formula III, molecular formula IV, molecular formula V, molecular formula VI or formula VII:

Molecular formula II: R ^ac , R ^f is a halogen atom or a (C1-C6)alkyl substituent or an aryl substituent, and R ^d represents a (C1-C6)alkyl substituent;

Molecular formula III: R ^bc , R ^f represents a halogen atom or a (C1-C6)alkyl substituent or an aryl substituent, and R ^d represents a (C1-C6)alkyl substituent;

Molecular formula IV: R ^ab , R ^f represents a halogen atom or a (C1-C6)alkyl substituent or an aryl substituent, and R ^d represents a (C1-C6)alkyl substituent;

Molecular formula V: R ^bc , R ^e , R ^f represents a halogen atom or a (C1-C6) alkyl substituent or an aryl substituent;

Molecular formula VI: R ^ab , R ^e , R ^f represents a halogen atom or a (C1-C6)alkyl substituent or an aryl substituent, and R ^d represents a (C1-C6)alkyl substituent;

Formula VII: R ^ac , R ^ef represents a halogen atom or a (C1-C6)alkyl substituent or an aryl substituent.

The polysubstituted quinoline coordinated doped compound is selected from the group consisting of ruthenium complex 1 to ruthenium complex 225 hereinafter.

The above synthetic method of the polysubstituted quinoline coordinated doping compound is as follows:

In addition, the present invention also provides the use of polysubstituted quinoline coordinated doped compounds in electroluminescent materials.

The invention has the beneficial effects that compared with the prior art, the invention discloses a novel electroluminescent material---the polysubstituted quinoline coordination doped compound compound and the preparation method thereof, and the related photoelectric physics of the compound Properties, and the use of the compound as an electroluminescent material in optoelectronic appliances. The preparation route and method involved therein have the advantages of versatility, high efficiency and suitable mass production cost in preparing the doped complex compound coordinated by the polysubstituted quinoline (quinoline 3, 4, 6 position). The heterocyclic compound formed by complexing a polysubstituted quinoline ligand of a polysubstituted phenyl group with Ir can greatly increase the fluorescence quantum efficiency (PLQE) of the luminescent material molecule. Based on the spectral characteristics of these molecules and the function of compound modification, it is clear that such molecules can be used to prepare high quality OLED related devices and applications.

DRAWINGS

BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a diagram showing the structure of an OLED using a polysubstituted quinoline coordinated doping compound as a light-emitting material according to the present invention.

Figure 2 is an emission spectrum of ruthenium complex 7 in CH2Cl2 and PMMA at room temperature.

3 is an illuminating I-V diagram of an OLED device made of ruthenium complex 7 at normal temperature.

Figure 4 is a graph showing the luminous current efficiency of an OLED device made of yttrium complex 7 at room temperature.

Figure 5: Electroluminescence spectrum of an OLED device made of complex 7

Detailed ways

The polysubstituted quinoline coordinated doping compound of the present invention has a molecular formula of I-VII, and the type I formula is as follows:

R ^a , R ^b , R ^c R ^e represents a hydrogen atom, a halogen atom, a (C1-C6) alkyl substituent or an aryl substituent (the related substituent may be substituted, substituted with (C1-C6) alkyl or Aryl substitution). R ^d represents a hydrogen atom or a (C1-C6)alkyl substituent. R ^f , R ^h represents a (C1-C6)alkyl substituent and an aryl substituent (the related substituent may be deuterated, substituted with (C1-C6)alkyl or substituted with aryl).

The (C1-C6)alkyl group means a straight or branched alkyl group having 1 to 6 carbon atoms, and such an alkyl group includes a methyl group, an ethyl group, a n-propyl group, an isopropyl group, an n-butyl group, Isobutyl, tert-butyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1,2-dimethylpropyl, 2,3-dimethyl Propyl and 1-ethylpropyl, cyclopentyl, cyclohexyl, 2-methyl-3-pentyl, 3,3-dimethyl-2-butyl.

In the type I molecule, R ^f and R ^h are independent of each other and represent a (C1-C6) alkyl chain. In general, R ^f and R ^h are identical to each other;

In the type I molecule, R ^a , R ^b and R ^c are independent of each other and represent a hydrogen atom, an alkyl or aryl group of (C1-C6);

The synthetic route of the above type I molecules is shown in the following figure:

The ligand modification includes 3,5 disubstituted (R ^d R ^d ), 4-substituted (R ^e ), and 3,4,5 trisubstituted (R ^d R ^e R ^d )phenyl in the 2-substituted phenyl group. The specific synthetic route of the ligand is: a polysubstituted quinoline is formed by an amine transesterification reaction, an Skraup ring condensation reaction under acid catalysis, and a hydroxyhalogenation reaction, and a ligand can be obtained by a Suzuki coupling reaction. (Chemical equation as shown above) This route avoids the suzuki coupling reaction of the alkyl group and the side reaction which competes with a plurality of reaction sites, which can improve the synthesis efficiency and reduce the difficulty of purification. A method of synthesizing a polysubstituted quinoline ligand coordination complex of Ir by a quinoline ligand, a diketone and Ir is a conventional method.

The above R ^a , R ^b , R ^c represent an H (or oxime) atom or a (C1-C6) alkyl substituent and an aryl substituent (the related substituent may be substituted by a deuterated, containing (C1-C6) alkyl group or Aryl substitution). R ^d represents a H atom or a (C1-C6) alkyl substituent. R ^e represents a H (or hydrazine) atom or a (C1-C6) alkyl substituent and an aryl substituent (the related substituent may be deuterated, substituted with a (C1-C6) alkyl group or substituted with an aryl group). ^f , R ^h represents a (C1-C6)alkyl substituent and an aryl substituent (the related substituent may be deuterated, substituted with (C1-C6)alkyl or substituted with aryl).

In the formula I formula, R ^f and R ^h are independent of each other and represent a (C1-C6) alkyl chain. In general, R ^f and R ^h are identical to each other.

In the type I molecule, R ^a , R ^b and R ^c are independent of each other and represent a hydrogen atom, an alkyl group or an aryl group of (C1-C6).

The polysubstituted quinoline-coordinated oxime compound further has a structure of the formula 2, the formula 3, the formula 4, the formula 5, the formula 6 or the formula 7, and the structural formula is as follows:

Each of R ^a , R ^c , R ^d and R ^e may exist independently or not. R ^ac , R ^de and R ^fg are independent of each other and belong to their parent groups (quinoline, phenyl and diketone). The substituent on the quinoline, 3,4,6-trisubstituted quinoline represents R ^a , R ^b , R ^c are all present separately, 4,6-disubstituted quinoline represents R ^b , R ^c alone exists, 3, 4 - Disubstituted quinolines represent R ^a , R ^b is present alone. On the phenyl group at the 2-position of quinoline, R ^d and R ^e may exist independently or not.

The relationship of the substituents in the formula 2-7, its group and definition are described as follows:

Molecular formula II: R ^ac , R ^f is a halogen atom or a (C1-C6)alkyl substituent or an aryl substituent, and R ^d represents a (C1-C6)alkyl substituent;

Molecular formula III: R ^bc , R ^f represents a halogen atom or a (C1-C6)alkyl substituent or an aryl substituent, and R ^d represents a (C1-C6)alkyl substituent;

Molecular formula IV: R ^ab , R ^f represents a halogen atom or a (C1-C6)alkyl substituent or an aryl substituent, and R ^d represents a (C1-C6)alkyl substituent;

Molecular formula V: R ^bc , R ^e , R ^f represents a halogen atom or a (C1-C6) alkyl substituent or an aryl substituent;

Molecular formula VI: R ^ab , R ^e , R ^f represents a halogen atom or a (C1-C6)alkyl substituent or an aryl substituent, and R ^d represents a (C1-C6)alkyl substituent;

Formula VII: R ^ac , R ^ef represents a halogen atom or a (C1-C6) alkyl substituent or an aryl substituent:

According to the above definition of R ^a -R ^h , the polysubstituted quinoline-coordinated hydrazine compound may be of the following structure: an anthracene compound 1-polysubstituted quinoline which is respectively named as a polysubstituted quinoline coordination. Position of the compound compound 225

Hereinafter, the above-mentioned polysubstituted quinoline-coordinated hydrazine compound 6,7,8,11,82,126,157,187,201 is exemplified (hereinafter referred to as ruthenium complex 6,7,8,11,82,126,157,187,201). , preparation method and optical properties of some polysubstituted quinoline coordination doped compounds, and specific application as an organic light-emitting material in light-emitting devices

Example 1 Preparation of ruthenium complex 11

R ^a = p-tolyl, R ^b = methyl, R ^c = phenyl, R ^d = methyl, R ^e = hydrogen, R ^f = methyl

(1) Synthesis of N-(4'-methyl-[1,1'-biphenyl]-4-yl)-3-oxo-2-phenylbutanamide. To a 100 mL sealed tube was added 4'-methyl-[1,1'-biphenyl]-4-amine (1 g, 5.5 mmol), ethyl 2-phenylacetoacetate (3.1 g, 15 mmol) and xylene ( 15 mL), after the reaction system N _{2 was} bubbled for three minutes, the temperature was slowly raised to 145 ° C, and stirred at 145 ° C for 16 hours. TLC (petroleum ether: ethyl acetate = 5:1) showed the reaction was completed, the reaction mixture was cooled to room temperature, product was precipitated, filtered, and dried in air to give a pale yellow N-(4'-methyl-[1,1'- Biphenyl]-4-yl)-3-oxo-2-phenylbutanamide (500 mg, yield 26%). ^{1 H NMR (300MHz, DMSO)} δ10.40 (s, 1H), 7.66 (d, J = 8.7Hz, 2H), 7.60 (d, J = 8.7Hz, 2H), 7.53 (d, J = 8.1Hz, 2H), 7.38 - 7.31 (m, 5H), 7.24 (d, J = 7.8 Hz, 2H), 5.00 (s, 1H), 2.33 (s, 3H), 2.19 (s, 3H).

(2) Synthesis of 4-methyl-3-phenyl-6-(p-tolyl)quinolin-2-ol. N-(4'-methyl-[1,1'-biphenyl]-4-yl)-3-oxo-2-phenylbutanamide (500 mg, 1.45 mmol) was added to a 100 mL three-necked flask. The reaction flask atmosphere was replaced, and 3 mL of concentrated sulfuric acid was added dropwise to the reaction system. The reaction system was heated to 50 ° C and stirred for 12 hours. TLC (petroleum ether: ethyl acetate = 1:1) showed the reaction was completed, the reaction mixture was cooled to room temperature, poured slowly into ice water, solids were precipitated, filtered, and dried in air to give pale yellow 4-methyl-3-phenyl -6-(p-tolyl)quinolin-2-ol (320 mg, yield 68%). ^{1 H NMR (500MHz, DMSO)} δ11.83 (s, 1H), 7.96 (s, 1H), 7.81 (d, J = 8.5Hz, 1H), 7.64 (d, J = 8.0Hz, 2H), 7.46- 7.43 (m, 2H), 7.42 - 7.36 (m, 2H), 7.28 (d, J = 7.5 Hz, 2H), 7.26 (d, J = 7.5 Hz, 2H), 2.35 (s, 3H), 2.34 (s) , 3H).

(3) Synthesis of 2-chloro-4-methyl-3-phenyl-6-(p-tolyl)quinoline. 4-ml-3-phenyl-6-(p-tolyl)quinolin-2-ol (320 mg, 1 mmol) was added to a 50 ml two-necked round bottom flask, and the atmosphere of the reaction flask was replaced with nitrogen, and 3 mL of phosphorus oxychloride was dropped. The reaction system was added dropwise. The reaction system was heated to 100 ° C and stirred for 18 hours. TLC (petroleum ether: ethyl acetate = 1:1) showed the reaction was completed, the reaction mixture was cooled to room temperature, poured slowly into ice water, solids were precipitated, filtered, washed with water, and dried in air to give pale yellow 2-chloro-4-methyl 3-Benzyl-6-(p-tolyl)quinoline (300 mg, 87%). ^{1 H NMR (300MHz, DMSO)} δ8.32 (s, 1H), 8.16 (d, J = 8.7Hz, 1H), 8.06 (d, J = 8.7Hz, 1H), 7.80 (d, J = 8.1Hz, 2H), 7.58-7.49 (m, 3H), 7.37-7.34 (m, 4H), 2.49 (s, 3H) 2.39 (s, 3H).

(4) Synthesis of 2-(3,5-dimethylphenyl)-4-methyl-3-phenyl-6-(p-tolyl)quinoline. To a 100 mL schlenk tube was added 2-chloro-4-methyl-3-phenyl-6-(p-tolyl)quinoline (300 mg, 0.87 mmol), 3,5-dimethylbenzene boronic acid (130.7 mg, 1.76 mmol). Potassium phosphate trihydrate (703 mg, 2.64 mmol), 2-biscyclohexylphosphine-2',6'-dimethoxybiphenyl (28.9 mg, 0.07 mmol), tris(dibenzylideneacetone)dipalladium ( 16.1 mg, 0.0176 mmol) and toluene (10 mL) were replaced with nitrogen in a reaction flask atmosphere. The reaction system was heated to 100 ° C and stirred for 12 hours. TLC (petroleum ether: ethyl acetate = 10:1) showed that the reaction was completed, the reaction mixture was diluted with ethyl acetate, filtered, and the filtrate was evaporated to dryness ( petroleum ether: ethyl acetate = 50:1) ,5-Dimethylphenyl)-4-methyl-3-phenyl-6-(p-tolyl)quinoline (300 mg, 70%). _{^{1 H NMR (300MHz, CDCl 3}} ) δ8.27-8.21 (m, 2H), 8.00 (dd, J = 8.7,1.8Hz, 1H), 7.67 (d, J = 8.1Hz, 2H), 7.34-7.28 ( m,5H), 7.14–7.12 (m, 2H), 6.92 (s, 2H), 6.82 (s, 1H), 2.58 (s, 3H), 2.44 (s, 3H), 2.17 (s, 6H)

(5) Synthesis of dimer 11. To a 15 ml sealed tube was added 2-(3,5-dimethylphenyl)-4-methyl-3-phenyl-6-(p-tolyl)quinoline (82.6 mg, 0.2 mmol), tris Lanthanum trichloride (14.1 mg, 0.04 mmol), ethylene glycol diethyl ether (3 mL) and water (1 mL) were replaced with nitrogen atmosphere. The reaction system was heated to 100 ° C and stirred for 12 hours. The reaction solution was cooled to room temperature, and a solid was precipitated, suction filtered, and dried in air to give dimer 11 (30 mg, 71%).

(6) Synthesis of ruthenium complex 11: Dimer 11 (100 mg, 0.047 mmol), pentane-2,4-dione (0.1 ml), sodium carbonate (32 mg, 10 mmol) and B were added to a 15 ml sealed tube. The diol ether (2 mL) was replaced with nitrogen in a reaction flask atmosphere, and the reaction system was heated to reflux for 12 hours. The reaction mixture was cooled to room temperature, and the solid was crystallised, filtered, and then evaporated to dryness (EtOAc (EtOAc:EtOAc) _{^{1 H NMR (300MHz, CDCl 3}} ) δ8.06 (d, J = 1.5Hz, 2H), 7.93 (d, J = 9.0Hz, 2H), 7.71-7.68 (m, 5H), 7.68-7.65 (m, 3H), 7.59-7.57 (m, 5H), 7.55-7.50 (m, 3H), 7.28 (d, J = 9.0 Hz, 4H), 6.39 (d, J = 4.8 Hz, 4H), 4.32 (s, 1H) ), 2.60 (s, 6H), 2.41 (s, 6H), 1.93 (s, 6H), 1.42 (s, 6H), 1.33 (s, 6H). MALDI-TOF MASS 1116.87 [M ⁺ ]Peak at 639nm, FWHM = 62 nm in DCM; Peak at 639 nm, FWHM = 58 nm in PMMA.

Example 2 Preparation of ruthenium complex 126

R ^a = methyl, R ^b = p-tolyl, R ^c = hydrogen, R ^d = methyl, R ^e = hydrogen, R ^f = methyl

(1) Synthesis of 3-oxo-N,3-di-p-tolylpropionamide. To a 100 ml sealed tube was added p-toluidine (2.7 g, 25 mmol), 3-oxo-3-p-tolyl-propionic acid ethyl ester (10.3 g, 50 mmol) and xylene (20 mL), and the reaction system N _{2 was} bubbled three minutes. Thereafter, the temperature was slowly raised to 145 ° C and stirred at 145 ° C for 16 hours. TLC (petroleum ether: ethyl acetate = 5:1) showed the reaction was completed, the reaction mixture was cooled to room temperature, product was precipitated, filtered, and dried in air to give white 3-oxo-N,3-di-p-tolylpropane Amide (3.4 g, 60%). ¹ H NMR (300MHz, CDCl ₃ ) δ 9.21 (s, 1H), 7.94 (d, J = 8.1 Hz, 2H), 7.46 (d, J = 7.5 Hz, 2H), 7.31 (d, J = 8.1 Hz) , 2H), 7.13 (d, J = 7.5 Hz, 2H), 4.07 (s, 1H), 4.04 (br, 1H), 2.44 (s, 3H), 2.32 (s, 3H).

(2) Synthesis of 6-methyl-4-(p-tolyl)quinolin-2-ol. To a 100 mL three-necked flask was added 3-oxo-N,3-di-p-tolylpropanamide (1 g , 2.4 mmol), the atmosphere of the reaction flask was replaced with nitrogen, and 3 mL of concentrated sulfuric acid was added dropwise to the reaction system. The reaction system was heated to 50 ° C and stirred for 12 hours. TLC (petroleum ether: ethyl acetate = 3:1) showed the reaction was completed, the reaction mixture was cooled to room temperature, poured slowly into ice water, solids were precipitated, filtered, and dried in air to give white 6-methyl-4-(p-toluene) Quinoline-2-ol (800 mg, 83%). ^{1 H NMR (300MHz, DMSO)} δ11.74 (s, 1H), 7.37-7.36 (m, 5H), 7.30 (d, J = 8.4Hz, 1H), 7.18 (s, 1H), 6.32 (s, 1H ), 2.41 (s, 3H), 2.26 (s, 3H).

(3) Synthesis of 2-chloro-6-methyl-4-(p-tolyl)quinoline. To a 50 ml two-necked round bottom flask was added 6-methyl-4-(p-tolyl)quinolin-2-ol (499 mg, 2 mmol), the atmosphere of the reaction flask was replaced with nitrogen, and 3.5 mL of phosphorus oxychloride was added dropwise. system. The reaction system was heated to 100 ° C and stirred for 18 hours. TLC (petroleum ether: ethyl acetate = 6:1) showed the reaction was completed, the reaction mixture was cooled to room temperature, poured slowly into ice water, solids were precipitated, filtered, washed with water and dried in air to give white 2-chloro-6- Base-4-(p-tolyl)quinoline (500 mg, 87%). ^{1 H NMR (500MHz, DMSO)} 7.93 (d, J = 8.5Hz, 1H), 7.69 (d, J = 8.5Hz, 1H), 7.63 (s, 1H), 7.46 (d, J = 8.0Hz, 2H) , 7.42–7.40 (m, 3H), 2.44 (s, 3H), 2.43 (s, 3H).

(4) Synthesis of 2-(3,5-dimethylphenyl)-6-methyl-4-(p-tolyl)quinoline. To a 100 ml round bottom flask was added 2-chloro-6-methyl-4-(p-tolyl)quinoline (1 g, 3.74 mmol) 3,5-xylene boronic acid (1.12 g, 7.48 mmol), potassium phosphate trihydrate (g, 14.96 mmol), 2-biscyclohexylphosphine-2',6'-dimethoxybiphenyl (mg, 0.30 mmol), tris(dibenzylideneacetone)dipalladium (mg, 0.075 mmol) and toluene (10 mL), the atmosphere of the reaction flask was replaced with nitrogen. The reaction system was heated to 100 ° C and stirred for 12 hours. TLC (petroleum ether: ethyl acetate = 10:1) showed that the reaction was completed, the reaction mixture was diluted with ethyl acetate, filtered, and the filtrate was evaporated to dryness ( petroleum ether: ethyl acetate = 50:1) , 5-dimethylphenyl)-6-methyl-4-(p-tolyl)quinoline (1.0 g, 79%). _{^{1 H NMR (300MHz, CDCl 3}} ) δ8.14 (d, J = 8.4Hz, 1H), 7.78 (s, 2H), 7.75 (s, 1H), 7.67 (s, 1H), 7.56 (d, J = 8.4 Hz, 1H), 7.47 (d, J = 7.8 Hz, 2H), 7.37 (d, J = 7.8 Hz, 2H), 7.10 (s, 1H), 2.50 (s, 3H), 2.48 (s, 3H) , 2.43 (s, 6H).

(5) Synthesis of dimer 126. To a 15 ml sealed tube was added 2-(3,5-dimethylphenyl)-6-methyl-4-(p-tolyl)quinoline (64.4 mg, 0.2 mmol), ruthenium trichloride trihydrate (14.1 Mg, 0.04 mmol), ethylene glycol diethyl ether (3 mL) and water (1 mL), nitrogen was bubbled for three minutes, and the reaction was heated to 120 ° C and stirred for 12 hours. The reaction solution was cooled to room temperature, and a solid was precipitated, filtered, and dried in air to give dimer 126 (25 mg, 76%).

(6) Synthesis of ruthenium complex 126. Dimer 126 (166.2 mg, 0.1 mmol), pentane-2,4-dione (40 mg, 0.4 mmol), sodium carbonate (53 mg, 0.5 mmol) and ethyl acetate (3 mL) Nitrogen gas was bubbled for three minutes, and the reaction system was heated to reflux for 12 hours. The reaction solution was cooled to room temperature, and the solid was precipitated, filtered, washed with diethyl ether, and dried in air to give ruthenium complex 126. ^{1 H NMR (300MHz, DMSO)} δ7.90 (d, J = 9.0Hz, 4H), 7.58 (s, 2H), 7.57-7.52 (m, 6H), 7.41 (d, J = 7.8Hz, 4H), 7.14 (d, J = 9.0 Hz, 2H), 6.53 (s, 2H), 4.37 (s, 1H), 2.52 (s, 6H), 2.34 (s, 12H), 1.37 (s, 6H), 1.34 (s) , 6H). MS (MALDI-TOF): 964.4 [M] ⁺ Emission peak in DCM at 626 nm, FWHM = 72 nm, peak in PMMA at 625 nm, FWHM = 64 nm.

Example 3 Preparation Method of Ruthenium Complex 201

R ^a = methyl, R ^b = p-tolyl, R ^c = hydrogen, R ^d = hydrogen, R ^e = methyl, R ^f = methyl

(1) Synthesis of dimer 201. To a 15 ml sealed tube was added 6-methyl-2,4-di-p-tolylquinoline (61.6 mg, 0.2 mmol), ruthenium trichloride trihydrate (14.1 mg, 0.04 mmol), ethylene glycol ether ( 3 mL) and water (1 mL) were bubbled with nitrogen for three minutes, and the reaction was heated to reflux for 12 hours. The reaction solution was cooled to room temperature, and the solid was crystallised, filtered, and dried in vacuo to give dimer 201 (25 mg, 76%).

(2) Synthesis of ruthenium complex 201. To a 75 ml sealed tube was added a dimer (160.6 mg, 0.1 mmol), pentane-2,4-dione (40 mg, 0.4 mmol), sodium carbonate (53 mg, 0.5 mmol) and ethyl ether (3 mL). Nitrogen gas was bubbled for three minutes, and the reaction system was heated to reflux for 12 hours. The reaction solution was cooled to room temperature, and the solid was crystallised, filtered, washed with diethyl ether and dried in vacuo to afford EtOAc (201 mg, 71%). ^{1 H NMR (300MHz, DMSO)} δ8.32 (d, J = 8.7Hz, 2H), 8.11 (s, 2H), 7.90 (d, J = 8.1Hz, 2H), 7.65 (d, J = 7.8Hz, 4H), 7.61 (s, 2H), 7.49 (d, J = 8.1 Hz, 4H), 7.37 (dd, J = 8.7, 1.5 Hz, 2H), 6.69 (d, J = 8.1 Hz, 2H), 6.20 ( s, 2H), 4.71 (s, 1H), 2.51 (s, 6H), 2.39 (s, 6H), 1.90 (s, 6H), 1.47 (s, 6H). MS MALDI-TOF 836.1 [M-acac] ⁺ Peak in DCM solution at RT at 611nm, FWHM 83nm, Peak in PMMA solution at RT at 609nm, FWHM 79nm.

Example 4 Preparation of ruthenium complex 187

R ^a = methyl, R ^b = isobutyl, R ^c = methyl, R ^d = methyl, R ^e = hydrogen, R ^f = isobutyl

(1) Synthesis of 2,5-dimethyl-3-oxo-N-(p-tolyl)hexanamide. Sealed tube was added to 100ml toluidine (107.12mg, 1mmol), 2,5- dimethyl-3-oxo - hexanoic acid ethyl ester (346.4mg, 2mmol) and xylene (2mL), the reaction system drum N ₂ After soaking for three minutes, the temperature was slowly raised to 145 ° C and stirred at 145 ° C for 16 hours. TLC (petroleum ether: ethyl acetate = 5:1) showed the reaction was completed, the reaction mixture was cooled to room temperature, product was precipitated, filtered, and dried in air to give white 2,5-dimethyl-3-oxo-N- ( p-Tolyl) hexanamide (120 mg, 40%). ¹ H NMR (300MHz, CDCl ₃ ) δ 8.22 (s, 1H), 7.39 (d, J = 7.8 Hz, 2H), 7.12 (d, J = 7.8 Hz, 2H), 3.54 (q, J = 7.2 Hz) , 1H), 2.48 (d, J = 6.9 Hz, 2H), 2.31 (s, 3H), 2.22 - 2.14 (m, 1H), 1.49 (d, J = 6.9 Hz, 3H), 0.94 - 0.91 (m, 6H).

(2) Synthesis of 4-isobutyl-3,6-dimethylquin-2-ol. 2,5-Dimethyl-3-oxo-N-(p-tolyl)hexanamide (1 g, 4 mmol) was added to a 100 mL three-necked flask, and the atmosphere of the reaction flask was replaced with nitrogen, and 3.5 mL of concentrated sulfuric acid was added dropwise to the reaction. system. The reaction system was heated to 50 ° C and stirred for 12 hours. TLC (petroleum ether: ethyl acetate = 3:1) showed the reaction was completed, the reaction mixture was cooled to room temperature, poured slowly into ice water, solids were precipitated, filtered, and dried in air to give pale yellow 4-isobutyl-3,6 - dimethylquin-2-ol (830 mg, 90%). _{^{1 H NMR (300MHz, CDCl 3}} ) δ11.55 (s, 1H), 7.50 (s, 1H), 7.25-7.17 (m, 2H), 2.78 (d, J = 7.2Hz, 2H), 2.36 (s, 3H), 2.11 (s, 3H), 1.98-1.89 (m, 1H), 0.95 (d, J = 6.6 Hz, 6H).

(3) Synthesis of 2-chloro-4-isobutyl-3,6-dimethylquinoline. To a 50 ml two-necked round bottom flask was added 4-isobutyl-3,6-dimethylquin-2-ol (800 mg, 3.5 mmol), the atmosphere of the reaction flask was replaced with nitrogen, and 3.5 mL of phosphorus oxychloride was added dropwise. reaction system. The reaction system was heated to 100 ° C and stirred for 18 hours. TLC (petroleum ether: ethyl acetate = 5:1) showed the reaction was completed, the reaction mixture was cooled to room temperature, poured slowly into ice water, solids were precipitated, filtered, washed with water, and dried in air to give pale yellow 2-chloro-4-iso Butyl-3,6-dimethylquinoline (830 mg, 93%). ^{1 H NMR (300MHz, DMSO)} δ7.89 (s, 1H), 7.79 (d, J = 8.4Hz, 1H), 7.56 (d, J = 8.4Hz, 1H), 3.05 (d, J = 7.2Hz, 2H), 2.53 (s, 3H), 2.49 (s, 3H), 2.02-1.93 (m, 1H), 0.94 (d, J = 6.6 Hz, 6H).

(4) Synthesis of 2-(3,5-dimethylphenyl)-4-isobutyl-3,6-dimethylquinoline. To a 100 mL schlenk tube was added 2-chloro-4-isobutyl-3,6-dimethylquinoline (800 mg, 3.23 mmol), 3,5-dimethylbenzene boronic acid (969.6 mg, 6.46 mmol), tris Potassium phosphate (4.3 g, 16.15 mmol), 2-biscyclohexylphosphine-2',6'-dimethoxybiphenyl (106.1 mg, 0.26 mmol), tris(dibenzylideneacetone)dipalladium (59 mg, 0.065 Methyl) and toluene (10 mL) were replaced with nitrogen in a reaction flask atmosphere. The reaction system was heated to 100 ° C and stirred for 12 hours. TLC (petroleum ether: ethyl acetate = 10:1) showed that the reaction was completed, the reaction mixture was diluted with ethyl acetate, filtered, and the filtrate was evaporated to dryness ( petroleum ether: ethyl acetate = 10:1) , 5-dimethylphenyl)-4-isobutyl-3,6-dimethylquinoline (700 mg, 55%). ¹ H NMR (500 MHz, CDCl ₃ ) δ 8.02 (s, 1H), 7.76 (s, 1H), 7.46 (d, J = 8.0 Hz, 1H), 7.10 (s, 2H), 7.05 (s, 1H) , 3.05 (d, J = 7.5 Hz, 2H), 2.57 (s, 3H), 2.38 (s, 6H), 2.37 (s, 3H), 2.15 - 2.13 (m, 1H), 1.04 (d, J = 6.5 Hz, 6H).

(5) Synthesis of dimer 187. Add 2-(3,5-dimethylphenyl)-4-isobutyl-3,6-dimethylquina to a 15 ml sealed tube The ruthenium (65.4 mg, 0.2 mmol), ruthenium trichloride trihydrate (14.1 mg, 0.04 mmol), ethylene glycol diethyl ether (3 mL) and water (1 mL) were placed under nitrogen atmosphere, and the reaction system was heated to reflux for 12 hours. The reaction solution was cooled to room temperature, and a solid was precipitated, filtered, and dried in air to give dimer 187 (30 mg, 87%).

(6) Synthesis of ruthenium complex 187. Dimer 187 (250 mg), 2,8-dimethyldecane-4,6-dione (0.1 ml), sodium carbonate (32 mg, 10 mmol) and ethylene glycol diethyl ether (2 mL) were added to a 15 ml sealed tube. The atmosphere of the reaction flask was replaced with nitrogen, and the reaction system was heated to reflux for 12 hours. The reaction solution was cooled to room temperature, and the solution was evaporated to dryness (yield: petroleum ether: ethyl acetate = 50:1). _{^{1 H NMR (500MHz, CDCl 3}} ) δ7.74 (d, J = 8.5Hz, 2H), 7.62 (s, 2H), 7.56 (s, 2H), 7.02 (d, J = 8.5Hz, 2H), 6.52 (s, 2H), 4.08 (s, 1H), 3.16–3.06 (m, 4H), 3.01 (s, 6H), 2.96-2.92 (m, 2H), 2.41 (s, 6H), 2.35 (s, 6H) ), 2.23–2.20 (m, 2H), 1.57-1.55 (m, 2H), 1.51–1.49 (m, 2H), 1.24 (s, 6H), 1.10 (d, J = 6.5 Hz, 6H), 1.08 ( d, J = 6.5 Hz, 6H), 0.47 (d, J = 6.5 Hz, 6H), 0.23 (d, J = 6.5 Hz, 6H). MS (MALDI-TOF): 1007.9 [M-1] ⁺ Peak in DCM at room temperature at 617 nm, FWHM = 68 nm. Peak in PMMA at room temperature at 618 nm, FWHM = 68 nm.

Example 5 Synthesis of Complex 82

R ^a = p-tolyl, R ^b = isobutyl, R ^c = hydrogen, R ^d = hydrogen, R ^e = methyl, R ^f = isobutyl

(1) Synthesis of 5-methyl-N-(4'-methyl-[1,1'-biphenyl]-4-yl)-3-oxohexanamide. Add a 4'-methyl-[1,1'-biphenyl]-4-amine (52.6 g, 287 mmol), ethyl 5-methyl-3-oxohexanoate (59.3) to a 1000 mL 3-neck round bottom flask. g, 344 mmol) and xylene (450 mL), after the reaction system N _{2 was} bubbled for three minutes, the temperature was slowly raised to 145 ° C, and stirred at 145 ° C for 3-4 hours. TLC (petroleum ether: ethyl acetate = 5:1) showed the reaction was completed, the reaction mixture was cooled to room temperature, product was precipitated, filtered, and dried in air to give pale yellow 5-methyl-N-(4'-methyl-[ 1,1'-Biphenyl]-4-yl)-3-oxohexanamide (46.1 g, 52%). ^{1 H NMR (300MHz, DMSO)} δ10.13 (s, 1H), 7.66-7.58 (m, 4H), 7.53 (d, J = 8.1Hz, 2H), 7.25 (d, J = 8.1Hz, 2H), 3.53 (s, 2H), 2.46 (d, J = 6.9 Hz, 2H), 2.33 (s, 3H), 2.11-2.02 (m, 1H), 0.89 (d, J = 6.6 Hz, 6H).

(2) Synthesis of 4-isobutyl-6-(p-tolyl)quinolin-2-ol. To a 250 ml 3-neck round bottom flask was charged 5-methyl-N-(4'-methyl-[1,1'-biphenyl]-4-yl)-3-oxohexanamide (18.3 g, 59.1 Methyl), the reaction atmosphere was replaced by nitrogen, 50 mL of concentrated sulfuric acid was added dropwise to the reaction system, and the reaction system was heated to 40-50 ° C and stirred for 12 hours. TLC (petroleum ether: ethyl acetate = 3:1) showed the reaction was completed, the reaction mixture was cooled to room temperature, poured slowly into ice water, solids were precipitated, filtered, washed with water and dried in air to give white 4-isobutyl-6- (p-Tolyl)quinolin-2-ol (15.5 g, 95%). _{^{1 H NMR (500MHz, CDCl 3}} ) δ9.16 (s, 0.8H, enol), 7.60 (d, J = 8.5Hz, 2H), 7.54 (d, J = 8.5Hz, 2H), 7.46 (d, J = 8.0 Hz, 2H), 7.23 (d, J = 8.0 Hz, 2H), 3.56 (s, 2H), 2.47 (d, J = 6.8 Hz, 2H), 2.38 (s, 3H), 2.20 (th, J) = 6.8, 6.6 Hz; 1H), 2.06 (s, 0.2 H), 0.97 (d, J = 6.6 Hz, 6H).

(3) Synthesis of 2-chloro-4-isobutyl-6-(p-tolyl)quinoline. To a 500 ml three-necked round bottom flask was added 4-isobutyl-6-(p-tolyl)quinolin-2-ol (1 g, 3.6 mmol), the reaction atmosphere was replaced with nitrogen, and 3 mL of phosphorus oxychloride was added dropwise. The system was slowly warmed to 100 ° C and stirred for 18 hours. TLC (petroleum ether: ethyl acetate = 6:1) showed the reaction was completed, the reaction mixture was cooled to room temperature, poured slowly into ice water, solids were precipitated, filtered, washed with water, and dried in air to obtain a dark yellow 2-chloro-4-iso Butyl-6-(p-tolyl)quinoline (1 g, 94%). ¹ H NMR (400 MHz, CDCl ₃ ) δ 8.09 (d, J = 2.0, 1H), 8.06 (d, J = 5.3 Hz, 1H), 7.94 (dd, J = 10.2, 2.0 Hz, 1H), 7.58 ( d, J = 8.1 Hz, 2H), 7.33 (d, J = 8.1 Hz, 2H), 7.22 (s, 1H), 2.94 (d, J = 7.3 Hz, 2H), 2.44 (s, 3H), 2.35 - 2.05 (m, 1H), 1.02 (d, J = 6.6 Hz, 6H).

(4) Synthesis of 2-(4-methylphenyl)-4-isobutyl-6-(p-tolyl)quinoline. Add 2-chloro-4-isobutyl-6 to a 500 ml round bottom flask -(p-tolyl)quinoline (4.8 g, 15.5 mmol), p-methylphenylboronic acid (4.2 g, 31 mmol), potassium phosphate trihydrate (20.6 g, 77.5 mmol), 2-dicyclohexylphosphine-2', 6'-dimethoxybiphenyl (509 mg, 1.24 mmol), tris(dibenzylideneacetone)dipalladium (284 mg, 0.31 mmol) and toluene (110 mL) were replaced with nitrogen, and the reaction mixture was heated to reflux for 12 hours. . TLC (petroleum ether: ethyl acetate = 10:1) showed that the reaction was completed, the reaction mixture was diluted with ethyl acetate, filtered, and the filtrate was evaporated to dryness ( petroleum ether: ethyl acetate = 10:1) Methylphenyl)-4-isobutyl-6-(p-tolyl)quinoline (4 g, 71%).

(5) Synthesis of dimer 82. To a 100 ml round bottom flask was charged 2-(4-methylphenyl)-4-isobutyl-6-(p-tolyl)quinoline (1.1 g, 3 mmol). Trihydrate ruthenium trichloride (195 mg, 0.6 mmol), ethylene glycol ether (15 mL) and water (5 mL) were replaced with a nitrogen atmosphere. The reaction system was heated to reflux for 12 hours. The reaction solution was cooled to room temperature, and a solid was precipitated, which was filtered, washed with diethyl ether (8 mL × 3), and dried in air to obtain a dimer 82 (500 mg, 87%).

(6) Synthesis of ruthenium complex 82. Add a dimer (650 mg, 0.34 mmol), 2,8-dimethylnonane-4,6-dione (304 mg, 1.65 mmol), sodium carbonate (350 mg, 3.3 mmol) and B to a 100 ml round bottom flask. The diol ether (20 mL) was replaced with nitrogen in a reaction flask atmosphere, and the reaction system was heated to reflux for 12 hours. The reaction solution was cooled to room temperature, and dried over EtOAc (EtOAc:EtOAc: _{^{1 H NMR (400MHz, CDCl 3}} ) δ8.49 (d, J = 9.1Hz, 2H), 8.05 (d, J = 2.0Hz, 2H), 7.84 (s, 2H), 7.73 (d, J = 8.1Hz , 2H), 7.58 (dd, 9.1, 2 Hz, 2H), 7.57 (dd, 8.0 Hz, 4H), 7.29 (d, J = 8.0 Hz, 4H), 6.77 (d, J = 8.1 Hz, 2H), 6.45 (s, 2H), 4.57 (s, 1H), 3.25 (dd, J = 13.5, 6.3 Hz, 2H), 2.99 (dd, J = 13.5, 7.7 Hz, 2H), 2.42 (s, 6H), 2.28– 2.22 (m, 2H), 1.99 (s, 6H), 1.74 (dd, J = 12.2, 5.4 Hz, 2H), 1.45 (dd, J = 12.4, 8.9 Hz, 2H), 1.33 (m, 2H), 1.17 (d, J = 6.6 Hz, 6H), 1.10 (d, J = 6.5 Hz, 6H), 0.45 (d, J = 6.6 Hz, 6H), 0.05 (d, J = 6.5 Hz, 6H). Peak at 596 nm , FWHM=71nm in DCM; Peak at 596nm, FWHM=67nm in PMMA

Synthesis of Complex 6 (DMPQ-TBH) 2Ir(divm)

R ^a = p-tolyl, R ^b = isobutyl, R ^c = hydrogen, R ^d = methyl, R ^e = hydrogen, R ^f = isobutyl patent WO2016072780 reports the complex

(1) Synthesis of 2-(3,5-methylphenyl)-4-isobutyl-6-(p-tolyl)quinoline. To a 500 ml round bottom flask was added 2-chloro-4-isobutyl-6-(p-tolyl)quinoline (22.3 g, 60 mmol), 1,3-dimethylphenylboronic acid (18 g, 120 mmol), tris Potassium phosphate (80 g, 300 mmol), 2-biscyclohexylphosphine-2',6'-dimethoxybiphenyl (1.97 g, 4.8 mmol), tris(dibenzylideneacetone)dipalladium (1.1 g, 1.2 mmol) And toluene (300 mL), the reaction atmosphere was replaced with nitrogen, and the reaction solution was heated under reflux for 12 hours. TLC (petroleum ether: ethyl acetate = 10:1) showed that the reaction was completed, the reaction mixture was diluted with ethyl acetate, filtered, and the filtrate was evaporated to dryness ( petroleum ether: ethyl acetate = 10:1) ,5-Dimethylphenyl)-4-isobutyl-6-(p-tolyl)quinoline (17.3 g, 76%). ¹ H NMR (400 MHz, CDCl ₃ ) δ 8.23 (d, J = 8.4 Hz, 1H), 8.14 (d, J = 2.0 Hz, 1H), 7.95 (dd, J = 8.4, 2.0 Hz, 1H), 7.76 (s, 2H), 7.66 (s, 1H), 7.63 (d, J = 8.0 Hz, 2H), 7.33 (d, J = 8.0 Hz, 2H), 7.11 (s, 1H), 3.03 (d, J = 7.2 Hz, 2H), 2.45 (s, 9H), 2.19 (ht, J = 7.2, 6.7 Hz, 1H), 1.58 (s, 6H), 1.04 (d, J = 6.7 Hz, 6H).

(2) Synthesis of dimer. To a 100 ml round bottom flask was added 2-(3,5-dimethylphenyl)-4-isobutyl-6-(p-tolyl)quinoline (1.9 g, 4.0). Methyl) ruthenium trichloride trihydrate (0.353 g, 1.0 mmol), ethylene glycol diethyl ether (15 mL) and water (5 mL). The reaction system was heated to reflux for 12 hours. The reaction solution was cooled to room temperature, and a solid was precipitated, filtered, washed with diethyl ether (8 mL × 3), and dried in air to obtain a dimer (2.3 g). .

(3) Synthesis of complex (DMPQ-TBH) ₂ Ir(divm). Add a dimer (2.3 g, 1.17 mmol), 2,8-dimethyldecane-4,6-dione (1.2 mL, 5.85 mmol), sodium carbonate (1.24 g, 11.7 mmol) to a 100 ml round bottom flask. ) and ethylene glycol ether (20 mL), the atmosphere of the reaction flask was replaced with nitrogen, and the reaction system was heated to reflux for 12 hours. The reaction was cooled to room temperature, worked spin column (petroleum ether: dichloromethane = 1: 1) to give a red complex _{(DMPQ-TBH) 2 Ir (} divm) (3.0g, 85%). _{^{1 H NMR (400MHz, CDCl 3}} ) δ8.04-7.96 (m, 4H), 7.86 (s, 2H), 7.61 (s, 2H), 7.53 (d, J = 7.9Hz, 4H), 7.52 (m, 2H), 7.27 (d, J = 7.9 Hz, 4H), 6.52 (s, 2H), 4.27 (s, 1H), 3.13 - 2.95 (m, 4H), 2.40 (s, 6H), 2.38 (s, 6H) ), 2.33-2.16 (m, 2H), 1.52-1.60 (m, 2H), 1.43-1.52 (m, 2H), 1.24-1.36 (m, 2H), 1.12 (d, J = 5.1 Hz, 12H), 0.51 (d, J = 6.5 Hz, 6H), 0.18 (d, J = 6.4 Hz, 6H). MS (MALDI-TOF): 1133.5 [M] ⁺ Peak at 615 nm, FWHM = 58 nm in DCM; Peak at 623 nm, FWHM=68nm in PMMA

Example 7 Synthesis of Ruthenium Complex 157

R ^a = p-tolyl, R ^b = isobutyl, R ^c = hydrogen, R ^d = methyl, R ^e = methyl, R ^f = isobutyl

(1) Synthesis of dimer 157. To a 15 ml sealed tube was added 4-isobutyl-6-(p-tolyl)-2-(3,4,5-trimethylphenyl)quinoline (393.3 mg, 1.0 mmol), trichlorotrichloride Plutonium (65.5 mg, 0.2 mmol), ethylene glycol diethyl ether (3 mL) and water (1 mL) were replaced with nitrogen, and the reaction system was heated to reflux for 12 hours. The reaction solution was cooled to room temperature, and a solid was precipitated, filtered, and dried in air to give dimer 157 (155 mg, 77%).

(2) Synthesis of ruthenium complex 157. Dimer (202.5 mg, 0.1 mmol), 2,8-dimethyldecane-4,6-dione (0.1 ml), sodium carbonate (53 mg, 0.5 mmol) and ethylene glycol were added to a 15 ml sealed tube. Diethyl ether (3 mL) was placed under nitrogen to replace the atmosphere of the reaction flask, and the reaction was heated to reflux for 12 hours. The reaction solution was cooled to room temperature, dried, and dried (EtOAc mjjjjjjjj _{^{1 H NMR (300MHz, CDCl 3}} ) δ7.97 (d, J = 1.8Hz, 2H), 7.88 (s, 1H), 7.84 (d, J = 6.6Hz, 3H), 7.63 (s, 2H), 7.57 -7.54 (m, 3H), 7.52 - 7.51 (m, 3H), 7.48 (d, J = 2.1 Hz, 1H), 7.28-7.25 (m, 3H), 4.25 (s, 1H), 3.03 (d, J) = 6.9 Hz, 4H), 2.40 (s, 12H), 2.31-2.14 (m, 4H), 2.13 (s, 0H), 2.01 (s, 6H), 1.57-1.55 (m, 2H), 1.50-1.51 ( m, 2H), 1.35 (s, 6H), 1.26 (s, 1H), 1.14-1.11 (m, 12H), 0.52 (d, J = 6.3 Hz, 6H), 0.22 (d, J = 6.3 Hz, 6H) MS (MALDI-TOF): 1160.6 [M] ⁺ Peak in DCM at room temperature at 610 nm, FWHM = 58 nm, Peak in PMMA at room temperature at 609 nm, FWHM = 51 nm.

Example 8 Synthesis of ruthenium complex 6

R ^a = p-tolyl, R ^b = isobutyl, R ^c = methyl, R ^d = methyl, R ^e = hydrogen, R ^f = methyl

(1) Synthesis of 2,5-dimethyl-N-(4'-methyl-[1,1'-biphenyl]-4-yl)-3-oxohexanamide. Add 4'-methyl-[1,1'-biphenyl]-4-amine (183 mg, 1.0 mmol), ethyl 2,5-dimethyl-3-oxohexanoate (346.4) to a 100 ml sealed tube. After the reaction system N _{2 was} bubbled for three minutes, the mixture was slowly heated to 145 ° C and stirred at 145 ° C for 16 hours. TLC (petroleum ether: ethyl acetate = 5:1) showed the reaction was completed, the reaction mixture was cooled to room temperature, product was precipitated, filtered, and dried in air to give pale yellow 2,5-dimethyl-N-(4'-A Base-[1,1'-biphenyl]-4-yl)-3-oxohexanamide (198 mg, 47%). ^{1 H NMR (300MHz, DMSO)} δ10.23 (s, 1H), 7.67 (d, J = 8.7Hz, 2H), 7.60 (d, J = 8.7Hz, 2H), 7.53 (d, J = 8.1Hz, 2H), 7.25 (d, J = 8.1 Hz, 2H), 3.66 (q, J = 6.9 Hz, 1H), 2.45 (t, J = 6.6 Hz, 2H), 2.33 (s, 3H), 2.12-1.98 ( m, 1H), 1.24 (d, J = 6.9 Hz, 3H), 0.85 (t, J = 6.6 Hz, 6H).

(2) Synthesis of 4-isobutyl-3-methyl-6-(p-tolyl)quinolin-2-ol. To a 100 mL three-necked flask was added 2,5-dimethyl-N-(4'-methyl-[1,1'-biphenyl]-4-yl)-3-oxohexanamide (1.61 g, 5 mmol), the atmosphere of the reaction flask was replaced with nitrogen, and 9 mL of concentrated sulfuric acid was added dropwise to the reaction system. The reaction system was heated to 50 ° C and stirred for 12 hours. TLC (petroleum ether: ethyl acetate = 3:1) showed the reaction was completed, the reaction mixture was cooled to room temperature, poured slowly into ice water, solids were precipitated, filtered and dried in air to give yellow 4-isobutyl-3-methyl -6-(p-Tolyl)quinolin-2-ol (1.3 g, 86%). _{^{1 H NMR (300MHz, CDCl 3}} ) δ11.69 (s, 1H), 7.86 (s, 1H), 7.71 (d, J = 8.4Hz, 1H), 7.57 (d, J = 8.1Hz, 2H), 7.36 (d, J = 8.4 Hz, 1H), 7.25 (d, J = 8.1 Hz, 2H), 2.89 (d, J = 7.2 Hz, 2H), 2.35 (s, 3H), 2.15 (s, 3H), 2.01 -1.94 (m, 1H), 0.98 (d, J = 6.6 Hz, 6H).

(3) Synthesis of 2-chloro-4-isobutyl-3-methyl-6-(p-tolyl)quinoline. To a 100 ml 3-neck round bottom flask was added 4-isobutyl-3-methyl-6-(p-tolyl)quinolin-2-ol (1 g, 3.3 mmol), and the atmosphere of the reaction flask was replaced with nitrogen. Phosphorus was added dropwise to the reaction system. The reaction system was heated to 100 ° C and stirred for 18 hours. TLC (petroleum ether: ethyl acetate = 6:1) showed the reaction was completed, the reaction mixture was cooled to room temperature, poured slowly into ice water, solids were precipitated, filtered, washed with water, and dried in air to obtain yellow 2-chloro-4-isobutyl 3-methyl-6-(p-tolyl)quinoline (950 mg, 90%).

Synthesis of 2-(3,5-dimethylphenyl)-4-isobutyl-3-methyl-6-(p-tolyl)quinoline. To a 100 mL schlenk tube was added 2-chloro-4-isobutyl-3-methyl-6-(p-tolyl)quinoline (900 mg, 2.8 mmol), 3,5-xylene boronic acid (836.5 mg, 5.6 Methyl) potassium phosphate trihydrate (3.73 g, 14 mmol), 2-biscyclohexylphosphine-2',6'-dimethoxybiphenyl (91.9 mg, 0.224 mmol), tris(dibenzylideneacetone) palladium (51.3 mg, 0.056 mmol) and toluene (10 mL) were replaced with a nitrogen atmosphere. The reaction system was heated to 100 ° C and stirred for 12 hours. TLC (petroleum ether: ethyl acetate = 10:1) showed that the reaction was completed, the reaction mixture was diluted with ethyl acetate, filtered, and the filtrate was evaporated to dryness ( petroleum ether: ethyl acetate = 50:1) , 5-dimethylphenyl)-4-isobutyl-3-methyl-6-(p-tolyl)quinoline (770 mg, 70%). _{^{1 H NMR (300MHz, CDCl 3}} ) δ8.14 (s, 1H), 8.13 (s, 1H), 7.86 (d, J = 8.1Hz, 1H), 7.59 (d, J = 7.8Hz, 2H), 7.30 (d, J = 7.8 Hz, 2H), 7.23 (s, 1H), 7.10 (s, 2H), 7.04 (s, 1H), 3.09 (d, J = 7.2 Hz, 2H), 2.41 (s, 3H) , 2.37 (s, 9H), 2.22–2.10 (m, 1H), 1.04 (d, J = 6.6 Hz, 6H).

(4) Synthesis of dimer 6. To a 15 ml sealed tube was added 2-(3,5-dimethylphenyl)-4-isobutyl-3-methyl-6-(p-tolyl)quinoline (393.2 mg, 1 mmol), tris Ammonium trichloride (70.5 mg, 0.2 mmol), ethylene glycol diethyl ether (3 mL) and water (1 mL) were replaced with nitrogen atmosphere. The reaction system was heated to 100 ° C and stirred for 12 hours. The reaction solution was cooled to room temperature, and a solid was precipitated, filtered, washed with diethyl ether and dried in vacuo to give dimer 6 (180 mg, 89%).

(5) Synthesis of ruthenium complex 6. Dimer 6 (202.5 mg, 0.1 mmol), pentane-2,4-dione (0.1 ml), sodium carbonate (53 mg, 0.5 mmol) and ethylene glycol diethyl ether (3 mL), nitrogen The atmosphere of the reaction flask was replaced, and the reaction system was heated to reflux for 12 hours. The reaction solution was cooled to room temperature, dried, and dried (EtOAc:EtOAc:EtOAc ^{1 H NMR (300MHz, DMSO)} δ7.96 (s, 2H), 7.84 (d, J = 9.0Hz, 2H), 7.62 (s, 2H), 7.50-7.47 (m, 6H), 7.24 (m, J = 7.5 Hz, 4H), 6.55 (s, 2H), 4.11 (s, 1H), 3.20 - 3.08 (m, 4H), 3.04 (s, 6H), 2.36 (d, J = 8.9 Hz, 12H), 2.18 (m, 1H), 2.00 (m, 1H), 1.31 (s, 6H), 1.17 (s, 6H), 1.09 (d, J = 6.6 Hz, 6H), 0.97 (d, J = 6.6 Hz, 6H) .MS (MALDI-TOF): 1074.4 [M-2] ⁺ Peak in DCM at room temperature at 631 nm, FWHM = 70 nm, Peak in PMMA at room temperature at 630 nm, FWHM = 62 nm.

Example 9 Synthesis of Ruthenium Complex 7

R ^a = p-tolyl, R ^b = isobutyl, R ^c = methyl, R ^d = methyl, R ^e = hydrogen, R ^f = isobutyl.

The above dimer (202.5 mg, 0.1 mmol), 2,8-dimethyldecane-4,6-dione (0.1 ml), sodium carbonate (53 mg, 0.5 mmol) and ethylene were added to a 15 ml sealed tube. Alcohol ether (3 mL) was replaced with nitrogen in a reaction flask atmosphere, and the reaction was heated to reflux for 12 hours. The reaction solution was cooled to room temperature, dried and dried (EtOAc mjjjjjjjjjj ^{1 H NMR (300MHz, DMSO)} δ7.99 (d, J = 1.5Hz, 2H), 7.89 (d, J = 9.0Hz, 2H), 7.67 (s, 2H), 7.51-7.50 (m, 4H), 7.50–7.46 (m, 2H), 7.27 (d, J = 7.8 Hz, 4H), 6.57 (s, 2H), 4.12 (s, 1H), 3.19–2.98 (m, 4H), 3.05 (s, 6H) , 2.40 (s, 6H), 2.38 (s, 6H), 2.31 - 2.24 (m, 2H), 1.62 - 1.54 (m, 2H), 1.42 - 1.36 (m, 2H), 1.30 (s, 6H), 1.36 -1.20 (m, 2H), 1.18-1.11 (m, 12H), 0.47 (d, J = 6.6 Hz, 6H), 0.26 (d, J = 6.6 Hz, 6H). MS (MALDI-TOF): 1160.6 [M] ⁺ Peak in DCM at room temperature at 629 nm, FWHM = 66 nm, Peak in PMMA at room temperature at 630 nm, FWHM = 60 nm.

Example 10 Synthesis of ruthenium complex 8

R ^a = p-tolyl, R ^b = isobutyl, R ^c = methyl, R ^d = methyl, R ^e = hydrogen, R ^f = isopropyl.

The above dimer (202.5 mg 0.1 mmol), 2,6-dimethylheptane-3,5-dione (0.1 ml), sodium carbonate (53 mg, 0.5 mmol) and ethylene glycol were added to a 15 ml sealed tube. Diethyl ether (3 mL) was placed under nitrogen to replace the atmosphere of the reaction flask, and the reaction was heated to reflux for 12 hours. The reaction mixture was cooled to room temperature, dried, and then evaporated, mjjjjjjj ^{1 H NMR (300MHz, DMSO)} δ8.14 (s, 2H), 7.79 (d, J = 9.3Hz, 2H), 7.71 (s, 2H), 7.65 (s, 2H), 7.62-7.59 (m, 4H ), 7.29 (d, J = 8.1 Hz, 4H), 6.45 (s, 2H), 4.26 (s, 1H), 3.18 (s, 4H), 3.03 (s, 6H), 2.35 (s, 6H), 2.31 (s, 6H), 2.21-2.11 (m, 2H), 1.77-1.66 (m, 2H), 1.13 (s, 6H), 1.08-1.05 (m, 12H), 0.61 (d, J = 6.6 Hz, 6H) ), 0.41 (d, J = 6.6 Hz, 6H). MS (MALDI-TOF): 1131.9 [M-1] ⁺ Peak in DCM at room temperature at 630 nm, FWHM = 63 nm, Peak in PMMA at room temperature at 631 nm, FWHM=59nm.

Example 11 Comparison of optical properties of iridium complexes 6, 7, 8, 11, 82, 126, 157, 187, 201 as phosphorescent materials and conventional phosphorescent red materials

(其中：Φ_s是样品的荧光量子产率，Φ_r是标样的荧光量子产率，η是溶液的折射率，A_s和A_r是样品和标样的荧光激发波长处的吸收值，Ι_s和Ι_r是样品和标样的荧光积分面积)采用相对法计算得到。将材料和已知量子产率的标物配置成相同浓度的聚甲基丙烯酸甲酯(PMMA)的三氯甲烷溶液，旋涂成膜，在相同的测量条件下，测得紫外吸收光谱(GENESYS 10S，Thermo)和荧光光谱(F97pro荧光分光光度计，棱光科技)。材料的光子能量(ET1)由公式E＝hν＝1240/λ(其中λ为材料PMMA膜的荧光光谱起始位置的切线波长)计算而来。)The ruthenium complexes 6, 7, 8, 11, 82, 126, 157, 187, 201 of the present invention are respectively used as phosphorescent materials and conventional phosphorescent red materials Ir(PQ) ₂ (acac), Ir(DMPQ) ₂ (acac) and ( DMPQ-TBH) ₂ Ir (divm) material optical properties were compared as follows: the bandgap value (Eg) and LUMO value of the material were measured by cyclic voltammetry (CV). The whole test process was carried out on the CHI600D electrochemical workstation (Shanghai Chenhua Instrument Co., Ltd.) in the glove box (Lab2000, Etelux), with the Pt column as the working electrode, Ag/AgCl as the reference electrode, and Pt wire as the auxiliary electrode. In the electrode system, the medium used in the test was 0.1 M tetrabutylammonium hexafluorophosphate (Bu ₄ NPF ₆ ) in dimethyl diamide (DMF). The measured potentials were all within the added ferrocene (Fc). Standard. The HOMO values of the materials were directly tested by the Model IPS-4 Ionization Energy Measurement System. The fluorescence quantum efficiency (PLQE) of the material is based on the formula

(where: Φ _s is the fluorescence quantum yield of the sample, Φ _r is the fluorescence quantum yield of the standard, η is the refractive index of the solution, and A _s and A _r are the absorption values at the fluorescence excitation wavelength of the sample and the standard, Ι _s and Ι _r are the fluorescence integral areas of the samples and standards) calculated using the relative method. The material and the known quantum yield standard were configured to the same concentration of polymethyl methacrylate (PMMA) in chloroform solution, spin-coated into a film, and the ultraviolet absorption spectrum was measured under the same measurement conditions (GENESYS). 10S, Thermo) and fluorescence spectra (F97pro Fluorescence Spectrophotometer, Prism). The photon energy (ET1) of the material is calculated from the formula E = hν = 1240 / λ (where λ is the tangential wavelength of the starting position of the fluorescence spectrum of the PMMA film of the material). )

a measured by cyclic voltammeter

b triplet energy

c PLQE efficiency is one unit of the luminous efficiency of Ir(PQ) ₂ (acac) at 298K.

Comparing the examples of the present invention in the above table with the published examples, the following characteristics can be obtained: based on the wavelength and efficiency of Ir(DMPQ) ₂ (acac) in PMMA, the Ir complex at the 4, 6 position of quinoline can be used. By shifting the spectrum red by 30 nm, the PLQE in the PMMA film is increased by about 20%. The Ir complex substituted at the 3, 4, and 6 positions of the quinoline can continue to red shift the luminescence spectrum by about 7 nm. The ligand in which the substituent is introduced at the para position of the phenyl group substituted at the 2-position of the quinoline can greatly improve the fluorescence quantum efficiency, such as the ruthenium complexes 82 and 157, and the spectrum has a blue shift of 14-27 nm. The highest film PLQE is a hetero complex of quinoline 4, 6-substituted and Ir substituted at the 3, 4, and 5 positions of phenyl. From the comparison of Eg (band gap value), it is understood that the above ruthenium complex can be used as a red light material, which is used as a display material to emit light, and the red light saturation is high.

Example 12 Comparison of ruthenium complex 6,7,8,11,82,126,157,187,201 as a phosphorescent luminescent material and a conventional phosphorescent red light material applied to a device

The above ruthenium complexes 6, 7, 8, 82, 187 were compared as a phosphorescent luminescent material with conventional phosphorescent red materials Ir(PQ) ₂ (acac) and Ir(DMPQ) ₂ (acac). The structure of the OLED device was designed as follows: ITO/ HAT-CN (10 nm) / TAPC (40 nm) / NPB: red dopant (95: 5, 20 nm) / Balq (10 nm) / Bphen (50 nm) / Liq (1 nm) / Al.

The crucible containing the OLED organic material and the crucible containing the metal aluminum particles are sequentially placed at the positions of the organic evaporation source and the inorganic evaporation source. The cavity is closed, and the initial vacuuming and high vacuum steps are performed, so that the internal vapor deposition degree of the OLED evaporation apparatus reaches 10E-7 Torr.

OLED evaporation film formation: the OLED organic evaporation source is turned on, and the OLED organic material is preheated at 100 ° C for a preheating time of 15 minutes to ensure further removal of moisture in the OLED organic material. Then, the organic material that needs to be evaporated is subjected to rapid heating and heat treatment, and the baffle above the evaporation source is opened until the evaporation source of the material has organic material running out, and the crystal oscillator detects the evaporation rate, and then slowly heats up. The temperature rise is 1~5°C until the evaporation rate is stable at 1A/sec. The baffle directly under the mask plate is opened to form the OLED film. When the organic film on the ITO substrate is observed at the computer end, the film is preset. When thick, close the mask baffle and the baffle directly above the evaporation source to close the evaporation source heater of the organic material. The evaporation process of other organic materials and cathode metal materials is as described above. The package is UV-cured for photocuring. The encapsulated samples were tested for IVL performance and the IVL equipment was tested with the Mc Science M6100. The device data comparison data test is shown in the following table:

As shown in Fig. 3 and Fig. 4, the device electroluminescence wavelength is mainly determined by the photoluminescence of the Ir complex itself. Under the same conditions, the efficiency of the device is also consistent with the PLQE trend of the Ir complex itself. . Therefore, the high PLQE polysubstituted quinoline-coordinated doped compound of the present invention can achieve higher device efficiency in other devices than existing red light materials.

Example 13 Application of the polysubstituted quinoline coordinated doping compound of the present invention in OLED

The polysubstituted quinoline-coordinated oxime compound compounds described herein are suitable for use in a variety of optical and optoelectronic devices, such as light absorbing devices such as solar and light sensors, light emitters, or devices having both light absorbing and light emitting capabilities. And markers for biological applications. The use of the polysubstituted quinoline-coordinated doped compound of the present invention in an optoelectronic device will be described below by taking an organic light-emitting diode (OLED) as an example.

1 shows a cross-sectional view of an OLED 1000. As shown, the OLED 1000 includes an anode 1004 over a substrate 1002 made of a transparent material such as indium tin oxide; a hole transport material layer (HTL) 1006 and an anode 1004. Connected; the light-emitting function layer 1008 is located above the hole transport material layer 1006, the light-emitting function layer 1008 includes the emitter and the body of the light-emitting material; the electron transport material layer (ETL) 1010 and a metal cathode layer 1012 are sequentially disposed on the light-emitting function. Above layer 1008. The OLED and similar light emitting devices may comprise a single layer or a laminate. In any aspect, any layer of the single or laminated layer may comprise indium tin oxide (ITO), MoO ₃ , Ni ₂ O ₃ , poly(3,4-ethylenedioxythiophene) (PEDOT), polystyrene sulfonate. Sodium (PSS), 4,4',4"-((1E,1'E,1"E)-cyclopropane-1,2,3-trimethylenetris(cyano-methyl)) Tris(2,3,5,6-tetrafluorobenzonitrile) (NHT-49), 2,2'-(perfluorodecalin-2,6-diyl)malononitrile (NHT-51), 2, 3,5,6-tetrafluorotetracyano-p-dioxane (F4-TCNQ), N,N'-di-1-naphthyl-N,N'-biphenyl-1,1'-biphenyl- 4,4' diamine (NPD), 1,1-cis ((di-4-p-tolylamino)phenyl)cyclohexane (TAPC), 2,6-cis (N-carbazolyl)-pyridine ( mCpy), 2,8-cis (diphenyl azide) dibenzothiophene (PO15), LiF, LiQ, Cs ₂ CO ₃ , CaCO ₃ , Al or a combination thereof. In this embodiment, the luminescent functional layer 1008 may comprise one or more compounds of the polysubstituted quinoline coordinated doping compound of the present invention, and the ruthenium complex 7 is selectively used in the experiment. Comes with a main material. The ETL layers 1010 and 1006 may also comprise one or more polysubstituted quinoline coordinated anthracene compound and another implant layer in proximity to the electrode. The material of the injection layer may include (electron injection layer) EIL, (hole injection layer) HIL, and CPL (cap layer), which may be in the form of a single layer or dispersed in a transmission material. The host material can be any suitable host material known in the art. The luminescent color of the OLED is determined by the luminescent energy (optical energy gap) of the luminescent functional layer 1008, and the luminescent energy (optical energy gap) of the luminescent functional layer 1008 is tuned by tuning the luminescent compound and/or the electronic structure of the host material. The hole transport material in the HTL layer 1006 and the electron transport material in the ETL layer 1010 can comprise any suitable hole transport body known in the art.

Example 14 Spectroscopic Testing of Ruthenium Complex 7 in CH ₂ Cl ₂ , PMMA

The ruthenium complex 7 prepared by the experiment was placed in CH2Cl2 and PMMA for spectral test. The results are shown in Fig. 2. It can be seen from the emission spectrum obtained by the measurement of this experiment that it can be excited by different excitation lights. Strong fluorescence is emitted, the two main peaks are at 629nm and 630nm, respectively, so the ruthenium complex 7 can be used to prepare a high saturation deep red light-emitting device.

Example 15 Electroluminescence spectrum of a device of ruthenium complex 7.

The electroluminescence spectroscopy test was performed on the device prepared by using the ruthenium complex 7 as a luminescent material, and the result is shown in FIG. 5, indicating that the ruthenium complex 7 is a high-saturation red light, and the material can fully satisfy the red color in the display. Degree requirements.

The basic principles and main features of the present invention and the advantages of the present invention are shown and described above. It should be understood by those skilled in the art that the present invention is not limited by the foregoing embodiments, and that the present invention is only described in the foregoing description and the description of the present invention, without departing from the spirit and scope of the invention. Various changes and modifications are intended to be included within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and their equivalents.

Claims (9)

A polysubstituted quinoline coordinated doped compound having the following molecular structural formula:

R ^a , R ^b , R ^c R ^e represents a hydrogen atom, a halogen atom, a (C1-C6) alkyl substituent or an aryl substituent (the related substituent may be substituted, substituted with (C1-C6) alkyl or Aryl substituted), R ^d represents a hydrogen atom or a (C1-C6)alkyl substituent, R ^f , R ^h represents a (C1-C6)alkyl substituent and an aryl substituent (the relevant substituent may be deuterated, Containing (C1-C6)alkyl substituted or aryl substituted). The polysubstituted quinoline coordinated doping compound according to claim 1, wherein the (C1-C6)alkyl group is a linear or branched alkyl group having 1 to 6 carbon atoms. Such alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1,2-dimethylpropyl, 2,3-dimethylpropyl and 1-ethylpropyl, cyclopentyl, cyclohexyl, 2-methyl-3-pentyl , 3,3-dimethyl-2-butyl. The polysubstituted quinoline-coordinated hydrazine compound according to claim 1, wherein the molecular structure formula of the polysubstituted quinoline-coordinated hydrazine compound is classified into the following six structures, which are respectively named as molecular formulas. II, Formula III, Formula IV, Formula V, Formula VI or Formula VII:

Molecular formula II: R ^ac , R ^f is a halogen atom, a (C1-C6) alkyl substituent or an aryl substituent, and R ^d represents a (C1-C6)alkyl substituent; Molecular formula III: R ^bc , R ^f represents a halogen atom, a (C1-C6)alkyl substituent or an aryl substituent, and R ^d represents a (C1-C6)alkyl substituent; Molecular formula IV: R ^ab , R ^f represents a halogen atom, a (C1-C6)alkyl substituent or an aryl substituent, and R ^d represents a (C1-C6)alkyl substituent; Molecular formula V: R ^bc , R ^e , R ^f represents a halogen atom, a (C1-C6) alkyl substituent or an aryl substituent; Molecular formula VI: R ^ab , R ^e , R ^f represents a halogen atom, a (C1-C6)alkyl substituent or an aryl substituent, and R ^d represents a (C1-C6)alkyl substituent; Formula VII: R ^ac , R ^ef represents a halogen atom, a (C1-C6)alkyl substituent or an aryl substituent. The polysubstituted quinoline coordinated doping compound according to claim 1, wherein: The substituted quinoline-coordinated hydrazine compound is selected from the group consisting of a polysubstituted quinoline-coordinated hydrazine compound 1 to a polysubstituted quinoline-coordinated hydrazine compound 225. The polysubstituted quinoline coordinated doping compound according to claim 1, wherein the polysubstituted quinoline coordinated doping compound is ruthenium complex 6, ruthenium complex 7, ruthenium complex 8 , ruthenium complex 11, ruthenium complex 82, ruthenium complex 126, ruthenium complex 157, ruthenium complex 187, ruthenium complex 201. A method for synthesizing a polysubstituted quinoline-coordinated hydrazine compound according to claim 1, wherein the synthesis route is as follows:

Ligand modifications include 3,5 disubstituted (R ^d R ^d ), 4-substituted (R ^e ) and 3,4,5 trisubstituted (R ^d R ^e R ^d )phenyl in the 2-substituted phenyl group, The specific synthetic route of the substituted quinoline-coordinated hydrazine compound is: a transesterification reaction, an acid-catalyzed Skraup ring condensation reaction and a hydroxyhalogenation reaction to form a polysubstituted quinoline, which can be obtained by a Suzuki coupling reaction. Body, (the chemical equation shown above) This route avoids the suzuki coupling reaction of the alkyl group and the side reaction of the multiple reaction sites, which can improve the synthesis efficiency and reduce the difficulty of purification; The above R ^a , R ^b , R ^c represent an H (or oxime) atom or a (C1-C6) alkyl substituent and an aryl substituent (the related substituent may be substituted by a deuterated, containing (C1-C6) alkyl group or Aryl substituted); R ^d represents a H atom or a (C1-C6) alkyl substituent, and R ^e represents a H (or fluorene) atom or a (C1-C6) alkyl substituent and an aryl substituent (related substituent It may be deuterated, containing (C1-C6)alkyl substituted or aryl substituted); R ^f , R ^h represents a (C1-C6) alkyl substituent and an aryl substituent (the relevant substituent may be deuterated, containing (C1-C6) alkyl substituted or aryl substituted). A method for synthesizing the ruthenium complex 11, the ruthenium complex 82, the ruthenium complex 126, the ruthenium complex 157, the ruthenium complex 187, the ruthenium complex 201, and the ruthenium complex 6 according to claim 5, wherein the synthesis route is respectively As follows: 合成 Complex 11 synthesis path is: (1) 4'-methyl-[1,1'-biphenyl]-4-amine, ethyl 2-phenylacetoacetate and xylene are mixed, and N2 is bubbled for three minutes, and then stirred at 145 ° C. TLC (petroleum ether: ethyl acetate = 5:1) showed that the reaction was completed, cooled to room temperature, filtered and dried to give the pale yellow product N-(4'-methyl-[1,1'-biphenyl]-4 -yl)-3-oxo-2-phenylbutanamide; (2) Under the protection of nitrogen, concentrated sulfuric acid is added dropwise to N-(4'-methyl-[1,1'-biphenyl]-4-yl)-3-oxo-2-phenylbutanamide. Heating to 50 ° C, stirring, TLC (petroleum ether: ethyl acetate = 1:1) showed the reaction was complete, cooled to room temperature, poured into ice water, solids were precipitated, and dried by filtration to give a pale yellow product 4-methyl-3-benzene Base-6-(p-tolyl)quinolin-2-ol; (3) Under the protection of nitrogen, add phosphorus oxychloride to 4-methyl-3-phenyl-6-(p-tolyl)quinolin-2-ol, heat to 100 ° C, and stir until TLC (petroleum) Ether: ethyl acetate = 1:1) showed the reaction was completed, the reaction mixture was cooled to room temperature, poured into ice water slowly, and the solid was precipitated, filtered, washed with water and dried to give a pale yellow product 2-chloro-4-methyl-3- Phenyl-6-(p-tolyl)quinoline; (4) 2-Chloro-4-methyl-3-phenyl-6-(p-tolyl)quinoline, 3,5-dimethylbenzeneboronic acid, potassium phosphate trihydrate, 2-dicyclohexylphosphine-2', Mix 6'-dimethoxybiphenyl, tris(dibenzylideneacetone)dipalladium and toluene, replace the atmosphere of the reaction flask with nitrogen, heat the reaction system to 100 ° C, and stir until TLC (petroleum ether: ethyl acetate = 10 :1) The reaction was completed, the reaction mixture was diluted with ethyl acetate, filtered, and the filtrate was evaporated to dryness (ethyl ether: ethyl acetate = 50:1) to give white 2-(3,5-dimethylphenyl)- 4-methyl-3-phenyl-6-(p-tolyl)quinoline; (5) 2-(3,5-Dimethylphenyl)-4-methyl-3-phenyl-6-(p-tolyl)quinoline, ruthenium trichloride trihydrate, ethylene glycol ether Mixing with water, replacing the atmosphere of the reaction flask with nitrogen, heating and stirring, cooling to room temperature, solid precipitation, suction filtration, and drying to obtain product dimer (30 mg, 71%); (6) Dimer 11, pentane-2,4-dione (0.1 ml), sodium carbonate and ethylene glycol ether were mixed, the reaction flask atmosphere was replaced with nitrogen, heated to reflux, cooled to room temperature until solid precipitated, and filtered. Solid cross column (petroleum ether: ethyl acetate = 30:1) to give a red ruthenium complex 11; The synthetic route of the ruthenium complex 126 is: (1) Add p-toluidine, 3-oxo-3-p-tolyl-propionic acid ethyl ester and xylene to the sealed tube, and react the system N _{2 for} three minutes, then stir at 145 ° C to TLC (petroleum ether: Ethyl acetate = 5:1) showed the reaction was completed, cooled to room temperature, and the precipitated product was filtered and dried to give white product, 3-oxo-N,3-di-p-tolylpropanamide; (2) Under nitrogen atmosphere, the concentrated sulfuric acid was added dropwise to 3-oxo-N,3-di-p-tolylpropionamide, heated to 50 ° C, and stirred until TLC (petroleum ether: acetic acid B) Ester = 3:1) shows the reaction is complete, cooled to room temperature, poured into ice water, solid precipitated, filtered and dried to give white product 6-methyl-4-(p-tolyl)quinolin-2-ol; (3) Under the atmosphere of a nitrogen-replacement reaction flask, phosphorus oxychloride was added dropwise to 6-methyl-4-(p-tolyl)quinolin-2-ol, and the mixture was stirred under heating to TLC (petroleum ether: ethyl acetate) =6:1) The reaction was completed, the reaction solution was cooled to room temperature, poured slowly into ice water, and solid was precipitated, filtered, washed with water and dried to give white product 2-chloro-6-methyl-4-(p-tolyl) Porphyrin (4) 2-Chloro-6-methyl-4-(p-tolyl)quinoline, 3,5-dimethylbenzeneboronic acid, potassium phosphate trihydrate, 2-dicyclohexylphosphine-2',6'-dimethyl Oxybiphenyl, tris(dibenzylideneacetone) dipalladium and toluene were mixed, the atmosphere of the reaction flask was replaced with nitrogen, heated to 100 ° C, and stirred until TLC (petroleum ether: ethyl acetate = 10:1) showed complete reaction. The liquid was diluted with ethyl acetate, filtered, and the filtrate was evaporated to drynessjjjjjjjjjjjjjjjjjjjj (p-tolyl)quinoline; (5) Mixing 2-(3,5-dimethylphenyl)-6-methyl-4-(p-tolyl)quinoline, ruthenium trichloride trihydrate, ethylene glycol ether and water, nitrogen drum After soaking for three minutes, heating and stirring, then cooling to room temperature, solid precipitation, filtration, and drying to obtain dimer 126; (6) Dimer 126, pentane-2,4-dione, sodium carbonate and ethylene glycol ether, nitrogen gas was bubbled for three minutes, heated to reflux, the reaction solution was cooled to room temperature, solid precipitated, filtered, ether Washing and drying to obtain a complex 126; The method of the ruthenium complex 201 is as follows: (1) 6-Methyl-2,4-di-p-tolylquinoline, cesium trichloride trihydrate, ethylene glycol ether and water were mixed, nitrogen was bubbled for three minutes, heated to reflux, and then cooled to room temperature. Solid precipitation, filtration, and drying to obtain dimer 201; (2) Dimer 201, pentane-2,4-dione, sodium carbonate and ethylene glycol ether were mixed, nitrogen was bubbled for three minutes, and after heating to reflux, the reaction solution was cooled to room temperature, and the solid was precipitated and filtered. Washing with ether and drying in air to obtain ruthenium complex 201; The synthetic route of ruthenium complex 187 is: (1) Add p-toluidine, 2,5-dimethyl-3-oxo-hexanoic acid ethyl ester and xylene to the sealed tube, and react the reaction system N _{2 for} three minutes, then stir to TL at 145 ° C. (Petroleum ether: ethyl acetate = 5:1) showed the reaction was completed, the reaction mixture was cooled to room temperature, and the product was precipitated, filtered, and dried to give white 2,5-dimethyl-3-oxo-N-(p-tolyl) Hexamide (2) adding 2,5-dimethyl-3-oxo-N-(p-tolyl)hexanamide to a three-necked flask, replacing the atmosphere of the reaction flask with nitrogen, and adding concentrated sulfuric acid to the reaction system at 50 ° C, Stirring to TLC (petroleum ether: ethyl acetate = 3:1) showed the reaction was completed, the reaction mixture was cooled to room temperature, poured into ice water, solids were precipitated, filtered, and dried in air to give pale yellow 4-isobutyl-3. 6-Dimethylquin-2-ol; (3) Add 4-isobutyl-3,6-dimethylquin-2-ol (800 mg, 3.5 mmol) to the vessel, replace the atmosphere of the reaction flask with nitrogen, and add phosphorus oxychloride dropwise to the reaction system, 100 °C, stirring to TLC (petroleum ether: ethyl acetate = 5:1) showed the reaction was complete, the reaction solution was cooled to room temperature, poured into ice water, solid precipitated, filtered, washed with water, dried to give a pale yellow 2-chloro-4- Isobutyl-3,6-dimethylquinoline; (4) adding 2-chloro-4-isobutyl-3,6-dimethylquinoline, 3,5-dimethylbenzeneboronic acid, potassium phosphate trihydrate, 2-dicyclohexylphosphine-2' to a chemical container, 6'-Dimethoxybiphenyl, tris(dibenzylideneacetone) dipalladium and toluene, nitrogen atmosphere was replaced with a reaction flask, heated to 100 ° C, stirred until TLC (petroleum ether: ethyl acetate = 10:1) The reaction was completed, the reaction mixture was diluted with ethyl acetate, filtered, and the filtrate was evaporated to dryness (ethyl ether: ethyl acetate = 10:1) to give white 2-(3,5-dimethylphenyl)-4-isobutyl Base-3,6-dimethylquinoline (700 mg, 55%); (5) Mixing 2-(3,5-dimethylphenyl)-4-isobutyl-3,6-dimethylquinoline, ruthenium trichloride trihydrate, ethylene glycol ether and water, nitrogen Displace the reaction flask atmosphere, heated to reflux, cooled to room temperature, solids precipitated, filtered, dried in air to obtain dimer 187; (6) The dimer 187,2,8-dimethyldecane-4,6-dione, sodium carbonate and ethylene glycol ether, nitrogen gas was substituted for the reaction flask atmosphere, and the reaction system was heated and refluxed, and the reaction liquid was cooled. To the room temperature, the solution was spin-dried through a column (petroleum ether: ethyl acetate = 50:1) to give a red ruthenium complex 187; The synthetic route of the ruthenium complex 82 is: (1) 4'-methyl-[1,1'-biphenyl]-4-amine, ethyl 5-methyl-3-oxohexanoate and xylene, and the reaction system N _{2 is} bubbled for three minutes. Stirring to TL ( petroleum ether: ethyl acetate = 5:1) at 145 ° C showed that the reaction was completed, the reaction mixture was cooled to room temperature, and the product was precipitated, filtered, and dried in air to give a pale yellow 5-methyl-N- (4'-Methyl-[1,1'-biphenyl]-4-yl)-3-oxohexanamide; (2) Nitrogen replacement reaction atmosphere, adding 5-methyl-N-(4'-methyl-[1,1'-biphenyl]-4-yl)-3-oxohexanamide dropwise to concentrated sulfuric acid Heat and stir to TLC (petroleum ether: ethyl acetate = 3:1). The reaction was completed, cooled to room temperature, poured into ice water, solids were precipitated, filtered, washed with water and dried in air to give white 4-isobutyl-6- (p-tolyl)quinolin-2-ol (15.5 g, 95%); (3) Nitrogen replacement reaction atmosphere Phosphorus oxychloride was added dropwise to 4-isobutyl-6-(p-tolyl)quinolin-2-ol, and stirred under heating to TLC (petroleum ether: ethyl acetate = 6:1) The reaction is shown to be complete, the reaction solution is cooled to room temperature, poured into ice water, the solid is precipitated, filtered, washed with water, and dried to give dark-yellow 2-chloro-4-isobutyl-6-(p-tolyl)quinoline; (4) A 500 ml round bottom flask was charged with 2-chloro-4-isobutyl-6-(p-tolyl)quinoline, p-methylbenzeneboronic acid, potassium phosphate trihydrate, 2-dicyclohexylphosphine-2', 6'-dimethoxybiphenyl, tris(dibenzylideneacetone)dipalladium and toluene, the reaction atmosphere was replaced with nitrogen, and refluxed to TLC (petroleum ether: ethyl acetate = 10:1). Diluted with ethyl acetate, filtered, and the filtrate was evaporated to dryness (EtOAc:EtOAc:EtOAc Quinoline (5) 2-(4-methylphenyl)-4-isobutyl-6-(p-tolyl)quinoline, ruthenium trichloride trihydrate, ethylene glycol ether and water were mixed, and the atmosphere of the reaction flask was replaced by nitrogen. , heated to reflux, cooled to room temperature, solids precipitated, filtered, washed with ether to dry to obtain dimer 82; (6) Dimer 82,2,8-dimethyldecane-4,6-dione, sodium carbonate and ethylene glycol ether, nitrogen atmosphere was replaced with a reaction flask, heated to reflux, cooled to room temperature, and dried. Crossing the column (petroleum ether: dichloromethane = 1:1) to obtain a red ruthenium complex 82; The synthetic route of ruthenium complex 157 is as follows: (1) 4-isobutyl-6-(p-tolyl)-2-(3,4,5-trimethylphenyl)quinoline, ruthenium trichloride trihydrate, ethylene glycol ether and water , the atmosphere of the reaction flask is replaced by nitrogen, and after heating and refluxing, the solid is precipitated, filtered, and dried to obtain a dimer 157; (2) Dimer 157,2,8-dimethyldecane-4,6-dione, sodium carbonate and ethylene glycol ether, nitrogen gas, replace the reaction flask atmosphere, heat reflux, cool, spin dry, cross column (petroleum ether: ethyl acetate = 30:1) to give a red ruthenium complex 157, The synthetic route of ruthenium complex 6 is as follows: (1) mixing 4'-methyl-[1,1'-biphenyl]-4-amine, ethyl 2,5-dimethyl-3-oxohexanoate and xylene, reaction system N ₂ drum After three minutes of soaking, stirring at 145 ° C to TLC (petroleum ether: ethyl acetate = 5:1) showed that the reaction was completed, cooled to room temperature, product was precipitated, filtered, and dried to give a pale yellow product 2,5-dimethyl- N-(4'-methyl-[1,1'-biphenyl]-4-yl)-3-oxohexanamide; (2) Nitrogen replacement reaction flask atmosphere, concentrated sulfuric acid was added dropwise 2,5-dimethyl-N-(4'-methyl-[1,1'-biphenyl]-4-yl)-3- Oxy hexanamide, heating and stirring to TLC (petroleum ether: ethyl acetate = 3:1) showed the reaction was complete, the reaction solution was cooled to room temperature, poured slowly into ice water, solid precipitated, filtered, and dried in air to obtain a yellow product 4 -isobutyl-3-methyl-6-(p-tolyl)quinolin-2-ol; (3) Nitrogen replacement reaction flask atmosphere, phosphorus oxychloride was added dropwise to 4-isobutyl-3-methyl-6-(p-tolyl)quinolin-2-ol, and stirred under heating to TLC (petroleum ether: Ethyl acetate = 6:1) showed the reaction was completed, the reaction mixture was cooled to room temperature, poured into ice water, and the solid was precipitated, filtered, washed with water and dried to give a yellow product 2-chloro-4-isobutyl-3-methyl- 6-(p-tolyl)quinoline; (4) 2-chloro-4-isobutyl-3-methyl-6-(p-tolyl)quinoline, 3,5-dimethylbenzeneboronic acid, potassium phosphate trihydrate, 2-dicyclohexylphosphine-2' , 6'-dimethoxybiphenyl, tris(dibenzylideneacetone) dipalladium and toluene were mixed, and the atmosphere of the reaction flask was replaced with nitrogen, and the mixture was heated and stirred until TLC (petroleum ether: ethyl acetate = 10:1). The reaction mixture was diluted with ethyl acetate, filtered, and the filtrate was evaporated to dryness (EtOAc:EtOAc:EtOAc -3-methyl-6-(p-tolyl)quinoline; (5) 2-(3,5-Dimethylphenyl)-4-isobutyl-3-methyl-6-(p-tolyl)quinoline, ruthenium trichloride trihydrate, ethylene glycol Mixing ether and water, replacing the atmosphere of the reaction flask with nitrogen, heating and stirring, then cooling the reaction solution to room temperature, solid precipitation, filtration, washing with ether, drying to obtain dimer 6; (6) Mix the dimer 6, pentane-2,4-dione, sodium carbonate and ethylene glycol ether, replace the reaction flask atmosphere with nitrogen, heat to reflux, cool to room temperature, spin dry, and pass the column (petroleum ether: Ethyl acetate = 30:1) gave a red ruthenium complex 6. The use of multi-substituted quinoline coordinated doped compounds in electroluminescent materials. The use of polysubstituted quinoline coordinated doped compounds as electroluminescent materials in optoelectronic appliances.

Images