TWI289594B - Luminescent material of organic light-emitting diode (OLED) - Google Patents

Abstract

The present invention relates to a compound having formula (I) suitable for luminescent material of organic light-emitting diodes (OLEDs); wherein the formula (I) can emits blue light. The present invention also discloses an organic electroluminescence device using the aforementioned compound having formula (I) as luminescent material.

Description

1289594 IX. Description of the Invention: TECHNICAL FIELD OF THE INVENTION The present invention relates to a novel compound which can be used as a luminescent material for organic electroluminescent diodes (OLEDs). [Prior Art] Recently, organic semiconductors and organic conductive materials have been intensively studied, and in particular, organic electric cooling devices using light-emitting elements of organic semiconductors have made remarkable progress. Organic electroluminescence (OEL) is a phenomenon in which an organic substance is excited by a corresponding electric energy under a certain electric field. In 1963, Pope et al. first studied the 10~20 μπ thick thick, anthracene early wafers. It was first discovered that after applying 400 volts across the crystal, it was observed that the onion emits blue fluorescence, making the organic electroluminescence The research has taken the first step, but it is not practical because of the difficulty in growing and large-area single crystals, and the required driving voltage is too large, and the luminous efficiency is inferior to that of inorganic materials. Subsequently, Helfrich2 and Williams3 and others continued their efforts to reduce the voltage to about 1 volt, obtaining an external quantum efficiency of about 5 ° / ❶ photon / electron, but because the thickness of the single crystal is too large, the driving voltage is also higher. The efficiency of converting electrical energy into light energy is too low. In 1982, Vinnett4 et al. used a vacuum evaporation method to make a 50 nm thick onion film, and further reduced the driving voltage to 30 volts to observe blue fluorescence, but the electron injection efficiency was too low and the onion film formation. The sex is not good, so its external quantum efficiency is only about 0.03%. After more than 20 years of sporadic development, there have been no major breakthroughs. 1289594 Until 1987, Eastman Kodak company Tang and VanSlyke first published organic light emitting diodes (OLEDs), which was a breakthrough development. They use aromatic diamine (HTM-2) as a hole transport layer material, and a good film-forming 8-hydroxyquinoline aluminum Alq3 (tris(8-hydroxyquinolinato)aluminum(III)) as an electron transport layer and a luminescent material. Vacuum evaporation is used to make a film of 60~70 nm, and a low work function magnesium-silver alloy is used as a cathode to improve the injection efficiency of electrons and holes. The organic small molecule luminescent material developed by the two electrodes is placed and energized to emit light, which produces green light with a wavelength of 530 nm, which exhibits low driving voltage and high quantum efficiency (> 1%). And the effects of component stability, etc., greatly improve the characteristics and practicality of organic small molecule electroluminescent devices. Then in 1990, the University of Cambridge, Cambridge

University) Friend et al. subsequently published polymer light-emitting diodes (PLEDs), which used fluoropolymer PPV (p-phenylene vinylene) as a luminescent material by spin coating. In the layer, a polymer electroluminescent device having a single-layer structure is produced, and since it has a simple process, a good polymer, and a semiconductor-like property, research on a total of polymer light-emitting materials has been rapidly developed. It is worth noting that OLED not only can self-illuminate, but also does not require a backlight module, and has low driving voltage, high brightness, high contrast, wide viewing angle, fast response, simple structure, and super. Compared with the current FPD with LCD as the mainstream. The advantages of thin film and light weight can be effectively applied to A?, Ming or 1289594 where it is made into display, photoelectric coupler, etc. If it is made on a soft substrate such as a plastic substrate, the device can be bent and folded for carrying, and The process is simple and is expected to significantly reduce costs. At present, more than 80 companies around the world have been competing to invest heavily in the development of organic electroluminescent display technology, which has become the mainstream of another display technology. In 1997, Japan's Pioneer first published a low-molecular monochromatic (green) passive display that successfully applied organic electroluminescent display technology to automotive instrument panels. Since then, the organic electroluminescent display has been commercialized and has been applied to small-sized panels such as TDK Corporation of Japan in 1998, Sic Bo Technology of 2002, Samsung, NTT Do Co Mo color mobile phone, and 2003 Kodak digital camera. Japan's Pioneer and Kodak Kodak also collaborate on a small-volume OLED monochrome and multicolor display, which has been officially applied to Motorola phones, and has been well received. Sanyo has also collaborated with Kodak to produce small sizes. The full color OLED sample is claimed to be mass-produced after 2001; Chi Mei has also released an active color display of more than 10 inches, making the organic electro-excitation technology more advanced. However, until now, OLEDs still have further improvements, including their color saturation, stability, luminous efficiency and longevity. This is closely related to the nature and process of the material itself. If it can break through, it should be expected to become the future. The trend of the display. In recent years, the industry has been working on organic electroluminescent materials, and has achieved good results. Red, blue and green are the three primary colors of light. The good three primary color efficiencies and solid colors are the basic requirements for achieving the full color display of 1289594. The development of green light, whether fluorescent or phosphorescent materials and components, is more remarkable than that of red light. In general, in terms of blue monochromatic materials, currently Sakamoto Shinko and Kodak have only high-efficiency, durable, light blue organic fluorescent materials, because of the high order, there is no good durable metal-phosphorescent material. The molecular structure design of the blue material in the OLED usually must explicitly consider whether the band gap and the molecular LUMO/HOMO energy level can be matched with the materials in the component. Luminescent materials are the most important materials in organic electroluminescent devices. Good luminescent materials must meet four conditions: (1) high quantum efficiency fluorescence characteristics, and the fluorescence spectrum is mainly distributed in the visible light region of 400~700 nm. (2) Good semiconductor characteristics, high conductivity, ability to conduct electrons or holes, or both; (3) good film formation, no pinholes in tens of nanometers of film (4) Good thermal stability. Most of the electron transport layer and the hole transport layer can be used as luminescent materials in the visible light region. Since most organic materials exceed a certain concentration, especially when they are sturdy, they will have self-quenching (self quencjjing) or concentration. The problem of concentration quenching leads to broadening of the emission peaks or red shifts, so they are generally doped in a low concentration manner in a host with some carrier properties. D〇pant emitter. Several design considerations for the guest illuminant used in the organic electroluminescent device are: (1) high fluorescence efficiency, (2) the absorption spectrum of the guest and the emission spectrum of the host should have a good overlap, so that the energy It can be effectively transmitted from the main body to the guest; (3) There are emission peaks of red, blue, green or yellow, and the emission peak is as narrow as possible to maintain the purity of the light color; (4) It has good stability and can be evaporated. 1289594 The above-mentioned limitations of organic electroluminescent materials, especially blue luminescent materials, * If further breakthroughs, will be helpful in the development of blue luminescent materials. • Therefore, the development of compounds for blue luminescent materials is a subject worthy of study. SUMMARY OF THE INVENTION An object of the present invention is to provide a light-emitting substance which can be used for an organic electroluminescent diode, particularly as a blue light-emitting substance. The present invention provides a compound having the following chemical formula (I)··

Ar1^^Yv^^Ar2 Chemical formula (I) where Ar! and Ar2 are

And wherein m=0-4, n=0-5; 1289594

Where γ is

Or a further object of the invention relates to a luminescent material for an organic electroluminescent diode (OLED) comprising a compound of formula (1) wherein Ari, Ar2 and lanthanide are as defined above. A further object of the present invention is to provide a blue light-emitting organic electroluminescent device [the device comprising an anode layer, a hole transport layer, a light-emitting layer, an electron transport layer and a cathode layer, wherein the anode layer, The hole transport layer, the light-emitting layer, the electron transport layer, and the cathode layer are sequentially disposed, and the light-emitting layer includes a compound of the formula (1), wherein the Ar, Ar2, and Y systems are the same as defined above. [Embodiment] The present invention provides a novel compound of formula (I) 1289594 ΑΤ 2 chemical formula (I)

Among them, Ar! and Ar2 are

And wherein m=0-4, n=0-5; wherein Y is

Or 11 1289594 Another embodiment of Xingben ^ Ming is an organic electroluminescent device comprising at least a blue-emitting compound having m (?), as shown in the first figure, the device 1 includes an anode dance i , == delivery! 2, an illuminating layer 3, an electron transport layer: and -3 Thunder two ', the aforementioned anode layer), the hole transfer layer 2, the luminescent layer "transfer layer 4 and the cathode layer 5 according to the foregoing In order to place, the front light-emitting layer 3 comprises a chemical formula (1): 4, ΑΓ 2 and Y are the same as defined above. The following examples illustrate the creation of the present invention by means of several embodiments and drawings. The following examples are for illustrative purposes only, and are not intended to limit the scope of the disclosure. Any person skilled in the art can further perform any movement and retouching according to the contents disclosed in the specification. To achieve maximum effectiveness, all those who are listed in this section of the month are referred to as full-text.

Synthesis of ί chelate 2a: The synthesis of compound 2a is as shown in Figure A, taking one

= 2 flasks, add 4_bromo-2-fluorotoluene (7.00 g? 37.03 mmol). NBS (6·59 g, 37.03 mmol), ΒΡΟ (0·45) G5 1.85 mmol), add 50 ml of four gasified carbon as solvent and heat to 叩. 〇 reflux for 5 hours. After returning to >JBL, it is extracted with ethyl acetate, and the water is removed by sulfuric acid to obtain a liquid oil. After the column column analysis (pure hexane, Rf = 〇·7), the oily liquid 2a (8·83 g, 89%) was obtained. Properties of Compound 2a: Lower, ln NMR (CDC13? 600 MHz): δ 7.24-7.20 (m? 3Η)5 4.41 12 1289594 (S, 2H) 13C NMR (CDC13, 150 MHz): δ160·3 (d, JCF = 253·5 Hz), 132.2, 127.9, 124.4 (d, JCF = 14·3 Hz), 123·0 (d, JCF = 9.2 Hz)? 119.5 (d, JCF = 24.3 Hz), 24.7 HRMS (70eV) Calcd for C7H5Br2F: 265.8742, found: 265.8728 Synthesis of compound 2b: Synthetic method with the synthesis of compound 2a. After the layer column analysis (pure hexane, Rf = 0.7), a colorless oily liquid 2b (92%) was obtained. The properties of compound 2b are as follows: !H NMR (CDC13, 400 MHz): δ 7.50 (t5 J = 7.6 Hz? 1H), 7.14 (d, J = 7·2 Hz, 1H), 7.04 (d, J = 7· 2 Hz, 1H), 4.39 (s, 2H) 13C NMR (CDC13? 100 MHz): 6161.2 (d, JCF = 251.5 Hz), 138.8, 134·1, 133·9, 125·9 (d, JCF = 13 · 1 Hz), 120·4 (d, JCF = 23.8 Hz), 24.8. HRMS (70eV) calcd for C7H5Br2F: 265.8742, found: 265.8733. Synthesis of 4 chelate 2c: Compound 2c was synthesized according to the second B diagram, taking a 50 ml flask, adding compound 3c (1.00 g, 45.25 mmol), using 20 ml of methanol as solvent, under ice bath NaBH4 (0·21 g, 54.32 mmol) was added. After half an hour of disruption, add a little water to stop the reaction. Extraction with ethyl acetate and removal of water over magnesium sulfate gave a colorless oil (0.98 g, 43.94 mmol). This oily liquid was placed in a 50 ml two-necked flask, and 5 ml of di-methane was used as a solvent, and ΡΒγ3 (1·78 g, 65·92 mmol) was added under ice bath. After 3 hours of stirring, the reaction was stopped by an ice bath under the action of a sodium hydride solid. After the column chromatography (pure hexane, Rf = 0.7), a colorless oily liquid 2c (1.09 g, 85%) was obtained. The properties of the compound 2c are as follows: !H NMR (CDC13, 400 ΜΗζ): δ 7.29 (t, J = 7·8 Hz, 1H), 7·16 (t, J = 7·8 Ηζ, 1 Η), 4·40 (s, 2Η) 13C NMR (CDC13? 100 MHz): 5160.3 (d, JCF = 252.6 13 1289594 Ηζ), 158·4 (d, JCF = 249·2 Ηζ), 131·2, 125·2 (d, JCF = 13.4 Hz), 123.2 (d, JCF = 11.2 Hz), 118.8 (d? JCF = 24.3 Hz)? 24.9 HRMS (70eV) calcd for C7H4Br2F2: 283.8648, found: 283.8651 ^(synthesis of complex 2d: synthesis The method was the same as the synthesis of compound 2c. After layer column analysis (pure hexane, Rf = 0.7), a colorless oily liquid 2d (82%) was obtained. The properties of compound 2d were as follows: !H NMR (CDC13, 400 MHz): δ 4.48 (s? 2H) 13C NMR (CDCI3, 100 MHz): 6158.0 (dd, JCF = 250.2, 22.2 Hz), 156.2 (dd? JCF = 248.2, 21.8 Hz)? 125.1 (t? JCF = 12.4 Hz), 118.8 ( t, JCF = 24.8 Hz), 24.7 HRMS (70 eV) calcd for C7H2Br2F4·· 319.8459, found: 319.8455. 4 Synthesis of the chelate 3a: According to the second C diagram, take a 100 ml double-necked flask and add the compound 2a (1·23 g, 4·59 mmol), NaHC03 (3.47 g, 41·34 mmol), add 35 1111〇]^8〇 The mixture is heated to 70 ° (: stirring for 1 hour. After returning to room temperature, it is extracted with ethyl acetate, washed with DMSO, and dehydrated with magnesium sulfate to obtain a colorless oily liquid. After layer column analysis, a colorless oil can be obtained. The liquid, after standing, gave a white solid 3a (0·68 g, 73%). The properties of compound 3a were as follows: !H NMR (CDCI3, 600 MHz): δ 10.16 (t, J = 1.5 Hz? 1H), 7 · 59 (t, J = 8·3 Hz, 1H), 7·29 (dd, J = 8.2, 2·1 Hz, 1H), 7·23 (dd, J = 8·4, 2·2 Hz, 1H) 13C NMR (CDC13, 150 MHz): δ185·5 (d, JCF = 5·4 Hz), 163.7 (d? JCF = 243.1 Hz), 129.7 (d5 JCF = 9.6 Hz), 129.3, 128.1, 122.8 ( D9 JCF = 8.1 Hz), 119.9 (d, JCF = 23.43⁄4) HRMS (70eV) calcd for C7H4BrFO: 201.9430, found: 201.9439 Synthesis of 4 chelate 3b: 1289594 Synthetic method with the synthesis of compound 3a. After the layer column analysis, a colorless oily liquid 3b (75%) was obtained. The properties of compound 3b are as follows: ^ !H NMR (CDC13? 400 MHz): δ 9.93 (s, 1Η)? 7.72 (t? J = 8·0 Hz, 1H), 7·58 (d, J = 8.2, 1H ), 7·52 (d, J = 8.0, '1H) 13C NMR (CDC13, 100 MHz): δ189·3, 164.1 (d, JCF = 244.2 Hz), 130.2, 129.1, 127.1, 122.2 (d, JCF = 88

Hz), 119.2 (d, JCF = 21.4 Hz) HRMS (70eV) calcd for C7H4BrFO: 201.9430, found: 201.9435 ' ^[Synthesis of chelate 3c: According to the second D diagram, take a 100 ml two-necked flask, Add compound lc (3.49 g, 12.85 mmol), 40 ml of distilled anhydrous ether as solvent, and slowly add n-butyl lithium (5·14 ml, 2·5Μ) at -78 °C. , 12.85 mmol). After stirring at this temperature for 10 minutes, ethyl formate (1.43 g, 19.29 mmol) was added. After returning to room temperature, the reaction was stopped by a little 2N ammonium sulfate solution, extracted with ethyl acetate, and dehydrated with magnesium sulfate to obtain a colorless oily liquid. After the layer column analysis, a colorless oily liquid was obtained, and after standing, a white solid 3c (1.68 g, 59%) was obtained. The properties of compound 3c are as follows: lU NMR (CDCls, 500 MHz): δ 10.10 (t, J = 2.5 Hz, 1H), 7.40 (dt, J = 6·2, 2·0 Hz, 1H), 7·34 ( Dd, J = 9·0, 4·2 Hz, 1H) 13C NMR (CDC13, 125 MHz): δ184·5 (d, JCF = 6·6 Hz), 159·4 (d, JCF = 257.3 Hz), 155.6 (d, JCF = 246.1 Hz), 123.9, 121.6 (d? JCF = 25.5 Hz), 116.8 (dd, JCF = 23.3, 10.0 Hz), 114.0 (d, JCF = 23.3 Hz) HRMS (70eV) calcd for C7H3BrF20 : 219.9335, found: 219.9322 Synthesis of 4 chelate 3d: Synthesis method is the same as compound 3c. After the layer column analysis, a colorless oily liquid was obtained, and after standing, a white solid 3d (51%) was obtained. The properties of compound 3d are as follows: 15 1289594 ^ NMR (CDC13, 600 MHz): δ 10·27 (s, 1H) 13C NMR (CDC13, 150 MHz): 6181.8, 146.5 (dd? JCF = 249.3, 22.5 Hz)? (dd, JCF = 247.6, 22.3 Hz)? 114.4 (t, JCF = 9.6 Hz), 107.3 (t, JCF = 21.6 Hz) HRMS (70eV) calcd for C7HBrF40: 255.9147, found: 255.9151 Synthesis of compound 4a: According to the second E diagram, take a 100 ml two-necked flask and add compound 3a (1.00 g, 4.93 mmol), ethylene glycol (1.73 g, 7.39 mmol), PTSA (0.1 g, 0·058 mmol), force 50 ml of benzene was added as a solvent and heated to reflux for 24 hours using a Dean-Stark apparatus. After returning to room temperature, the reaction was quenched by the addition of sodium bicarbonate solids, and concentrated under reduced pressure. EtOAc EtOAc (EtOAc: EtOAc: The properties of the compound 4a are as follows: NMR (CDC13, 400 ΜΗζ): δ 7·41 (t, J = 8·2 Hz, 1H), 7·28 (dd, J = 8·2, 2·0 Ηζ, 1Η) , 7·24 (dd, J = 8·2, 2·0 Ηζ, 1Η), 6·03 (s, 1Η), 4·13-4.09 (m, 2Η), 4·03-4·00 (m , 2Η) 13C NMR (CDC13? 100 MHz): 6160.8 (d, JCF = 251.9 Hz)? 128.9, 127.4, 124.5 (d? JCF = 12.2 Hz), 123.3 (d, JCF = 9.1 Hz)? 119.2 (d, JCF = 22.9 Hz), 98.4, 65.4 HRMS (70 eV) calcd for C9H8BrF02: 245.9692, found: 245.9688 Synthesis of compound 4b: Synthesis of compound 4a. After the rapid layer analysis of the dream gel, a colorless oily liquid was obtained, and after standing, a white solid 4b (99%) was obtained. The properties of compound 4b are as follows: lH NMR (CDCI3, 400 MHz): δ 7.54 (t5 J = 8.0 Hz9 1H) 5 7·23 (t, J = 8·2, 1H), 7.12 (d, J = 8·2, 1H),5·76 (s,1H), 4·21-4·00 (m,4H) 13C NMR (CDC13, 100 MHz): δ158·6 (d, JCF = 248·8 Hz), 134.5, 131.8 , 128.2, 121·7, 117·5 (d, JCF = 23.2 Hz), 99.6, 65.8 HRMS (70 eV) calcd for C9H8BrF02: 245.9692, found: 1289594 245.9688 Synthesis of compound 4c: Synthesis of compound 4a. A colorless oily liquid was obtained after rapid layer analysis of the silicone, and a white solid 4c (99%) was obtained after standing. The properties of compound 4c are as follows: ]H NMR (CDC13? 400 MHz): δ 7.30-7.27 (m, 2Η)? 5.99 (s,1Η), 4·13·4·01 (m,4Η) 13C NMR (CDC13, 100 MHz): δ158·8 (dd, JCF = 243·6, 21.8 Hz)? 157.6 (dd, JCF = 242.8, 22.2 Hz), 126.2, 122.9, 118.5, 107.2, 103.6, 65.40000 HRMS (70eV) calcd for C9H8BrF202· · 263.9597, found: 263.9591 4 匕5 mad synthesis: According to the third A picture, take a 100 ml two-necked flask, add compound 4a (1.00 g, 4.05 mmol), diphenylamine (0.68 g, 4·05 mmol), sodium tert-butoxide (0.46 g, 4.81 mmol), Pd2 (dba) 3 (74·3 mg, 0·081 mmol), DPPF (89·8) Mg, 0·16 mmol), vacuumed for 1 min, added 35 ml of toluene as a solvent, and heated to reflux for 12 hours. After the reaction is completed, the reaction is stopped by adding a little water, extracted with ethyl acetate, and the water is removed by magnesium sulfate. After draining, a dark brown viscous liquid is obtained, and after analysis of the silica gel column (pure hexane·ethyl acetate = 10:1) , Rf = 0.6) gives a pale yellow viscous liquid (1·13 g, 3.48 mmol). The viscous liquid was added to a 50 ml double-necked flask, and 20 ml of acetone was used as a solvent. After adding 1 ml of 1N hydrochloric acid, the mixture was mixed for half an hour, extracted with ethyl acetate, and the water was removed by magnesium sulfate. After drying, a pale yellow solid 5a was obtained. 1.00g, 85 %). The properties of the compound 5a are as follows: NMR (CDC13, 600 ΜΗζ): δ 10.09 (s, 1H), 7.63 (t, J = 8·3 Ηζ, 1 Η), 7·34 (t, J = 8·4 Ηζ, 4H ;J, 7.20-7 16 (m, 7Η), 6.70 (dd, J = 8.8, 2.1 Ηζ, 1Η), 6·55 (dd, J = 13·5, 2·1 Hz, 1H), 13C NMR (CDC13, 150 MHz): δ185.1 (d, JCF = 5.4 Hz), 165.9 (d, JCF = 255.2 Hz)? 154.9 (d? JCF = 11.6 Hz) / 17 1289594 145.2, 129.8, 129·4 ( d, JCF = 3·2 Ηζ), 126·6, 125.8, 116·4 (d, JCF = 8·6 Hz), 114·3, 104·5 (d, JCF = 24·9 Hz) HRMS (70eV Calcd for C19H14FNO: 291.1059, found: 291.1055 Synthesis of compound 5b: Synthetic method with the synthesis of compound 5a. After drying, 5b (84%) of pale yellow solid was obtained. The properties of compound 5b are as follows: lU NMR (CDC13? MHz): δ 9.92 (s? 1Η)? 7.58-7.54 (m, 2Η), 7·42 (dd, J = 8·8, 2·1 Hz, 1Η), 7·29 (t, J = 11· 4 Hz, 4H), 7·11 (t, J = 8·2 Hz, 2H), 7·05 (d, J = 8·4 Hz, 4H) 13C NMR (CDC13, 100 MHz): δ189·5, 157·3 (d, JCF = 251.2 Hz), 146.5 (d, JCF = 11.6 Hz), 135.2, 132.1 (d/ JCF = 23·2 Hz ), 129.3, 126·9, 125.9, 124.6, 122.1, 112.3 (d, JCF = 23.9 Hz) HRMS (70 eV) calcd for C19H14FNO: 291.1059, found: 291.1058 Synthesis of compound 5c: Synthesis of the same compound as compound 5a. After drying, a pale yellow solid 5c (79%) was obtained. The properties of compound 5c were as follows: NMR (CDC13, 600 ΜΗζ): δ 10·12 (d, J = 2·5 Hz, 1 Η), 7·49 (dd , J = 11·3, 6·2 Hz, 1Η), 7·28 (t, J = 8·0 Ηζ, 4H), 7·12 (t, J = 7·4 Hz, 2H), 7·05 (t, J = 7·9 Hz, 4H), 6·74 (dd, J = 11·6, 6·2 Hz, 1H), I3C NMR (CDC13, 150 MHz): δ184·5 (d, JCF = 4·1 Hz), 161.2 (d9 JCF = 253.4 Hz)? 151.9 (d, JCF = 248.9 Hz), 145.9, 142.4 (t, JCF = 10·9 Hz), 129.3 (d, JCF = 29·8 Hz) , 124.8, 124.3, 118.4 (dd, JCF = 10.2, 5.6 Hz), 115.3 (dd, JCF = 22.2, 2.0 Hz), 111.9 (d? JCF = 25.5 Hz) HRMS (70eV) calcd for C19H13F2NO: 309.0965, found: 309.0971 Synthesis of Compound 6a: 1289594 The synthesis of Compound 6a is based on Figure 3B, taking a 25 ml single-necked flask and adding the compound to di-mercaptobiphenyl (4,4'-bis _chloromethyl_biphenyl) (1.00 g, 3.98 mmol), triethyl phosphite (0.99 g, 5.97 mmol) heated to 150 ° C for 12 hours, cooled to room temperature, heated to 100 ° under vacuum The unreacted P(〇Et)3 was distilled off, and the undistilled portion was the product 6a (1·76 g, 97%). The properties of compound 6a are as follows: !H NMR (CDC139 400 MHz): δ 7.53 (d? J = 8.0 Hz, 4H)5 7.36 (d, J = 8.0 Hz, 4H), 4.06-4.02 (m, 8H), 3.18 '(d, J' = 22.0 Hz, 4H), 1·26 (t, J = 6·8 Hz, 12H) ' 13C NMR (CDC13? 100 MHz): 6139.0, 130.5, 130.0, 126·8, 61· 8, 33.1 (d, JCP = 135·8 Hz), 16·1 'HRMS (70eV) calcd for C2〇H28〇6P2·· 426.1361,found: 426.1365 Synthesis of 4 conjugate 7: Synthesis of compound 7 In the third C picture, take a 1 〇〇ml flask and add 4-fluorophenylamine (1.00 g, 8.99 mmol), 1-bromo-4-fluoroaniline (l-bromo-4-fluorobenzene). (1·57 g, 8.99 mmol), sodium tert-butoxide (1·04 g, 10.79 mmol), Pd2(dba)3 (0·16 g, 0·18 mmol) DPPF (0·20 g, 〇·36 mmol) was pumped under vacuum for 10 minutes, and 35 ml of toluene was added as a solvent, and the mixture was heated under reflux for 12 hours. After the reaction is completed, the reaction is stopped by adding a little water, extracted with ethyl acetate, and the water is removed by magnesium sulfate. After draining, a dark brown viscous liquid is obtained, and after analysis of the silica gel column (pure hexane: ethyl acetate = 10:1), Rf = 0.7) gave a white solid 7 (1.31 g, 71%). The properties of compound 7 are as follows: !H NMR (CDC13? 400 MHz): δ 6.94-6.92 (m, 8H), 5·42 (s, 1H) 13C NMR (CDC13? 100 MHz): 5159.8 (d? JCF = 253.2 Hz), 142.6, 118.6, 112.3 (d? JCF = 21.2 Hz) HRMS (70 eV) calcd for C12H9F2N: 205.0703, found: 205.0708 1289594 Synthesis of compound 5d: The synthesis method is the same as that of compound 5a. After drying, a pale yellow solid was obtained 5d (88%). The properties of compound 5d are as follows: ln NMR (CDC13? 600 MHz): δ 9.78 (s? 1Η)? 7.65 (d5 J =8·2 Hz, 2H), 7.13-7.11 (m, 4H), 7.03 (t, J = 8·0 Hz, 4H)? 6.90 (d? J = 8.2 Hz? 2H) 13C NMR (CDC13? 150 MHz): δ 190.3, 160.1 (d? JCF = 244.8 Hz), 153.3, 141·9, 131.4, 129·0, 128·0 (d, JCF = 8·0 Hz), 118·3, 116.7 (d, JCF = 22·7 Hz) HRMS (70eV) calcd for C19H13F2NO: 309.0965, found: 309.0969 Synthesis of compound 6b : For the synthesis of compound 6b, refer to the third E diagram, take a 100 ml two-necked flask and add 4-bromo-2-fluorotoluene (1·00 g, 37·03 mmol). Ni(COD) 2 (1·46 g, 5.31 mmol) was taken from a glove box, and 10 ml of distilled DMF was added as a solvent. Heat to 40 ° C for 12 hours. After returning to room temperature, it was extracted with ethyl acetate, and water was removed by magnesium sulfate to obtain a brown oily liquid. After the layer column analysis (pure hexane, Rf = 0.5), a colorless oily liquid (〇·53 g) was obtained. Add this oily liquid to a 50ml two-necked flask, add NBS (0·43 g, 2.43 mmol), BPO (0.05 g, 0·21 mmol), add 20 ml of four gasified carbon as solvent, heat to 80 °C reflux for 5 hours. After returning to room temperature, extraction with ethyl acetate and removal of water by magnesium sulfate gave a pale yellow oily liquid. After layer column analysis (pure hexane, Rf = 0.2) gave a white solid (0.67 g). This solid was purified according to the method of compound 6a to give white solid 6b (0.83 g, 68%). The properties of compound 6b are as follows: !H NMR (CDC13? 600 MHz): δ 7.37 (dt, J = 7.9? 2.5 Hz, 2H), 7·25 (d, J = 8·0 Hz, 2H), 7·20 (d, J = 9·2 Hz, 2H), 4.04-3.99 (m5 8H), 3.17 (d, J = 21.7 Hz, 4H), 1·22 (t, J = 7. 4 Hz, 12H) 13C NMR (CDC13, 150 MHz): δ 160.9 (dd, JCF = 245.7, 20 1289594 7·2 Hz), 140.3, 132.1 (d, JCF = 4·1 Hz), 122·4, 118.5, 113·6 ( d, JCF = 23·3 Hz), 62·1, 25.9 (d, JCP = 139·7 Hz), 16.2 HRMS (70 eV) calcd for C22H30F2 〇6P2: 490.1486, found: 490.1481 Synthesis of 4 conjugate 8c: For the synthesis of compound 8c, refer to the third F diagram, take a 1 双 ml double flask, add compound 9c (1·00 g, 2.91 mmol), vacuum for 10 minutes, add 35 ml THF as solvent, and ice bath. Sodium tert-butoxide (0·31 g, 3.21 mmol) was added directly, and after stirring for 30 minutes, compound 5 (0·88 g, 3.21 mmol) was dissolved in 10 ml of THF and added to the neck. In the bottle. After reacting for 8 hours, the reaction was quenched by the addition of 2N ammonium chloride solution, and extracted with ethyl acetate. After layer column analysis (purely calcined, Rf = 0·5), a yellow-green solid 8c (1.02 g, 76%) was obtained. The properties of compound 8c are as follows: NMR (CDC13, 600 MHz): δ 7.44 (d, J = 8.8 Ήζ? 2H), 7.39-7.30 (m, 6H)? 7.20 (d, J = 8.4 Hz, 4H)? 7.16- 7.12 (m, 4H), 7.07 (d, J = 16·2 Hz, 1H) 13C NMR (CDC13, 150 MHz): δ 155·6 (dd, JCF = 241.7, 21.2 Hz), 155.5 (dd, JCF = 242.3, 21.5 Hz), 148.2, 147·2, 131·9 (d, JCF = 4·1 Hz), 130.1, 129.3, 129.2, 127.7, 124·6 (d, JCF = 14·6 Hz), 123·4, 122·9, 120·3 (d, JCF = 27·5 Hz), 116·7, 112·8 (dd, JCF = 24·9, 4·1 Hz), 106·6 (dd, JCF = 23·9, 10·2 Hz) HRMS (70 eV) calcd for C26H18BrF2N: 461.0591, found: 461.0597 Synthesis of 4 conjugate 8d: Synthesis of the synthesis of compound 8c. After drying, a pale yellow solid was obtained 8d (69%). The properties of the compound 8d are as follows: 4 NMR (CDC13, 600 ΜΗζ): δ 7·45 (d, J = 16·7 Hz, 1H), 7·40 (d, J = 8·5 Ηζ, 2Η), 7 · 30 (t, J = 8·0 Hz, 4Η), 7·15 (d, J = 7·8 Hz, 4H), 7.10-7.06 (m, 4H), 6·90 (d, J = 16· 7 Hz, 1H) 21 1289594 13C NMR (CDC13, 150 MHz): δ 148.7 (d, JCF = 25.5 Hz), 147·2 (d, JCF = 9·9 Hz), 145·0 (dd, JCF = 245.0 , 15·9 Hz), 144·5 (dd, JCF = 250·6, 13·4 Hz), 137·3 (t, JCF = 8·3 Hz), 129.9, 129.4, 127·7, 124.9, 123.5 , 122.5, 116.9 (t, JCF = 13.4 Hz)? 111.0, 96.7 (t? JCF = 22.7 Hz) HRMS (70eV) calcd for C26H16BrF4N: 497.0402, found: 497.0408 Synthesis of 4 conjugate 9a · According to the fourth A Figure, synthesis method with the synthesis of compound 6a. After purification, a pale yellow oily liquid 9a (98%) was obtained. The properties of compound 9a are as follows: !H NMR (CDC13? 600 MHz): δ 7.21-7.20 (m? 3H)? 4·05·4·01 (m, 4H), 3.11 (d, J = 21.6 Hz, 2H) , 1.23 (t, J = 7.05 Hz, 6H) 13C NMR (CDC13, 150 MHz): δ 160.5 (d, JCF = 249.9 Hz), 132.7, 127.4, 120.9 (d, JCF = 4·8 Hz), 119.0 (d, JCF = 25.2 Hz)? 118.5 (d? JCF = 15.5 Hz), 62.3 (d, JCF = 6.0 Hz), 26.0 (d5 JCP = 140.1 Hz), 16.2 HRMS (70eV) calcd for CnH15BrF03P: 323.9926, Found: 323.9928 Synthesis of 4 chelate 9b · Synthesis method Synthesize with compound 6a. After purification, a pale yellow oily liquid 9b (96%) was obtained. The properties of compound 9b are as follows: !H NMR (CDC135 400 MHz): δ 7.28 (d, J = 8.2 Hz, 1H)? 7·18-7·13 (m, 1H), 4·11-4·04 (m , 4H), 3·12 (d, J = 22.0 Hz, 2H), 1.26 (t, J = 7·06 Hz, 6H) 13C NMR (CDC13, 100 MHz): δ 159.8 (d? JCF = 251.3 Hz) , 157.2 (d? JCF = 248.1 Hz), 123.6 (d? JCF = 13.5

Hz), 120·8 (d, JCF = 25·5 Hz), 116.8 (d, JCF = 23.3

Hz), 113.2 (d, JCF = 23.1 Hz), 62.3, 25.8 (d? JCP = 139.6 Hz), 16.5 HRMS (70eV) calcd for CuH14BrF203P: 341.9832, found: 341.9832 22 1289594 4 Synthesis of the complex 9c: Synthesis The method is the same as the synthesis of compound 6a. After purification, a pale yellow oily liquid 9c (97%) was obtained. The properties of compound 9c are as follows: !H NMR (CDC13? 400 MHz): δ 4.14-4.06 (m? 4Η)5 3.23 (d, J = 21.2 Ηζ, 2 Η), 1·28 (t, J = 7· 02 Ηζ,6Η) 13C NMR (CDC13, 100 MHz): δ 146.8 (dd, JCF = 249.3, 22·5 Hz), 144-8 (dd, JCF = 247.6, 22.3 Hz), 114·4 (t, JCF = 9·6 Hz), 107·1 (t, JCF = 21.6 Hz), 62·7, 26·2 (d, JCP = 142.2 Hz), 16.6 HRMS (70eV) calcd for CnH12BrF403P: 377.9644, found: 377.9649 Synthesis of 10a: Compound 10a was synthesized in the same manner as in Figure 4B. A 100 ml two-necked flask was added, and compound 9a (1·00 g, 3.07 mmol) was added thereto, and the mixture was vacuumed for 10 minutes, and 35 ml of THF was added as a solvent. Sodium tert-butoxide (0.33 g, 3.38 mmol) was added directly to the bath. After stirring for 30 minutes, compound 3a (0·62 g, 3·08 mmol) was dissolved in 10 ml of THF and added to the flask. in. After 8 hours of reaction, the reaction was quenched by the addition of 2N ammonium chloride solution, and extracted with ethyl acetate. After the layer column analysis (pure hexane, Rf = 0.7), a white solid l 〇a (1.01 g, 88 %) was obtained. The properties of compound 10a are as follows: lU NMR (CDCI3, 600 MHz): δ 7.48 (t, J = 8.1 Hz? 2H)? 7.31-7.27 (m, 4H), 7.24 (s, 2H) 13C NMR (CDC135 1 50 MHz ): δ 160.0 (d, JCF = 253.5 Hz), 128.4, 128.1, 124.4 (d, JCF = 11·7 Hz), 122·9, 122.2 (d? JCF = 9.6 Hz)? 119.9 (d, JCF = 25.4 Hz) HRMS (70 eV) calcd for C14H8Br2F2: 371.8961, found: 371.8965 Synthesis of Compound 10b: Synthetic method with the synthesis of compound 10a. After layer column analysis (pure hexane, Rf = 0.7), a white solid l 〇b (83 %) was obtained. The properties of compound 10b are as follows: 23 1289594 # NMR (CDC13, 600 MHz): δ 7·33 (dd, J = 8·9, 6.4 Hz, 2H), 7·29 (dd, J = 9·3, 5· 7 Hz, 2H), 7·16 (s, 2H) 13C NMR (CDC13, 150 MHz): δ 155.9 (d, JCF = 249.8 Hz), 155.7 (d, JCF = 242·7 Hz), 125·1 ( Dd, JCF = 13.7, 6·6 Hz), 122·9 (d, JCF = 27.2 Hz), 120.8 (d, JCF = 27.2 Hz) 9 113.4 (d? JCF = 24.9 Hz)? 108.7 (dd5 JCF = 23.1 , 10.1 Hz) HRMS (70 eV) calcd for Ci4H6Br2F4: 407.8772, found: 407.8777 Synthesis of compound 10c: Synthetic method with the synthesis of compound l〇a. After layer column analysis (pure hexane, Rf = 0.7), a white solid 10c (79 〇/〇) was obtained. The properties of the compound 10c are as follows: !H NMR (CDC13, 600 MHz): δ 7.16 (s5 2H) 13C NMR (CDC13, 150 MHz): δ 145·1 (dd, JCF = 246·3, 15·9 Hz), 144·8 (dd, JCF = 251·8, 11.2 Hz), 122.5, 115.5 (t9 JCF = 12.8 Hz), 99.7 (t, JCF = 22.7 Hz) HRMS (70eV) calcd for C14H2Br2F8: 479.8396, found: 479.8391 Synthesis of 11: Compound 11 was synthesized in the same manner as in Figure C, taking a 150 ml two-necked flask, adding distilled aniline (5.00 g, 53.67 mmol), CaC03 (16·11 g, 160.99 mmol) and vacuuming for 10 minutes. 1-Chloro-3-methylbut-2-ene (12.35 g, 118.06 mmol) and 50 ml of DMF were added as a solvent, and the mixture was stirred at 65 ° C for 3 hours. The reaction was stopped by adding 50 ml of water, extracted with ethyl acetate, and the organic layer was washed three times with brine to remove DMF. 3 ml of concentrated hydrochloric acid was added to the organic layer to precipitate a large amount of white solid, which was filtered using a filter paper to obtain a white solid (13.12 g, 49.37 mmol). This white solid was placed in a 150 ml Erlenmeyer flask, polyphosphoric acid (48.56 g) was added, and the mixture was reacted for 24 hours using a mechanical stirrer, and neutralized with a saturated sodium hydrogencarbonate solution to stop the reaction. It is extracted with acetic acid 24 1289594 ethyl acetate, and the water is removed by magnesium sulfate to obtain a brown viscous liquid. After the column was analyzed (pure hexane, Rf = 〇·5), a brown viscous liquid 11 (5.17 g, 42%) was obtained. The properties of compound 11 are as follows: !H NMR (CDC13, 600 MHz): δ 6.71-6.65 (m? 3H)? 3.53 (t, J = 6·8 Hz, 4H), 2·00 (t, J = 6· Hz 147.7, 134.3 : 229.1830, found: 229.1836 " Synthesis of ib compound 12b: Synthesis of compound 12b As shown in Figure 4D, a 100 ml two-necked flask was added, and compound 11 (3.00 g, 13.08 mmol), DMF 30 ml, ice was added. P0C13 (2.01 g, 13.09 mmol) was slowly added dropwise under a bath, and after stirring for 20 minutes, the mixture was heated to 80 ° C and stirred for 16 hours. After returning to room temperature, the reaction mixture was poured into 1 ml of ice water, neutralized with aqueous sodium sulfate, and extracted with dichloromethane. A brown solid (2.59 g) was obtained after column chromatography. Take a 100 ml two-necked flask, add methyltriphenylphosphonium iodide (4.13 g, 11.57 mmol), dehydrated THF 50 ml, and slowly add n-butyl chain (n-BuLi) in an ice bath. (4·6 ml, 11.59 mmol, 2·5 Μ), after stirring for 30 minutes in an ice bath, the brown solid was dissolved in 5 ml of THF, and the mixture was stirred for 6 hours. After returning to room temperature, the reaction was stopped by adding 10 ml of water, extracted with ethyl acetate, and water was removed by magnesium sulfate to obtain a brown viscous liquid. After layer column analysis (pure hexane, Rf = 0.5), a white solid 12b (2·08 g, 62%) was obtained. #化合物12b The properties are as follows: NMR (CDC13, 400 ΜΗζ): δ 7·20 (s, 2H), 6.68 (dd, J = 17.4, 10.6 Ηζ, 1 Η), 5·57 (d, J = 17 ·6 Ηζ,1Η),5·04 (d,J=10·8 Ηζ,1Η),3·23 (t,J=6·2 Hz, 4Η),1·83 (t,J=6·0 Ηζ,4Η),1·38 (s,12Η) 13C NMR (CDC13,100 ΜΗζ): δ 140·4,137·3,130.1, 25 1289594 124.8, 122.0, 108.0, 46.7, 36·8, 32·2 , 31·1 HRMS (70eV) calcd for C18H25N: 255.1987, found: 255.1982 2. Preparation of compounds 13a to 13g and 14a to 14d of formula (I): Synthesis of compound 13a: Synthesis of compound 13a as shown in the fifth figure Take a 150 ml two-necked flask, add phosphate 6a (1·63 g, 3.58 mmol) and sodium tert_butoxide (0·76 g, 78.76 mmol), vacuum for half an hour, add 50 ml of anhydrous THF and stir for one hour in an ice bath. Further, aldehyde 5a (2·19 g, 7.52 mmol) was dissolved in 5 ml of THF and added to the above mixture for 20 hours. The reaction was quenched by the addition of a little water and extracted with ethyl acetate. Re-precipitation with dichloromethane and n-hexane gave a pale yellow-green solid 13a (2.14 g, 82%). The properties of compound 13a are as follows: !H NMR (CDC13, 600 MHz): δ 7.58 (d? J = 8.4 Hz? 4H)5 7.56 (d, J = 8·4 Hz, 4H), 7.43 (t, J = 8 ·6 Hz, 2H), 7·29-7·26 (m, 8H), 7.12 (d, J = 8·2 Hz, 8H), 7·07 (d, J = 7·8 Hz, 8H), 6.80 (dd, J = 8·5, 2·2 Hz, 2H), 6·72 (dd, J = 8·9, 2·2 Hz, 2H) 13C NMR (CDC13, 150 MHz): δ160·9 ( d, JCF = 247.7 Hz), 148.5 (d, JCF = 10.1 Hz), 146.9, 139.6, 136.7, 129.5, 128.0, 127.2, 127.1, 127.0, 125.1, 123.8, 120.8, 118.5 (d, JCF = 12.5 Hz)? 117.9, 109.1 (d5 JCF = 25.2 Hz) HRMS (70eV) calcd for C52H38F2N2: 728.3003, found: 728.3003 The structure of compound 13a is as follows:

Q

N ύ

26 1289594 Synthesis of 4 chelate 13b: Synthesis method is the same as compound 13a. After purification, a pale yellow-green solid 13b (77%) was obtained. The properties of compound 13b are as follows: lU NMR (CDC13, 600 MHz): δ 7.69 (d? J = 8.0 Hz5 4H)? 7.62 (d, J = 8.1 Hz, 4H), 7·34_7·31 (m, 10H), 7.27 (d, J = 8·1 Hz, 2H), 7.20 (t, J = 8·2 Hz, 2H), 7.14-7.12 (m, 12H), 7.11-7.08 (m, 4H) 13C NMR (CDC13? 150 MHz): 5158.0 (d? JCF = 249.8 Hz), 147.1, 139.8, 136.1, 135.3 (d, JCF = 6.3 Hz), 133.8 (d, JCF = 10·5 Hz), 129.1, 128.8, 128.6, 127.1, 123.2, 122.6, 122.5, 114.3 (d, JCF = 19·9 Hz) HRMS (70eV) calcd for C52H38F2N2: 728.3003, found: 728.3005 The structure of compound 13b is as follows:

> [Synthesis of the chelate 13c: Synthesis method is the same as the synthesis of the compound 13a. After purification, a pale yellow-green solid 13c (77%) was obtained. The properties of the compound 13c are as follows: NMR (CDC13, 600 ΜΗζ): δ 7·62 (d, J = 8.4 Hz, 4H), 7·58 (d, J = 8·4 Ηζ, 4 Η), 7·31 (dd , J = 11·6, 6·8 Ηζ, 2Η), 7.27-7.25 (m, 8Η), 7·19 (s, 2Η), 7.11(s, 2Η), 7·05-7·02 (m, 12Η),6·82 (dd,J = 11·2, 6·8 Ηζ, 2Η) 13C NMR (CDC13? 150 MHz): 6156.5 (d5 JCF = 246.2 Hz), 153.8 (d, JCF = 246.5 Hz), 146.8, 140.1, 136·2, 134.6 (d, JCF = 11·1 Hz), 130·1, 129.3, 127.2, 123.3, 123.0, 121·8 (d, JCF = 7.2 Hz), 119.7, 114.6 (d, JCF = 25.7 Hz)? 113.8 (d? JCF = 23.3 Hz) HRMS (70eV) calcd for C52H36F4N2: 764.2815, found: 764.2811 The structure of compound 13c is as follows: 27 1289594 PF f\

Synthesis of Compound 13d: Synthesis method is the same as the synthesis of Compound 13a. After purification, a pale yellow-green solid was obtained 13d (81%). The properties of compound 13d are as follows: *H NMR (CDC13? 600 MHz): δ 7.59 (d? J = 8.4 Hz? 4H)? 7·54 (d, J = 8·4 Hz, 4H), 7·37 (dd , J = 8.8, 2.4 Hz, 4H), 7.09 (s, 2H), 7.06-7.03 (m, 12H), 7.02 (s, 2H), 6·99_6·94 (m, 8H) 13C NMR (CDC13, 150 MHz): δ158·9 (d, JCF = 241.9 Hz), 147.5, 139.4, 136.6, 131.2, 128.1, 127.4, 127.0, 126.7, 126·5, 126·1 (d, JCF = 7.7 Hz), 122.3, 116.2 (d, JCF = 22.5 Hz) HRMS (70eV) calcd for C52H36F4N2: 764.2815, found: 764.2811 The structure of compound 13d is as follows:

Synthesis of 4 chelate 13e: Synthesis method is the same as compound 13a. After purification, a pale yellow-green solid 13e (79%) was obtained. The properties of the compound 13e are as follows: 4 NMR (CDC13, 600 ΜΗζ): δ 7.63 (t, J = 8·1 Hz, 2H), 7·40 (d, J = 8·6 Hz, 4H), 7·36 ( Dd, J = 8.1, 1·6 Hz, 2H), 7.29 (dd, J = 11·8, 1·5 Hz, 2H), 7.27-7.24 (m, 8H), 7.15 (s, 4H), 7.12 7.10 (m, 8H), 7.05-7.02 (m, 8H) 13C NMR (CDC13, 150 MHz): δ160·6 (d, JCF = 248·3 Hz), 147·8, 147.5, 139.6 (d, JCF = 7.4 Hz), 131·2, 130.7, 129.3, 127.6, 127.2, 124.9 (d? JCF = 12.0 Hz) 5 28 1289594 124.6, 123.2 (d, JCF = 17·9 Hz), 122.3, 118·6, 113· 8 (d, JCF = 23.3 Hz) HRMS (70eV) calcd for C52H38F2N2: 728.3003, found: 728.3003 The structure of compound 13e is as follows:

Synthesis of compound 13f: Compound 13f synthesis method As shown in the fifth figure, a 100 ml double-necked flask was added, and compound 8c (1.00 g, 2.16 mmol) was added, and Ni(COD)2 was weighed in a glove box. 65 g, 2·38 mmol), add 20 ml of distilled DMF as solvent. After recrystallization purification (hexane: methylene chloride = 10 ··1), a yellow-yellow solid 13f (0.86 g, 52%) was obtained. The properties of compound 13f are as follows: lU NMR (CDC13? 600 MHz): δ 7.41 (d? J = 8.7 Hz? 4H)? 7·38·7·36 (m, 2H), 7·30-7·27 (m , 8H), 7.16-7.12 (m, 14H), 7·09·7·05 (m, 8H) 13C NMR (CDC13? 150 MHz): 6155.8 (d? JCF = 244.8 Hz), 148.1, 147.3, 131.9, 130.4, 129.3, 127.8, 127·1 (d, JCF = 8·7 Hz), 124.7, 123·3, 123.1, 121·4 (d, JCF = 15.0 Hz), 117·8 (d, JCF = 25.5 Hz) ), 117.4, 112.9 (d, JCF = 21.6 Hz) HRMS (70eV) calcd for C52H36F4N2: 764.2815,found: 764.2819 The structure of compound 13f is as follows:

Synthesis of 4 mer compound 13g: Synthesis method is the same as compound 13f. After recrystallization and purification, yellow 29 1289594 color solid 13 g (43%) was obtained. The properties of compound 13g are as follows: !H NMR (CDC13? 600 MHz): δ 7.51 (d5 J = 16.7 Hz, * 2H), 7·42 (d, J = 7·8 Hz, 4H), 7.29-7.24 (m , 8H), 7.13-7.12 (m, 8H), 7.08-7.04 (m, 8H), 6.98 (d, J = 16·7 Hz, 2H) 13C NMR (CDC13, 150 MHz): δ148·9, 147.1, 144.5 (dd, JCF = 241.2, 22.8 Hz), 144.2 (dd, JCF = 240·1, 22·5 Hz), 138·0 (t, JCF = 8·5 Hz), 129·9, 129·3, 128.1, 124.9, 123.6, 122.3, 111.3 HRMS (70eV) calcd for C52H32F8N2: 836.2438, found: 836.2442 The structure of compound 13g is as follows:

The test values of UV, PL and Φ of the above compounds 13a to 13g are shown in the following Table 13a 13b 13c 13d 13e 13f 13g UV 394 386 396 396 406 406 416 PL 469 471 463 472 505 509 527 Φ 0.82 0.83 0.81 0.91 0.93 0.91 0.92 4 Synthesis of the compound 14a: Compound 14a was synthesized in the same manner as in the sixth figure. A 150 ml double flask was charged, and compound 12a (1.59 g, 5.87 mmol), compound 10a (1.00 g, 2.67 mmol), Pd (OAc) was added. 2 (29.9 mg, 0.13 mmol), PPh4Br (0.22 g, 0·53 mmol) and NaOAc (0.91 g, 13.4 mmol), vacuumed for 1 hour, added 15 ml of DMF in water, and heated to 100 Stir at °C for 16 hours. The reaction was stopped by the addition of 50 ml of water. At this time, a large amount of a yellow solid was precipitated, and solids were collected. After the column analysis, a dark yellow solid 14a (1·59 g, 1289594 79%) was obtained. The properties of the compound 14a are as follows: NMR (CDC13, 600 ΜΗζ): δ 7·58 (t, J = 8·0 Hz, 2H), 7·36 (d, J = 8·5 Ηζ, 4 Η), 7.32 (s, 2Η), 7.28-7.22 (m, 10Η), 7.18 (d, J = 10·1 Ηζ, 2Η), 7·11 (d, J = 7·6 Ηζ, 8Η), 7·06-7 · 03 (m, 10 Η), 6.92 (d, J = 10·5 Ηζ, 2Η) 13C NMR (CDC135 150 MHz): 5160.7 (d, JCF = 248.4 Hz), 147·8, 147.4, 139.1 ( d, JCF = 7·8 Hz), 130.8, 129.4, 129.3, 127·5, 126·9, 125·4, 124·7, 124.0, 123.9, 123.2 (d5 JCF = 8.7 Hz), 122.4, 122.2, 112.8 (d5 JCF = 22.1 Hz) HRMS (70eV) calcd for C54H40F2N2: 754.3160, found: 754.3156 The structure of compound 14a is as follows:

Synthesis of Compound 14b·· Synthesis method is the same as Synthesis of Compound 14a. After purification, a pale orange solid 14b (62%) was obtained. The properties of compound 14b are as follows: !H NMR (CDC13, 600 ΜΗζ): δ 7·38 (d, J = 8·7 Hz, 4H), 7.30-7·25 (m, 12Η), 7·21 (s, 4Η),7·11-7·07 (m,10Η), 7.05-7.02 (m? 8H) • 13C NMR (CDC13, 150 MHz): δ156·6 (d, JCF = 241·8

Hz), 156.3 (d, JCF = 243.5 Hz), 148.0 (d, JCF = 241.8 Hz), 147.3, 131.5, 130.5, 129.3, 129.1, 127.7, 124.7, 123.8, 123.3, 122.4, 122.3 (d, JCF = 19.4 Hz)? 117.6, 113.0 (dy JCF = 25.1 Hz), 112.7 (d, JCF = 24.0 Hz) HRMS (70eV) calcd for C54H38F4N2: 790.2971, found: 790.2975 The structure of compound 14b is as follows:

31 1289594 Synthesis of 4 chelate 14c: Synthesis method is the same as compound 14a. After purification, a pale orange solid 14c (50%) was obtained. The properties of compound 14c are as follows: ]H NMR (CDC 139 600 MHz): δ 7.45 (d, J = 16.4 Hz, 4H), 7·39 (d, J = 8·6 Hz, 4H), 7·26 (t, J = 8·1 Hz, 8H), 7.11 (d, J = 7.8 Hz, 8H), 7.07-7.03 (m, 8H), 6.95 (s, 2H) 13C NMR (CDC13? 150 MHz): 5148.7, 147.2, 144.7 (dd, JCF = 242.3, 23.5 Hz), 144.3 (dd, JCF = 239.5, 22.1 Hz), 137.1 (t, JCF = 8.7 Hz), 130.2, 129·4, 127.9, 125.0, 123.6, 122.6, 122.0, 116·7, 113.7 (t, JCF = 12·5 Hz), 111.7 HRMS (70 eV) calcd for C54H34F8N2: 862.2594, found: 862.2591 The structure of compound 14c is as follows:

Synthesis of Compound 14d: Synthesis method is the same as the synthesis of Compound 14a. After purification, an orange solid was obtained 14d (42%). The properties of compound 14d are as follows: !H NMR (CDC13? 600 MHz): δ 7.46-7.39 (m? 6H), 6.85 (d, J = 8.2 Hz, 2H), 6.64 (d, J = 8·7 Hz, 2H ), 3·43 (t, J = 5·3 Hz, 8H), 2·29 (t, J = 5·1 Hz, 8H), 1.75 (s, 24H) 13C NMR (CDC13, 150 MHz): 5144.2 , 143.1 (d? JCF = 249.1 Hz)? 142.8 (d, JCF = 243.2 Hz), 138.0 (d? JCF = 9·8 Hz), 135.2, 128.7, 127.7, 123.2, 121.1, 108.5, 104.8, 49.6, 35.0 , 29.7, 25.7 HRMS (70eV) calcd for C5〇H5〇F8N2: 830.3846, found: 830.3849 The structure of compound 14d is as follows: 32 1289594

14d The test values of UV, PL and φ of the aforementioned compounds 14a to 14d are shown in the following table.

14a 14b 14c 14d W 424 435 443 447 FL 523 555 573 One H|1 579 Φ 0.92 9S5 9M Real array II: It has the "b learning (I) free material" and the organic light emitting diode (OLED) Properties of Materials In the present invention, a compound of the formula (I) can be used as a luminescent material for an OLED. In this embodiment, compounds 13a and 13c are respectively taken as donors, ADN is used as the main body, CuPc is the hole injection layer, and NPB and Alq3 are the hole transport layer and the electron transport layer, respectively. The device structure is shown in Figure 7: ITO/CuPc (30nm) / NPB (40 nm) / 3% Compound 13a or 13c is doped with ADN (30 nm) / Alq3 (30 nm) / Mg: Ag (10 :l) (50 nm) / Ag composition. After the compounds 13a and 13c were formed into a component by a doping method, measurement of some properties was carried out and compared with the blue main emitter ADN. The eighth figure shows the comparison of the luminescence spectra (EL) of the compounds 13a, 13c and ADN at the current density J == l〇mA/em2. From the figure, the compounds 13a and 13c are single peaks, and the waveforms are similar. ^There is no other material such as ADN or NPB. Even at the art density, the EL spectrum remains unchanged. It can be seen that the applied voltage changes, and the emission spectrum of the element f has almost no effect, indicating that this element can be Maintain good luminescence properties. Further comparing with the illuminant ', it can be found that since the compounds 13a, 13c are fluorine-containing in the structure 33 1289594, the HOMO energy level in the molecular structure is pulled down and the energy gap of the molecule is increased, so the EL spectrum is It has a blue shift phenomenon and is closer to blue than ADN. It can be seen that the compound of the present invention is a bluer illuminant and can solve the problem that the blue color of the existing blue dopant in the current OLED is too shallow and can be full. The degree is better than the south. The data of the components made by the applicant using the compounds 13a, 13c and ADN are summarized in Table 3. The values of the different current densities (J = 20, 100 mA/cm2) are recorded in the table to observe the effect of the components. It can be seen from Table 3 that the luminances of the compounds 13a and 13c are much larger than those of the ADN, and the luminescence wavelength is closer to the blue luminescence region than the ADN. Table 3. Characteristic data of ADN, compound 13a and compound 13c

Compound Brigjbtness (ed/m2) EQE{%) PE(cd/A) Voliag^ (V) cm A»N 276* 1300^ L56 IA7 U8 UO 0'78 0,S9 S56 6M X«(US Y*0, 09 (448面面) m im 5602 17992 3.51 3.45 5.60 2Λ6 L7Q 1038 X«0J2 Y«021 (4$2 legs) I3t 135$ 6239 21423 3J? 3Λ9 6M 624 2,84 2.04 751 9M X*0J6 Y«0J5 < 458 _) a. J=20mA/on2, b. I=l()() mA/an2, c is the maximum luminosity, and d is the maximum emission wavelength. The figure is the voltage of compound 13a, 13c and ADN. Comparison of brightness relationship. An ideal luminescent material should not only have good luminous efficiency under high current density, but also be able to achieve the brightness requirement under low voltage driving. From the figure and Table 1, we can find that The starting voltages of the compounds 13a, 13c and ADN are about 75 V-10V, the maximum brightness of AND is about 5619 cd/m2 at a voltage of 10 V, and the brightness of the compounds 13a and 13c is continuously increased by 13⁄4 at a voltage of 10V to 14V. Phenomenon, the maximum degree of exemption is about 34 1289594 17992 and 21423cd/m2 at voltage 14V, respectively, thus showing that the compound of the present invention can help the main illuminant when used as a guest illuminant. Improve the luminosity of OLEDs. The tenth to twelfth graphs show the relationship between current density and external quantum efficiency, current density and energy efficiency, current density and luminous efficiency of compounds 13a, i3c and ADN. As shown, at j = 20 mA/cm2, the external quantum efficiency I of ADN is 156, and the luminous efficiency (LE·) and energy efficiency (p0wer efflcienCy, Ρ·Ε) are 0.781 m/W and 1.38 cd, respectively. /A, however, the external quantum efficiencies iW of the compounds 13a and 13c are 3·51 and 3.57, the LE· is 2·16 lm/W, 2.84 lm/W, and the Ρ·Ε· is 5.69 cd/A, 6.78 cd/ A, it is shown that the compounds 13a, 13c have higher external quantum efficiency, luminous efficiency or energy efficiency than adn, and it can be inferred that the compound of the present invention can make the external quantum efficiency, luminous efficiency, energy efficiency of the element due to the addition of fluorine atoms. The compound of the formula (I) is the same as the other compounds 15a-15e of the formula (I). The preparation method is as described in the first embodiment, and the chemical formula of I5a-15e is as follows:

15a 35 1289594

In addition, the properties of the compounds of 15a-15e are shown in Table 4: 15a 15b 15c 15d 15e EL 463nm - 473nm 478nm PL 498nm - 468nm - a further embodiment 36 1289594, all the features of the dew may be the same as other methods, Each feature of the two roads may be selectively replaced by phase-specific or similar-purpose features. Therefore, all the features disclosed in this specification are only one example of equal or similar features. .祁 祁 [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ The second figure is a synthesis method of the compound of the formula (1) of the present invention; wherein A is a compound of 2a, 2b; ^ is a synthesis method of compound 2e, 2d, c is a compound 3; a compound 3c , 3d synthesis method, e is a synthesis method of compound 4a, 4b, 4c. The second figure is a synthesis method of the precursor of the compound of the formula (1) of the present invention, wherein A is a compound 5 & 51, 5 (the synthesis method of B is a synthesis method of the compound 6a, and C is a synthesis of the compound 7) In the method, D is a synthesis method of the compound 5d, E is a compound-compound synthesis method, and F is a synthesis method of the compound 8c, 8d. The fourth diagram is a synthesis method of the precursor of the compound of the formula (1) of the present invention, wherein A For the synthesis of compounds 9a, 9b, 9c, B is a synthesis of compounds 10a, 10b, 10c, c is a synthesis of compound u, and D is a synthesis of compound 12b. Figure 5 is a compound of the invention I3a, 13g The sixth scheme is the composition of the compound I4a, 14g of the present invention. The seventh diagram is a diagram of the 37 1289594 electromechanical luminescence device of the compound of the present invention as a blue light luminescent material.

The eighth graph is a comparison of EL electroluminescence spectra of the compounds 13a, 13c and ADN of the present invention. The ninth graph is a graph comparing the voltage and brightness of the compounds 13a, 13c and ADN of the present invention. The tenth graph is a graph comparing the relationship between the current density of the compounds 13a, 13c and ADN of the present invention and the external quantum efficiency. The eleventh graph is a graph comparing the relationship between the current density and the energy efficiency of the compounds 13a, 13c and ADN of the present invention. Fig. 12 is a graph showing the relationship between the current density and the luminous efficiency of the compounds 13a, 13c and ADN of the present invention. [Main component symbol comparison description] 1 anode layer 2 hole injection layer 3 hole transfer layer 4 light-emitting layer 5 electron transfer 6 cathode layer 10 organic electroluminescent device 38

Claims (1)

\ \ 1289594 X. Patent application scope: 1. A compound of the following chemical formula (I): Aj: 2 Chemical formula (I) wherein Ari and Ar2 are m=0-4, n=0-5, and m is different from η system; 39 1289594 ^, m, n are defined as above. The compound of claim 1, wherein the aforementioned chemical formula (I) is 3. The compound of claim 1, wherein the aforementioned t formula (I) is 13b • The compound of claim 1, wherein the above-mentioned indigenous W system can be 5. The compound of claim 1, wherein the aforementioned chemical formula (I) is 1289594 13d 6. The compound according to claim 1, wherein the aforementioned chemical formula (1) is 7. The compound of claim 1, wherein the aforementioned chemical formula (I) is 8. The compound of claim 1, wherein the aforementioned chemical formula (I) is J3g 〇 9. The compound of claim 1, wherein the aforementioned chemical formula (I) is 10. The compound of claim 1, wherein the aforementioned chemical formula (1) is 14b 41 1289594 11. The compound of claim 1, wherein the aforementioned chemical formula (1) is 14e 12. The compound according to claim 1, wherein the aforementioned chemical formula (1) is 13. The compound of claim 1, wherein the aforementioned chemical formula (I) is 14. A blue light-emitting organic electroluminescent device comprising: an anode layer; Φ a hole injection layer; a hole transfer layer; a light-emitting layer; an electron transport layer; and a cathode layer; The hole transport layer, the hole transport layer, the light emitting layer, the electron transport layer and the cathode layer are disposed in the foregoing order, and the foregoing light emitting layer comprises a compound of the formula (I), wherein the ΑΓι, the 12 and the lanthanide The foregoing definitions are the same. The organic electroluminescence device of the blue light emitting device of claim 14, wherein the chemical formula (1) is 16. The blue light-emitting organic electroluminescent device according to claim 14, wherein the aforementioned chemical formula (I) is 17. The blue light-emitting organic electroluminescent device according to claim 14, wherein the aforementioned chemical formula (I) is 18. The blue light-emitting organic electroluminescent device according to claim 14, wherein the chemical formula (1) is 19. The blue light-emitting organic electroluminescent device according to claim 14, wherein the aforementioned chemical formula (I) is 20. The blue light-emitting organic electroluminescent device according to claim 14, wherein the aforementioned chemical formula (I) is 43 1289594 The organic electroluminescence device of the blue light emitting device of claim 14, wherein the chemical formula (I) is 22. The blue light-emitting organic electroluminescent device according to claim 14, wherein the aforementioned chemical formula (I) is 23. The blue light-emitting organic electroluminescent device according to claim 14, wherein the aforementioned chemical formula (I) is 24. The blue light-emitting organic electroluminescent device according to claim 14, wherein the aforementioned chemical formula (I) is 25. The blue light-emitting organic electroluminescent device according to claim 14, wherein the aforementioned chemical formula (I) is 26. The blue light emitting organic electro-excitation 44 1289594 illuminating device according to claim 14, wherein the aforementioned chemical formula (i) is 45