CN1315764C - Conjugate derivative material of 9-phenyl-9-pyrenyl fluorene substituted pyrene its preparation method and application - Google Patents

Abstract

The invention belongs to the technical field of photoelectric materials, and specifically relates to a class of 9-phenyl-9-pyrenylfluorene substituted pyrene conjugated derivative materials and a preparation method and application thereof. This type of compound is a high-efficiency light-emitting system that introduces the structure of 9-phenyl-9-pyrenylfluorene into pyrene. Its advantages are: cheap raw materials, simple synthesis method; Excimers; have strong hole injection ability, hole transport ability and electron transport ability, which can simplify the device process. The electroluminescent device prepared by using the material of the invention has obtained satisfactory results in terms of brightness, luminous efficiency, voltage resistance stability and the like. Such materials can be widely used in the fields of organic electronics such as organic electroluminescent materials, organic integrated circuits, organic solar cells, organic field effect tubes, dye lasers, organic nonlinear optical materials, and fluorescent probes.

Description

9-phenyl-9-pyrenylfluorene-substituted pyrene conjugated derivative material and its preparation method and application

technical field

The invention belongs to the field of optoelectronic materials and application technology, and specifically relates to a conjugated derivative material of pyrene substituted by 9-phenyl-9-pyrenylfluorene and a preparation method thereof, and the application of this type of material to organic/polymer electronics Luminescent materials, organic integrated circuits, organic solar cells, organic field effect transistors, dye lasers, organic nonlinear optical materials and fluorescent probes and other organic electronics fields.

technical background

Due to the rapid development of information technology, people put forward higher and higher requirements for information display technology. In 1987, Tang et al. from Kodak Corporation of the United States made a double-layer organic electroluminescent device (OLED [Tang, _CW ; Van Slyke, SA Appl .Phys.Lett.1987,51,913.], which started the epoch-making progress of organic electroluminescence. In 1990, Friend[Burroughes, JH; Bradley, DDC; Brown, AB; Marks , RN; Mackay, K.; Friend, RH; Bum, PL; Holmes, ABNature 1990, 347, 539.] et al first reported the electroluminescence of polystyrene vinylene (PPV), in 1991 Heeger group [Brown, D.; Heeger, AJAppl.Phys.Lett 1991,58,1982] has made the orange-red LED that spin-coating film is made, has opened the research of polymer electroluminescent material and device (PLED) since then. Relatively Compared with the existing cathode ray display (CRT), liquid crystal display (LCD), plasma display (PDP), and inorganic semiconductor LED display technologies, the organic/polymer flat display technology with organic materials as the light-emitting layer has the ability to It has the advantages of low power consumption, easy realization of large-screen display, continuously adjustable luminous color, wide viewing angle, active luminescence, fast response speed, rigid display and flexible display, etc. All these advantages are incomparable to inorganic semiconductor materials, so they have attracted great attention. Scientists, governments and industries of various countries pay great attention. There are two key technologies in organic/polymer flat display technology, one is the process of preparing devices, and the other is the development of luminescent materials and carrier transport materials with excellent comprehensive properties.

For luminescent materials, green light is relatively mature, while blue and red light materials still need to be improved. Pyrene has the characteristics of high fluorescence efficiency due to its large conjugated aromatic ring, but it is also because of this large planar structure that it is easy to cause the aggregation of chromophores to produce excitoassociates and exciplexes, which makes the original good The efficiency of the blue light material is reduced, and the luminous wavelength is red-shifted and broadened. Therefore, the present invention inhibits the aggregation of chromophores to obtain high thermal stability by introducing 9-phenyl-9-pyrenylfluorene groups, and at the same time, it is used to improve the hole injection ability. Materials of this structure not only have good hole transport ability, but also have good electron transport ability. So far, there are no relevant literature and patent reports at home and abroad.

At the same time, the conjugated derivatives of pyrene substituted by 9-phenyl-9-pyrenylfluorene in OFET, organic solar cells and organic laser fields also show high carrier transport performance and high luminous efficiency.

Contents of the invention

The object of the present invention is to propose a light-emitting material for high-efficiency and long-life OLED devices, its preparation method and application.

The invention introduces 9-phenyl-9-pyrenylfluorene into the large-planar aromatic structure of pyrene ring, and synthesizes an organic photoelectric material with high performance from the perspectives of material modification and electronic structure modulation. At the same time, the application of such materials in the field of organic electronics such as organic/polymer electroluminescent materials, organic integrated circuits, organic solar cells, organic field effect tubes, dye lasers, organic nonlinear optical materials, and fluorescent probes will be studied.

The present invention adopts Suzuki coupling chain reaction to synthesize a class of 9-phenyl-9-pyrene fluorene-substituted pyrene conjugated derivative material, and the molecular structure of the compound is as follows.

Structural Formula 1 Structural Formula 2

Wherein, A is (9-phenyl-9-pyrenyl) fluorenyl or (spiro-9-phenyl-9-pyrenyl) fluorenyl, wherein fluorenyl is monosubstituted (2-position of fluorene) or disubstituted ( 2 and 7 positions of fluorene); B is a hydrogen atom or a pyrenyl group (monosubstituted at 1 position). The following are typical materials for materials of the invention:

(1) For structural formula one

① Take A as (9-phenyl-9-pyrenyl) fluorenyl (monosubstituted), and when B is hydrogen, the structure is as follows:

Compound I, Mw: 642.8

②When A is (9-phenyl-9-pyrenyl)fluorenyl (disubstituted), and B is pyrenyl, the structure is as follows:

Compound II, Mw: 843.0

③When A is spiro-(9-phenyl-9-pyrenyl)fluorenyl (monosubstituted), and B is hydrogen, the structure is as follows:

Compound III, Mw: 640.8

④ When A is spiro-(9-phenyl-9-pyrenyl)fluorenyl (disubstituted), and B is pyrenyl, the structure is as follows:

Compound IV, Mw: 841.0

(2) For the general structural formula two

① Take A as spiro-(9-phenyl-9-pyrenyl)fluorenyl (monosubstituted), and when pyrene is double-substituted at the 2 and 7 positions, the structure is as follows:

Compound V, Mw: 1079.3

② Take A as (9-phenyl-9-pyrenyl)fluorenyl (monosubstituted), and when pyrene is 2, 7-position double substituted, the structure is as follows:

Compound VI, Mw: 1083.3

③When A is a spiro-(9-phenyl-9-pyrenyl)fluorenyl group (monosubstituted), and pyrene is a mixture of 1,6 disubstituted and 3,6 disubstituted, the structure is as follows:

Compound VII, Mw: 1066.3

④ When A is (9-phenyl-9-pyrenyl) fluorenyl (monosubstituted), and pyrene is a mixture of 1,6 disubstituted and 3,6 disubstituted, the structure is as follows:

* for another replacement position

Compound VIII, Mw: 1070.3

The preparation method of above-mentioned compound all is to adopt Suzuki even chain reaction:

M+N——→Target

Among them, M and N are two reaction precursors, and Target represents the obtained target product. Suzuki chain reaction conditions are as follows: two reaction precursors M, N, K ₂ CO ₃ (or NaCO ₃ ), toluene and a catalytic amount of Ph(PPh ₃ ) ₄ are mixed, and then heated to a temperature of 60-100°C. The reaction time is 10-36 hours, the reaction is anaerobic reaction, and the reaction is protected from light. Adding a phase transfer catalyst during the reaction can increase the yield. After the reaction is completed, the aqueous phase is added for liquid separation, then extracted, and finally purified by recrystallization or column chromatography.

For different compounds, the difference lies in the synthesis of precursors M and N, as follows:

(1) Preparation of compound I and compound II:

Their respective routes are as follows:

Among them, step (i) bromobenzene reacts with magnesium to generate Grignard reagent (phenylmagnesium bromide) under anhydrous and oxygen-free conditions, and then reacts with fluorenone (2-bromofluorenone or 2,7-dibromofluorenone) to form Corresponding format magnesium salt, the time is 4～6 hours, finally the magnesium hydrochloride that will generate is acidified, obtains compound 11; Step (ii) prepares precursor M, the Friedel-Craft reaction of fluorenol and excess pyrene under acid catalysis, specifically In order to drop the dissolved fluorenol into the solution of excess pyrene (≥2 equivalents), add acid (in order to avoid by-products, preferably ≤1 equivalent), heat up to 40-80°C, and the reaction time is 10-30 minutes After separation and purification, two precursors M are obtained. When X takes H, the precursor M is 12a; when X takes Br, the precursor M is 12b; step (iii) prepares the precursor N, namely pyrene borate . Use one equivalent of NBS reagent to bromide pyrene (direct bromination of bromine is also possible, but attention should be paid to controlling the titration rate, otherwise polybrominated pyrene is generated); the lithiated halogen atom is replaced by butyllithium, and the reaction is carried out at -78 degrees; Add methyl borate or isopropyl borate to react for 15-30 hours, then hydrolyze with acid to generate corresponding pyrene boronic acid, and then esterify with pinacol to obtain precursor N; or replace lithiated halogen atoms with butyllithium Afterwards, the precursor N can also be obtained by directly adding the corresponding borate ester, which is denoted as compound 13; the method adopted in step (iv) is the reaction of Suzuki, and the amount ratio of the two precursor substances for preparing compound I is compound 12a: compound 13 =1: 0.8～1.2 (the increase in the amount of compound 12a or 13 can improve the yield, but some waste of raw materials), the ratio of the reactants to prepare compound II is compound 12b: compound 13=1: 2～2.2 (the increase in the amount of compound 13 can Make productive rate improve, but raw material wastes some).

(2) Preparation of compound III and compound IV:

The synthetic route of precursor M is as follows:

Among them, step: (i) pyrene boronate (i.e. compound 13) reacts with excess 1,2-dibromobenzene (>1 equivalent) to generate compound 22 through suzuki reaction; step (ii) uses lithiation reagent (the most commonly used butyllithium) lithiated compound 22 was reacted at -78°C for 40 to 120 minutes to generate the corresponding lithium salt 23; step (iii) lithium salt 23 was the same as fluorenone (2-bromofluorenone or 2,7-dibromofluorenone ketone) for 50 to 90 minutes, and then acidified to generate the corresponding fluorenol 24; step (iv) finally undergoes an acid-catalyzed ring closure reaction (actually a Friedel-Craft reaction) to generate precursor M, that is, compound 25 (most A simple operation is to dissolve fluorenol 24 in glacial acetic acid, then heat to 90-110°C, drop hydrochloric acid, and stir for 1-5 hours to obtain the ring-closing product). Wherein, when X is H, the precursor M is 25a; when X is Br, the precursor M is 25b, and the precursor N is still compound 13;

When synthesizing the target product, Suzuki reaction is adopted. When compound III is synthesized, the amount ratio of substance is compound 25a: compound 13=1: 0.8～1.2: when compound IV is synthesized, the amount ratio of substance is compound 25b: compound 13=1: 2.0 ~2.2.

(3) Synthesis of Compound V and Compound VI:

The synthetic route of precursor N is as follows:

Among them, there are two methods for the synthesis of intermediate 31, the first one is generated by biphenyl and dichloroethane under the catalysis of aluminum chloride, the reaction time is 20 to 50 minutes, and the reaction temperature is 40 to 70°C (Friedel-Craft reaction ); the second is the catalytic hydrogenation of pyrene (Pd/C is the catalyst), and the room temperature reaction takes 20 to 30 minutes. Then bromination to obtain intermediate 32, the catalyst is anhydrous FeCl ₃ , the equivalent is 1-10% of the reactant, and the reaction time is 1-4 hours; then bromine water (1mmol bromine dissolved in carbon disulfide 20-60mL) is used to eliminate the bromination Hydrogen to get 2,7-dibromopyrene 33; dibromopyrene 33 replaces lithiated halogen atom by butyllithium (at -78 ° C), adding at least 2 times the equivalent of methyl borate or isopropyl borate, reaction 15 ~30 hours, then hydrolyze with acid to generate the corresponding pyrene bisboronic acid, and then esterify with pinacol to obtain pyrene bisboronic acid ester 34; or directly add the corresponding boron after butyllithium replaces the lithiated halogen atom Esters can also be used to obtain pyrene bis-boronate 34, and pyrene bis-boronate 23 is the precursor N.

When the precursor M is compound 25a, it is compound 34: compound 25a=1: 2.0～2.2 according to the amount of substance ratio, and compound V is obtained under the Suzuki reaction conditions; when the precursor M is compound 12a, it is compound 34 according to the amount of substance ratio: When compound 12a=1:2.0～2.2, compound VI can be obtained under Suzuki reaction conditions.

(4) Synthesis of compound VII, VIII:

The synthetic route of precursor N is as follows:

Wherein, accurate two equivalents of NBS reagent or bromine water are dropped into the pyrene solution, and the dropping time is greater than 2 (such as 2-5) hours. After the dropping, continue to stir at room temperature for 2 to 6 hours, and remove the solvent by distillation under reduced pressure (such as using The direct bromination of bromine also needs to add reducing agents such as sodium thiosulfate to remove excess bromine), and then recrystallize to obtain 1,6-dibromopyrene and 1,8-dibromopyrene mixture (the ratio of the two is about 1: 1) 41; Compound 41 replaces the lithiated halogen atom with butyl lithium (at -78°C), adds at least 2 times the equivalent of methyl borate or isopropyl borate to react for 15 to 30 hours, and then hydrolyzes with acid, then The corresponding pyrene bisboronic acid is generated, and then esterified with pinacol to obtain compound 42; or after butyllithium replaces the lithiated halogen atom, directly adding the corresponding borate ester can also obtain compound 42. Compound 42 is precursor N.

When the precursor M is compound 25a, compound 42:compound 25a=1:2.0～2.2 according to the amount of substance, Suzuki reaction conditions to obtain compound VII; when the precursor M is compound 12a, compound 42 according to the amount of substance : Compound 12a = 1: 2.0-2.2, Suzuki reaction conditions give compound VIII.

The structure of the material was characterized by nuclear magnetic resonance (NMR), chromatography-mass on-line (GC-MS), laser desorption time-of-flight mass spectrometry (LDI-TOF-MS), gel chromatography (GPC), and tested by thermogravimetric analysis and differential thermal analysis. The thermal stability of the materials was tested, their spectral properties were determined by UV and fluorescence analysis, and their electrochemical properties were characterized by cyclic voltammetry.

On this basis, devices were designed to evaluate various light emission behaviors of conjugated derivative materials of 9-phenyl-9-pyrenylfluorene substituted pyrene. Devices are designed and studied for carrier injection and transport performance, material luminescence performance, host-guest energy transfer behavior and light amplification behavior when used as white light and phosphorescent host materials. The transparent anode is made on a glass or plastic substrate, and then the hole injection and transport material is vacuum evaporated on the conductive layer, and the compound in the present invention is evaporated as a light-emitting layer or a doped host material, and then a layer of electron transport is evaporated. layer, and finally the cathode is evaporated. The experimental results show that the conjugated derivatives of pyrene substituted by 9-phenyl-9-pyrenylfluorene can be used as carrier injection and transport materials, luminescent materials, white light and phosphorescent host materials with excellent comprehensive performance. In addition, this type of compound material can be applied in the fields of organic electronics such as organic integrated circuits, organic solar cells, organic field effect transistors, dye lasers, organic nonlinear optical materials, and fluorescent probes.

Main advantage of the present invention:

1. The synthesis process is simple and the raw materials are cheap, so the cost is low.

2. Due to the existence of large conjugated aromatic rings such as pyrene, the hole injection and transport capabilities are effectively improved, and the device efficiency is also improved, and it may be used for carrier injection or transport layer materials.

3. By introducing 9-phenyl-9-pyrenylfluorene units, the thermal stability of the large aromatic ring of pyrene is improved, and it is also avoided that they are easy to crystallize and easily generate excitoassociates and exciplexes. shortcoming. Thus, the high stability of the 9-position diaryl substituted fluorene and the high efficiency of the large aromatic ring of pyrene can be combined.

4. Effective modulation of fluorescence emission spectrum and triplet energy level, thus forming a good host material.

5. It has high carrier transport ability and is suitable as transport material and OTFT material.

6. It has obvious light amplification phenomenon and is suitable as an organic laser material.

Description of drawings

Figure 1. Absorption and photoluminescence spectra of 2P9PPF, and solid-state luminescence spectra.

Figure 2. Absorption and photoluminescence spectra of DPPPF, and solid-state luminescence spectra.

Figure 3. Performance of device ITO/TCTA(8nm)/2P9PPF(30nm) or DPPPF(30nm)/BCP(40nm)/Mg:Ag(d1,d2). Among them, a) voltage-brightness curve b) current efficiency-current density c) power efficiency-current density.

Detailed ways

In order to better understand the content of the patent of the present invention, the technical solution of the present invention will be further described through specific examples below. Specifically, it includes synthesis, property determination and device preparation. However, these examples do not limit the present invention.

Example 1: Synthesis of 2-pyrenyl-9-phenyl-9-pyrenylfluorene (2P9PPF) (Compound I).

(1) Synthesis of 2-bromo-9-phenylfluoren-9-ol (2-Bromo-9-phenyl-fluoren-9-ol)

Use magnesium scraps (0.58g, 24mmol), a small amount of iodine and bromine benzyl ((4.48g, 29mmol) in anhydrous ether (or anhydrous tetrahydrofuran) (30mL) to make phenylmagnesium bromide Grignard reagent, the reagent used Dilute with 20mL of anhydrous ether, and then add anhydrous tetrahydrofuran dissolved with 2-bromofluorenone (3.77g, 14.6mmol) dropwise into Grignard reagent, stir for 4h, add saturated ammonium chloride solution for hydrogenolysis after cooling for 2h. The reaction mixture Extract twice with dichloromethane, wash with water, then dry with anhydrous magnesium sulfate.Use ethyl acetate/petroleum ether=10:1 as eluent column chromatography on silica gel to obtain light yellow solid (4.65g, 13.8mmol ), yield 94%)). ¹ HNMR (400MHz, CDCl3) δ (ppm): 7.65 (d, J = 8.0Hz, 1H); 7.44-7.55 (m, 3H); 7.32-7.4 (m, 3H); 7.23-7.31 (m, 5H) ; 2.45 (s, 1H); MS (m/z, EI, 70 eV): Calcd.for C ₁₉ H ₁₃ ⁷⁹ BrO 336.01, found 336; Calcd.for C ₁₉ H ₁₃ ⁸¹ BrO 338.01, found 338.

(2) Synthesis of 2-bromo-9-phenyl-9-pyrenylfluorene (2-bromo-9-phenyl1-9-pyrenylfluorene)

Pyrene (6g, 30mmol) and trifluoromethanesulfonic acid (6.0mmol) were dissolved in 200mL of chloroform, and then 2-bromo-9-phenylfluoren-9-ol (2.0g, 6mmol) dissolved in chloroform was gradually dropwise into the system, and the system was heated to 60° C. and stirred for 20 minutes. Add excess saturated sodium bicarbonate solution to end the reaction, separate the layers to obtain an organic phase, which is then washed twice with saturated sodium bicarbonate. The combined aqueous phases were extracted three times with dichloromethane, and the organic phases were combined and dried over anhydrous magnesium sulfate. A white solid (2.3 g, 79%) was obtained by silica gel column chromatography using petroleum ether/dichloromethane=5:1 as the eluent. ¹ HNMR (400MHz, CDCl3) δ (ppm): 7.90-8.20 (m, 8H); 7.78-7.86 (broad, 2H); 7.64-7.76 (m, 3H); 7.56-7.64 (broad, 1H); 7.52 ( d, J=8.0Hz, 1H); 7.39 (t, 8.0Hz, 1H); 7.16-7.26 (broad, 5H). LDI-TOF-MS (m/z): Calcd.for C ₃₅ H ₂₁ ⁷⁹ Br 520.1 , found 520.8; Calcd. for C ₃₅ H ₂₁ ⁸¹ Br 522.1, found 522.2.

(3) Synthesis of 1-(4,4,5,5-tetramethyl-1,3,2-dioxoboronate-2-yl)pyrene (1-(4,4,5,5-tetramethyl -1,3,2-dioxaborolan-2-yl)pyrene)

The DMF (150mL) solution of NBS (3.6g, 20mmol) was dropped into the DMF solution (250mL) of pyrene (8.1g, 40mmol) dropwise, and then stirred for 2 hours after the dripping was completed. After the reaction system was treated with hydrochloric acid, it was washed with di The aqueous phase was extracted several times with dichloromethane. The solvent was distilled off under reduced pressure, and then the origin pigment was removed by column chromatography using petroleum ether as an eluent. The obtained crude product was dried in a vacuum oven. After dissolving this product in anhydrous THF and cooling to -78°C, n-butyllithium (1.6M solution in cyclohexane) (25 mL, 40 mmol) was dropped into the system with a syringe. After the system was reacted at -78°C for 2 hours, methyl triborate (20g, 190mmol) was reacted at -78°C for another 2 hours, then the system was allowed to rise slowly to room temperature for another 36 hours, and 2M hydrochloric acid (300mL) was added to hydrolyze 8 Hour. Add saturated sodium bicarbonate solution to separate the layers, and extract twice more with dichloromethane. The combined organic phase was dried with anhydrous magnesium sulfate, the solvent was removed by rotary evaporation, and vacuum-dried at 30°C. This product was dissolved in dichloromethane, added pinacol (23g, 200mmol) and refluxed for 4 hours. The solvent was removed by rotary evaporation, and the product (3.6 g, 55%) was obtained by column chromatography using petroleum ether/ethyl acetate=(10:1) as the eluent. ¹ HNMR (400MHz, CDCl3) δ (ppm): 9.10 (d, J = 9.2Hz, 1H); 8.56 (d, J = 7.6Hz, 1H); 8.25-7.98 (m, 7H); 1.51 (s, 12H ).LDI-TOF-MS(m/z): Calcd.for C ₂₂ H ₂₁ ¹⁰ BO ₂ 328.2, found 328.1; Calcd.for C ₂₂ H ₂₁ ¹¹ BO ₂ 329.2, found 329.1.

(4) Synthesis of 2-pyrenyl-9-phenyl-9-pyrenylfluorene (2-pyrenyl-9-phenyl-9-pyrenylfluroene) (2P9PPF)

2-Bromo-9-phenyl-9-pyrenylfluorene (0.78g, 1.5mmol), 1-(4,4,5,5-tetramethyl-1,3,2-dioxoboronate- 2-yl)pyrene (0.5 g, 1.5 mmol), palladium tetrakis(triphenylphosphine) (0.05 mmol) and 2M potassium carbonate solution were mixed in a flask containing 150 mL of toluene. The reaction system was heated to 90°C for 48 hours. Add saturated sodium bicarbonate solution to end the reaction, extract twice with dichloromethane, dry the combined organic phase with anhydrous magnesium sulfate, remove the solvent by rotary evaporation, use petroleum ether/dichloromethane = 4:1 as eluent silica gel Column chromatography gave a white solid (0.75 g, 78%). ¹ HNMR (400MHz, CDCl3) δ (ppm): 8.15 (t, J = 9.2Hz, 4H); 8.08-7.90 (m, 15H); 7.90-7.80 (d, J = 8.0Hz, 2H); 7.76-7.66 (t, J=9.2Hz, 3H); 7.46(t, J=7.6Hz); 7.40-7.30(m, 3H); 7.30-7.18(m, 2H). ¹³ CNMR(400MHz, CDCl3)δ(ppm) ：152.35，147.18，140.81，140.05，139.22，137.77，131.63，131.23，131.05，130.73，130.58，130.39，129.82，129.13，128.55，128.26，128.11，127.79，127.68，127.58，126.90，126.82，126.40，126.17，125.37 , 125.24, 125.18, 124.94, 124.83, 120.82, 120.71, 67.18. LDI-TOF-MS (m/z): Calcd. for C ₅₁ H ₃₀ 642.2, found 642.4. Anal. Calcd. C, 95.30; H, 4.70. found C, 95.25, H, 4.62.

The chemical structural formula of 2P9PPF is as follows:

Compound I

Embodiment 2: to the ultraviolet absorption spectrum of the trimer 2P9PPF (product in embodiment 1) containing anthracene and pyrene fluorene in 9 positions, photoluminescence spectrum, spectral thermal stability and quantum efficiency measurement:

Dissolve 2P9PPF in dichloromethane dilute solution, and use Shimadzu UV-3150 ultraviolet-visible spectrometer and RF-530XPC fluorescence spectrometer to measure the absorption and emission spectra. The photoluminescence spectrum was measured at the maximum absorption wavelength (351 nm) of ultraviolet absorption. The solid film is formed by dropping the solution on a transparent glass plate after the solvent evaporates. The fluorescence quantum efficiency of the solution was measured by using a 10 ⁻⁶ M solution of 9,10-diphenylanthracene (quantum efficiency 0.9) in cyclohexane as a standard.

The maximum absorption peak of the 2P9PPF solution at greater than 300nm is 351nm, and the maximum emission of the photoluminescence spectrum is 408nm.

The maximum emission wavelength of the solid film is 462nm. There is no obvious change in the spectrum after the solid film is annealed at 150°C for 24 hours under nitrogen atmosphere, which shows that the spectral stability is very good due to the good thermal stability. See attached drawing 1 for details.

Example 3: Synthesis and spectrometry of 2,7-dipyrenyl-9-phenyl-9-pyrenylfluorene (DPPPF) (compound II).

The synthetic method similar to 2P9PPF can synthesize 2,7-dipyrenyl-9-phenyl-9-pyrenylfluorene (DPPPF), but 2,7-dibromofluorene is used for fluorene, and during the even chain reaction, 1-(4 , the amount of 4,5,5-tetramethyl-1,3,2-dioxoboronate 2-yl)pyrene should be greater than that of 2,7-dibromo-9-phenyl-9-pyrenylfluorene double.

The NMR, MS and elemental analysis data of DPPPF are as follows. ¹ H-NMR (400MHz, CDCl3) δ (ppm): 8.24-8.12 (m, 8H); 8.10-7.92 (m, 19H); 7.77 (dd, J=8.4Hz, 1.6Hz, 2H); 7.64 (d , 8.4Hz, 2H); 7.46 (s, 2H); 7.34-7.28 (s, 3H); 7.27-7.22 (m, 2H). ¹³ C-NMR (400MHz, CDCl3) δ (ppm): 152.80, 140.92, 139.04，137.75，131.63，131.06，130.76，130.62，129.27，128.56，128.48，127.85，127.60，126.98，126.57，126.18，125.37，125.28，125.04，124.98，124.88.LDl-TOF-MS(m/z)：Calcd .for C ₆₇ H ₃₈ 842.3, found 842.2. Anal. Calcd. C, 95.46; H, 4.54; found C, 95.36; H, 4.58.

Using a method similar to 2P9PPF can measure UV absorption and photoluminescence spectra. The photoluminescence spectrum was measured at the maximum absorption wavelength (352 nm) of ultraviolet absorption.

The maximum absorption peak of TPPF solution above 300nm is 352nm, and the maximum emission of photoluminescence spectrum is 424nm.

The maximum emission wavelength of the solid film is 450nm. The solid film was annealed at 150°C for 24 hours under a nitrogen atmosphere, and the spectrum did not change significantly, which indicated that the spectral stability was very good due to the good thermal stability. See attached drawing 2 for details.

The structure of DPPPF is as follows:

Compound II

Embodiment 4: the electroluminescence device preparation of 2P9PPF and DPPPF

The device structure is ITO/TCTA(8nm)/2P9PPF or DPPPF(30nm)/BCP(40nm)/Mg:Ag. The specific preparation method is to sequentially mix 4,4',4"-tri(N-carbazolyl)triphenylamine (4,4',4"-tri(N-carbazolyl)triphenylamine) under a pressure of 10 ^-4 Pa (TCTA), 2P9PPF or DPPPF, 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline ) (BCP), and then steam the Mg:Ag alloy electrode. The start-up voltage of the device is 4 and 3.5 V, the maximum brightness is ~17000cd/m ² and ~19000cd/m ² , the maximum current efficiency is greater than 2.0 and 2.5cd/A, and the maximum power efficiency is greater than 0.6 and 0.9lm/w. See attached drawing 4 for details.

Example 5: Synthesis of 2,7-bis(9'-phenyl-9'-pyrenylfluoren-2-yl)pyrene (2,7-di(9'-phenyl-9'-pyrenylfluoren-2-yl) pyrene) (Compound VI).

(1) Synthesis of 2,7-dibromopyrene. In 2,7-dibromo-4,5,7,9-tetrahydropyrene (4.41g, 12.1mmol) in carbon disulfide (300mL) solution dropwise into bromine (4.26g, 26.6mmol) in carbon disulfide (300mL) solution , the time for adding drops is 3 hours. The reaction was stirred for an additional hour. The solvent was distilled off to obtain 4.3 g of the product with a yield of 99%. LDI-TOF-MASS: 358.

(2) Synthetic pyrene bis-boronate, synthetic method is the same as pyrene mono-boronate (see embodiment 1)

(3) Preparation of product by coupling chain reaction: 2-bromo-9-phenyl-9-pyrenylfluorene and pyrene bisboronate can be used to obtain the product through Suzuki reaction. LDI-TOF-MASS: 1083.

Compound VI

The synthetic methods of compounds III, IV, V, VII, VIII are all similar to compounds I, II. Its spectral performance, spectral stability and electroluminescent performance are similar to compounds I and II.

Claims (4)

1. The conjugated derivative material of pyrene substituted by 9-phenyl-9-pyrenylfluorene is characterized in that it has the following general structural formula: Structural Formula 1 Structural Formula 2 Among them, A is (9-phenyl-9-pyrenyl) fluorenyl or (spiro-9-phenyl-9-pyrenyl) fluorenyl, wherein fluorenyl is 2-position monosubstituted fluorenyl or 2-position and 7 A disubstituted fluorenyl group; B is a hydrogen atom or a monosubstituted pyrenyl group. 2. The conjugated derivative material according to claim 1, characterized in that it has any one of the following structures: (1) For structural formula one ① When A is a monosubstituted (9-phenyl-9-pyrenyl) fluorenyl group and B is hydrogen, the structure is as follows:

           Compound I, Mw: 642.8 ② When A is a disubstituted (9-phenyl-9-pyrenyl) fluorenyl group and B is a pyrenyl group, the structure is as follows:

           Compound II, Mw: 843.0 ③ When A is a monosubstituted spiro-(9-phenyl-9-pyrenyl)fluorenyl, and B is hydrogen, the structure is as follows: Compound III, Mw: 640.8 ④ When A is a disubstituted spiro-(9-phenyl-9-pyrenyl)fluorenyl group and B is a pyrenyl group, the structure is as follows:

         Compound IV, Mw: 841.0 (2) For the general structural formula two ① When A is monosubstituted spiro-(9-phenyl-9-pyrenyl)fluorenyl, and pyrene is 2 and 7 double-substituted, the structure is as follows:            Compound V, Mw: 1079.3 ② When A is monosubstituted (9-phenyl-9-pyrenyl) fluorenyl, and pyrene is 2, 7 double-substituted, the structure is as follows:

      Compound VI, Mw: 1083.3 ③When A is a monosubstituted spiro-(9-phenyl-9-pyrenyl)fluorenyl, and pyrene is a mixture of 1,6 disubstituted and 3,6 disubstituted, the structure is as follows: * for another replacement position           Compound VII, Mw: 1066.3 ④ When A is a monosubstituted (9-phenyl-9-pyrenyl) fluorenyl group, and pyrene is a mixture of 1,6 disubstituted and 3,6 disubstituted, the structure is as follows: * for another replacement position          Compound VIII, Mw: 1070.3 3. A method for preparing the conjugated derivative material as claimed in claim 1 or 2, characterized in that the Suzuki chain reaction is adopted: M+N→Target Where M and N are two reaction precursors, Target represents the target product obtained, the Suzuki even chain reaction conditions are Ph(PPh ₃ ) ₄ /K ₂ CO ₃ or NaCO ₃ /toluene, and the reaction temperature is 60-100°C. The reaction time is 10 to 36 hours, and the reaction is anaerobic reaction, protected from light; where: (1) Preparation of compound I and compound II: Its preparation route is as follows:

Wherein, step (i) bromobenzene generates Grignard reagent with magnesium under anhydrous and oxygen-free conditions, and then reacts with fluorenone to generate corresponding Grignard magnesium salt for 4 to 6 hours, and finally acidifies the generated magnesium hydrochloride to obtain the compound 11; step (ii) to prepare precursor M, the Friedel-Craft reaction of fluorenol and excess pyrene under acid catalysis, specifically drop the dissolved fluorenol into the solution of excess pyrene, add acid, and heat up to 40-80 ℃, the reaction time is 10 to 30 minutes, and after separation and purification, two precursors M are obtained. When X takes H, the precursor M is 12a; when X takes Br, the precursor M is 12b; step (iii) preparation Precursor N, that is, pyrene boronate, uses one equivalent of NBS reagent pyrene bromide, and replaces the lithiated halogen atom with butyllithium, and the reaction is carried out at -78 degrees; add methyl borate or isopropyl borate to react for 15~ After 30 hours, it is hydrolyzed with acid to generate the corresponding pyrene boronic acid, which is then esterified with pinacol to obtain the precursor N; Precursor N is denoted as compound 13; step (iv) adopts the reaction of Suzuki, the amount ratio of the two precursor substances of compound I is compound 12a: compound 13=1: 0.8～1.2, the reactant ratio of preparing compound II is Compound 12b:Compound 13=1:2～2.2; (1) Preparation of compound III and compound IV: The synthetic route of precursor M is as follows:

Wherein, step (i) pyrene borate is reacted with excess 1,2-dibromobenzene to generate compound 22 through suzuki; step (ii) reacts lithiated compound 22 with a lithiation reagent at -78°C for 40 to 120 minutes, Generate the corresponding lithium salt 23; step (iii) react lithium salt 23 with fluorenone for 50-90 minutes, and then acidify to generate the corresponding fluorenol 24; step (iv) finally undergo ring closure reaction under acid catalysis to generate precursor M, That is, compound 25; wherein, when X is H, the precursor M is 25a; when X is Br, the precursor M is 25b, and the precursor N is still compound 13; Using Suzuki reaction, when compound III is synthesized, the amount ratio of substances is compound 25a: compound 13=1: 0.8～1.2; when compound IV is synthesized, the amount ratio of substances is compound 25b: compound 13=1: 2.0～2.2; (3) Synthesis of compound V and compound VI: The synthetic route of precursor N is as follows: Among them, there are two methods for the synthesis of intermediate 31, the first is generated by biphenyl and dichloroethane under the catalysis of aluminum chloride, the reaction time is 20 to 50 minutes, and the reaction temperature is 40 to 70 ° C; the second is Catalytic hydrogenation of pyrene, reaction at room temperature for 20 to 30 minutes, and then bromination to obtain intermediate 32, the catalyst is anhydrous FeCl ₃ , the equivalent is 1 to 10% of the reactant, and the reaction time is 1 to 4 hours; Bromine water eliminates hydrogen bromide to obtain 2,7-dibromopyrene 33; dibromopyrene 33 replaces lithiated halogen atoms with butyllithium, adds at least 2 times the equivalent of methyl borate or isopropyl borate, and reacts for 15 to 30 hours , and then hydrolyzed with acid to generate the corresponding pyrene bisboronic acid, and then esterified with pinacol to obtain pyrene bisboronic acid ester 34; Pyrene bisboronate 34 can be obtained; When the precursor M is compound 25a, it is compound 34: compound 25a=1: 2.0～2.2 according to the amount of substance ratio, and compound V is obtained under the Suzuki reaction conditions; when the precursor M is compound 12a, it is compound 34 according to the amount of substance ratio: When compound 12a=1:2.0～2.2, the Suzuki reaction conditions give compound VI; (4) Synthesis of compound VII, VIII: The synthetic route of precursor N is as follows:

Among them, accurate two equivalents of NBS reagent or bromine water is dropped into the pyrene solution, and the dropping time is longer than 2 hours. After the dropping is completed, the stirring is continued at room temperature for 2 to 6 hours, the solvent is distilled off under reduced pressure, and then recrystallized to obtain 1,6- The mixture 41 of dibromopyrene and 1,8-dibromopyrene; compound 41 replaces the lithiated halogen atom by butyllithium, and adds at least 2 times the equivalent of methyl borate or isopropyl borate to react for 15 to 30 hours, and then use acid Hydrolysis will generate the corresponding pyrene bisboronic acid, and then esterify with pinacol to obtain compound 42; or after butyllithium replaces the lithiated halogen atom, directly add the corresponding borate ester to obtain compound 42; When the precursor M is compound 25a, compound 42:compound 25a=1:2.0～2.2 according to the amount of substance, Suzuki reaction conditions to obtain compound VII; when the precursor M is compound 12a, compound 42 according to the amount of substance : Compound 12a = 1: 2.0-2.2, Suzuki reaction conditions give compound VIII. 4. The application of the conjugated derivative according to claim 1 or 2, characterized in that it is used as a light-emitting layer material of an organic electroluminescence device, a host material for white light, a host material for phosphorescence, or an electron or hole carrier transport material , organic integrated circuit materials, organic laser materials, semiconductor materials for organic field effect transistors, organic solar cell materials and organic nonlinear optical materials.

Images