White light emitting material, preparation method and application thereof

Abstract

This invention discloses a white light-emitting material, comprising bridging units Ar and different light-emitting units, the light-emitting units being connected through bridging units Ar. This invention also discloses a preparation method and application of the above-mentioned light-emitting material. The white light-emitting material obtained by this invention is constructed by embedding TADF light-emitting units of different colors into the polymer backbone, designing different types of TADF units and bridging units, and then applying it to electroluminescent devices. The white light-emitting material obtained by this invention uses a small amount of TADF units, and the content is easily adjustable. The synthesis method is simple and can be mass-produced. It has good solubility and film-forming properties, is suitable for solution processing, and has a broad emission spectrum. The electroluminescent devices made from it have tunable light color, and light color conversion can be achieved by simply adjusting the voltage, and it has good electroluminescent performance.

Description

Technical Field

[0001] This invention belongs to the field of organic light-emitting materials, specifically relating to a white light-emitting material, its preparation method, and its application. Background Technology

[0002] Solution-processed white organic light-emitting diodes (OLEDs) have attracted significant attention in the fields of screen display and solid-state lighting due to their low cost, large-area processing capability, and flexible display, demonstrating great application potential. Among them, color-tunable white OLEDs can adapt to different life scenarios, making them a light environment-friendly material. For example, high-brightness cool light during the day energizes and invigorates people, while dim warm white light at night avoids eye fatigue and sleep disturbances. Therefore, color-tunable white OLEDs can meet the different color light needs of people's daily natural circadian rhythms. In recent years, thermally activated delayed fluorescence (TADF) polymers have attracted widespread attention due to their theoretically achievable 100% internal quantum transfer efficiency. TADF polymers possess a small singlet and triplet energy difference (ΔE). ST The internal quantum efficiency (EV) of this polymer is typically less than 0.30 eV. Therefore, the triplet energy level of this polymer can absorb heat from the surrounding environment and undergo reverse intersystem crossing to the singlet state, achieving 100% internal quantum conversion efficiency. Currently, the color gamut of TADF polymers covers the entire visible spectrum, and the external quantum efficiency of monochromatic OLED devices from blue, green to red has exceeded 18%, comparable to commercially available phosphorescent materials. However, no work on color-tunable WOLEDs based on TADF polymers has been reported to date.

[0003] There are generally two methods for constructing WOLED devices based on TADF polymers: one is to use a host / TADF polymer physical mixture system as the emissive layer, and the other is to use a single white polymer (TADF) as the emissive layer. The first strategy, involving two or more materials, often results in unavoidable phase separation, leading to dark spots and a significant decrease in device performance. Conversely, using a single TADF-SWP as the emissive layer effectively avoids phase separation, resulting in a smooth film morphology and facilitating high-efficiency electroluminescent device performance. TADF-SWPs are typically constructed from donors and acceptors. These polymers exhibit strong intramolecular charge transfer and polarity, leading to severe intermolecular and internal component interactions, resulting in low luminous efficiency. Furthermore, since white light requires the simultaneous presence of blue, green, and red colors, TADF-SWPs need to contain multiple light-emitting units to broaden the polymer's emission spectrum, thus approximating the white light spectrum. Achieving a balance between energy transfer and exciton extraction among the various luminescent components within TADF-SWP is a significant challenge. Furthermore, to realize the tunable color characteristic of TAD-SWP, precise control of the proportions of the various luminescent components within the polymer is required. This allows for incomplete energy transfer between the different luminescent units, resulting in white light emission with tunable color. Therefore, developing solution-processable, color-tunable WOLEDs based on TADF-SWP is both a tremendous challenge and an urgent need. Summary of the Invention

[0004] Therefore, the technical problem to be solved by the present invention is that there is no existing solution-processable color-tunable WOLED based on TADF-SWP, thereby providing a method for preparing white light emitting materials and their applications.

[0005] The present invention adopts the following technical solution:

[0006] This invention provides a white light-emitting material, wherein the light-emitting material has the structure shown in Formula I:

[0007]

[0008] Among them, the light-emitting unit B includes an aromatic heterocycle of C12-C200 that emits blue light, the light-emitting unit G includes an aromatic heterocycle of C12-C200 that emits green light, and the light-emitting unit R includes an aromatic heterocycle of C12-C200 that emits red light.

[0009] The bridging unit Ar includes aromatic rings or aromatic heterocycles of C6-C200;

[0010] n is 1 to 800, 0 < m < 1, 0 < h < 1, 0 ≤ x < 1, 0 ≤ y < 1, 0 < z < 1, where x and y are not both equal to 0.

[0011] Furthermore, the luminescent unit B is a blue luminescent unit based on thermally activated delayed fluorescence, and its aromatic heterocycle has one or more substituents, which are independently selected from H, D, F, Cl, Br, I, -CN, -NO2, -CF3, -OH, -SH, -NH, -NH2, C1-C30 straight alkanes, C3-C60 branched alkanes, C3-C30 cycloalkyl, C1-C60 alkoxy / alkoxythiol, and C6-C60 aryl / heteroaryl / ether / aromatic heteroether; wherein, the heteroatom of the heteroaromatic group can be independently selected from Si, Ge, N, P, O, S, and Se;

[0012] The luminescent unit G is a green luminescent unit based on thermally activated delayed fluorescence. Its aromatic heterocycle has one or more substituents, which are independently selected from H, D, F, Cl, Br, I, -CN, -NO2, -CF3, -OH, -SH, -NH, -NH2, C1-C30 straight alkanes, C3-C60 branched alkanes, C3-C30 cycloalkyl, C1-C60 alkoxy / alkoxythiol, and C6-C60 aryl / heteroaryl / ether / aromatic heteroether; wherein, the heteroatom of the heteroaromatic group can be independently selected from Si, Ge, N, P, O, S, and Se.

[0013] The luminescent unit R is a red luminescent unit based on thermally activated delayed fluorescence. Its aromatic heterocycle has one or more substituents, which are independently selected from H, D, F, Cl, Br, I, -CN, -NO2, -CF3, -OH, -SH, -NH, -NH2, C1-C30 straight alkanes, C3-C60 branched alkanes, C3-C30 cycloalkyl, C1-C60 alkoxy / alkoxythiol, and C6-C60 aryl / heteroaryl / ether / aromatic heteroether; wherein, the heteroatom of the heteroaromatic group can be independently selected from Si, Ge, N, P, O, S, and Se.

[0014] The bridging unit Ar includes an aromatic ring or aromatic heterocycle with substituents, wherein the substituents are independently selected from H, D, F, Cl, Br, I, -CN, -NO2, -CF3, -OH, -SH, -NH, -NH2, C1-C30 straight alkanes, C3-C60 branched alkanes, C3-C30 cycloalkyl, C1-C60 alkoxy / alkoxythiol, and C6-C60 aryl / heteroaryl / ether / aromatic heteroether; wherein the heteroatom of the heteroaromatic group can be independently selected from Si, Ge, N, P, O, S, and Se.

[0015] The x is 0≤x≤0.80, more preferably 0≤x≤0.70, and most preferably 0≤x≤0.60; the y is 0≤y≤0.60, more preferably 0≤y≤0.50, and most preferably 0≤y≤0.40; the z is 0.0001≤z≤0.35, more preferably 0.0005≤z≤0.20, and most preferably 0.0005≤z≤0.10.

[0016] Preferably, the light-emitting unit B includes the following basic structures i-1 to i-12, and each basic structure may further include various substituent-derived structures:

[0017]

[0018] Among them, W1, W2, W3, W4, W5, W6, W7, W8, W9 and W 10 The heteroatoms of the heteroaromatic groups are independently selected from one or more of the following: H, D, F, Cl, Br, I, -CN, -NO2, -CF3, -OH, -SH, -NH, -NH2, C1-C30 straight alkanes, C3-C60 branched alkanes, C3-C30 cycloalkyl groups, C1-C60 alkoxy / alkoxythiol groups, and C6-C60 aryl / heteroaryl / ether / aromatic heteroether groups; wherein the heteroatoms of the heteroaromatic groups are independently selected from Si, Ge, N, P, O, S, and Se.

[0019] The light-emitting unit G includes the following basic structures ii-1 to ii-17, and each basic structure may also contain various substituent-derived structures:

[0020]

[0021] Wherein, Q1, Q2, Q3, Q4, Q5, Q6, Q7 and Q8 are independently selected from one or more H, D, F, Cl, Br, I, -NO2, -CF3, -OH, -SH, -NH, -NH2, C1-C30 straight alkanes, C3-C60 branched alkanes, C3-C30 cycloalkyl, C1-C60 alkoxy / alkoxythiol, C6-C60 aryl / heteroaryl / ether / aromatic heteroether; wherein, the heteroatoms of the heteroaromatic groups are independently selected from Si, Ge, N, P, O, S, Se.

[0022] The luminescent unit R includes the following basic structures iii-1 to iii-18, and each basic structure may also contain various substituent-derived structures:

[0023]

[0024] Wherein, P1, P2, P3, P4, P5, P6, P7 and P8 are independently selected from linear alkanes containing one or more H, D, F, Cl, Br, I, -NO2, -CN, -CF3, -OH, -SH, -NH, -NH2, C1-C30, branched alkanes, C3-C60, cycloalkyl, C1-C60, alkoxy / alkimitol, C6-C60, aryl / heteroaryl / ether / aromatic heteroether; wherein, the heteroatoms of the heteroaromatic groups are independently selected from Si, Ge, N, P, O, S, Se.

[0025] The bridging unit Ar includes the basic structures iv-1 to iv-36 as shown below, and each basic structure can also contain various substituent-derived structures:

[0026]

[0027]

[0028] Wherein, Q1, Q2, Q3 and Q4 are independently selected from one or more H, D, F, Cl, Br, I, -CN, -NO2, -CF3, -OH, -SH, -NH, -NH2, C1-C30 straight alkanes, C3-C60 branched alkanes, C3-C30 cycloalkyl, C1-C60 alkoxy / alkoxythiol, C6-C60 aryl / heteroaryl / ether / aromatic heteroether; wherein, the heteroatoms of the heteroaromatic groups are independently selected from Si, Ge, N, P, O, S, Se.

[0029] Furthermore, the white light-emitting material comprises the structures shown in formulas 1-1 to 3-35 below. These structural formulas are merely illustrative of the invention's concept; any appropriate and common modifications made based on them should be included within the scope of protection of this invention. For example, replacing the light-emitting unit B in the following molecules with other light-emitting units of formulas i-1 to i-12, or replacing the light-emitting unit G in the following molecules with other light-emitting units of formulas ii-1 to ii-17, or replacing the light-emitting unit R in the following molecules with other light-emitting units of formulas iii-1 to iii-18, or replacing the bridging unit Ar in the following molecules with other bridging units of formulas iv-1 to iv-36 in claim 7:

[0030]

[0031]

[0032]

[0033]

[0034]

[0035]

[0036]

[0037]

[0038]

[0039]

[0040]

[0041]

[0042] This invention also provides a method for preparing the above-mentioned white light emitting material.

[0043] By coupling compounds having structures of formula II and formula IV with compounds having structures of formula V and formula VI, luminescent materials with the structure shown in formula I are obtained; or

[0044] Alternatively, compounds having structures of formula III and formula IV can be coupled with compounds having structures of formula V and formula VI to obtain luminescent materials with the structure shown in formula I.

[0045] Alternatively, compounds having structures of formula II, formula III, and formula IV can be coupled with compounds having structures of formula V and formula VI to obtain luminescent materials with the structure shown in formula I.

[0046] Alternatively, compounds having structures of formula VII and formula IX can be coupled with compounds having structures of formula V and formula VI to obtain luminescent materials with the structure shown in formula I; or

[0047] Alternatively, compounds having structures of formula VIII and formula IX can be coupled with compounds having structures of formula V and formula VI to obtain luminescent materials with the structure shown in formula I.

[0048] Alternatively, compounds having structures of formula VII, VIII, and IX can be coupled with compounds having structures of formula V and VI to obtain luminescent materials with the structure shown in formula I.

[0049]

[0050] This invention also provides applications of white light-emitting materials, which are used in the fabrication of electroluminescent devices, such as WOLEDs.

[0051] The technical solution of this invention has the following advantages:

[0052] (1) The white light-emitting material obtained in this invention is constructed by embedding TADF light-emitting units of different colors into the polymer backbone and designing different types of TADF units and bridging units, and then applying it to electroluminescent devices. This invention achieves multi-peak emission spectra by adjusting the content of each light-emitting component through fine-matrix manipulation and utilizing the incomplete energy transfer of various internal components, thus obtaining a white light polymer. This provides a simple and feasible approach for developing solution-processed white OLED devices, demonstrating broad application prospects. Furthermore, devices prepared from this type of material also exhibit voltage-dependent tunable light color characteristics.

[0053] (2) In the white light emitting material obtained by the present invention, there is a certain angle between the bridging unit Ar and the TADF emitting unit, which causes the molecular structure to be non-planar and reduces the aggregation characteristics of the emitting unit; the substituents on the bridging unit Ar are used to increase the solubility of the molecule, while introducing steric hindrance to reduce intermolecular aggregation.

[0054] (3) The white light emitting material obtained by this invention has a small amount of TADF unit and the content is easy to adjust. The synthesis method is simple and it can be mass-produced. It has good solubility and film-forming properties, is suitable for solution processing, and has a wide emission spectrum. The electroluminescent device made from it has the characteristic of adjustable light color. The light color conversion can be achieved by simply adjusting the voltage, and it has good electroluminescent performance. Attached Figure Description

[0055] To more clearly illustrate the specific embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the specific embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are some embodiments of the present invention. For those skilled in the art, other drawings can be obtained from these drawings without creative effort.

[0056] Figure 1 The absorption, room temperature fluorescence, and low temperature phosphorescence spectra of the thin film made from the white light emitting material obtained in Example 1 of this invention are shown.

[0057] Figure 2 The absorption, room temperature fluorescence, and low temperature phosphorescence spectra of the thin film made from the white light emitting material obtained in Example 2 of this invention are shown.

[0058] Figure 3 The absorption, room temperature fluorescence, and low temperature phosphorescence spectra of the thin film made from the white light emitting material obtained in Example 4 of this invention are shown.

[0059] Figure 4 The absorption, room temperature fluorescence, and low temperature phosphorescence spectra of the thin film made from the white light emitting material obtained in Example 7 of this invention are shown.

[0060] Figure 5 This is the transient fluorescence decay spectrum of the thin film prepared from the white light emitting material obtained in Example 1 of this invention;

[0061] Figure 6 This is the transient fluorescence decay spectrum of the thin film prepared from the white light emitting material obtained in Example 2 of this invention;

[0062] Figure 7 This is a current density-voltage-brightness curve of the device made from the white light emitting material obtained in Examples 1, 2, 4 and 7 of this invention;

[0063] Figure 8 This is an external quantum efficiency-brightness curve of the device made from the white light emitting material obtained in Examples 1, 2, 4 and 7 of this invention;

[0064] Figure 9 This is a current efficiency-brightness curve of the device made from the white light emitting material obtained in Examples 1, 2, 4 and 7 of this invention.

[0065] Figure 10 This is a power efficiency-brightness curve of the device made from the white light emitting material obtained in Examples 1, 2, 4 and 7 of this invention;

[0066] Figure 11 This is a graph showing the electroluminescence spectrum of a device made from the white light-emitting material obtained in Example 1 of this invention as a function of voltage.

[0067] Figure 12 This is a graph showing the electroluminescence spectrum of a device made from the white light-emitting material obtained in Example 2 of this invention as a function of voltage.

[0068] Figure 13 This is a graph showing the electroluminescence spectrum of a device made from the white light-emitting material obtained in Example 4 of the present invention as a function of voltage.

[0069] Figure 14 This is a graph showing the electroluminescence spectrum of a device made from the white light-emitting material obtained in Example 7 of the present invention as a function of voltage.

[0070] Figure 15 This is an atomic force measurement height diagram of the chlorobenzene solution spin-coated thin film of the white light emitting material obtained in Example 1 of this invention;

[0071] Figure 16 This is an atomic force measurement height diagram of the chlorobenzene solution spin-coated thin film of the white light emitting material obtained in Example 2 of the present invention;

[0072] Figure 17 This is an atomic force measurement height diagram of the chlorobenzene solution spin-coated thin film of the white light emitting material obtained in Example 4 of this invention;

[0073] Figure 18 This is an atomic force diagram of the height of the thin film spin-coated with chlorobenzene solution of the white light emitting material obtained in Example 7 of this invention. Detailed Implementation

[0074] The following embodiments are provided to better understand the present invention and are not limited to the preferred embodiments described. They do not constitute a limitation on the content and scope of protection of the present invention. Any product that is the same as or similar to the present invention, derived by any person under the guidance of the present invention or by combining the features of the present invention with other prior art, falls within the protection scope of the present invention.

[0075] For experiments where specific steps or conditions are not specified, the procedures and conditions described in the literature within this field can be followed. Reagents or instruments whose manufacturers are not specified are all commercially available standard products.

[0076] The white light-emitting materials obtained in Examples 1-7 of the specific embodiments of the present invention correspond to the compounds with the following structures in the specification.

[0077]

[0078]

[0079] Example 1

[0080] This embodiment provides a method for preparing a white light-emitting material, and the specific preparation process is as follows:

[0081]

[0082] (1) 2-(N-phenyl)aminobenzoate methyl ester (9.1 g, 40.0 mmol) was added to a 500 mL three-necked flask, the gas was purged several times under argon protection, anhydrous and oxygen-free tetrahydrofuran (20 mL) was added and stirred to dissolve, and then the tetrahydrofuran solution of freshly prepared Grignard reagent hexyl magnesium bromide (160.0 mmol) was slowly added to the reaction system. After the addition was complete, the reaction was carried out at room temperature for 14 hours. The reaction solution was poured into a dilute hydrochloric acid aqueous solution (400 mL, 1 mol / L), extracted with dichloromethane, and the solvent was removed by rotary evaporation of the organic phase under reduced pressure to obtain the intermediate. The intermediate, 40 mL of glacial acetic acid and 10 mL of concentrated hydrochloric acid were added to a 250 mL single-necked flask and refluxed at 80 °C for 50 hours. After cooling to room temperature, the reaction solution was poured into 200 mL of water, extracted with dichloromethane, dried with anhydrous sodium sulfate, filtered, and the solvent was removed by rotary evaporation of the organic phase under reduced pressure. The crude product was separated by silica gel column chromatography (dichloromethane / petroleum ether, v / v = 1:3). After removing the solvent by rotary evaporation under reduced pressure, 6 mL of petroleum ether was added for dilution. The product was recrystallized at room temperature and then recrystallized in a refrigerator. After filtration, the filter cake was washed with ethanol to obtain 7.6 g of pale green crystals, which was compound 1, with a yield of 55%. 1 H NMR (400MHz, DMSO-d6): δ (ppm) 8.57 (s, 1H), 7.18 (d, J = 7.1Hz, 2H), 6.98 (d, J = 15.0Hz, 2H), 6.73 (d, J = 14.9Hz, 2 H),6.64(d,J=9.0Hz,2H),1.87–1.73(m,4H),1.13–0.98(m,13H),0.84(t,J=14.9Hz,5H),0.74(t,J=6.9Hz,6H).

[0083] (2) Compound 1 (500 mg, 1.43 mmol), 2-(4-bromophenyl)-[1,3,5]triazine 583 mg (1.50 mmol), palladium acetate (16.1 mg, 0.072 mmol), tris(tert-butylphosphine)tetrafluoroborate (75 mg, 0.257 mmol), and potassium carbonate (593 mg, 4.29 mmol) were added to a 100 mL two-necked flask. The mixture was evacuated and purged with argon three times. Anhydrous and oxygen-free toluene (15 mL) was then added. The reaction was carried out at 120 °C for 15 hours. After cooling to room temperature, the mixture was extracted with dichloromethane and water, and the organic phase was collected. The organic phase was dried over anhydrous sodium sulfate, filtered, and the solvent was removed by rotary evaporation under reduced pressure. Recrystallization with dichloromethane and petroleum ether yielded 500 mg of a yellow solid, which was compound 2, in 80% yield. 1H NMR (400MHz, Chloroform-d): δ (ppm) 9.01 (d, J = 8.5Hz, 2H), 8.82 (dd, J = 8.1, 1.6Hz, 4H), 7.68-7.57 (m, 6H), 7.49 (d, J = 8.4Hz, 2H), 7.3 3(dd,J=7.5,1.7Hz,2H),6.96-6.85(m,4H),6.23(dd,J=7.9,1.4Hz,2H),2.02-1.92(m,4H),1.23-1.07(m,16H),0.82(t,J=6.8Hz,6H).

[0084] (3) Compound 2 (490 mg, 0.746 mmol) was added to a 50 mL single-necked round-bottom flask, and tetrahydrofuran (20 mL) was added. N-bromosuccinimide (279 mg, 1.566 mmol) was added under ice bath conditions, and the reaction was allowed to proceed to room temperature for 15 hours. The mixture was extracted with dichloromethane, washed three times with water, and the organic phase was collected. The organic phase was dried over anhydrous sodium sulfate, filtered, and the solvent was removed by rotary evaporation under reduced pressure. The mixture was recrystallized from dichloromethane, petroleum ether, and ethanol to give 547 mg of a yellow solid, which was compound 3, with a yield of 90%. 1 H NMR (400MHz, Chloroform-d): δ (ppm) 9.01 (d, J = 8.5Hz, 2H), 8.81 (dd, J = 8.2, 1.5Hz, 4H), 7.69-7.56 (m, 6H), 7.42 (d, J = 8.5Hz, 2H), 7. 38(d,J=2.3Hz,2H),7.01(dd,J=8.9,2.2Hz,2H),6.10(d,J=8.9Hz,2H),1.98-1.83(m,4H),1.28-1.04(m,16H),0.84(t,J=6.8Hz,6H).

[0085] (4) Methyl 2-(N-p-methylphenyl)amino-5-methylbenzoate (27.9 g, 109.4 mmol) was added to a 500 mL three-necked flask, and the mixture was purged several times under argon protection. Anhydrous and oxygen-free tetrahydrofuran (120 mL) was added and stirred to dissolve the methyl 2-methylbenzoate. Then, a tetrahydrofuran solution of freshly prepared Grignard reagent hexyl magnesium bromide (156 mL, 2.9 mol / L) was slowly added to the reaction system. After the addition was complete, the reaction was allowed to proceed at room temperature for 16 h. The reaction solution was then poured into a dilute hydrochloric acid aqueous solution (400 mL, 1 mol / L) and dissolved in diethyl ether. Extraction was performed, and the solvent was removed by rotary evaporation under reduced pressure in the organic phase to obtain the intermediate. The intermediate, 240 mL of glacial acetic acid, and 60 mL of concentrated hydrochloric acid were added to a 500 mL single-necked flask, and the mixture was refluxed at 80 °C for 120 h. After cooling to room temperature, the reaction solution was poured into 200 mL of water, extracted with water and dichloromethane, dried over anhydrous sodium sulfate, filtered, and the solvent was removed by rotary evaporation under reduced pressure in the organic phase. The mixture was diluted with 20 mL of petroleum ether, recrystallized at room temperature, and then recrystallized in a refrigerator. After filtration, the filter cake was washed with ethanol to obtain 29.5 g of pale yellow crystals, which is compound 4, with a yield of 71%. 1 H NMR (400MHz, DMSO) δ8.30 (s, 1H), 6.97 (s, 2H), 6.79–6.77 (d, J = 8Hz, 2H), 6.53–6.51 (d, J = 8Hz, 2H), 3.31 (s,6H),2.19(s,4H),1.80–1.76(m,4H),1.11–1.05(m,8H),0.87–0.79(m,4H),0.76–0.73(t,J=6Hz,6H).

[0086] (5) 1,2-bis(4-bromophenyl)ethane-1,2-dione (7.2 g, 19.5 mmol), compound 4 (15.1 g, 40.0 mmol), palladium acetate (438 mg, 2.0 mmol), tri-tert-butylphosphine tetrafluoroborate (2.0 g, 7.0 mmol), and potassium carbonate (16.2 g, 117.1 mmol) were added to a 200 mL pear-shaped flask. The mixture was purged several times under argon protection. Anhydrous and oxygen-free toluene (120 mL) was added, and the mixture was heated to 120 °C and refluxed for 23 h. After the reaction was completed, the system was cooled to room temperature, extracted with water and dichloromethane, dried over anhydrous sodium sulfate, filtered, and the organic phase was removed by rotary evaporation under reduced pressure. The organic phase was then separated by silica gel column chromatography (petroleum ether: dichloromethane = 5:1). After removing the solvent by rotary evaporation under reduced pressure, the mixture was dried under vacuum to obtain 17.8 g of red solid powder, which was compound 5, with a yield of 95%. 1HNMR (500MHz, Chloroform-d): δ (ppm) 8.26 (d, J = 10Hz, 4H), 7.45 (d, J = 10Hz, 4H), 7.09 (s, 4H), 6.73 (d, J = 10Hz, 4H), 6.07(d,J=10Hz,4H),2.27(s,12H),1.94–1.91(m,8H),1.19–1.12(m,24H),1.07–1.02(m,8H),0.81(t,J=15Hz,12H).

[0087] (6) Compound 5 (3.2 g, 3.3 mmol) and 4,5-diamino-3,6-dibromophthalonitrile (1.0 g, 3.3 mmol) were added to a 500 mL single-necked round-bottom flask, followed by the addition of glacial acetic acid (120 mL). The mixture was heated to 120 °C and refluxed for 24 h. After the reaction was complete, the system was cooled to room temperature, and 100 mL of cold water was added. A large amount of black solid precipitated immediately. The system was poured into 200 mL of ice water, filtered, washed several times with water, and the filter cake was dried under vacuum. The residue was separated by silica gel column chromatography (petroleum ether: dichloromethane = 1:1), and the solvent was removed by rotary evaporation under reduced pressure. After vacuum drying, 3.1 g of blackish-white solid powder was obtained, which was compound 6, with a yield of 75%. 1H NMR (400MHz, Chloroform-d): δ (ppm) 7.93 (d, J = 10Hz, 4H), 7.35 (d, J = 10Hz, 4H), 7.08 (s, 4H), 6.55 (d, J = 10 Hz, 4H), 6.04 (d, J = 10Hz, 4H), 2.20 (s, 12H), 1.95–1.91 (m, 8H), 1.18–1.07 (m, 32H), 0.80 (t, J = 10Hz, 12H).

[0088] (7) Accurately weigh compound 3 (40.7 mg, 0.05 mmol), compound 6 (0.6 mg, 0.0005 mmol), 2,7-dibromo-9-heptadecylcarbazole (253.3 mg, 0.4495 mmol) (112.5 mg, 0.1996 mmol), 2,7-dipinacolborate-9-heptadecylcarbazole (328.8 mg, 0.50 mmol), and bis(tris(o-methylphenyl)phosphine)palladium dichloride (4 mg, 0.005 mmol) into 50 mL. In a Schlenk flask, under argon protection and multiple purgings, 20 mL of anhydrous and oxygen-free tetrahydrofuran was added, stirred to dissolve, and heated to 75 °C for 0.5 h. Then, 2 mL of tripotassium phosphate aqueous solution (2 mmol / mL) was added, and the mixture was heated to 90 °C for 26 h. 0.20 g of phenylboronic acid (1.6 mmol) dissolved in 2 mL of tetrahydrofuran was added to the system and reacted for 6 h. 0.3 mL of bromobenzene was added to the system and reacted for 6 h. Sodium diethylaminothiocarbamate (0.5 g) dissolved in 15 mL of water was added to the reaction solution, and stirring was continued for 24 h. The mixture was cooled to room temperature, transferred with dichloromethane, washed three times with water, and partially evaporated under reduced pressure to remove the solvent to a remaining 2–3 mL solution. After cooling to room temperature, methanol was added dropwise to precipitate the solution, resulting in a light orange polymer. The polymer was filtered, extracted with acetone for 24 h, and the residue was dried to obtain 370 mg of light orange solid, with a yield of 89%, which is the white light-emitting material 1-1. 1 ¹H NMR (400MHz, Chloroform-d): δ (ppm) 9.10, 8.86, 8.85, 8.25 (br), 7.93 (br), 7.75 (br), 7.63 (br), 7.49, 7.36, 6.44, 4.76 (br), 2.46 (br), 2.06 (br), 1.34, 1.18 (br), 0.83-0.80 (br). The obtained luminescent material was analyzed, and the number-average molecular weight M was measured by GPC. n The value is 54732, and the molecular weight distribution index (PDI) is 3.35.

[0089] Example 2

[0090] This embodiment provides a method for preparing a white light-emitting material, and the specific preparation process is as follows:

[0091]

[0092] (1) Accurately weigh compound 3 (8.1 mg, 0.01 mmol) and compound 6 (1.2 mg, 0.001 mmol) obtained in Example 1, 2,7-dibromo-9-heptadecylcarbazole (275.5 mg, 0.489 mmol), 2,7-dipinacolborate-9-heptadecylcarbazole (328.8 mg, 0.50 mmol), and bis(tris(o-methylphenyl)phosphine)palladium dichloride (4 mg, 0.005 mmol) into 50 mL. In a Schlenk flask, under argon protection and multiple purgings, 20 mL of anhydrous and oxygen-free tetrahydrofuran was added, stirred to dissolve, and heated to 75 °C for 0.5 h. Then, 2 mL of tripotassium phosphate aqueous solution (2 mmol / mL) was added, and the mixture was heated to 90 °C for 26 h. 0.20 g of phenylboronic acid (1.6 mmol) dissolved in 2 mL of tetrahydrofuran was added to the system and reacted for 6 h. 0.3 mL of bromobenzene was added to the system and reacted for 6 h. Sodium diethylaminothiocarbamate (0.5 g) dissolved in 15 mL of water was added to the reaction solution, and stirring was continued for 24 h. The mixture was cooled to room temperature, transferred with dichloromethane, washed three times with water, and partially evaporated under reduced pressure to remove the solvent to a remaining 2–3 mL solution. After cooling to room temperature, methanol was added dropwise to precipitate the solution, resulting in a light orange polymer. The polymer was filtered, extracted with acetone for 24 h, and the residue was dried to obtain 375 mg of light orange solid, with a yield of 89%, which yielded white light-emitting material 1-2. 1 ¹H NMR (400MHz, Chloroform-d): δ (ppm) 9.10, 8.86, 8.85, 8.26 (br), 7.93 (br), 7.75 (br), 7.63 (br), 7.36, 6.46, 4.77 (br), 2.47 (br), 2.06 (br), 1.34, 1.18 (br), 0.83–0.80 (br). The obtained polymers were analyzed, and the number-average molecular weight M was measured by GPC. n The value is 66834, and the molecular weight distribution index (PDI) is 4.08.

[0093] Example 3

[0094] This embodiment provides a method for preparing a white light-emitting material, and the specific preparation process is as follows:

[0095]

[0096] (1) Compound 1 (500 mg, 1.43 mmol), 2-(4-bromophenyl)thiathanth-5,5,10,10-tetraoxide (622 mg, 1.43 mmol), palladium acetate (16.1 mg, 0.072 mmol), tris(tert-butylphosphine)tetrafluoroborate (75 mg, 0.257 mmol), and potassium carbonate (593 mg, 4.29 mmol) were added to a 100 mL two-necked flask. The mixture was evacuated and purged with argon three times. Anhydrous and oxygen-free toluene (15 mL) was then added. The reaction was carried out at 120 °C for 15 hours. After cooling to room temperature, the mixture was extracted with dichloromethane and water, and the organic phase was collected. The organic phase was dried over anhydrous sodium sulfate, filtered, and the solvent was removed by rotary evaporation under reduced pressure. The mixture was recrystallized from dichloromethane and petroleum ether to give 805 mg of a white solid, which was compound 7, with a yield of 80%. 1 H NMR (400MHz, Chloroform-d): δ (ppm) 9.13 (d, J = 8.2Hz, 2H), 8.79 (dd, J = 8.4, 1.6Hz, 4H), 7.68-7.57 (m, 6H), 7.46 (d, J = 8.8Hz, 2H), 7. 42(d,J=2.6Hz,2H),7.03(dd,J=9.2,2.4Hz,2H),6.14(d,J=8.6Hz,1H),1.99-1.85(m,4H),1.28-1.02(m,16H),0.84(t,J=6.8Hz,6H).

[0097] (2) Compound 7 (525 mg, 0.746 mmol) was added to a 50 mL single-necked round-bottom flask, and tetrahydrofuran (20 mL) was added. N-bromosuccinimide (279 mg, 1.566 mmol) was added under ice bath conditions, and the reaction was allowed to proceed to room temperature for 15 hours. The mixture was extracted with dichloromethane, washed three times with water, and the organic phase was collected. The organic phase was dried over anhydrous sodium sulfate, filtered, and the solvent was removed by rotary evaporation under reduced pressure. Recrystallization was performed with dichloromethane, petroleum ether, and ethanol to give 572 mg of a white solid, which was compound 8, in 89% yield. 1 H NMR (400MHz, Chloroform-d): δ (ppm) 9.18 (d, J = 8.2Hz, 2H), 8.82 (dd, J = 8.4, 1.8Hz, 4H), 7.69-7.58 (m, 6H), 7.45 (d, J = 2.3 Hz,2H),7.06(dd,J=9.2,2.4Hz,2H),6.18(d,J=8.6Hz,1H),2.01-1.88(m,4H),1.26-1.01(m,16H),0.84(t,J=6.9Hz,6H).

[0098] (3) Compound 1 (500 mg, 1.43 mmol), 6-bromo-2-(4-tert-butylphenyl)-1H-benzyl-1,3(2H)-dione (580 mg, 1.43 mmol), palladium acetate (16.1 mg, 0.072 mmol), tris(tert-butylphosphine)tetrafluoroborate (75 mg, 0.257 mmol), and potassium carbonate (593 mg, 4.29 mmol) were added to a 100 mL two-necked flask. The mixture was evacuated and purged with argon three times. Anhydrous and oxygen-free toluene (15 mL) was added. The reaction was carried out at 120 °C for 15 hours. After cooling to room temperature, the mixture was extracted with dichloromethane and water, and the organic phase was collected. The organic phase was dried over anhydrous sodium sulfate, filtered, and the solvent was removed by rotary evaporation under reduced pressure. The mixture was recrystallized from dichloromethane and petroleum ether to give 805 mg of a red solid, which was compound 9, with a yield of 80%. 1 H NMR (400MHz, Chloroform-d): δ (ppm) 8.87 (d, J = 7.6 Hz, 1H), 8.69 (dd, J = 7.2, 1.2 Hz, 1H), 8.10 (dd, J = 8.4 ,1.2Hz,1H),7.84(d,J=7.7Hz,1H),7.67(dd,J=8.4,7.2Hz,1H),7.63–7.58(m,2H),7.55(dd,J=7.8,1.6H z,2H),7.29(d,J=8.5Hz,3H),6.97(td,J=7.6,1.3Hz,2H),6.88(ddd,J=8.7,7.2,1.6Hz,2H),5.99(dd,J= 8.2,1.2Hz,2H),1.98-1.83(m,4H),1.81(m,6H),1.40(s,9H),1.28-1.02(m,16H),0.84(t,J=6.8Hz,6H).

[0099] (4) Compound 9 (504 mg, 0.746 mmol) was added to a 50 mL single-necked round-bottom flask, and tetrahydrofuran (20 mL) was added. N-bromosuccinimide (279 mg, 1.566 mmol) was added under ice bath conditions, and the reaction was allowed to proceed to room temperature for 15 hours. The mixture was extracted with dichloromethane, washed three times with water, and the organic phase was collected. The organic phase was dried over anhydrous sodium sulfate, filtered, and the solvent was removed by rotary evaporation under reduced pressure. The mixture was recrystallized from dichloromethane, petroleum ether, and ethanol to give 534 mg of a red solid, which was compound 10, with a yield of 86%. 1H NMR (400MHz, Chloroform-d): δ (ppm) 8.86 (d, J = 7.7Hz, 1H), 8.71 (dd, J = 7.3, 1.4Hz, 1H), 7.95(dd,J=8.5,1.2Hz,1H),7.78(d,J=7.7Hz,1H),7.70(dd,J=8.5,7.2Hz,1H),7.65–7. 54(m,4H),7.28(s,2H),6.98(dd,J=8.8,2.3Hz,2H),5.87(d,J=8.8Hz,2H),1.98-1.83(m ,4H),1.83(s,3H),1.73(s,3H),1.40(s,9H),1.28-1.02(m,16H),0.84(t,J=6.8Hz,6H).

[0100] (5) Accurately weigh compound 8 (8.6 mg, 0.01 mmol), compound 10 (0.8 mg, 0.001 mmol), 3,6-dibromo-9-heptadecylcarbazole (275.5 mg, 0.489 mmol), 3,6-dipinacolborate-9-heptadecylcarbazole (328.8 mg, 0.50 mmol), and bis(tris(o-methylphenyl)phosphine)palladium dichloride (4 mg, 0.005 mmol) into 50 mL. In a Schlenk flask, under argon protection and multiple purgings, 20 mL of anhydrous and oxygen-free tetrahydrofuran was added, stirred to dissolve, and heated to 75 °C for 0.5 h. Then, 2 mL of tripotassium phosphate aqueous solution (2 mmol / mL) was added, and the mixture was heated to 90 °C for 26 h. 0.20 g of phenylboronic acid (1.6 mmol) dissolved in 2 mL of tetrahydrofuran was added to the system and reacted for 6 h. 0.3 mL of bromobenzene was added to the system and reacted for 6 h. Sodium diethylaminothiocarbamate (0.5 g) dissolved in 15 mL of water was added to the reaction solution, and stirring was continued for 24 h. The mixture was cooled to room temperature, transferred with dichloromethane, washed three times with water, and partially evaporated under reduced pressure to remove the solvent to a remaining 2–3 mL solution. After cooling to room temperature, methanol was added dropwise to precipitate the solution, resulting in a light orange polymer. The polymer was filtered, extracted with acetone for 24 h, and the residue was dried to obtain 360 mg of a light yellow solid, with a yield of 86%, which yielded the white light-emitting material 2-7. 1 ¹H NMR (400MHz, Chloroform-d): 9.10, 8.86, 8.85, 8.26 (br), 7.93 (br), 7.75 (br), 7.63 (br), 7.49, 7.36, 6.45, 4.76 (br), 2.46 (br), 2.06 (br), 1.34, 1.18 (br), 0.83–0.80 (br). The obtained polymers were analyzed, and the number-average molecular weight M was measured by GPC. nThe value is 36290, and the molecular weight distribution index (PDI) is 3.52.

[0101] Example 4

[0102] This embodiment provides a method for preparing a white light-emitting material, and the specific preparation process is as follows:

[0103]

[0104] (1) p-tert-butylphenol (8.30 g, 55.20 mmol), 2,5-dibromo-1,3-difluorobenzene (5.00 g, 18.40 mmol), and cesium carbonate (18.00 g, 55.20 mmol) were added to a 250 mL round-bottom two-necked flask. The mixture was evacuated and purged with argon three times. Then, ultra-dry DMF (50 mL) was added, and the reaction was carried out at 110 °C for 17 hours. After cooling to room temperature, the reaction solution was extracted with dichloromethane, and the organic phase was washed three times with water. The organic phase was dried with anhydrous sodium sulfate, filtered, and the solvent was removed by rotary evaporation under reduced pressure. The crude product was purified by column chromatography (dichloromethane / petroleum ether, v / v = 1 / 12), and the solvent was removed by rotary evaporation under reduced pressure. After vacuum drying, 7.00 g of white solid, namely compound 11, was obtained, with a yield of 72%. 1 HNMR (600MHz, Chloroform-d): δ (ppm) δ = 7.40 (d, J = 8.8Hz, 4H), 6.98 (d, J = 8.8Hz, 4H), 6.73 (s, 2H), 1.34 (s, 18H).

[0105] (2) Compound 11 (5.00 g, 9.40 mmol) was added to a 100 mL round-bottom two-necked flask, and the mixture was evacuated and purged with argon three times. 25 mL of ultra-dry 1,3,5-trimethylbenzene was added. Under ice bath conditions, a hexane solution of n-butyllithium (2.5 M, 3.8 mL, 9.60 mmol) was added dropwise, and the reaction was carried out at room temperature for 2 hours. Boron tribromide (7.80 g, 31.02 mmol) was added at room temperature, and the reaction was carried out at room temperature for 1 hour. N,N'-diisopropylethylamine (4.50 g, 34.80 mmol) was added in multiple batches, and the reaction was carried out at 180 °C for 30 hours. The mixture was cooled to room temperature, quenched with ethanol, and extracted with dichloromethane. The organic phase was dried over anhydrous sodium sulfate, filtered, and the solvent was removed by rotary evaporation under reduced pressure to approximately 4–5 mL. Recrystallization with dichloromethane, petroleum ether, and ethanol yielded 2.60 g of a white solid, which was compound 12, with a yield of 62%. 1 H NMR (400MHz, Chloroform-d): δ (ppm) 8.73 (d, J = 2.3Hz, 2H), 7.79 (dd, J = 8.8, 2.4Hz, 2H), 7.48 (d, J = 8.8Hz, 2H), 7.38 (s, 2H), 1.48 (s, 18H).

[0106] (3) Compound 12 (2.00 g, 4.34 mmol), compound 1 (1.97 g, 5.64 mmol), palladium acetate (48.7 mg, 0.22 mmol), tris(tert-butylphosphine)tetrafluoroborate (227 mg, 0.78 mmol), and potassium carbonate (1.80 g, 13.02 mmol) were added to a 100 mL two-necked flask. The mixture was evacuated and purged with argon three times. Anhydrous and oxygen-free toluene (15 mL) was added. The reaction was carried out at 120 °C for 14 hours. After cooling to room temperature, the mixture was extracted with dichloromethane and water, and the organic phase was collected. The organic phase was dried over anhydrous sodium sulfate, filtered, and the solvent was removed by rotary evaporation under reduced pressure. The mixture was recrystallized from dichloromethane and petroleum ether to give 2 g of white solid, which was compound 13, with a yield of 63%. 1 H NMR (400MHz, Chloroform-d): δ (ppm) 8.79 (d, J = 2.4Hz, 2H), 7.80 (dd, J = 8.8, 2.3Hz, 2H), 7.49 (d, J = 8.8Hz, 2H), 7.32 (d, J = 8.9Hz, 2H) ,7.14(s,2H),6.92–6.86(m,2H),6.27(d,J=9.0,Hz,2H),2.00–1.96(m,4H),1.51(s,18H),1.22–1.04(m,16H),0.84(t,J=6.6Hz,6H).

[0107] (4) Compound 13 (181 mg, 0.248 mmol) was added to a 50 mL single-necked round-bottom flask, and tetrahydrofuran (12 mL) was added. N-bromosuccinimide (97 mg, 0.543 mmol) was added under ice bath conditions, and the reaction was allowed to proceed to room temperature for 17 hours. The mixture was extracted with dichloromethane, washed three times with water, and the organic phase was collected. The organic phase was dried over anhydrous sodium sulfate, filtered, and the solvent was removed by rotary evaporation under reduced pressure. The mixture was recrystallized from dichloromethane, petroleum ether, and ethanol to give 200 mg of a white solid, which was product 14, with a yield of 91%. 1 H NMR (400MHz, Chloroform-d): δ (ppm) 8.79 (d, J = 2.4Hz, 2H), 7.81 (dd, J = 8.7, 2.4Hz, 2H), 7.50 (d, J = 8.7Hz, 2H), 7.37 (d, J = 2.2Hz, 2H), 7.07 (s, 2H) ,6.99(dd,J=8.9,2.2Hz,2H),6.14(d,J=8.9Hz,2H),1.93–1.90(4H),1.5 1(s,18H),1.25–1.18(m,12H),1.13–1.08(m,4H),0.87(t,J=6.8Hz,6H).

[0108] (5) Accurately weigh compound 14 (8.9 mg, 0.01 mmol), compound 10 (0.8 mg, 0.001 mmol), 3,6-dibromo-9-heptadecylcarbazole (275.5 mg, 0.489 mmol), 3,6-dipinacolborate-9-heptadecylcarbazole (328.8 mg, 0.50 mmol), and bis(tris(o-methylphenyl)phosphine)palladium dichloride (4 mg, 0.005 mmol) into 50 mL. In a Schlenk flask, under argon protection and multiple purgings, 20 mL of anhydrous and oxygen-free tetrahydrofuran was added, stirred to dissolve, and heated to 75 °C for 0.5 h. Then, 2 mL of tripotassium phosphate aqueous solution (2 mmol / mL) was added, and the mixture was heated to 90 °C for 26 h. 0.20 g of phenylboronic acid (1.6 mmol) dissolved in 2 mL of tetrahydrofuran was added to the system and reacted for 6 h. 0.3 mL of bromobenzene was added to the system and reacted for 6 h. Sodium diethylaminothiocarbamate (0.5 g) dissolved in 15 mL of water was added to the reaction solution, and stirring was continued for 24 h. The mixture was cooled to room temperature, transferred with dichloromethane, washed three times with water, and partially evaporated under reduced pressure to remove the solvent to a remaining 2–3 mL solution. After cooling to room temperature, methanol was added dropwise to precipitate the solution, resulting in a light orange polymer. The polymer was filtered, extracted with acetone for 24 h, and the residue was dried to obtain 365 mg of a light yellow solid, with a yield of 86%, which yielded the white light-emitting material 2-10. 1 ¹H NMR (400MHz, Chloroform-d): 9.10, 8.87, 8.86, 8.26 (br), 7.94 (br), 7.75 (br), 7.64 (br), 7.50, 7.37, 7.04, 6.45, 5.96, 4.77 (br), 2.47 (br), 2.07 (br), 1.34, 1.19 (br), 0.83–0.80 (br). The obtained polymers were analyzed, and the number-average molecular weight M was measured by GPC. n The value is 42456, and the molecular weight distribution index (PDI) is 3.47.

[0109] Example 5

[0110] This embodiment provides a method for preparing a white light-emitting material, and the specific preparation process is as follows:

[0111]

[0112] (1) Accurately weigh compound 14 (88.8 mg, 0.10 mmol), compound 3 (8.1 mg, 0.01 mmol), compound 10 (0.8 mg, 0.001 mmol), 2,7-dibromo-9-heptadecylcarbazole (219.2 mg, 0.389 mmol), 2,7-dipinacolborate-9-heptadecylcarbazole (328.8 mg, 0.50 mmol), and bis(tris(o-methylphenyl)phosphine)palladium dichloride (4 mg, 0.005 mmol) into 50 mL. In a Schlenk flask, under argon protection and multiple purgings, 20 mL of anhydrous and oxygen-free tetrahydrofuran was added, stirred to dissolve, and heated to 75 °C for 0.5 h. Then, 2 mL of tripotassium phosphate aqueous solution (2 mmol / mL) was added, and the mixture was heated to 90 °C for 26 h. 0.20 g of phenylboronic acid (1.6 mmol) dissolved in 2 mL of tetrahydrofuran was added to the system and reacted for 6 h. 0.3 mL of bromobenzene was added to the system and reacted for 6 h. Sodium diethylaminothiocarbamate (0.5 g) dissolved in 15 mL of water was added to the reaction solution, and stirring was continued for 24 h. The mixture was cooled to room temperature, transferred with dichloromethane, washed three times with water, and partially evaporated under reduced pressure to remove the solvent to a remaining 2–3 mL solution. After cooling to room temperature, methanol was added dropwise to precipitate the solution, resulting in a light orange polymer. The polymer was filtered, extracted with acetone for 24 h, and the residue was dried to obtain 350 mg of a light yellow solid, with a yield of 83%, which is the white light-emitting material 3-1. 1 ¹H NMR (400MHz, Chloroform-d): 9.12, 8.87, 8.85, 8.25 (br), 7.93 (br), 7.75 (br), 7.64 (br), 7.49, 7.37, 7.05, 6.45, 5.97, 4.76 (br), 2.46 (br), 2.08 (br), 1.34, 1.20 (br), 0.83–0.80 (br). The obtained polymer was analyzed, and the number-average molecular weight M was measured by GPC. n The value is 33468, and the molecular weight distribution index (PDI) is 2.80.

[0113] Example 6

[0114] This embodiment provides a method for preparing a white light-emitting material, and the specific preparation process is as follows:

[0115]

[0116] (1) Compound 1 (1.50 g, 3.70 mmol), (4-bromophenyl)phenyl ketone (0.97 g, 3.70 mmol), tris(dibenzylacetone)palladium (60 mg, 0.066 mmol), tris(tert-butylphosphine)tetrafluoroborate (95 mg, 0.171 mmol), and cesium carbonate (3.62 g, 11.1 mmol) were added to a 100 mL two-necked flask. The mixture was evacuated and purged with argon three times. Anhydrous and oxygen-free toluene (15 mL) was then added. The reaction was carried out at 120 °C for 16 hours. After cooling to room temperature, the mixture was extracted with dichloromethane and water, and the organic phase was collected. The organic phase was dried over anhydrous sodium sulfate, filtered, and the solvent was removed by rotary evaporation under reduced pressure. The crude product was purified by column chromatography (dichloromethane / petroleum ether, v / v = 1 / 2), the solvent was removed by rotary evaporation under reduced pressure, and the product was recrystallized with dichloromethane and petroleum ether to give 1.35 g of red solid, which is compound 15, with a yield of 69%. 1 H NMR (400MHz, Chloroform-d): δ (ppm) 8.06 (d, J = 8.4Hz, 2H), 7.90 (d, J = 7.1Hz, 2H), 7.64 (t, J = 6.8Hz, 1H), 7.54 (t, J = 7.5Hz, 2H), 7.40 (d, J = 8.4Hz, 2H), 7 .32(dd,J=7.6,1.6Hz,2H),6.91(dt,J=14.6,7.2Hz,4H),6.15(dd,J=8.0,1 .3Hz,2H),1.96(d,J=15.9Hz,4H),1.29–1.01(m,16H),0.80(t,J=6.8Hz,6H)

[0117] (2) Compound 15 (0.99 g, 1.87 mmol) was added to a 50 mL single-necked round-bottom flask, and tetrahydrofuran (20 mL) was added. N-bromosuccinimide (722 mg, 4.06 mmol) was added under ice bath conditions, and the reaction was allowed to proceed to room temperature for 17 hours. The mixture was extracted with dichloromethane, washed three times with water, and the organic phase was collected. The organic phase was dried over anhydrous sodium sulfate, filtered, and the solvent was removed by rotary evaporation under reduced pressure. The crude product was purified by column chromatography (dichloromethane / petroleum ether, v / v = 1 / 2), and the solvent was removed by rotary evaporation under reduced pressure to give 1.25 g of green solid, which was compound 16, with a yield of 97%. 1H NMR (400MHz, Chloroform-d): δ (ppm) 8.06 (d, J = 8.3Hz, 2H), 7.89 (d, J = 7.1Hz, 2H), 7.65 (t, J = 7.4Hz, 1H), 7.55 (t, J = 7.6Hz, 2H), 7.36 (dd, J=9.1,5.3Hz,4H),7.02(dd,J=8.8,2.2Hz,2H),6.02(d,J=8.8Hz,2H),1.89(d,J=16.4Hz,4H),1.27–0.94(m,16H),0.83(t,J=6.8Hz,6H).

[0118] (3) Accurately weigh compound 14 (88.8 mg, 0.10 mmol), compound 16 (6.9 mg, 0.01 mmol), compound 6 (1.2 mg, 0.001 mmol), 3,6-dibromo-9-heptadecylcarbazole (219.2 mg, 0.389 mmol), 3,6-dipinacolborate-9-heptadecylcarbazole (328.8 mg, 0.50 mmol), and bis(tris(o-methylphenyl)phosphine)palladium dichloride (4 mg, 0.005 mmol) into 50 mL. In a Schlenk flask, under argon protection and multiple purgings, 20 mL of anhydrous and oxygen-free tetrahydrofuran was added, stirred to dissolve, and heated to 75 °C for 0.5 h. Then, 2 mL of tripotassium phosphate aqueous solution (2 mmol / mL) was added, and the mixture was heated to 90 °C for 26 h. 0.20 g of phenylboronic acid (1.6 mmol) dissolved in 2 mL of tetrahydrofuran was added to the system and reacted for 6 h. 0.3 mL of bromobenzene was added to the system and reacted for 6 h. Sodium diethylaminothiocarbamate (0.5 g) dissolved in 15 mL of water was added to the reaction solution, and stirring was continued for 24 h. The mixture was cooled to room temperature, transferred with dichloromethane, washed three times with water, and partially evaporated under reduced pressure to remove the solvent to a remaining 2–3 mL solution. After cooling to room temperature, methanol was added dropwise to precipitate the solution, resulting in a light orange polymer. The polymer was filtered, extracted with acetone for 24 h, and the residue was dried to obtain 350 mg of a light yellow solid, with a yield of 83%, which is the white light-emitting material 3-1. 1 ¹H NMR (400MHz, Chloroform-d): 9.08, 8.86, 8.81, 8.24 (br), 7.92 (br), 7.72 (br), 7.60 (br), 7.45, 7.37, 7.05, 6.45, 5.97, 4.74 (br), 2.46 (br), 2.09 (br), 1.34, 1.21 (br), 0.84–0.81 (br). The obtained polymer was analyzed, and the number-average molecular weight M was measured by GPC. n The value is 33468, and the molecular weight distribution index (PDI) is 2.80.

[0119] Example 7

[0120] This embodiment provides a method for preparing a white light-emitting material, and the specific preparation process is as follows:

[0121]

[0122] (1) Accurately weigh compound 14 (88.8 mg, 0.10 mmol), compound 3 (8.1 mg, 0.01 mmol), compound 10 (0.8 mg, 0.001 mmol), 3,6-dibromo-9-heptadecylcarbazole (219.2 mg, 0.389 mmol), 3,6-dipinacolborate-9-heptadecylcarbazole (328.8 mg, 0.50 mmol), and bis(tris(o-methylphenyl)phosphine)palladium dichloride (4 mg, 0.005 mmol) into 50 mL. In a Schlenk flask, under argon protection and multiple purgings, 20 mL of anhydrous and oxygen-free tetrahydrofuran was added, stirred to dissolve, and heated to 75 °C for 0.5 h. Then, 2 mL of tripotassium phosphate aqueous solution (2 mmol / mL) was added, and the mixture was heated to 90 °C for 26 h. 0.20 g of phenylboronic acid (1.6 mmol) dissolved in 2 mL of tetrahydrofuran was added to the system and reacted for 6 h. 0.3 mL of bromobenzene was added to the system and reacted for 6 h. Sodium diethylaminothiocarbamate (0.5 g) dissolved in 15 mL of water was added to the reaction solution, and stirring was continued for 24 h. The mixture was cooled to room temperature, transferred with dichloromethane, washed three times with water, and partially evaporated under reduced pressure to remove the solvent to a remaining 2–3 mL solution. After cooling to room temperature, methanol was added dropwise to precipitate the solution, resulting in a light orange polymer. The polymer was filtered, extracted with acetone for 24 h, and the residue was dried to obtain 358 mg of a light yellow solid, with a yield of 84%, which is the white light-emitting material 3-12. 1 ¹H NMR (400MHz, Chloroform-d): 9.13, 8.81, 8.70, 8.25 (br), 7.98 (br), 7.73 (br), 7.60 (br), 7.44, 7.35, 7.02, 6.45, 5.97, 4.71 (br), 2.46 (br), 2.08 (br), 1.35, 1.21 (br), 0.83–0.80 (br). The obtained polymer was analyzed, and the number-average molecular weight M was measured by GPC. n The value is 31378, and the molecular weight distribution index (PDI) is 2.56.

[0123] Experimental Example 1

[0124] (1) The solubility of the luminescent materials obtained in Examples 1, 2, 4 and 7 in chlorobenzene was measured to be 50, 30, 28 and 45 mg / mL, respectively, indicating that the white light luminescent material obtained in this invention has good solubility in the commonly used solvent chlorobenzene.

[0125] (2) The white light polymers obtained in Examples 1-7 were dissolved in chlorobenzene (10 mg / mL), and thin films (approximately 40 nm thick) were prepared by spin coating (2000 rpm). The ultraviolet absorption spectrum and photoluminescence spectrum of the films were tested. Table 1 below shows the photoluminescence properties of the polymer films obtained in each example. Figure 1-4 The images show the UV absorption, room temperature fluorescence, and low temperature phosphorescence spectra of Examples 1, 2, 4, and 7, respectively.

[0126] Table 1 Photoluminescence properties

[0127] Example Absorption peak wavelength [nm] Emission peak wavelength [nm] 1 394 424,459,513 2 391 425,452,494,607 3 395 424,452,516,608 4 395 423,454,513 5 392 423,454,518,612 6 398 424,456,516,612 7 393 431,452,513,607

[0128] As can be seen from the data in Table 1, the white light emitting materials obtained in each embodiment of the present invention all have multiple emission peaks and exhibit a broad emission spectrum.

[0129] Experimental Example 2

[0130] The white light emitting materials obtained in Examples 1-7 were dissolved in chlorobenzene, and the thin films prepared by spin coating in Example 1 were subjected to transient fluorescence decay spectroscopy tests. Figure 5 and Figure 6 The transient fluorescence decay spectra of the films from Examples 1 and 2 are shown below. It can be seen that both Examples 1 and 2 exhibit delayed fluorescence characteristics. Table 2 below shows the short lifetime (τ) of the white light-emitting materials obtained in the examples. P ) and long lifespan (τ) D ):

[0131] Table 2 Short Lifetime (τ) P ) and long lifespan (τ) D )

[0132] Example <![CDATA[τ P [ns]]]> <![CDATA[τ D [μs] <!-- 33 -->]]> 1 17.5 3.5 2 23.9 4.4 3 18.4 3.6 4 21.2 4.2 5 17.9 3.8 6 23.2 4.0 7 23.8 3.9

[0133] As can be seen from the table above, the long lifetimes are all in the microsecond range, which conforms to the TADF characteristics and is conducive to achieving high inverse intersystem crossing rates, making them suitable for WOLED devices prepared by solution processing.

[0134] Experimental Example 3

[0135] Electroluminescence properties were measured based on Examples 1-7 to illustrate the application of the luminescent material of the present invention in electroluminescent devices. The structure of the electroluminescent device is: ITO / PEDOT:PSS (40nm) / emitters (40nm) / PO-T2T (20nm) / ANT-BIZ (30nm) / Liq (1nm) / Al (100nm). Wherein, ITO is conductive glass, PEDOT:PSS is poly(3,4-ethylenedioxythiophene) / polystyrene sulfonate, PO-T2T is (1,3,5-triazine-2,4,6-triyl)tris(phenyl-3,1-diyl)tris(diphenylphosphine oxychloride), ANT-BIZ is (1-(4-(10-([1,1'-diphenyl]-4-yl)anthracene-9-yl)phenyl)-2-ethyl-1H-benzo[d]-imidazolium), and Liq is 8-hydroxyquinoline-lithium.

[0136] Figure 7-10 The following table shows the device performance diagrams of the luminescent materials obtained in Examples 1, 2, 4 and 7. Table 3 below shows the device characterization results of each example.

[0137] Table 3 Electroluminescence properties

[0138]

[0139] The results show that the electroluminescent devices in the embodiments of the present invention all have multiple emission peaks, exhibit a broad emission spectrum, and have color coordinates (CIE) close to standard white light, with a high white light color rendering index (CRI), and the highest CRI value can reach 89. Figure 11-14 The graphs show the electroluminescence spectra of devices made from the luminescent materials of Examples 1, 2, 4 and 7 as a function of voltage. It can be seen that the spectra of these devices all change with voltage and all have good electroluminescent device performance.

[0140] Test Example 4

[0141] The white light-emitting materials obtained in Examples 1, 2, 4 and 7 were dissolved in chlorobenzene and thin films were prepared by spin coating using the method in Example 1. The atomic force test height map was measured to obtain the roughness (RMS) value of the thin film. Figure 15-18 The atomic force diagrams are of the chlorobenzene solution spin-coated films of the luminescent materials in Examples 1, 2, 4 and 7, respectively. It can be seen that the coarseness values ​​of Examples 1, 2, 4 and 7 are all less than 1 nm, indicating that these polymers have good film-forming properties.

[0142] Obviously, the above embodiments are merely illustrative examples for clear explanation and are not intended to limit the implementation. Those skilled in the art will recognize that other variations or modifications can be made based on the above description. It is neither necessary nor possible to exhaustively list all possible implementations here. However, obvious variations or modifications derived therefrom are still within the scope of protection of this invention.

Claims

1. A white light-emitting material, characterized in that, The luminescent material has the structure shown in Formula I: ； Wherein, the luminescent unit B is selected from the structures shown in Formulas i-1 to i-12: ； Among them, W1, W2, W3, W4, W5, W6, W7, W8, W9 and W 10 They are independently selected from H, D, C1-C30 straight alkanes, and C3-C60 branched alkanes; The luminescent unit G is selected from any of the following structures: ； Wherein, O1, O2, O3, O4, O5, O6 and O7 are independently selected from H, D, straight-chain alkanes with 1 to 30 carbon atoms, and branched-chain alkanes with 3 to 60 carbon atoms; The luminescent unit R is selected from any of the following structures: ； Wherein, P1, P2, P3, P4, P5, P6, P7 and P8 are independently selected from H, D, straight-chain alkanes with 1 to 30 carbon atoms, and branched-chain alkanes with 3 to 60 carbon atoms; The bridging unit Ar is selected from any of the following structures: ； Wherein, Q1 is independently selected from H, D, straight-chain alkanes with 1 to 30 carbon atoms, and branched-chain alkanes with 3 to 60 carbon atoms; n is 1 to 800, 0 < m < 1, 0 < h < 1, 0 ≤ x < 1, 0 ≤ y < 1, 0 < z < 1, and x and y are not simultaneously equal to 0.

2. The white light-emitting material according to claim 1, characterized in that, The x is 0 ≤ x ≤ 0.80, the y is 0 ≤ y ≤ 0.60, and the z is 0.0001 ≤ z ≤ 0.

35.

3. The white light-emitting material according to claim 2, characterized in that, The x is 0 ≤ x ≤ 0.70, the y is 0 ≤ y ≤ 0.50; the z is 0.0005 ≤ z ≤ 0.

20.

4. The white light-emitting material according to claim 3, characterized in that, The x is 0 ≤ x ≤ 0.60; the y is 0 ≤ y ≤ 0.40; the z is 0.0005 ≤ z ≤ 0.

10.

5. The white light-emitting material according to any one of claims 1-4, characterized in that, The white light luminescent material includes the structures shown in Formulas 1-1 to 3-35: 。 6. The method for preparing the white light-emitting material according to any one of claims 1-5, characterized in that, Coupling a compound having the structure of Formula II and a compound having the structure of Formula IV with a compound having the structure of Formula V and a compound having the structure of Formula VI to obtain a luminescent material having the structure shown in Formula I; Or, coupling a compound having the structure of Formula III and a compound having the structure of Formula IV with a compound having the structure of Formula V and a compound having the structure of Formula VI to obtain a luminescent material having the structure shown in Formula I; Or, coupling a compound having the structure of Formula II, a compound having the structure of Formula III and a compound having the structure of Formula IV with a compound having the structure of Formula V and a compound having the structure of Formula VI to obtain a luminescent material having the structure shown in Formula I; Or, coupling a compound having the structure of Formula VII and a compound having the structure of Formula IX with a compound having the structure of Formula V and a compound having the structure of Formula VI to obtain a luminescent material having the structure shown in Formula I; Or, coupling a compound having the structure of Formula VIII and a compound having the structure of Formula IX with a compound having the structure of Formula V and a compound having the structure of Formula VI to obtain a luminescent material having the structure shown in Formula I; Or, coupling a compound having the structure of Formula VII, a compound having the structure of Formula VIII and a compound having the structure of Formula IX with a compound having the structure of Formula V and a compound having the structure of Formula VI to obtain a luminescent material having the structure shown in Formula I; 。 7. The application of the white light-emitting material according to any one of claims 1-5, characterized in that, Applied to the preparation of electroluminescent devices.

Images