Multi-Arm Monomolecular White Light-Emitting Materials, Preparation Method and Application Thereof

Abstract

The present invention discloses multi-arm monomolecular white light-emitting materials, preparation method and application thereof. Benzene ring is used as a core, and penta-substituted pyrene and an electron-withdrawing group or an group electron-donating group Ar are used as arms to prepare the multi-arm monomolecular white light-emitting materials; wherein Ar is one of the electron-withdrawing groups such as nitro, cyano, tertiary amine cation, trifluoromethyl, trichloromethyl, sulfonic acid group, formyl, acyl, carboxyl, methoxy, pyridyl, diphenyl sulfone, triazinyl and anthracenedione; or one of the electron-donating groups such as pyrenyl, 9-carbazolyl, 2-thienyl, diphenylamino, tert-butyl diphenylamino, 9-phenoxazinyl, acridinyl, spiro-bifluorenyl, spirofluorenyl acridinyl, alkylamino, dialkylamino, amino and hydroxyl. The present invention simply combines a synthesis method to prepare multi-arm monomolecular white light-emitting materials with novel structure, high fluorescence quantum efficiency, excellent spectrum stability and electroluminescence performance and high color purity, and achieves the preparation of a highly efficient and spectrally stable electroluminescent devices with high color rendering index.

Claims

1. A multi-arm monomolecular white light-emitting material, characterized by having the following general structural formula: ##STR00016## In the general structural formula, a benzene ring is used as a core, and penta-substituted pyrene and Ar are used as arms, wherein Ar is an electron-withdrawing group or an electron-donating group.

2. The multi-arm monomolecular white light-emitting material according to claim 1, characterized in that Ar is selected from one of the electron-withdrawing groups such as bromine, fluorine, nitro, cyano, tertiary amine cation, trifluoromethyl, trichloromethyl, sulfonic acid group, formyl, acyl, carboxyl, methoxy, pyridyl, diphenyl sulfone, triazinyl and anthracenedione.

3. The multi-arm monomolecular white light-emitting material according to claim 1, characterized by having the following structural formulas when Ar is an electron-withdrawing group including cyano, trifluoromethyl, pyridyl and triazinyl: ##STR00017## ##STR00018##

4. The multi-arm monomolecular white light-emitting material according to claim 1, characterized in that Ar is selected from one of the electron-donating groups such as pyrenyl, 9-carbazolyl, 2-thienyl, diphenylamino, tert-butyl diphenylamino, 9-phenoxazinyl, acridinyl, spiro-bifluorenyl, spirofluorenyl acridinyl, alkylamino, dialkylamino, amino and hydroxyl.

5. The multi-arm monomolecular white light-emitting material according to claim 1, characterized by having the following structural formulas when Ar is an electron-donating group including pyrenyl, 9-carbazolyl, 2-thienyl and spirofluorenyl acridinyl: ##STR00019## ##STR00020##

6. A preparation method of a multi-arm monomolecular white light-emitting material according to any of claim 1, characterized in that the multi-arm monomolecular white light-emitting material is prepared from the raw material of pentabromobenzene containing Ar functional group (Ph5Br—Ar) and 1-pyrenyl boronic acid ester through Suzuki coupling reaction, with the reaction equation as follows: ##STR00021##

7. The preparation method of a multi-arm monomolecular white light-emitting material according to claim 6, characterized by comprising the following steps: step 1: mixing a reactant of Ph5Br—Ar and 1-pyrenyl boronic acid ester, a catalyst tetrakis (triphenylphosphine) palladium, and a phase transfer catalyst tetrabutylammonium bromide in a dark place under nitrogen atmosphere, dissolving in potassium carbonate and toluene, and reacting at 90-110° C. for 24-72 h in a dark place; and step 2: after the reaction, cooling to room temperature, extracting the resulting mixed solution with an organic solvent DCM and a saturated salt solution, drying the separated organic layer, performing suction filtration, separating and purifying the mixture obtained by concentrating the solution through column chromatography, and drying to obtain a target product.

8. The preparation method of a multi-arm monomolecular white light-emitting material according to claim 6, characterized in that the molar ratio of Ph5Br—Ar to 1-pyrenyl boronic acid ester is 1:9-1:15.

9. The volume ratio of potassium carbonate to toluene is 1:(2-3), and the molar mass ratio of tetrakis (triphenylphosphine) palladium catalyst to phase transfer catalyst tetrabutylammonium bromide to Ph5Br—Ar is (0.2-0.4):(0.1-0.3):1.

10. A use of a multi-arm monomolecular white light-emitting material according to claim 1, characterized in that the material is used as a functional layer material of optoelectronic devices including organic electroluminescent devices, flexible electronic devices and stretchable electronic devices.

Description

BRIEF DESCRIPTION OF THE FIGURES

[0014] FIG. 1 shows the cyclic voltage-current curves (CV curves) of compounds A, B, and C.

[0015] FIG. 2 shows the thermal weight loss curves of compounds A, B, E, F, and H.

[0016] FIG. 3 shows the luminance-voltage curves of compounds B, D and G.

[0017] FIG. 4 shows the powder X-ray diffraction patterns of compounds A, B, C, D, E, F, G, and H.

[0018] FIG. 5 is the fluorescence emission spectra of compound B.

[0019] FIG. 6 is the mass spectra of compound A.

DESCRIPTION OF THE PRESENT INVENTION

[0020] ##STR00007##

[0021] A multi-arm monomolecular white light-emitting material has the following general structural formula:

[0022] In the general structural formula, a multi-arm monomolecular white light-emitting material is prepared from a benzene ring as a core, penta-substituted pyrene and Ar as arms, and functional groups, wherein Ar is one of the electron-withdrawing groups such as bromine, fluorine, nitro, cyano, tertiary amine cation, trifluoromethyl, trichloromethyl, sulfonic acid group, formyl, acyl, carboxyl, methoxy, pyridyl, diphenyl sulfone, triazinyl and anthracenedione; or one of the electron-donating groups such as pyrenyl, 9-carbazolyl, 2-thienyl, diphenylamino, tert-butyl diphenylamino, 9-phenoxazinyl, acridinyl, spiro-bifluorenyl, spirofluorenyl acridinyl, alkylamino, dialkylamino, amino and hydroxyl.

[0023] Based on the preparation method of the multi-arm monomolecular white light-emitting material, a series of multi-arm monomolecular white light-emitting materials are prepared from the raw material of pentabromobenzene containing Ar functional group (Ph5Br—Ar) and 1-pyrenyl boronic acid ester (molar ratio: 1:9-1:15) through Suzuki coupling reaction in a dark place under nitrogen atmosphere.

Example 1

[0024] Preparation of Compound A

##STR00008##

[0025] Ph5Br—CN (500 mg, 1.02 mmol), 1-pyrenyl boronic acid ester (3.33 g, 10.15 mmol) and tetrabutylammonium bromide (TBAB) (98.17 mg, 0.30 mmol) were added to a 100 mL two-necked flask, sealed, wrapped in foil paper to avoid light, and pumped with nitrogen for three times. Then, a catalyst tetrakis (triphenylphosphine) palladium Pd (PPh.sub.3).sub.4 (351.9 mg, 0.30 mmol) was added rapidly to the flask that was pumped with nitrogen for three times. Finally, the bubbled toluene (24 mL) and 2M K.sub.2CO.sub.3 solution (8 mL) were injected into the reaction flask and reacted at 95° C. for 48 h. After the reaction, the solution was extracted with the organic solvent DCM and saturated salt solution for three times to separate an organic layer, which was dried with MgSO.sub.4. The mixture obtained by concentrating the solution after suction filtration was separated and purified by column chromatography, and dried in a vacuum drying oven to obtain the product Ph5Py-CN (714 mg, yield: 63.8%). MALDI-TOF-MS (m/z): calcd for C.sub.87H.sub.45N, Molecular Weight: 1104.32, Exact Mass: 1103.36, Found: 1101.96 (M.sup.+).

Example 2

[0026] Preparation of Compound B

##STR00009##

[0027] Hexabromobenzene (500 mg, 0.91 mmol), 1-pyrenyl boronic acid ester (3.57 g, 10.88 mmol) and tetrabutylammonium bromide (TBAB) (87.7 mg, 0.27 mmol) were added to a 100 mL two-necked flask, sealed with rubber stoppers, wrapped in foil paper to avoid light, and pumped with nitrogen for three times. Then, a catalyst Pd (PPh.sub.3).sub.4 (314.3 mg, 0.27 mmol) was added rapidly to the flask that was pumped with nitrogen for three times. Finally, the bubbled toluene (24 mL) and 2M K.sub.2CO.sub.3 aqueous solution (8 mL) were injected into the reaction flask and reacted at 95° C. for 48 h. After the reaction, the solution was extracted with the organic solvent DCM and saturated salt solution for three times to separate an organic layer, which was dried with MgSO.sub.4. The crude product obtained by concentrating the solution after suction filtration was separated and purified by column chromatography, and dried in a vacuum drying oven to obtain the product Ph6Py (670 mg, yield: 72.8%). MALDI-TOF-MS (m/z): calcd for C.sub.102H.sub.54, Molecular Weight: 1279.55, Exact Mass: 1278.42, Found: 1276.65 (M.sup.+).

Example 3

[0028] Preparation of Compound C

##STR00010##

[0029] Ph5Br-Py (500 mg, 0.92 mmol), 1-pyrenyl boronic acid ester (3.57 g, 9.19 mmol) and tetrabutylammonium bromide (TBAB) (74.0 mg, 0.23 mmol) were added to a 100 mL two-necked flask, sealed with rubber stoppers, wrapped in foil paper to avoid light, and pumped with nitrogen for three times. Then, a catalyst Pd (PPh.sub.3).sub.4 (265.4 mg, 0.23 mmol) was added rapidly to the flask that was pumped with nitrogen for three times. Finally, the bubbled toluene (24 mL) and 2M K.sub.2CO.sub.3 aqueous solution (8 mL) were injected into the reaction flask and reacted at 95° C. for 48 h. After the reaction, the solution was extracted with the organic solvent DCM and saturated salt solution for three times to separate an organic layer, which was dried with MgSO.sub.4. The crude product obtained by concentrating the solution after suction filtration was separated and purified by column chromatography, and dried in a vacuum drying oven to obtain the product Ph6Py (780 mg, yield: 73.6%). MALDI-TOF-MS (m/z): calcd for C.sub.91H.sub.49N, Molecular Weight: 1156.40, Exact Mass: 1155.39, Found: 1155.92 (M.sup.+).

Example 4

[0030] Preparation of Compound D

##STR00011##

[0031] Ph5Br-Tz (500 mg, 0.91 mmol), 1-pyrenyl boronic acid ester (3.00 g, 9.15 mmol) and tetrabutylammonium bromide (TBAB) (73.7 mg, 0.23 mmol) were added to a 100 mL two-necked flask, sealed with rubber stoppers, wrapped in foil paper to avoid light, and pumped with nitrogen for three times. Then, a catalyst Pd(PPh.sub.3).sub.4 (264.3 mg, 0.23 mmol) was added rapidly to the flask that was pumped with nitrogen for three times. Finally, the bubbled toluene (24 mL) and 2M K.sub.2CO.sub.3 aqueous solution (8 mL) were injected into the reaction flask and reacted at 95° C. for 48 h. After the reaction, the solution was extracted with the organic solvent DCM and saturated salt solution for three times to separate an organic layer, which was dried with MgSO.sub.4. The crude product obtained by concentrating the solution after suction filtration was separated and purified by column chromatography, and dried in a vacuum drying oven to obtain the product Ph6Py (692 mg, yield: 65.3%). MALDI-TOF-MS (m/z): calcd for C.sub.89H.sub.47N.sub.3, Molecular Weight: 1158.38, Exact Mass: 1157.38, Found: 1158.22 (M.sup.+).

Example 5

[0032] Preparation of Compound E

##STR00012##

[0033] Ph5Br-Cz (500 mg, 0.79 mmol), 1-pyrenyl boronic acid ester (2.59 g, 7.90 mmol) and tetrabutylammonium bromide (TBAB) (63.7 mg, 0.23 mmol) were added to a 100 mL two-necked flask, sealed with rubber stoppers, wrapped in foil paper to avoid light, and pumped with nitrogen for three times. Then, a catalyst Pd (PPh.sub.3).sub.4 (228.3 mg, 0.20 mmol) was added rapidly to the flask that was pumped with nitrogen for three times. Finally, the bubbled toluene (24 mL) and 2M K.sub.2CO.sub.3 aqueous solution (8 mL) were injected into the reaction flask and reacted at 95° C. for 48 h. After the reaction, the solution was extracted with the organic solvent DCM and saturated salt solution for three times to separate an organic layer, which was dried with MgSO.sub.4. The crude product obtained by concentrating the solution after suction filtration was separated and purified by column chromatography, and dried in a vacuum drying oven to obtain the product Ph6Py (687 mg, yield: 70.0%). MALDI-TOF-MS (m/z): calcd for C.sub.98H.sub.53N, Molecular Weight: 1244.51, Exact Mass: 1243.42, Found: 1143.96 (M.sup.+).

Example 6

[0034] Preparation of Compound F

##STR00013##

[0035] Ph5Br-Tp (500 mg, 0.91 mmol), 1-pyrenyl boronic acid ester (2.99 g, 9.10 mmol) and tetrabutylammonium bromide (TBAB) (73.3 mg, 0.23 mmol) were added to a 100 mL two-necked flask, sealed with rubber stoppers, wrapped in foil paper to avoid light, and pumped with nitrogen for three times. Then, a catalyst Pd (PPh.sub.3).sub.4 (262.8 mg, 0.23 mmol) was added rapidly to the flask that was pumped with nitrogen for three times. Finally, the bubbled toluene (24 mL) and 2M K.sub.2CO.sub.3 aqueous solution (8 mL) were injected into the reaction flask and reacted at 95° C. for 48 h. After the reaction, the solution was extracted with the organic solvent DCM and saturated salt solution for three times to separate an organic layer, which was dried with MgSO.sub.4. The crude product obtained by concentrating the solution after suction filtration was separated and purified by column chromatography, and dried in a vacuum drying oven to obtain the product Ph6Py (850 mg, yield: 80.2%). MALDI-TOF-MS (m/z): calcd for C.sub.90H.sub.48S, Molecular Weight: 1161.43, Exact Mass: 1160.35, Found: 1161.26 (M.sup.+).

Example 7

[0036] Preparation of Compound G

##STR00014##

[0037] Ph5Br—Pa (500 mg, 0.77 mmol), 1-pyrenyl boronic acid ester (2.53 g, 7.71 mmol) and tetrabutylammonium bromide (TBAB) (62.1 mg, 0.19 mmol) were added to a 100 mL two-necked flask, sealed with rubber stoppers, wrapped in foil paper to avoid light, and pumped with nitrogen for three times. Then, a catalyst Pd (PPh.sub.3).sub.4 (222.7 mg, 0.19 mmol) was added rapidly to the flask that was pumped with nitrogen for three times. Finally, the bubbled toluene (24 mL) and 2M K.sub.2CO.sub.3 aqueous solution (8 mL) were injected into the reaction flask and reacted at 95° C. for 48 h. After the reaction, the solution was extracted with the organic solvent DCM and saturated salt solution for three times to separate an organic layer, which was dried with MgSO.sub.4. The crude product obtained by concentrating the solution after suction filtration was separated and purified by column chromatography, and dried in a vacuum drying oven to obtain the product Ph6Py (682 mg, yield: 70.3%). MALDI-TOF-MS (m/z): calcd for C.sub.98H.sub.53NO, Molecular Weight: 1260.51, Exact Mass: 1259.41, Found: 1260.16 (M.sup.+).

Example 8

[0038] Preparation of Compound H

##STR00015##

[0039] Ph5Br-spiro AC (500 mg, 0.63 mmol), 1-pyrenyl boronic acid ester (2.06 g, 6.28 mmol) and tetrabutylammonium bromide (TBAB) (50.6 mg, 0.16 mmol) were added to a 100 mL two-necked flask, sealed with rubber stoppers, wrapped in foil paper to avoid light, and pumped with nitrogen for three times. Then, a catalyst Pd (PPh.sub.3).sub.4 (181.3 mg, 0.16 mmol) was added rapidly to the flask that was pumped with nitrogen for three times. Finally, the bubbled toluene (24 mL) and 2M K.sub.2CO.sub.3 aqueous solution (8 mL) were injected into the reaction flask and reacted at 95° C. for 48 h. After the reaction, the solution was extracted with the organic solvent DCM and saturated salt solution for three times to separate an organic layer, which was dried with MgSO.sub.4. The crude product obtained by concentrating the solution after suction filtration was separated and purified by column chromatography, and dried in a vacuum drying oven to obtain the product Ph6Py (643 mg, yield: 72.8%). MALDI-TOF-MS (m/z): calcd for C.sub.111H.sub.61N, Molecular Weight: 1408.72, Exact Mass: 1407.48, Found: 1407.86 (M.sup.+).

Example 9: Preparation of OLED Device

[0040] ITO glass was ultrasonically cleaned and treated with oxygen plasma to obtain the square resistance of 10 Ω/cm.sup.2. The hole injection layer was PEDOT or PVK, and the luminescent layer was any one of compound A, compound B, compound C, compound D, compound E, compound F, compound G, or compound H, which were amorphous and had good film-forming property. Both the hole injection layer and the luminescent layer were coated by spinning. The cathode electrode was Ca/AI or UFA, respectively; wherein the minimum start-up voltage of the OLED device prepared based on compound B was 3.12 V and the maximum luminance was 8865 cd/m.sup.2.

[0041] In addition to several cases described in the above embodiments, the following conditions shall fall within the applicable scope of the present invention by reason of similar preparation method as the above embodiments; that is, Ar is one of the electron-withdrawing groups such as bromine, fluorine, nitro, cyano, tertiary amine cation, trifluoromethyl, trichloromethyl, sulfonic acid group, formyl, acyl, carboxyl, methoxy, pyridyl, diphenyl sulfone, triazinyl and anthracenedione; or one of the electron-donating groups such as pyrenyl, 9-carbazolyl, 2-thienyl, diphenylamino, tert-butyl diphenylamino, 9-phenoxazinyl, acridinyl, spiro-bifluorenyl, spirofluorenyl acridinyl, alkylamino, dialkylamino, amino and hydroxyl.

[0042] The description of the embodiments of the inventor is only for a better understanding of the present invention. It should be noted that the present invention is not limited to these embodiments, and any equivalent transformations made according to the technical solutions of the present invention are within the protection scope of the present invention.