CN112661771B - Star-shaped fluorescent material based on asymmetric carbazole condensed rings and preparation method and application thereof - Google Patents
Star-shaped fluorescent material based on asymmetric carbazole condensed rings and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a star-shaped fluorescent material based on asymmetric carbazole condensed rings, and a preparation method and application thereof. The structural formula of the star-shaped fluorescent material based on the asymmetric carbazole fused rings is shown in the formula I:
the star-shaped fluorescent material based on the asymmetric carbazole condensed rings is a rigid conjugated molecule, and has good thermal stability and high fluorescence quantum yield; the spatial structure can effectively inhibit fluorescence quenching; the material has good hole and electron injection and transmission capability and bipolar transmission characteristic; the hybrid-local charge transfer state has the characteristics of hybrid-local charge transfer state, can obtain high exciton utilization rate and realize high efficiency; the performance is superior to that of a star fluorescent material based on carbazole symmetric condensed rings; the organic electroluminescent material has good solubility, can be dissolved in common organic solvents, is suitable for solution processing and ink-jet printing, can form a compact film, can prepare a luminescent layer, and is beneficial to preparing electroluminescent devices with excellent appearance; as a luminescent layer of a device, the external quantum efficiency is more than 9 percent, and the device has wide development prospect.
Description
Technical Field
The invention relates to the technical field of organic semiconductor materials, in particular to a star-shaped fluorescent material based on asymmetric carbazole fused rings, and a preparation method and application thereof.
Background
The electronic or optoelectronic industries such as organic material light emitting diodes (OLEDs), organic field effect transistors, organic solar cells, etc. are rapidly developing. Products based on organic light emitting diodes are published for a long time, but the vacuum evaporation process is adopted for preparing OLED devices at present, instruments and equipment are expensive, and the material utilization rate is low (about 20%), so that the price of OLED products is high. For preparing high-performance OLED light-emitting devices, organic functional materials are required to have good photoelectric properties, for example, as a charge transport layer, a host material of a light-emitting layer should have good bipolar transport properties, appropriate HOMO/LUMO energy levels, and high exciton utilization rate. Carbazole has good molecular planarity and higher transmission characteristic, and is beneficial to increasing radiation transition rate and improving luminous efficiency. The invention takes carbazole as a central construction unit, increases the planarity of molecules by widening a conjugated structure, and constructs a star-shaped fluorescent material of a carbazole fused ring. The molecule has the characteristics of high fluorescence quantum yield, high exciton utilization rate, higher and balanced carrier transmission capability, easily-adjusted spectrum and the like, and can be used for preparing a high-efficiency organic light-emitting diode.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a star-shaped fluorescent material based on asymmetric carbazole condensed rings. The material has good steric hindrance, effectively avoids fluorescence quenching caused by intermolecular aggregation in a solid state, obtains high-efficiency stable device performance, is suitable for solution processing, ink-jet printing and vacuum evaporation, and has great application potential.
The invention also aims to provide a preparation method of the star-shaped fluorescent material based on the asymmetric carbazole condensed rings.
The invention further aims to provide application of the star-shaped fluorescent material based on the asymmetric carbazole condensed rings.
The purpose of the invention is realized by the following technical scheme: a star-shaped fluorescent material based on asymmetric carbazole fused rings has a structural formula shown in formula I:
in the formula I, R is one of linear chain, branched chain or cyclic alkyl or alkoxy with 1-20 carbon atoms, linear chain, branched chain or cyclic alkenyl with 2-20 carbon atoms, linear chain, branched chain or cyclic alkynyl with 2-20 carbon atoms, linear chain, branched chain or cyclic alkylcarbonyl with 2-20 carbon atoms, aryl or heteroaryl with 4-20 ring atoms, aralkyl or heteroarylalkyl with 4-20 ring atoms, aryloxy or heteroaryloxy with 4-20 ring atoms, and arylalkoxy or heteroarylalkoxy with 4-20 ring atoms.
Ar is one of the following structures:
wherein R is one of a linear, branched or cyclic alkyl or alkoxy group having 1 to 20 carbon atoms, a linear, branched or cyclic alkenyl group having 2 to 20 carbon atoms, a linear, branched or cyclic alkynyl group having 2 to 20 carbon atoms, a linear, branched or cyclic alkylcarbonyl group having 2 to 20 carbon atoms, an aryl or heteroaryl group having 4 to 20 ring atoms, an aralkyl or heteroarylalkyl group having 4 to 20 ring atoms, an aryloxy or heteroaryloxy group having 4 to 20 ring atoms, an arylalkoxy or heteroarylalkoxy group having 4 to 20 ring atoms.
Preferably, Ar is
The structural formula of the star-shaped fluorescent material based on the asymmetric carbazole fused ring is shown as a formula II or III:
the preparation method of the star-shaped fluorescent material based on the asymmetric carbazole condensed rings comprises the following steps:
(1) uniformly mixing 2, 7-dibromo-9H-carbazole, an R-Br alkyl chain, potassium carbonate and a solvent N, N-dimethylformamide, reacting, and cooling to room temperature to obtain a compound a;
(2) under the protection of nitrogen, uniformly mixing the compound a with 1, 4-p-diphenylboronic acid pinacol ester, a palladium catalyst, a potassium carbonate solution and a solvent toluene, reacting, and cooling to obtain a compound b;
(3) uniformly mixing the compound b, Ar-Br, a palladium catalyst, a potassium carbonate solution and a solvent toluene, reacting, and cooling to obtain a compound c;
(4) uniformly mixing the compound c, N-bromosuccinimide and a solvent trichloromethane, reacting, and cooling to obtain a compound d;
(5) uniformly mixing the compound d, 2-tributyltin thiophene, a palladium catalyst and a solvent toluene, reacting, and cooling to obtain a compound e;
(6) uniformly mixing the compound e, N-bromosuccinimide and a solvent trichloromethane, reacting, and cooling to obtain a compound f;
(7) uniformly mixing a compound f, ferric trichloride, nitromethane and a solvent dichloromethane, reacting, and cooling to obtain a compound g;
(8) and uniformly mixing the compound g, Ar boric acid ester, a palladium catalyst, a potassium carbonate solution and a solvent toluene, reacting, and cooling to obtain the star-shaped fluorescent material based on the asymmetric carbazole condensed rings.
In the steps (2), (3), (5) and (8), the palladium catalyst is at least one selected from tetrakis (triphenylphosphine) palladium, palladium acetate, bis (triphenylphosphine) palladium dichloride and tris (dibenzylideneacetone) dipalladium; bis (triphenylphosphine) palladium dichloride is preferred.
In the step (1), the molar ratio of the 2, 7-dibromo-9H-carbazole to the R-Br alkyl chain is 1: 1-100.
In the step (1), the molar volume ratio of the 2, 7-dibromo-9H-carbazole to the solvent N, N-dimethylformamide is 1mol: 0.01-10L.
In the step (1), the molar ratio of the 2, 7-dibromo-9H-carbazole to the potassium carbonate is 1: 0.01-1.
The molar ratio of the compound a to the 1, 4-p-diphenylboronic acid pinacol ester in the step (2) is 1: 1-100.
The molar ratio of the compound a to the potassium carbonate in the step (2) is 1: 0.01-1.
The molar ratio of the compound a to the palladium catalyst in the step (2) is 1: 0.01-1.
The molar volume ratio of the compound a to the solvent toluene in the step (2) is 1mol: 0.01-10L.
The molar ratio of the compound b to Ar-Br in the step (3) is 1: 1-100.
The molar ratio of the compound b to the potassium carbonate in the step (3) is 1: 0.01-1.
The molar ratio of the compound b to the palladium catalyst in the step (3) is 1: 0.01-1.
The molar volume ratio of the compound b to the solvent toluene in the step (3) is 1mol: 0.01-10L.
The molar ratio of the compound c to the N-bromosuccinimide in the step (4) is 1: 2-10.
The molar volume ratio of the compound c to the solvent trichloromethane in the step (4) is 1mol: 0.01-10L.
The molar ratio of the compound d to the 2-tributyltin thiophene in the step (5) is 1: 1-100.
The molar ratio of the compound d to the palladium catalyst in the step (5) is 1: 0.01-1.
The molar volume ratio of the compound d to the solvent toluene in the step (5) is 1mol: 0.01-10L.
The molar ratio of the compound e to the N-bromosuccinimide in the step (6) is 1: 2-10.
The molar volume ratio of the compound e to the chloroform solvent in the step (6) is 1mol: 0.01-10L.
In the step (7), the molar ratio of the compound f to ferric trichloride is 1: 2-100.
The molar ratio of the compound f to the nitromethane in the step (7) is 1: 4-100.
The molar volume ratio of the compound f to the solvent dichloromethane in the step (7) is 1mol: 0.01-100L.
The molar ratio of the compound g to the Ar borate in the step (8) is 1: 2-100.
The molar ratio of the compound g to the potassium carbonate in the step (8) is 1: 0.01-1.
The molar ratio of the compound g to the palladium catalyst in the step (8) is 1: 0.01-1.
The molar volume ratio of the compound g to the solvent toluene in the step (8) is 1mol: 0.01-10L.
The reaction described in the steps (1) to (8) is a reflux stirring reaction.
The temperature of the reflux stirring reaction is 60-200 ℃, and the time is 1-24 h; preferably 8-24 h.
The cooling in steps (1) to (8) is cooling to room temperature.
The compounds described in steps (1) to (8) are extracted with dichloromethane, the organic phase is dried over magnesium sulfate, the solvent is dried by spinning, and the product is purified by silica gel chromatography and then used in the next step or as the final product.
And (3) carrying out the steps (1) to (8) under the protection of nitrogen.
R of the R-Br alkyl chain in the step (1) is one of a linear chain, branched chain or cyclic alkyl or alkoxy group with 1-20 carbon atoms, a linear chain, branched chain or cyclic alkenyl group with 2-20 carbon atoms, a linear chain, branched chain or cyclic alkynyl group with 2-20 carbon atoms, a linear chain, branched chain or cyclic alkylcarbonyl group with 2-20 carbon atoms, an aryl or heteroaryl group with 4-20 ring atoms, an aralkyl or heteroarylalkyl group with 4-20 ring atoms, an aryloxy or heteroaryloxy group with 4-20 ring atoms and an arylalkoxy or heteroarylalkoxy group with 4-20 ring atoms.
Ar-Br in the step (3) and Ar in the Ar boric acid ester in the step (8) are one of the following structures:
the preparation method of the star-shaped fluorescent material based on the asymmetric carbazole condensed rings has the following synthetic route:
the star-shaped fluorescent material based on the asymmetric carbazole condensed rings is applied to the preparation of organic electroluminescent devices.
The star-shaped fluorescent material based on the asymmetric condensed ring of carbazole is used for preparing a light-emitting layer of an organic electroluminescent device.
The organic electroluminescent device is a light emitting diode, an organic field effect transistor, an organic solar cell or an organic laser diode.
The preparation method specifically comprises the step of preparing the star fluorescent material into a small molecular pure film, or preparing the star fluorescent material and a host/guest material into a mixed film to be used as a light emitting layer of the organic electroluminescent device.
The star-shaped fluorescent material is dissolved by adopting an organic solvent, and is formed into a film through spin coating, ink-jet printing or printing.
Compared with the prior art, the invention has the following advantages and effects:
(1) the preparation method of the star-shaped fluorescent material based on the asymmetric carbazole condensed rings has the advantages of strong universality, mild synthesis conditions, high synthesis yield and the like, and can be popularized and applied to industrial amplified synthesis and production.
(2) The star-shaped fluorescent material based on the asymmetric carbazole condensed rings is a rigid conjugated molecule, and has good thermal stability and high fluorescence quantum yield; the spatial structure can effectively inhibit fluorescence quenching; the material has good hole and electron injection and transmission capability and bipolar transmission characteristic; has the hybrid-local charge transfer (HLCT) state characteristic, can obtain high exciton utilization rate and realize high efficiency.
(3) The performance of the star-shaped fluorescent material based on the asymmetric carbazole condensed rings is superior to that of the star-shaped fluorescent material based on the symmetric carbazole condensed rings; the organic electroluminescent material has good solubility, can be dissolved in common organic solvents, is suitable for solution processing and ink-jet printing, can form a compact film, can prepare a luminescent layer, and is beneficial to preparing electroluminescent devices with excellent appearance; as a luminous layer of the device, the external quantum efficiency is more than 9 percent, and the device has wide development prospect. By further optimizing the comprehensive performance of the molecules, the method can have larger development potential in other organic electronic fields.
Drawings
Fig. 1 is a plot of external quantum efficiency versus luminance for the luminescent layer material at S1.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the present invention is not limited thereto. The method is a conventional method unless otherwise specified. The starting materials are commercially available from the open literature unless otherwise specified. The reaction substrates 2, 7-dibromo-9H-carbazole, 1-bromooctane, and 2-tributylstannothiophene used in the examples were purchased from Suzhou Nakai science and technology Co., Ltd, and the remaining reaction solvents used were commercially available.
Example 1
A star-shaped fluorescent material based on asymmetric carbazole fused rings and having a chemical structure of S1 is synthesized by the following steps:
(1) synthesis of Compound a: under the protection of nitrogen, 2, 7-dibromo-9H-carbazole (10mmol), 1-bromo-octane (11mmol), potassium carbonate (0.1mmol) and 70mL of DMF solvent are added into a three-necked flask. After stirring the reaction at reflux for 10 hours, it was cooled to room temperature. Extracting with dichloromethane, drying the organic phase with magnesium sulfate, and spin-drying the solvent to obtain a crude product. And (5) purifying by using a silica gel chromatographic column to obtain the target compound a, wherein the yield is 89%. 1 H NMR、 13 CNMR, MS and element analysis show that the obtained compound is a target product.
(2) Synthesis of Compound b: under the protection of nitrogen, adding a compound a (10mmol), 1, 4-p-diphenylboronic acid pinacol ester (40mmol), a bis (triphenylphosphine) palladium dichloride catalyst (0.1mmol), a potassium carbonate solution (1mmol) and 70mL of a toluene solvent into a three-necked flask, and uniformly mixing. After stirring the reaction at reflux for 12 hours, it was cooled to room temperature. Extracting with dichloromethane, drying the organic phase with anhydrous magnesium sulfate, and spin-drying the solvent to obtain a crude product. And purifying by a silica gel chromatographic column to obtain the target compound b, wherein the yield is 80%. 1 H NMR、 13 CNMR, MS and element analysis show that the obtained compound is a target product.
(3) Synthesis of Compound c: under the protection of nitrogen, a three-necked flask is filled with a compound b (10mmol), 2-bromo-9-octyl-9H-carbazole (11mmol), a bis (triphenylphosphine) palladium dichloride catalyst (0.1mmol), 2mL of a 2M potassium carbonate solution and 30mL of a toluene solution. After stirring the reaction at reflux for 24 hours, it was cooled to room temperature. Extracting with dichloromethane, drying the organic phase with anhydrous magnesium sulfate, and spin-drying the solvent to obtain a crude product. And purifying by a silica gel chromatographic column to obtain the target compound c, wherein the yield is 75%. 1 H NMR、 13 CNMR, MS and element analysis, the results show that the obtained compound is the target product.
(4) Synthesis of Compound dComprises the following steps: under the protection of nitrogen, compound c (10mmol), N-bromosuccinimide (NBS, 40mmol) and 50mL of chloroform solvent are added into a three-necked flask. And (3) after refluxing, stirring and reacting for 8 hours, extracting by using dichloromethane, drying an organic phase by using anhydrous magnesium sulfate, and spin-drying a solvent to obtain a crude product. And purifying by a silica gel chromatographic column to obtain the target compound d, wherein the yield is 89%. 1 H NMR、 13 CNMR, MS and element analysis, the results show that the obtained compound is the target product.
(5) Synthesis of Compound e: under nitrogen protection, a three-necked flask was charged with compound d (10mmol), 2-tributyltin thiophene (40mmol), bis (triphenylphosphine) palladium dichloride catalyst (0.1mmol), and 50mL of toluene solvent. After stirring the reaction at reflux for 12 hours, it was cooled to room temperature. Extracting with dichloromethane, drying the organic phase with anhydrous magnesium sulfate, and spin-drying the solvent to obtain a crude product. Purifying by silica gel chromatography column to obtain the target compound e, wherein the yield is 90%. 1 H NMR、 13 CNMR, MS and element analysis, the results show that the obtained compound is the target product.
(6) Synthesis of Compound f: under the protection of nitrogen, compound e (10mmol), N-bromosuccinimide (NBS, 40mmol) and 50mL of chloroform solvent were added to a three-necked flask. And (3) after refluxing, stirring and reacting for 8 hours, extracting by using dichloromethane, drying an organic phase by using anhydrous magnesium sulfate, and spin-drying a solvent to obtain a crude product. And purifying by a silica gel chromatographic column to obtain the target compound f, wherein the yield is 89%. 1 H NMR、 13 CNMR, MS and element analysis, the results show that the obtained compound is the target product.
(7) Synthesis of Compound g: under nitrogen protection, compound f (10mmol), ferric trichloride (20mmol), nitromethane (100mmol) and 250mL of dichloromethane solvent were added to a three-necked flask. And (3) after refluxing, stirring and reacting for 8 hours, extracting by using dichloromethane, drying an organic phase by using anhydrous magnesium sulfate, and spin-drying a solvent to obtain a crude product. Purifying by silica gel chromatographic column to obtain the target compound g, wherein the yield is 85%. 1 H NMR、 13 The results of CNMR, MS and elemental analysis show that the obtained compound is a target product.
(8) Synthesis of star-shaped fluorescent material based on asymmetric carbazole fused ring and with chemical structural formula of S1The composition is as follows: under the protection of nitrogen, compound g (10mmol), 9-octyl-2- (4,4,5, 5-trimethyl-1, 3, 2-dioxaborolan-2-yl-) -9H-carbazole (30mmol), bis (triphenylphosphine) palladium dichloride catalyst (0.1mmol), 2mL of 2M potassium carbonate solution and 30mL of toluene solution were added to a three-necked flask. After stirring the reaction at reflux for 24 hours, it was cooled to room temperature. Extracting with dichloromethane, drying the organic phase with anhydrous magnesium sulfate, and spin-drying the solvent to obtain a crude product. Purifying by silica gel chromatography to obtain the target compound S1 with the yield of 75%. 1 H NMR、 13 CNMR, MS and element analysis, the results show that the obtained compound is the target product.
Example 2
A star-shaped fluorescent material based on asymmetric carbazole fused rings and having a chemical structure of S2 is synthesized by the following steps:
(1) synthesis of Compound a: under the protection of nitrogen, 2, 7-dibromo-9H-carbazole (10mmol), 1-bromo-octane (11mmol), potassium carbonate (0.1mmol) and 70mL of DMF solvent are added into a three-necked flask. After stirring at reflux for 10 hours, it was cooled to room temperature. Extracting with dichloromethane, drying the organic phase with magnesium sulfate, and spin-drying the solvent to obtain a crude product. And purifying by a silica gel chromatographic column to obtain the target compound a, wherein the yield is 87%. 1 H NMR、 13 CNMR, MS and element analysis show that the obtained compound is a target product.
(2) Synthesis of Compound b: under the protection of nitrogen, adding a compound a (10mmol), 1, 4-p-diphenylboronic acid pinacol ester (40mmol), a bis (triphenylphosphine) palladium dichloride catalyst (0.1mmol), a potassium carbonate solution (1mmol) and 70mL of a toluene solvent into a three-necked flask, and uniformly mixing. After stirring the reaction at reflux for 12 hours, it was cooled to room temperature. Extracting with dichloromethane, drying the organic phase with anhydrous magnesium sulfate, and spin-drying the solvent to obtain a crude product. And purifying by a silica gel chromatographic column to obtain the target compound b, wherein the yield is 83%. 1 H NMR、 13 CNMR, MS and element analysis, the results show that the obtained compound is the target product.
(3) Synthesis of Compound c: under the protection of nitrogen, compound b (10mmol) and 3-diphenyl [ b, d ] are added into a three-mouth bottle]Thiophene 5, 5-bifluorene (11mmol), bis (triphenylphosphine) palladium dichloride catalyst (0.1mmol), 2mL of 2M potassium carbonate solution, and 30mL of toluene solution. After stirring at reflux for 24 hours, it was cooled to room temperature. Extracting with dichloromethane, drying the organic phase with anhydrous magnesium sulfate, and spin-drying the solvent to obtain a crude product. And purifying by a silica gel chromatographic column to obtain the target compound c, wherein the yield is 78%. 1 H NMR、 13 CNMR, MS and element analysis, the results show that the obtained compound is the target product.
(4) Synthesis of Compound d: under the protection of nitrogen, compound c (10mmol), N-bromosuccinimide (NBS, 40mmol) and 50mL of chloroform solvent are added into a three-necked flask. And (3) after refluxing, stirring and reacting for 8 hours, extracting by using dichloromethane, drying an organic phase by using anhydrous magnesium sulfate, and spin-drying a solvent to obtain a crude product. And purifying by a silica gel chromatographic column to obtain the target compound d, wherein the yield is 86%. 1 H NMR、 13 CNMR, MS and element analysis, the results show that the obtained compound is the target product.
(5) Synthesis of Compound e: under nitrogen protection, a three-necked flask was charged with compound d (10mmol), 2-tributyltin thiophene (40mmol), bis (triphenylphosphine) palladium dichloride catalyst (0.1mmol), and 50mL of toluene solvent. After stirring at reflux for 12 hours, it was cooled to room temperature. Extracting with dichloromethane, drying the organic phase with anhydrous magnesium sulfate, and spin-drying the solvent to obtain a crude product. And purifying by a silica gel chromatographic column to obtain the target compound e, wherein the yield is 89%. 1 H NMR、 13 CNMR, MS and element analysis, the results show that the obtained compound is the target product.
(6) Synthesis of Compound f: under the protection of nitrogen, compound e (10mmol), N-bromosuccinimide (NBS, 40mmol) and 50mL of chloroform solvent are added into a three-necked flask. And (3) after refluxing, stirring and reacting for 8 hours, extracting by using dichloromethane, drying an organic phase by using anhydrous magnesium sulfate, and spin-drying a solvent to obtain a crude product. And purifying by a silica gel chromatographic column to obtain the target compound f, wherein the yield is 80%. 1 H NMR、 13 CNMR, MS and element analysis, the results show that the obtained compound is the target product.
(7) Synthesis of Compound g: under nitrogen protection, compound f (10mmol), ferric trichloride (20mmol), nitromethane (100mmol) and 250mL of dichloromethane solvent were added to a three-necked flask. And (3) after refluxing, stirring and reacting for 8 hours, extracting by using dichloromethane, drying an organic phase by using anhydrous magnesium sulfate, and spin-drying a solvent to obtain a crude product. And purifying by a silica gel chromatographic column to obtain the target compound g, wherein the yield is 82%. 1 H NMR、 13 CNMR, MS and element analysis, the results show that the obtained compound is the target product.
(8) Synthesis of star-shaped fluorescent material based on asymmetric carbazole fused ring with chemical structural formula of S2: under the protection of nitrogen, compound g (10mmol), 9-octyl-2- (4,4,5, 5-trimethyl-1, 3, 2-dioxaborolan-2-yl-) dibenzo [ b, d ] is added into a three-neck flask]Thiophene 5, 5-dibenzothiophene (20mmol), bis (triphenylphosphine) palladium dichloride catalyst (0.1mmol), 2mL of 2M potassium carbonate solution, and 30mL of toluene solution. After stirring at reflux for 24 hours, it was cooled to room temperature. Extracting with dichloromethane, drying the organic phase with anhydrous magnesium sulfate, and spin-drying the solvent to obtain a crude product. Purifying by silica gel chromatography to obtain the target compound S2 with the yield of 78%. 1 H NMR、 13 CNMR, MS and element analysis, the results show that the obtained compound is the target product.
Comparative example 1
A star-shaped fluorescent material based on carbazole fused rings and having a chemical structure of S3 is disclosed, wherein the synthetic route is as follows:
(1) synthesis of Compound a: under the protection of nitrogen, 2,3,6, 7-tetrabromo-9H-carbazole (10mmol), 1-bromo-octane (11mmol), potassium carbonate (0.1mmol) and 70mL of DMF solvent are added into a three-necked flask. After stirring the reaction at reflux for 10 hours, it was cooled to room temperature. Extracting with dichloromethane, drying the organic phase with magnesium sulfate, and spin-drying the solvent to obtain a crude product. And purifying by a silica gel chromatographic column to obtain the target compound a, wherein the yield is 89%. 1 H NMR、 13 CNMR, MS and element analysis, the results show that the obtained compound is the target product.
(2) Synthesis of Compound b: under the protection of nitrogen, a three-necked flask is added with compound a (10mmol), 2-tributyltin thiophene (40mmol), 50mL of toluene solvent and bis (triphenylphosphine) palladium dichloride catalyst (0.1 mmol). After stirring the reaction at reflux for 12 hours, it was cooled to room temperature. Extracting with dichloromethane, drying the organic phase with anhydrous magnesium sulfate, and spin-drying the solvent to obtain a crude product. And purifying by a silica gel chromatographic column to obtain the target compound b, wherein the yield is 90%. 1 H NMR、 13 CNMR, MS and element analysis, the results show that the obtained compound is the target product.
(3) Synthesis of Compound c: under nitrogen protection, compound b (10mmol), ferric trichloride (20mmol), nitromethane (100mmol) and 250mL of dichloromethane solvent were added to a three-necked flask. And (3) after refluxing, stirring and reacting for 8 hours, extracting by using dichloromethane, drying an organic phase by using anhydrous magnesium sulfate, and spin-drying a solvent to obtain a crude product. And purifying by using a silica gel chromatographic column to obtain the target compound c, wherein the yield is 85%. 1 H NMR、 13 CNMR, MS and element analysis, the results show that the obtained compound is the target product.
(4) Synthesis of Compound d: under the protection of nitrogen, compound c (10mmol), N-bromosuccinimide (NBS, 45mmol) and 50mL of chloroform solvent were placed in a three-necked flask. And (3) after refluxing, stirring and reacting for 8 hours, extracting by using dichloromethane, drying an organic phase by using anhydrous magnesium sulfate, and spin-drying a solvent to obtain a crude product. And purifying by a silica gel chromatographic column to obtain the target compound d, wherein the yield is 89%. 1 H NMR、 13 CNMR, MS and element analysis, the results show that the obtained compound is the target product.
(5) Synthesis of Star-shaped fluorescent Material having the chemical formula S3: under the protection of nitrogen, a three-necked flask was charged with compound d (10mmol), 9-octyl-2- (4,4,5, 5-trimethyl-1, 3, 2-dioxaborolan-2-yl-) -9H-carbazole (50mmol), bis (triphenylphosphine) palladium dichloride catalyst (0.1mmol), 2mL of a 2M potassium carbonate solution, and 30mL of a toluene solution. After stirring the reaction at reflux for 24 hours, it was cooled to room temperature. Extracting with dichloromethane, drying the organic phase with anhydrous magnesium sulfate, and spin-drying the solvent to obtain a crude product. And purifying by a silica gel chromatographic column to obtain the target compound d, wherein the yield is 75%. 1 H NMR、 13 CNMR, MS and element analysis, the results show that the obtained compound is the target product.
Comparative example 2
A star-shaped fluorescent material based on carbazole fused rings and having a chemical structure of S4 is disclosed, wherein the synthetic route is as follows:
(1) synthesis of Compound a: under the protection of nitrogen, 2,3,6, 7-tetrabromo-9H-carbazole (10mmol), 1-bromo-octane (11mmol), potassium carbonate (0.1mmol) and 70mL of DMF solvent are added into a three-necked flask. After stirring the reaction at reflux for 10 hours, it was cooled to room temperature. Extracting with dichloromethane, drying the organic phase with magnesium sulfate, and spin-drying the solvent to obtain a crude product. And purifying by a silica gel chromatographic column to obtain the target compound a, wherein the yield is 89%. 1 H NMR、 13 CNMR, MS and element analysis, the results show that the obtained compound is the target product.
(2) Synthesis of Compound b: under nitrogen protection, a three-necked flask was charged with compound a (10mmol), 2-tributyltin thiophene (50mmol), and 50mL of toluene solvent and bis (triphenylphosphine) palladium dichloride catalyst (0.1 mmol). After stirring the reaction at reflux for 12 hours, it was cooled to room temperature. Extracting with dichloromethane, drying the organic phase with anhydrous magnesium sulfate, and spin-drying the solvent to obtain a crude product. And purifying by a silica gel chromatographic column to obtain the target compound b, wherein the yield is 90%. 1 H NMR、 13 CNMR, MS and element analysis show that the obtained compound is the target product.
(3) Synthesis of Compound c: under nitrogen protection, compound b (10mmol), ferric trichloride (20mmol), nitromethane (100mmol) and 250mL of dichloromethane solvent were added to a three-necked flask. And (3) after refluxing, stirring and reacting for 8 hours, extracting by using dichloromethane, drying an organic phase by using anhydrous magnesium sulfate, and spin-drying a solvent to obtain a crude product. And purifying by a silica gel chromatographic column to obtain the target compound c, wherein the yield is 85%. 1 H NMR、 13 CNMR, MS and element analysis, the results show that the obtained compound is the target product.
(4) TransformingSynthesis of Compound d: under the protection of nitrogen, compound c (10mmol), N-bromosuccinimide (NBS, 40mmol) and 50mL of chloroform solvent are added into a three-necked flask. And (3) after refluxing, stirring and reacting for 8 hours, extracting by using dichloromethane, drying an organic phase by using anhydrous magnesium sulfate, and spin-drying a solvent to obtain a crude product. Purifying by silica gel chromatographic column to obtain the target compound d, wherein the yield is 89%. 1 H NMR、 13 CNMR, MS and element analysis, the results show that the obtained compound is the target product.
(5) Synthesis of Star-shaped fluorescent Material having the chemical formula S4: under the protection of nitrogen, compound d (10mmol), 9-octyl-2- (4,4,5, 5-trimethyl-1, 3, 2-dioxaborolan-2-yl-) dibenzo [ b, d ] is added into a three-neck flask]Thiophene 5, 5-dioxide (50mmol), bis (triphenylphosphine) palladium dichloride catalyst (0.1mmol), 2mL of 2M potassium carbonate solution, and 30mL of toluene solution. After stirring the reaction at reflux for 24 hours, it was cooled to room temperature. Extracting with dichloromethane, drying the organic phase with anhydrous magnesium sulfate, and spin-drying the solvent to obtain a crude product. And purifying by a silica gel chromatographic column to obtain the target compound d, wherein the yield is 76%. 1 H NMR、 13 CNMR, MS and element analysis, the results show that the obtained compound is the target product.
Determination of properties of the star-shaped fluorescent materials S1, S2, S3 and S4 based on asymmetric/symmetric condensed carbazole rings prepared in examples 1 and 2 and comparative examples 3 and 4:
preparation of organic light emitting diode
Indium Tin Oxide (ITO) glass with the square resistance of 15 omega, which is prepared in advance, is taken, ultrasonic cleaning is carried out by acetone, deionized water and isopropanol in sequence, and plasma treatment is carried out for 10 minutes. Then, 2,3,6,7,10, 11-hexacyano-1, 4,5,8,9, 12-Hexaazatriphenylene (HATCN) with the thickness of 5nm as a hole injection layer, 4 '-cyclohexylbis [ N, N-bis (4-methylphenyl) aniline ] (TAPC) with the thickness of 25nm as a hole transport layer, 4' -tris (carbazole-9-yl) triphenylamine (TCTA) with the thickness of 15nm as an exciton blocking layer, the carbazole asymmetric/symmetric condensed ring star-shaped fluorescent material of the invention with the thickness of 20nm as a light emitting layer, 1,3, 5-tris (1-phenyl-1H-benzimidazole-2-yl) benzene (TPBi) with the thickness of 40nm as an electron transport layer, lithium fluoride (LiF) with the thickness of 1nm as an electron injection layer, and the ITO layer are sequentially evaporated on the surface of the ITO in a vacuum evaporation device, Aluminum (Al) 100nm thick was used as the cathode. The electroluminescence properties of each of the light emitting materials are shown in table 1 below.
TABLE 1
| Luminescent layer material | Maximum external quantum efficiency (%) | Maximum luminance (cd m) -2 ) |
| S1 | 9.2 | 25000 |
| S2 | 9.0 | 24000 |
| S3 | 5.5 | 13000 |
| S4 | 5.8 | 15000 |
As can be seen from table 1, the external quantum efficiency and the maximum luminance of the star-shaped phosphors S1 and S2 having the carbazole-based asymmetric condensed rings are greater than those of the star-shaped phosphors S3 and S4 having the carbazole-based asymmetric condensed rings.
Fig. 1 is a curve of external quantum efficiency versus luminance of the device when S1 is a material of the light emitting layer, and it can be found that the device has very high efficiency, the external quantum efficiency reaches 9.2%, and the efficiency roll-off of the device is small.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (9)
1. A star-shaped fluorescent material based on asymmetric carbazole fused rings is characterized in that the structural formula is shown as the formula I:
ar is one of the following structures:
in the formula I and Ar, R is a straight chain or branched chain alkyl with 1-20 carbon atoms.
2. The star-shaped fluorescent material based on asymmetric carbazole condensed rings according to claim 1,
the structural formula of the star-shaped fluorescent material based on the asymmetric carbazole condensed ring is shown as a formula S1 or a formula S2:
3. the method for preparing a star-shaped fluorescent material based on asymmetric carbazole fused rings according to claim 1, comprising the following steps:
(1) uniformly mixing 2, 7-dibromo-9H-carbazole, an R-Br alkyl chain, potassium carbonate and a solvent N, N-dimethylformamide, reacting, and cooling to room temperature to obtain a compound a;
(2) under the protection of nitrogen, uniformly mixing the compound a with 1, 4-p-diphenylboronic acid pinacol ester, a palladium catalyst, a potassium carbonate solution and a solvent toluene, reacting, and cooling to obtain a compound b;
(3) uniformly mixing the compound b, Ar-Br, a palladium catalyst, a potassium carbonate solution and a solvent toluene, reacting, and cooling to obtain a compound c;
(4) uniformly mixing the compound c, N-bromosuccinimide and a solvent trichloromethane, reacting, and cooling to obtain a compound d;
(5) uniformly mixing the compound d, 2-tributyltin thiophene, a palladium catalyst and a solvent toluene, reacting, and cooling to obtain a compound e;
(6) uniformly mixing the compound e, N-bromosuccinimide and a solvent trichloromethane, reacting, and cooling to obtain a compound f;
(7) uniformly mixing a compound f, ferric trichloride, nitromethane and a solvent dichloromethane, reacting, and cooling to obtain a compound g;
(8) and uniformly mixing the compound g, Ar boric acid ester, a palladium catalyst, a potassium carbonate solution and a solvent toluene, reacting, and cooling to obtain the star-shaped fluorescent material based on the asymmetric carbazole condensed rings.
4. The method for preparing a star-shaped fluorescent material based on asymmetric carbazole fused rings according to claim 3, wherein in the steps (2), (3), (5) and (8), the palladium catalyst is at least one selected from tetrakis (triphenylphosphine) palladium, palladium acetate, bis (triphenylphosphine) palladium dichloride and tris (dibenzylideneacetone) dipalladium.
5. The preparation method of the star-shaped fluorescent material based on the asymmetric carbazole condensed rings according to claim 4, wherein in the steps (2), (3), (5) and (8), the palladium catalyst is bis (triphenylphosphine) palladium dichloride.
6. The preparation method of the star-shaped fluorescent material based on the asymmetric carbazole condensed rings according to any one of claims 3 to 5,
in the step (1), the molar ratio of the 2, 7-dibromo-9H-carbazole to the R-Br alkyl chain is 1: 1-100;
in the step (1), the molar volume ratio of the 2, 7-dibromo-9H-carbazole to the solvent N, N-dimethylformamide is 1mol: 0.01-10L;
in the step (1), the molar ratio of the 2, 7-dibromo-9H-carbazole to the potassium carbonate is 1: 0.01-1;
the molar ratio of the compound a to the 1, 4-p-diphenylboronic acid pinacol ester in the step (2) is 1: 1-100;
the molar ratio of the compound a to the potassium carbonate in the step (2) is 1: 0.01-1;
the molar ratio of the compound a to the palladium catalyst in the step (2) is 1: 0.01-1;
the molar volume ratio of the compound a to the solvent toluene in the step (2) is 1mol: 0.01-10L;
the molar ratio of the compound b to Ar-Br in the step (3) is 1: 1-100;
the molar ratio of the compound b to the potassium carbonate in the step (3) is 1: 0.01-1;
the molar ratio of the compound b to the palladium catalyst in the step (3) is 1: 0.01-1;
the molar volume ratio of the compound b to the solvent toluene in the step (3) is 1mol: 0.01-10L;
the molar ratio of the compound c to the N-bromosuccinimide in the step (4) is 1: 2-10;
the molar volume ratio of the compound c to the solvent trichloromethane in the step (4) is 1mol: 0.01-10L;
the molar ratio of the compound d to the 2-tributylstanniophene in the step (5) is 1: 1-100;
the molar ratio of the compound d to the palladium catalyst in the step (5) is 1: 0.01-1;
the molar volume ratio of the compound d to the solvent toluene in the step (5) is 1mol: 0.01-10L;
the molar ratio of the compound e to the N-bromosuccinimide in the step (6) is 1: 2-10;
the molar volume ratio of the compound e to the chloroform solvent in the step (6) is 1mol: 0.01-10L;
the molar ratio of the compound f to ferric trichloride in the step (7) is 1: 2-100;
the molar ratio of the compound f to the nitromethane in the step (7) is 1: 4-100;
the molar volume ratio of the compound f to the solvent dichloromethane in the step (7) is 1mol: 0.01-100L;
the molar ratio of the compound g to Ar borate in the step (8) is 1: 1-100;
the molar ratio of the compound g to the potassium carbonate in the step (8) is 1: 0.01-1;
the molar ratio of the compound g to the palladium catalyst in the step (8) is 1: 0.01-1;
the molar volume ratio of the compound g to the solvent toluene in the step (8) is 1mol: 0.01-10L.
7. The preparation method of star-shaped fluorescent material based on carbazole asymmetric condensed rings according to any one of claims 3 to 5, characterized in that,
the reaction in the steps (1) - (8) is a reflux stirring reaction;
the temperature of the reflux stirring reaction is 60-200 ℃, and the time is 1-24 h;
extracting the compound in the steps (1) to (8) by adopting dichloromethane, drying an organic phase by using magnesium sulfate, spin-drying a solvent, purifying by adopting a silica gel chromatographic column, and then using the product for the next reaction or being a final product;
the cooling in the steps (1) to (8) is cooling to room temperature;
and (3) carrying out the steps (1) to (8) under the protection of nitrogen.
8. Use of a star-shaped fluorescent material based on asymmetric carbazole fused rings according to claim 1 or 2 for the preparation of organic electroluminescent devices,
the star-shaped fluorescent material based on asymmetric carbazole condensed rings is used for preparing a light-emitting layer of an organic electroluminescent device;
the organic electroluminescent device is a light emitting diode, an organic field effect transistor, an organic solar cell or an organic laser diode.
9. The application of claim 8, wherein the preparation is specifically to prepare the star-shaped fluorescent material into a pure small molecule film, or prepare the star-shaped fluorescent material and a host/guest material into a mixed film as a light emitting layer of an organic electroluminescent device;
the star-shaped fluorescent material is dissolved by adopting an organic solvent, and is formed into a film through spin coating, ink-jet printing or printing.
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