CN113185502A - Thioxanthone-based thermally induced delayed fluorescent material and preparation method thereof - Google Patents
Thioxanthone-based thermally induced delayed fluorescent material and preparation method thereof Download PDFInfo
- Publication number
- CN113185502A CN113185502A CN202110523113.XA CN202110523113A CN113185502A CN 113185502 A CN113185502 A CN 113185502A CN 202110523113 A CN202110523113 A CN 202110523113A CN 113185502 A CN113185502 A CN 113185502A
- Authority
- CN
- China
- Prior art keywords
- thioxanthone
- fluorescent material
- formula
- delayed fluorescent
- induced delayed
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
- C07D409/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing three or more hetero rings
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1007—Non-condensed systems
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1044—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1092—Heterocyclic compounds characterised by ligands containing sulfur as the only heteroatom
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Electroluminescent Light Sources (AREA)
Abstract
The invention belongs to the technical field of photoelectric display devices, and particularly relates to a thioxanthone-based thermally induced delayed fluorescent material and a preparation method thereof. The invention provides a thioxanthone-based thermally induced delayed fluorescent material, which has a structural formula shown as a formula (I): the invention also provides a preparation method of the thioxanthone-based thermally induced delayed fluorescent material, which comprises the following steps: carrying out coupling reaction on the compound shown in the formula (II) and 2-bromo-8- (pyridine-1-yl) thioxanthene to obtain a compound shown in the formula (I); the invention provides a thioxanthone-based thermally induced delayed fluorescent material and a preparation method thereof, and solves the technical problems of few types of existing red light materials and low device efficiency.
Description
Technical Field
The invention relates to the technical field of photoelectric display devices, in particular to a thioxanthone-based thermally induced delayed fluorescent material and a preparation method thereof.
Background
In recent years, scientists have been interested in developing a new generation of delayed organic electroluminescent materials based on the conversion of triplet excitons into singlet excitons, such as organic electroluminescent materials having a triplet-triplet delayed fluorescence effect and a thermally activated delayed fluorescence effect, due to the low efficiency of conventional fluorescent organic light emitting diodes and the high cost of phosphorescent organic light emitting diodes. Among them, TADF materials are the fastest growing. In the electroluminescent tricolor material, the molecular synthesis of the material is difficult due to the red TADF. Therefore, the number of red molecular species is relatively small, and the device efficiency is not high.
Disclosure of Invention
The invention provides a thioxanthone-based thermally induced delayed fluorescent material and a preparation method thereof, and solves the technical problems of few types of existing red light materials and low device efficiency.
The invention provides a thioxanthone-based thermally induced delayed fluorescent material, which has a structural formula shown as a formula (I):
wherein X is N, O or S.
Preferably, it has the structural formula
The invention also provides a preparation method of the thioxanthone-based thermally induced delayed fluorescent material, which comprises the following steps: carrying out coupling reaction on the compound shown in the formula (II) and 2-bromo-8- (pyridine-1-yl) thioxanthene to obtain a compound shown in the formula (I);
preferably, the compound represented by the formula (II) is prepared by the following steps: carrying out coupling reaction on a compound shown as a formula (III) and diboron pinacol ester to prepare a compound shown as a formula (II);
preferably, the time of the coupling reaction is 12-72 h.
Preferably, the coupling reaction time is 36 h.
The invention has the following beneficial effects:
the emission wavelength of the TADF material prepared by the embodiment of the invention is 600-650nm, the color coordinates of the TADF material are shown as red light emission, the fluorescence quantum yield of the TADF material prepared by the embodiment of the invention is more than 70%, and the delay decay lifetime tau d (mu s) of the TADF material is smaller, which shows that the roll-off of the electroluminescent efficiency of the TADF material is smaller.
The TADF material prepared by the embodiment of the invention has gradually increased brightness, starting voltage and delta ESTTaper down, where the optimal device performance data is: the on-off voltage was 3.8V, and the luminance was 14748cd/m2The maximum external quantum efficiency can reach 22.5%, and the external quantum efficiencies of the TADF materials prepared by the embodiment of the invention are all above 15%, which shows that reverse system jump of T1-S1 exists in the molecular structure, and the external quantum efficiency does not change greatly along with the increase of the current efficiency in the embodiment of the invention, which shows that the electroluminescent device stability of the TADF materials prepared by the embodiment of the invention is better.
Drawings
FIG. 1 is a HOMO energy level diagram of a TADF material made in accordance with the present invention;
FIG. 2 is a LUMO energy level diagram of a TADF material produced according to the present invention;
FIG. 3 is a PL spectrum for an embodiment of the present invention;
FIG. 4 is a current density-voltage curve of an electroluminescent device made in accordance with an embodiment of the present invention;
FIG. 5 is a voltage-luminance curve of an electroluminescent device made in accordance with an embodiment of the present invention;
fig. 6 is an external quantum efficiency-current density curve of an electroluminescent device made in accordance with an embodiment of the present invention.
Detailed Description
The present invention will be described in further detail with reference to specific examples, which are not intended to limit the present invention in any manner. Reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated.
Example 1
Thianthrene (4.32g,20mmol), liquid bromine (9.59g,60mmol) and 100mL of acetic acid were added to a 250mL three-necked round-bottomed flask, heated under reflux under an argon atmosphere and reacted at 80 ℃ for 10 hours. Stopping the reaction, cooling to room temperature, washing the reaction solution for 2-3 times, concentrating the reaction solution, purifying the reaction solution by a chromatographic column, wherein the silica gel has 200-300 meshes, and the eluent is petroleum ether/ethyl acetate (1:3) to obtain 2, 8-dibromothianthrene (5.98g, the yield is about 80%) according to the chemical reaction equation:
example 2
To a suspension of 2, 8-dibromothianthrene (4.63g, 10mmol) in anhydrous THF (120mL) under a nitrogen atmosphere at-78 deg.C was added dropwise n-butyllithium (6.4mL, 12.8mmol, 2.0M in cyclohexane). Stirring was continued for 3h, then 5-phenyl-5, 10-dihydrophenazine (3.10g, 12mmol) was added, the mixed solution was warmed to 15 ℃ and after stirring for 5 h, the reaction was monitored by TLC, the resulting organic compound was extracted with dichloromethane, the residue obtained was dissolved in dichloromethane (50ml) and after stirring at room temperature for 4h, the organic phase was dried over anhydrous magnesium sulfate. The crude product obtained was subjected to silica gel column chromatography (petroleum ether: dichloromethane (3: 2) as eluent) to give the product 2-bromo-8- (pyridin-1-yl) thioxanthene (2.22g, 65% yield) according to the equation:
example 3
Mixing a compound (3.21,8mmol) shown in formula (III), pinacol diboron (2.54g, 10mmol), and CH3COOK (4.9g,50mmol) and freshly distilled toluene (100mL) are weighed in a 200mL reaction flask in sequence, argon is introduced for 5min, then the catalyst 1, 1' -bis-diphenylphosphino ferrocene palladium Dichloride (DPPF) (200mg) is added, a plug is screwed, and the reaction is carried out for 24h at 90 ℃. Purification by extraction gave the product compound of formula (II) (2.42g, 61% yield) according to the chemical reaction equation:
example 4
A compound of formula (II) (2.48g, 5mmol) and 2-bromo-8- (pyridin-1-yl) thioxanthene(4.95g，10mmol)，K2CO3A mixture of (2M, 50mL), toluene (120mL), ethanol (50mL) and triphenylamine borate (2.97g, 8mmol) was added to a 250mL three-neck flask. After stirring at room temperature under an argon atmosphere for 20 minutes, tetrakis (triphenylphosphine) palladium (0) (0.575g, 0.5mmol) was added to the mixed solution. Heat to 90 ℃ and stir for 12 hours. The extraction reaction mixture was purified with DCM and further purified by silica gel column chromatography to give the product compound 1(3.53g, 63% yield) according to the chemical reaction equation:
example 5
The difference between this example and example 4 is: the reaction time of example 5 was 24h and the reaction time of example 4 was 12h, to finally obtain the product, Compound 2(3.89g, 67% yield).
Example 6
The difference between this example and example 4 is: the reaction time for example 6 was 36h and the reaction time for example 4 was 12h, to finally obtain the product, Compound 3(4.132g, 66% yield).
Example 7
The difference between this example and example 4 is: the reaction time for example 7 was 72h and the reaction time for example 4 was 12h, to finally obtain the product, Compound 4(4.18g, 65% yield).
In conclusion, the fluorescence quantum yield is tested by a HAMAMATSU C11347 fluorescence quantum tester; TADF material was tested for brightness, ignition voltage, etc. using a Keithley236 instrument and calibrated with a silicon photodiode. Transient lifetime testing and delayed lifetime were determined using an EdinburghInsumentsFLS 980 spectrometer. Outside the nitrogen glove box, the Electroluminescence (EL) spectra and the color coordinates CIE are determined with an optical analyzer, model integrating sphere IS-080, photresearchpr 705, respectively, after the device has been encapsulated.
The preparation process of the device comprises the following steps:
1) and putting the film developing frame with the ITO glass substrate in acetone, isopropanol, a washing solution and deionized water, and ultrasonically treating the possibly residual stains, such as photoresist and the like, on the surface of the ITO glass substrate by using an ultrasonic device and improving interface contact. Then drying in a vacuum oven;
2) placing the ITO in an oxygen Plasma etching instrument, continuously bombarding the ITO for 30 minutes by using O2Plasma, and completely removing possible residual organic matters on the surface of the ITO glass substrate;
3) HAT-CN was spin-coated on the ITO to a thickness of 10nm, and functions to reduce the influence of leakage current while increasing hole injection. Then drying the mixture in a vacuum oven for 12 hours at a temperature of 75 ℃;
4) in a glove box under nitrogen atmosphere, α -NPD was spin-coated on the HAT-CN layer to a thickness of about 40nm and heated at 100 ℃ for 30 minutes to remove the residual solvent.
5) And a layer of PPF-doped luminous organic film is spin-coated on the PVK layer, and the thickness of the PPF-doped luminous organic film is 80 nm. Heating and annealing for 20 minutes at the temperature of 80 ℃ on a heating table to remove residual solvent and improve the appearance of the luminescent layer film;
6) in the vacuum evaporation chamber, a layer of lithium fluoride (LiF) which is helpful for electron injection is firstly evaporated on the luminescent layer, and the thickness is 1 nm. Then, a layer of aluminum (Al) cathode is evaporated, and the thickness is 150 nm. The effective area of the device is 0.18cm2. The thickness of the organic layer was measured by a quartz crystal monitoring thickness gauge. The device is prepared by polar curing and encapsulating in ultraviolet light with epoxy resin and thin-layer glass. The final device structure is
ITO(120nm)/HAT-CN(10nm)/α-NPD(40nm)/emitter:PPF(80nm)/LiF(1nm)/Al(150nm)
Fig. 1 and 2 are graphs of HOMO level and LUMO level of the TADF material prepared according to the present invention, respectively, and it can be seen from fig. 1 and 2 that the separation effect of HOMO level and LUMO level orbitals is good, and the TADF material exhibits obvious characteristics.
FIG. 3 is a PL spectrum of an example of the present invention, and it can be seen from FIG. 3 that the emission wavelengths of the compounds prepared in the example of the present invention are all in the red region, wherein Table 1 shows photophysical data of TADF materials prepared in examples 4-7 of the present invention. Specifically, UV-Vis absorption and PL data were both at a concentration of 1X 10-5Of MMeasurement in toluene solution. Introducing N into the solution to be measured before phi PL and fluorescence attenuation measurement2。
TABLE 1 photophysical data for TADF materials obtained in examples 4-7 of the invention
As can be seen from Table 1, the emission wavelengths of the TADF materials prepared by the inventive examples 4-7 are all 600-650nm, and the color coordinates thereof are all shown as red light emission, the fluorescence quantum yields of the TADF materials prepared by the inventive examples 4-7 are all above 70%, and the decay lifetime τ d (μ s) of the invention is small, which indicates that the roll-off of the electroluminescence efficiency of the invention is small.
The compounds prepared in examples 4-7 are TADF luminescent materials, wherein HAT-CN and alpha-NPD respectively refer to 1,4,5,8,9, 12-hexaazatriphenylene hexacyano-nitrile and 4,4' -bis (N- (naphthalene-1-yl) -N-phenylamino) biphenyl, the external quantum efficiency-current density curve of the electroluminescent device is shown in FIG. 4, the current density-voltage curve is shown in FIG. 5, and the voltage-luminance curve is shown in FIG. 6, wherein the specific electroluminescent performance data are shown in Table 2.
TABLE 2 data on the electroluminescence properties of TADF materials obtained in examples 4 to 7 according to the invention
| Examples | Von | L(cd/m2) | EQE(％) | △EST |
| Example 4 | 4.2 | 11324 | 15.3 | 0.029 |
| Example 5 | 3.9 | 11364 | 17.4 | 0.023 |
| Example 6 | 3.8 | 14748 | 22.5 | 0.016 |
| Example 7 | 3.9 | 14231 | 21.4 | 0.015 |
As can be seen from FIGS. 4 to 6 and Table 2, TADF materials obtained in examples 4 to 7 of the present invention exhibited gradually increased luminance, lighting voltage and Δ E with increasing degree of reactionSTGradually decreased, wherein the TADF material obtained in example 6 has the best performance, the lighting voltage is 3.8V, and the brightness is 14748cd/m2The maximum external quantum efficiency can reach 22.5%, and the TADF materials prepared by the embodiments 4 to 7 of the invention have the external quantum efficiency of more than 15%, which shows that T exists in the molecular structure1-S1And the external quantum efficiency does not change much with the increase of the current efficiency in the examples of the present invention, indicating that TADFs produced in examples 4 to 7 of the present inventionThe electroluminescent device of the material has better stability.
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 (6)
1. A thioxanthone-based thermally-induced delayed fluorescent material is characterized by having a structural formula shown as a formula (I):
wherein X is N, O or S.
2. The thioxanthone-based thermally-induced delayed fluorescent material according to claim 1, wherein the structure formula is
3. A preparation method of a thioxanthone-based thermally-induced delayed fluorescent material is characterized by comprising the following steps: carrying out coupling reaction on the compound shown in the formula (II) and 2-bromo-8- (pyridine-1-yl) thioxanthene to obtain a compound shown in the formula (I);
4. the method for preparing a thioxanthone-based thermally-induced delayed fluorescent material according to claim 3, wherein the compound represented by the formula (II) is prepared by the following steps: carrying out coupling reaction on a compound shown as a formula (III) and diboron pinacol ester to prepare a compound shown as a formula (II);
5. the method for preparing a thioxanthone-based thermally-induced delayed fluorescent material according to claim 3, wherein the coupling reaction time is 12-72 hours.
6. The method for preparing a thioxanthone-based thermally-induced delayed fluorescent material according to claim 3, wherein the coupling reaction time is 36 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110523113.XA CN113185502A (en) | 2021-05-13 | 2021-05-13 | Thioxanthone-based thermally induced delayed fluorescent material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110523113.XA CN113185502A (en) | 2021-05-13 | 2021-05-13 | Thioxanthone-based thermally induced delayed fluorescent material and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113185502A true CN113185502A (en) | 2021-07-30 |
Family
ID=76981606
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110523113.XA Withdrawn CN113185502A (en) | 2021-05-13 | 2021-05-13 | Thioxanthone-based thermally induced delayed fluorescent material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113185502A (en) |
-
2021
- 2021-05-13 CN CN202110523113.XA patent/CN113185502A/en not_active Withdrawn
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Wan et al. | Multifunctional electron-transporting indolizine derivatives for highly efficient blue fluorescence, orange phosphorescence host and two-color based white OLEDs | |
| CN111662190A (en) | Organic compound containing pyrene or aza-pyrene and application thereof | |
| CN106986814A (en) | A kind of compound as core using dimethyl anthrone and its application on organic electroluminescence device | |
| CN103525399B (en) | Bipolarity phosphorescence host compound, preparation method and application and electroluminescent device | |
| CN103787822B (en) | Containing anthracene compounds, its preparation method and application thereof, organic luminescent device | |
| CN111153858B (en) | Star-shaped electroluminescent material based on phenanthroimidazole unit and preparation method and application thereof | |
| WO2021036158A1 (en) | Organic small molecule hole injection/transport material and preparation method therefor and application thereof | |
| CN108516970B (en) | Heterocyclic bridged phenyl ethylene derivatives, and preparation method and application thereof | |
| CN113173927A (en) | Pyridyl quinoxaline delayed luminescence derivative and preparation method thereof | |
| CN113185502A (en) | Thioxanthone-based thermally induced delayed fluorescent material and preparation method thereof | |
| CN112661743B (en) | Naphthothiodibenzofuran-based green light micromolecule and preparation method and application thereof | |
| CN111018863B (en) | Compound taking pyrrole [1, 2-a ] quinoxaline as receptor and application thereof | |
| CN110724105B (en) | Triphenylene nitrogen-containing seven-membered ring compound and preparation method and application thereof | |
| CN113173926A (en) | Naphtho-selenadiazole delayed fluorescent material and preparation method thereof | |
| CN108863871B (en) | Pyrene derivative electroluminescent material and preparation method and application thereof | |
| CN113234096A (en) | Red light thermal activation delayed fluorescence material and preparation method thereof | |
| CN112694433A (en) | Organic small molecule hole transport material and preparation method and application thereof | |
| CN109748899B (en) | Compound containing ketone and application thereof in organic electroluminescent device | |
| CN113185526A (en) | Green light thermal activation delayed fluorescent material and preparation method thereof | |
| CN113185525A (en) | Thermal activation delayed fluorescent material and preparation method thereof | |
| CN113173950A (en) | Phosphoric acid delayed fluorescent material and preparation method thereof | |
| CN113214277A (en) | Pyrenyl thiophene derivative and preparation method thereof | |
| CN110526938B (en) | Deep blue photo-thermal activation delayed fluorescence material, preparation method thereof and electroluminescent device | |
| CN111909170B (en) | Organic electroluminescent compound, preparation method thereof and organic electroluminescent device comprising organic electroluminescent compound | |
| CN114478393B (en) | Organic luminescent material with high exciton utilization rate and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WW01 | Invention patent application withdrawn after publication |
Application publication date: 20210730 |
|
| WW01 | Invention patent application withdrawn after publication |