Light thermally activated delayed fluorescence (TADF) material, preparing method thereof, and electroluminescent device

Abstract

The present invention provides a thermally activated delayed fluorescent material, a method for preparing the same, and an electroluminescent device including a compound consisting of a receptor A and a donor D, the compound having a molecular structure of D-A shown in Formula 1:
D-A   Formula 1 wherein the receptor A is selected from any one of the following structural formulas: ##STR00001## wherein R is selected from any one of the following structural formulas: ##STR00002## ##STR00003##
and the donor D is selected from any one of the following structural formulas: ##STR00004## ##STR00005##

Claims

1. A thermal activated delayed fluorescent material, comprising a compound consisting of a receptor A and a donor D, the compound having a molecular structure of D-A shown in Formula 1:
D-A   Formula 1 wherein the receptor A is selected from any one of the following structural formulas: ##STR00028## wherein R is selected from any one of the following structural formulas, wherein a dash line represents a bond connecting the R group to the receptor A: ##STR00029## ##STR00030##  and wherein the donor D is selected from any one of the following structural formulas: ##STR00031## ##STR00032##

2. A method of preparing a thermal activated delayed fluorescent material, comprising the following steps: Step S10, adding a compound A-X and a compound D-H to a solution containing an alkali, wherein X is a halogen, and A is any one of the following structural formulas: ##STR00033## where R is selected from any one of the following structural formulas, wherein a dash line represents a bond connecting the R group to the receptor A: ##STR00034## ##STR00035## and D is any one of the following structural formulas: ##STR00036## ##STR00037## Step S20, adding a palladium catalyst to the solution containing the alkali under an inert gas for reaction at a first temperature for a first period of time to obtain a reaction solution; Step S30, cooling the reaction solution to a second temperature to obtain a mixture; Step S40, separating the thermal activated delayed fluorescent material from the mixture, wherein the thermal activated delayed fluorescent material comprises a compound consisting of a receptor A and a donor D, the compound having a molecular structure shown in Formula 1:
D-A   Formula 1.

3. The method of preparing the thermal activated delayed fluorescent material according to claim 2, wherein the first temperature is 80° C.; and the second temperature is room temperature.

4. The method of preparing the thermal activated delayed fluorescent material according to claim 2, wherein the first period of time ranges from 12 hours to 36 hours.

5. The method of preparing the thermal activated delayed fluorescent material according to claim 2, wherein in the step S10, the solution containing the alkali is tetrahydrofuran and the alkali is sodium carbonate.

6. The method of preparing the thermal activated delayed fluorescent material according to claim 2, wherein the step S30 further comprises extracting, water washing, dehydrating, filtrating, and centrifugal drying the reaction solution to obtain the mixture.

7. The method of preparing the thermal activated delayed fluorescent material according to claim 2, wherein the step S40 is performed by column chromatography, and the eluent used in the column chromatography is petroleum ether and dichloromethane in a volume ratio of 1:2.

8. The method of preparing the thermal activated delayed fluorescent material according to claim 2, wherein the compound A-X is 6-bromo-2-(4-(1,2,2-triphenylvinyl)phenyl)-benzene[de]isoquinoline-1,3-dione, and the compound D-H is phenothiazine.

9. An electroluminescent device, comprising: a substrate layer; a hole injection layer disposed on the substrate layer; a hole transport layer disposed on the hole injection layer; a light emitting layer disposed on the hole transport layer; an electron transport layer disposed on the light emitting layer; and a cathode layer disposed on the electron transport layer, wherein the light emitting layer comprises the thermal activated delayed fluorescent material of claim 1.

10. The electroluminescent device according to claim 9, wherein: the base layer is made of material comprising ITO; the hole injection layer is made of material comprising 2,3,6,7,10,11-hexacyano-1,4,5,8,9,12-hexaazatriphenylene; the hole transport layer is made of material comprising 4,4′-cyclohexyl bis[N,N-bis(4-methylphenyl)aniline]; the electron transport layer is made of material comprising 1,3,5-tris(3-(3-pyridyl)phenyl)benzene; and the cathode layer is made of material comprising lithium fluoride and aluminum.

Description

BRIEF DESCRIPTION OF DRAWINGS

(1) In order to more clearly illustrate the embodiments or the technical solutions of the existing art, the drawings illustrating the embodiments or the existing art will be briefly described below. Obviously, the drawings in the following description merely illustrate some embodiments of the present invention. Other drawings may also be obtained by those skilled in the art according to these figures without paying creative work.

(2) FIG. 1 is a flow chart showing a method for preparing a thermally activated delayed fluorescent material according to an embodiment of the present invention.

(3) FIG. 2 is a fluorescence emission spectrum of a compound according to an embodiment of the present invention.

(4) FIG. 3 is a schematic structural diagram of an electroluminescent device according to an embodiment of the invention.

DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS

(5) Embodiments of the present invention provide a thermally activated delayed fluorescent (TADF) material, wherein a series of thermally activated delayed fluorescent molecules containing imide acceptors are synthesized through a sophisticated molecular design. By functionally modifying a nitrogen atom of the imide structure, for example, introducing a tetraphenylvinyl group having aggregation-induced enhanced luminescence (AIEE) and a silicon-containing group of large sterically hindered group, a non-doped device of high efficiency can be achieved. Alternately, electron or hole mobility of the TADF molecule can be adjusted by introducing an electron donor or an electron acceptor, or Tg and Td of the TADF molecule can be adjusted by introducing a group, to realize preparation of a series of TADF organic light emitting diodes (OLEDs) of high performance using these luminescent materials.

(6) To achieve the above object, the present invention provides a thermal activated delayed fluorescent material, including a compound consisting of a receptor A and a donor D, the compound having a molecular structure of D-A shown in Formula 1:
D-A   Formula 1

(7) wherein the receptor A is selected from any one of the following structural formulas:

(8) ##STR00016##

(9) wherein R is selected from any one of the following structural formulas, wherein a dash line represents a bond connecting the R group to the receptor A:

(10) ##STR00017## ##STR00018##
and

(11) wherein the donor D is selected from any one of the following structural formulas:

(12) ##STR00019## ##STR00020##

(13) Referring to FIG. 1, FIG. 1 is a flow chart showing a method for preparing a thermally activated delayed fluorescent material according to an embodiment of the present invention. As shown in FIG. 1, the method for preparing a thermally activated delayed fluorescence (TADF) material according to an embodiment of the present invention includes the following steps:

(14) Step S10, adding a compound A-X and a compound D-H to a solution containing an alkali, wherein X is a halogen, and A is any one of the following structural formulas:

(15) ##STR00021##

(16) where R is selected from any one of the following structural formulas, wherein a dash line represents a bond connecting the R group to the receptor A:

(17) ##STR00022## ##STR00023##

(18) and D is any one of the following structural formulas:

(19) ##STR00024## ##STR00025##

(20) Step S20, adding a palladium catalyst to the solution containing the alkali under an inert gas for reaction at a first temperature for a first period of time to obtain a reaction solution;

(21) Step S30, cooling the reaction solution to a second temperature to obtain a mixture;

(22) Step S40, separating the thermal activated delayed fluorescent material from the mixture, wherein the thermal activated delayed fluorescent material includes a compound consisting of a receptor A and a donor D, the compound having a molecular structure shown in Formula 1:
D-A   Formula 1.

(23) According to an embodiment of the invention, in the method of preparing the thermal activated delayed fluorescent material, the first temperature is 80° C.; and the second temperature is room temperature.

(24) According to an embodiment of the invention, in the method of preparing the thermal activated delayed fluorescent material, the first period of time ranges from 12 hours to 36 hours.

(25) According to an embodiment of the invention, in the method of preparing the thermal activated delayed fluorescent material, in the step S10, the solution containing the alkali is tetrahydrofuran and the alkali is sodium carbonate.

(26) According to an embodiment of the invention, in the method of preparing the thermal activated delayed fluorescent material, the step S30 further includes extracting, water washing, dehydrating, filtrating, and centrifugal drying the reaction solution to obtain the mixture.

(27) According to an embodiment of the invention, in the method of preparing the thermal activated delayed fluorescent material, the step S40 is performed by column chromatography, and the eluent used in the column chromatography is petroleum ether and dichloromethane in a volume ratio of 1:2.

(28) According to an embodiment of the invention, in the method of preparing the thermal activated delayed fluorescent material, the compound A-X is 6-bromo-2-(4-(1,2,2-triphenylvinyl)phenyl)-benzene[de]isoquinoline-1,3-dione, and the compound D-H is phenothiazine.

EXAMPLE 1

(29) In the specific Example 1 of the present invention, a thermal activation delayed fluorescent material was provided, which was a target compound having a molecular structure shown in Formula 2:

(30) ##STR00026##

(31) The target compound having a molecular structure of Formula 2 was synthesized by a reaction based on a synthetic route shown in Reaction Scheme 1:

(32) ##STR00027##

(33) The detailed synthesis steps of Compound 1 are as follows:

(34) 7-Bromophenyl [de,h]isobenzopyran-1,3-dione (3.27 g, 10 mmol), 4-(1,2,2-triphenylethylene)aniline (3.47 g, 10 mmol, and ethanol (20 mL) were added to a 100 mL schlenk bottle, for reaction under argon gas atmosphere by heating to reflux overnight. After the reaction solution was cooled to room temperature, the reaction solution was extracted three times with dichloromethane (DCM), followed by washing three times with water, then dried over anhydrous sodium sulfate, and then filtered and spin-dried. The crude product was chromatographed by a 200-300 mesh silica gel column and eluted with DCM:EtOAc (V/V=1:2). After that, the product was rotary-evaporated and dried in vacuum to obtain a yellow solid (4.96 g, 82% yield). HRMS [M+H]+ calcd. for C38H24BrNO2: 605.0990; found: 605.1003.

(35) 6-Bromo-2-(4-(1,2,2-triphenylvinyl)phenyl)-phenyl[de]isoquinoline-1,3 -dione (3.03 g, 5 mmol), phenothiazine azine (1.09 g, 5.5 mmol), 100 mL of tetrahydrofuran and 25 mL of a 1.6 M sodium carbonate solution were placed in a 250 mL three-necked flask, and purged with argon gas. Then, tetrakis(triphenylphosphine)palladium (0.24 g, 0.2 mmol) was added, and the mixture was refluxed at 80° C. for 24 h. After the reaction solution was cooled to room temperature, it was extracted three times with DCM, then washed three times, followed by drying over anhydrous sodium sulfate, and then filtered and spin-dried.

(36) Column chromatography was carried out by a 200-300 mesh silica gel column with an eluent of petroleum ether:DCM (1:2, V/V) to obtain 2.97 g of a red solid, and yield was 82%. HRMS [M+H]+ calcd. for C50H32N2SO2: 724.2184; found: 724.2198.

(37) Specifically, Compound 1 was defined to have the molecular structure shown in Formula 2. Compound 1 was examined, and the fluorescence emission spectrum of Compound 1 under a pure film is shown in FIG. 2

(38) The characteristic parameters of lowest singlet state (S100), lowest triplet energy level (T1), and photoluminescence quantum yield (PLQY) of Compound 1 were analyzed based on B3LYP theory, and the analysis results are shown in Table 1.

(39) TABLE-US-00001 TABLE 1 PL Peak S100 T.sub.1 ΔE.sub.ST PLQY Compound (nm) (eV) (eV) (eV) (%) Compound 1 667 2.05 1.91 0.14 87

(40) PL peak is the photoluminescence peak, S100 is the lowest singlet energy level, T1 is the lowest triplet energy level, and ΔEST is the energy level difference between the lowest singlet energy level and the lowest triplet energy level.

(41) As can be known from FIG. 2 and Table 1, Compound 1 of Example 1 of the present invention satisfies the performance requirements.

(42) Furthermore, an embodiment of the present invention also provides an electroluminescent device including the above-described thermally activated delayed fluorescent (TADF) material.

(43) Referring to FIG. 3, in particular, the electroluminescent device 100 includes: a substrate layer 1; a hole injection layer 2 disposed on the substrate layer 1; a hole transport layer 3 disposed on the hole injection layer 2; a light emitting layer 4 disposed on the hole transport layer 3; an electron transport layer 5 disposed on the light emitting layer 4; and a cathode layer 6 disposed on the electron transport layer 5, wherein the light emitting layer 4 includes the thermal activated delayed fluorescent (TADF) material.

(44) According to an embodiment of the invention, in the electroluminescent device, the base layer is made of material including ITO; the hole injection layer is made of material including 2,3,6,7,10,11-hexacyano-1,4,5,8,9,12-hexaazatriphenylene; the hole transport layer is made of material including 4,4′-cyclohexyl bis[N,N-bis(4-methylphenyl)aniline]; the electron transport layer is made of material including 1,3,5-tris(3-(3-pyridyl)phenyl)benzene; and the cathode layer is made of material including lithium fluoride and aluminum.

(45) Specifically, the device 100 was fabricated using Compound 1 as the light-emitting layer 4, and the performance of the device 100 was measured. The substrate layer 1 and the hole injection layer 2 in the device 100 had a thickness of 30 nm. The hole transport layer 3 had a thickness of 40 nm. The light-emitting layer 4 of the device 100 had a thickness of 40 nm. The electron transport layer 5 had a thickness of 40 nm. In the cathode 5, the lithium fluoride in the cathode 500 had a thickness of 1 nm, and the aluminum had a thickness of 100 nm.

(46) The current-brightness-voltage characteristics of the device 100 was further measured by a Keithley source measurement system (Keithley 2400 Sourcemeter, Keithley 2000 Currentmeter) with a calibrated silicon photodiode.

(47) The electroluminescence spectrum was measured by a French JY SPEX CCD3000 spectrometer. All measurements were conducted at room temperature under ambient atmosphere. The performance data of the device 100 is shown in Table 2 below, and the device 100 meets the performance requirements.

(48) TABLE-US-00002 TABLE 2 maximum external maximum quantum brightness EL peak efficiency Device 1 (cd/m.sup.2) (nm) (%) Compound 1 1395 679 15

(49) Accordingly, embodiments of the present invention provide a thermally activated delayed fluorescent (TADF) material, wherein a series of thermally activated delayed fluorescent molecules containing imide acceptors are synthesized through a sophisticated molecular design. By functionally modifying a nitrogen atom of the imide structure, for example, introducing a tetraphenylvinyl group having aggregation-induced enhanced luminescence (AIEE) and a silicon-containing group of large sterically hindered group, a non-doped device of high efficiency can be achieved. Alternately, electron or hole mobility of the TADF molecule can be adjusted by introducing an electron donor or an electron acceptor, or Tg and Td of the TADF molecule can be adjusted by introducing a group, to realize preparation of a series of TADF organic light emitting diodes (OLEDs) of high performance using these luminescent materials.

(50) While the present invention has been described by way of example and in terms of the preferred embodiments, it is to be understood that the present invention is not limited to the disclosed embodiments. To the contrary, it is intended to cover various modifications and similar arrangements. Therefore, the scope of the appended claims should be accorded the broadest interpretation so as to encompass all such modifications and similar arrangements.