CN113979903B - Organic thermal activation delayed fluorescence material containing phenylsulfone-spirofluorene structural unit, preparation method and application - Google Patents

Organic thermal activation delayed fluorescence material containing phenylsulfone-spirofluorene structural unit, preparation method and application Download PDF

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CN113979903B
CN113979903B CN202111347081.9A CN202111347081A CN113979903B CN 113979903 B CN113979903 B CN 113979903B CN 202111347081 A CN202111347081 A CN 202111347081A CN 113979903 B CN113979903 B CN 113979903B
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spirofluorene
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CN113979903A (en
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余玲
赵陈粤
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Hangzhou Normal University
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Abstract

The invention discloses an organic thermal activation delay fluorescent material containing a phenyl sulfone-spirofluorene structural unit, which belongs to the technical field of organic luminescent materials, wherein the organic thermal activation delay fluorescent material containing the phenyl sulfone-spirofluorene structural unit adopts aromatic substituted amino or aromatic heterocyclic amino as a donor unit, a phenyl sulfone structure as an acceptor unit and phenyl sulfone as a strong acceptor unit, so that intramolecular charge transfer is facilitated; in addition, the sp3 hybridized carbon atoms in the spiro structure separate the donor from the acceptor unit to form a face-to-face geometric conformation, so that space charge transfer can be realized, and the exciton utilization rate is improved. The organic thermal activation delay fluorescent material of the phenyl sulfone-spirofluorene structural unit prepared by the invention has the advantages of easily available raw materials, low cost, simple and efficient synthesis, easy purification of products, higher yield, good hole/electron transmission performance, high fluorescence quantum yield, and convenient mass production, and can be widely applied to the field of organic electroluminescent devices.

Description

Organic thermal activation delayed fluorescence material containing phenylsulfone-spirofluorene structural unit, preparation method and application
Technical Field
The invention relates to the technical field of organic luminescent materials, in particular to an organic thermal activation delay fluorescent material containing phenyl sulfone-spirofluorene structural units, a preparation method and application thereof.
Background
Organic Light Emitting Diodes (OLEDs) have gained a great breakthrough in recent decades as "fantasy displays" and have found widespread use in the field of full-color displays. The OLED has a series of advantages of high response speed, low heat generation, small volume, light weight, self-luminescence, low power consumption, low driving voltage, wide material source, low cost and the like, and has remarkable commercial potential due to the rapid increase of market demands in recent years.
OLED light-emitting materials can be broadly divided into three types, conventional fluorescent materials, phosphorescent materials, and Thermally Activated Delayed Fluorescence (TADF) materials. Due to spin inhibition, triplet excitons cannot emit light by direct radiation, and conventional fluorescent materials can emit light by only singlet excitons, with the theoretical maximum quantum efficiency of only 25%. The phosphorescence material breaks spin forbidden resistance by using heavy metal atom coordination and utilizing strong spin orbit coupling action, and can emit light by utilizing singlet state and triplet state excitons at the same time, and the theoretical highest quantum efficiency reaches 100%. The TADF material is firstly proposed by Adachi subject group of Jiuzhou university in 2009 (A.Endo, M.Ogasawara, A.Takahashi, D.Yokoyama, Y.Kato, C.Adachi, adv.Mater.2009,21,4802.) for the first time, and obtains a great breakthrough in 2012, and the conversion from triplet state exciton to singlet state exciton is realized by improving the rate of the reverse intersystem crossing, so that the internal quantum efficiency of 100% is realized, the use of heavy metal elements is avoided, the synthesis cost is low, the corresponding device efficiency is equivalent to that of a phosphorescent device, and the TADF material is one of the current research hot spots in the organic photoelectric field.
Most of TADF materials in the present stage adopt D-pi-A conjugated molecular structures, aggregation quenching is easy to occur, and the efficiency of the device is seriously attenuated. While achieving TADF by space charge transfer can more effectively reduce the overlap of the Highest Occupied Molecular Orbital (HOMO) and the Lowest Unoccupied Molecular Orbital (LUMO), currently such materials have few molecular species and need extensive and systematic investigation.
In the Chinese patent document with publication number of CN110862341A, a carbazole derivative containing dicyanovinyl with aggregation-induced emission (AIE) effect is disclosed, dicyanovinyl is taken as an electron acceptor, carbazolyl is taken as an electron donor, and the compound disclosed by the invention can generate steric hindrance in the interior of a molecule and cause distortion of a molecular conformation by combining with the carbazole derivative by utilizing the strong electron withdrawing capability of a nitrile group, so that the compound has a remarkable AIE effect.
The Chinese patent document with publication number of CN112225747A discloses a thermally-induced delayed fluorescence organic luminescent material, which takes cyclic fluorenone dithiophene as a framework, and forms a bipolar organic micromolecule luminescent material by connecting different donor units and acceptor units, thus being widely applied to the fields of organic electroluminescent devices, anti-counterfeiting, chemical biological detection, biological imaging and the like.
Disclosure of Invention
The invention provides an organic thermal activation delayed fluorescent material containing a phenyl sulfone-spirofluorene structural unit, which is simple and efficient in synthesis, has good hole/electron transmission performance and high fluorescence quantum yield, is convenient for large-scale production, and can be widely applied to the field of organic electroluminescent devices.
The technical scheme adopted is as follows:
an organic thermally activated delayed fluorescence material containing a phenylsulfone-spirofluorene structural unit, which has a structure shown in formulas I-1 to I-5:
wherein R is halogen, ar is aromatic substituted amino and aromatic heterocyclic amino.
Preferably, the aromatic substituted amine group comprises
Preferably, the aromatic heterocyclic amino group has a structure shown as II-1 to II-8:
the organic thermal activation delay fluorescent material containing the phenylsulfone-spirofluorene structural unit adopts aromatic substituted amino or aromatic heterocyclic amino as a donor unit, the phenylsulfone structure is taken as an acceptor unit, and the phenylsulfone is taken as a strong acceptor unit, so that intramolecular charge transfer is facilitated; in addition, the sp3 hybridized carbon atoms in the spiro structure separate the donor from the acceptor unit to form a face-to-face geometric conformation, so that space charge transfer can be realized, and the exciton utilization rate is improved.
The invention also provides a preparation method of the organic thermal activation delay fluorescent material containing the phenyl sulfone-spirofluorene structural unit, wherein the organic thermal activation delay fluorescent material containing the phenyl sulfone-spirofluorene structural unit is obtained by reacting a compound A with a compound B and then reacting with a compound C;
the compound A isWherein X is halogen;
the compound B isWherein X is halogen;
the compound C has a structure shown in III-1 to III-9:
specifically, the preparation method comprises the following steps:
(1) Reacting a compound A with a compound B in the presence of alkali, amino acid, copper catalyst and hydrogen peroxide to obtain an intermediate;
the intermediate has a structure shown as IV-1 to IV-3, wherein X 1 ,X 2 ,X 3 ,X 4 ,X 5 All being halogen, X 4 And X 5 Is halogen of different species;
(2) The intermediate and a compound C react in the presence of alkali, a palladium catalyst and tri-tert-butyl phosphine tetrafluoroborate in a molar ratio of 1:1-3 to obtain the organic thermal activation delayed fluorescence material with the structure shown in I-1-I-5 and containing phenyl sulfone-spirofluorene structural units.
Specifically, the preparation method further comprises the following steps:
the organic thermal activation delay fluorescent material containing the phenyl sulfone-spirofluorene structural unit with the structure shown as I-1, I-2 and I-4 reacts with a compound C in a molar ratio of 1:1-1.5 in the presence of alkali, palladium catalyst and tri-tert-butyl phosphine tetrafluoroborate to obtain the organic thermal activation delay fluorescent material containing the phenyl sulfone-spirofluorene structural unit with the structure shown as I-3 or I-5.
Preferably, in step (1), the preparation method of the intermediate comprises the following steps:
reacting a compound A with a compound B in a molar ratio of 1:1-3 in the presence of alkali, amino acid, copper catalyst and hydrogen peroxide to obtain an intermediate with a structure shown as IV-1 or IV-2;
or reacting the intermediate with the structure shown as IV-1 with another compound B in the molar ratio of 1:1-1.5 in the presence of alkali, amino acid, copper catalyst and hydrogen peroxide to obtain the intermediate with the structure shown as IV-3.
Preferably, the base is an organic base or a metal carbonate; the amino acid is glycine; the copper catalyst is cuprous chloride, cuprous bromide or cuprous iodide; the palladium catalyst is palladium acetate.
The invention also provides application of the organic thermal activation delay fluorescent material containing the phenyl sulfone-spirofluorene structural unit in the photoelectric field.
The invention also provides an organic electroluminescent device prepared from the organic thermal activation delayed fluorescence material containing phenyl sulfone-spirofluorene structural units, which comprises a conductive glass substrate, a hole transport layer, a hole injection layer, an organic luminescent layer, an electron injection layer, an electron transport layer and a cathode layer, and is characterized in that: the organic light-emitting layer contains the organic thermal activation delay fluorescent material containing the phenyl sulfone-spirofluorene structural unit.
Compared with the prior art, the invention has the beneficial effects that:
(1) The organic thermal activation delayed fluorescent material containing phenyl sulfone-spirofluorene unit combination prepared by the invention takes aromatic substituted amino or aromatic heterocyclic amino as a donor unit, phenyl sulfone as an acceptor unit, aromatic substituted amino or aromatic heterocyclic amino is introduced to improve carrier mobility, the light emission of a compound can be regulated and controlled by changing the corresponding aromatic substituted amino or aromatic heterocyclic amino, and the combination of the phenyl sulfone-spirofluorene unit can be used for designing and utilizing space charge transfer effect, so that the light emitting efficiency of the material is further improved.
(2) The organic thermal activation delayed fluorescent material containing the phenyl sulfone-spirofluorene structural unit prepared by the invention has the advantages of easily available raw materials, low cost, simple and efficient synthesis, easy purification of products, higher yield, good hole/electron transmission performance, high fluorescence quantum yield, and convenient mass production, and can be widely applied to the field of organic electroluminescent devices.
(3) The electroluminescent device prepared by the organic thermal activation delayed fluorescent material containing the phenyl sulfone-spirofluorene structural unit has excellent performance, and the device efficiency reaches 17.8 percent, which is far higher than that of a common fluorescent device.
Drawings
FIG. 1 shows the UV-visible absorption spectrum and fluorescence spectrum of an organic thermally activated delayed fluorescence material containing phenylsulfone-spirofluorene structural unit prepared in example 2 in toluene solution.
FIG. 2 is a graph showing the transient light-induced spectral decay of the organic thermally activated delayed fluorescence material containing phenylsulfone-spirofluorene structural units prepared in example 9 in toluene solution.
Fig. 3 is a structural diagram of the organic electroluminescent device manufactured in application example 1, in which 1 is a conductive glass substrate, 2 is a hole injection layer, 3 is a hole transport layer, 4 is an organic light emitting layer, 5 is an electron transport layer, 6 is an electron injection layer, and 7 is a cathode layer.
Detailed Description
The invention is further elucidated below in connection with the drawings and the examples. It is to be understood that these examples are for illustration of the invention only and are not intended to limit the scope of the invention.
Example 1
The synthetic route for intermediate (1) is shown below:
9, 9-bis (4-iodophenyl) -fluorene (2.0 g,3.5 mmol), 4-fluorobenzylthiol (0.45 g,3.5 mmol), potassium hydroxide (0.39 g,7.0 mmol), cuprous iodide (0.04 g,0.2 mmol) and glycine (0.05 g,0.7 mmol) were dissolved in 60mL of ultra-dry 1, 4-dioxane solvent, heated to reflux for 16h, distilled under reduced pressure, added 60mL of ethanol and 40mL of 30% hydrogen peroxide solution, heated to reflux for 24h, extracted with dichloromethane and water, and purified by column chromatography to give intermediate (1) as a white solid (yield 66%).
In this example, the synthetic route of the organic thermally activated delayed fluorescence material containing phenylsulfone-spirofluorene structural units is as follows:
intermediate (1) (1.5 g,2.5 mmol), diphenylamine (0.51 g,3.0 mmol), sodium t-butoxide (0.58 g,6.0 mmol), palladium acetate (0.025 g,0.1 mmol), tri-t-butylphosphine tetrafluoroborate (0.087 g,0.3 mmol) and 60mL of toluene were added together to a 150mL round bottom flask, refluxed at 110℃for 48 hours, extracted with dichloromethane and water, distilled under reduced pressure, and purified by column chromatography to give an organic thermally activated delayed fluorescence material containing a phenylsulfone-spirofluorene structural unit (yield 90%).
Theoretical value of elemental analysis C 43 H 30 FNO 2 S (%): C80.23,H 4.70,F 2.95,N 2.18,O4.97,S 4.98; found values: and C80.20,H 4.72,F 2.94,N 2.18,O4.97,S 4.97.
Example 2
The synthetic route for intermediate (2) is shown below:
9- (4-bromophenyl) -9- (4-iodophenyl) fluorene (1.84 g,3.5 mmol), 4-bromophenyl thiophenol (0.67 g,3.5 mmol), potassium hydroxide (0.39 g,7.0 mmol), cuprous iodide (0.04 g,0.2 mmol) and glycine (0.05 g,0.7 mmol) were dissolved in 60mL of ultra-dry 1, 4-dioxane solvent, heated under reflux for 16h, distilled under reduced pressure, further 60mL of ethanol and 40mL of 30% hydrogen peroxide solution were added, heated under reflux for 24h, extracted with dichloromethane and water, and purified by column chromatography to give intermediate (2) as a white solid (yield 56%).
In this example, the synthetic route of the organic thermally activated delayed fluorescence material containing phenylsulfone-spirofluorene structural units is as follows:
intermediate (2) (1.5 g,2.4 mmol), 9' -dimethylacridine (0.63 g,3.0 mmol), sodium t-butoxide (0.58 g,6.0 mmol), palladium acetate (0.025 g,0.1 mmol), tri-tert-butylphosphine tetrafluoroborate (0.087 g,0.3 mmol) and 60mL of toluene were added together to a 150mL round bottom flask, refluxed at 110℃for 48h, extracted with dichloromethane and water, distilled under reduced pressure, and purified by column chromatography to give an organic thermally activated delayed fluorescent material containing phenyl sulfone-spirofluorene structural units (yield 84%).
Theoretical value of elemental analysis C 46 H 34 BrNO 2 S (%): C74.19,H 4.60,Br 10.73,N 1.88,O 4.30,S 4.30; found values: and C74.21,H 4.58,Br 10.70,N 1.89,O 4.30,S 4.29.
The ultraviolet-visible absorption spectrum and the fluorescence spectrum of the organic thermal activation delayed fluorescence material containing the phenyl sulfone-spirofluorene structural unit prepared in the embodiment are shown in fig. 1, two curves in the figure are respectively ultraviolet-visible absorption spectrum (dotted line) and fluorescence spectrum (solid line), wherein the emission peak of the fluorescence spectrum is at 375nm, and the half-peak width is narrower, so that the organic thermal activation delayed fluorescence material is a near ultraviolet material.
Example 3
Using intermediate (2) prepared in example 2, the organic thermally activated delayed fluorescence material containing a phenylsulfone-spirofluorene structural unit was synthesized by the following route:
intermediate (2) (1.5 g,2.4 mmol), carbazole (0.40 g,2.4 mmol), sodium t-butoxide (0.58 g,6.0 mmol), palladium acetate (0.025 g,0.1 mmol), tri-t-butylphosphine tetrafluoroborate (0.087 g,0.3 mmol) and 60mL of toluene were added together in a 150mL round bottom flask, refluxed for 48h at 110 ℃, extracted with dichloromethane and water, distilled under reduced pressure, and purified by column chromatography to give an organic heat-activated delayed fluorescence material containing phenylsulfone-spirofluorene structural units (yield 87%).
Theoretical value of elemental analysis C 43 H 28 BrNO 2 S(％)：C 73.50,H 4.02,Br 11.37,N 1.99,O 4.55,S4.56; found values: and C73.49,H 4.01,Br 11.35,N 2.00,O 4.55,S 4.55.
Example 4
Using intermediate (2) prepared in example 2, the organic thermally activated delayed fluorescence material containing a phenylsulfone-spirofluorene structural unit was synthesized by the following route:
intermediate (2) (1.5 g,2.4 mmol), phenoxazine (1.11 g,6.0 mmol), sodium t-butoxide (1.16 g,12.0 mmol), palladium acetate (0.05 g,0.2 mmol), tri-t-butylphosphine tetrafluoroborate (0.18 g,0.6 mmol) and toluene 90mL were added together to a 150mL round bottom flask, refluxed for 48h at 110 ℃, extracted with dichloromethane and water, distilled under reduced pressure, purified by column chromatography to give an organic heat-activated delayed fluorescence material containing phenyl sulfone-spirofluorene structural units (yield 74%).
Theoretical value of elemental analysis C 55 H 36 N 2 O 4 S (%): C80.47,H 4.42,N 3.41,O 7.80,S3.91; found values: and C80.49,H 4.40,N 3.40,O 7.80,S 3.90.
Example 5
The organic thermally activated delayed fluorescence material containing a phenylsulfone-spirofluorene structural unit obtained in example 2 was used to synthesize an organic thermally activated delayed fluorescence material containing a phenylsulfone-spirofluorene structural unit in the implementation of the route of the following formula:
the organic heat-activated delayed fluorescence material containing a phenylsulfone-spirofluorene structural unit (1.9 g,2.5 mmol), 5-phenyl-5, 10-dihydrophenazine (0.77 g,3.0 mmol), sodium t-butoxide (0.58 g,6.0 mmol), palladium acetate (0.025 g,0.1 mmol), tri-tert-butylphosphine tetrafluoroborate (0.087 g,0.3 mmol) and 60mL of toluene obtained in example 2 were added together to a 150mL round-bottom flask, refluxed for 48 hours at 110℃and extracted with methylene chloride and water, distilled under reduced pressure, and purified by column chromatography to obtain the organic heat-activated delayed fluorescence material containing a phenylsulfone-spirofluorene structural unit (yield 81%).
Theoretical value of elemental analysis C 64 H 47 N 3 O 2 S (%): C83.36,H 5.14,N 4.56,O 3.47,S3.48; found values: C83.33,H 5.12,N 4.54,O 3.48,S 3.50;
example 6
The synthetic route of intermediate (3) is shown below:
using the intermediate (1) produced in example 2, intermediate (1) (2.0 g,3.3 mmol), 4-bromophenylthiophenol (0.81 g,4.3 mmol), potassium hydroxide (0.37 g,6.6 mmol), cuprous iodide (0.04 g,0.2 mmol) and glycine (0.05 g,0.7 mmol) were dissolved in 60mL of ultra-dry 1, 4-dioxane solvent, heated under reflux for 24 hours, distilled under reduced pressure, further added with 60mL of ethanol and 40mL of 30% hydrogen peroxide solution, heated under reflux for 24 hours, extracted with dichloromethane and water, and purified by column chromatography to give intermediate (3) as a white solid (yield 80%).
In this example, the synthetic route of the organic thermally activated delayed fluorescence material containing phenylsulfone-spirofluorene structural units is as follows:
intermediate (3) (1.7 g,2.5 mmol), diphenylamine (0.51 g,3.0 mmol), sodium t-butoxide (0.58 g,6.0 mmol), palladium acetate (0.025 g,0.1 mmol), tri-t-butylphosphine tetrafluoroborate (0.087 g,0.3 mmol) and 60mL of toluene were added together to a 150mL round bottom flask, refluxed at 110℃for 48 hours, extracted with dichloromethane and water, distilled under reduced pressure, and purified by column chromatography to give an organic thermally activated delayed fluorescence material containing a phenylsulfone-spirofluorene structural unit (yield 90%).
Theoretical value of elemental analysis C 49 H 34 FNO 4 S 2 (%): C75.08,H 4.37,F 2.42,N 1.79,O8.16,S 8.18; found values: C75.05,H 4.38,F 2.42,N 1.78,O 8.16 the number of the components,S 8.16。
example 7
Using intermediate (3) prepared in example 6, the organic thermally activated delayed fluorescence material containing a phenylsulfone-spirofluorene structural unit was synthesized by the following route:
intermediate (3) (1.7 g,2.5 mmol), carbazole (0.59 g,3.5 mmol), sodium t-butoxide (0.58 g,6.0 mmol), palladium acetate (0.025 g,0.1 mmol), tri-t-butylphosphine tetrafluoroborate (0.087 g,0.3 mmol) and 60mL of toluene were added together in a 150mL round bottom flask, refluxed at 110℃for 48 hours, extracted with dichloromethane and water, distilled under reduced pressure, and purified by column chromatography to give an organic heat-activated delayed fluorescence material containing a phenylsulfone-spirofluorene structural unit (yield 90%).
Theoretical value of elemental analysis C 49 H 32 FNO 4 S 2 (%): C75.27,H 4.13,F 2.43,N 1.79,O8.18,S 8.20; found values: and C75.30,H 4.12,F 2.43,N 1.79,O8.18,S 8.20.
Example 8
Using intermediate (3) prepared in example 6, the organic thermally activated delayed fluorescence material containing a phenylsulfone-spirofluorene structural unit was synthesized by the following route:
intermediate (3) (1.7 g,2.5 mmol), iminostilbene (0.58 g,3.0 mmol), sodium t-butoxide (0.58 g,6.0 mmol), palladium acetate (0.025 g,0.1 mmol), tri-t-butylphosphine tetrafluoroborate (0.087 g,0.3 mmol) and 60mL of toluene were added together to a 150mL round bottom flask, refluxed at 110℃for 48 hours, extracted with dichloromethane and water, distilled under reduced pressure, and purified by column chromatography to give an organic heat-activated delayed fluorescence material containing a phenylsulfone-spirofluorene structural unit (yield 77%).
Theoretical value of elemental analysis C 51 H 34 FNO 4 S 2 (％)：C 75.82,H4.24,F 2.35,N 1.73,O7.92,S 7.94; found values: and C75.80,H 4.22,F 2.34,N 1.73,O 7.94,S 7.94.
Example 9
The synthetic route for intermediate (4) is shown below:
9, 9-bis (4-iodophenyl) -fluorene (2.0 g,3.5 mmol), 4-bromothiophenol (1.34 g,7.0 mmol), potassium hydroxide (0.8 g,14.4 mmol), cuprous iodide (0.06 g,0.4 mmol) and glycine (0.05 g,0.7 mmol) were dissolved in 90mL of ultra-dry 1, 4-dioxane solvent, heated under reflux for 48h, distilled under reduced pressure, added 40mL of ethanol and 80mL of 30% hydrogen peroxide solution, heated under reflux for 24h, extracted with dichloromethane and water, and purified by column chromatography to give intermediate (4) as a white solid (yield 56%).
In this example, the synthetic route of the organic thermally activated delayed fluorescence material containing phenylsulfone-spirofluorene structural units is as follows:
intermediate (4) (1.7 g,2.5 mmol), 9' -dimethylacridine (0.53 g,3.0 mmol), sodium t-butoxide (0.58 g,6.0 mmol), palladium acetate (0.025 g,0.1 mmol), tri-tert-butylphosphine tetrafluoroborate (0.087 g,0.3 mmol) and 60mL of toluene were added together to a 150mL round bottom flask, refluxed at 110℃for 48h, extracted with dichloromethane and water, distilled under reduced pressure, and purified by column chromatography to give an organic thermally activated delayed fluorescent material containing phenyl sulfone-spirofluorene structural units (yield 60%).
Theoretical value of elemental analysis C 52 H 38 BrNO 4 S 2 (%): C70.58,H 4.33,Br 9.03,N 1.58,O 7.23,S 7.25; found values: and C70.60,H 4.35,Br 9.05,N 1.59,O 7.21,S 7.25.
The transient state light-induced spectrum decay curve of the organic thermal activation delayed fluorescence material containing the phenyl sulfone-spirofluorene structural unit prepared in the embodiment in toluene solution is shown in fig. 2, two curves in the graph are transient state light-induced spectrum decay curves under aerobic condition and anaerobic condition respectively, obvious TADF characteristics can be observed, and the service life is shorter.
Example 10
Using intermediate (4) prepared in example 6, the organic thermally activated delayed fluorescence material containing a phenylsulfone-spirofluorene structural unit was synthesized by the following route:
intermediate (4) (2.3 g,3.0 mmol), phenoxazine (1.28 g,7.0 mmol), sodium t-butoxide (1.16 g,12.0 mmol), palladium acetate (0.05 g,0.2 mmol), tri-t-butylphosphine tetrafluoroborate (0.18 g,0.6 mmol) and toluene 90mL were added together to a 150mL round bottom flask, refluxed at 110 ℃ for 48h, extracted with dichloromethane and water, distilled under reduced pressure, and purified by column chromatography to give an organic heat-activated delayed fluorescence material containing phenylsulfone-spirofluorene structural units (yield 71%).
Theoretical value of elemental analysis C 61 H 40 N 2 O 6 S 2 (%): C76.23,H 4.20,N 2.91,O 9.99,S6.67; found values: and C76.22,H 4.21,N 2.90,O 9.99,S 6.64.
Example 11
The organic thermally activated delayed fluorescence material containing a phenylsulfone-spirofluorene structural unit was synthesized by using the organic thermally activated delayed fluorescence material containing a phenylsulfone-spirofluorene structural unit prepared in example 9, according to the following formula:
the organic heat-activated delayed fluorescence material containing a phenylsulfone-spirofluorene structural unit (2.1 g,2.4 mmol), phenoxazine (0.53 g,2.9 mmol), sodium t-butoxide (0.58 g,6.0 mmol), palladium acetate (0.025 g,0.1 mmol), tri-t-butylphosphine tetrafluoroborate (0.09 g,0.3 mmol) and toluene 90mL obtained in example 9 were added together in a 150mL round bottom flask, refluxed at 110℃for 48h, extracted with methylene chloride and water, distilled under reduced pressure, and purified by column chromatography to give compound XI (yield 74%).
Theoretical value of elemental analysis C 64 H 46 N 2 O 5 S 2 (%): C77.87,H 4.70,N 2.84,O 8.10,S6.50; found values: and C77.92,H 4.71,N 2.84,O 8.11,S 6.51.
Application example 1
The organic electroluminescent device structure prepared by the organic thermal activation delayed fluorescence material containing the phenyl sulfone-spirofluorene structural unit comprises the following components: ITO/MoO 3 (8 nm)/TAPC (50 nm)/mcP: 5% Emitters (compound of the present invention)/TmPyPB (40 nm)/LiF (1 nm)/Al (100 nm).
As shown in FIG. 3, the organic electroluminescent device prepared from the organic thermally activated delayed fluorescence material containing phenyl sulfone-spirofluorene structural unit comprises a conductive glass substrate 1, a hole injection layer 2 (molybdenum trioxide MoO) 3 ) Hole transport layer 3 (4, 4' -cyclohexylbis [ N, N-bis (4-methylphenyl) aniline)]TAPC), an organic light-emitting layer 4 (mCP host material and organic heat-activated delayed fluorescence material containing phenyl sulfone-spirofluorene structural unit prepared by the present invention), an electron transport layer 5 (3, 3'- [5' - [3- (3-pyridyl) phenyl)][1,1':3',1 "-terphenyl ]]-3, 3' -diyl]Bipyridine TmPyPB), electron injection layer 6 (lithium fluoride LiF), 7 is a cathode layer (aluminum Al).
The device preparation process is as follows: electroluminescent devices are fabricated according to methods known in the art, such as those disclosed in the references (adv. Mater.2004,16,537.); the specific method comprises the following steps: vapor deposition of MoO of 8nm on cleaned conductive glass (ITO) substrate under high vacuum condition 3 50nm TAPC,20nm light emitting layer, 40nm TmPyPB,1nm LiF and 120nm Al.
The device performance test data are shown in the following table:
as shown in the table, the maximum current efficiency of the device applying the compound can reach 28.7cd/A, the starting voltage is only 3.6V at the minimum, the efficiency attenuation performance is good, and the quantum efficiency is higher than that of the device applying the traditional fluorescent material.
Compared with other fluorescent materials, the invention adopts a structure of combining phenyl sulfone and spirofluorene units, and can regulate and control the luminescence of the compound by changing the corresponding aromatic substituted amino or aromatic heterocyclic amino while applying space charge transfer property, and the adopted raw materials can be synthesized by a simple method in a laboratory or can be directly purchased from the market, so that the synthesis route is simple and efficient, and the method is suitable for large-scale practical production. The electroluminescent device has high quantum efficiency and high efficiency attenuation performance, and can be applied to the field of OLED display.
While the foregoing embodiments have been described in detail in connection with the embodiments of the invention, it should be understood that the foregoing embodiments are merely illustrative of the invention and are not intended to limit the invention, and any modifications, additions, substitutions and the like made within the principles of the invention are intended to be included within the scope of the invention.

Claims (4)

1. An organic thermally activated delayed fluorescence material containing a phenylsulfone-spirofluorene structural unit, which is characterized by having a structure represented by formulas I-1 to I-4:
wherein R is halogen, ar is aromatic substituted amino and aromatic heterocyclic amino;
the aromatic substituted amino is
The aromatic heterocyclic amino is of a structure shown as II-1 to II-8:
2. the method for preparing the organic thermal activation delay fluorescent material containing the phenyl sulfone-spirofluorene structural unit according to claim 1, wherein the organic thermal activation delay fluorescent material containing the phenyl sulfone-spirofluorene structural unit is obtained by reacting a compound A with a compound B and then reacting with a compound C;
the compound A isWherein X is halogen;
the compound B isWherein X is halogen;
the compound C has a structure shown in III-1 to III-9:
the preparation method comprises the following steps:
(1) Reacting a compound A with a compound B in the presence of alkali, amino acid, copper catalyst and hydrogen peroxide to obtain an intermediate; the intermediate has a structure shown as IV-1 to IV-3:
wherein X is 1 ,X 2 ,X 3 ,X 4 ,X 5 All being halogen, X 4 And X 5 Is halogen of different species;
(2) The intermediate and a compound C react in the molar ratio of 1:1-3 in the presence of alkali, palladium catalyst and tri-tert-butyl phosphine tetrafluoroborate to obtain the organic thermal activation delayed fluorescence material containing phenyl sulfone-spirofluorene structural unit with the structure shown in I-1-I-4.
3. The method for preparing an organic thermally activated delayed fluorescence material containing a phenylsulfone-spirofluorene structural unit according to claim 2, wherein the base is an organic base or a metal carbonate; the amino acid is glycine; the copper catalyst is cuprous chloride, cuprous bromide or cuprous iodide; the palladium catalyst is palladium acetate.
4. Use of an organic thermally activated delayed fluorescence material containing phenylsulfone-spirofluorene structural units according to claim 1 in the preparation of an organic electroluminescent device.
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