CN113845505B - Spirofluorene derivative amine compound and organic electroluminescent device comprising the same - Google Patents

Spirofluorene derivative amine compound and organic electroluminescent device comprising the same Download PDF

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CN113845505B
CN113845505B CN202111219509.1A CN202111219509A CN113845505B CN 113845505 B CN113845505 B CN 113845505B CN 202111219509 A CN202111219509 A CN 202111219509A CN 113845505 B CN113845505 B CN 113845505B
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spirofluorene derivative
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CN113845505A (en
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王湘成
何为
何睦
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Shanghai Yaoyi Electronic Technology Co ltd
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Abstract

The invention discloses a spirofluorene derivative amine compound and an organic electroluminescent device containing the same, wherein the chemical structure of the compound is that
Figure DDA0003312014960000011
X 1 –X 4 In adjacent substituents X 1 And X 2 、X 2 And X 3 、X 3 And X 4 At least one group of
Figure DDA0003312014960000012
Connection, Y 2 And Y 3 Selected from-CRR' -, O, S or N, respectively, and are not simultaneously oxygen, Y 1 Selected from single bond, O, S, -NR-or-CRR' -, R 1 –R 3 Independently selected from hydrogen, substituted or unsubstituted alkyl or alkoxy, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, or are combined with adjacent groups to form a substituted or unsubstituted ring, a-c are selected from 0-4, L is absent or phenylene, ar 1 And Ar is a group 2 Independently selected from substituted or unsubstitutedSubstituted aryl, substituted or unsubstituted heteroaryl, or combined with an adjacent group to form a substituted or unsubstituted ring; the spirofluorene derivative amine compound can be used as a hole transport material to prolong the service life of a device.

Description

Spirofluorene derivative amine compound and organic electroluminescent device comprising the same
Technical Field
The invention belongs to the field of organic electroluminescent materials, and particularly relates to a spirofluorene derivative amine compound and an organic electroluminescent device containing the same.
Background
At present, 9'9-spirofluorene has the advantages of excellent hole transport capacity, lower sublimation temperature and the like as a hole transport material component unit of an organic electroluminescent device (OLED), but 9'9-spirofluorene still has the defect of structural stability, and is mainly characterized in that the spirofluorene has an electron withdrawing function and is easy to break bonds and crack when being connected with amine. If the power supply group is added on the basis of the spirofluorene, the structural stability of the spirofluorene amine compound is facilitated, and the spirofluorene derivative extends the advantages of the spirofluorene, so that the spirofluorene compound has high electron mobility, and meanwhile, the energy level adjustment, the solubility improvement and the structural stability are better improved. Based on the above, the present invention is based on molecular structure design, and a new spirofluorene derivative amine compound is tried and proposed for the first time, specifically as follows.
Disclosure of Invention
The invention provides a spirofluorene derivative amine compound, which has a chemical structure as shown in chemical formula 1:
Figure BDA0003312014940000011
in chemical formula 1, X 1 –X 4 In adjacent substituents X 1 And X 2 、X 2 And X 3 、X 3 And X 4 At least one group of
Figure BDA0003312014940000012
Ligation, other is hydrogen, is the ligation site, Y 2 And Y 3 respectively-CRR' -, O, S or N, and are not simultaneously oxygen;
Y 1 selected from single bond, O, S, -NR-or-CRR' -;
R 1 –R 3 each independently selected fromHydrogen, a substituted or unsubstituted alkyl or alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 ring-forming carbon atoms, a substituted or unsubstituted heteroaryl group having 5 to 30 ring-forming carbon atoms, or a substituted or unsubstituted ring formed by combining adjacent groups;
a-c are each independently selected from integers from 0 to 4;
l is absent or phenylene;
Ar 1 and Ar is a group 2 Each independently selected from a substituted or unsubstituted aryl group having 6 to 30 ring-forming carbon atoms, a substituted or unsubstituted heteroaryl group having 5 to 30 ring-forming carbon atoms, or a combination of adjacent groups to form a substituted or unsubstituted ring.
Compared with the prior art, the invention has the beneficial effects that: the spirofluorene derivative amine compound disclosed by the invention is beneficial to the structural stability of the compound by adding the power supply group on the 9, 9-spirofluorene derivative, and meanwhile, the spirofluorene derivative has high electron mobility, is better improved in the aspects of energy level adjustment, solubility improvement and structural stability, and can be used as a hole transport material to prolong the service life of a device.
Drawings
Fig. 1 is a schematic structural view of a bottom-emission organic electroluminescent device in an embodiment.
Fig. 2 is a schematic structural view of a top-emission organic electroluminescent device in an embodiment.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more clear, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings of the embodiments of the present invention. It will be apparent that the described embodiments are some, but not all, embodiments of the invention. All other embodiments, which can be made by a person skilled in the art without creative efforts, based on the described embodiments of the present invention fall within the protection scope of the present invention.
The spirofluorene derivative amine compound provided by the invention has a chemical structure as shown in chemical formula 1:
Figure BDA0003312014940000021
in chemical formula 1, X 1 –X 4 In adjacent substituents X 1 And X 2 、X 2 And X 3 、X 3 And X 4 At least one group of
Figure BDA0003312014940000022
Ligation, other is hydrogen, is the ligation site, Y 2 And Y 3 respectively-CRR' -, O, S or N, and are not simultaneously oxygen; y is Y 1 Selected from single bond, O, S, -NR-or-CRR' -;
R 1 –R 3 each independently selected from hydrogen, substituted or unsubstituted alkyl or alkoxy groups having 1 to 20 carbon atoms, substituted or unsubstituted aryl groups having 6 to 30 ring-forming carbon atoms, substituted or unsubstituted heteroaryl groups having 5 to 30 ring-forming carbon atoms, or combined with adjacent groups to form a substituted or unsubstituted ring;
a-c are each independently selected from integers from 0 to 4;
l is absent or phenylene;
Ar 1 and Ar is a group 2 Each independently selected from a substituted or unsubstituted aryl group having 6 to 30 ring-forming carbon atoms, a substituted or unsubstituted heteroaryl group having 5 to 30 ring-forming carbon atoms, or a combination of adjacent groups to form a substituted or unsubstituted ring.
The description of the substituents in the spirofluorene derivative amine-like compound shown in chemical formula 1 is as follows, but is not limited thereto.
"substituted or unsubstituted" means substituted with one or more substituents selected from the group consisting of: hydrogen, deuterium, halogen, nitrile, nitro, hydroxyl, carbonyl, ester, imide, amino, phosphine oxide, alkoxy, aryloxy, alkylthio, arylthio, alkylsulfonyl, arylsulfonyl, silyl, boron, alkyl, cycloalkyl, alkenyl, aryl, aralkyl, aralkenyl, alkylaryl, alkylamino, aralkylamino, heteroarylamino, arylamino, and heterocyclyl, or unsubstituted; or a substituent linking two or more of the above substituents, or unsubstituted, such as "a substituent linking two or more substituents" includes a biphenyl group, i.e., a biphenyl group may be an aryl group or a substituent linking two phenyl groups.
"aryl" may be a monocyclic aryl group including phenyl, biphenyl, terphenyl, tetrabiphenyl, pentabiphenyl, or a polycyclic aryl group including naphthyl, anthracenyl, phenanthrenyl, pyrenyl, perylenyl, fluorenyl, the above description of aryl groups being applicable to arylene groups, except that arylene groups are divalent.
"heteroaryl" includes one or more of N, O, P, S, si and Se as heteroatoms, having 5 to 30 carbon atoms, including pyridyl, pyrrolyl, pyrimidinyl, pyridazinyl, furanyl, thienyl, imidazolyl, pyrazolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, triazolyl, diazolyl, thiadiazolyl, dithiazolyl, tetrazolyl, pyranyl, thiopyranyl, pyrazinyl, oxazinyl, dioxanyl, triazinyl, tetrazinyl, quinolinyl, isoquinolinyl, quinolinyl, quinazolinyl, quinoxalinyl, naphthyridinyl, acridinyl, xanthenyl, phenanthridinyl, naphthyridinyl, triazaindenyl, indolyl, indolizinyl, phthalazinyl, pyridopyrimidinyl, pyridopyrazinyl, pyrazinyl, benzothiazolyl, benzoxazolyl, benzimidazolyl, benzothienyl, benzofuranyl, dibenzothienyl, dibenzofuranyl, carbazolyl, benzocarbazolyl, indolocarbazolyl, phenazoindenyl, imidazopyrrolyl, imidazopyridinyl, phenazinyl, phenazophenanthridinyl; the above description of heteroaryl groups applies to heteroarylene groups, except that the heteroarylene group is divalent.
According to some embodiments, the spirofluorene derivative amine-like compound represented by chemical formula 1 is selected from one of chemical formulas 1-1, 1-2, and 1-3:
Figure BDA0003312014940000041
the substituents in chemical formulas 1-1, 1-2 and 1-3 are the same as in chemical formula 1.
According to some embodiments, the spirofluorene derivative amine-like compound represented by chemical formula 1 is selected from any one of the following chemical structures:
Figure BDA0003312014940000042
Figure BDA0003312014940000051
the spirofluorene derivative amine compound shown in chemical formulas 1-1, 1-2 and 1-3 in the invention has the following synthetic general formula:
Figure BDA0003312014940000052
the following synthesis examples 1 to 7 describe in detail the preparation methods of the above-mentioned compounds A1, A2, A8, a15, a20, a30, a44, the raw materials of which are not noted are commercially available, and the synthesis of other compounds in the present invention is similar to the synthesis examples 1 to 7.
Synthesis example 1
In this synthesis example, compound A1 was synthesized, and the technical route is as follows:
Figure BDA0003312014940000061
synthesis of A1-3: a1-1 (15 g,44.6 mmol), A1-2 (8.9 g,44.6 mmol), potassium carbonate (11.9 g,89.2 mmol) and tetrakis (triphenylphosphine) palladium (1 g,0.89 mmol) were successively added to a three-necked flask, 150mL of toluene, 30mL of ethanol and 30mL of water were further added, the system was replaced with nitrogen for 3 times, the temperature of the reaction solution was raised to reflux, and the reaction was continued with stirring for 4 hours. The reaction solution was cooled to 70℃and allowed to stand for separation, the upper organic phase was washed with 50mL of water and separated, and the upper organic phase was passed through a silica gel column. The organic phase was concentrated to about 50mL of toluene, 120mL of petroleum ether was gradually added, solids precipitated, stirred for 2 hours, suction filtration, washing of the cake with a small amount of petroleum ether, heating of a mixed solution of 50mL of toluene and 120mL of ethanol was carried out, stirring was carried out for 2 hours at 40℃and the solids were filtered and dried to obtain 12g of the A1-3 compound in 73.6% yield.
Synthesis of A1-5: a clean three-necked flask was charged with A1-3 (10 g,27.4 mmol), tetrahydrofuran (100 mL) was further added, the nitrogen was replaced 3 times, and the temperature was lowered to 0 ℃. N-butyllithium (10.9 mL,27.4 mmol) was added dropwise to the reaction solution, and after 20min the reaction was stirred at 0deg.C for 30min. Next, A1-4 (5.3 g,25 mmol) was added to the reaction solution, and the reaction solution was warmed to room temperature of 25℃and reacted for 1 hour. The reaction solution was cooled to 0 ℃, 100mL of saturated ammonium chloride solution was added, the solution was separated, the aqueous phase was extracted once with EA, the organic phase was concentrated, passed through a silica gel column (100-200 mesh, mobile phase petroleum ether: ethyl acetate=5:1), and the solvent was evaporated and dried to give a solid. The solid is added into a clean three-neck flask, dichloromethane (100 mL) is added, the temperature is reduced to 0 ℃, boron trifluoride diethyl etherate solution (2 mL) is added into the reaction liquid dropwise, the temperature of the reaction liquid is raised to 25 ℃ after the addition, the reaction is carried out for 1h, a large amount of solid is separated out, 100mL of petroleum ether is added into the reaction liquid, the stirring is carried out for 1h, 8g of off-white solid is obtained through suction filtration, and the yield is 66%.
Synthesis of A1: a1-5 (6 g,12.4 mmol), A1-6 (3.0 g,12.4 mmol), tris (dibenzylideneacetone) dipalladium (0.2 g,0.248 mmol), tri-tert-butylphosphine (0.6 mL,0.62 mmol), sodium tert-butoxide (3.7 g,37.2 mmol) and toluene (50 mL) were added to a three-necked flask, the reaction mixture was heated to reflux with nitrogen, stirred for 120min, the reaction mixture was cooled to 80℃and the hot superheated silica gel column, the mother liquor was concentrated to 20mL, 20mL of ethanol was added, stirred at room temperature for 1h, filtered, 50mL of toluene was added to the solid, dissolved at reflux, 50mL of petroleum ether was added, stirred at room temperature for 2h, filtered and dried to give 6g of A1 solid with a yield of 69.9%.
Synthesis example 2
In this synthesis example, compound A2 was synthesized, and the technical route is as follows:
Figure BDA0003312014940000071
synthesis of A2-3: compound A2-3 was obtained in the same manner as compound A1-3 in example 1, except that compound A2-1 was used in place of compound A1-1.
Synthesis of A2-5: compounds A2 to 5 were obtained in the same manner as in the compounds A1 to 5 in example 1, except that compounds A2 to 3 were used in place of compounds A1 to 3.
Synthesis of A2: compound A2 was obtained in the same manner as compound A1 in example 1, except that compounds A2-5 were used instead of compounds A1-5.
Synthesis example 3
In this synthesis example, compound A8 was synthesized, and the technical route is as follows:
Figure BDA0003312014940000072
synthesis of A8-3: compound A8-3 was obtained in the same manner as in Compound A1-3 in example 1, except that Compound A8-1 was used in place of Compound A1-1 and Compound A8-2 was used in place of Compound A1-2.
Synthesis of A8-5: compound A8-5 was obtained in the same manner as in Compound A1-5 in example 1, except that Compound A8-3 was used in place of Compound A1-3.
Synthesis of A8: compound A8 was obtained in the same manner as compound A1 in example 1 except that compounds A8-5 were used instead of compounds A1-5.
Synthesis example 4
In this synthesis example, compound a15 was synthesized, and the technical route is as follows:
Figure BDA0003312014940000073
synthesis of A15-3: compound A15-3 was obtained in the same manner as in Compound A1-3 in example 1, except that Compound A15-1 was used in place of Compound A1-1 and Compound A15-2 was used in place of Compound A1-2.
Synthesis of A15-5: compound A15-5 was obtained in the same manner as in Compound A1-5 in example 1, except that Compound A15-3 was used in place of Compound A1-3.
Synthesis of a 15: compound a15 was obtained in the same manner as compound A1 in example 1, except that compound a15-5 was used instead of compound A1-5 and compound a15-6 was used instead of compound A1-6.
Synthesis example 5
In this synthesis example, compound a20 was synthesized, and the technical route is as follows:
Figure BDA0003312014940000081
synthesis of A20-3: compound A20-3 was obtained in the same manner as in Compound A1-3 in example 1, except that Compound A20-1 was used in place of Compound A1-1.
Synthesis of A20-5: compound A20-5 was obtained in the same manner as in Compound A1-5 in example 1, except that Compound A20-3 was used in place of Compound A1-3 and Compound A20-4 was used in place of Compound A1-4.
Synthesis of a 20: compound a20 was obtained in the same manner as compound A1 in example 1, except that compound a20-5 was used instead of compound A1-5.
Synthesis example 6
In this synthesis example, compound a30 was synthesized, and the technical route is as follows:
Figure BDA0003312014940000082
synthesis of A30-3: compound A30-3 was obtained in the same manner as in Compound A1-3 in example 1, except that Compound A30-1 was used in place of Compound A1-1 and Compound A30-2 was used in place of Compound A1-2.
Synthesis of A30-5: compound A30-5 was obtained in the same manner as in Compound A1-5 in example 1, except that Compound A30-3 was used in place of Compound A1-3 and Compound A30-4 was used in place of Compound A1-4.
Synthesis of a 30: compound a30 was obtained in the same manner as compound A1 in example 1, except that compound a30-5 was used instead of compound A1-5 and compound a30-6 was used instead of compound A1-6.
Example 7
Compound 44 was synthesized in this synthesis example, the technical route is as follows:
Figure BDA0003312014940000091
synthesis of A44-3: compound A44-3 was obtained in the same manner as in Compound A1-3 in example 1, except that Compound A44-1 was used in place of Compound A1-1.
Synthesis of A44-5: compound A44-5 was obtained in the same manner as in Compound A1-5 in example 1, except that Compound A44-3 was used in place of Compound A1-3 and Compound A44-4 was used in place of Compound A1-4.
Synthesis of a 44: compound a44 was obtained in the same manner as compound A1 in example 1, except that compound a44-5 was used instead of compound A1-5.
The invention also provides application of the spirofluorene derivative amine compound in an organic electroluminescent device, in particular to application of the spirofluorene derivative amine compound as a hole transport layer material of the organic electroluminescent device in a top light-emitting device, a bottom light-emitting device or a serial device. The organic electroluminescent device prepared in the following device embodiments, including the first electrode, the second electrode, and one or more organic material layers disposed between the first electrode and the second electrode, is a bottom or top light emitting device structure (as shown in fig. 1 or 2), and the organic material layers may be a single-layer structure, or may be a multi-layer tandem structure in which two or more organic material layers are laminated, such as a structure having a hole injection layer, a hole transport layer, a light emitting layer, a hole transport layer, an electron injection layer, etc. as the organic material layers, may be prepared using a common method and material for preparing an organic electroluminescent device. The spirofluorene derivative amine compound of the present invention can be used in various light colors such as red light, green light, blue light, white light, etc., and the following device examples 1 to 7 respectively use the above-mentioned compounds A1, A2, A8, a15, a20, a30, a44 as hole transporting materials.
Device example 1
The preparation process of the single blue bottom-emitting non-tandem organic electroluminescent device is as follows according to the structure shown in figure 1: forming a transparent anode ITO film layer with a film thickness of 150nm on a glass substrate 101 to obtain a first electrode 102 as anode, and evaporating
Figure BDA0003312014940000092
And the compound->
Figure BDA0003312014940000093
As the hole injection layer 103, the mixture ratio was 3:97 (mass ratio), then the compound A1 of the present invention was vapor-deposited to a thickness of 100nm to obtain the first hole transport layer 104, and then the compound +_20 nm was vapor-deposited>
Figure BDA0003312014940000101
A second hole transport layer 105 was obtained, and then +.>
Figure BDA0003312014940000102
And->
Figure BDA0003312014940000103
0nm, a blue light emitting unit 106 was fabricated, and then 10nm +.>
Figure BDA0003312014940000104
An electron blocking layer 107 is formed and then vapor deposited
Figure BDA0003312014940000105
And->
Figure BDA0003312014940000106
Hole transport layer 108 was formed at a ratio of 4:6 (mass ratio) to a thickness of 30nm, followed by vapor deposition to form ytterbium metal at a thickness of 1nm, and then forming silver metal at 100nm as a double-layer ytterbium/silver metal as second electrode 109.
The above-mentioned compounds A2, A8, A15, A20, A30, A44 and the compounds of comparative examples 1 and 2 were used in device examples 2 to 7, respectively
Figure BDA0003312014940000107
Instead of using the compound A1 of example 1 as the hole transport layer 104 to fabricate a blue organic electroluminescent device, the resulting organic electroluminescent device was subjected to a luminescence efficiency performance test as shown in table 1.
TABLE 1
Figure BDA0003312014940000108
Figure BDA0003312014940000111
As can be seen from Table 1, the spirofluorene derivative amine compound of the present invention is used as a hole transport layer material of a blue bottom-emission non-tandem organic electroluminescent device, and the obtained device has low driving voltage, high luminous efficiency and long service life.
In addition, the spirofluorene derivative amine compound can be used as a hole transport layer 105 of a top light-emitting device shown in fig. 1, or as hole transport layers 104 and/or 105 of a bottom light-emitting device shown in fig. 2, or as a multi-layer hole transport layer material of a tandem organic electroluminescent device, and the obtained device effect is also remarkable.
In addition, the invention also provides a display device comprising any one of the organic electroluminescent devices.

Claims (9)

1. A spirofluorene derivative amine compound having a chemical structure as shown in chemical formula 1:
Figure FDA0004118901350000011
in chemical formula 1, X 1 –X 4 In adjacent substituents X 1 And X 2 、X 2 And X 3 、X 3 And X 4 At least one group of
Figure FDA0004118901350000012
Ligation, other is hydrogen, is the ligation site, Y 2 And Y 3 Are all-CRR' -;
Y 1 selected from O, S, -NR-or-CRR' -;
r, R' are all methyl groups;
R 1 –R 3 each independently selected from hydrogen, unsubstituted alkyl or alkoxy groups having 1 to 20 carbon atoms, unsubstituted aryl groups having 6 to 30 ring-forming carbon atoms, unsubstituted heteroaryl groups having 5 to 30 ring-forming carbon atoms, or an adjacent group, to form an unsubstituted ring;
a-c are each independently selected from integers from 0 to 4;
l is absent or phenylene;
Ar 1 and Ar is a group 2 Each independently selected from an unsubstituted aryl group having 6 to 30 ring-forming carbon atoms, an unsubstituted heteroaryl group having 5 to 30 ring-forming carbon atoms, or a combination of adjacent groups to form an unsubstituted ring.
2. A spirofluorene derivative amine-like compound according to claim 1, wherein the spirofluorene derivative amine-like compound represented by chemical formula 1 is selected from one of chemical formulas 1-1, 1-2 and 1-3:
Figure FDA0004118901350000013
/>
Figure FDA0004118901350000021
the substituents in chemical formulas 1-1, 1-2 and 11-3 are the same as in chemical formula 1.
3. A spirofluorene derivative amine compound according to claim 1 or 2, wherein the aryl group is a monocyclic aryl group or a polycyclic aryl group, the monocyclic aryl group being selected from phenyl, biphenyl, terphenyl, tetrabiphenyl or pentabiphenyl, the polycyclic aryl group being selected from naphthyl, anthracenyl, phenanthrenyl, pyrenyl, perylenyl or fluorenyl.
4. A spirofluorene derivative amine-like compound according to claim 1 or 2, wherein the hetero atom in the heteroaryl group is selected from one or more of N, O, P, S, si and Se, selected from the group consisting of pyridyl, pyrrolyl, pyrimidinyl, pyridazinyl, furanyl, thienyl, imidazolyl, pyrazolyl, isoxazolyl, thiazolyl, isothiazolyl, triazolyl, diazolyl, thiadiazolyl, dithiazolyl, tetrazolyl, pyranyl, thiopyranyl, pyrazinyl, thiazinyl, dioxanyl, triazinyl, tetrazinyl, isoquinolyl, quinolinyl, quinazolinyl, quinoxalinyl, naphthyridinyl, acridinyl, xanthenyl, phenanthridinyl, naphthyridinyl, triazaindenyl, indolyl, indolizinyl, phthalazinyl, pyridopyrimidinyl, pyridopyrazinyl, pyrazinyl, benzothiazolyl, benzoxazolyl, benzimidazolyl, benzothienyl, benzofuranyl, dibenzothienyl, dibenzofuranyl, carbazolyl, benzocarbazolyl, dibenzocarbazolyl, indolocarbazolyl, indenocarbazolyl, phenazinyl, phenanthroline, imidazopyridyl, or benzimidazolyl.
5. A spirofluorene derivative amine-like compound according to claim 1, wherein the spirofluorene derivative amine-like compound represented by chemical formula 1 is selected from any one of the following chemical structures:
Figure FDA0004118901350000022
/>
Figure FDA0004118901350000031
6. use of the spirofluorene derivative amine-like compound according to any one of claims 1 to 5 in an organic electroluminescent device.
7. An organic electroluminescent device comprising the spirofluorene derivative amine-like compound as claimed in any one of claims 1 to 5.
8. The organic electroluminescent device according to claim 7, wherein the spirofluorene derivative amine-like compound is used as a hole transporting material of the organic electroluminescent device.
9. A display device comprising the organic electroluminescent device as claimed in claim 7 or 8.
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