KR101769764B1 - Novel organic semiconductor compound and organic light emitting device using the same - Google Patents
Novel organic semiconductor compound and organic light emitting device using the same Download PDFInfo
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- KR101769764B1 KR101769764B1 KR1020150173745A KR20150173745A KR101769764B1 KR 101769764 B1 KR101769764 B1 KR 101769764B1 KR 1020150173745 A KR1020150173745 A KR 1020150173745A KR 20150173745 A KR20150173745 A KR 20150173745A KR 101769764 B1 KR101769764 B1 KR 101769764B1
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- South Korea
- Prior art keywords
- heteroaryl
- independently
- aryl
- organic semiconductor
- organic
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 86
- 239000004065 semiconductor Substances 0.000 title claims abstract description 52
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- 125000003118 aryl group Chemical group 0.000 claims description 49
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 47
- -1 nitro, hydroxy Chemical group 0.000 claims description 37
- 125000005549 heteroarylene group Chemical group 0.000 claims description 32
- 125000000923 (C1-C30) alkyl group Chemical group 0.000 claims description 27
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 27
- 229910052739 hydrogen Inorganic materials 0.000 claims description 24
- 239000001257 hydrogen Substances 0.000 claims description 24
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 22
- 125000000732 arylene group Chemical group 0.000 claims description 22
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- 239000000126 substance Substances 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 15
- 229910052698 phosphorus Inorganic materials 0.000 claims description 15
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- 229910052736 halogen Inorganic materials 0.000 claims description 11
- 150000002367 halogens Chemical class 0.000 claims description 11
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- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 7
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- QBLFZIBJXUQVRF-UHFFFAOYSA-N (4-bromophenyl)boronic acid Chemical compound OB(O)C1=CC=C(Br)C=C1 QBLFZIBJXUQVRF-UHFFFAOYSA-N 0.000 description 3
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- SGNJNVMRIULYLO-UHFFFAOYSA-N 10,10-diphenyl-5h-benzo[b][1,4]benzazasiline Chemical compound C12=CC=CC=C2NC2=CC=CC=C2[Si]1(C=1C=CC=CC=1)C1=CC=CC=C1 SGNJNVMRIULYLO-UHFFFAOYSA-N 0.000 description 3
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- HVHDPYRQZHBUDX-UHFFFAOYSA-N CN1c(cccc2)c2[Si+](c2ccccc2)(c2ccccc2)c2c1cccc2 Chemical compound CN1c(cccc2)c2[Si+](c2ccccc2)(c2ccccc2)c2c1cccc2 HVHDPYRQZHBUDX-UHFFFAOYSA-N 0.000 description 3
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- DMEVMYSQZPJFOK-UHFFFAOYSA-N 3,4,5,6,9,10-hexazatetracyclo[12.4.0.02,7.08,13]octadeca-1(18),2(7),3,5,8(13),9,11,14,16-nonaene Chemical group N1=NN=C2C3=CC=CC=C3C3=CC=NN=C3C2=N1 DMEVMYSQZPJFOK-UHFFFAOYSA-N 0.000 description 1
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- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0803—Compounds with Si-C or Si-Si linkages
- C07F7/0805—Compounds with Si-C or Si-Si linkages comprising only Si, C or H atoms
- C07F7/0807—Compounds with Si-C or Si-Si linkages comprising only Si, C or H atoms comprising Si as a ring atom
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- C—CHEMISTRY; METALLURGY
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- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0803—Compounds with Si-C or Si-Si linkages
- C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
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- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
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Abstract
The present invention relates to a novel organic semiconductor compound and an organic electroluminescent device using the same. More specifically, the organic semiconductor compound according to the present invention is a rigid azasilane derivative having an intramolecular electron donor and an electron acceptor, and is capable of realizing excellent oxidation stability and light emission characteristics, and an organic electroluminescent device employing the same Not only has a high purity blue having high quantum efficiency but also a high purity.
Description
The present invention relates to a novel organic semiconductor compound and an organic electroluminescent device using the same, and more particularly, to an azacillin derivative exhibiting thermally activated delayed fluorescence (TADF) and an organic electroluminescent device using the same. .
Recently, as the development of the display industry has accelerated, a display device having a high performance function is required. The display device can be generally divided into a light emitting display device and a non-light emitting display device. Examples of the light emitting display device include a cathode ray tube (CRT) and a light emitting diode (LED) LCD). In the case of a liquid crystal display (LCD), which has been mainly used as a display window of TVs, notebooks, mobile phones and the like until recently, since it is a backlight system that emits light from behind, it is not only thick but also has a low color purity, Therefore, it has many disadvantages such as the invisible side view and the residual image due to the slow reaction speed.
As a solution to this problem, many companies are actively studying organic light-emitting diodes (OLEDs, organic light-emitting diodes). Such OLEDs are self-emissive and require no back- The speed is also faster than LCD and it is superior to LCD in almost all aspects such as low direct current driving voltage, wide viewing angle, light weight thin type, possibility of flexible display, and has been attracted attention as next generation display. Recently, It is acknowledged.
Recently, interest in thermally activated delayed fluorescence (TADF) materials, which are evaluated as third-generation OLED materials, is growing, following fluorescent materials and phosphorescent materials. The thermally activated delayed fluorescence (TADF) material is a material that converts triplet excitons into singletons and converts them into light, unlike a phosphorescent material that converts singlet excitons into triplets and converts them to light. It is a material that can overcome the limitation of lifetime and efficiency of blue and red phosphorescent materials because 100% internal quantum efficiency is possible because it can change both singlet and triplet excitons to light theoretically. Research on this is being activated.
A representative mechanism of the thermally activated delayed fluorescence (TADF) described above is a triplet-triplet annihilation (TTA) and a reverse intersystem crossing (RISC) By converting it into a singular term. At this time, although the TTA is currently used for fluorescent blue and green devices having high efficiency, internal triplet efficiency is low due to the fact that one triplet is formed due to the disappearance of two triplet. On the other hand, RISC has the advantage that all excitons can be converted into light because it can theoretically convert all triplets into singletons, thereby achieving high internal quantum efficiency.
Accordingly, the present inventors have developed a novel organic semiconductor compound exhibiting thermally activated delayed fluorescence (TADF) through reverse intersystem crossing (RISC), and by using it, have achieved an external quantum efficiency of more than 20% The present inventors have completed the present invention in order to provide an organic electroluminescent device having an organic electroluminescent device.
It is an object of the present invention to provide azasilane derivatives having high thermal stability, optical properties and chemical stability.
It is still another object of the present invention to provide an organic electroluminescent device having high efficiency and long life characteristics by employing the azacillin derivative.
The present invention includes an organic semiconductor compound represented by the following general formula (1).
[Chemical Formula 1]
[In the above formula (1)
Ar is hydrogen, (C3-C30) cycloalkyl, (C3-C30) heterocycloalkyl, (C3-C30) heteroaryl or (C6-C30) aryl;
L 1 and L 2 are each independently a single bond, (C3-C30) cycloalkylene, (C3-C30) heterocycloalkylene, (C3-C30) heteroarylene or (C6-C30) arylene;
Z is a single bond, -C (R 11 ) (R 12 ) -, -C = C (R 11 ) (R 12 ) -, -N (R 11 ) O (R 11) -, -SO 2 -, oxadiazolyl alkylene or binary or a unsubstituted triazolyl alkylene, wherein R 11 and R 12 are each independently hydrogen, (C1-C30) alkyl, cyano, nitro (C3-C30) cycloalkyl, (C3-C30) heterocycloalkyl, (C3-C30) heteroaryl or (C6-C30) aryl;
R 1 and R 2 are each independently hydrogen, (C 3 -C 30) heteroaryl or (C 6 -C 30) aryl;
Wherein said cycloalkyl, heterocycloalkyl, heteroaryl and aryl of said Ar together with said cycloalkylene, heterocycloalkylene, heteroarylene and arylene of said L 1 to L 2 , triazolylene of said Z and R 1 to R heteroaryl and aryl 2 are each independently (C1-C30) alkyl, halogen, cyano, nitro, hydroxy, (C1-C30) alkoxy, (C3-C30) cycloalkyl, (C3-C30) heterocycloalkyl alkyl, (C3-C30) heteroaryl, (C6-C30) aryl, and -P = O (R 13) ( R 14) may be further substituted with one or more selected from the group, wherein R 13 and R 14 consisting of (C3-C30) heterocycloalkyl, (C3-C30) heteroaryl or (C6-C30) heteroaryl, each of which is optionally substituted by one or more substituents independently selected from the group consisting of (C1-C30) alkyl, cyano, nitro, Wherein said heterocycloalkyl, heteroaryl, heterocycloalkylene and heteroarylene are optionally substituted with one or more heteroatoms selected from B, N, O, S, P (= O) And a.]
The present invention also relates to a process for preparing an organic semiconductor compound represented by the following general formula (1) by reacting a compound represented by the following general formula (5) with a compound represented by the following general formula (6) And an organic semiconductor compound.
[Chemical Formula 5]
[Chemical Formula 6]
[Chemical Formula 1]
[In the formulas (1), (5) and (6)
Ar is hydrogen, (C3-C30) cycloalkyl, (C3-C30) heterocycloalkyl, (C3-C30) heteroaryl or (C6-C30) aryl;
Ar 'is (C3-C30) cycloalkylene, (C3-C30) heterocycloalkylene, (C3-C30) heteroarylene or (C6-C30) arylene;
L 1 and L 2 are each independently a single bond, (C3-C30) cycloalkylene, (C3-C30) heterocycloalkylene, (C3-C30) heteroarylene or (C6-C30) arylene;
Z is a single bond, -C (R 11 ) (R 12 ) -, -C = C (R 11 ) (R 12 ) -, -N (R 11 ) O (R 11) -, -SO 2 -, oxadiazolyl alkylene or binary or a unsubstituted triazolyl alkylene, wherein R 11 and R 12 are each independently hydrogen, (C1-C30) alkyl, cyano, nitro (C3-C30) cycloalkyl, (C3-C30) heterocycloalkyl, (C3-C30) heteroaryl or (C6-C30) aryl;
R 1 and R 2 are each independently hydrogen, (C 3 -C 30) heteroaryl or (C 6 -C 30) aryl;
X 1 and X 2 are each independently halogen;
Wherein said cycloalkyl, heterocycloalkyl, heteroaryl and aryl of said Ar together with said cycloalkylene, heterocycloalkylene, heteroarylene and arylene of said L 1 to L 2 , triazolylene of said Z and R 1 to R heteroaryl and aryl 2 are each independently (C1-C30) alkyl, halogen, cyano, nitro, hydroxy, (C1-C30) alkoxy, (C3-C30) cycloalkyl, (C3-C30) heterocycloalkyl alkyl, (C3-C30) heteroaryl, (C6-C30) aryl, and -P = O (R 13) ( R 14) may be further substituted with one or more selected from the group, wherein R 13 and R 14 consisting of (C3-C30) heterocycloalkyl, (C3-C30) heteroaryl or (C6-C30) heteroaryl, each of which is optionally substituted by one or more substituents independently selected from the group consisting of (C1-C30) alkyl, cyano, nitro, Wherein said heterocycloalkyl, heteroaryl, heterocycloalkylene and heteroarylene are optionally substituted with one or more heteroatoms selected from B, N, O, S, P (= O) And a.]
The present invention provides an organic electroluminescent device (OLED) comprising the organic semiconductor compound represented by Formula 1 above.
The organic semiconducting compound according to the present invention is an azacillin derivative having an electron donor and an electron acceptor in a molecule, and can realize a high efficiency and a high color purity with a small difference in singlet energy level and triplet energy level.
The organic electroluminescent device employing the compound according to the present invention solves the problem caused by heat generated during driving, the low purity of the organic film forming material, the lowering of the luminescence property and the lowering of the color purity due to the π-stacking, , The stability of the device can be improved and the long-life characteristics can be obtained.
Therefore, the compound according to the present invention has bipolar characteristics in a material, has excellent quantum efficiency and long life, and can be used as a hole transport material, a light emitting material (phosphorescent host) or a thermally activated delayed fluorescence (TADF ) Dopants. ≪ / RTI >
1 to 3 are UV-vis absorption spectra and PL spectra on the solution and film of the organic semiconductor compound according to Examples 1 to 3 and Examples 3 to 7,
4 is a cyclic voltammetry diagram of organic semiconductor compounds according to Examples 1 and 2,
5 is an EL spectrum of the organic electroluminescent device manufactured in Example 10 and Example 18,
6 is a graph showing EQE according to the current density of the organic electroluminescent device manufactured in Example 10 and Example 18,
FIG. 7 is a graph of current density-voltage-luminance of the organic electroluminescent device manufactured in Example 10. FIG.
The organic semiconductor compound according to the present invention has a small triplet-free energy difference and can have high luminous efficiency and high purity color purity. In addition, it has excellent thermal stability and long life characteristics.
The novel organic semiconductor compound according to the present invention may be represented by the following general formula (1).
[Chemical Formula 1]
[In the above formula (1)
Ar is hydrogen, (C3-C30) cycloalkyl, (C3-C30) heterocycloalkyl, (C3-C30) heteroaryl or (C6-C30) aryl;
L 1 and L 2 are each independently a single bond, (C3-C30) cycloalkylene, (C3-C30) heterocycloalkylene, (C3-C30) heteroarylene or (C6-C30) arylene;
Z is a single bond, -C (R 11 ) (R 12 ) -, -C = C (R 11 ) (R 12 ) -, -N (R 11 ) O (R 11) -, -SO 2 -, oxadiazolyl alkylene or binary or a unsubstituted triazolyl alkylene, wherein R 11 and R 12 are each independently hydrogen, (C1-C30) alkyl, cyano, nitro (C3-C30) cycloalkyl, (C3-C30) heterocycloalkyl, (C3-C30) heteroaryl or (C6-C30) aryl;
R 1 and R 2 are each independently hydrogen, (C 3 -C 30) heteroaryl or (C 6 -C 30) aryl;
Wherein said cycloalkyl, heterocycloalkyl, heteroaryl and aryl of said Ar together with said cycloalkylene, heterocycloalkylene, heteroarylene and arylene of said L 1 to L 2 , triazolylene of said Z and R 1 to R heteroaryl and aryl 2 are each independently (C1-C30) alkyl, halogen, cyano, nitro, hydroxy, (C1-C30) alkoxy, (C3-C30) cycloalkyl, (C3-C30) heterocycloalkyl alkyl, (C3-C30) heteroaryl, (C6-C30) aryl, and -P = O (R 13) ( R 14) may be further substituted with one or more selected from the group, wherein R 13 and R 14 consisting of (C3-C30) heterocycloalkyl, (C3-C30) heteroaryl or (C6-C30) heteroaryl, each of which is optionally substituted by one or more substituents independently selected from the group consisting of (C1-C30) alkyl, cyano, nitro, Wherein said heterocycloalkyl, heteroaryl, heterocycloalkylene and heteroarylene are optionally substituted with one or more heteroatoms selected from B, N, O, S, P (= O) And a.]
&Quot; Heteroaryl " as defined in the present invention is an organic radical derived from aromatic hydrocarbons by the removal of one hydrogen. The term " heteroaryl " To 8 ring atoms, and includes a single or fused ring system, suitably containing from 3 to 7, preferably 5 or 6, ring atoms in each ring And includes a form in which a plurality of heteroaryls are connected by a single bond,
The organic semiconductor compound represented by Formula 1 has stable azacyclinic properties, high thermal stability, and oxidation stability, and thus the organic electroluminescent device employing the organic semiconductor compound can have remarkably improved lifetime characteristics.
Further, due to the structural characteristics of the organic semiconductor compound represented by the formula (1), it can have improved electron affinity and electron mobility, thereby exhibiting very high luminous efficiency and energy efficiency.
According to an embodiment of the present invention, the organic semiconductor compound may be selected from the group consisting of a single bond and a structure represented by the following formula: L < 1 > and L < 2 > independently from each other in order to have high luminous efficiency due to an increase in delamination of aromatic rings But is not limited thereto.
[In the above structure,
Wherein each of R 21 to R 24 is independently selected from the group consisting of hydrogen, (C 1 -C 30) alkyl, halogen, cyano, (C 3 -C 30) cycloalkyl, (C 3 -C 30) heterocycloalkyl, (C 3 -C 30) C6-C30) aryl.
In addition, the organic semiconductor compound according to an embodiment of the present invention has a symmetrical diphenyl azacyl group on both sides with -L 1 -ZL 2 - as a linking group, and thus, a rigid ) Structure, so that the charge separation can be made more effective, and the electron mobility can be remarkably improved.
The organic semiconductor compound according to an embodiment of the present invention can show a tendency to shift to the blue region by expanding the energy gap between HOMO and LUMO by introducing diphenyl azacyl group into the mother nucleus. Therefore, the organic semiconductor compound according to the present invention can replace the conventional phosphorescent host material or overcome the disadvantages of the phosphorescent host, and can also have good properties as the TADF material as the third generation light emitting region.
In order to realize the above-mentioned effects, the organic semiconductor compound according to an embodiment of the present invention may be an organic semiconductor compound represented by the following formula (2), but is not limited thereto.
(2)
[In the formula (2)
L 1 and L 2 are each independently a single bond, (C3-C30) cycloalkylene, (C3-C30) heterocycloalkylene, (C3-C30) heteroarylene or (C6-C30) arylene;
Z is a single bond, -C (R 11 ) (R 12 ) -, -C = C (R 11 ) (R 12 ) -, -N (R 11 ) O (R 11) -, -SO 2 -, oxadiazolyl alkylene or binary or a unsubstituted triazolyl alkylene, wherein R 11 and R 12 are each independently hydrogen, (C1-C30) alkyl, cyano, nitro (C3-C30) cycloalkyl, (C3-C30) heterocycloalkyl, (C3-C30) heteroaryl or (C6-C30) aryl;
R 1 and R 2 are each independently hydrogen, (C 3 -C 30) heteroaryl or (C 6 -C 30) aryl;
Wherein said cycloalkyl, heterocycloalkyl, heteroaryl and aryl of said Ar together with said cycloalkylene, heterocycloalkylene, heteroarylene and arylene of said L 1 to L 2 , triazolylene of said Z and R 1 to R heteroaryl and aryl 2 are each independently (C1-C30) alkyl, halogen, cyano, nitro, hydroxy, (C1-C30) alkoxy, (C3-C30) cycloalkyl, (C3-C30) heterocycloalkyl alkyl, (C3-C30) heteroaryl, (C6-C30) aryl, and -P = O (R 13) ( R 14) may be further substituted with one or more selected from the group, wherein R 13 and R 14 consisting of (C3-C30) heterocycloalkyl, (C3-C30) heteroaryl or (C6-C30) heteroaryl, each of which is optionally substituted by one or more substituents independently selected from the group consisting of (C1-C30) alkyl, cyano, nitro, Wherein said heterocycloalkyl, heteroaryl, heterocycloalkylene and heteroarylene are optionally substituted with one or more heteroatoms selected from B, N, O, S, P (= O) And a.]
The organic semiconductor compound according to an exemplary embodiment of the present invention may have a high melting point and a glass transition temperature to have improved thermal stability and oxidation stability and may be an organic semiconductor compound represented by the following
(3)
[Formula 3]
L 1 and L 2 are each independently a single bond, (C3-C30) cycloalkylene, (C3-C30) heterocycloalkylene, (C3-C30) heteroarylene or (C6-C30) arylene;
R 41 and R 42 are each independently hydrogen, (C 3 -C 30) heteroaryl or (C 6 -C 30) aryl;
Wherein said heteroaryl and aryl of each of said L 1 to L 2 cycloalkylene, heterocycloalkylene, heteroarylene and arylene, and said R 41 and R 42 are each independently selected from the group consisting of (C 1 -C 30) alkyl, halogen, cyano (C3-C30) heterocycloalkyl, (C3-C30) heteroaryl, (C6-C30) aryl and -P = O (R 13 ) (R 14 ), and R 13 and R 14 are each independently selected from the group consisting of (C 1 -C 30) alkyl, cyano, nitro, hydroxy (C3-C30) heteroaryl or (C6-C30) aryl, said heterocycloalkyl, heteroaryl, heterocycloalkylene and heteroarylene being optionally substituted with one or more substituents selected from the group consisting of B , N, O, S, P (= O), Si and P.
In view of having excellent light conversion efficiency and thermal stability, it may be an organic semiconductor compound represented by the following
[Chemical Formula 4]
[Formula 4]
R 1 and R 2 are each independently selected from the group consisting of phenyl, naphthyl, biphenyl, terphenyl, anthryl, indenyl, fluorenyl, phenanthryl, triphenylenyl, pyrenyl, perylen, Cyclohexyl, cycloheptyl, cyclohexyl, cycloheptyl, cyclohexyl, cycloheptyl, cyclohexyl, cyclohexyl, cycloheptyl, cyclohexyl, cycloheptyl, cyclohexyl, cycloheptyl, (C1-C30) heteroaryl wherein each of said aryl and heteroaryl is independently selected from the group consisting of (C1-C30) alkyl, (C1-C30) alkyl, (C3-C30) cycloalkyl, (C3-C30) from heterocycloalkyl, (C3-C30) heteroaryl, (C6-C30) aryl, and the group consisting of -P = O (R 13) ( R 14) can be further substituted with one or more is selected, and the R 13 and R 14 are each independently alkyl (C1-C30), Cyano, nitro, hydroxy, (C3-C30) cycloalkyl, (C3-C30) heterocycloalkyl, (C3-C30) heteroaryl or (C6-C30) aryl;
The organic semiconductor compound according to an embodiment of the present invention may have a high melting point and a glass transition temperature and thus may have improved thermal stability and oxidation stability. Preferably, -L 1 -ZL 2 - Structure, but is not limited thereto.
[In the above structure,
R 31 to R 34 are each independently selected from the group consisting of hydrogen, (C 1 -C 30) alkyl, halogen, cyano, nitro, hydroxy, (C 1 -C 30) alkoxy, (C 3 -C 30) cycloalkyl, (C3-C30) heteroaryl, (C6-C30) aryl, and -P = O (R 13) ( R 14) wherein R 13 is selected from the group consisting of and R 14 is a (C1- each independently C30) alkyl, cyano, nitro, hydroxy, (C3-C30) cycloalkyl, (C3-C30)
At this time, the solubility of the -L 1 -ZL 2 - in the organic solvent can be controlled appropriately by controlling the substituent of -L 1 -ZL 2 -. By controlling the fine emission wavelength and the performance according to the kind of the substituent, Properties can be implemented.
The organic semiconductor compound according to an embodiment of the present invention may be selected from the following structures, but is not limited thereto.
The organic semiconducting compound according to an embodiment of the present invention may have silicon (Si) introduction of azacillin and two kinds of aryl groups in the silicon, and in particular, it has a phenyl group, Can be suppressed to the utmost, so that a short wavelength of blue can be realized, high color purity can be obtained, and furthermore, an intramolecular electron donor can be introduced to have bipolar characteristics. That is,
It can be used as a fluorescent host or dopant using TADF phenomenon or as a phosphorescent host.
Further, it has an advantage that a new energy level having a small energy gap can be generated to increase the charge mobility in the molecule.
The above-described organic semiconductor compound can be produced by a Suzuki coupling reaction, a styrene coupling reaction or the like, and is not limited to the following production method. In addition to the above-mentioned production method, Of course.
The present invention relates to a process for preparing an organic semiconductor compound represented by the following general formula (1) by reacting a compound represented by the following general formula (5) with a compound represented by the following general formula (6) And an organic semiconductor compound.
[Chemical Formula 5]
[Chemical Formula 6]
[Chemical Formula 1]
[In the formulas (1), (5) and (6)
Ar is hydrogen, (C3-C30) cycloalkyl, (C3-C30) heterocycloalkyl, (C3-C30) heteroaryl or (C6-C30) aryl;
Ar 'is (C3-C30) cycloalkylene, (C3-C30) heterocycloalkylene, (C3-C30) heteroarylene or (C6-C30) arylene;
L 1 and L 2 are each independently a single bond, (C3-C30) cycloalkylene, (C3-C30) heterocycloalkylene, (C3-C30) heteroarylene or (C6-C30) arylene;
Z is a single bond, -C (R 11 ) (R 12 ) -, -C = C (R 11 ) (R 12 ) -, -N (R 11 ) O (R 11) -, -SO 2 -, oxadiazolyl alkylene or binary or a unsubstituted triazolyl alkylene, wherein R 11 and R 12 are each independently hydrogen, (C1-C30) alkyl, cyano, nitro (C3-C30) cycloalkyl, (C3-C30) heterocycloalkyl, (C3-C30) heteroaryl or (C6-C30) aryl;
R 1 and R 2 are each independently hydrogen, (C 3 -C 30) heteroaryl or (C 6 -C 30) aryl;
X 1 and X 2 are each independently halogen;
Wherein said cycloalkyl, heterocycloalkyl, heteroaryl and aryl of said Ar together with said cycloalkylene, heterocycloalkylene, heteroarylene and arylene of said L 1 to L 2 , triazolylene of said Z and R 1 to R heteroaryl and aryl 2 are each independently (C1-C30) alkyl, halogen, cyano, nitro, hydroxy, (C1-C30) alkoxy, (C3-C30) cycloalkyl, (C3-C30) heterocycloalkyl alkyl, (C3-C30) heteroaryl, (C6-C30) aryl, and -P = O (R 13) ( R 14) may be further substituted with one or more selected from the group, wherein R 13 and R 14 consisting of (C3-C30) heterocycloalkyl, (C3-C30) heteroaryl or (C6-C30) heteroaryl, each of which is optionally substituted by one or more substituents independently selected from the group consisting of (C1-C30) alkyl, cyano, nitro, Wherein said heterocycloalkyl, heteroaryl, heterocycloalkylene and heteroarylene are optionally substituted with one or more heteroatoms selected from B, N, O, S, P (= O) And a.]
At this time, it is preferable that the above step is carried out in an organic solvent, but it goes without saying that the reaction can also be carried out in a melted state without using a solvent. The organic solvent is not limited as long as it can completely dissolve the reactant, but specific examples thereof include toluene, methanol, ethanol, benzene, n-heptane, tetrahydrofuran (THF), chloroform, .
The present invention also provides an organic electroluminescent device comprising the above-described compounds. Here, the organic electroluminescent device includes a first electrode; A second electrode; And one or more organic layers interposed between the first electrode and the second electrode, and the organic layer may include a compound according to the present invention.
The compound represented by the above-mentioned formula (1) can be applied to various organic electroluminescent devices, and such organic electroluminescent devices can be used in flat panel display devices, flexible display devices, monochromatic or white flat panel illumination devices and monochromatic or white flexible illumination devices But it is not limited to this.
In general, the organic electroluminescent device according to the present invention will be described below, but the present invention is not limited thereto.
An organic electroluminescent device OLED manufactured according to a preferred embodiment of the present invention may include an anode, a cathode, and an organic layer disposed therebetween.
The organic layer of the organic electroluminescent device OLED may include at least one of an auxiliary layer (buffer layer), a hole injection layer, a hole transport layer, a light emitting layer, a hole blocking layer, an electron transport layer and an electron injection layer , The compound of
The compound represented by the general formula (1) according to the present invention may be included in at least one of the organic material layers. More specifically, the organic material layer may include a buffer layer, a hole injection layer, a hole transport layer, The electron transport layer, the electron transport layer, the electron injection layer, and the like.
The organic light emitting diode OLED according to an exemplary embodiment of the present invention may be formed by depositing a metal or a conductive material on a substrate using a PVD (physical vapor deposition) method such as sputtering or e-beam evaporation A metal oxide or an alloy thereof may be deposited to form an anode and an organic layer including at least one of a hole injecting layer, a hole transporting layer, a light emitting layer, an electron transporting layer, and an electron injecting layer may be formed thereon, ≪ / RTI > The auxiliary layer (buffer layer) may be formed between the hole transporting layer and the light emitting layer, or between the electron transporting layer and the light emitting layer,
In addition to such a method, the organic layer may be formed by sequentially depositing a negative electrode material, an organic material layer, and a positive electrode material on a substrate, and the organic material layer may be formed by sequentially depositing an auxiliary layer (buffer layer), a hole injecting layer, a hole transporting layer, Layer or the like, but it is not limited thereto and may be a single-layer structure.
In addition, the organic material layer may be formed using a variety of polymer materials by a solvent process such as a spin coating process, a dip coating process, a doctor blading process, a screen printing process, an inkjet printing process or a thermal transfer process, Layer.
In the organic electroluminescent device OLED, the compound according to the present invention may be included in the light emitting layer, and the compound represented by the formula (1) may be a blue light emitting material and may be thermally activated delayed Fluorescence, TADF) can be used as a dopant material.
In the organic electroluminescent device OLED, the substrate may be formed of a material selected from the group consisting of polyethylene terephthalate (PEN), polyethylene naphthalate (PEN), polyperopylene (PP), polyimide (PI), polycarbornate (PC) , Plastics including polyoxyethylene (POM), acrylonitrile styrene copolymer (ABS), acrylonitrile butadiene styrene copolymer and TAC (triacetyl cellulose).
On the substrate, an anode is located. Such an anode injects holes into the hole injection layer located thereon. As the anode material, a material having a large work function is preferably used so as to smoothly inject holes into the organic material layer. Specific examples of the cathode material that can be used in the present invention include metals such as vanadium, chromium, copper, zinc, and gold, or alloys thereof; Metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); ZnO: Al or SnO 2: a combination of a metal and an oxide such as Sb; Conductive polymers such as poly (3-methylthiophene), poly [3,4- (ethylene-1,2-dioxy) thiophene] (PEDT), polypyrrole and polyaniline; And the like, but are not limited thereto.
A hole injection layer is located on the anode. The conditions required for the material of the hole injection layer are that the hole injection efficiency from the anode is high and the injected holes must be efficiently transported. For this purpose, the ionization potential is small, the transparency to visible light is high, and the stability against holes is excellent. As the hole injecting material, it is preferable that the highest occupied molecular orbital (HOMO) of the hole injecting material be between the work function of the anode material and the HOMO of the surrounding organic layer. Specific examples of the hole injecting material include metal porphyrine, oligothiophene, arylamine-based organic materials, hexanitrile hexaazatriphenylene, quinacridone-based organic materials, perylene-based organic materials, Anthraquinone, polyaniline and a polythiophene-based conductive polymer, but are not limited thereto.
A hole transport layer is disposed on the hole injection layer. The hole transport layer transports holes from the hole injection layer to a light emitting layer disposed thereon, and plays a role of high hole mobility, stability to holes, and electrons. In addition to these general requirements, materials that require heat resistance to the device and have a glass transition temperature (Tg) of 70 ° C or higher are desirable when used for vehicle display. Materials satisfying such conditions are NPD (or NPB) ), A spiro-arylamine compound, a perylene-arylamine compound, an azacycloheptatriene compound, bis (diphenylvinylphenyl) anthracene, a silicon germanium oxide compound, or a silicon-based arylamine compound.
A light emitting layer is disposed on the hole transporting layer. The organic light emitting layer is a layer in which holes and electrons injected from the anode and the cathode respectively recombine to emit light, and the organic light emitting layer is made of a material having high quantum efficiency. As the luminescent material, a material capable of emitting light in the visible light region by transporting and combining holes and electrons from the hole transporting layer and the electron transporting layer, is preferably a material having good quantum efficiency for fluorescence or phosphorescence. More preferably, (1). ≪ / RTI > At this time, the above-mentioned light emitting layer can realize more excellent light emitting efficiency and high color purity by including the compound according to the present invention in the light emitting layer.
An electron transporting layer is disposed on the light emitting layer. Such an electron transporting layer requires a material capable of efficiently injecting electrons with a high electron injection efficiency from a cathode disposed thereon. For this purpose, it is required to be made of a material having high electron affinity, high electron transfer rate and excellent stability against electrons. Specific examples of the electron transporting material satisfying such conditions include an Al complex of 8-hydroxyquinoline; Complexes containing Alq 3 ; Organic radical compounds; Hydroxyflavone-metal complexes, and the like, but are not limited thereto.
An electron injection layer may be laminated on the electron transport layer. The electron injection layer may be a metal complex compound such as Balq, Alq3, Be (bq) 2, Zn (BTZ) 2, Zn (phq) 2, PBD, spiro-PBD, TPBI or Tf-6P; aromatic compounds with imidazole rings; boron compounds; And the electron injecting layer may be formed in a thickness range of 100 to 300 angstroms.
Finally, a cathode is positioned on the electron injection layer. Such a cathode plays a role of injecting electrons. The material used for the cathode is not limited as long as it uses a material used in a cathode in the art, and a metal having a low work function is more preferable for efficient electron injection. Specific examples thereof include suitable metals such as tin, magnesium, indium, calcium, sodium, lithium, aluminum, and silver; Or their suitable alloys; Can be used. Also, an electrode having a two-layer structure such as lithium fluoride and aluminum, lithium oxide and aluminum, strontium oxide and aluminum, etc., having a thickness of 100 μm or less may be used.
As described above, the compound represented by
The organic electroluminescent device including the compound according to the present invention may be a top emission type, a back emission type, or a both-sided emission type.
Hereinafter, the present invention will be described in more detail with reference to Examples. However, the following examples are intended to illustrate the present invention, and the scope of the present invention is not limited thereto.
(Example 1)
Synthesis of 5- (4,6-diphenyl-1,3,5-triazin-2-yl) phenyl) -10,10-diphenyl-5,10-dihydrodibenzo [b, e] [1,4] azasiline Produce
[Step 1] Preparation of bis (2-bromophenylamine)
Well after the 2-bromoaniline in dried 500 mL three-necked flask round-bottom flask, (15 g, 0.087 mol) and 1-bromo-2-iodobenzene ( 29.6 g, 0.105 mol) was dissolved in Toluene 200 mL Sodium tert -butoxide (16.76 g, 0.174 mol), Pd (dppf) Cl 2 (12.76 g, 0.017 mol) and Pd 2 dba 3 (7.98 gg, 0.009 mol) were added and the mixture was refluxed for 12 hours. After completion of the reaction, the solvent was removed and extracted three times with methylene chloride. The organic layer was dried over MgSO 4 , and the solvent was removed using a rotary evaporator. The solvent was removed by column chromatography using n-hexane as a solvent to obtain 18.3 g (yield: 64%) of a colorless oil. .
1 H-NMR (300 MHz, CDCl 3) [ppm] δ = 7.64-7.61 (d, 2H), 7.35-7.32 (d, 2H), 7.28-7.22 (t, 2H), 6.91-6.85 (t, 2H ), 6.50 (s, 1 H).
[Step 2] Preparation of N, N-bis (2-bromophenyl) -N- (4-methoxybenzyl) amine
Bis (2-bromophenylamine) (39 g, 119.2 mmol), NaH (3.43 g, 143.1 mol) and DMF (250 ml) were placed in a well-dried 500 mL three-neck round bottom flask under nitrogen atmosphere and the mixture was stirred at room temperature Lt; / RTI > Then, 1- (chloromethyl) -4-methoxybenzene (20.54 g, 131.2 mol) was added dropwise and the mixture was stirred at room temperature for 14 hours. After completion of the reaction, 500 ml of distilled water was added dropwise to the reaction product, and the precipitated solid was separated by filtration. The filtered solid was redissolved in methylene chloride and extracted three times. The organic layer was dried over MgSO 4 , and the solvent was removed using a rotary evaporator. The solvent was separated by column chromatography using a solvent of mc / hexane = 3: 1 to obtain 46.8 g (yield: 87%) of a compound .
1 H-NMR (300 MHz, DMSO) [ppm] δ = 7.64-7.61 (d, 2H), 7.5 (d, 2H), 7.3 (t, 2H), 7.0 (m, 4H), 6.80 (d, 2H ), 4.7 (s, 2H), 3.7 (s, 3H).
[Step 3] Preparation of 5- (4-methoxybenzyl) -10,10-diphenyl-5,10-dihydrodibenzo [b, e] [1,4] azasiline
2-bromo-N- (2-bromophenyl) -N- (4-methoxybenzyl) aniline (9.00 g, 20.1 mmol) and 60 ml of ether were added to a well-dried 150 mL three- The reaction temperature was cooled to 0 ° C and 2.5 M n-BuLi / Hex (17.7 mL, 44.2 mmol) was added dropwise. Dichlorodiphenylsilane (5.6 g, 22.1 mmol) dissolved in 20 mL of ether was added dropwise while maintaining the reaction temperature for 30 minutes, followed by stirring at room temperature for 4 hours. After completion of the reaction, the solvent was removed, and extracted three times with ethyl acetate. The organic layer was dried over MgSO 4 , and the solvent was removed using a rotary evaporator. The solvent was removed by column chromatography using a methylene dichloride / hexane (3/1) solvent to obtain 7.8 g (yield = 75% ≪ / RTI >
1 H-NMR (300 MHz, D 2 O / DMSO) [ppm] δ = 7.47-7.36 (m, 12H), 7.34-7.31 (t, 2H), 7.04-7.00 (m, 6H), 6.83-6.80 ( d, 2H), 5.19 (s, 2H), 3.71 (s, 3H).
[Step 4] Preparation of 10,10-diphenyl-5,10-dihydrodibenzo [b, e] [1,4] azasiline
(4-methoxybenzyl) -10,10-diphenyl-5,10-dihydrodibenzo [b, e] [1,4] azasiline (37 g, 78.8 mmol) and DDQ 19.67 g, 86.6 mmol), 370 mL of toluene and 37 mL of H 2 O were placed in a round flask, and the mixture was stirred at 80 ° C for 14 hours. After completion of the reaction, the solvent was removed, and extracted three times with ethyl acetate. The organic layer was dried over MgSO 4 , and the solvent was removed using a rotary evaporator. The solvent was separated by column chromatography using hexane / ethyl acetate (7/1) to obtain 7.5 g (yield = 27% .
1 H-NMR (300 MHz, D 2 O / DMSO) [ppm] δ = 9.43 (s, 1H), 7.48-7.32 (m, 14H), 7.10-7.07 (m, 2H), 6.90-6.85 (m, 2H).
[Step 5] Synthesis of 5- (4- (4,6-diphenyl-1,3,5-triazin-2-yl) phenyl) -10,10-diphenyl-5,10-dihydrodibenzo [b, 4] Preparation of azasiline
To a well-dried 30 mL three-neck round bottom flask was added 2- (4-bromophenyl) -4,6-diphenyl-1,3,5-triazine (0.5 g, 1.29 mmol), 10,10- diphenyl-5,10-dihydrodibenzo (0.14 g, 1.93 mmol), tris (tertbutyl) phosphine (0.03 g, 0.13 mmol) and Pd 2 (dba) 3 (0.06 g, 8.1 mmol) was dissolved in 5 ml of toluene, followed by stirring at 110 ° C for 12 hours. After completion of the reaction, water was poured and extracted three times with chloroform. The organic layer was dried over MgSO 4 and the solvent was removed using a rotary evaporator. The solvent was separated by column chromatography using MC / n-Hexane (2/1) to obtain 0.54 g (yield = 63% ).
1 H-NMR (300 MHz, CDCl 3) [ppm] δ = 9.05-9.02 (d, 2H), 8.85-8.82 (d, 4H), 7.69-7.59 (m, 12H), 7.54-7.52 (d, 2H ), 7.45-7.38 (m, 6H), 7.24-7.18 (t, 2H), 7.01-6.97 (t, 2H), 6.58-6.55 (d, 2H).
13 C-NMR (500 MHz, CDCl 3 , 隆): 171.88, 171.10, 149.70, 147.71, 136.11, 136.02, 135.82, 135.23, 132.69, 131.68, 131.29, 130.41, 129.63, 129.03, 128.73, 127.94, 120.31, 117.52, 116.26
Mass: C 45 H 32 N 4 Si calcd. 656.24; found. 656.24
(Example 2)
Synthesis of 5- (4- (4,6-diphenyl-1,3,5-triazin-2-yl) biphenyl) -10,10-diphenyl-5,10- dihydrodibenzo [b, Manufacture of azasiline
[Step 1] Synthesis of 5- (4,6-diphenyl-1,3,5-triazin-2-yl) -biphenyl-10,10-diphenyl-5,10- dihydrodibenzo [b, 1,4] azasiline
To a well-dried 30 mL three-neck round bottom flask was added 2- (4'-bromo- [1,1'-biphenyl] -4-yl) -4,6-diphenyl-1,3,5-triazine (0.16 g, 1.61 mmol), tris (tertbutyl) amide, and 10,10-diphenyl-5,10-dihydrodibenzo [b, e] [1,4] azacilline (0.34 g, 0.97 mmol) phosphine (0.02 g, 0.11 mmol) and Pd 2 (dba) 3 (0.05 g, 0.05 mmol) were dissolved in 5 ml of toluene and the mixture was stirred at 110 ° C for 12 hours. After completion of the reaction, 100 ml of water was poured and extracted three times with 100 ml of chloroform. The organic layer was dried over MgSO 4 , and the solvent was removed using a rotary evaporator. The solvent was separated by column chromatography using a solvent of MC / n-Hexane (2/1) to obtain 0.34 g (yield = 43% ).
1 H-NMR (300 MHz, CDCl 3) [ppm] δ = 8.95-8.92 (d, 2H), 8.86-8.82 (d, 4H), 8.00-7.93 (m, 4H), 7.69-7.62 (m, 12H ), 7.46-7.40 (m, 8H), 7.24-7.20 (t, 2H), 7.00-6.95 (t, 2H), 6.58-6.55 (d, 2H).
13 C-NMR (500 MHz, CDCl 3 , 隆): 171.75, 159.10, 149.96, 136.28, 136.10, 135.42, 132.57, 131.89, 130.37,129.74,129.64,129.57,129.02,128.69,127.92,127.39,120.03,117.27
Mass: C 51 H 36 N 4 Si calcd. 732.27; found. 732.27
(Example 3)
Preparation of 10,10-diphenyl-5- (4- (4-phenylquinazolin-2-yl) phenyl) -5,10-dihydrodibenzo [b, e] [1,4] azasiline
[Step 1] Preparation of (4-bromophenyl) boronic acid
30 g (127 mmol) of 1,4-dibromobenzene and anhydrous tetrahydrofuran (THF) were placed in a 500 mL two-neck round flask and stirred. When the reaction mixture was suspended, liquid nitrogen was used to cool the flask to -78 ° C and 45.8 mL of 2.5 M n-BuLi (115 mmol) was added slowly. The temperature was gradually raised to room temperature and then stirred for 1 hour. Again using liquid nitrogen, the temperature of the flask was cooled to -78 ° C and 48 g (58.7 mL, 254 mmol) of triisopropylborate was rapidly added. After 6 hours of reaction at room temperature, the reaction was terminated with ice and 2 N HCl aqueous solution. methylene chloride (MC), the solvent was removed, and the solution was added to hexane. The product was boiled, filtered and dried to obtain 13 g of the compound (yield = 51%).
[Step 2] Preparation of 2- (4-bromophenyl) -4-phenylquinazoline
Of 17 g (85 mmol) in 3-neck round bottom flask of 500 mL (4-bromophenyl) boronic acid and put into the 2-chloro-4-phenylquinazoline of 18.34 g (76 mmol) thereto,
8 g of 2- (4-bromophenyl) -4-phenylquinazoline (yield = 26%) was obtained.
1 H-NMR (300 MHz, CDCl 3) [ppm] δ = 8.62-8.60 (d, 2H), 8.21-8.18 (d, 2H), 8.17-8.14 (d, 2H), 7.95-7.88 (m, 3H ), 7.68-7.56 (m, 6H).
[Step 3] Preparation of 10,10-diphenyl-5- (4- (4-phenylquinazolin-2-yl) phenyl) -5,10-dihydrodibenzo [b, e] [1,4] azasiline
B], [e] [1,4] thiophene-2-carboxylic acid (4-bromophenyl) -4-phenylquinazoline t-butoxide (0.6 g, 6. 23 mmol), tris (tertbutyl) phosphine (0.08 g, 0.45 mmol) and Pd 2 (dba ) 3 (0.2 g, 0.2 mmol) were dissolved in toluene (20 ml), and the mixture was stirred at 110 占 폚 for 12 hours. After completion of the reaction, water was poured and extracted three times with chloroform. The organic layer was dried over MgSO 4 , and the solvent was removed using a rotary evaporator. The solvent was separated by column chromatography using a solvent of MC / n-Hexane (3/1) to obtain 1 g of the compound (yield = 38% ).
1 H-NMR (300 MHz, CDCl 3) [ppm] δ = 8.95-8.92 (d, 2H), 8.24-8.19 (t, 2H), 7.96-7.93 (t, 3H), 7.69-7.61 (m, 10H ), 7.50-7.38 (m, 8H), 7.21-7.15 (t, 2H), 6.98-6.93 (t, 2H), 6.58-6.55 (d, 2H).
(Example 4)
Preparation of 10,10-diphenyl-5- (4- (4-phenylquinazolin-2-yl) phenyl) -5,10-dihydrodibenzo [b, e] [1,4] azasiline
[Step 1] Production of 10,10-diphenyl-5- (4- (4-phenylquinazolin-2-yl) phenyl) -5,10-dihydrodibenzo [b, e] [1,4] azasiline
A solution of 2-chloro-4-phenylquinazoline (0.4 g, 1.66 mmol), 10,10-diphenyl-5,10-dihydrodibenzo [b, e] [1,4] azacilline (0.32 g, 3.32 mmol), tris (tertbutyl) phosphine (0.03 g, 0.17 mmol) and Pd 2 (dba) 3 (0.08 g) were dissolved in 20 ml of toluene, Lt; / RTI > for 12 hours. After completion of the reaction, water was poured and extracted three times with chloroform. The organic layer was dried over MgSO 4 , and the solvent was removed using a rotary evaporator. The solvent was separated by column chromatography using a MC / n-Hexane (3/1) solvent to obtain 0.3 g (yield = 33% ).
1 H-NMR (300 MHz, CDCl 3) [ppm] δ = 7.89-7.84 (m, 3H), 7.62-7.46 (m, 15H), 7.24-7.13 (m, 9H).
(Example 5)
Preparation of 5,5'- (sulfonylbis (4,1-phenylene)) bis (10,10-diphenyl-5,10-dihydrodibenzo [b, e] [1,4] azasiline
[Step 1] Preparation of bis (4-bromophenyl) sulfane
To a well-dried 250 mL three-neck round bottom flask was added 1-bromo-4-iodobenzene (11.3 g, 40 mmol), sodium sulfide nonahydrate (5.76 g, 24 mmol), CuI (0.76 g, 40 mmol) and DMF (80 ml) were added and stirred. And the mixture was stirred at a reaction temperature of 120 占 폚 for 18 hours. After completion of the reaction, H 2 O was added to the resulting solid, and the resulting solid was filtered three times using MC. The organic layer was dried over MgSO 4 and the solvent was removed using a rotary evaporator. The solvent was separated by column chromatography using 100% hexane to obtain 3.7 g (yield = 45%) of the compound.
1 H-NMR (300 MHz, CDCl 3) [ppm] δ = 7.47-7.42 (d, 4H), 7.22-7.18 (d, 4H).
[Step 2]
Bis (4-bromophenyl) sulfane (9 g, 26.2 mmol), 50 mL of 30% hydrogen peroxide and 100 mL of acetic acid were added to a well-dried 250 mL three-necked round bottom flask and stirred at 100 ° C for 10 hours. The reaction was terminated three times using methylene chloride (MC). The extracted organic layer was washed with MgSO 4 to remove water, the solvent was removed using a rotary evaporator, and the product was separated by column chromatography using MC to obtain 5 g (yield = 51%) of a compound.
1 H-NMR (300 MHz, CDCl 3) [ppm] δ = 7.81-7.79 (d, 4H), 7.68-7.65 (d, 4H).
[Step 3] Preparation of 5,5'- (sulfonylbis (4,1-phenylene)) bis (10,10-diphenyl-5,10-dihydrodibenzo [b, e] [1,4] azasiline
A well-dried 100 mL three-neck round bottom flask was charged with 4,4'-sulfonylbis (bromobenzene) (0.7 g, 1.86 mmol), 10,10-diphenyl-5,10-dihydrodibenzo [b, (0.36 g, 3.72 mmol), tris (tertbutyl) phosphine (0.04 g, 0.19 mmol) and Pd 2 (dba) 3 (0.09 g) were dissolved in 20 ml of toluene Followed by stirring at 110 DEG C for 24 hours. After completion of the reaction, water was poured and extracted three times with chloroform. The organic layer was dried over MgSO 4 and the solvent was removed using a rotary evaporator. The solvent was removed by column chromatography using EA / n-Hexane (1/3) to obtain 1.7 g (yield = 46% ).
1 H-NMR (300 MHz, CDCl 3 ) [ppm] δ = 7.93-7.90 (d, 4H), 7.60-7.58 (d, 4H), 7.55-7.52 (d, 8H), 7.37-7.29 ), 7.22-7.19 (d, 4H), 7.13-7.08 (t, 4H), 6.81-6.78 (d, 4H).
(Example 6)
Preparation of bis (4- (10,10-diphenyldibenzo [b, e] [1,4] azasilin-5 (10H) -yl) phenyl) methanone
Preparation of bis (4- (10,10-diphenyldibenzo [b, e] [1,4] azasilin-5 (10H) -yl) phenyl) methanone
Bis (4-bromophenyl) methanone (0.7 g, 2.1 mmol), 10,10-diphenyl-5,10-dihydrodibenzo [b, e] [1,4] azacilline (1.58 g, 2.1 mmol) was added to a well dried 100 mL three- (0.04 g, 0.21 mmol) and Pd 2 (dba) 3 (0.09 g, 0.1 mmol) were dissolved in 20 ml of toluene, Followed by stirring at 110 ° C for 24 hours. After completion of the reaction, water was poured and extracted three times with chloroform. The organic layer was dried over MgSO 4 , and the solvent was removed using a rotary evaporator. The solvent was separated by column chromatography using EA / n-hexane (1/3) to obtain 1.5 g (yield = 38% ).
1 H-NMR (300 MHz, CDCl 3 ) [ppm]? = 8.07-8.04 (d, 4H), 7.63-7.60 (d, 12H), 7.43-7.36 (m, 16H), 7.29-7.24 ), 7.06-7.01 (t, 4H), 6.65-6.62 (d, 4H).
(Example 7)
Synthesis of 5- (3- (4,6-diphenyl-1,3,5-triazin-2-yl) phenyl) -10,10-diphenyl-5,10- dihydrodibenzo [b, e] [1,4] azasiline Produce
[Step 1] Synthesis of 5- (3- (4,6-diphenyl-1,3,5-triazin-2-yl) phenyl) -10,10-diphenyl-5,10- dihydrodibenzo [b, 4] Preparation of azasiline
A well-dried 100 mL three-necked round bottom flask was charged with 2- (3-bromophenyl) -4,6-diphenyl-1,3,5-triazine (1 g, 2.58 mmol), 10,10- diphenyl-5,10-dihydrodibenzo (0.5 g, 5.15 mmol), tris (tertbutyl) phosphine (0.05 g, 0.26 mmol) and Pd 2 (dba) 3 (0.12 g, 0.13 mmol) was dissolved in 15 ml of toluene, followed by stirring at 110 ° C for 12 hours. After completion of the reaction, water was poured and extracted three times with chloroform. The organic layer was dried over MgSO 4 , and the solvent was removed using a rotary evaporator. The solvent was separated by column chromatography using MC / n-Hexane (1/3) to obtain 1.24 g (yield = 73% ).
1 H-NMR (300 MHz, CDCl 3) [ppm] δ = 9.01-8.97 (d, 1H), 8.79-8.74 (t, 5H), 7.90-7.85 (t, 1H), 7.73-7.55 (m, 13H ), 7.48-7.41 (m, 6H), 7.24-7.18 (t, 2H), 7.01-6.97 (t, 2H), 6.57-6.54 (d, 2H).
(Example 8)
Preparation of 10,10-diphenyl-5- (3- (4-phenylquinazolin-2-yl) phenyl) -5,10-dihydrodibenzo [b, e] [1,4] azasiline
[Step 1] Preparation of 10,10-diphenyl-5- (3- (4-phenylquinazolin-2-yl) phenyl) -5,10-dihydrodibenzo [b, e] [1,4] azasiline
4-phenylquinazoline (1.5 g, 4.15 mmol), 10,10-diphenyl-5,10-dihydrodibenzo [b, e] [1,4] thiophene was added to a well-dried 100 mL three- Pd 2 (dba) 3 (0.2 g, 0.21 mmol) and tris (tertbutyl) phosphine (0.08 g, 0.42 mmol) and Na-t-butoxide (1.48 g, 4.15 mmol) And the mixture was stirred at 110 ° C for 12 hours. After completion of the reaction, water was poured and extracted three times with chloroform. The organic layer was dried over MgSO 4 , and the solvent was removed using a rotary evaporator. The solvent was separated by column chromatography using MC / n-Hexane (1/3) to obtain 2 g (yield = 75% ).
1 H-NMR (300 MHz, CDCl 3 ) [ppm] δ = 8.92-8.89 (d, IH), 8.68-8.67 (s, IH), 8.17-8.12 (d, 2H), 7.94-7.79 ), 7.70-7.58 (m, 10H), 7.45-7.38 (m, 7H), 7.20-6.14 (t, 2H), 6.97-6.92 (t, 2H), 6.59-6.56 (d, 2H).
(Example 9)
Preparation of bis (3- (10,10-diphenyldibenzo [b, e] [1,4] azasilin-5 (10H) -yl) phenyl) methanone
[Step 1] Preparation of bis (3- (10,10-diphenyldibenzo [b, e] [1,4] azasilin-5 (10H)
Bis (3-bromophenyl) methanone (1 g, 2.94 mmol), 10,10-diphenyl-5,10-dihydrodibenzo [b, e] [1,4] azacilline Pd 2 (dba) 3 (0.13 g, 0.15 mmol) and tris (tertbutyl) phosphine (0.06 g, 0.29 mmol) were dissolved in 15 ml of toluene Followed by stirring at 110 ° C for 24 hours. After completion of the reaction, water was poured and extracted three times with chloroform. The organic layer was dried over MgSO 4 , and the solvent was removed using a rotary evaporator. The solvent was separated by column chromatography using an EA / n-Hexane (3: 1) solvent to obtain 2 g (yield = 35% ).
1 H-NMR (300 MHz, CDCl 3 ) [ppm] δ = 8.02-8.00 (d, 2H), 7.79-7.74 (t, 4H), 7.65-7.51 (m, 14H), 7.43-7.36 ), 7.08-7.02 (t, 4H), 6.88-6.83 (t, 4H), 6.36-6.33 (d, 4H).
(Example 10) Production of organic electroluminescent device using the compound obtained from Example 1
Transparent electrode ITO thin film cells obtained from glass for OLED were ultrasonically cleaned using trichlorethylene, acetone, ethanol and distilled water sequentially, and stored in isopropanol before use.
The composition of the device is as follows: Glass / indium tin oxide (ITO) / 4% ReO 3 : mCP 45 nm / mCP 15 nm /
ITO
(Example 11-18) Fabrication of organic electroluminescent device
An organic electroluminescent device was prepared in the same manner as in Example 10 except that the compounds obtained in Examples 2 to 9 were used instead of the compounds obtained in Example 1 used in the light emitting layer.
Example 1 In order to evaluate the thermal stability of the organic semiconductor compound of the produced respectively from 1-9, the thermal analysis using TGA (Thermo Gravimetric Analysis) and DSC (Differential Scanning Calorimetry) (
In order to evaluate the UV absorption spectrum and the PL (photoluminescence) spectrum of each of the organic semiconductor compounds prepared in Examples 1 to 9, each of the organic semiconductor compounds of Examples 1 to 9 was dissolved in toluene at a concentration of 0.2 mM And UV absorption spectra were measured using a Shimadzu UV-350 Spectrometer. Each of the organic semiconductor compounds of Examples 1 to 9 was diluted with toluene to a concentration of 10 mM, and Xenon ) Spectra were measured using an ISC PC1 Spectrofluorometer equipped with a lamp. The results are shown in Table 1 and Figs. In addition, according to the graph of Example 7 of FIG. 3, the organic semiconductor compound according to the present invention has a solvatochromic effect according to the polarity of the solvent. Thus, it is expected that the organic semiconductor compound according to the present invention can be used as a light emitting material using TADF phenomenon.
As shown in the results of Table 1, the energy level of the organic semiconductor compound synthesized in Examples 1 to 9 was found to have an energy band gap in the range of 2.91 eV to 3.23 eV, As a result, it was found that the temperature at which 5% decomposition of the organic semiconductor compound according to the present invention occurs is 400 ° C or more, and that the compound is thermally stable because decomposition does not occur even at such a high temperature.
Further, Examples 1 to 7 according to the present invention have high oxidation stability because HOMO values are as low as 5.50, 6.08, 5.57, 5.17, 5.46, 5.49 eV, and 5.16 eV, It can be expected.
FIG. 4 is a graph showing the results of the measurement of the cyclic voltammetry (CV) (electrolyte: 0.1 M Bu 4 NClO 4 / solvent: CH 2 Cl 2 / electrode: three electrode system (working electrode: GC, Reference electrode: Ag / AgCl, auxiliary electrode: Pt)).
5 shows the EL spectrum (10 mA / cm 2) of an organic electroluminescent device employing an organic semiconductor compound according to the present invention (Examples 10 and 18) using a Spectroradiometer CS1000A (Konicha Minolta sensing Inc.). 6 is a graph showing the EQE according to the current density of the organic electroluminescent device employing the organic semiconductor compound according to the present invention (Examples 10 and 18), and Fig. 7 is a graph showing the EQE according to the present invention Voltage-luminance graph of an organic electroluminescent device employing a current density-voltage-luminance graph.
As described above, the organic semiconducting compound according to the present invention imparts a bipolar property by introducing an acceptor unit to a substituent group having a diphenyl azacyl group as a basic skeleton, and the energy electron density distribution in HOMO and LUMO is completely separated, It is possible to realize a delayed fluorescence characteristic using TADF through RISC. Due to such characteristics, the organic EL device employing the organic electroluminescent device can remarkably improve the efficiency, thereby realizing excellent quantum efficiency of more than 20% It is possible to obtain higher surface efficiency and a high purity deep blue light emission characteristic in the resonance structure.
In addition, the organic semiconductor compound according to the present invention is expected to be effectively utilized as a fluorescent dopant or a phosphorescent host using a TADF phenomenon that requires a structural bipolarity. Using this property, the organic semiconductor compound can be employed as a TADF host or a dopant material, It is expected that the present invention can be effectively applied to the employed light emitting system of a phosphorescent device.
Claims (10)
[Chemical Formula 1]
[In the above formula (1)
Ar is phenyl, triazinyl, dibenzo [b, e] [1,4] azasilinyl or quinazolinyl, said phenyl, triazolyl, dibenzo [b, e] [1,4] Quinazolinyl may each be independently substituted with pyridinyl, phenyl or cyano;
L 1 and L 2 is a single bond, each independently, (C3-C30) heteroarylene, or (C6-C30) arylene, and the hetero arylene and arylene are each independently (C1-C30) alkyl, (C3 -C30) heteroaryl or (C6-C30) aryl;
Z is a single bond, -C = C (R 11) (R 12) -, -C (= O) -, -P = O (R 11) -, -SO 2 -, oxadiazolyl alkylene or substituted or unsubstituted Substituted triazolyl,
R 11 and R 12 are each independently cyano, nitro, hydroxy, (C3-C30) heteroaryl or (C6-C30) aryl;
R 1 and R 2 are hydrogen;
Wherein said heteroaryl and said heteroarylene comprise at least one heteroatom selected from B, N, O, S, P (= O), Si and P.
Wherein L 1 and L 2 are each independently a single bond and an organic semiconductor compound selected from the following structures:
[In the above structure,
Wherein R 21 to R 24 are each independently hydrogen, (C 1 -C 30) alkyl, (C 3 -C 30) heteroaryl or (C 6 -C 30) aryl.
An organic semiconductor compound represented by the following formula (2):
(2)
[In the formula (2)
L 1 and L 2 is a single bond, each independently, (C3-C30) heteroarylene, or (C6-C30) arylene, and the hetero arylene and arylene are each independently (C1-C30) alkyl, (C3 -C30) heteroaryl or (C6-C30) aryl;
Z is a single bond, -C = C (R 11) (R 12) -, -C (= O) -, -P = O (R 11) -, -SO 2 -, oxadiazolyl alkylene or substituted or unsubstituted Each of R 11 and R 12 is independently cyano, nitro, hydroxy, (C3-C30) heteroaryl or (C6-C30) aryl;
R 1 and R 2 are hydrogen;
Wherein said heteroaryl and said heteroarylene comprise at least one heteroatom selected from B, N, O, S, P (= O), Si and P.
An organic semiconductor compound represented by the following formula (3);
(3)
[Formula 3]
L 1 and L 2 is a single bond, each independently, (C3-C30) heteroarylene, or (C6-C30) arylene, and the hetero arylene and arylene are each independently (C1-C30) alkyl, (C3 -C30) heteroaryl or (C6-C30) aryl;
R 41 and R 42 are each independently hydrogen or phenyl;
Wherein said heteroaryl and said heteroarylene comprise at least one heteroatom selected from B, N, O, S, P (= O), Si and P.
-L 1 -ZL 2 - is selected from the following structures;
[In the above structure,
R 31 to R 34 are each independently hydrogen, (C 1 -C 30) alkyl, (C 3 -C 30) heteroaryl, or (C 6 -C 30) aryl.
An organic semiconductor compound selected from the following structures;
[Chemical Formula 5]
[Chemical Formula 6]
[Chemical Formula 1]
[In the formulas (1), (5) and (6)
Ar is phenyl, triazinyl, dibenzo [b, e] [1,4] azasilinyl or quinazolinyl, said phenyl, triazolyl, dibenzo [b, e] [1,4] Quinazolinyl may each be independently substituted with pyridinyl, phenyl or cyano;
Ar 'is phenylene, triazienylene, dibenzo [b, e] [1,4] azaSilinylene or quinazolinylene, and the phenylene, triazolylene, dibenzo [b, ] Azasilinylene or quinazolinylene may each be independently substituted with pyridinyl, phenyl or cyano;
L 1 and L 2 is a single bond, each independently, (C3-C30) heteroarylene, or (C6-C30) arylene, and wherein the heteroarylene and arylene are each independently (C1-C30) alkyl, (C3 -C30) heteroaryl or (C6-C30) aryl;
Z is a single bond, -C = C (R 11) (R 12) -, -C (= O) -, -P = O (R 11) -, -SO 2 -, oxadiazolyl alkylene or substituted or unsubstituted Each of R 11 and R 12 is independently cyano, nitro, hydroxy, (C3-C30) heteroaryl or (C6-C30) aryl;
R 1 and R 2 are hydrogen;
X 1 and X 2 are each independently halogen;
Wherein said heteroaryl and said heteroarylene comprise at least one heteroatom selected from B, N, O, S, P (= O), Si and P.
Wherein the organic solvent is toluene, methanol, ethanol, benzene, n-heptane, tetrahydrofuran (THF), chloroform or a mixed solvent thereof.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR20140182141 | 2014-12-17 | ||
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| US10686139B2 (en) | 2016-05-26 | 2020-06-16 | Samsung Display Co., Ltd. | Nitrogen-containing compound and organic electroluminescence device including the same |
| US10777753B2 (en) | 2017-07-12 | 2020-09-15 | Samsung Display Co., Ltd. | Heterocyclic compound and organic electroluminescence device including the same |
| US11174427B2 (en) | 2016-12-01 | 2021-11-16 | Samsung Display Co., Ltd. | Aromatic compound and organic electroluminescence device including the same |
| US11271169B2 (en) | 2017-08-24 | 2022-03-08 | Samsung Display Co., Ltd. | Nitrogen-containing compound and organic electroluminescence device including the same |
| US11374182B2 (en) | 2018-09-11 | 2022-06-28 | Samsung Display Co., Ltd. | Organic electroluminescence device and amine compound for organic electroluminescence device |
| US11563187B2 (en) | 2017-11-15 | 2023-01-24 | Samsung Display Co., Ltd. | Nitrogen-containing compound-containing compound and organic electroluminescence device including the same |
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| CN106380454A (en) * | 2016-08-16 | 2017-02-08 | 盐城工学院 | Organic electroluminescence materials, a luminescent device and a manufacturing method of the device |
| KR20180037645A (en) * | 2016-10-04 | 2018-04-13 | 삼성디스플레이 주식회사 | Polycyclic compound and organic electroluminescence device including the same |
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| JP2006083167A (en) * | 2004-08-19 | 2006-03-30 | Chemiprokasei Kaisha Ltd | Phenazacillin derivative, and hole-transporting material, hole injection material and light-emitting layer host material, and organic el element containing the same |
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| JP2006083167A (en) * | 2004-08-19 | 2006-03-30 | Chemiprokasei Kaisha Ltd | Phenazacillin derivative, and hole-transporting material, hole injection material and light-emitting layer host material, and organic el element containing the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10686139B2 (en) | 2016-05-26 | 2020-06-16 | Samsung Display Co., Ltd. | Nitrogen-containing compound and organic electroluminescence device including the same |
| US11174427B2 (en) | 2016-12-01 | 2021-11-16 | Samsung Display Co., Ltd. | Aromatic compound and organic electroluminescence device including the same |
| US10777753B2 (en) | 2017-07-12 | 2020-09-15 | Samsung Display Co., Ltd. | Heterocyclic compound and organic electroluminescence device including the same |
| US11271169B2 (en) | 2017-08-24 | 2022-03-08 | Samsung Display Co., Ltd. | Nitrogen-containing compound and organic electroluminescence device including the same |
| US11563187B2 (en) | 2017-11-15 | 2023-01-24 | Samsung Display Co., Ltd. | Nitrogen-containing compound-containing compound and organic electroluminescence device including the same |
| US11374182B2 (en) | 2018-09-11 | 2022-06-28 | Samsung Display Co., Ltd. | Organic electroluminescence device and amine compound for organic electroluminescence device |
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| KR20160073914A (en) | 2016-06-27 |
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