Triazine compounds substituted with bulky groups
11530201 · 2022-12-20
Assignee
Inventors
- Benjamin Schulze (Dresden, DE)
- Ansgar Werner (Dresden, DE)
- Elena Galan (Dresden, DE)
- Regina Luschtinetz (Dresden, DE)
- Qiang Huang (Dresden, DE)
- Kipo Jang (Gyeonggi-do, KR)
- Hyungsun Kim (Gyeonggi-do, KR)
Cpc classification
C07D405/04
CHEMISTRY; METALLURGY
H10K85/6574
ELECTRICITY
C07D409/04
CHEMISTRY; METALLURGY
International classification
Abstract
The present invention relates to a triazine compound according to formula 1: suitable for use as a layer material for electronic devices, and to an organic semiconductor layer comprising at least one compound according to formula 1, as well as to an organic electronic device comprising at least one organic semiconductor layer, and a method of manufacturing the same. ##STR00001##
Claims
1. A triazine compound according to formula 1: ##STR00069## wherein X is O, S or Se; a, b, c, d are selected from 0 or 1, wherein 1≤a+b+c+d≤3; n is selected from 0, 1 or 2, Ar.sup.1 is selected from C.sub.1 to C.sub.16 alkyl, substituted or unsubstituted C.sub.6 to C.sub.40 aryl, substituted or unsubstituted C.sub.3 to C.sub.40 heteroaryl, wherein the substituents of the substituted C.sub.6 to C.sub.40 aryl and substituted C.sub.3 to C.sub.40 heteroaryl are selected from C.sub.1 to C.sub.16 alkyl, C.sub.1 to C.sub.16 alkoxy, C.sub.3 to C.sub.16 branched alkyl, C.sub.3 to C.sub.16 cyclic alkyl, C.sub.3 to C.sub.16 branched alkoxy, C.sub.3 to C.sub.16 cyclic alkoxy, partially or perfluorinated C.sub.1 to C.sub.16 alkyl, partially or perfluorinated C.sub.1 to C.sub.16 alkoxy, partially or perdeuterated C.sub.1 to C.sub.16 alkyl, partially or perdeuterated C.sub.1 to C.sub.16 alkoxy, C.sub.6 to C.sub.24 aryl, C.sub.3 to C.sub.25 heteroaryl, -PX(R.sup.1).sub.2, D, F or CN, wherein R.sup.1 is independently selected from C.sub.1 to C.sub.16 alkyl, C.sub.1 to C.sub.16 alkoxy, partially or perfluorinated C.sub.1 to C.sub.16 alkyl, partially or perfluorinated C.sub.1 to C.sub.16 alkoxy, partially or perdeuterated C.sub.1 to C.sub.16 alkyl, partially or perdeuterated C.sub.1 to C.sub.16 alkoxy, C.sub.6 to C.sub.18 aryl, C.sub.3 to C.sub.25 heteroaryl; Ar.sup.2, Ar.sup.3, Ar.sup.4, Ar.sup.5 and Ar.sup.6 are independently selected from substituted or unsubstituted C.sub.6 to C.sub.12 aryl or substituted or unsubstituted C.sub.4 to C.sub.10 heteroaryl, wherein the substituent of the substituted C.sub.6 to C.sub.12 aryl or substituted C.sub.4 to C.sub.10 heteroaryl is selected from C.sub.1 to C.sub.6 alkyl, C.sub.1 to C.sub.6 alkoxy, partially or perdeuterated C.sub.1 to C.sub.6 alkyl, partially or perdeuterated C.sub.1 to C.sub.6 alkoxy, partially or perfluorinated C.sub.1 to C.sub.6 alkyl, partially or perfluorinated C.sub.1 to C.sub.6 alkoxy, D, F, or CN.
2. The triazine compound of formula 1 according to claim 1, wherein X is selected from O or S.
3. The triazine compound of formula 1 according to claim 1, wherein Ar.sup.1 is selected from C.sub.1 to C.sub.12 alkyl, substituted or unsubstituted C.sub.6 to C.sub.24 aryl or substituted or unsubstituted C.sub.3 to C.sub.36 heteroaryl, wherein the substituents of the substituted C.sub.6 to C.sub.24 aryl and substituted C.sub.3 to C.sub.36 heteroaryl are selected from C.sub.1 to C.sub.12 alkyl, C.sub.1 to C.sub.12 alkoxy, partially or perfluorinated C.sub.1 to C.sub.12 alkyl, partially or perfluorinated C.sub.1 to C.sub.16 alkoxy, partially or perdeuterated C.sub.1 to C.sub.12 alkyl, partially or perdeuterated C.sub.1 to C.sub.16 alkoxy, C.sub.6 to C.sub.18 aryl, C.sub.3 to C.sub.25 heteroaryl, D, F or CN.
4. The triazine compound of formula 1 according to claim 1, wherein Ar.sup.1 is selected from the group comprising unsubstituted C.sub.6 to C.sub.24 aryl and C.sub.6 or C.sub.12 aryl.
5. The triazine compound of formula 1 according to claim 1, wherein Ar.sup.1 is independently selected from B1 to B6, wherein B1 to B6 are substituted or unsubstituted non-heteroaryl groups: ##STR00070##
6. The triazine compound of formula 1 according to claim 1, wherein Ar.sup.1 may be independently selected from structures C1 to C5: ##STR00071## wherein R.sup.1 is independently selected from C.sub.1 to C.sub.16 alkyl, C.sub.1 to C.sub.16 alkoxy, partially or perfluorinated C.sub.1 to C.sub.16 alkyl, partially or perfluorinated C.sub.1 to C.sub.16 alkoxy, partially or perdeuterated C.sub.1 to C.sub.16 alkyl, partially or perdeuterated C.sub.1 to C.sub.16 alkoxy, C.sub.6 to C.sub.18 aryl, C.sub.3 to C.sub.25 heteroaryl.
7. The triazine compound of formula 1 according to claim 1, wherein at least one to at most three substituents of Ar.sup.2, Ar.sup.3, Ar.sup.5 and Ar.sup.6 are independently selected from unsubstituted C.sub.6 to C.sub.12 aryl or unsubstituted C.sub.4 to C.sub.10 heteroaryl phenyl, biphenyl, naphthyl, pyridyl, quinolinyl, quinazolinyl.
8. The triazine compound of formula 1 according to claim 1, wherein Ar.sup.4 are independently selected from unsubstituted C.sub.6 to C.sub.12 aryl or unsubstituted C.sub.4 to C.sub.10 heteroaryl, phenyl, biphenyl, naphthyl, pyridyl, quinolinyl, quinazolinyl.
9. The triazine compound of formula 1 according to claim 1, wherein n=0 or 1.
10. The triazine compound of formula 1 according to claim 1, wherein a, b, c and d are selected from the group comprising a=1, b=0, c=0 and d=1, a=0, b=0, c=0 and d=1, a=0, b=0, c=1 and d=1, a=0, b=1, c=1 and d=0, and a=1, b=1, c=1 and d=0.
11. The triazine compound of formula 1 according to claim 1, wherein the triazine compound is selected from D1 to D9: ##STR00072## ##STR00073## ##STR00074##
12. An organic semiconductor layer comprising at least one triazine compound of formula 1 according to claim 1.
13. The organic semiconductor layer according to claim 12, further comprising a metal containing compound selected from the group comprising a metal, metal salt, organic metal complex, organic monovalent metal complex, divalent metal complex, LiQ and alkali borate.
14. An organic electronic device comprising an organic semiconductor layer according to claim 12, wherein at least one organic semiconductor layer comprises a triazine compound of formula 1.
15. The organic electronic device according to claim 14, wherein the electronic device is a light emitting device, thin film transistor, a battery, a display device or a photovoltaic cell.
16. The triazine compound of formula 1 according to claim 1, wherein Ar.sup.1 is independently selected from B7 to B23, wherein B7 to B23 are substituted or unsubstituted annelated non-heteroaryl groups: ##STR00075## ##STR00076## ##STR00077## wherein the substituent R.sup.2 is independently selected from H, C.sub.1 to C.sub.16 alkyl, partially or perfluorinated C.sub.1 to C.sub.16 alkyl, partially or perdeuterated C.sub.1 to C.sub.16 alkyl, C.sub.1 to C.sub.16 alkoxy, C.sub.3 to C.sub.16 branched alkyl, C.sub.3 to C.sub.16 cyclic alkyl, C.sub.3 to C.sub.16 branched alkoxy, C.sub.3 to C.sub.16 cyclic alkoxy, C.sub.6 to C.sub.24 aryl and C.sub.3 to C.sub.25 heteroaryl.
17. The triazine compound of formula 1 according to claim 1, wherein Ar.sup.1 is independently selected from B24 to B31, wherein B24 to B31 are selected from the group comprising a dibenzofurane or dibenzothiophene group: ##STR00078##
18. The triazine compound of formula 1 according to claim 1, wherein Ar.sup.1 is independently selected from B32 to B34, wherein B32 to B34 are unsubstituted pyridine groups: ##STR00079##
19. The triazine compound of formula 1 according to claim 1, wherein Ar.sup.1 is independently selected from B35 to B62, wherein B35 to B62 are unsubstituted or substituted hetero arylene groups: ##STR00080## ##STR00081## ##STR00082## ##STR00083## wherein the substituent R.sup.2 is independently selected from H, C.sub.1 to C.sub.16 alkyl, partially or perfluorinated C.sub.1 to C.sub.16 alkyl, partially or perdeuterated C.sub.1 to C.sub.16 alkyl, C.sub.1 to C.sub.16 alkoxy, C.sub.3 to C.sub.16 branched alkyl, C.sub.3 to C.sub.16 cyclic alkyl, C.sub.3 to C.sub.16 branched alkoxy, C.sub.3 to C.sub.16 cyclic alkoxy, C.sub.6 to C.sub.24 aryl and C.sub.3 to C.sub.25 heteroaryl.
20. The triazine compound of formula 1 according to claim 1, wherein Ar.sup.1 is independently selected from B63 to B65, wherein B63 to B65 are unsubstituted annelated hetero arylene groups: ##STR00084##
21. The triazine compound of formula 1 according to claim 1, wherein Ar.sup.1 is independently selected from B66 to B67, wherein B66 and B67 are nitrile substituted phenyl groups: ##STR00085##
22. The triazine compound of formula 1 according to claim 1, wherein Ar.sup.i is independently selected from B68 to B70, wherein B68 to B70 are nitrile substituted biphenyl groups: ##STR00086##
23. The triazine compound of formula 1 according to claim 1, wherein Ar.sup.1 is independently selected from B71 to B77, wherein B71 to B77 are carbazole groups: ##STR00087## wherein the substituent R.sup.2 is independently selected from H, C.sub.1 to C.sub.16 alkyl, partially or perfluorinated C.sub.1 to C.sub.16 alkyl, partially or perdeuterated C.sub.1 to C.sub.16 alkyl, C.sub.1 to C.sub.16 alkoxy, C.sub.3 to C.sub.16 branched alkyl, C.sub.3 to C.sub.16 cyclic alkyl, C.sub.3 to C.sub.16 branched alkoxy, C.sub.3 to C.sub.16 cyclic alkoxy, C.sub.6 to C.sub.24 aryl and C.sub.3 to C.sub.25 heteroaryl.
Description
DESCRIPTION OF THE DRAWINGS
(1) These and/or other aspects and advantages of the present invention will become apparent and more readily appreciated from the following description of the exemplary embodiments, taken in conjunction with the accompanying drawings, of which:
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(8) Reference will now be made in detail to the exemplary aspects, examples of which are illustrated in the accompanying drawings, wherein like reference numerals refer to the like elements throughout. The exemplary embodiments are described below, in order to explain the aspects, by referring to the figures.
(9) Herein, when a first element is referred to as being formed or disposed “on” a second element, the first element can be disposed directly on the second element, or one or more other elements may be disposed there between. When a first element is referred to as being formed or disposed “directly on” a second element, no other elements are disposed there between.
(10) The term “contacting sandwiched” refers to an arrangement of three layers whereby the layer in the middle is in direct contact with the two adjacent layers.
(11) The organic light emitting diodes according to an embodiment of the present invention may include a hole transport region; an emission layer; and a first electron transport layer comprising a compound according to formula 1.
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(18) Organic Semiconductor Layer
(19) According to another aspect an organic semiconductor layer may comprises at least one triazine compound of formula 1 and/or formula 1a.
(20) According to one embodiment the organic semiconductor layer may comprises at least one triazine compound of formula 1 and further comprises a metal, metal salt or organic alkali metal complex, preferably alkali metal complex, more preferably LiQ or alkali borate.
(21) According to one embodiment the organic semiconductor layer may comprises at least one triazine compound of formula 1 and further comprises a metal, metal salt or organic metal complex, preferably an organic monovalent or divalent metal complex, more preferably LiQ or alkali borate.
(22) According to one embodiment the organic semiconductor layer may comprises at least one triazine compound of formula 1 and LiQ.
(23) According to one embodiment the organic semiconductor layer may comprises at least one triazine compound of formula 1 and alkali borate.
(24) According to one embodiment, wherein at least one organic semiconductor layer is arranged between the emission layer and the cathode, preferably between the auxiliary electron transport layer and the cathode.
(25) In another embodiment, the organic semiconductor layer is arranged between the emission layer and the electron transport layer.
(26) According to one embodiment, the organic semiconductor layer is arranged between the first and second emission layer. The organic semiconductor layer can be an electron transport layer, an emission layer, a hole blocking layer, a charge generation layer and/or an electron injection layer, preferably an electron transport layer or a charge generation layer, and more preferred an electron transport layer.
(27) According to one embodiment, the organic semiconductor layer can be arranged between a photoactive layer and a cathode layer, preferably between an emission layer or light-absorbing layer and the cathode layer, preferably the organic semiconductor layer is an electron transport layer.
(28) According to one embodiment, the organic semiconductor layer may comprise at least one alkali halide or alkali organic complex.
(29) An organic semiconductor layer comprises a triazine compound according to formula 1 or 1a is essentially non-emissive or non-emitting.
(30) Organic Electronic Device
(31) An organic electronic device according to the invention comprises at least one organic semiconductor layer, wherein at least one organic semiconductor layer comprises a triazine compound according to formula 1.
(32) An organic electronic device according to one embodiment, which comprises at least one organic semiconductor layer that comprises a triazine compound according to formula 1, wherein this layer is essentially non-emissive or non-emitting.
(33) According to one embodiment, the organic electronic device may comprises at least one organic semiconductor layer comprising triazine compound of formula 1 that is an electron transport layer, an emission layer, a hole blocking layer, a charge generation layer and/or an electron injection layer, preferably an electron transport layer or a charge generation layer, more preferred an electron transport layer.
(34) An organic electronic device according to one embodiment may include a substrate, an anode layer, an organic semiconductor layer comprising triazine compound of formula 1, and a cathode layer.
(35) The organic electronic device according to according to one embodiment may comprises at least one organic semiconductor layer, wherein the organic semiconductor layer comprising triazine compound of formula 1 is arranged between a photoactive layer and a cathode layer, preferably between an emission layer or light-absorbing layer and the cathode layer, preferably the organic semiconductor layer is an electron transport layer
(36) The organic electronic device according to according to one embodiment may comprises at least one organic semiconductor layer comprising triazine compound of formula 1, wherein the at least one organic semiconductor layer further comprises at least one alkali halide or alkali organic complex.
(37) An organic electronic device according to one embodiment comprises at least one organic semiconductor layer comprising at least one triazine compound of formula 1, at least one anode layer, at least one cathode layer and at least one emission layer, wherein the organic semiconductor layer comprising at least one triazine compound of formula 1 is preferably arranged between the emission layer and the cathode layer.
(38) An organic electronic device according to one embodiment comprises at least one organic semiconductor layer comprising at least one triazine compound of formula 1 and further comprises at least one alkali halide or alkali organic complex.
(39) An organic electronic device according to one embodiment comprises at least one organic semiconductor layer, at least one anode layer, at least one cathode layer and at least one emission layer, wherein the organic semiconductor layer comprising at least one triazine compound of formula 1 is preferably arranged between the emission layer and the cathode layer. Preferably the at least one organic semiconductor layer is an electron transport layer.
(40) An organic light-emitting diode (OLED) according to the invention may include an anode, a hole transport layer (HTL), an emission layer (EML), an electron transport layer (ETL) comprising at least one triazine compound of formula 1, and a cathode, which are sequentially stacked on a substrate. In this regard, the HTL, the EML, and the ETL are thin films formed from organic compounds.
(41) An organic electronic device according to one embodiment can be a light emitting device, thin film transistor, a battery, a display device or a photovoltaic cell, and preferably a light emitting device. A light emitting device can be an OLED.
(42) According to one embodiment the OLED may have the following layer structure, wherein the layers having the following order:
(43) an anode layer, a hole injection layer, optional a first hole transport layer, optional a second hole transport layer, an emission layer, an electron transport layer comprising triazine compound of formula 1 according to the invention, an electron injection layer, and a cathode layer.
(44) According to another aspect of the present invention, there is provided a method of manufacturing an organic electronic device, the method using: at least one deposition source, preferably two deposition sources and more preferred at least three deposition sources.
(45) The methods for deposition that can be suitable comprise: deposition via vacuum thermal evaporation; deposition via solution processing, preferably the processing is selected from spin-coating, printing, casting; and/or slot-die coating.
(46) According to various embodiments of the present invention, there is provided a method using: a first deposition source to release the triazine compound of formula 1 according to the invention, and a second deposition source to release the alkali halide or alkali organic complex, preferably a lithium halide or lithium organic complex;
the method comprising the steps of forming the electron transport layer stack; whereby for an organic light-emitting diode (OLED): the first electron transport layer is formed by releasing the triazine compound of formula 1 according to the invention from the first deposition source and the alkali halide or alkali organic complex, preferably a lithium halide or lithium organic complex from the second deposition source.
(47) According to various embodiments of the present invention, the method may further include forming on the anode electrode an emission layer and at least one layer selected from the group consisting of forming a hole injection layer, forming a hole transport layer, or forming a hole blocking layer, between the anode electrode and the first electron transport layer.
(48) According to various embodiments of the present invention, the method may further include the steps for forming an organic light-emitting diode (OLED), wherein on a substrate a first anode electrode is formed, on the first anode electrode an emission layer is formed, on the emission layer an electron transport layer stack is formed, preferably a first electron transport layer is formed on the emission layer and a second electron transport layer is formed on the first electron transport layer and the second electron transport layer comprises a triazine compound of formula 1, and finally a cathode electrode is formed, optional a hole injection layer, a hole transport layer, and a hole blocking layer, formed in that order between the first anode electrode and the emission layer, optional an electron injection layer is formed between the electron transport layer stack and the cathode electrode.
(49) According to various embodiments of the present invention, the method may further include forming an electron injection layer on a first electron transport layer. However, according to various embodiments of the OLED of the present invention, the OLED may not comprise an electron injection layer.
(50) According to various embodiments, the OLED may have the following layer structure, wherein the layers having the following order:
(51) an anode, first hole transport layer, second hole transport layer, emission layer, optional second electron transport layer, first electron transport layer comprising triazine compound of formula 1 according to the invention, optional a second electron transport layer, optional an electron injection layer, and a cathode.
(52) According to another aspect of the invention, it is provided an electronic device comprising at least one organic light emitting device according to any embodiment described throughout this application, preferably, the electronic device comprises the organic light emitting diode in one of embodiments described throughout this application. More preferably, the electronic device is a display device.
(53) Hereinafter, the embodiments are illustrated in more detail with reference to examples. However, the present disclosure is not limited to the following examples. Reference will now be made in detail to the exemplary aspects.
(54) Preparation of Triazine Compounds of Formula 1
(55) Triazine compounds of formula 1 may be prepared as described below.
Preparation of 2-(dibenzo[b,d]furan-3-yl)-4-phenyl-6-(4′-phenyl-[1,1′:2′,1″-terphenyl]-4-yl)-1,3,5-triazine
(56) ##STR00033##
2-(4-chlorophenyl)-4-(dibenzo[b,d]furan-3-yl)-6-phenyl-1,3,5-triazine
(57) ##STR00034##
A flask was flushed with nitrogen and charged with 2-chloro-4-(4-chlorophenyl)-6-phenyl-1,3,5-triazine (26.1 g, 86.3 mmol), dibenzo[b,d]furan-3-ylboronic acid (19.2 g, 90.7 mol), Pd(PPh.sub.3).sub.4 (2.0 g, 1.73 mmol), and K.sub.2CO.sub.3 (23.8 g, 173.0 mmol). A mixture of deaerated THF/water (2:1, 405 mL) was added and the reaction mixture was heated to 75° C. under a nitrogen atmosphere for 5 h. After cooling down to 5° C., the resulting precipitate was isolated by suction filtration and washed with THF and n-hexane, followed by water and methanol. The crude product was dissolved in a mixture of hot chloroform and toluene (1:1), then n-hexane was added until precipitation begins. After stirring for 30 min at room temperature, the precipitate was collected by suction filtration and washed with n-hexane. After trituration with toluene and drying, 34.3 g (92%) of a pale yellow solid were obtained.
2-(dibenzo[b,d]furan-3-yl)-4-phenyl-6-(4′-phenyl-[1,1′:2′,1″-terphenyl]-4-yl)-1,3,5-triazine
(58) ##STR00035##
(59) A flask was flushed with nitrogen and charged with 2-(4-chlorophenyl)-4-(dibenzo[b,d]furan-3-yl)-6-phenyl-1,3,5-triazine (11.2 g, 25.9 mmol), 2-([1,1′:3′,1″-terphenyl]-4′-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (11.1 g, 31.1 mol), chloro(crotyl)(2-dicyclohexylphosphino-2′,6′-dimethoxybiphenyl)palladium(II) (0.31 g, 0.51 mmol), and K.sub.3PO.sub.4 (11.0 g, 51.9 mmol). A mixture of deaerated THF/water (4:1, 250 mL) was added and the reaction mixture was heated to 50° C. under a nitrogen atmosphere for 17 h. After cooling down to room temperature, the resulting precipitate was isolated by suction filtration and washed with THF. The crude product was dissolved in chlorobenzene and filtered through a pad of Florisil. After rinsing with additional chlorobenzene, the filtrate was evaporated to dryness and the residue was triturated with methanol. Further purification was achieved by recrystallization from chlorobenzene and o-xylene to yield 7.5 g (46%) of a white solid after drying. Final purification was achieved by sublimation. m/z=628 ([M+H].sup.+).
Preparation of 2-(dibenzo[b,d]furan-3-yl)-4-(2′,6′-diphenyl-[1,1′:4′,1″-terphenyl]-4-yl)-6-phenyl-1,3,5-triazine
(60) ##STR00036##
4,4,5,5-tetramethyl-2-(5′-phenyl-[1,1′:3′,1″-terphenyl]-2′-yl)-1,3,2-dioxaborolane
(61) ##STR00037##
(62) To a stirred solution of 2′-bromo-5′-phenyl-1,1′:3′,1″-terphenyl (60.0 g, 155.7 mmol) in THF (950 mL) at −80° C. was added n-butyllithium in n-hexane (129.6 mL, 33 wt %, 323.9 mmol) and the mixture was slowly warmed up to −60° C. during 4 hours. The green solution was then cooled down to −80° C. and 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (86.9 g, 467.2 mmol) was added slowly. The mixture was stirred overnight while the temperature gradually increased to room temperature. Methanol was added and the crude reaction mixture was evaporated to dryness. The residue was dissolved in chloroform and extracted with water three times. The organic phase was dried over MgSO.sub.4, filtered and evaporated to dryness. After trituration with n-hexane and drying, 42.2 g (62%) of a white solid were obtained.
2-(dibenzo[b,d]furan-3-yl)-4-(2′,6′-diphenyl-[1,1′:4′,1″-terphenyl]-4-yl)-6-phenyl-1,3,5-triazine
(63) ##STR00038##
(64) A flask was flushed with nitrogen and charged with 2-(4-chlorophenyl)-4-(dibenzo[b,d]furan-3-yl)-6-phenyl-1,3,5-triazine (10.0 g, 23 mmol), 4,4,5,5-tetramethyl-2-(5′-phenyl-[1,1′:3′,1″-terphenyl]-2′-yl)-1,3,2-dioxaborolane (12.0 g, 27.7 mol), chloro(crotyl)(2-dicyclohexylphosphino-2′,6′-dimethoxybiphenyl)palladium(II) (0.28 g, 0.46 mmol), and K.sub.3PO.sub.4 (9.8 g, 46.1 mmol). A mixture of deaerated THF/water (4:1, 290 mL) was added and the reaction mixture was heated to 50° C. under a nitrogen atmosphere for two days. Additional chloro(crotyl)(2-dicyclohexylphosphino-2′,6′-dimethoxybiphenyl)-palladium(II) (0.28 g, 0.46 mmol) was added and the reaction mixture was heated to 70° C. under a nitrogen atmosphere for five days. After cooling down to room temperature, the formed precipitate was collected by suction filtration and washed with water and methanol. The crude product was dissolved in hot chlorobenzene and filtered through a pad of silica gel. After rinsing with additional hot chlorobenzene, the combined filtrates were concentrated in vacuo and the obtained precipitate was isolated by suction filtration and washed with n-hexane. After recrystallization from THF and drying, 4.1 g (27%) of a pale yellow solid were obtained. Final purification was achieved by sublimation. m/z=704 ([M+H].sup.+).
Preparation of 2-(dibenzo[b,d]furan-3-yl)-4-(3′,5′-diphenyl-[1,1′:4′,1″-terphenyl]-4-yl)-6-phenyl-1,3,5-triazine
(65) ##STR00039##
2-(3′,5′-diphenyl-[1,1′:4′,1″-terphenyl]-4-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane
(66) ##STR00040##
(67) A flask was flushed with nitrogen and charged with 5′-(4-bromophenyl)-3′-phenyl-1,1′:2′,1″-terphenyl (11.0 g, 23.8 mmol), bis(pinacolato)diboron (6.7 g, 26.2 mmol), Pd(dppf)Cl.sub.2 (1.0 g, 1.4 mmol), and potassium acetate (5.8 g, 59.6 mmol). Dry and deaerated DMF (110 mL) was added and the reaction mixture was heated to 80° C. under a nitrogen atmosphere for 22 hours. Subsequently, all volatiles were removed in vacuo, water and dichloromethane were added and the organic phase was washed with water four times. After drying over MgSO.sub.4, the organic phase was filtered through a pad of Florisil. After rinsing with additional dichloromethane, the filtrate was concentrated to a minimal amount and precipitation was induced by addition of n-hexane. The precipitate was collected by suction filtration, washed with n-hexane and dried to yield 10.4 g (86%) of an off-white solid.
2-(dibenzo[b,d]furan-3-yl)-4-(3′,5′-diphenyl-[1,1′:4′,1″-terphenyl]-4-yl)-6-phenyl-1,3,5-triazine
(68) ##STR00041##
(69) A flask was flushed with nitrogen and charged with 2-(3′,5′-diphenyl-[1,1′:4′,1″-terphenyl]-4-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (5.0 g, 9.8 mmol), 2-chloro-4-(dibenzo[b,d]furan-3-yl)-6-phenyl-1,3,5-triazine (7.1 g, 20.0 mol), Pd(PPh.sub.3).sub.4 (0.48 g, 0.42 mmol), and K.sub.2CO.sub.3 (5.8 g, 41.9 mmol). A mixture of deaerated 1,4-dioxane/water (5:1, 120 mL) was added and the reaction mixture was heated to reflux under a nitrogen atmosphere overnight. After cooling down to room temperature, the formed precipitate was collected by suction filtration and washed with water, methanol and n-hexane. The crude product was dissolved in hot toluene and filtered through a pad of silica gel. After rinsing with additional hot toluene, the combined filtrates were concentrated in vacuo and, after the addition of n-hexane, the obtained precipitate was isolated by suction filtration and washed with n-hexane. After trituration with toluene and drying, 4.0 g (29%) of a white solid were obtained. Final purification was achieved by sublimation. m/z=704 ([M+H].sup.+).
Preparation of 2-(dibenzo[b,d]furan-3-yl)-4-phenyl-6-(4′,5′,6′-triphenyl-[1,1′:2′,1″:4″,1′″-quaterphenyl]-4′″-yl)-1,3,5-triazine
(70) ##STR00042##
2-(dibenzo[b,d]furan-3-yl)-4-phenyl-6-(4′,5′,6′-triphenyl-[1,1′:2′,1″:4″,1′″-quaterphenyl]-4′″-yl)-1,3,5-triazine
(71) ##STR00043##
(72) A flask was flushed with nitrogen and charged with 2-(4-chlorophenyl)-4-(dibenzo[b,d]furan-3-yl)-6-phenyl-1,3,5-triazine (15 g, 34.6 mmol), 4,4,5,5-tetramethyl-2-(3′,4′,5′-triphenyl-[1,1′:2′,1″-terphenyl]-4-yl)-1,3,2-dioxaborolane (30.4 g, 52 mmol), chloro(crotyl)(2-dicyclohexylphosphino-2′,6′-dimethoxybiphenyl)-palladium(II) (0.63 g, 1.04 mmol), and K.sub.3PO.sub.4 (14.7 g, 69 mmol). A mixture of deaerated THF/water (4:1, 375 mL) was added and the reaction mixture was heated to 45° C. under a nitrogen atmosphere for 46 h. Subsequently, all volatiles were removed in vacuo and the residue was dissolved in dichloromethane/water. The aqueous phase was removed and the organic phase was washed with water four times, dried over MgSO.sub.4 and filtered over a pad of florisil. The filtrate was concentrated in vacuo and acetonitrile was added. The formed precipitate was collected by suction filtration and washed with acetonitrile. After trituration with ethyl acetate and drying in vacuo, 25.7 g (87%) of a white solid were obtained. Final purification was achieved by sublimation. m/z=856 ([M+H].sup.+).
(73) Scheme for the Preparation of Triazine Compound of Formula 1 with a, b and c=1:
(74) ##STR00044##
2-(dibenzo[b,d]furan-3-yl)-4-phenyl-6-(3′,4′,5′-triphenyl-[1,1′:2′,1″-terphenyl]-3-yl)-1,3,5-triazine
(75) ##STR00045##
(76) A flask was flushed with nitrogen and charged with 2-chloro-4-(dibenzo[b,d]furan-3-yl)-6-phenyl-1,3,5-triazine (10 g, 27.9 mmol), 4,4,5,5-tetramethyl-2-(3′,4′,5′-triphenyl-[1,1′:2′,1″-terphenyl]-3-yl)-1,3,2-dioxaborolane (17.2 g, 29.4 mmol), Pd(PPh.sub.3).sub.4 (0.65 g, 0.56 mmol), and K.sub.2CO.sub.3 (7.7 g, 55.8 mmol). A mixture of deaerated THF/water (2:1, 200 mL) was added and the reaction mixture was heated to reflux under a nitrogen atmosphere for 26 h. After cooling down to 10° C., the formed precipitate was collected by suction filtration and washed with THF and n-hexane. The solid was dissolved in chloroform and the organic phase was extracted with water three times, dried over MgSO.sub.4 and filtered through a pad of silica gel and florisil. The filtrate was concentrated in vacuo and n-hexane was added. The formed precipitate was collected by suction filtration and washed with n-hexane. After trituration with toluene and drying in vacuo, 15.8 g (72%) of a white solid were obtained. Final purification was achieved by sublimation. m/z=780 ([M+H]+).
2-(dibenzo[b,d]furan-3-yl)-4-phenyl-6-(3′,4′,5′-triphenyl-[1,1′:2′,1″-terphenyl]-4-yl)-1,3,5-triazine
(77) ##STR00046##
(78) Following the procedure described above using 2-chloro-4-(dibenzo[b,d]furan-3-yl)-6-phenyl-1,3,5-triazine (10 g, 27.9 mmol), 4,4,5,5-tetramethyl-2-(3′,4′,5′-triphenyl-[1,1′:2′,1″-terphenyl]-4-yl)-1,3,2-dioxaborolane (18 g, 30.7 mmol), Pd(PPh.sub.3).sub.4 (0.65 g, 0.56 mmol), K.sub.2CO.sub.3 (7.7 g, 55.8 mmol), THF/water (2:1, 200 mL), and 20 h reaction time, 14.3 g (65%) of a white solid were obtained. Final purification was achieved by sublimation. m/z=780 ([M+H].sup.+).
(79) ##STR00047##
2-([1,1′-biphenyl]-4-yl)-4-chloro-6-(dibenzo[b,d]furan-3-yl)-1,3,5-triazine
(80) ##STR00048##
(81) A flask was flushed with nitrogen and charged with 2-([1,1′-biphenyl]-4-yl)-4,6-dichloro-1,3,5-triazine (80 g, 264.8 mmol), dibenzo[b,d]furan-3-ylboronic acid (44.9 g, 211.8 mmol), Pd(PPh.sub.3).sub.4 (15.3 g, 13.2 mmol), and K.sub.2CO.sub.3 (91.5 g, 662 mmol). A mixture of deaerated toluene/THF/water (1:1:1, 1200 mL) was added and the reaction mixture was heated to 65° C. under a nitrogen atmosphere for 6 h. After cooling down to room temperature, the precipitate was collected by suction filtration and washed with water and toluene. The solid was dissolved in hot toluene and filtered through a pad of silica gel. The filtrate was allowed to cool down to room temperature and the resulting precipitate was collected by suction filtration and washed toluene. After drying in vacuo, 32.7 g (28%) of a white solid were obtained. Final purification was achieved by sublimation.
2-([1,1′-biphenyl]-4-yl)-4-(dibenzo[b,d]furan-3-yl)-6-(3′,4′,5′-triphenyl-[1,1′:2′,1″-terphenyl]-4-yl)-1,3,5-triazine
(82) ##STR00049##
(83) Following the procedure described above using 2-([1,1′-biphenyl]-4-yl)-4-chloro-6-(dibenzo[b,d]furan-3-yl)-1,3,5-triazine (18 g, 41.5 mmol), 4,4,5,5-tetramethyl-2-(3′,4′,5′-triphenyl-[1,1′:2′,1″-terphenyl]-4-yl)-1,3,2-dioxaborolane (26.7 g, 45.6 mmol), Pd(PPh.sub.3).sub.4 (0.96 g, 0.83 mmol), K.sub.2CO.sub.3 (11.5 g, 83 mmol), THF/water (4:1, 500 mL), and 21 h reaction time, 25.9 g (73%) of a white solid were obtained. Final purification was achieved by sublimation. m/z=856 ([M+H].sup.+).
Preparation of 2-(Dibenzo[b,d]furan-3-yl)-4-(naphthalen-2-yl)-6-(3′,4′,5′-triphenyl-[1,1′:2′,1″-terphenyl]-4-yl)-1,3,5-triazine
(84) ##STR00050##
2-Chloro-4-(dibenzo[b,d]furan-3-yl)-6-(naphthalen-2-yl)-1,3,5-triazine
(85) ##STR00051##
(86) A flask was flushed with nitrogen and charged with 2,4-dichloro-6-(naphthalen-2-yl)-1,3,5-triazine (32.9 g, 119.1 mmol), dibenzo[b,d]furan-3-ylboronic acid (25.3 g, 119.1 mol) and K.sub.2CO.sub.3 (41.2 g, 297.8 mmol). A mixture of deaerated toluene/ethanol/water (1:1:1, 495 mL) was added followed by Pd(PPh.sub.3).sub.4 (6.88 g, 5.9 mmol). The reaction mixture was heated to 45° C. under nitrogen atmosphere for 7 h. The reaction mixture was cooled with an ice bath, the precipitate collected by suction filtration and washed with toluene, water and methanol. Drying under vacuum yielded 26.1 g (54%) of an off-white solid.
2-(Dibenzo[b,d]furan-3-yl)-4-(naphthalen-2-yl)-6-(3′,4′,5′-triphenyl-[1,1′:2′,1″-terphenyl]-4-yl)-1,3,5-triazine
(87) ##STR00052##
(88) Following the general procedure described above using 2-Chloro-4-(dibenzo[b,d]furan-3-yl)-6-(naphthalen-2-yl)-1,3,5-triazine (20 g, 49 mmol), 4,4,5,5-tetramethyl-2-(3′,4′,5′-triphenyl-[1,1′:2′,1″-terphenyl]-4-yl)-1,3,2-dioxaborolane (31.5 g, 53.9 mol), K.sub.2CO.sub.3 (13.5 g, 98.1 mmol), Pd(PPh.sub.3).sub.4 (1.13 g, 0.98 mmol), THF/water (4:1, 500 mL), and 3 d reaction time, 38 g (93%) of a pale yellow solid were obtained. Final purification was achieved by sublimation. m/z=830 ([M+H].sup.+).
Preparation of 2,4-di([1,1′-biphenyl]-4-yl)-6-(3′,4′,5′-triphenyl-[1,1′:2′,1″-terphenyl]-4-yl)-1,3,5-triazine
(89) ##STR00053##
2,4-di([1,1′-biphenyl]-4-yl)-6-(3′,4′,5′-triphenyl-[1,1′:2′,1″-terphenyl]-4-yl)-1,3,5-triazine
(90) ##STR00054##
(91) Following the general procedure described above using 2,4-di([1,1′-biphenyl]-4-yl)-6-chloro-1,3,5-triazine (10 g, 23.8 mmol), 4,4,5,5-tetramethyl-2-(3′,4′,5′-triphenyl-[1,1′:2′,1″-terphenyl]-3-yl)-1,3,2-dioxaborolane (14.6 g, 25 mmol), Pd(dppf)Cl.sub.2 (0.87 g, 1.2 mmol), K.sub.2CO.sub.3 (6.57 g, 47.6 mmol), toluene/ethanol/water (9:3:2, 160 mL), and 2.5 h reaction time, 16.0 g (80%) of a white solid were obtained after repeated precipitation from dichloromethane with tert.-butyl methyl ether. Final purification was achieved by sublimation. m/z=842 ([M+H].sup.+).
Preparation of 2,4-Bis(dibenzo[b,d]furan-3-yl)-6-(3′,4′,5′-triphenyl-[1,1′:2′,1″-terphenyl]-4-yl)-1,3,5-triazine
(92) ##STR00055##
2-Chloro-4-(dibenzo[b,d]furan-3-yl)-6-(3′,4′,5′-triphenyl-[1,1′:2′,1″-terphenyl]-4-yl)-1,3,5-triazine
(93) ##STR00056##
(94) A flask was flushed with nitrogen and charged with 2,4-dichloro-6-(dibenzo[b,d]furan-3-yl)-1,3,5-triazine (40.5 g, 128.3 mmol), 4,4,5,5-tetra-methyl-2-(3′,4′,5′-triphenyl-[1,1′:2′,1″-terphenyl]-4-yl)-1,3,2-dioxaborolane (60 g, 102.6 mol), Pd(dppf)Cl.sub.2 (4.69 g, 6.41 mmol), and K.sub.2CO.sub.3 (44.2 g, 320 mmol). A mixture of deaerated toluene/THF/water (1:1:1, 1050 mL) was added and the reaction mixture was heated to 65° C. under a nitrogen atmosphere for 21 h. Then the mixture was allowed to cool to room temperature and the precipitate was collected by suction filtration. The solid was washed with water and n-hexane and dried in vacuo. Then the solid was suspended in dichloromethane and stirred overnight. After filtration, the solid was dried again in vacuo to yield 29.3 g (39%) of beige solid.
2,4-Bis(dibenzo[b,d]furan-3-yl)-6-(3′,4′,5′-triphenyl-[1,1′:2′,1″-terphenyl]-4-yl)-1,3,5-triazine
(95) ##STR00057##
(96) A flask was flushed with nitrogen and charged with 2-chloro-4-(dibenzo[b,d]furan-3-yl)-6-(3′,4′,5′-triphenyl-[1,1′:2′,1-terphenyl]-4-yl)-1,3,5-triazine (15 g, 20.3 mmol), dibenzo[b,d]furan-3-ylboronic acid (5.17 g, 24.3 mol), Pd(dppf)Cl.sub.2 (0.29 g, 0.4 mmol), and K.sub.2CO.sub.3 (5.61 g, 40.6 mmol). A mixture of deaerated THF/water (4.3:1, 185 mL) was added and the reaction mixture was heated to 75° C. under a nitrogen atmosphere for 2 h. Additional 200 mL deaerated THF were added to the suspension and heating and stirring continued for 18 h. After cooling to room temperature, the precipitate was collected by suction filtration and washed with THF and water. The solid was triturated with hot chloroform. Subsequently, the solid was dissolved in hot chlorobenzene and filtered through a pad of silica gel. The filtrate was concentrated under reduced pressure and the obtained precipitate isolated by suction filtration. After drying in vacuo, 8.7 g (50° C.) of a white solid were obtained. Final purification was achieved by sublimation. m/z=870 ([M+H].sup.+).
(97) The chemical structure, calculated HOMO, LUMO and dipole moment of compounds of formula 1 and comparative example ETM-1 are shown in Table 1.
(98) TABLE-US-00001 TABLE 1 Calculated Calculated Dipole Referred HOMO LUMO moment to as: Structure (eV) (eV) (Debye) ETM-1
General Procedure for Fabrication of OLEDs
(99) For top emission devices, Examples 1 to 9 and comparative example 1, a glass substrate was cut to a size of 50 mm×50 mm×0.7 mm, ultrasonically cleaned with isopropyl alcohol for 5 minutes and then with pure water for 5 minutes, and cleaned again with UV ozone for 30 minutes, to prepare the substrate. 100 nm Ag were deposited on the substrate at a pressure of 10.sup.−5 to 10.sup.−7 mbar to form the anode.
(100) Then, 92 vol.-% Biphenyl-4-yl(9,9-diphenyl-9H-fluoren-2-yl)-[4-(9-phenyl-9H-carbazol-3-yl)phenyl]-amine (CAS 1242056-42-3) with 8 vol.-% 2,2′,2″-(cyclopropane-1,2,3-triylidene)tris(2-(p-cyanotetrafluorophenyl)acetonitrile) was vacuum deposited on the anode, to form a HIL having a thickness of 10 nm. Then, Biphenyl-4-yl(9,9-diphenyl-9H-fluoren-2-yl)-[4-(9-phenyl-9H-carbazol-3-yl)phenyl]-amine was vacuum deposited on the HIL, to form a HTL having a thickness of 118 nm.
(101) Then N,N-bis(4-(dibenzo[b,d]furan-4-yl)phenyl)-[1,1′:4′,1″-terphenyl]-4-amine (CAS 1198399-61-9) was vacuum deposited on the HTL, to form an electron blocking layer (EBL) having a thickness of 5 nm.
(102) Then 97 vol.-% H09 (Sun Fine Chemicals) as EML host and 3 vol.-% BD200 (Sun Fine Chemicals) as fluorescent blue dopant were deposited on the EBL, to form a blue-emitting EML with a thickness of 20 nm.
(103) Then the hole blocking layer is formed with a thickness of 5 nm by depositing 2,4-diphenyl-6-(4′,5′,6′-triphenyl-[1,1′:2′,1′″:3′″,1′″:3′″,1″″-quinquephenyl]-3″″-yl)-1,3,5-triazine on the emission layer.
(104) Then, the electron transporting layer is formed on the hole blocking layer according to Examples 1 to 9 and comparative example 1 with a the thickness of 31 nm. The electron transport layer comprises 50 wt.-% matrix compound and 50 wt.-% of alkali organic complex, see Table 2.
(105) Then, the electron injection layer is formed on the electron transporting layer by deposing Yb with a thickness of 2 nm.
(106) Ag is evaporated at a rate of 0.01 to 1 Å/s at 10.sup.−7 mbar to form a cathode with a thickness of 11 nm.
(107) A cap layer of Biphenyl-4-yl(9,9-diphenyl-9H-fluoren-2-yl)-[4-(9-phenyl-9H-carbazol-3-yl)phenyl]-amine is formed on the cathode with a thickness of 75 nm.
(108) The OLED stack is protected from ambient conditions by encapsulation of the device with a glass slide. Thereby, a cavity is formed, which includes a getter material for further protection.
(109) To assess the performance of the inventive examples compared to the prior art, the current efficiency is measured at 20° C. The current-voltage characteristic is determined using a Keithley 2635 source measure unit, by sourcing a voltage in V and measuring the current in mA flowing through the device under test. The voltage applied to the device is varied in steps of 0.1V in the range between 0V and 10V. Likewise, the luminance-voltage characteristics and CIE coordinates are determined by measuring the luminance in cd/m.sup.2 using an Instrument Systems CAS-140CT array spectrometer for each of the voltage values. The cd/A efficiency at 10 mA/cm.sup.2 is determined by interpolating the luminance-voltage and current-voltage characteristics, respectively.
(110) Lifetime LT of the device is measured at ambient conditions (20° C.) and 30 mA/cm.sup.2, using a Keithley 2400 sourcemeter, and recorded in hours.
(111) The brightness of the device is measured using a calibrated photo diode. The lifetime LT is defined as the time till the brightness of the device is reduced to 97% of its initial value.
(112) The light output in external efficiency EQE and power efficiency (1 m/W efficiency) are determined at 10 mA/cm.sup.2 for top emission devices.
(113) To determine the efficiency EQE in % the light output of the device is measured using a calibrated photodiode.
(114) To determine the power efficiency in 1 m/W, in a first step the luminance in candela per square meter (cd/m2) is measured with an array spectrometer CAS140 CT from Instrument Systems which has been calibrated by Deutsche Akkreditierungsstelle (DAkkS). In a second step, the luminance is then multiplied by 7 and divided by the voltage and current density.
(115) Top Emission Devices
(116) In Table 2 is shown the performance of in organic electronic device comprising an organic semiconductor layer comprising triazine compound of formula 1 and an alkali organic complex.
(117) In comparative example 1 compound ETM-1 was used as matrix compound:
(118) ##STR00068##
(119) In comparative example 1, compound ETM-1 was used as matrix compound. The organic semiconductor layer comprises 50 vol.-% ETM-1 and 50 vol.-% LiQ. The operating voltage is 3.5 V and the cd/A efficiency is 8 cd/A. The lifetime is 37 hours.
(120) In Example 1, the organic semiconductor layer comprises 50 vol.-% compound of formula 1 MX1 and 50 vol.-% LiQ. The operating voltage is 3.5 V. The cd/A efficiency is 8 cd/A and the lifetime is improved to 47 hours.
(121) In Examples 2 to 9, further compounds of formula 1 have been tested in an organic semiconductor layer comprising 50 vol.-% compound of formula 1 and 50 vol.-% LiQ. The lifetime is always improved, see Table 2.
(122) TABLE-US-00002 TABLE 2 Performance data of organic electroluminescent device comprising an organic semiconductor layer comprising triazine compound of formula 1 and an alkali organic complex Concentration Thickness cd/A Concentration of alkali electron Operating efficiency of matrix Alkali organic transport voltage at at LT97 at Matrix compound organic complex layer 10 mA/cm.sup.2 10 mA/cm.sup.2 30 mA/cm.sup.2 compound (vol.-%) complex (vol.-%) (nm) (V) (cd/A) (h) Comparative ETM-1 50 LiQ 50 31 3.5 8.0 37 example 1 Example 1 MX1 50 LiQ 50 31 3.5 8.0 47 Example 2 MX2 70 LiQ 30 31 3.4 7.9 46 Example 3 MX3 50 LiQ 50 31 3.5 7.8 59 Example 4 MX4 50 LiQ 50 31 3.6 7.8 50 Example 5 MX5 50 LiQ 50 31 3.7 7.9 68 Example 6 MX6 50 LiQ 50 31 3.6 7.9 49 Example 7 MX7 70 LiQ 30 31 3.5 8.1 46 Example 8 MX8 50 LiQ 50 31 3.5 7.7 68 Example 9 MX9 50 LiQ 50 31 3.5 8.0 47
Technical Effect of the Invention
(123) As can be seen in Table 1 that the LUMO energy level (eV) of the compositions of examples 1 to 9 according to formula 1 are very low.
(124) In summary, improved lifetime and more negative LUMO energy level (eV) may be achieved when the organic semiconductor layer comprises a triazine compound of formula 1. High performance may be achieved for a wide range of alkali organic complexes
(125) While this invention has been described in connection with what is presently considered to be practical exemplary embodiments, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims. Therefore, the aforementioned embodiments should be understood to be exemplary but not limiting the present invention in any way.