SEE ADDENDUM

Abstract

The present invention relates to an organic semiconducting material comprising a compound comprising at least one dibenzo [c,h) acridine group and at least one CN-group, organic electronic devices comprising the same and display devices comprising the same.

Claims

1. Organic semiconducting material comprising a compound (I), the compound (I) comprising at least one dibenzo[c,h]acridine group and at least one CN-group, wherein the compounds represented by the following formulas (1) to (5) are excluded ##STR00033## ##STR00034##

2. Organic semiconducting material according to claim 1, wherein the compound (I) is represented by the following formula (Ia) ##STR00035## wherein R.sup.1 to R.sup.13 are independently selected from the group consisting of H, D, F, Cl, Br, I, substituted or unsubstituted C.sub.1 to C.sub.18 alkyl, substituted or unsubstituted C.sub.6 to C.sub.42 aryl, substituted or unsubstituted C.sub.3 to C.sub.42 heteroaryl, or CN, wherein two or more groups selected from R.sup.1 to R.sup.13 may be linked to form a non-aromatic ring; wherein at least one of R.sup.1 to R.sup.13 is CN or a group substituted with at least one CN; wherein the one or more substituent(s), if present in one of the groups R.sup.1 to R.sup.13, are independently selected from the group consisting of D, F, Cl, Br, I, C.sub.1 to C.sub.18 alkyl, C.sub.6 to C.sub.36 aryl, C.sub.6 to C.sub.42 heteroaryl, R.sup.14R.sup.15P=O with R.sup.14 and R.sup.15 independently being C.sub.1 to C.sub.18 alkyl or C.sub.6 to C.sub.24 aryl, and CN.

3. Organic semiconducting material according to claim 2, wherein one of R.sup.1 to R.sup.13 is independently selected from the group consisting of CN-substituted C.sub.6 to C.sub.42 aryl, CN-substituted C.sub.3 to C.sub.42 heteroaryl or CN, and the remaining R.sup.1 to R.sup.13 are H.

4. Compound according to claim 2, wherein R.sup.1 to R.sup.13 are independently selected from the group consisting of substituted or unsubstituted C.sub.6 to C.sub.42 aryl and H, wherein the one or more substituent(s), if present, are independently selected from C.sub.1 to C.sub.18 alkyl.

5. Organic semiconducting material according to claim 2, wherein R.sup.7 is CN-substituted C.sub.6 to C.sub.42 aryl, wherein further substituent(s), if present, are independently selected from C.sub.1 to C.sub.18 alkyl; and the remaining R.sup.1 to R.sup.6 and R.sup.8 to R.sup.13 are H.

6. Organic semiconducting material according to claim 2, wherein at least one of R.sup.1 to R.sup.13 is C.sub.12 to C.sub.18 aryl substituted with at least one CN-group and optionally further substituted with at least one C.sub.1 to C.sub.4 alkyl group.

7. Organic semiconducting material according to claim 6, wherein R.sup.7 is C.sub.12 to C.sub.18 aryl substituted with a CN-group and optionally further substituted with at least one C.sub.1 to C.sub.4 alkyl group and the remaining R.sup.1 to R.sup.6 and R.sup.8 to R.sup.13 are H.

8. Organic semiconducting material according to claim 1, wherein the compound (I) is a compound represented by one of the following structures A-1 to A-7 ##STR00036## ##STR00037##

9. Organic semiconducting material according to claim 1, wherein the organic semiconducting material further comprises at least one electrical dopant.

10. Organic electronic device comprising a first electrode, a second electrode and a semiconducting layer arranged between the first electrode and the second electrode, wherein the semiconducting layer comprises the organic semiconducting material according to claim 1.

11. Organic electronic device according to claim 10, wherein the semiconducting layer is an electron transport layer, an electron injection layer or an electron generating layer.

12. Organic electronic device according to claim 10, wherein the organic electronic device is an organic light emitting device, an organic photovoltaic device or an organic transistor.

13. Organic electronic device according to claim 12, wherein the organic light emitting device is an organic light emitting diode.

14. Display device comprising at least one organic light emitting devices according to claim 12.

15. Compound comprising at least one dibenzo[c,h]acridine group and at least one nitrile group, wherein compounds represented by the following formulas (1) to (22) are excluded. ##STR00038## ##STR00039## ##STR00040## ##STR00041## ##STR00042## ##STR00043##

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0202] 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:

[0203] FIG. 1 is a schematic sectional view of an organic light-emitting diode (OLED), according to an exemplary embodiment of the present invention;

[0204] FIG. 2 is a schematic sectional view of an OLED, according to an exemplary embodiment of the present invention.

[0205] FIG. 3 is a schematic sectional view of a tandem OLED comprising a charge generation layer, according to an exemplary embodiment of the present invention.

DETAILED DESCRIPTION

[0206] Reference will now be made in detail to the exemplary embodiments of the present invention, 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 of the present invention, by referring to the figures.

[0207] Herein, when a first element is referred to as being formed or disposed “on” or “onto” 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” or “directly onto” a second element, no other elements are disposed there between.

[0208] FIG. 1 is a schematic sectional view of an organic light-emitting diode (OLED) 100, according to an exemplary embodiment of the present invention. The OLED 100 includes a substrate 110, an anode 120, a hole injection layer (HIL) 130, a hole transport layer (HTL) 140, an emission layer (EML) 150, an electron transport layer (ETL) 160. The electron transport layer (ETL) 160 is formed on the EML 150. Onto the electron transport layer (ETL) 160, an electron injection layer (EIL) 180 is disposed. The cathode 190 is disposed directly onto the electron injection layer (EIL) 180.

[0209] Instead of a single electron transport layer 160, optionally an electron transport layer stack (ETL) can be used.

[0210] FIG. 2 is a schematic sectional view of an OLED 100, according to another exemplary embodiment of the present invention. FIG. 2 differs from FIG. 1 in that the OLED 100 of FIG. 2 comprises an electron blocking layer (EBL) 145 and a hole blocking layer (HBL) 155.

[0211] Referring to FIG. 2, the OLED 100 includes a substrate 110, an anode 120, a hole injection layer (HIL) 130, a hole transport layer (HTL) 140, an electron blocking layer (EBL) 145, an emission layer (EML) 150, a hole blocking layer (HBL) 155, an electron transport layer (ETL) 160, an electron injection layer (EIL) 180 and a cathode electrode 190.

[0212] Preferably, the organic semiconducting layer comprising a compound (I) or consisting of a compound (I) may be an EML, an HBL or an ETL.

[0213] FIG. 3 is a schematic sectional view of a tandem OLED 200, according to another exemplary embodiment of the present invention. FIG. 3 differs from FIG. 2 in that the OLED 200 of FIG. 3 further comprises a charge generation layer (CGL) and a second emission layer (151).

[0214] Referring to FIG. 3, the OLED 200 includes a substrate 110, an anode 120, a first hole injection layer (HIL) 130, a first hole transport layer (HTL) 140, a first electron blocking layer (EBL) 145, a first emission layer (EML) 150, a first hole blocking layer (HBL) 155, a first electron transport layer (ETL) 160, an n-type charge generation layer (n-type CGL) 185, a hole generating layer (p-type charge generation layer; p-type GCL) 135, a second hole transport layer (HTL) 141, a second electron blocking layer (EBL) 146, a second emission layer (EML) 151, a second hole blocking layer (EBL) 156, a second electron transport layer (ETL) 161, a second electron injection layer (EIL) 181 and a cathode 190.

[0215] Preferably, the organic semiconducting layer comprising a compound (I) or consisting of a compound (I) may be the first EML, first HBL, first ETL, n-type CGL and/or second EML, second HBL, second ETL.

[0216] While not shown in FIG. 1, FIG. 2 and FIG. 3, a sealing layer may further be formed on the cathode electrodes 190, in order to seal the OLEDs 100 and 200. In addition, various other modifications may be applied thereto.

[0217] Hereinafter, one or more exemplary embodiments of the present invention will be described in detail with, reference to the following examples. However, these examples are not intended to limit the purpose and scope of the one or more exemplary embodiments of the present invention.

Experimental Part

[0218] The invention is furthermore illustrated by the following example which are illustrative only and non-binding.

[0219] Preparation of Inventive Compounds:

SYNTHESIS OF PRECURSORS

[0220] ##STR00020##

3′-bromo-5′-chloro-[1,1′-biphenyl]-3-carbonitrile

[0221] ##STR00021##

[0222] 3′-bromo-5′-chloro-[1,1′-biphenyl]-3-carbonitrile was synthesized following the procedure described in the literature for the synthesis of 3′-bromo-5′-chloro-[1,1′-biphenyl]-4-carbonitrile (Journal of Medicinal Chemistry, 56(13), 5473-5494; 2013)

3′-chloro-5′-(phenanthren-9-yl)-[1,1′-biphenyl]-4-carbonitrile

[0223] ##STR00022##

[0224] A flask was flushed with nitrogen and charged with phenanthren-9-ylboronic acid (9.7 g, 43.8 mmol), 3′-bromo-5′-chloro-[1,1′-biphenyl]-4-carbonitrile (12.8 g, 43.8 mmol), tetrakis(triphenylphosphin)palladium(0) (1.0 g, 0.9 mmol), and potassium carbonate (12.0 g, 87.5 mmol). A mixture of deaerated toluene/THF/water (1:1:0.5, 174 mL) was added and the reaction mixture was heated to 90° C. under a nitrogen atmosphere over 23 hours. After cooling down to room temperature, the solvent was removed under reduced pressure. The crude product was then dissolved in chloroform (600 mL) and the organic phase was washed with water (4×100 mL). After drying over MgSO.sub.4, the organic phase was filtered through a silicagel pad. The filtrate was concentrated under reduced pressure and n-hexane (250 mL) was added to the resulting oil. The resulting suspension was stirred at room temperature overnight. The precipitate was collected by suction filtration and washed with n-hexane. Crude product was used directly in the next step.

SYNTHESIS OF FINAL COMPOUNDS

3′-(dibenzo[c,h]acridin-7-yl)-[1,1′-biphenyl]-3-carbonitrile A1

[0225] ##STR00023##

[0226] A flask was flushed with argon and charged with 7-(3-bromophenyl)dibenzo[c,h]acridine (15.0 g, 34.0 mmol), (3-cyanophenyl)boronic acid (6.1 g, 41.4 mmol), potassium carbonate (14.3 g, 103.6 mmol) in deaerated water (45 mL) and deaerated glyme (175 mL). Tetrakis(triphenylphosphin)palladium(0) (798 mg, 0.69 mmol) was added and the reaction mixture was heated to 95° C. under an argon atmosphere overnight. After cooling down to room temperature, the resulting precipitate was isolated by suction filtration and washed with glyme (2×5 mL), water (500 mL), glyme (5 ml) again and n-hexane (2×10 mL). The crude product was then dissolved in dichloromethane (500 mL) and filtered through a pad of silica. After rinsing with additional dichloromethane (400 mL), the filtrate was concentrated under reduced pressure. The resulting precipitate was isolated by suction filtration and washed with n-hexane. Finally, it was dissolved in dichloromethane (300 mL). Toluene (100 mL) was added and the dichloromethane was removed under reduced pressure. The resulting precipitate was recrystallized in dimethylformamide (70 mL) to yield 8.8 g (55%) of a colourless solid after drying. Final purification was achieved by sublimation. HFLC/ESI-MS: m/z=457 ([M+II]+).

3′-(dibenzo[c,h]acridin-7-yl)-[1,1′-biphenyl]-4-carbonitrile A2

[0227] ##STR00024##

[0228] A flask was flushed with argon and charged with 7-(3-bromophenyl)dibenzo[c,h]acridine (20.0 g, 46.0 mmol), (4-cyanophenyl)boronic acid (8.1 g, 55.3 mmol) and tetrakis(triphenylphosphin)palladium(0) (1.1 g, 0.9 mmol) A deaerated aqueous solution of potassium carbonate (19.1 g, 138.0 mmol), water (70 mL) and deaerated glyme (230 mL) were added and the reaction mixture was heated to 95 ° C. under an argon atmosphere overnight. After cooling down to room temperature, the phases were separated and glyme was removed under reduced pressure. The crude product was then dissolved in dichloromethane and filtered through a pad of silica. After rinsing with additional dichloromethane, the filtrate was concentrated under reduced pressure, n-hexane was added and the solution was stirred over 1 hour. The resulting precipitate was isolated by suction filtration and washed with n-hexane. The crude product was further purified by recrystallization from toluene to yield 19.2 g (91%) of a colourless solid after drying. Final purification was achieved by sublimation. HPLC/ESI-MS: m/z=457 ([M+H]+).

4′(dibenzo[c,h]acridin-7-yl)-[1,1′-biphenyl]-3-carbonitrile A3

[0229] ##STR00025##

[0230] A flask was flushed with nitrogen and charged with 7-(4-bromophenyl)dibenzo[c,h]acridine (10.0 g, 23.0 mmol), (3-cyanophenyl)boronic acid (4.1 g, 27.6 mmol) and potassium carbonate (9.5 g, 69.0 mmol). A mixture of deaerated glyme/water—6.5:1 (265 mL) and tetrakis(triphenylphosphin)palladium(0) (532 mg, 0.5 mmol) were added and the reaction mixture was heated to 100° C. under a nitrogen atmosphere overnight. After cooling down to room temperature, the resulting precipitate was isolated by suction filtration and washed with toluene (50 mL), water (40 mL) and methanol (60 mL). The crude product was then dissolved in hot chlorobenzene (500 mL), filtered through a pad of silica and rinsed with additional hot chlorobenzene (600 mL). After cooling down to room temperature overnight, the resulting precipitate was isolated by suction filtration to yield 6.2 g (57%) of a bright yellow solid after drying. Final purification was achieved by sublimation. HPLC/ESI-MS: m/z=457.1 ([M+H].sup.+).

4(dibenzo[c,h]acridin-7-yl)-[1,1′:3,1″-terphenyl]-4-carbonitrile A4

[0231] ##STR00026##

[0232] A suspension of 7-(4-bromophenyl)dibenzo[c,h]acridine (10.0 g, 23.0 mmol), 3′-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-[1,1′-biphenyl]-4-carbonitrile (8.4 g, 27.6 mmol) and [1,1′-bis(diphenylphosphino)ferrocene]dichloropalladium(II) (505 mg, 0.69 mmol) in toluene/THF/water—4:1:1 (140 mL) was degassed with nitrogen. Potassium carbonate (6.36 g, 46.0 mmol) was added and the reaction mixture was heated to 70° C. under a nitrogen atmosphere overnight. After cooling down to room temperature, the resulting precipitate was isolated by suction filtration and washed with water (50 mL), methanol (50 mL), toluene (2×50 mL) and additional methanol (50 mL). The crude product was then dissolved in hot chloroform and filtered through a pad of florisil. After rinsing with additional hot chloroform (250 mL), the filtrate was concentrated under reduced pressure to a volume of 200 mL and n-hexane (200 mL) was added. The resulting precipitate was collected by suction filtration and washed with n-hexane (50 mL) The crude product was further purified by recrystallization from chlorobenzene to yield 8.7 g (71%) of a light yellow solid after drying. Final purification was achieved by sublimation. HPLC/ESI-MS: m/z=533.1 ([M+H]+).

4″-(dibenzo[c,h]acridin-7-yl)-[1,1′:4′,1″-terphenyl]-3-carbonitrile A5

[0233] ##STR00027##

[0234] A suspension of 7-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)dibenzo[c,h]acridine (5.0 g, 10.4 mmol), 4′-bromo-[1,1′-biphenyl]-3-carbonitrile (3.2 g, 12.5 mmol) and [1,1′-Bis(diphenylphosphino)ferrocene]dichloropalladium (II) (228 mg, 0.3 mmol) in toluene/THF/ water—4:1:1 (140 mL) was degassed with nitrogen. Potassium carbonate (6.4 g, 46.0 mmol) was added and the reaction mixture was heated to 70° C. under a nitrogen atmosphere overnight. Additional [1,1′-Bis(diphenylphosphino)ferrocene]dichloropalladium (II) (114 mg, 0.15 mmol) and toluene (50 mL) was added and the reaction mixture was heated to 80° C. under a nitrogen atmosphere overnight. After cooling down to room temperature, the resulting precipitate was isolated by suction filtration and washed with toluene, water and methanol. The crude product was further purified by Soxhlet extraction with chlorobenzene overnight. After cooling down to room temperature, the resulting precipitate was isolated by suction filtration and washed with methanol to yield 2.6 g (47%) of a beig solid after drying. Final purification was achieved by sublimation. HPLC/ESI-MS: 99.94% , m/z=533.1 ([M+H].sup.+).

4″-(dibenzo[c,h]acridin-7-yl)-[1,1′:4′,1″-terphenyl]-4-carbonitatile A6

[0235] ##STR00028##

[0236] A flask was flushed with nitrogen and charged with 7-(4-bromophenyl)dibenzo[c,h]acridine (10.0 g, 23.0 mmol), 4′-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-[1,1′-biphenyl]-4-carbonitrile (8.4 g, 27.6 mmol) and [1,1′-Bis(diphenylphosphino)ferrocene]dichloropalladium(II) (505 mg, 0.7 mmol). A mixture of deaerated Toluene/THF 7:3 (230 mL) and a deaerated solution of potassium carbonate (6.4 g, 46.0 mmol) in water (23 mL) was added and the reaction mixture was heated to 80° C. under a nitrogen atmosphere overnight. After cooling down to room temperature, the resulting precipitate was isolated by suction filtration and washed with water and methanol. The crude product was further purified by soxhlet extraction with chlorobenzene over 48 h. After cooling down to room temperature, the resulting precipitate was isolated by suction filtration, washed with methanol and further purified by trituration in chlorobenzene to yield 7.0 g (57%) of a slightly grey solid. Final purification was achieved by sublimation. HPLC/ESI-MS: m/z=533.2 ([M+H].sup.+).

4′-(dibenzo[c,h]acridin-7-yl)-2-methyl-[1,1′-biphenyl]-4-carbonitrile A7

[0237] ##STR00029##

[0238] A flask was flushed with nitrogen and charged with 7-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenybdibenzo[c,h]acridine (10.0 g, 20.8 mmol) and 4-bromo-.sub.3-methylbenzonitille (4.5 g, 22.9 mmol). A deaerated solution of potassium carbonate (5.74 g, 41.5 mmol) in water (21 mL), a mixture of deaerated (toluene/THF—3:1) (170 mL) and [1,1′-bis(diphenylphosphino)ferrocene]dichloropalladium(II) (304 mg, 0.4 mmol) were added and the reaction mixture was heated to 80° C. under a nitrogen atmosphere over 96 h. After cooling down to room temperature, the resulting precipitate was isolated by suction filtration and washed with water (700 mL) and methanol (20 mL). The crude product was then dissolved in hot chlorobenzene (800 mL) and filtered through a pad of silica. After rinsing with additional hot chlorobenzene (500 mL), the filtrate was concentrated under reduced pressure to a volume of 200 mL. After cooling down to room temperature, the resulting precipitate was isolated by suction filtration and washed with n-hexane (10 mL) to yield 7.9 g (81%) of a yellow solid after drying. Final purification was achieved by sublimation. HPLC/ESI-MS: m/z=471.2 ([M+H].sup.+).

Device Examples

[0239] ##STR00030## ##STR00031##

[0240] H09 is an emitter host and BD200 is a fluorescent emitter, both supplied by SFC, Korea.

[0241] LiQ is lithum 8-hydroxyquinolinolate.

[0242] Comparative State-of-Art Compounds

##STR00032##

[0243] Experimental Blue OLED I

[0244] On a 100 nm thick silver anode vacuum deposited on a glass substrate, following layers were vacuum deposited in the given order: 10 nm thick HIL consisting of F1 and PD1 in weight ratio 92:8; 118 nm thick HTL consisting of neat F1, 5 nm thick EBL consisting of neat F2, 20 nm thick EML consisting of H09 and BD200 in weight ratio 97:3, 20 nm thick HBL consisting of F3, 31 nm thick ETL consisting of the inventive or comparative electron transport matrix compound and LiQ in weight ratio 50:50; 2 nm thick EIL consisting of neat Yb, 13 nm thick cathode consisting of Ag and Mg in weight ratio 90:10, and 75 nm thick cap layer consisting of neat F1. The obtained results are shown in Table 1.

TABLE-US-00001 TABLE 1 Tg Voltage Current efficiency lifetime compound [° C.] [V] [cd/A] [h] A1 97 3.54 7.47 62 A2 109 3.57 7.62 53 A3 103 3.53 7.21 49 A4 124 3.49 7.14 32 A5 120 3.58 7.41 55 A6 3.63 7.31 67 A7 3.52 7.80 64 B1 117 3.59 7.21 88 B2 123 3.51 8.62 32

[0245] Experimental Blue OLED II

[0246] In the experimental blue OLED I, the auxiliary HBL compound F3 has been replaced with compound F4. The obtained results are shown in Table 2.

TABLE-US-00002 TABLE 2 Voltage Current lifetime compound [V] efficiency [cd/A] [h] A1 3.63 7.0 94 A2 3.61 7.1 78 A3 3.60 6.9 90 A4 3.57 6.8 106 A5 3.67 6.7 92 A6 3.72 6.7 99 A7 3.63 7.1 100 B1 3.70 6.4 141

[0247] The features disclosed in the foregoing description and in the dependent claims may, both separately and in any combination thereof, be material for realizing the aspects of the disclosure made in the independent claims, in diverse forms thereof.