Organic light emitting device and compounds for use in same

Abstract

Specific polycyclic compounds of the general formula (I) and a process for its preparation, an electronic device comprising at least one of these compounds, an emitting layer, preferably present in an electronic device, comprising at least one compound of general formula (I) and the use of compounds according to general formula (I) in an electronic device as a host material, a charge transporting material, charge and/or exciton blocking material, preferably as a host material or an electron transporting material. ##STR00001##

Claims

1. A polycyclic compound represented by formula (I): ##STR00096## wherein, R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.8, R.sup.9, R.sup.10, R.sup.11, R.sup.12, R.sup.13 and R.sup.14 are independently of each other hydrogen, an unsubstituted or substituted C.sub.6-C.sub.24aryl group, an unsubstituted or substituted C.sub.1-C.sub.30heteroaryl group, an unsubstituted or substituted C.sub.1-C.sub.25alkyl group, an unsubstituted or substituted C.sub.7-C.sub.25aralkyl group, an unsubstituted or substituted C.sub.5-C.sub.12cycloalkyl group, —NR.sup.15R.sup.16, —OR.sup.17, —SR.sup.18, —SiR.sup.19R.sup.20R.sup.21, —CN or halogen, wherein two of R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.8, R.sup.9, R.sup.10, R.sup.11 and R.sup.12, if present at adjacent carbon atoms, together may form an unsubstituted or substituted C.sub.6-C.sub.18aryl ring; L.sub.1 is a direct bond, an unsubstituted or substituted C.sub.6-C.sub.24arylene group, or an unsubstituted or substituted C.sub.1-C.sub.30heteroarylene group; and Ar.sup.1 is an unsubstituted or substituted C.sub.6-C.sub.24aryl group, or an unsubstituted or substituted C.sub.1-C.sub.30heteroaryl group; R.sup.15 and R.sup.16 are independently of each other H, a C.sub.6-C.sub.18aryl group which is unsubstituted or substituted by at least one C.sub.1-C.sub.18alkyl group or at least one C.sub.1-C.sub.18alkoxy group, a C.sub.1-C.sub.18alkyl group or a C.sub.1-C.sub.18alkyl group, which is interrupted by at least one O, or R.sup.15 and R.sup.16 together form a five or six membered aliphatic, aromatic or heteroaromatic ring; R.sup.17 and R.sup.18 are independently of each other H, a C.sub.6-C.sub.18aryl group which is unsubstituted or substituted by at least one C.sub.1-C.sub.18alkyl group or at least one C.sub.1-C.sub.18alkoxy group, a C.sub.1-C.sub.18alkyl group or a C.sub.1-C.sub.18alkyl group, which is interrupted by at least one O; R.sup.19, R.sup.20 and R.sup.21 are independently of each other a C.sub.1-C.sub.18alkyl group, a C.sub.6-C.sub.18aryl group which is unsubstituted or substituted by at least one C.sub.1-C.sub.18alkyl group.

2. The polycyclic compound according to claim 1, wherein Ar.sup.1 is an unsubstituted or substituted C.sub.6-C.sub.16aryl group, or an unsubstituted or substituted C.sub.3-C.sub.15heteroaryl group.

3. The polycyclic compound according to claim 1, wherein L.sub.1 is a direct bond, an unsubstituted or substituted C.sub.6-C.sub.13arylene group, or an unsubstituted or substituted C.sub.3-C.sub.12heteroarylene group.

4. The polycyclic compound according to claim 1, wherein R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.8, R.sup.9, R.sup.10, R.sup.11, R.sup.12, R.sup.13 and R.sup.14 are independently of each other hydrogen, an unsubstituted or substituted C.sub.6-C.sub.10aryl group, an unsubstituted or substituted C.sub.3-C.sub.13heteroaryl group, an unsubstituted or substituted C.sub.1-C.sub.8alkyl group, —CN or halogen; wherein two of R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.8, R.sup.9, R.sup.10, R.sup.11 and R.sup.12, if present at adjacent carbon atoms, together may form an unsubstituted or substituted C.sub.6-C.sub.18aryl ring.

5. The polycyclic compound according to claim 1, represented by one of the following formula (Ia) or (Ib) ##STR00097##

6. The polycyclic compound according to claim 1, wherein L.sup.1 is a direct bond, and Ar.sup.1 is an unsubstituted or substituted fluoranthene group, or an unsubstituted or substituted quinazoline group, an unsubstituted or substituted benzoquinazoline group, or a group of formula (A) ##STR00098## wherein X is O, NR, CR′.sub.2 or S, R is an unsubstituted or substituted C.sub.6-C.sub.10 aryl group; R′ is C.sub.1-C.sub.4-alkyl; m is 0, 1, 2, 3 or 4; n is 0, 1, 2 or 3; R″ and R′″ are independently of each other an unsubstituted or substituted C.sub.6-C.sub.24aryl group, an unsubstituted or substituted C.sub.1-C.sub.30heteroaryl group, an unsubstituted or substituted C.sub.1-C.sub.25alkyl group, an unsubstituted or substituted C.sub.7-C.sub.25aralkyl group, an unsubstituted or substituted C.sub.5-C.sub.12cycloalkyl group, —NR.sup.15R.sup.16, —OR.sup.17, —SR.sup.18, —SiR.sup.19R.sup.20R.sup.21, —CN or halogen, and the dotted line is a bonding site.

7. A process for the preparation of a compound according to the general formula (I) as defined in claim 1, at least comprising step (A) or step (A*): (A) Coupling a compound of formula (IIa) ##STR00099## with a compound of formula ##STR00100## wherein Y is a halide selected from the group consisting of I, F, Cl and Br, or a pseudohalide selected from the group consisting of mesylate, triflate, tosylate and nonaflate, or (A*) In the case that L.sup.1 is not a single bond—coupling a compound of formula (IIb) ##STR00101## with a compound of formula ##STR00102## wherein one of Q.sup.1 and Q.sup.2 is a halide selected from the group consisting of I, F, Cl and Br, or a pseudohalide selected from the group consisting of mesylate, triflate, tosylate and nonaflate; and the other of Q.sup.1 and Q.sup.2 is BZ.sub.2, and Z is C.sub.1-C.sub.8alkyl, OH, or O—C.sub.1-C.sub.8alkyl, wherein the two alkyl groups in the group BZ.sub.2 may form together with the B and the two oxygen atoms a cyclic group which may be unsubstituted or substituted and/or fused.

8. An electronic device comprising at least one compound as defined in claim 1.

9. The electronic device according to claim 8, comprising a cathode, an anode, and a plurality of organic thin film layers provided between the cathode and the anode, the organic thin film layers comprising an emitting layer comprising the at least one compound of general formula (I).

10. The electronic device according to claim 9, wherein the emitting layer comprises a phosphorescent material, which is an ortho-metallated complex comprising a metal atom selected from iridium (Ir), osmium (Os) and platinum (Pt).

11. An electronic equipment comprising the electronic device according to claim 8.

12. An emitting layer comprising at least one compound of general formula (I) as defined in claim 1.

Description

EXAMPLES

(1) Compounds Synthesized

(2) ##STR00072##

(3) 1-Naphthaleneboronic acid (15.48 g, 90 mmol) and 2-bromo-6-chlorobenzaldehyde (19.7 g, 90 mmol) were dissolved in 200 mL of THF. To the solution was added potassium fluoride (15.7 g, 270 mmol) dissolved in 50 mL of water, and the mixture was evacuated and purged with Argon gas. Then, .sup.tBu.sub.3P—HBF.sub.4 (2.09 g, 7.2 mmol) and Pd.sub.2(dba).sub.3 (3.30 g, 3.6 mmol) were added to the mixture, and the mixture was stirred at 50° C. overnight. The reaction mixture was cooled at room temperature, and the solid was removed by filtration. The filtrate was extracted with ethyl acetate. The organic layer was collected, dried with MgSO4, and concentrated. The crude product was purified by column chromatography on silica gel eluting with a mixed solvent of heptane and dichloromethane to yield 16.4 g (68%) of 1-1 as a white powder.

(4) LC-MS: 267 [M+H]

(5) ##STR00073##

(6) (Methoxymethyl)triphenylphosphonium chloride (11.0 g, 32.1 mmol) was suspended in 80 mL of THF, and potassium t-butoxide (3.24 g, 28.9 mmol) were added. The suspension was stirred at room temperature for 1 h. 1-1 (4.28 g, 16.1 mmol) dissolved in 16 mL of THF was added to the suspension at room temperature, and the mixture was stirred at room temperature overnight. The mixture was filtered, washed out with dichloromethane, and then the filtrate was concentrated. The crude product was purified by column chromatography eluting with heptane and dichloromethane to yield 7.68 g of 1-2 as a beige solid.

(7) The product was used for the next reaction without further purification.

(8) ##STR00074##

(9) 1-2 (11.8 g, 40 mmol) was dissolved in 200 mL of dichloromethane, and the solution was cooled at 0° C. To the solution was added dropwise methanesulfonic acid (2.28 g, 23.7 mmol) at 0° C., and the mixture was stirred at room temperature overnight. The reaction mixture was gradually poured into ice-water. The layers were separated, and the aqueous layer was extracted with dichloromethane. The organic layer was dried with MgSO.sub.4. After removal of the solvent, the crude product was purified by column chromatography on silica gel eluting with a mixed solvent of heptane and dichloromethane to yield 6.76 g (64%) of 1-3 as a beige solid.

(10) LC-MS: 264 [M+H]

(11) ##STR00075##

(12) 1-3 (4.89 g, 18.6 mmol), 4, 4, 4′, 4′, 5, 5, 5′, 5′-Octamethyl-2, 2′-bi-1, 3, 2-dioxaborolane (5.67 g, 22.3 mmol), and potassium acetate (4.57 g, 46.5 mmol) were suspended in 25 mL of 1,4-dioxane. Then, Pd.sub.2(dba).sub.3 (256 mg, 0.28 mmol) and s-Phos (229 mg, 0.56 mmol) were added, and the mixture was refluxed overnight under Argon atmosphere. The reaction mixture was cooled at room temperature, the solid was removed by filtration, and the filtrate was washed with water. The organic layer was dried with MgSO.sub.4. After removal of the solvent, the crude product was purified by column chromatography on silica gel eluting with a mixed solvent of toluene and heptane to yield 4.88 g (74%) of 1-4 as a beige solid.

(13) The product was used for the next reaction without further purification.

(14) ##STR00076##

(15) 1-4 (4.78 g, 13.5 mmol) and 1-bromo-2-nitrobenzene (2.86 g, 14.2 mmol) were dissolved in 81 mL of toluene and 41 mL of ethanol, and potassium acetate (3.73 g, 27.0 mmol) dissolved in 14 mL of water was added there. Then, Pd(PPh.sub.3).sub.4 (468 mg, 0.41 mmol) was added. After the mixture was evacuated and purged with Argon, the mixture was stirred at 80° C. for 3.5 h. The crude product was taken up in dichloromethane-heptane and partly evaporated. The precipitated solid was filtered off to yield 4.21 g (89%) of 1-5 as a yellow powder.

(16) LC-MS: 349 [M+H]

(17) ##STR00077##

(18) 1-5 (3.46 g, 9.90 mmol) and triphenylphosphine (7.79 g, 29.7 mmol) were suspended into 10 mL of 1,2-dichlorobenzene, and the mixture was stirred at 200° C. for 25 h. The reaction mixture was cooled at room temperature, and the solvent was evaporated under vacuum. The crude product was purified by column chromatography on silica gel eluting with a mixed solvent of toluene and cyclohexane to yield 2.38 g (76%) of 1-6 as a yellow solid.

(19) LC-MS: 317 [M+H]

(20) ##STR00078##

(21) 1-6 (1.06 g, 3.34 mmol), 2-chloro-[1]benzopyrano[4,3,2-de]quinazoline (851 mg, 3.34 mmol)(prepared according to the Scheme disclosed in WO2017109727), and potassium carbonate (923 mg, 6.68 mmol) were suspended in 17 mL of DMF. The mixture was stirred at 140° C. for 4 h. The reaction mixture was diluted with ethanol and water, and filtered off. The crude product was recrystallized with a mixed solvent of chlorobenzene and toluene to yield 1.56 g (87%) of Compound 1 as a yellow solid.

(22) LC-MS: 536 [M+H]

(23) ##STR00079##

(24) 1-6 (1.20 g, 3.78 mmol), 2-chloro-4-phenylquinazoline (1.00 g, 4.16 mmol), and sodium tert-butoxide (509 mg, 5.29 mmol) were added to 21 mL of toluene. Then, .sup.tBu.sub.3P—HBF.sub.4 (88 mg, 0.302 mmol) and Pd.sub.2(dba).sub.3 (69 mg, 0.076 mmol) were added to the mixture. After the mixture was evacuated and purged with Argon gas three times, the mixture was stirred at 110° C. for 15 h. The reaction mixture was diluted with ethanol and filtered off. The solid was washed with toluene, ethanol, and water. The solid was dried under vacuum at 70° C. The crude product was purified by column chromatography on silica gel eluting with a mixed solvent of dichloromethane and heptane to yield 1.44 g (73%) of Compound 2 as a yellow solid.

(25) LC-MS: 521 [M+H]

(26) ##STR00080##

(27) 1-6 (1.60 g, 5.04 mmol), 3-bromofluoranthene (1.47 g, 5.04 mmol), and sodium tert-butoxide (678 mg, 7.06 mmol) were added to 50 mL of xylene. Then, xantphos (146 mg, 0.252 mmol) and Pd.sub.2(dba).sub.3 (115 mg, 0.126 mmol) were added to the mixture. After the mixture was evacuated and purged with Argon gas three times, the mixture was stirred at 145° C. for 15.5 h. The reaction mixture was diluted with ethanol and filtered off. The solid was washed with toluene, ethanol and water. The solid was dried in vacuum at 70° C. The crude product was purified by column chromatography on silica gel eluting with a mixed solvent of dichloromethane and heptane to yield 2.38 g (91%) of Compound 3 as a yellow solid.

(28) LC-MS: 517 [M+H]

(29) ##STR00081##

(30) 1-6 (1.07 g, 3.37 mmol), 8-chloro-fluoranthene (798 mg, 3.37 mmol), and sodium tert-butoxide (454 mg, 4.72 mmol) were added to 19 mL of xylene. Then, .sup.tBu.sub.3P—HBF.sub.4 (78 mg, 0.270 mmol) and Pd.sub.2(dba).sub.3 (62 mg, 0.067 mmol) were added to the mixture. After the mixture was evacuated and purged with Argon gas three times, the mixture was stirred at 135° C. for 40 h. The reaction mixture was filtered off. The solid was washed with toluene, ethanol and water. The solid was dried under vacuum at 70° C. The crude product was purified by column chromatography on silica gel eluting with a mixed solvent of dichloromethane and heptane to yield 1.60 g (92%) of Compound 4 as a yellow solid.

(31) LC-MS: 517 [M+H]

(32) ##STR00082##

(33) 1-6 (1.06 g, 3.34 mmol), (3-bromophenyl)-3-fluoranthene (1.19 g, 3.34 mmol), and sodium tert-butoxide (449 mg, 4.68 mmol) were added to 19 mL of xylene. Then, .sup.tBu.sub.3P—HBF.sub.4 (78 mg, 0.270 mmol) and Pd.sub.2(dba).sub.3 (62 mg, 0.067 mmol) were added to the mixture. After the mixture was evacuated and purged with Argon gas three times, the mixture was stirred at 135° C. for 40 h. The reaction mixture was filtered off. The solid was washed with toluene, ethanol and water. The solid was dried in vacuum at 70° C. The crude product was purified by column chromatography on silica gel eluting with a mixed solvent of toluene and heptane to yield 1.83 g (92%) of Compound 5 as a yellow solid.

(34) LC-MS: 593 [M+H]

(35) ##STR00083##

(36) 9-Phenanthreneboronic acid (11.10 g, 50.0 mmol) and 2-bromo-6-chlorobenzaldehyde (11.0 g, 50.0 mmol) were dissolved in 200 mL of THF. To the solution was added potassium fluoride (8.72 g, 150 mmol) dissolved in 50 mL of water, and the mixture was evacuated and purged with Argon gas. Then, .sup.tBu.sub.3P—HBF.sub.4 (1.60 g, 5.50 mmol) and Pd.sub.2(dba).sub.3 (2.34 g, 2.55 mmol) were added to the mixture, and the mixture was stirred at 60° C. overnight. The reaction mixture was cooled at room temperature, and the solid was removed by filtration. The filtrate was extracted with ethyl acetate. The organic layer was collected, dried with MgSO4, and concentrated. The crude product was purified by column chromatography on silica gel eluting with a mixed solvent of heptane and toluene to yield 11.1 g (70%) of 6-1 as a white powder.

(37) LC-MS: 316 [M+H]

(38) ##STR00084##

(39) (Methoxymethyl)triphenylphosphonium chloride (4.83 g, 14.1 mmol) was suspended in 30 mL of THF, and sodium t-butoxide (1.22 g, 12.67 mmol) were added. The suspension was stirred at room temperature for 1 h. 6-1 (2.23 g, 7.04 mmol) dissolved in 15 mL of THF was added to the suspension at room temperature, and the mixture was stirred at room temperature overnight. The mixture was filtered, and washed out with dichloromethane, and then the filtrate was concentrated. The crude product was purified by column chromatography eluting with heptane and dichloromethane to yield 2.10 g of 6-2 as a beige solid.

(40) The product was used for the next reaction without further purification.

(41) ##STR00085##

(42) 6-2 (8.75 g, 25.4 mmol) was dissolved in 127 mL of dichloromethane, and the solution was cooled at 0° C. To the solution was added dropwise methanesulfonic acid (2.28 g, 23.7 mmol) at 0° C., and the mixture was stirred at room temperature overnight. The reaction mixture was gradually poured into ice-water. The layers were separated, and the aqueous layer was extracted with dichloromethane. The organic layer was dried with MgSO.sub.4. After removal of the solvent, the crude product was purified by column chromatography on silica gel eluting with a mixed solvent of heptane and dichloromethane to yield 6.68 g (84%) of 6-3 as a white solid.

(43) LC-MS: 313 [M+H]

(44) ##STR00086##

(45) 6-3 (6.65 g, 21.3 mmol), 4, 4, 4′, 4′, 5, 5, 5′, 5′-octamethyl-2, 2′-bi-1, 3, 2-dioxaborolane (6.48 g, 25.5 mmol), and potassium acetate (5.22 g, 53.1 mmol) were suspended in 112 mL of 1,4-dioxane. Then, Pd.sub.2(dba).sub.3 (389 mg, 0.43 mmol) and s-Phos (262 mg, 0.64 mmol) were added, and the mixture was refluxed overnight under Argon atmosphere. The reaction mixture was cooled at room temperature, the solid was removed by filtration, and the filtrate was washed with water. The organic layer was dried with MgSO.sub.4. After removal of the solvent, the crude product was purified by column chromatography on silica gel eluting with a mixed solvent of toluene and heptane to yield 6.00 g (70%) of 6-4 as a beige solid.

(46) The product was used for the next reaction without further purification.

(47) ##STR00087##

(48) 6-4 (6.00 g, 14.8 mmol) and 1-bromo-2-nitrobenzene (3.15 g, 15.6 mmol) were dissolved in 74 mL of toluene and 37 mL of ethanol, and potassium acetate (4.10 g, 29.7 mmol) dissolved in 12 mL of water was added there. Then, Pd(PPh.sub.3).sub.4 (514 mg, 0.45 mmol) was added. The mixture was evacuated and backfilled with Argon, and then the mixture was stirred at 80° C. for 17 h. The reaction mixture was passed through celite, and washed out with toluene. The layers were separated, and the aqueous layer was extracted with toluene. The organic layer was washed with brine, and dried with MgSO4. The crude product was recrystallized with ethyl acetate and heptane to yield 5.24 g (88%) of 6-5 as a yellow powder.

(49) LC-MS: 399 [M+H]

(50) ##STR00088##

(51) 6-5 (5.24 g, 13.12 mmol) and triphenylphosphine (10.32 g, 39.4 mmol) were suspended into 1,2-dichlorobenzene (3 mL), and stirred at 180° C. overnight. The reaction mixture was cooled at room temperature, and the solvent was evaporated under vacuum. The crude product was purified by column chromatography on silica gel eluting with a mixed solvent of dichloromethane and heptane to yield 4.13 g (86%) of 6-6 as a yellow solid.

(52) LC-MS: 367 [M+H]

(53) ##STR00089##

(54) 6-6 (517 mg, 1.41 mmol), 3-bromofluoranthene (515 mg, 1.83 mmol), and sodium tert-butoxide (190 mg, 1.98 mmol) were added to 8 mL of xylene. Then, xantphos (65 mg, 0.112 mmol) and Pd.sub.2(dba).sub.3 (52 mg, 0.056 mmol) were added to the mixture. After the reaction mixture was evacuated and purged with Argon gas three times, the mixture was stirred at 145° C. for 17.5 h. The reaction mixture was filtered off. The solid was washed with toluene, ethanol, and water. The solid was dried under vacuum at 70° C. The crude product was purified by column chromatography on silica gel eluting with chloroform to yield 324 mg (41%) of Compound 6 as a yellow solid.

(55) LC-MS: 567 [M+H]

APPLICATION EXAMPLES

Comparative Application Example 1

(56) A glass substrate with 120 nm-thick indium-tin-oxide (ITO) transparent electrode (manufactured by Geomatec Co., Ltd.) used as an anode was first cleaned with isopropanol in an ultrasonic bath for 10 min. To eliminate any possible organic residues, the substrate was exposed to an ultraviolet light and ozone for further 30 min. This treatment also improved the hole injection properties of the ITO. The cleaned substrate was mounted on a substrate holder and loaded into a vacuum chamber. Thereafter, the organic materials specified below were applied by vapor deposition to the ITO substrate at a rate of approx. 0.2-1 Å/sec at about 10.sup.−6-10.sup.−8 mbar. As a hole injection layer, 5 nm-thick of compound HI was applied. Then 220 nm-thick of compound HT1 was applied as hole transporting layer 1. Subsequently, a mixture of 2% by weight of an emitter compound (EM), 98% by weight of a host (Comparative compound 1) were applied to form a 40 nm-thick phosphorescent-emitting layer. On the emitting layer, 30 nm-thick layer of coevaporated compound ET and Liq at ratio 1:1 by weight was applied as an electron transport layer. Finally, 1 nm-thick Liq was deposited as an electron injection layer and 80 nm-thick Al was then deposited as a cathode to complete the device. The device was sealed with a glass lid and a getter in an inert nitrogen atmosphere with less than 1 ppm of water and oxygen. To characterize the OLED, the current-voltage characteristic was measured in combination with the luminance to determine current efficiency and driving voltage (V). Driving voltage (V) and current efficiency were given at current density of 10 mA/cm.sup.2. Lifetime of devices was measured at constant current of 50 mA/cm.sup.2. The device results are shown in Table 1.

(57) ##STR00090## ##STR00091##

Comparative Application Examples 2 and 3

(58) Comparative Application Example 1 was repeated except for using Comparative compound 2 and 3 in place of the host (Comparative compound 1). The device results are shown in Table 1.

(59) ##STR00092##

Application Example 1-3

(60) Comparative Application Example 1 was repeated except for using each compound shown in Table 1 in place of the host (Comparative compound 1). The device results are shown in Table 1.

(61) TABLE-US-00001 TABLE 1 Current Effi- Appl. Ex. Host Voltage, V ciency, cd/A LT95, h Comp. Appl. Ex. 1 Comparative 4.03 20.93 2.6 Compound 1 Comp. Appl. Ex. 2 Comparative 4.13 18.04 8.2 Compound 2 Comp. Appl. Ex. 3 Comparative 3.68 18.87 29 Compound 3 Appl. Ex. 1 Compound 1 4.14 21.03 288 Appl. Ex. 2 Compound 2 4.42 21.06 402 Appl. Ex. 3 Compound 3 3.58 23.54 114

(62) The results shown in Table 1 demonstrated that lifetime was much improved by keeping low driving voltage and high current efficiency in the case that an inventive compound 1, 2, or 3 was used as a host in an OLED.