NOVEL COMPOUND AND ORGANIC ELECTRONIC DEVICE USING THE SAME

Abstract

A novel compound is disclosed, which comprises: a 7-membered ring segment, which is formed by a cis-stilbene segment and a bridge atom with four bonds; and an acridine segment connecting to the bridge atom of the 7-membered ring segment. In addition, an organic electronic device is also disclosed, and an organic layer therein comprises the novel compound of the present invention.

Claims

1. A compound comprising: a 7-membered ring segment, which is formed by a cis-stilbene segment and a bridge atom with four bonds; and an acridine segment connecting to the bridge atom of the 7-membered ring segment.

2. The compound of claim 1, wherein the bridge atom is C or Si.

3. The compound of claim 1, which is represented by the following formula (I): ##STR00030## wherein, each of R.sub.1 and R.sub.2 independently is halogen, C.sub.1-C.sub.10 alkyl, C.sub.1-C.sub.10 alkoxy, C.sub.3-C.sub.20 cycloalkyl, C.sub.3-C.sub.20 heterocycloalkyl, NR.sub.aR.sub.b, CN, aryl, heteroaryl, carbazoyl, or R.sub.c-R.sub.d; each of R.sub.3, R.sub.4 and R.sub.5 independently is H, halogen, C.sub.1-C.sub.10 alkyl, C.sub.1-C.sub.10 alkenyl, C.sub.1-C.sub.10 alkoxy, C.sub.3-C.sub.20 cycloalkyl, C.sub.3-C.sub.20 heterocycloalkyl, NO.sub.2, OH, NR.sub.aR.sub.b, CN, aryl, or heteroaryl; and Ar is an aromatic ring, wherein each of R.sub.a and R.sub.b independently is H, C.sub.1-C.sub.10 alkyl or aryl; R.sub.c is aryl; and R.sub.d is H, C.sub.1-C.sub.10 alkyl, C.sub.1-C.sub.10 alkoxy, CN or aryl.

4. The compound of claim 3, wherein R.sub.1 and R.sub.2 are the same.

5. The compound of claim 3, wherein R.sub.1 and R.sub.2 are NR.sub.aR.sub.b, and R.sub.a is aryl, and R.sub.b is C.sub.1-C.sub.10 alkyl or aryl.

6. The compound of claim 5, wherein each of R.sub.a and R.sub.b independently is phenyl, naphthyl, or anthryl unsubstituted or substituted with C.sub.1-C.sub.10 alkyl, C.sub.1-C.sub.10 alkoxy or CN.

7. The compound of claim 3, which is represented by the following formula (I-1): ##STR00031##

8. The compound of claim 3, which is represented by the following formula (I-2): ##STR00032##

9. The compound of claim 3, wherein R.sub.1 and R.sub.2 are the following substituent (II-1): ##STR00033## wherein X is H or C.sub.1-C.sub.10 alkyl, C.sub.1-C.sub.10 alkoxy, or CN.

10. The compound of claim 9, wherein X is H, methyl, ethyl, methoxy, or ethoxy.

11. The compound of claim 3, wherein R.sub.1 and R.sub.2 are Br, pyridyl phenyl, naphthyl, anthryl or carbazoyl.

12. The compound of claim 3, wherein R.sub.1 and R.sub.2 are phenyl unsubstituted or substituted with methoxy, ethoxy, or CN.

13. The compound of claim 3, wherein R.sub.1 and R.sub.2 are R.sub.c-R.sub.d, in which R.sub.c is phenylene, R.sub.d is phenyl unsubstituted or substituted with methoxy, ethoxy, or CN.

14. The compound of claim 3, which is represented by the following formulas (III-1) to (III-12): ##STR00034## ##STR00035## ##STR00036##

15. The compound of claim 3, having glass transition temperatures (T.sub.g) ranged from 118 C. to 163 C., decomposition temperatures (T.sub.d) ranged from 400 C. to 465 C. and/or oxidation potentials ranged from 0.06 V to 0.87 V or the reduction potential ranged from 1.89 to 2.32 V.

16. The compound of claim 3, which is applied to an organic light emitting device, an organic solar cell device, an organic thin film transistor, an organic photodetector, a flat panel display, a computer monitor, a television, a billboard, a light for interior or exterior illumination, a light for interiror or exterior signaling, a heads up display, a fully transparent display, a flexible display, a laser printer, a telephone, a cell phone, a tablet computer, a laptop computer, a digital camera, a camcorder, a viewfinder, a micro-display, a vehicle, a large area wall, a theater or stadium screen, or a sign.

17. An organic electronic device, comprising: a first electrode; a second electrode; and an organic layer disposed between the first electrode and the second electrode, and comprising a compound comprising: a 7-membered ring segment, which is formed by a cis-stilbene segment and a bridge atom with four bonds; and an acridine segment connecting to the 7-membered ring segment by sharing the bridge atom, wherein the bridge atom in the compound is C or Si.

18. The organic electronic device of claim 17, wherein the compound is represented by the following formula (I): ##STR00037## wherein, each of R.sub.1 and R.sub.2 independently is halogen, C.sub.1-C.sub.10 alkyl, C.sub.1-C.sub.10 alkoxy, C.sub.3-C.sub.20 cycloalkyl, C.sub.3-C.sub.20 heterocycloalkyl, NR.sub.aR.sub.b, CN, aryl, heteroaryl, carbazoyl, or R.sub.c-R.sub.d; each of R.sub.3, R.sub.4 and R.sub.5 independently is H, halogen, C.sub.1-C.sub.10 alkyl, C.sub.1-C.sub.10 alkenyl, C.sub.1-C.sub.10 alkoxy, C.sub.3-C.sub.20 cycloalkyl, C.sub.3-C.sub.20 heterocycloalkyl, NO.sub.2, OH, NR.sub.aR.sub.b, CN, aryl, or heteroaryl; and Ar is an aromatic ring, wherein each of R.sub.a and R.sub.b independently is H, C.sub.1-C.sub.10 alkyl or aryl; R.sub.c is aryl; and R.sub.d is H, C.sub.1-C.sub.10 alkyl, C.sub.1-C.sub.10 alkoxy, CN or aryl.

19. The organic electronic device of claim 17, wherein the organic electronic device is an organic light emitting device, and the organic layer is a hole transport layer, an electron transport layer or a light emitting layer.

20. The organic electronic device of claim 17, wherein the organic electronic device is an organic solar cell device, and the organic layer is a carrier transport layer.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0037] FIG. 1 is a perspective view showing an OLED device of the prior art;

[0038] FIG. 2 is a perspective view showing an OLED device of the present invention; and

[0039] FIG. 3 is a perspective view showing an organic solar cell device of the present invention.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT

[0040] The present invention has been described in an illustrative manner, and it is to be understood that the terminology used is intended to be in the nature of description rather than of limitation. Many modifications and variations of the present invention are possible in light of the above teachings. Therefore, it is to be understood that within the scope of the appended claims, the invention may be practiced otherwise than as specifically described.

Example 1

Preparation of Compound of Formula (III-6)

[0041] ##STR00012##

[0042] The compound of the formula (III-6) was prepared by using the following steps.

[0043] 30 mM 2-bromo-triphenylamine of 37.5 mL was dissolved in 100 mL of anhydrous tetrahydrofuran (THF), and the obtained solution was placed in an environment of 78 C. for standing. Then, 12 mL of n-butyllithium in hexanes solution (30 mM) from a n-butyllithium solution 2.5 M in hexanes was added dropwise into the solution and the obtained reaction mixture was stirred for 30 min. 20 mM 3,7-dibromo-dibenzosuberenone (7.32 g 3,7-dibromo-dibenzosuberenone) dissolved in 20 mL of anhydrous THF was added into the reaction mixture dropwise, 10 mL of saturated aqueous sodium bicarbonate solution was added into the reaction mixture for executing a quenching reaction, and then THF was removed by rotary evaporation. The obtained product was treated with an extracting process by using dichloromethane, and an liquid extract was obtained. Then, 5 g magnesium sulfate was added into the liquid extract, the extract liquid extract was treated with a filtering process and a drying process sequentially, and the product was treated with a rotary evaporating process to obtain an intermediate product.

[0044] The following steps can be used for obtaining a clear crystalline intermediate product.

[0045] The obtained intermediate product was dissolved in 60 ml acetic acid, followed by adding 0.6 mL of concentrated hydrochloric acid (12 N) therein. The reaction mixture was reacted for 16 hours at 120 C. by using a reflux device, and then cooled down to 0 C. 60 mL hexane was added into the reaction mixture, and a Buchner funnel is used to treat the reaction mixture with a filtering process to obtain a precipitate. The precipitate was washed with hexane for 3 times to obtain a solid material. The solid material was treated with a recrystallization process by using dichloromethane/hexane to obtain a clear crystal solid, which is represented by the formula (III-6).

[0046] Data for the compound of the formula (III-6): m.p. 335.2 C. (DSC); M.W.: 591.33; .sup.1H NMR (500 MHz, CDCl.sub.3) 6.25 (d, J=8.0, 2H), 6.48 (s, 2H), 6.68 (t, J=8.0, 2H), 6.87 (td, J=8.0, 1.2, 2H), 7.02 (d, J=8.0, 2H), 7.09-7.16 (m, 4H), 7.32 (d, J=1.6, 2H), 7.45 (d, J=8.0, 2H), 7.56 (t, J=8.0, 1H), 7.69 (t, J=8.0, 2H); HR-MS calcd for C.sub.33H.sub.21Br.sub.2N: 589.0041. found: 589.0053. Anal. Calcd for C.sub.33H.sub.21Br.sub.2N: C, 67.03; H, 3.58; N, 2.37. found: C, 67.25; H, 3.62; N, 2.25; TLC R.sub.f 0.40 (CH.sub.2Cl.sub.2/hexane, 1/3).

[0047] Hereinafter, various exemplary compounds of the present invention can be fabricated by treating certain chemical reaction method to the key intermediate product of clear crystalline materials represented by the chemical formula (III-6), such as Hartwig coupling reactions.

Example 2

Preparation of Compound of Formula (III-1)

[0048] ##STR00013##

[0049] The compound of the formula (III-1) was prepared via the following scheme I.

##STR00014##

[0050] First, the compound of the chemical formula (III-6) (99%) 4730.8 mg (8 mmol), Pd.sub.2(dba).sub.3 (135 mg, 0.15 mmol), sodium tert-butoxide (2304 mg, 24 mmol), dppf (108 mg, 0.18 mmol) and diphenylamine (3046 mg, 18 mmol) was dissolved in toluene 200 mL under nitrogen gas, followed by refluxing the obtained mixture for 18 hours. Then, the reaction mixture was quenched with water (200 mL), and the aqueous layer was separated and extracted with CH.sub.2Cl.sub.2 (3200 mL). The combined organic layers were dried (MgSO.sub.4), filtered, and evaporated, and the obtained crude solid was re-crystallized from CH.sub.2C.sub.2/n-hexane to afford 2783 mg of a pure product, which is represented by the formula (III-1).

[0051] Data for the compound of the formula (III-1): T.sub.m 318 C. (DSC); T.sub.g 124 C.; M.W.: 767.98; .sup.1H NMR (400 MHz, CDCl.sub.3) 7.38 (t, J=3.2 Hz, 3H), 7.16 (dd, J=7.6 2H), 7.04 (t, J=8.0 Hz, 8H), 6.97 (d, J=2.0 Hz, 2H), 6.91 (q, J=8.0 Hz, 6H), 6.78-6.74 (m, 10H), 6.70 (t, J=6.0 Hz, 2H), 6.54 (dd, J=8.4 Hz, 2H), 6.3 (s, 2H), 6.25 (m, 2H); .sup.13C NMR (100 MHz, CDCl.sub.3) 150.0, 146.7, 146.2, 140.5, 135.8, 135.4, 133.3, 132.2, 131.4, 130.5, 129.1, 127.8, 127.5, 125.7, 125.5, 124.5, 122.8, 120.5, 119.1, 114.1, 56.7; HR-MS calcd for C.sub.57H.sub.41N.sub.3: 767.3300. found: 767.3312. Anal. Calcd for C.sub.57H.sub.41N.sub.3: C, 89.15; H, 5.38; N, 5.47. found: C, 89.07; H, 5.32; N, 5.38; TLC R.sub.f 0.2 (CH.sub.2Cl.sub.2/hexanes, 1/6).

Example 3

Preparation of Compound of Formula (III-2)

[0052] ##STR00015##

[0053] The process for preparing the compound of formula (III-2) is similar to that illustrated in Example 2, except the diphenylamine used in Example 2 was substituted with 4,4-dimethoxydiphenylamine (4.15 g, 18 mmol) in the present example.

[0054] Data for the compound of the formula (III-2): T.sub.m 267 C. (DSC); T.sub.g 127 C. (DSC); TLC R.sub.f 0.30 (acetone/hexanes=1/4); .sup.1H NMR (400 MHz, CDCl.sub.3) 3.70 (s, 12H), 5.84 (d, J=8.0, 2H), 6.25 (s, 2H), 6.32 (d, J=8.0, 2H), 6.43 (dd, J=8.0, 2.4, 2H), 6.62-6.88 (m, 24H), 7.14 (dd, J=8.0, 1.6, 2H), 7.42-7.45 (m, 3H); .sup.13C NMR (100 MHz, CDCl.sub.3) 55.28, 113.92, 114.42, 116.68, 120.45, 124.58, 125.20, 126.27, 126.88, 127.91, 129.04, 130.60, 131.20, 132.15, 133.37, 135.64, 135.86, 139.95, 140.55, 146.73, 149.90, 155.45; HR-MS calcd for C.sub.61H.sub.49N.sub.3O.sub.4: 887.3723 found: 887.3683.

Example 4

Preparation of Compound of Formula (III-3)

[0055] ##STR00016##

[0056] A mixture of chemical formula III-6 (2.50 g, 5.0 mmol), (3-cyanophenyl)boronic acid (1.628 g, 11.0 mmol), Pd(PPh.sub.3).sub.4 (350 mg, 0.30 mmol), and sodium carbonate (2.70 g, 25 mmol) in DME (50 mL) and distilled water (10 mL) was refluxed for 24 h under argon. The mixture was then extracted with CH.sub.2Cl.sub.2. The combined organic extracts were dried over anhydrous MgSO.sub.4 and concentrated by rotary evaporation. The crude product was purified by column chromatography on silica gel using 1:1 CH.sub.2Cl.sub.2/Hexanes as eluent to afford a greenish-yellow solid 2.09 g (yield, 76%).

[0057] Data for the compound of the formula (III-3): T.sub.m 293 C. (DSC); T.sub.g 129 C. (DSC); TLC R.sub.f 0.30 (dichloromethane/hexanes=1/1); .sup.1H NMR (400 MHz, CDCl.sub.3) 7.69 (t, J=8.0, 2H), 7.53-7.57 (m, 7H), 7.40-7.46 (m, 4H), 7.21-7.33 (m, 8H), 6.86 (td, J=8.0, 0.8, 2H), 6.69 (td, J=8.0, 0.8, 2H), 6.64 (s, 2H), 6.26 (dd, J=8.0, 0.8, 2H); .sup.13C NMR (100 MHz, CDCl.sub.3) 149.81, 136.31, 136.24, 134.14, 133.12, 132.90, 131.81, 131.45, 130.97, 130.79, 130.16, 130.84, 129.50, 127.04, 124.16, 121.04, 118.70, 114.29, 114.21, 112.90, 57.52; HR-MS calcd for C.sub.47H.sub.29N.sub.3: 635.2361. found: 635.2356.

Example 5

Preparation of Compound of Formula (III-4)

[0058] ##STR00017##

[0059] The compound of the formula (III-4) was prepared via the following scheme II.

##STR00018##

[0060] First, the compound of the chemical formula (III-6) (99%) 1182.7 mg (2.0 mmol), Pd (PPh.sub.3).sub.4 (130 mg, 0.11 mmol), potassium carbonate (1105.7 mg, 8 mmol), and 4-pyridinylboronicacid (614.6 mg, 5 mmol), were dissolved in DMF/H.sub.2O (30 mL/3 mL) under nitrogen gas, followed by refluxing the obtained mixture under 130 C. and stirring for 48 hours. Then, The reaction mixture was quenched with water (20 mL), and The aqueous layer was separated and extracted with CH.sub.2Cl.sub.2 (320 mL). The combined organic layers were dried (MgSO.sub.4. 0.5 g), filtered, and evaporated; and the obtained crude solid was re-crystallized from CH.sub.2Cl.sub.2/n-hexane to afford 908.3 mg of a pure product, which is represented by the formula (III-4).

[0061] Data for the compound of the formula (III-4): T.sub.m 430 C. (DSC); T.sub.g 119.4 C.; T.sub.d: 428 C.; M.W.: 589.71; .sup.1H NMR (400 MHz, CDCl.sub.3) 8.55 (d, J=6 Hz, 4H), 7.66 (t, J=7.6 2H), 7.62 (d, J=1.6 Hz, 2H), 7.56 (t, J=7.6 Hz, 2H), 7.35-7.3 (m 6H), 7.26-7.23 (m, 2H), 9.15 (dd, J=4.4 Hz, 4H), 6.88 (t, J=7.2 Hz, 2H), 6.71 (d, J=3.44 Hz, 2H), 6.67 (s, 2H), 6.27 (d, J=8.4 Hz, 2H); .sup.13C NMR (100 MHz, CDCl.sub.3) 150.17, 149.77, 147.51, 140.86, 137.08, 136.25, 133.98, 133.1, 132.95, 132.52, 131.34, 131.10, 128.68, 127.11, 124.23, 121.12, 121.03, 114.25, 77.25, 57.55; HR-MS calcd for C.sub.43H.sub.29N.sub.3: 587.7105. found: 587.7100; TLC R.sub.f 0.16 (Acetone/hexanes, 1/3).

Example 6

Preparation of Compound of Formula (III-5)

[0062] ##STR00019##

[0063] A mixture of chemical formula (III-6) (1.773 g, 3.0 mmol), cuprous cyanide (1.100 g, 12.0 mmol) in degasses DMF (12 mL) was refluxed for 18 h under argon. The mixture was then cooled to rt and concentrated under reduced pressure. An aqueous solution of ammonia (2M, 150 mL) was added and the mixture was extracted with CH.sub.2Cl.sub.2. The combined organic extracts were dried over anhydrous MgSO.sub.4 (2.5 g) and concentrated by rotary evaporation. The crude product was purified by column chromatography on silica gel using 1:1 CH.sub.2Cl.sub.2/Hexanes as eluent to afford a yellow solid 0.986 g (yield: 68%).

[0064] Data for the compound of the formula (III-5): T.sub.m 348 C. (DSC); T.sub.g 120 C. (DSC); TLC R.sub.f 0.30 (EtOAc/hexanes=1/3); .sup.1H NMR (400 MHz, CDCl.sub.3) 7.72 (t, J=8.0, 2H), 7.61-7.56 (m, 3H), 7.46 (d, J=8.0, 2H), 7.31-7.27 (m, 4H), 6.96 (dd, J=8.0, 1.2, 2H), 6.91 (td, J=8.0, 0.8, 2H), 6.69-6.65 (m, 4H), 6.29 (d, J=8.0, 2H); .sup.13C NMR (100 MHz. CDCl.sub.3) 8149.69, 140.86, 140.05, 136.66, 134.30, 132.71, 132.69, 132.58, 132.30, 131.32, 131.04, 128.83, 128.78, 127.85, 121.40, 118.66, 114.87, 112.05, 57.01; HR-MS calcd for C.sub.35H.sub.21N.sub.3:483.1735. found: 483.1740.

Example 7

Preparation of Compound of Formula (III-7)

[0065] ##STR00020##

[0066] The compound of the formula (III-7) was prepared via the following scheme III.

##STR00021##

[0067] 30 mmol of 9-(2-bromophenyl)-carbazole of 9.63 grams was dissolved in 37.5 mL of anhydrous tetrahydrofuran (THF), and the obtained solution was placed in an environment of 78 C. for standing. Then, 18.8 mL of n-butyllithium in hexanes solution (30 mmol) from a n-butyllithium solution 1.6 M in hexanes was added dropwise into the solution and the obtained reaction mixture was stirred for 30 min. 20 mmol of 3,7-dibromo-dibenzosuberenone (7.32 g) dissolved in 20 mL of anhydrous THF was added into the reaction mixture dropwise. 10 mL of saturated aqueous sodium bicarbonate solution was added into the reaction mixture for executing a quenching reaction, and then THF was removed by rotary evaporation. The obtained product was treated with an extracting process by using dichloromethane (50 mL), and a liquid extract was obtained. Then, 5 g magnesium sulfate was added into the liquid extract, the liquid extract was treated with a drying process and a filtering process sequentially, and the product was treated with a rotary evaporating process to obtain an intermediate product.

[0068] The following steps can be used for obtaining a clear crystalline intermediate product.

[0069] The obtained intermediate product was dissolved in 60 ml acetic acid, followed by adding 0.6 mL of concentrated hydrochloric acid (12 N) therein. The reaction mixture was reacted for 16 hours at 120 C. by using a reflux device, and then cooled down to 0 C. 60 mL hexane was added into the reaction mixture, and a Buchner funnel is used to treat the reaction mixture with a filtering process to obtain a precipitate. The precipitate was washed with hexane (20 mL) for 3 times to obtain a solid material. The solid material was treated with a recrystallization process by using dichloromethane/hexane to obtain a clear crystal solid, which is represented by the formula (III-7).

[0070] Data for the compound of the formula (III-7): m.p. 342.6 C. (DSC); M.W.: 589.32; .sup.1H NMR (500 MHz, CDCl.sub.3) 6.57 (s, 2H), 6.88 (d, J=0.2, 2H), 7.00-7.18 (m, 5H), 7.34-7.42 (m, 4H), 7.63 (t, J=8.0, 11), 7.84 (dd, J=8.0, 0.4, 1H), 8.17 (d. J=8.0, 1H), 8.23 (d, J=8.0, 1H), 8.29 (d, J=8.0, 1H); .sup.13C NMR (100 MHz, CDCl.sub.3) 57.25, 113.34, 113.37, 113.99, 114.03, 118.19, 118.25, 120.99, 121.04, 121.13, 121.17, 122.35, 122.40, 123.10, 123.77, 125.93, 125.99, 126.06, 126.82, 126.87, 128.20, 129.74, 130.68, 130.73, 130.77, 131.25, 131.29, 131.56, 131.78, 134.51, 134.56, 137.11, 138.29, 138.58, 138.87, 149.23; HR-MS calcd for C.sub.33H.sub.19Br.sub.2N: 586.9884 found: 586.9879. HR-MS calcd for C.sub.33H.sub.21Br.sub.2N: 586.9884. found: 586.9869. Anal. Calcd for C.sub.33H.sub.19Br.sub.2N: C, 67.26; H, 3.25; N, 2.38. found: C, 67.21; H, 3.43; N, 2.28; TLC R.sub.f 0.65 (CH.sub.2Cl.sub.2/hexane, 1/3).

Example 8

Preparation of Compound of Formula (III-8)

[0071] ##STR00022##

[0072] First, the compound of the chemical formula (III-7) (99%) 1.185 mg (2 mmol), Pd.sub.2(dba).sub.3 (115 mg, 0.12 mmol), sodium tert-butoxide (768 mg, 8.0 mmol), dppf (91 mg, 0.16 mmol) and diphenylamine (742 mg, 4.4 mmol) was dissolved in toluene 20 mL under nitrogen gas, followed by refluxing the obtained mixture for 24 hours. Then, the reaction mixture was quenched with water (200 mL), and the aqueous layer was separated and extracted with CH.sub.2Cl.sub.2 (3200 mL). The combined organic layers were dried (MgSO.sub.4), filtered, and evaporated, and the obtained crude solid was re-crystallized from CH.sub.2Cl.sub.2/n-hexane to afford 1072 mg of a pure product, which is represented by the formula (III-8).

[0073] Data for the compound of the formula (III-8): T.sub.m 259 C. (DSC); T.sub.g 118 C. (DSC); TLC R.sub.f 0.35 (dichloromethane/hexanes=1/2.5); .sup.1H NMR (400 MHz, CDCl.sub.3) 6.35 (s, 2H), 6.41 (s, 1H), 6.60-6.62 (d, J=8.0, 10H), 6.70 (t. J=8.0, 4H), 6.86 (t, J=8.0, 8H), 6.93 (t, J=8.0, 1H), 7.00 (d, J=8.0, 2H), 7.11-7.16 (m, 2H), 7.28-7.38 (m, 4H), 7.47 (t, J=8.0, 1H), 7.68 (d, J=8.0, 1H), 7.72 (d, J=8.0, 1 H), 7.85 (d, J=8.0, 1 H), 8.06 (d, J=8.0, 1H); HR-MS calcd for C.sub.57H.sub.39N.sub.3: 765.3144. found: 765.3118.

Example 9

Preparation of Compound of Formula (III-9)

[0074] ##STR00023##

[0075] The compound of the formula (III-9) was prepared via the following scheme IV.

##STR00024##

[0076] In a pressure tube bis(4-methoxyphenyl)amine (5.04 g, 22 mmol), 3,7-dibromospiro[dibenzo[a,d][7]annulene-5,8-indolo[3,2,1-de]acridine](5.90 g, 10 mmol) was mixed with sodium t-butoxide (4.66 g, 44 mmol), Pd(dba).sub.2 (dba=(1E,4E)-1,5-diphenylpenta-1,4-dien-3-one, 230 mg), 1,2-bis(diphenylphosphino)ferrocene, (220 mg) in toluene (100 mL) under nitrogen atmosphere. This was heated at 80 C. for 36 h. After the completion of the reaction the volatiles were removed by evaporation. The residue was triturated with water and extracted with dichloromethane. The combined organic layer was dried over anhydrous sodium sulfate and evaporated in vacuum to produce a crude product. It was adsorbed on silica gel and purified by column chromatography by using hexane/dichloromethane mixture as eluant. White solid; yield 6.21 g (70%)

[0077] Data for the compound of the formula (III-9): T.sub.m 236 C. (DSC); T.sub.g 135 C. (DSC); TLC R.sub.f 0.35 (dichloromethane/hexanes=1/2.5): .sup.1H NMR (400 MHz, CDCl.sub.3) 3.63 (s, 12H), 6.24 (s, 2H), 6.35 (s, 2H), 6.42-6.50 (m, 10H), 6.53-6.57 (m, 7H), 6.93-6.97 (m, 3H), 7.13-7.19 (m, 2H), 7.28-7.38 (m, 4H), 7.48-7.51 (m, 1H), 7.72-7.74 (m, 2H), 7.91 (d. J=8.4 Hz, 1H), 8.07 (d, J=7.6 Hz, 1H); .sup.13C NMR (100 MHz, CDCl.sub.3) 155.6, 147.9, 147.3, 139.6, 139.4, 138.0, 134.4, 134.0, 133.9, 132.7, 131.1, 127.8, 127.5, 126.8, 126.4, 12.2, 125.9, 125.5, 123.3, 122.7, 121.6, 120.7, 119.3, 116.6, 116.5, 114.3, 113.3, 112.9, 57.6, 55.3; HR-MS calcd for C.sub.61H.sub.47N.sub.3O.sub.4: 885.3567. found: 885.3569.

Example 10

Preparation of Compound of Formula (III-10)

[0078] ##STR00025##

[0079] A mixture of 3,7-dibromospiro[dibenzo[a,d][7]annulene-5,8-indolo[3,2,1-de]acridine] (1.47 g, 2.5 mmol), (3-cyanophenyl)boronic acid (0.808 g, 5.5 mmol), Pd(PPh.sub.3).sub.4 (144 mg, 0.12 mmol), and sodium carbonate (2.65 g, 25 mmol) in DME (50 mL) and distilled water (15 mL) was refluxed for 24 h under argon. The mixture was then extracted with CH.sub.2Cl.sub.2. The combined organic extracts were dried over anhydrous MgSO.sub.4 and concentrated by rotary evaporation. The crude product was purified by column chromatography on silica gel using 1:1 CH.sub.2Cl.sub.2/Hexanes (R.sub.f=0.3) as eluent to afford a greenish-yellow solid. Yield: 76%.

[0080] Data for the compound of the formula (III-10): .sup.1H NMR (400 MHz, CDCl.sub.3) 6.77 (s, 2H), 7.09 (s, 3H), 7.16-7.21 (m, 3H), 7.25-7.29 (m, 4H), 7.31 (s, 2H), 7.35-7.38 (m, 3H), 7.42 (d, J=7.6 Hz, 2H), 7.45-7.52 (m, 2H), 7.59-7.63 (m, 2H), 7.82 (d, J=8.0 Hz, 1H), 8.13 (d, J=7.6 Hz, 1H), 8.27 (d, J=8.4 Hz, 2H). .sup.13C NMR (100 MHz, CDCl.sub.3) 148.37, 141.46, 139.37, 138.20, 135.45, 135.35, 135.08, 133.55, 133.14, 132.25, 131.64, 130.83, 130.38, 129.65, 128.34, 127.18, 126.25, 126.08, 125.03, 123.79, 123.31, 122.58, 121.39, 121.35, 118.79, 118.28, 114.06, 113.43, 113.00, 58.29: HR-MS calcd for C.sub.47H.sub.27N.sub.3 (633.2205) found: 633.2201.

Example 11

Preparation of Compound of Formula (III-11)

[0081] ##STR00026##

[0082] The compound of the formula (III-11) was prepared via the following scheme V.

##STR00027##

[0083] A mixture of 3,7-dibromospiro[dibenzo[a,d][7]annulene-5,8-indolo [3,2,1-de]acridine] (1.18 g, 2.0 mmol), 4-(4,4,5,5-tetramethyl-1,3-dioxolan-2-yl)-[1,1-biphenyl]-3-carbonitrile (1.35 g, 4.4 mmol), Pd(PPh.sub.3).sub.4 (116 mg, 0.10 mmol), and sodium carbonate (2.12 g, 20 mmol) in DME (50 mL) and distilled water (10 mL) was refluxed for 24 h under argon. The mixture was then extracted with CH.sub.2Cl.sub.2. The combined organic extracts were dried over anhydrous MgSO.sub.4 and concentrated by rotary evaporation. The crude product was purified by column chromatography on silica gel using 1:1 CH.sub.2Cl.sub.2/Hexanes (R.sub.f=0.25) as eluent to afford a greenish-yellow solid. Yield: 73%.

[0084] Data for the compound of the formula (III-11): .sup.1H NMR (400 MHz, CDCl.sub.3) 6.75 (s, 2H), 7.05-7.09 (m, 1H), 7.12-7.14 (m, 4H), 7.19 (s, 3H), 7.30-7.40 (m, 10H), 7.46-7.48 (m, 2H), 7.55-7.58 (m, 3H), 7.60-7.62 (m, 2H), 7.78 (td, J=8.0 Hz, 1.6 Hz, 2H), 7.75 (t, J=1.6 Hz, 2H), 7.82 (d, J=7.6 Hz, 1H), 8.14 (dd, J=8.0 Hz, 0.8 Hz, 1H), 8.27 (t, J=7.6 Hz, 2H); .sup.13C NMR (100 MHz, CDCl.sub.3) 148.29, 141.87, 140.21, 139.52, 138.70, 138.46, 137.67, 135.44, 135.15, 133.32, 132.85, 132.54, 131.82, 131.32, 130.82, 130.55, 129.72, 127.98, 127.42, 127.32, 126.94, 126.40, 124.91, 123.77, 123.27, 122.35, 121.37, 121.13, 118.96, 113.91, 113.38, 113.10, 58.27; HR-MS calcd for C.sub.59H.sub.35N.sub.3: 785.2831. found: 785.2834.

Example 12

Preparation of Compound of Formula (III-12)

[0085] ##STR00028##

[0086] A mixture of 3,7-dibronmospiro[dibenzo[a,d][7]annulene-5,8-indolo [3,2,1-de]acridine] (1.77 g, 3.0 mmol), cuprous cyanide (1.105 g, 12.0 mmol) in degasses DMF (12 mL) was refluxed for 18 h under argon. The mixture was then cooled to rt and concentrated under reduced pressure. An aqueous solution of ammonia (2M, 150 mL) was added and the mixture was extracted with CH.sub.2Cl.sub.2. The combined organic extracts were dried over anhydrous MgSO.sub.4 (2.5 g) and concentrated by rotary evaporation. The crude product was purified by column chromatography on silica gel using 1:1 CH.sub.2Cl.sub.2/Hexanes as eluent to afford a yellow solid 1.015 g (yield: 70%).

[0087] Data for the compound of the formula (III-12): T.sub.m 388 C. (DSC); T.sub.g 144 C. (DSC); TLC R.sub.f 0.25 (EtOAc/hexanes=1/3); .sup.1H NMR (400 MHz, CDCl.sub.3) 8.29 (t, J=8.0, 2H), 8.18 (d, J=8.0, 1H), 7.87 (d, J=8.0, 1H), 7.66 (t, J=8.0, 1H), 7.43 (t, J=8.0, 2H), 7.32-7.12 (m, 9H), 7.00 (t, J=8.0, 1H), 6.74 (s, 2H); .sup.13C NMR (100 MHz, CDCl.sub.3) 140.00, 138.32, 136.78, 135.11, 134.51, 134.36, 133.05, 132.65, 131.22, 130.82, 129.41, 128.80, 127.28, 125.91, 125.67, 124.05, 123.26, 122.86, 121.43, 121.25, 118.79, 118.25, 114.47, 113.53, 112.21, 57.28; HR-MS calcd for C.sub.35H.sub.19N.sub.3: 481.1579. found: 481.1571.

Steady-State Photophysical Measurements

[0088] Absorption spectra were measured on a SP-8001 Diode Array spectrometer by using spectrophotometric grade CH.sub.2Cl.sub.2 (10 mM in CH.sub.2Cl.sub.2). Emission spectra (in 10 mM) were measured on (a FP-6500 luminescence spectrometer upon excitation at the absorption maxima of the longest absorption band in the same solvent. The emission spectra measured in CH.sub.2Cl.sub.2 (10 mM) were normalized by their emission maxima to the same intensity (maximum intensity 1). Fluorescence quantum yield (.sub.f, %) calculation were integrated emission area of the fluorescent spectra and compared the value to the same area measured for Coumarin 1.sup.2c (.sub.f=0.90, CH.sub.2Cl.sub.2) or Coumarin 6 (.sub.f=0.78, EtOH) in CH.sub.2Cl.sub.2 (in 10 mM). The quantum yields are calculated by using the following equation 1. Where A stands for area of fluorescent emission for sample (i.e. the compounds of formulas (III-1) to (III-3)) and Coumarin 1 or Coumarin 6; a is absorbance for sample and Coumarin 1 or Coumarin 6; and n is the refractive indices of solvent for sample and Coumarin 1 or Coumarin 6 (the refractive index (n) for CH.sub.2Cl.sub.2=1.42; for EtOH=1.36).

.sup.sample.sub.f=(A.sub.sample/A.sub.standard)(a.sub.standard/a.sub.sample)(n.sub.sample/n.sub.standard).sup.2.sup.standard.sub.f[Equation 1]

Cyclic Voltammetry (CV) Measurements

[0089] CV experiments were carried out with 1.0 mM of one substrate in a given anhydrous, degassed solvent containing 0.1 M tetrabutylammonium perchlorate or phosphate (n-Bu.sub.4NClO.sub.4 or n-Bu.sub.4NPF.sub.6) as a supporting electrolyte on a Chinstruments CH1604A potentiostat. A platinum wire electrode was used as a counter electrode, and a glassy carbon electrode was used as a working electrode. Ag/AgCl was used as a reference electrode.

Differential Scanning Calorimetry (DSC) Analyses

[0090] DSC measurements were performed on a SEIKO SSC 5200 DSC Computer/Thermal Analyzer. The samples were first heated (20 C./min) to melt and then quenched with liquid nitrogen. Glass transition temperatures (T.sub.g) were recorded by heating (10 C./min) the cooled samples.

Thermogravimetric Analyses (TGA)

[0091] TGA measurements were performed on a SEIKO TG/DTA200 instrument by the Northern Instrument Center of Taiwan. Melting points were measured on a Hargo MP-2D instrument.

Property Evaluations of Compounds of Formulas (III-1) to (III-12)

[0092] The data of glass transition temperature (T.sub.g), decomposition temperature (T.sub.d), the longest peak wavelength value of absorption spectrum (.sub.max), and the longest peak wavelength value of photoluminescence spectrum (PL .sub.max) of the compounds of the formulas (III-1) to (III-12) are measured and recorded in the following Table 1. From the Table 1, it is able to know that these compounds provided by the present invention have glass transition temperatures (T.sub.g) ranged from 118 C. to 163 C. and decomposition temperatures (T.sub.d) ranged from 400 C. to 465 C. That means the compounds of provided by the present invention possess excellent thermal stability, and are not easy to decompose under high voltage and high current density operation conditions.

TABLE-US-00001 TABLE 1 Compound T.sub.g ( C.) T.sub.d ( C.) .sub.max (nm) PL .sub.max (nm) Formula (III-1) 124 400 432 452 Formula (III-2) 127 415 437 470 Formula (III-3) 150 435 428 449 Formula (III-4) 119 423 366 514 Formula (III-5) 120 415 374 403, 552 Formula (III-8) 118 429 431 460 Formula (III-9) 135 439 437 477 Formula (III-10) 132 441 365 461 Formula (III-11) 163 465 374 426, 447 Formula (III-12) 144 431 374 390, 523

[0093] Moreover, the oxidation potential and the reduction potential of the compounds provided by the present invention can be measured by way of cyclic voltammetry (CV); therefore, the highest occupied molecular orbital energy level (E.sub.HOMO) and lowest unoccupied molecular orbital energy level (E.sub.L) of the compounds provided by the present invention can also be calculated based on the measured oxidation potential (E.sub.1/2.sup.ox) and the reduction potential (E.sub.1/2.sup.red). With reference to following Table 2. E.sub.1/2.sup.ox, E.sub.1/2.sup.red, E.sub.HOMO, and E.sub.LUMO of the compounds of the present invention are recorded. From the Table 2, the persons skilled in OLED material art are able to know that the compounds provided by the present invention have the E.sub.HOMO ranged from 4.86 eV to 5.47 eV and the E.sub.LUMO ranged from 2.16 eV to 2.74 eV. Moreover, the compounds provided by the present invention also have the oxidation potentials ranged from 0.06 V to 0.87 V or have the reduction potential ranged from 1.89 to 2.32 V.

TABLE-US-00002 TABLE 2 E.sub.1/2.sup.ox E.sub.1/2.sup.red E.sub.g E.sub.HOMO E.sub.LUMO Compound (V) (V) (eV) (eV) (eV) Formula (III-1) 0.68 2.74 5.48 2.74 Formula (III-2) 0.28 2.64 5.08 2.64 Formula (III-3) 0.67 2.28 2.94 5.47 (5.79) 2.53 (2.85) Formula (III-4) 0.74 2.15 3.05 5.54 3.44 Formula (III-5) 0.70 1.91 3.21 5.57 2.36 Formula (III-8) 0.69 2.70 5.49 2.79 Formula (III-9) 0.06 2.70 4.86 2.16 Formula (III-10) 0.87 2.26 3.01 5.66 2.65 Formula (III-11) 0.84 2.32 2.93 5.64 2.71 Formula (III-12) 0.76 1.89 3.20 5.56 2.36

[0094] Furthermore, in order to prove that the compounds of the present invention can indeed be applied in OLEDs for being as a hole-blocking type electron transport layer, a plurality of OLED devices for control groups and experiment groups have been designed and manufactured.

[0095] All the materials were either commercially available or synthesized as described in this experiment and were subjected to gradient sublimation under high vacum prior to use. The substrate was an indium tin oxide (ITO) coated glass sheet with a sheer resistance of 30 W/. Pre-patterned ITO substrates were cleaned sequentially by sonication in a detergent solution, doubly distilled water, and EtOH for 5 min in turn before being blown dry with a stream of nitrogen. The ITO substrate was then treated with oxygen plasma for 5 min before being loaded into the vacuum chamber. The organic layers were deposited thermally at a rate of 0.1-0.3 nm/s in a chamber (ULVAC, TU-12RE) under a pressure of 510 Torr. Device were constructed with 40 nm of the hole transporting layer (HTL), 40 nm of the light-emitting layer (LEL), 10 nm of the hole-blocking layer (HBL), 40 nm of the electron-transporting layer (ETL), 1 nm of LiF as the electron-injecting layer (EIL), and 150 nm of Al as the cathode, respectively. In addition, 1,4,5,8,9,11-Hexaazatriphenylene-hexacarbonitrile (HATCN) is used as the HIL; 4,4-Cyclohexylidenebis [N,N-bis(4-methylphenyl)benzenamine] (TAPC) is used as the HT01. Herein, the material used in each layer is summarized in the following Table 3.

TABLE-US-00003 TABLE 3 LEL Cathode EIL ETL HBL Blue dopant Host HTL Anode Embodiment 1 Al LiF Alq.sub.3 BCP Formula BANE NPB/ HIL/ITO III-1 HT01 Embodiment 2 Al LiF Alq.sub.3 BCP Formula BANE NPB/ HIL/ITO III-2 HT01 Embodiment 3 Al LiF Alq.sub.3 BCP Formula BANE NPB/ HIL/ITO III-8 HT01 Comparative Al LiF Alq3 BCP Formula 5A Formula 5A NPB/ HIL/ITO embodiment 1 HT01 Embodiment 4 Al LiF Formula BCP Formula 5A BANE NPB/ HIL/ITO III-3 HT01 Embodiment 5 Al LiF Formula BCP Formula 5A BANE NPB/ HIL/ITO III-10 HT01 Comparative Al LiF Alq3 BCP Formula 5A BANE NPB/ HIL/ITO embodiment 2 HT01

[0096] In the Table 3, Alq3 is the abbreviation of Tris-(8-hydroxyquinoline)aluminum, BCP is the abbreviation of 2,9-Dimethyl-4,7-diphenyl-1,10-phenanthroline, and BANE is the abbreviation of 10,10-di(biphenyl-4-yl)-9,9-bianthracene. In addition, spirobifluorene is represented by following chemical formula 5A; and the compound of the following chemical formula 5B can also be used as the dopant emitter.

##STR00029##

[0097] Furthermore, it is able to know that the materials of TPBi, DPyPA. BmPyPb, and ET01 recorded in the Table 3 are also used as OLED device's electron transport layers. However, the present invention is not limited thereto.

[0098] FIG. 2 is a perspective view showing the OLED devices provided above. The OLED device of the present invention comprises: a first electrode 12; a second electrode 18; and an organic layer disposed between the first electrode 12 and the second electrode 18. Herein, the first electrode 12 is a cathode, and a substrate 11 is disposed therebelow. The second electrode 18 is an anode. The organic layer comprises: an electron-injection layer 13, an electrode-transporting layer 14, a hole-blocking layer 15, a light-emitting layer 16, and a hole transporting layer 17, sequentially laminated on the first electrode 12.

[0099] Herein, Current-voltage-light intensity (I-V-L) characteristics and EL spectra were measured and recorded by PRECISE GAUGE, EL-1003; and the turn-on voltage (V.sub.on), the external quantum efficiency (.sub.ext), the current efficiency (.sub.c), the power efficiency (.sub.p), and the maximum luminance (L.sub.max) of the OLED devices are listed in the following Table 4.

TABLE-US-00004 TABLE 4 .sub.max Von .sub.ext .sub.c/.sub.p L.sub.max (nm) (V) (%) (%) (cd/m.sup.2) Embodiment 1 452 3.0 2.8 4.2/1.5 7563 Embodiment 2 452 3.0 3.1 4.3/1.8 6585 Embodiment 3 452 2.8 3.2 4.3/1.6 7960 Comparative 452 3.3 4.5 5.0/4.3 9898 embodiment 1 Embodiment 4 452 2.8 8.0 9.1/7.1 50000 Embodiment 5 452 3.4 7.5 8.0/6.6 54640 Comparative 452 3.4 2.6 2.0/0.8 5256 embodiment 2

[0100] With reference to the measured data of the blue fluorescent OLED devices in the Table 4, one can find that the OLED devices using double hole transport layer of Embodiments 1-3 show excellent .sub.ext, .sub.c, .sub.p, and L.sub.max and are comparable to the OLED devices using single emitting layer of Comparative embodiment 1. Among them, Embodiment 2 (Compound of formula (III-2)) shows the best results, where the .sub.ext is 3.1%, .sub.c is 4.3 cd/A, .sub.p is 1.8 lm/w, and L.sub.max is 6585 cd/m.sup.2.

[0101] In addition, the measured data also reveals that the OLED devices using single dopant emitting layer of Embodiment 2 shows excellent .sub.ext, .sub.c, .sub.p, and L.sub.max and is superior to the OLED devices using single dopant emitting layer of Comparative embodiment 2. Moreover, the commercial OLED device using single dopant emitting layer of Embodiments 4 and 5 by using Compound of formula (III-3) and (III-10) as the ETL also shows excellent .sub.ext, .sub.c, .sub.p, and L.sub.max, which is at least three times superior to the OLED devices using single dopant emitting layer of Comparative embodiment 2.

[0102] Furthermore, device life time evaluation tests for the blue fluorescent OLEDs have also been completed based on a starting luminance of 1,000 cd/cm.sup.2. Life time evaluation test results reveal that the decay half lifetimes (LT.sub.50) of the green phosphorescent OLED for Embodiment 4 is 903 hours. In addition, the decay half lifetime (LT.sub.50) for the blue fluorescent OLEDs of Comparative embodiment 2 is measured as 930 hours.

[0103] In conclusion, the compounds of the present invention have glass transition temperatures ranged from 118 C. to 163 C., decomposition temperatures ranged from 400 C. to 465 C., reversible electron transport property, and balanced charges motilities.

[0104] Moreover, a variety of experimental data have proved that the compounds of the present invention can indeed be used as a hole-transporting type emitters and dopant emitters for OLEDs; moreover, the experimental data also reveal that the OLEDs using the compounds of the present invention are able to show good to excellent external quantum efficiency (.sub.ext), current efficiency (.sub.c), power efficiency (.sub.p), maximum luminance (L.sub.max), and device lifetime performances better than the conventional or commercial OLEDs.

[0105] Furthermore, from the results shown in Table 4, it can be concluded that the compounds of the present invention, especially the compounds of the formulas (III-1) to (III-3), can be used as a dopant as well as a host emitter for the light emitting layer of OLEDs.

[0106] Except for the aforementioned OLED devices, the present invention also provides an organic solar cell, which is shown in FIG. 3. The organic solar cell of one embodiment of the present invention comprises: a first electrode 21; a second electrode 22; and an organic layer 23 disposed between the first electrode 21 and the second electrode 22 and comprising any one of the compounds of the formulas (III-1), (III-2), and (III-7). In the organic solar cell of the present invention, the organic layer 23 is served as a carrier transport layer.

[0107] Except for the aforementioned OLED device and organic solar cell device, the compounds provided by the present invention can be applied to various organic electronic devices, such as an organic thin film transistor, an organic photodetector, a flat panel display, a computer monitor, a television, a billboard, a light for interior or exterior illumination, a light for interiror or exterior signaling, a heads up display, a fully transparent display, a flexible display, a laser printer, a telephone, a cell phone, a tablet computer, a laptop computer, a digital camera, a camcorder, a viewfinder, a micro-display, a vehicle, a large area wall, a theater or stadium screen, or a sign. However, the present invention is not limited thereto.

[0108] Although the present invention has been explained in relation to its preferred embodiment, it is to be understood that many other possible modifications and variations can be made without departing from the spirit and scope of the invention as hereinafter claimed.