Compound and organic electronic device using the same

Abstract

Provided are a novel compound and an organic electronic device using the same. The novel compound is represented by the following Formula (I): ##STR00001## wherein X.sup.1 and X.sup.2 are each independently C(R.sup.3), the two (R.sup.3)s are the same or different, and the two (R.sup.3)s are joined together to form a first aryl ring; X.sup.3 and X.sup.4 are each independently C(R.sup.b), the two (R.sup.b)s are the same or different, the two (R.sup.b)s are joined to form a second aryl ring, and the second aryl ring is a polycyclic aromatic ring.

Claims

1. A compound represented by the following Formula (I): ##STR00186## wherein X.sup.1 and X.sup.2 are each independently C(R.sup.a), the two (R.sup.a)s are the same or different, and the two (R.sup.a)s are joined together to form a first aryl ring; wherein X.sup.3 and X.sup.4 are each independently C(R.sup.b), the two (R.sup.b)s are the same or different, and the two (R.sup.b)s are joined to form a second aryl ring, and the second aryl ring is a polycyclic aromatic ring; wherein Z.sup.1 to Z.sup.12 are each independently selected from the group consisting of: a hydrogen atom, a deuterium atom, a halogen group, a cyano group, a nitro group, an alkyl group having 1 to 40 carbon atoms, an alkenyl group having 2 to 40 carbon atoms, an alkynyl group having 2 to 40 carbon atoms, a cycloalkyl group having 3 to 60 ring carbon atoms, a heterocyeloalkyl group having 3 to 60 ring carbon atoms, an aryl group having 6 to 60 ring carbon atoms, a heteroaryl group having 3 to 60 ring carbon atoms, an alkoxy group having 1 to 40 carbon atoms, an aryloxy group having 6 to 60 ring carbon atoms, an alkylsilyl group having 1 to 40 carbon atoms, an arylsilyl group having 6 to 60 ring carbon atoms, an alkylboron group having 1 to 40 carbon atoms, an arylboron group having 6 to 60 ring carbon atoms, a phosphine group having 1 to 40 carbon atoms, and a phosphine oxide group having 1 to 40 carbon atoms.

2. The compound as claimed in claim 1, wherein the polycyclic aromatic ring is selected from the group consisting of: naphthalene ring, anthracene ring, phenanthrene ring, pyrene ring, 9,9-dimethylfluorene ring, benzophenanthrene ring, benzopyrene ring, fluoranthene ring, triphenylene ring and benzofluoranthene ring.

3. The compound as claimed in claim 1, wherein the compound is represented by any one of the following Formulae (I-I) to (I-XII): ##STR00187## ##STR00188## ##STR00189## ##STR00190## wherein n1 is a positive integral from 0 to 4, and T is selected from the group consisting of: a hydrogen atom, a deuterium atom, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and a phenyl group.

4. The compound as claimed in claim 1, wherein the first aryl ring extended from X.sup.1 and X.sup.2 is a substituted or unsubstituted 6 to 60-membered carbon ring.

5. The compound as claimed in claim 4, wherein the substituted or unsubstituted 6 to 60-membered carbon ring is selected from the group consisting of: a substituted or unsubstituted benzene ring, a substituted or unsubstituted naphthalene ring, a substituted of unsubstituted anthracene ring, a substituted or unsubstituted phenanthrene ring, a substituted or unsubstituted pyrene ring, a substituted or unsubstituted benzopyrene ring, a substituted or unsubstituted fluoranthene ring, a substituted or unsubstituted benzofluoranthene ring, and a substituted or unsubstituted fluorene ring.

6. The compound as claimed in claim 5, wherein the substituted or unsubstituted 6 to 60-membered carbon ring is a substituted or unsubstituted benzene structure.

7. The compound as claimed in claim 1, wherein at least one of Z.sup.1 to Z.sup.8 in formula (I) is selected from the group consisting of: an alkyl group having 1 to 40 carbon atoms and substituted with at least one functional group, an alkenyl group having 2 to 40 carbon atoms and substituted with at least one functional group, an alkynyl group having 2 to 40 carbon atoms and substituted with at least one functional group, a cycloalkyl group having 3 to 60 ring carbon atoms and substituted with at least one functional group, a heterocycloalkyl group having 3 to 60 ring carbon atoms and substituted with at least one functional group, an aryl group having 6 to 60 ring carbon atoms and substituted with at least one functional group, a heteroaryl group having 3 to 60 ring carbon atoms containing at least one nitrogen atom, an alkoxy group having 1 to 40 carbon atoms and substituted with at least one functional group, an aryloxy group having 6 to 60 ring carbon atoms and substituted with at least one functional group, an alkylsilyl group having 1 to 40 carbon atoms and substituted with at least one functional group, an arylsilyl group having 6 to 60 ring carbon atoms and substituted with at least one functional group, an alkylboron group having 1 to 40 carbon atoms and substituted with at least one functional group, an arylboron group having 6 to 60 ring carbon atoms, a phosphine group having 1 to 40 carbon atoms and substituted with at least one functional group, and a phosphine oxide group having 1 to 40 carbon atoms and substituted with at least one functional group, wherein said functional group is selected from the group consisting of: a cyano group, a nitro group, a trifluoromethyl group, a fluor group, and a chloro group.

8. The compound as claimed in claim 1, wherein at least one of Z.sup.1 to Z.sup.8 in Formula (I) is selected from the group consisting of: ##STR00191## ##STR00192## ##STR00193## ##STR00194## ##STR00195## wherein R.sup.1 to R.sup.7 are each independently selected from the group consisting of: a hydrogen atom, a deuterium atom, a halogen group a cyano group, a nitro group, an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkynyl group having 2 to 12 carbon atoms, a cycloalkyl group having 3 to 30 ring carbon atoms, a heterocycloalkyl group having 3 to 30 ring carbon atoms, an aryl group having 6 to 30 ring carbon atoms, a heteroaryl group having 3 to 20 ring carbon atoms, an alkoxy group having 1 to 40 carbon atoms, an aryloxy group having 6 to 30 ring carbon atoms, an alkylsilyl group having 1 to 40 carbon atoms, an arylsilyl group having 6 to 30 ring carbon atoms, an alkylboron group having 1 to 40 carbon atoms, an arylboron group having 6 to 30 ring carbon atoms, a phosphine group having 1 to 30 carbon atoms, and a phosphine oxide group having 1 to 30 carbon atoms; wherein n is a positive integral from 0 to 4, m is a positive integral from 0 to 3, o is a positive integral from 0 to 3, and the total of m and o is not more than 5.

9. The compound as claimed in claim 1, wherein at least one of Z.sup.1, Z.sup.2. Z.sup.3, Z.sup.6, Z.sup.7, and Z.sup.8 in Formula (I) is selected from the group consisting of: ##STR00196## ##STR00197## ##STR00198## ##STR00199## ##STR00200## wherein R.sup.1 to R.sup.7 are each independently selected from the group consisting of: a hydrogen atom, a deuterium atom, a halogen group, a cyano group, a nitro group, an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkynyl group having 2 to 12 carbon atoms, a cycloalkyl group having 3 to 30 ring carbon atoms, a heterocycloalkyl group having 3 to 30 ring carbon atoms, an aryl group having 6 to 30 ring carbon atoms, a heteroaryl group having 3 to 20 ring carbon atoms, an alkoxy group having 1 to 40 carbon atoms, an aryloxy group having 6 to 30 ring carbon atoms, an alkylsilyl group having 1 to 40 carbon atoms, an arylsilyl group having 6 to 30 ring carbon atoms, an alkylboron group having 1 to 40 carbon atoms, an arylboron group having 6 to 30 ring carbon atoms, a phosphine group having 1 to 30 carbon atoms, and a phosphine oxide group having 1 to 30 carbon atoms; wherein n is a positive integral from 0 to 4, m is a positive integral from 0 to 3, o is a positive integral from 0 to 3, and the total of m and o is not more than 5; wherein Z.sup.4 and Z.sup.5 are each independently selected from the group consisting of: a hydrogen atom, a deuterium atom, a halogen group, a cyano group, a nitro group, an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, and an alkynyl group having 2 to 12 carbon atoms.

10. The compound as claimed in claim 1, wherein at least one of Z.sup.2, Z.sup.3, Z.sup.6, and Z.sup.7 in Formula (I) is selected from the group consisting of: ##STR00201## ##STR00202## ##STR00203## ##STR00204## ##STR00205##

11. The compound as claimed in claim 1, wherein at least one of Z.sup.1, Z.sup.2, Z.sup.3, Z.sup.6, Z.sup.7, and Z.sup.8 in Formula (I) is a substituted triazine group with two phenyl groups, two pyridine groups, two pyrimidine groups, two pyrazine groups, two pyridazine groups, two phenylpyridine groups, two phenylpyrimidine groups, two phenylpyrazine groups, or two phenylpyridazine groups.

12. The compound as claimed in claim 1, wherein Z.sup.9 to Z.sup.12 in Formula (I) are each independently selected from the group consisting of: a hydrogen atom, a deuterium atom, a halogen group, a cyano group, a nitro group, an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, and an alkynyl group having 2 to 12 carbon atoms.

13. The compound as claimed in claim 1, wherein the compound is selected from the group consisting of: ##STR00206## ##STR00207## ##STR00208##

14. An organic electronic device, comprising a first electrode, a second electrode, and an organic layer disposed between the first electrode and the second electrode, wherein the organic layer comprises the compound as claimed in claim 1.

15. The organic electronic device as claimed in claim 14, wherein the organic electronic device is an organic light emitting device.

16. The organic electronic device as claimed in claim 15, wherein the organic light emitting device comprises: a hole injection layer formed on the first electrode; a hole transport layer formed on the hole injection layer; an emission layer formed on the hole transport layer; an electron transport layer formed on the emission layer, wherein the organic layer is the electron transport layer; and an electron injection layer formed between the electron transport layer and the second electrode.

17. The organic electronic device as claimed in claim 15, wherein the organic light emitting device comprises: a hole injection layer formed on the first electrode; a hole transport layer formed on the hole injection layer; an emission layer formed on the hole transport layer; a hole blocking layer formed on the emission layer, wherein the organic layer is the bole blocking layer; an electron transport layer formed on the hole blocking layer; and an electron injection layer formed between the electron transport layer and the second electrode.

18. The organic electronic device as claimed in claim 14, wherein the compound is selected from the group consisting of: ##STR00209## ##STR00210## ##STR00211##

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 illustrates a schematic cross-sectional view of an OLED.

(2) FIGS. 2 to 13 are respectively .sup.1H nuclear magnetic resonance (NMR) spectra of Compounds I to XII.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

(3) Hereinafter, one skilled in the arts can easily realize the advantages and effects of a novel compound and an organic light emitting device using the same in accordance with the present invention from the following examples. It should be understood that the descriptions proposed herein are just preferable examples only for the purpose of illustrations, not intended to limit the scope of the invention. Various modifications and variations could be made in order to practice or apply the present invention without departing from the spirit and scope of the invention.

(4) Synthesis of Intermediate A1

(5) Intermediate A1 used for preparing a novel compound was synthesized by the following steps. The synthesis pathway of the Intermediate A1 was summarized in Scheme A1.

(6) ##STR00055##

(7) Step 1: Synthesis of Intermediate A1-1

(8) A mixture of 3-bromodibenzo[a,d]cyclohepten-5-one (86 g, 1.0 eq). N-bromosuccinimide (NBS) (106 g, 2 eq). benzyl peroxide (0.7 g, 0.01 eq) in carbon tetrachloride (CCl.sub.4) (430 ml) was heated to 85 C. The reaction was monitored by high performance liquid chromatography (HPLC). After completion of a reaction, the precipitate was separated by filtration and washed with CH.sub.3OH and then purified by recrystalization. The purified product was concentrated to dryness, whereby a white solid product was obtained in an amount of 123 g and a yield of 92.3%.

(9) The solid product was identified as Intermediate A1-1 by a field desorption mass spectroscopy (FD-MS) analysis. PD-MS analysis: C.sub.15H.sub.9Br.sub.3O: theoretical value of 444.94 and observed value of 444.94.

(10) Step 2: Synthesis of Intermediate A1-2

(11) The obtained Intermediate A1-1 (116.0 g, 1.0 eq) was dissolved in 960 ml of furan/THF(v/v=2/1), and the reaction was cooled to 0 C. and then treated with potassium tert-butoxide (K-OtBu) (87.8 g, 3.0 eq). The reaction was allowed to stir at 0 C. for hour, and then stirred at room temperature for another 12 hours. Quenched by DI water, the organic layer was recovered by solvent extraction operation and dried over sodium sulfate. The solvent was removed from the organic layer by distillation under reduced pressure, and the resulting residue was purified by silica gel column chromatography. The purified product was concentrated to dryness, whereby a light yellow solid product was obtained in an amount of 46.8 g and a yield of 51.1%.

(12) The solid product was identified as Intermediate A1-2 by FD-MS analysis. FD-MS analysis C.sub.19H.sub.11BrO.sub.2: theoretical value of 351.19 and observed value of 351.19.

(13) Step 3: Synthesis of Intermediate A1-3

(14) A suspension of Intermediate A1-2 (53.5 g, 1.0 eq) and 5% Pd/C (8.1 g, 0.025 eq) in 535 ml of ethyl acetate (EA) was stirred for 3 hours to 6 hours under a hydrogen atmosphere (H.sub.2) provided by a balloon of hydrogen. The resulting mixture was filtered through a pad of celite and washed with EA, and the filtrate was concentrated under reduced pressure to obtain 100 g (100%) of yellow solid product.

(15) The solid product was identified as Intermediate A1-3 by FD-MS analysis. FD-MS analysis C.sub.19H.sub.13BrO.sub.2: theoretical value of 353.21 and observed value of 353.21. The intermediate A1-3 can be directly used in the following step without further purification.

(16) Step 4: Synthesis of Intermediate A1-4

(17) Intermediate A1-3 (53 g, 1.0 eq) and p-toluenesulfonic acid (PTSA) (57 g, 2.0 eq) in 530 ml of toluene was heated to reflux for 12 hours. The reaction mixture was cooled to room temperature and then quenched with a saturated aqueous solution of NaHCO.sub.3 and extracted with CH.sub.2Cl.sub.2. The organic layer was washed with water, brine and dried with anhydrous Na.sub.2SO.sub.4 subsequently. Then the resulting solution was concentrated under reduced pressure and purified by column chromatography on silica gel with CH.sub.2Cl.sub.2/hexane 1/1 (v/v) as eluent, whereby a light yellow solid product was obtained in an amount of 46.0 g and a yield of 91.5%.

(18) The solid product was identified as Intermediate A1 by FD-MS analysis. FD-MS analysis C.sub.19H.sub.11BrO: theoretical value of 335.19 and observed value of 335.19.

(19) Synthesis of Intermediate A2

(20) Intermediate A2 used for preparing a novel compound was synthesized in a similar manner as Intermediate A1through steps 1 to 4, except that the starting material 3-bromodibenzo[a,d]cyclohepten-5-one was replaced by 2-bromodibenzo[a,d]cyclohepten-5-one (CAS No. 198707-82-3). The synthesis pathway of Intermediate A2 was summarized in Scheme A2. All intermediates were analyzed according to the methods as described above, and the results were listed in Table 1.

(21) ##STR00056##

(22) Synthesis of Intermediate A3

(23) Intermediate A3 used for preparing a novel compound was synthesized in a similar manner as Intermediate A1 through steps 1 to 4except that the starting material 3-bromodibenzo[a,d]cyclohepten-5-one was replaced by 3,7-dihromodibenzo[a,d]cyclohepten-5-one (CAS No. 226946-20-9). The synthesis pathway of Intermediate A3 was summarized in Scheme A3. All intermediates were analyzed as described above, and the results were listed in Table 1.

(24) ##STR00057##

(25) TABLE-US-00001 TABLE 1 chemical structures, yields, formulae, and mass (M.sup.+) analyzed by FD-MS of intermediates. Intermediate A1-1 A1-2 A1-3 A1 Chemical Structure 0 Yield 92.3% 60.3% NA 91.5% Formula C.sub.15H.sub.9Br.sub.3O C.sub.19H.sub.11BrO.sub.2 C.sub.19H.sub.13BrO.sub.2 C.sub.19H.sub.11BrO Mass(M.sup.+) 444.94 351.19 353.21 335.19 Intermediate A2-1 A2-2 A2-3 A2 Chemical Structure Yield 91.5% 58.2% NA 93.5% Formula C.sub.15H.sub.9Br.sub.3O C.sub.19H.sub.11BrO.sub.2 C.sub.19H.sub.13BrO.sub.2 C.sub.19H.sub.11BrO Mass(M.sup.+) 444.94 351.19 353.21 335.19 Intermediate A3-1 A3-2 A3-3 A3 Chemical Structure Yield 93.7% 75.8% NA 93.0% Formula C.sub.15H.sub.8Br.sub.4O C.sub.19H.sub.10Br.sub.2O.sub.2 C.sub.19H.sub.12Br.sub.2O.sub.2 C.sub.19H.sub.10Br.sub.2O Mass(M.sup.+) 523.84 430.09 432.11 414.09

(26) Modifications of Intermediates A1 to A3

(27) In addition to the Intermediates A1 to 3, one person skilled in the art can adopt other starting materials and successfully synthesize other desired intermediates through a reaction mechanism similar to Scheme A1 to A3. Applicable modifications of Intermediates A1 to A3 may be for example, but not limited to, Intermediates A4 to A15 as follows.

(28) ##STR00070## ##STR00071##

(29) Synthesis of Intermediates b1 to B4 and B6

(30) Intermediates B1 to B4 and B6 were synthesized by reacting 1-bromo-2-iodobenzene and aryl boronic acid (Regent A). A general synthesis pathway for Intermediate Bn was summarized in Scheme B1. In the following Scheme B1 Reactant A may be an one of Reactants A1 to A4 and A6 as listed in Table 2, and Intermediate Bn ma be an one of foresaid Intermediates B1 to B4 and B6.

(31) ##STR00072##

(32) According to the Scheme B1, each of the Intermediates B1 to B4 and B6 was synthesized by the steps as follows.

(33) 1-bromo-2-iodobenzene (1.0 eq), Reactant A (1.2 eq), potassium carbonate (3.0 eq), 200 ml of toluene, tri(m-tolyl)phosphine (P(m-toyl).sub.3) (0.06 eq) and Pd(OAc).sub.2 (0.015 eq) were mixed and stirred at 80 C. for 12 hours. The reaction mixture was then cooled to room temperature, and an organic layer was extracted with saturated aqueous solution of sodium chloride and EA and dried over magnesium sulfate, and then treated with activated characoal, followed by filtering with silica gel. After a solid prepared by concentrating the filtrate under reduced pressure was suspended in hexane, the suspension was filtered again and washed with hexane to obtain Intermediate Bn. All intermediates were analyzed according to the methods as described above, and the results were listed in Table 2.

(34) TABLE-US-00002 TABLE 2 Reactant A used for preparing Intermediates B1 to B4 and B6, and the chemical structures, yields, formulae, and mass analyzed by FD-MS of Intermediates B1 to B4 and B6. Intermediate Bn Reactant A Yield Formula/ Chemical Structure Chemical Structure (%) Mass (M.sup.+) 91.0 C.sub.16H.sub.11Br/ 283.16 90.7 C.sub.21H.sub.17Br/ 349.26 90.2 C.sub.20H.sub.13Br/ 333.22 0 86.5 C.sub.22H.sub.13Br/ 357.24 80 C.sub.24H.sub.15Br/ 383.28

(35) Synthesis of Intermediates B5

(36) In addition to Scheme B1, another synthesis pathway for Intermediate B5 was summarized in Scheme B2.

(37) ##STR00083##

(38) Step 1: Synthesis of Intermediate B5-1

(39) A mixture of dichloro bis-(triphenylphosphine) palladium (0.05 eq) and 2-bromobenzaldehyde (1 eq) in THF (0.13 to 0.15 M) was added with triethylamine (3.0 eq). After being stirred for 10 min at room temperature, phenyl acetylene (1.5 eq) and copper iodide (0.05 eq) were added to the mixture. The resulting mixture was stirred at room temperature for 24 h. The reaction mixture was quenched with saturated aqueous of NH.sub.4Cl, extracted with EtOAc three times, and washed with brine. The organic layers were dried over Na.sub.2SO.sub.4 and concentrated under a reduced pressure after filtration. The crude mixture was purified by silica-gel column chromatography to obtain Intermediate B5-1 in a yield of 92.4%. The product was identified as Intermediate B5-1 by FD-MS analysis. FD-MS analysis: C.sub.15H.sub.10O: theoretical value of 206.64 and observed value of 206.64.

(40) Step 2: Synthesis of Intermediate B5

(41) A mixture of intermediate B5-1 (1.0 eq) and Cu(OTf).sub.2 (0.05 eq) in 1,2-dichloroethane (5 times of Intermediate B5-1) were added with 1-(2-bromoethynyl)benzene(1.2 eq) and CF.sub.3CO.sub.2H (1.0 eq) successively at room temperature under argon atmosphere. The resulting mixture was stirred at 100 C. for 15 min and then cooled to room temperature. A saturated aqueous solution of NaHCO.sub.3 was added, and the mixture was extracted with ether three times. The combined extracts were washed with brine, dried over MgSO.sub.4, and evaporated to leave the crude product. The crude product was then purified by silica gel column chromatography using hexane as an eluent to give Intermediate B5 (yield 80%). The product was identified as intermediate B5 by FD-MS analysis. FD-MS analysis: C.sub.16H.sub.11Br: theoretical value of 283.16 and observed value of 283.16.

(42) Modifications of Intermediates B1 to B6

(43) In addition to the Intermediates B1 to B6, one person skilled in the art can adopt any dihalobenzenes other than 1-bromo-2-iodobenzene and any aryl boronic acids other than Reactants A1 to A5 to successfully synthesize other desired Intermediates Bn through a reaction mechanism similar to Scheme B1. Moreover, one person skilled in the art also can adopt any halo-aromatic aldehyde other than 2-bromobenzaldehyde and any aromatic alkyne other than ethynylbenzene to successfully synthesize other desired Intermediates Bn through a reaction mechanism similar to Scheme B2. Applicable modifications of Intermediates B1 to B6 may be, for example, but not limited to, Intermediates B7 and B14 as follows.

(44) ##STR00084## ##STR00085##

(45) Synthesis of Intermediates Cn

(46) The foresaid Intermediates B1 to B14, especially the foresaid Intermediates B1 to B5 were further adopted to synthesize Intermediate Cn. A general synthesis pathway for Intermediate Cn was summarized in Scheme C. In the following Scheme C1, Intermediate An may be any one of foresaid Intermediates A1 to A15 or the like, Intermediate Bn may be any one of foresaid Intermediates B1 to B14 or the like, and Intermediate Cn may be any one of Intermediates C1 to C11 as listed in Table 3-1 or the like. Intermediates C1 to C11 were each synthesized by the following steps.

(47) ##STR00086##

(48) Step 1: Synthesis of Alcohol Intermediate

(49) Intermediate Bn (1.0 eq) was dissolved in 120 mL of anhydrous THF (0.4M), and cooled to 78 C. n-Butyllithium (n-BuLi)(2.5 M,1.0 eq) was slowly added to the above cooled solution, and reaction mass was stirred for 1 h. After 1 h of stirring, Intermediate An (0.7 eq) was added to the reaction solution and stirred for additional 3 h at room temperature. After the completion of the reaction, it was quenched by saturated solution of ammonium chloride, and extracted with organic solvent. The organic layer was separated, concentrated, and recrystallized with petroleum ether to obtain a white solid product.

(50) The white solid product was identified as alcohol intermediate by FD-MS analysis. Take intermediate C1-1 as an example, FD-MS analysis: C.sub.37H.sub.23BrO.sub.2: theoretical value of 579.48 and observed value of 579.48.

(51) The alcohol intermediate could be directly used in step 2 without further purification. Each alcohol intermediate synthesized by reacting different Intermediates An with Intermediates Bn was identified by FD-MS. The chemical structure of each alcohol intermediate was listed in Table 3-1.

(52) Step 2: Synthesis of Intermediate Cn

(53) Alcohol intermediate (1.0 eq), acetic acid (w/v=1/3 to the reactant) and H.sub.2SO.sub.4(5 drops) were mixed, and the mixture was stirred at 110 C. for 6 hours. The solvent was then removed under reduced pressure, and the residue was purified with column chromatography. The residual mass was recrystallized with toluene to obtain a white solid product.

(54) The solid product was identified by FD-MS analysis. The chemical structures, yields, formulae, and mass analyzed by FD-MS of Intermediates C1 to C11 were listed in Table 3-1.

(55) TABLE-US-00003 TABLE 3-1 Intermediates An and Bn used for preparing Intermediates C1 to C11, chemical structures of alcohol intermediates, and chemical structures, yields, formulae, and mass analyzed by FD-MS of Intermediates C1 to C11. Alcohol Intermediate Cn Intermediate Intermediate intermediate Yield Formula/ An Bn Chemical Structure Chemical Structure (%) Mass (M.sup.+) A1 B1 93 C.sub.35H.sub.21Br/ 521.46 A2 B1 0 91 C.sub.35H.sub.21Br/ 521.46 A3 B1 76 C.sub.35H.sub.20Br.sub.2/ 600.34 A1 B5 81 C.sub.35H.sub.21Br/ 521.45 A3 B5 68 C.sub.35H.sub.20Br.sub.2/ 600.34 A1 B2 87 C.sub.40H.sub.27Br/ 587.55 A3 B2 00 61 C.sub.40H.sub.26Br.sub.2/ 666.44 A1 B3 01 02 83 C.sub.39H.sub.23Br/ 571.5 A3 B3 03 04 77 C.sub.39H.sub.22Br.sub.2/ 650.4 A1 B4 05 06 95 C.sub.41H.sub.23Br/ 595.53 A3 B4 07 08 73 C.sub.41H.sub.22Br.sub.2/ 674.42

(56) Modifications of Intermediates C1 to C11

(57) In addition to the intermediates C1 to C11, one person skilled in the art can adopt any Intermediate An other than Intermediates A1 to A4 anchor any Intermediate Bn other than Intermediates B1 to B5 to successfully synthesize other desired intermediates Cn through a reaction mechanism similar to Scheme C1. Applicable modifications of Intermediates C1 to C11 may be, for example, but not limited to, Intermediates C12 to C23 as follows.

(58) ##STR00109## ##STR00110## ##STR00111##

(59) Synthesis of Intermediate Cn-B

(60) The foresaid Intermediate Cn could be further modified into an Intermediate Cn-B through Miyaura borylation reaction. Intermediate Cn-Bwas directed to a compound derived from Intermediate Cn whose bromo group was replaced by (pinacolato)boron group. A synthesis pathway of Intermediate Cn-B was summarized in Scheme C1-B. Intermediate Cn-B was synthesized by the following steps.

(61) ##STR00112##

(62) A mixture of bis(pinacolato)diboron (1.2 eq), Intermediate C1(1.0 eq), 1,1-bis(diphenylphosphino)-ferrocene dichloropalladium II)((PdCl.sub.2(dppf)) (0.015 eq) and potassium acetate (KOAc) (3.0 eq) in anhydrous 1,4-dioxane (0.3 M) was stirred at 110 C. for 8 hours under nitrogen atmosphere. After cooling to room temperature, the solvent was then removed under reduced pressure, and the residue was purified via column chromatography to obtain a pale yellow solid product.

(63) The pale yellow solid product was identified by FD-MS analysis. The chemical structures, yields, formulae, and mass analyzed by FD-MS of Intermediates Cn-B were listed in Table 3-2.

(64) TABLE-US-00004 TABLE 3-2 Intermediate Cn used for preparing Intermediate Cn-B and chemical structures, yields, formulae, and mass analyzed by FD-MS of Intermediates Cn-B. Intermediate Cn Intermediate Cn-B Yield Yield Formula/ Chemical Structure (%) Chemical Structure (%) Mass(M.sup.+) 93 94 C.sub.41H.sub.33BO.sub.2/ 568.51 91 98 C.sub.41H.sub.33BO.sub.2/ 568.51 81 95 C.sub.41H.sub.33BO.sub.2/ 568.51 87 0 93 C.sub.46H.sub.39BO.sub.2/ 634.63 83 95 C.sub.45H.sub.35BO.sub.2/ 618.59 95 97 C.sub.47H.sub.35BO.sub.2/ 642.59

(65) Modifications Intermediate Cn-B

(66) In addition to the Intermediates C1-B, C2-B, C4-B, C6-B, C8-B, and C10-B, one person skilled in the art can adopt any one of Intermediates Cn other than Intermediates C1, C2, C4, C6, C8, and C10 to undergo a Miyaura borylation reaction to successfully synthesize other desired intermediates as follows.

(67) ##STR00125## ##STR00126##

(68) Synthesis of Novel Compounds

(69) Each of Intermediates C1 to C11 and C1-B to C11-B could be reacted with various reactants to synthesize various claimed novel compounds. The general synthesis pathway of the claimed novel compound was summarized in Scheme I. In the following Scheme I, Reactant B may be any one of Reactants B1 to B34 as listed in Table 4, and Intermediate C may be any one of foresaid Intermediates Cn and Cn-B. The compounds were each synthesized by the following steps.

(70) ##STR00127##

(71) TABLE-US-00005 TABLE 4 chemical structure and CAS No. of Reactants B1 to B34. Reactant No. Reactant B1 Reactant B2 Reactant B3 Chemical Structure 0 CAS No. [126747-14-6] [774-53-8] [1319255-85-0] Reactant No. Reactant B4 Reactant B5 Reactant B6 Chemical Structure CAS No. [29509-91-9] [916653-46-8] [7089-68-1] Reactant No. Reactant B7 Reactant B8 Reactant B9 Chemical Structure CAS No. [29874-83-7] [867044-33-5] [3842-55-5] Reactant No. Reactant B10 Reactant B11 Reactant B12 Chemical Structure CAS No. [181219-01-2] [6484-25-9] [1009033-87-7] Reactant No. Reactant B13 Reactant B14 Reactant B15 Chemical Structure 0 CAS No. [329214-79-1] [1260106-29-3] Reactant No. Reactant B16 Reactant B17 Reactant B18 Chemical Structure CAS No. [867044-33-5] [150255-96-2] [406482-73-3] Reactant No. Reactant B19 Reactant B20 Reactant B21 Chemical Structure CAS No. [952514-79-3] [1588407-97-9] [1300115-09-6] Reactant No. Reactant B22 Reactant B23 Reactant B24 Chemical Structure 0 CAS No. [3114-52-1] [1616231-57-2] [1421599-34-9] Reactant No. Reactant B25 Reactant B26 Reactant B27 Chemical Structure CAS No. [99682-89-0] [170230-28-1] Reactant No. Reactant B28 Reactant B29 Reactant B30 Chemical Structure Reactant No. Reactant B31 Reactant B32 Chemical Structure Reactant No. Reactant B33 Reactant B34 Chemical Structure 0

(72) A mixture of Intermediate Cn (1.0 eq), Pd(OAc).sub.2(0.01 eq), Pt(Cy).sub.2(2-biphenyl) 0.04 eq), toluene/ethanol (0.5M, v/v=10/1), 3.0 M potassium carbonate solution, and Reactant Bn (1.2 eq) was stirred at 100 C. for 12 h under nitrogen atmosphere. After the completion of the reaction, water and toluene were added to the reaction mass. Subsequently, the organic layer was recovered by solvent extraction operation and dried over sodium sulfate. The solvent was then removed from the organic layer under reduced pressure, and the resulting residue was purified by silica gel column chromatography. The obtained residue was recrystallized with toluene to obtain white solid as the claimed novel compound.

(73) Reactant B and Intermediate C adopted to synthesize Compounds I to XII were listed in Table 5. Compounds I to XII were identified by H.sup.1-NMR and FD-MS, and the chemical structure, yield, formula and mass of each of Compounds I to XII were also listed in Table 5. According to FIGS. 2 to 13 and the results of FD-MS, the chemical structure of Compounds I to XII were identified as follows.

(74) TABLE-US-00006 TABLE 5 reactants and intermediates adopted to prepare Compounds I to XII and their yields, formulae, and FD-MS data. Claimed Compound Reactant Intermediate Formula/ No. No. Chemical Structure Yield Mass (M.sup.+) B1 C1 86 C.sub.42H.sub.25N/ 543.65 B9 C1-B 81 C.sub.50H.sub.31N.sub.3/ 673.8 B8 C1 89 C.sub.54H.sub.34N.sub.2/ 710.86 B3 C1 91 C.sub.45H.sub.28N.sub.2/ 596.72 B5 C1-B 85 C.sub.47H.sub.28N.sub.2 620.76 B11 C1-B 84 C.sub.49H.sub.30N.sub.2 646.79 B4 C8-B 82 C.sub.55H.sub.34N.sub.2 722.89 B2 C4-B 71 C.sub.45H.sub.28N.sub.2/ 596.73 B5 C6-B 0 76 C.sub.52H.sub.34N.sub.2 686.86 B2 C10-B 66 C.sub.51H.sub.30N.sub.2 670.81 B9 C2-B 93 C.sub.50H.sub.31N.sub.3 673.82 B10 C11 72 C.sub.51H.sub.30N.sub.2 670.81

(75) Modifications of Compounds I to XII

(76) In addition to the Compounds I to XII, one person skilled in the art can react any Intermediate C, i.e., the foresaid Intermediate Cn or Cn-B, with any Reactant B through a reaction mechanism similar to Scheme I to synthesize other desired claimed novel compounds.

(77) Preparation of OLED devices

(78) A glass substrate coated with an ITO layer (abbreviated in ITO substrate) in a thickness of 1500 was placed in distilled water containing a detergent dissolved therein, and was ultrasonically washed. The detergent was a product manufactured by Fischer Co., and the distilled water was distilled water filtered, twice through a filter (Millipore Co.). After the ITO layer had been washed for 30 minutes, it was ultrasonically washed twice with distilled water for 10 minutes. After the completion of washing, the glass substrate was ultrasonically washed with isopropyl alcohol, acetone and methanol solvents and then dried, after which it was transported to a plasma cleaner. Then the substrate was cleaned with oxygen plasma for 5 minutes, and then transferred to a vacuum evaporator.

(79) After that, various organic materials and metal materials were sequentially deposited on the ITO substrate to obtain the OLED device of Examples 1 to 29. The vacuum degree during the deposition was maintained at 110.sup.6 to 310.sup.7 torr. Herein, the ITO substrate was deposited with a first hole injection layer (HIL-1), a second hole injection layer (HIL-2), a first hole transporting layer (HTL-1), a second hole transporting layer (HTL-2), a blue/green/red emission layer (BEL/GEL/REL), an electron transporting layer (ETL), an electron injection layer (EIL), and a cathode (Cthd).

(80) Herein, HAT was a material for forming HIL-1 and was a dopant for forming HIL-2; HI-2 was a material for forming HIL-2; HT-1 and HT-2 were respectively materials for forming HTL-1 and HTL-2; conventional ET and novel compounds of the present invention were materials for forming ETL; Liq was a dopant for forming ETL and was a material for forming EIL. RH/GH/BH were host materials for forming REL/GEL/BEL, and RD/GD/BD were dopants for forming REL/GEL/BEL. The main difference of the OLEDs between Examples and Comparative Examples was that the ETL of OLED in the following comparative examples was made of BCP but the ETLs of OLEDs in the following examples were made of the novel compounds of the present invention as listed in Table 5. The detailed chemical structures of foresaid commercial materials were listed in Table 6.

(81) TABLE-US-00007 TABLE 6 chemical structures of commercial materials for OLED devices. HAT HI-2 HT-1 HT-2 BH BD 0 GH GD RH RD Liq BCP

(82) Preparation of Red OLED Devices

(83) To prepare the red OLED device, multiple organic layers were respectively deposited on the ITO substrate according to the sequence as listed in Table 7, and the materials and the thicknesses of the organic layers in red OLED devices were also listed in Table 7.

(84) TABLE-US-00008 TABLE 7 coating sequence, materials and thickness of the organic layers in red OLED device. Coating Sequence Layer Material Thickness 1 HIL-1 HAT 100 2 HIL-2 HI-2 doped with 5.0 wt % of HAT 2100 3 HTL-1 HT-1 100 4 HTL-2 HT-2 100 5 REL RH doped with 3.5 wt % of RD 300 6 ETL Commercial ET/novel compounds 350 doped with 35.0 wt % of Liq 7 EIL Liq 15 8 Cthd Al 1500

(85) Preparation Green OLED Devices

(86) To prepare the green OLED device, multiple organic layers were respectively deposited on the ITO substrate according to the sequence as listed in Table 8. and the materials and the thicknesses of the organic layers in green OLED devices were also listed in Table 8.

(87) TABLE-US-00009 TABLE 8 coating sequence, materials and thickness of the layers in green OLED device. Coating Sequence Layer Material Thickness 1 HIL-1 HAT 100 2 HIL-2 HI-2 doped with 5.0 wt % of HAT 2100 3 HTL-1 HT-1 100 4 HTL-2 HT-2 100 5 GEL GH doped with 10.0 wt % of GD 300 6 ETL Commercial ET/novel compounds 350 doped with 35.0 wt % of Liq 7 EIL Liq 15 8 Cthd Al 1500

(88) Preparation of Blue OLED Devices

(89) To prepare the blue OLED device, multiple organic layers were respectively deposited on the ITO substrate according to the sequence as listed in Table 9, and the materials and the thicknesses of the organic layers in blue OLED devices were also listed in Table 9.

(90) TABLE-US-00010 TABLE 9 coating sequence, materials and thickness of the layers in blue OLED device. Coating Sequence Layer Material Thickness 1 HIL-1 HAT 100 2 HIL-2 HI-2 doped with 5.0 wt % of HAT 2100 3 HTL-1 HT-1 100 4 HTL-2 HT-2 100 5 BEL BH doped with 3.5 wt % of BD 300 6 ETL Commercial ET/novel compounds 350 doped with 35.0 wt % of Liq 7 EIL Liq 15 8 Cthd Al 1500

(91) Performance of OLED Device

(92) To evaluate the performance of OLED devices, red, green, and blue OLED devices were measured by PR650 as photometer and Keithley 2400 as power supply. Color coordinates (x,y) were determined according to the CIE chromaticity scale (Commission Internationale de L'Eclairage, 1931). The results were shown in Table 10. For the blue and red OLED devices, the data were collected at 1000 nits. For the green OLED devices, the data were collected at 3000 nits.

(93) The materials of ETL, color and data of CIE, driving voltage, current efficiency, and external quantum efficiency (EQE) of Examples 1 to 29 and Comparative Examples 1 to 3 were listed in Table 10.

(94) TABLE-US-00011 TABLE 10 materials of ETL, characteristics and performance of OLED devices of Examples 1 to 29 and Comparative Examples 1 to 3. Current Effi- OLED Material of Voltage ciency EQE device No. ETL Color, CIE (x, y) (V) (cd/A) (%) Example 1 Compound I B (0.130, 0.151) 5.09 10.5 7.67 Example 2 Compound B (0.129, 0.152) 4.04 11.4 7.78 II Example 3 Compound B (0.130, 0.163) 6.02 8.10 6.31 III Example 4 Compound B (0.129, 0.155) 6.00 9.12 6.56 IV Example 5 Compound B (0.129, 0.153) 4.85 9.85 7.25 V Example 6 Compound B (0.129, 0.155) 4.98 10.8 7.56 VI Example 7 Compound B (0.130, 0.147) 4.97 10.2 6.86 VII Example 8 Compound B (0.129, 0.156) 4.83 10.7 7.15 VIII Example 9 Compound B (0.129, 0.150) 5.05 8.79 6.41 IX Example 10 Compound B (0.129, 0.151) 4.13 10.5 6.86 X Example 11 Compound B (0.129, 0.150) 4.76 10.5 6.44 XI Example 12 Compound B (0.129, 0.159) 4.47 10.0 6.71 XII Comparative BCP B (0.130, 0.142) 6.71 6.98 4.88 Example 1 Example 13 Compound I G (0.314, 0.638) 4.60 76.9 17.42 Example 14 Compound G (0.311, 0.639) 2.98 77.9 17.95 II Example 15 Compound G (0.313, 0.639) 4.59 71.0 17.0 IV Example 16 Compound G (0.320, 0.635) 3.08 74.9 20.01 V Example 17 Compound G (0.313, 0.639) 3.45 72.0 17.87 VI Example 18 Compound G (0.317, 0.637) 3.32 75.6 18.95 VIII Example 19 Compound G (0.315, 0.638) 3.33 74.4 18.75 IX Example 20 Compound G (0.310, 0.641) 3.80 75.1 17.05 X Example 21 Compound G (0.319, 0.637) 3.89 82.2 17.74 XI Comparative BCP G (0.313, 0.638) 4.67 70.3 16.95 Example 2 Example 22 Compound R (0.659, 0.339) 4.05 24.3 16.37 II Example 23 Compound R (0.658, 0.340) 4.10 25.0 17.16 IV Example 24 Compound R (0.658, 0.340) 3.64 24.6 17.37 V Example 25 Compound R (0.659, 0.339) 4.06 24.2 16.38 VI Example 26 Compound R (0.660, 0.338) 3.78 24.2 16.58 VIII Example 27 Compound R (0.662, 0.337) 3.82 24.5 16.99 IX Example 28 Compound R (0.659, 0.339) 4.12 28.1 20.88 X Example 29 Compound R (0.660, 0.338) 3.90 24.6 16.12 XI Comparative BCP R (0.659, 0.340) 4.16 24.1 16.05 Example 3

(95) Based on the results, in comparison with the commercial electron transport material, adopting Compounds I to XII as the electron transport material can reduce the driving voltage and improve the current efficiency and the external quantum efficiency of the red, green, or blue OLEDs. It demonstrated that the novel compound or the present invention is suitable as an electron transport material for any color OLEDs, and allows the OLEDs using the same to have low driving voltage and improved current efficiency as well as improved external quantum efficiency.

(96) Even though numerous characteristics and advantages of the present invention have been set forth in the foregoing description, it together with details of the structure and features of the invention, the disclosure is illustrative only. Changes may be made in the details, especially in matters of quantity, position, and arrangement of substitution groups within the principles of the invention to the full extent indicated by the broad general meaning of the terms in which the appended claims are expressed.