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 Y is an oxygen atom or a sulfur atom; 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; 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 or a heteroaryl ring.

Claims

1. A compound represented by the following Formula (I): ##STR00229## 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 together to form a second aryl ring or a heteroaryl ring; wherein Y is an oxygen atom or a sulfur atom; wherein at least one of Z.sup.1 to Z.sup.8 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 ring 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 fluoro group, and a chloro group; wherein the others of Z.sup.1 to Z.sup.8, Z.sup.9 and Z.sup.10 are each independently selected from the group consisting of: a hydrogen atom, a deuterium atom, a halogen group, a cyano group, a nitro group, a trifluoromethyl 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 heterocycloalkyl 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 compound is represented by ##STR00230## ##STR00231## ##STR00232## ##STR00233## ##STR00234## ##STR00235## wherein A.sup.1 and A.sup.2 are each independently C(R.sup.c), the two (R.sup.c)s are the same or different, and the two (R.sup.c)s are joined together to form an aromatic structure contained in the second aryl ring or the heteroaryl ring; wherein each Z.sup.11 is selected from the group consisting of: a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and a phenyl group.

3. The compound as claimed in claim 2, wherein the aromatic structure extended from A.sup.1 and A.sup.2 is a substituted or unsubstituted 6 to 20-membered carbon aromatic cyclic structure.

4. The compound as claimed in claim 3, wherein the substituted or unsubstituted 6 to 20-membered carbon aromatic cyclic structure is selected from the group consisting of: a substituted or unsubstituted benzene structure, a substituted or unsubstituted naphthalene structure, a substituted or unsubstituted anthracene structure, a substituted or unsubstituted phenanthrene structure, a substituted or unsubstituted pyrene structure, a substituted or unsubstituted fluoranthene structure, a substituted or unsubstituted benzofluoranthene structure, and a substituted or unsubstituted fluorene structure.

5. 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.

6. The compound as claimed in claim 5, 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 or unsubstituted anthracene ring, a substituted or unsubstituted phenanthrene ring, a substituted or unsubstituted pyrene ring, a substituted or unsubstituted fluoranthene ring, a substituted or unsubstituted benzofluoranthene ring, and a substituted or unsubstituted fluorene structure.

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

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: ##STR00236## ##STR00237## ##STR00238## ##STR00239## ##STR00240## ##STR00241## 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, a trifluoromethyl 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 an integer from 0 to 4, m is an integer from 0 to 3, o is an integer 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.2, Z.sup.3, Z.sup.6, and Z.sup.7 in Formula (I) is selected from the group consisting of: ##STR00242## ##STR00243## ##STR00244## ##STR00245## ##STR00246## ##STR00247## 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, a trifluoromethyl 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 an integer from 0 to 4, m is an integer from 0 to 3, o is an integer from 0 to 3, and the total of m and o is not more than 5; wherein Z.sup.1, Z.sup.4, Z.sup.5, Z.sup.8 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: ##STR00248## ##STR00249## ##STR00250## ##STR00251## ##STR00252##

11. The compound as claimed in claim 1, wherein Z.sup.9 and Z.sup.10 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.

12. The compound as claimed in claim 1, wherein the compound is selected from the group consisting of: ##STR00253## ##STR00254## ##STR00255## ##STR00256##

13. 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.

14. The organic electronic device as claimed in claim 13, wherein the organic electronic device is an organic light emitting device.

15. The organic electronic device as claimed in claim 14, 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.

16. The organic electronic device as claimed in claim 14, 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 hole 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.

17. The organic electronic device as claimed in claim 13, wherein the compound is selected from the group consisting of: ##STR00257## ##STR00258## ##STR00259## ##STR00260##

Description

BRIEF DESCRIPTION OF THE DRAWINGS

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

(2) FIGS. 2 to 18 are respectively .sup.1H nuclear magnetic resonance (NMR) spectra of Compounds 1 to 17.

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) ##STR00077##

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

(8) A mixture of 3-bromodibenzo[a,d]cyclohepten-5-one (CAS No. 3973-53-3) (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) (5 times of starting materials) was heated to 65 C. to 70 C. The reaction progress was monitored by high performance liquid chromatography (HPLC). After completion of the reaction, the precipitate was separated by filtration and washed with CH.sub.3OH, which was then purified by recrystallization. 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 field desorption mass spectroscopy (FD-MS) analysis. FD-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

(11) Intermediate A1-1 (1.0 eq) in dimethyl sulfoxide(DMSO) (w/v=1/3 to the reactants) was heated to 70 C. The reaction was monitored by HPLC. After completion of the reaction, the reaction mixture was quenched with ice water. The precipitate was separated by filtration and then purified by column chromatography on silica gel. Intermediate A1 was obtained as pale yellow solid in 93% yield.

(12) The solid product was identified as Intermediate A1 by FD-MS analysis. FD-MS analysis C.sub.15H.sub.9BrO: theoretical value of 285.14 and observed value of 285.14.

(13) Synthesis of Intermediate A2

(14) Intermediate A2 used for preparing a novel compound was synthesized in a similar manner as Intermediate A1 through steps 1 and 2, 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.

(15) ##STR00078##

(16) Synthesis of Intermediate A3

(17) Intermediate A3 used for preparing a novel compound was synthesized in a similar manner as Intermediate A1 through steps 1 and 2, except that the starting material 3-bromodibenzo[a,d]cyclohepten-5-one was replaced by 3,7-dibromodibenzo[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

(18) ##STR00079##

(19) TABLE-US-00001 TABLE 1 chemical structures, yields, formulae, and mass (M.sup.+) analyzed by FD-MS of intermediates. Intermediate A1-1 A1 Chemical Structure 0 Yield 92.3% 93% Formula C.sub.15H.sub.9Br.sub.3O C.sub.15H.sub.9BrO Mass(M.sup.+) 444.94 285.14 Intermediate A2-1 A2 Chemical Structure Yield 91.5% 87% Formula C.sub.15H.sub.9Br.sub.3O C.sub.15H.sub.9BrO Mass(M.sup.+) 444.94 285.14 Intermediate A3-1 A3 Chemical Structure Yield 93.7% 90% Formula C.sub.15H.sub.8Br.sub.4O C.sub.15H.sub.8Br.sub.2O Mass(M.sup.+) 523.84 364.03

(20) Modifications of Intermediates A1 to A3

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

(22) ##STR00086## ##STR00087##

(23) Synthesis of Intermediates B1 to B4

(24) Intermediates B1 to B4 were synthesized by reacting 1-fluoro-2-nitrobenzene and phenol derivatives. A general synthesis pathway for Intermediate Bn was summarized in Scheme B-1. In the following Scheme B-1, Reactant An may be any one of Reactants A1 to A4 as listed in Table 2-1, and Intermediate Bn may be any one of Intermediates B1 to B4.

(25) ##STR00088##

(26) According to Scheme B-1, each of Intermediates B1 to B4 was synthesized by Steps 1 to 3 as follows.

(27) Step 1: Synthesis of Intermediate Bn-1

(28) The mixture of Ar.sup.1OH (referred Reactant An, 1 eq.), 1-fluoro-2-nitrobenzene (50 g, 1 eq.), and cesium carbonate (Cs.sub.2CO.sub.3) (230.9 g, eq.) in DMF (2080 ml, 0.17M) was stirred at 90 C. under an argon atmosphere. After the completion of the reaction, DMF was distilled out. The residue was quenched with water, extracted with ethyl acetate (EA) and dried over magnesium sulfate, followed by concentration under reduced pressure after filtration. The crude mixture was purified by silica-gel column chromatography, and then identified as Intermediate Bn-1 by FD-MS analysis. Take Intermediate B1-1 as an example, FD-MS analysis: C.sub.12H.sub.9NO.sub.3: theoretical value of 215.2 and observed value of 215.2.

(29) Step 2: Synthesis of Intermediate Bn-2

(30) The mixture of intermediate Bn-1 (1 eq.), 5% Pd/C (10 g, 0.015 eq) in C.sub.2H.sub.5OH (680 ml, 0.5M) was stirred at 70 C. Hydrazine monohydrate (N.sub.2H.sub.4*H.sub.2O) (31.6 g, 2 eq.) was then slowly added to the mixture. After the completion of the reaction, the solution was filtered through a pad of Celite, followed by concentration under reduced pressure to obtain the product. The product was identified as intermediate Bn-2 by FD-MS analysis. Take Intermediate B1-2 as an example, FD-MS analysis: C.sub.12H.sub.11NO: theoretical value of 185.22 and observed value of 185.22.

(31) Step 3: Synthesis of Intermediate Bn

(32) The mixture of intermediate Bn-2 (1 eq.), p-toluenesulfonic acid monohydrate (PTSA*H.sub.2O) (172.5 g, 3 eq) in acetonitrile (ACN)(224 ml, 1.3 M) was cooled to 5 C. by using an ice bath. Sodium nitrite (NaNO.sub.2)(41.7 g, 2 eq.) in 240 ml water was added dropwise. After the addition was finished, the mixture was kept at 5 C. 1 hr. The resulting diazonium salt was treated slowly with potassium iodide (KI) (100 g, 2 eq.) in 300 ml water. After the completion of the reaction, the residue was extracted with EA and the combined organic layer was washed with a 10% Na.sub.2SO.sub.3(aq) and then dried over Na.sub.2SO.sub.4. The organic layer was concentrated under reduced pressure after filtration. The crude mixture was purified by silica-gel column chromatography to obtain intermediate Bn.

(33) The chemical structure of Ar.sup.1OH used for synthesizing Intermediate Bn, i.e., Intermediates B1 to B4, the yield, and the chemical structures of the products obtained in Steps 1 to 3 were listed in Table 2-1. All Intermediates Bn, including Intermediates B1 to B4, were analyzed by FD-MS, and the results were listed in Table 2-1.

(34) TABLE-US-00002 TABLE 2-1 Reactant An used for preparing Intermediates B1 to B4, and the chemical structures, yields, formulae, and mass analyzed by FD-MS of Intermediates B1 to B4. Reactant An Intermediate Bn-1 Chemical Chemical Yield Structure Structure (%) 0 89.2% Reactant Intermediate A1 B1-1 92% Reactant Intermediate A2 B2-1 91.6% Reactant Intermediate A3 B3-1 93% Reactant Intermediate A4 B4-1 Intermediate Bn Yield (%)/ Intermediate Bn-2 Formula/ Chemical Yield Chemical Mass Structure (%) Structure (M.sup.+) 95.7% 78.2%/ C.sub.12H.sub.9IO/ 296.1 Intermediate Intermediate B1-2 B1 95.3% 00 83%/ C.sub.16H.sub.11IO/ 346.16 Intermediate Intermediate B2-2 B2 01 94.6% 02 86%/ C.sub.18H.sub.11IO.sub.2/ (386.18) Intermediate Intermediate B3-2 B3 03 94% 04 81%/ C.sub.21H.sub.17IO/ 412.26 Intermediate Intermediate B4-2 B4

(35) Synthesis of Intermediate B5 to B8

(36) Unlike Intermediates B1 to B4, Intermediates B5 to B8 were synthesized by reacting 2-bromobenzenethiol and aryl iodide. Another general synthesis pathway for Intermediate Bn was summarized in Scheme B-2. In the following Scheme B-2, Reactant An may be any one of Reactants A5 to A8 as listed in Table 2-2 or the like, and Intermediate Bn may be any one of Intermediates B5 to B8.

(37) ##STR00105##

(38) According to the Scheme B-2, a mixture of tris(dibenzylideneacetone)dipalladium(0) (Pd.sub.2(dba).sub.3)(0.5% eq), bis[(2-diphenylphosphino)phenyl] ether (DPEphos) (0.01 eq), and sodium tert-butoxide (NaOtBu) (1.5 eq) was added to a screw-cap vial followed by toluene and a stir bar. IAr.sup.1 (referred Reactant An, 1 eq.) and 2-bromobenzenethiol (1.05 eq) were added. The vial was sealed and the mixture was stirred at 100 C. for 1 h. The crude mixture was filtered through a pad of Celite and the filtrate was concentrated. The residue was purified by filtration through a short column of silica gel and eluted with heptane to give Intermediate Bn.

(39) The chemical structure of Ar.sup.1I used for synthesizing Intermediate Bn, i.e., Intermediates B5 to B8, the chemical structures of the Intermediate Bn, and the yield were listed in Table 2-2. All Intermediates Bn, including Intermediates B5 to B8, were analyzed by FD-MS, and the results were listed in Table 2-2.

(40) Table 2-2: Reactant An used for preparing Intermediates B5 to B8, and the chemical structures, yields, formulae, and mass analyzed by FD-MS of Intermediates B5 to B8.

(41) TABLE-US-00003 Reactant An Intermediate B Formula/ Chemical Structure Chemical Structure Yield Mass (M.sup.+) 06 07 85.6% C.sub.12H.sub.9BrS/ 265.17 Reactant A5 Intermediate B5 08 09 83.7% C.sub.16H.sub.11BrS/ 315.23 Reactant A6 Intermediate B6 0 80.5% C.sub.18H.sub.11BrOS/ 355.25 Reactant A7 Intermediate B7 88% C.sub.21H.sub.17BrS/ 381.33 Reactant A8 Intermediate B8

(42) Modifications of Intermediates B1 to B4

(43) In addition to the Intermediates B1 to B4, one person skilled in the art can adopt any halonitrobenzenes other than 1-fluoro-2-nitrobenzene and any phenol derivatives other than Reactants A1 to A4 to successfully synthesize other desired Intermediate Bn through a reaction mechanism similar to Scheme B-1. Applicable modifications of Intermediates B1 to B4 may be, for example, but not limited to, Intermediates B9 to B20 as follows.

(44) ##STR00114## ##STR00115##

(45) Modifications of Intermediates B5 to B8

(46) In addition to the Intermediates B5 to B8, one person skilled in the art can adopt any halobenzenethiols other than 2-bromonzenethiol and any aryl iodidesother other than Reactants A5 to A8 to successfully synthesize other desired Intermediate Bn through a reaction mechanism similar to Scheme B-2. Applicable modifications of Intermediates B5 to B8 may be, for example, but not limited to, Intermediates B21 to B36 as follows.

(47) ##STR00116## ##STR00117## ##STR00118##

(48) Synthesis of Intermediate Cn

(49) The foresaid Intermediates B1 to B36, especially Intermediates B1 to B8, could be further adopted to synthesize Intermediate Cn. A general synthesis pathway for Intermediate Cn was summarized in Scheme C-1. In the following Scheme C-1, 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 B36 or the like, and Intermediate Cn may be any one of Intermediates C1 to C10 as listed in Table 3-1 or the like. Intermediates C1 to C10 were each synthesized by the following steps.

(50) ##STR00119##

(51) Step 1: Synthesis of Intermediate Cn-1

(52) Intermediate Bn (1.0 eq) was dissolved in 120 mL of anhydrous tetrahydrofuran (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 the 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 25 C. 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.

(53) The white solid product was analyzed by FD-MS, and the result was listed in Table 3-1. The chemical structures of Intermediates Cn-1 were listed in Table 3-1.

(54) Step 2: Synthesis of Intermediate Cn

(55) The foresaid Intermediate Cn-1 (1.0 eq), acetic acid (w/v=1/3 to the reactants) and H.sub.2SO.sub.4 (5 drops) were mixed, and then stirred at 110 C. for 6 h. 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.

(56) The solid product was identified by FD-MS analysis. The chemical structures, yields, formulae, and mass analyzed by FD-MS of Intermediates C1 to C10 were listed in Table 3-1.

(57) TABLE-US-00004 TABLE 3-1 Intermediates An and Bn used for preparing Intermediates C1 to C10, chemical structures of Intermediates Cn-1, and chemical structures of Intermediates Cn, yields, formulae, and mass analyzed by FD-MS of Intermediates C1 to C10. Intermediate Cn-1 Intermediate Cn Inter- Inter- Chemical Structure/ mediate mediate Yield Formula/ Yield An Bn Chemical Structure (%) Mass (M.sup.+) (%) A1 B1 0 86 86 Intermediate C1-1/ Intermediate C1/ C.sub.27H.sub.19BrO.sub.2/ C.sub.27H.sub.17BrO/ 455.34 437.33 A3 B1 84 86 Intermediate C2-1 Intermediate C2/ C.sub.27H.sub.16Br.sub.2O/ 516.22 A1 B2 85 89 Intermediate C3-1 Intermediate C3 A1 B3 92 93 Intermediate C4-1 Intermediate C4 A1 B4 80 87 Intermediate C5-1 Intermediate C5 A1 B5 0 85 80 Intermediate C6-1 Intermediate C6 A2 B5 77 92 Intermediate C7-1 Intermediate C7 A1 B6 80 84 Intermediate C8-1 Intermediate C8 A1 B7 76 82 Intermediate C9-1 Intermediate C9 A1 B8 77 90 Intermediate C10-1 Intermediate C10

(58) Modifications of Intermediates C1 to C10

(59) In addition to the Intermediates C1 to C10, one person skilled in the art can adopt any intermediate An other than Intermediates A1 to A3 and any Intermediate Bn other than Intermediates B1 to B8 to successfully synthesize other desired Intermediate Cn through a reaction mechanism similar to Scheme C-1. Applicable modifications of Intermediates C1 to C10 may be, for example, but not limited to, Intermediates C11 to C50 as follows.

(60) ##STR00140## ##STR00141## ##STR00142## ##STR00143## ##STR00144## ##STR00145## ##STR00146## ##STR00147## ##STR00148##

(61) Synthesis of Intermediate Cn-B

(62) The foresaid Intermediate Cn could be further modified into an Intermediate Cn-B through Miyaura borylation reaction. Intermediate Cn-B was 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.

(63) ##STR00149##

(64) A mixture of bis(pinacolato)diboron (1.2 eq), Intermediate Cn (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 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.

(65) 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.

(66) TABLE-US-00005 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.+) 0 86 96 C.sub.33H.sub.29BO.sub.3/ 484.39 Intermediate C1 Intermediate C1-B 89 95 C.sub.37H.sub.31BO.sub.3/ 534.45 Intermediate C3 Intermediate C3-B 93 93 C.sub.39H.sub.31BO.sub.4/ 574.47 Intermediate C4 Intermediate C4-B 87 92 C.sub.42H.sub.37BO.sub.3/ 600.55 Intermediate C5 Intermediate C5-B 80 96 C.sub.33H.sub.29BO.sub.2S/ 500.46 Intermediate C6 Intermediate C6-B 0 92 94 C.sub.33H.sub.29BO.sub.2S/ 500.46 Intermediate C7 Intermediate C7-B 84 90 C.sub.37H.sub.31BO.sub.2S/ 550.52 Intermediate C8 Intermediate C8-B 82 94 C.sub.39H.sub.31BO.sub.3S/ 590.54 Intermediate C9 Intermediate C9-B 90 88 C.sub.42H.sub.37BO.sub.2S/ 616.62 Intermediate C10 Intermediate C10-B

(67) Modifications of Intermediate Cn-B

(68) In addition to the Intermediate Cn-B, one person skilled in the art can adopt any one of foresaid Intermediates Cn to undergo a Miyaura borylation reaction to successfully synthesize other desired Intermediate Cn-B.

(69) Synthesis of Novel Compounds

(70) Each of the foresaid Intermediates Cn and Cn-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 B30 as listed in Table 4, and Intermediate C may be any one of the foresaid Intermediates Cn and Cn-B or the like. The compounds were each synthesized by the following steps.

(71) ##STR00168##

(72) TABLE-US-00006 TABLE 4 chemical structures and CAS No. of Reactants B1 to B30. Reactant Reactant B1 Reactant B2 No. Chemical Structure 0 CAS No. [126747-14-6] [329214-79-1] Reactant Reactant B3 Reactant B4 No. Chemical Structure CAS No. [1260106-29-3] [916653-46-8] Reactant Reactant B5 Reactant B6 No. Chemical Structure CAS No. [29874-83-7] [29509-91-9] Reactant Reactant B7 Reactant B8 No. Chemical Structure CAS No. [3842-55-5] [952514-79-3] Reactant Reactant B9 Reactant B10 No. Chemical Structure CAS No. [1588407-97-9] [1300115-09-6] Reactant Reactant B11 Reactant B12 No. Chemical Structure 0 CAS No. [150255-96-2] [406482-73-3] Reactant Reactant B13 Reactant B14 No. Chemical Structure CAS No. [181219-01-2] [1319255-85-0] Reactant Reactant B15 Reactant B16 No. Chemical Structure CAS No. [6484-25-9] [3114-52-1] Reactant Reactant B17 Reactant B18 No. Chemical Structure CAS No. [867044-33-5] [7089-68-1] Reactant Reactant B19 Reactant B20 No. Chemical Structure CAS No. [1616231-57-2] [1421599-34-9] Reactant Reactant B21 Reactant B22 No. Chemical Structure 0 CAS No. [99682-89-0] [170230-28-1] Reactant Reactant B23 Reactant B24 No. Chemical Structure Reactant Reactant B25 Reactant B26 No. Chemical Structure Reactant Reactant B27 Reactant B28 No. Chemical Structure Reactant Reactant B29 Reactant B30 No. Chemical Structure

(73) A mixture of Intermediate C (1.0 eq), palladium(II) acetate (Pd(OAc).sub.2)(0.01 eq), P(Cy).sub.2(2-biphenyl) (0.04 eq), toluene/ethanol (0.5M, v/v=10/1), potassium carbonate solution (K.sub.2CO.sub.3) (3.0 M), and Reactant Bn (2.1 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 a white solid product as the claimed novel compound.

(74) Reactant Bn and Intermediate C adopted to synthesize Compounds 1 to 17 were listed in Table 5. Compounds 1 to 17 were identified by H.sup.1-NMR and FD-MS, and the chemical structure, yield, formula and mass of each of Compounds 1 to 17 were also listed in Table 5. According to FIGS. 2 to 18 and the results of FD-MS, the chemical structures of Compounds 1 to 17 were identified as follows.

(75) TABLE-US-00007 TABLE 5 reactants and intermediates adopted to prepare Compounds 1 to 17 and their yields, formulae, and FD-MS data. Claimed Compound Intermediate Reactant Chemical Structure of Yield Formula/ No. No. Claimed Compound (%) Mass (M.sup.+) C1-B B7 85 C.sub.42H.sub.27N.sub.3O/ 589.68 Compound 1 C1 B1 00 88 C.sub.34H.sub.21NO/ 459.54 Compound 2 C1 B8 01 80 C.sub.46H.sub.30N.sub.2O/ 626.74 Compound 3 C1-B B4 02 73 C.sub.39H.sub.24N.sub.2O/ 536.62 Compound 4 C2 B11 03 90 C.sub.41H.sub.24N.sub.2O/ 560.64 Compound 5 C3-B B7 04 88 C.sub.46H.sub.29N.sub.3O/ 639.74 Compound 6 C4-B B7 05 80 C.sub.48H.sub.29N.sub.3O.sub.2/ 679.76 Compound 7 C5-B B7 06 78 C.sub.51H.sub.35N.sub.3O/ 705.84 Compound 8 C6 B3 07 76 C.sub.37H.sub.24N.sub.2S/ 528.66 Compound 9 C6-B B5 08 92 C.sub.41H.sub.26N.sub.2S/ 578.72 Compound 10 C6-B B6 09 90 C.sub.43H.sub.28N.sub.2S/ 604.76 Compound 11 C6-B B7 0 91 C.sub.42H.sub.27N.sub.3S/ 605.75 Compound 12 C6-B B10 70 C.sub.42H.sub.17D.sub.10N.sub.3S/ 615.81 Compound 13 C7-B B7 88 C.sub.42H.sub.27N.sub.3S/ 605.75 Compound 14 C8-B B7 76 C.sub.46H.sub.29N.sub.3S/ 655.81 Compound 15 C9-B B7 80 C.sub.48H.sub.29N.sub.3OS/ 695.83 Compound 16 C10-B B7 73 C.sub.51H.sub.35N.sub.3S/ 721.91 Compound 17

(76) Modifications of Compounds 1 to 17

(77) In addition to the Compounds 1 to 17, one person skilled in the art can react any Intermediate C, i.e., the foresaid Intermediate Cn or Cn-B, with any Reactant Bn through a reaction mechanism similar to Scheme I to synthesize other desired claimed novel compounds.

(78) Preparation of OLED Devices

(79) A glass substrate coated with ITO layer (abbreviated as 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.

(80) After that, various organic materials and metal materials were sequentially deposited on the ITO substrate to obtain the OLED device of Examples 1 to 35 and Comparative Examples 1 to 6. 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 hole transporting layer(HTL), a blue/green/red emission layer (BEL/GEL/REL), an electron transporting layer (ETL), an electron injection layer (EIL), and a cathode (Cthd).

(81) Herein, HI was a material for forming HIL-1 and HIL-2; HI-D was a material for forming HIL-1; HT was a material for forming HTL; novel compounds of the present invention and commercial ETs (BCP and TPBi) were materials for forming ETL; Liq was a material for forming ETL and EIL. RH/GH/BH was host material for forming REL/GEL/BEL, and RD/GD/BD was dopant for forming REL/GEL/BEL. The main difference of the OLEDs between the Examples and Comparative Examples was that the ETL of the OLED in the following comparative examples was made of BCP or TPBi but the ETL of the OLED in the following examples was 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.

(82) TABLE-US-00008 TABLE 6 chemical structures of commercial materials for OLED devices. HI HI-D HT RD 0 RH GD GH BD BH Liq BCP (commercial ET) TPBi (commercial ET)

(83) Preparation of Red OLED Devices

(84) 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.

(85) TABLE-US-00009 TABLE 7 coating sequence, materials and thickness of the organic layers in red OLED device. Coating Sequence Layer Material Thickness 1 HIL-1 HI doped with 3.0 wt % of HI-D 100 2 HIL-2 HI 2200 3 HTL HT 100 4 REL RH doped with 3.5 wt % of RD 300 5 ETL Commercial ET/novel compounds 350 doped with 35.0 wt % of Liq 6 EIL Liq 15 7 Cthd Al 1500

(86) Preparation of Green OLED Devices

(87) 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.

(88) TABLE-US-00010 TABLE 8 coating sequence, materials and thickness of the layers in green OLED device. Coating Sequence Layer Material Thickness 1 HIL-1 HI doped with 3.0 wt % of HI-D 100 2 HIL-2 HI 1400 3 HTL HT 100 4 GEL GH doped with 10.0 wt % of GD 400 5 ETL Commercial ET/novel compounds 350 doped with 35.0 wt % of Liq 6 EIL Liq 15 7 Cthd Al 1500

(89) Preparation of Blue OLED Devices

(90) 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.

(91) TABLE-US-00011 TABLE 9 coating sequence, materials and thickness of the layers in blue OLED device. Coating Sequence Layer Material Thickness 1 HIL-1 HI doped with 3.0 wt % of HI-D 100 2 HIL-2 HI 850 3 HTL HT 100 4 BEL BH doped with 3.5 wt % of BD 250 5 ETL Commercial ET/novel compounds 350 doped with 35.0 wt % of Liq 6 EIL Liq 15 7 Cthd Al 1500

(92) Performance of OLED Device

(93) 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.

(94) The materials of ETL, color and data of CIE, driving voltage, current efficiency, and external quantum efficiency of Examples 1 to 35 (E1 to E35) and Comparative Example 1 to 6 (C1 to C6) were listed in Table 10.

(95) TABLE-US-00012 TABLE 10 materials of ETL, colors, CIEs, voltages, current efficiencies, and external quantum efficiency of OLED devices of Examples 1 to 35 and Comparative Examples 1 to 6. Current External Exam- Volt- Effi- Quantum ple Material age ciency Efficiency No. of ETL CIE(x, y) (V) (cd/A) (%) E1 Compound 2 B(0.135, 0.153) 4.08 10.2 6.2 E2 Compound 1 B(0.129, 0.155) 4.43 7.98 5.62 E3 Compound 3 B(0.129, 0.157) 4.11 9.3 6.42 E4 Compound 4 B(0.130, 0.144) 4.49 7.01 4.92 E5 Compound 5 B(0.129, 0.156) 3.97 9.32 6.58 E6 Compound 6 B(0.130, 0.149) 4.49 7.58 5.25 E7 Compound 7 B(0.130, 0.150) 4.56 7.65 5.32 E8 Compound 8 B(0.103, 0.152) 4.02 8.49 5.38 E9 Compound 9 B(0.129, 0.151) 3.71 10.3 6.19 E10 Compound 10 B(0.129, 0.17) 4.03 10.4 7.11 E11 Compound 12 B(0.129, 0.164) 4.27 8.33 5.62 E12 Compound 13 B(0.129, 0.155) 4.35 7.91 5.57 E13 Compound 14 B(0.129, 0.158) 3.7 9.7 6.34 E14 Compound 15 B(0.129, 0.163) 4.44 7.59 5.32 C1 BCP B(0.129, 0.154) 5.66 7.49 4.62 C2 TPBi B(0.129, 0.154) 5.65 7.33 4.61 E15 Compound 2 G(0.329, 0.635) 3.9 76.2 17.62 E16 Compound 1 G(0.315, 0.639) 3.8 78.2 17.52 E17 Compound 3 G(0.316, 0.638) 3.83 79.6 17.66 E18 Compound 5 G(0.316, 0.638) 3.92 77.7 17.85 E19 Compound 6 G(0.316, 0.637) 3.99 76.8 17.6 E20 Compound 7 G(0.315, 0.638) 4.17 74.4 16.21 E21 Compound 8 G(0.329, 0.629) 4.15 79.6 17.98 E22 Compound 9 G(0.322, 0.634) 3.72 79.7 18.06 E23 Compound 10 G(0.312, 0.639) 3.7 78.1 17.47 E24 Compound 11 G(0.337, 0.624) 4.24 75.8 18.25 E25 Compound 12 G(0.325, 0.632) 3.95 78.9 18.19 E26 Compound 13 G(0.321, 0.635) 3.84 75.3 17.12 E27 Compound 14 G(0.313, 0.638) 4.11 78.5 17.9 E28 Compound 15 G(0.319, 0.636) 4.01 77.8 17.62 C3 BCP G(0.308, 0.643) 5.42 72.4 16.1 C4 TPBi G(0.306, 0.643) 6.34 68.9 14.86 E29 Compound 2 R(0.660, 0.337) 3.95 28.5 21.53 E30 Compound 3 R(0.659, 0.339) 4.25 27.9 21.85 E31 Compound 5 R(0.658, 0.34) 3.91 28.9 21.67 E32 Compound 9 R(0.657, 0.34) 4.11 27.9 21.766 E33 Compound 10 R(0.659, 0.338) 3.94 28.2 22.18 E34 Compound 12 R(0.657, 0.341) 3.92 29.6 20.71 E35 Compound 14 R(0.66, 0.338) 3.96 28.6 22.45 C5 BCP R(0.659, 0.339) 5.4 27.7 20.23 C6 TBPi R(0.659, 0.339) 5.81 27.1 19.65

(96) Based on the results, in comparison with the commercial electron transport material, adopting Compounds 1 to 15 as the electron transport material can reduce the driving voltage and improve the current efficiency of the red, green, or blue OLEDs. It demonstrates that the novel compound of 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.

(97) Even though numerous characteristics and advantages of the present invention have been set forth in the foregoing description, 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 shape, size, and arrangement of parts 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.