Compound and organic electronic device using the same

Abstract

The present specification relates to a novel compound and an organic electronic device using the same.

Claims

1. A compound represented by the following Formula (I): ##STR00253## 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 an 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 heteroaryl ring containing at least one furan group, at least one thiophene group, or at least one thiophene S,S-dioxide group; wherein Z.sup.1 to Z.sup.12 are each independently selected from the group consisting of: a hydrogen atom, a deuterium atom, a trifuloromethyl group, 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 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 the following Formulae (I-I) to (I-XVIII): ##STR00254## ##STR00255## ##STR00256## ##STR00257## ##STR00258## ##STR00259## 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 heteroaryl ring extended from X.sup.3 and X.sup.4.

3. The compound as claimed in claim 2, wherein the aromatic structure contained in the heteroaryl ring 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 fluorene structure, a substituted or unsubstituted pyrene structure, a substituted or unsubstituted benzophenanthrene structure, a substituted or unsubstituted benzopyrene structure, a substituted or unsubstituted fluoranthene structure, and a substituted or unsubstituted benzofluoranthene structure.

5. The compound as claimed in claim 1, wherein the 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 fluorene ring, a substituted or unsubstituted pyrene ring, a substituted or unsubstituted benzophenanthrene ring, a substituted or unsubstituted benzopyrene ring, a substituted or unsubstituted fluoranthene ring, and a substituted or unsubstituted benzofluoranthene ring.

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: 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.

9. 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: ##STR00260## ##STR00261## ##STR00262## ##STR00263## ##STR00264## wherein R.sup.1 to R.sup.7 are each independently selected from the group consisting of: a hydrogen atom, a deuterium atom, a trifluoromethyl group, 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, anarylsilyl 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.

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: ##STR00265## ##STR00266## ##STR00267## ##STR00268## ##STR00269## wherein R.sup.1 to R.sup.7 are each independently selected from the group consisting of: a hydrogen atom, a deuterium atom, a trifluoromethyl group, 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.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.

11. The compound as claimed in claim 10, 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: ##STR00270## ##STR00271## ##STR00272## ##STR00273## ##STR00274##

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: ##STR00275## ##STR00276## ##STR00277## ##STR00278## ##STR00279## ##STR00280## ##STR00281##

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 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.

18. The organic electronic device as claimed in claim 14, wherein the compound is selected from the group consisting of: ##STR00282## ##STR00283## ##STR00284## ##STR00285## ##STR00286## ##STR00287## ##STR00288##

Description

BRIEF DESCRIPTION OF THE DRAWINGS

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

(2) FIGS. 2 to 28 are respectively .sup.1H nuclear magnetic resonance (NMR) spectra of Compounds I to XXVII.

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) ##STR00103##

(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) (5 times of starting material) was heated to 85 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 white solid products were 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. 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 A1-2

(11) The obtained Intermediate A1-1 (116.0 g, 1.0 eq) and furan (1.5 eq) were dissolved in THF (1.0 M), 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 1 hour, and then stirred at room temperature for additional 12 hours. After completion of the reaction, the reaction was quenched by DI water and 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 a yield of 60.3%.

(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 (1.0 eq) and 5% Pd/C (0.025 eq) in ethyl acetate (EA, 2.0 M) 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 a 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) (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 A1 through 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) ##STR00104##

(22) Synthesis of Intermediate A3

(23) Intermediate A3 used for preparing a novel compound was synthesized in a similar manner as Intermediate A 1 through steps 1 to 4, 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 Table 1.

(24) ##STR00105##

(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 06 07 08 09 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 0 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 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.

(28) ##STR00118## ##STR00119##

(29) Synthesis of Intermediates B1 to B6

(30) Intermediates B1 to B6 were synthesized by reacting 1-bromo-2-iodobenzene and heteroarylboronic acid (Reactant An). A general synthesis pathway for Intermediate Bn was summarized in Scheme B. In the following Scheme B, Reactant An may be any one of Reactants A1 to A6 as listed in Table 2 or the like, and Intermediate Bn may be any one of Intermediates B1 to B6.

(31) ##STR00120##

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

(33) Water and toluene were poured into a round-bottomed flask, fitted with a condenser and argon flow, and bubbled through with argon. Potassium carbonate (1.5 eq), 1-bromo-2-iodobenzene (1.0 eq), Reactant An (1.2 eq), potassium carbonate (3.0 eq), 200 ml of toluene, PPh.sub.3(0.06 eq)and Pd(OAc).sub.2 (0.015 eq) were mixed and stirred at 70 C. for 5 hours in an oil bath. After reaction was completed, the reaction mixture was allowed to be cooled to room temperature, and an organic layer was extracted with saturated aqueous solution of sodium chloride and EA and dried over magnesium sulfate, 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 Bn, including Intermediates B1 to B6, were analyzed according to the methods as described above, and the results were listed in Table 2.

(34) TABLE-US-00002 TABLE 2 Reactant An used for preparing Intermediates B1 to B6, and the chemical structures, yields, formulae, and mass analyzed by FD-MS of Intermediates B1 to B6. Intermediate Bn Reactant An Formula/ Chemical Structure Chemical Structure Yield Mass (M.sup.+) 85% C.sub.18H.sub.11BrO/ 323.18 87% C.sub.18H.sub.11BrO/ 323.18 80% C.sub.18H.sub.11BrO/ 323.18 88% C.sub.18H.sub.11BrS/ 339.25 0 84% C.sub.18H.sub.11BrS/ 339.25 63% C.sub.18H.sub.11BrS/ 339.25

(35) Modifications of Intermediates B1 to B6

(36) 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 heteroarylboronic acids other than Reactants A1 to A6 to successfully synthesize other desired Intermediate Bn through a reaction mechanism similar to Scheme B. Applicable modifications of Intermediates B1 to B6 may be, for example, but not limited to, Intermediates B7 and B8 as follows.

(37) ##STR00133##

(38) Synthesis of Intermediate C

(39) The foresaid Intermediates B1 to B8, especially Intermediates B1 to B6, could be further adopted to synthesize Intermediate Cn. A general synthesis pathway for Intermediate Cn was summarized in Scheme C1. In the following Scheme C1, Inteiniediate 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 B8 or the like, and Intermediate Cn may be any one of Intermediates C1 to C9 as listed in Table 3-1 or the like. Intermediates C1 to C9 were each synthesized by the following steps.

(40) ##STR00134##

(41) Step 1: Synthesis of Alcohol Intermediate

(42) 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 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.

(43) 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.

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

(45) Step 2: Synthesis of Intermediate Cn

(46) 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 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.

(47) The solid product was identified by FD-MS analysis. The chemical structures, yields, formulae, and mass analyzed by FD-MS of Intermediates C1 to C9 were listed in Table 3-1.

(48) TABLE-US-00003 TABLE 3-1 Intermediates An and Bn used for preparing Intermediates C1 to C9, chemical structures of alcohol intermediates, and chemical structures, yields, formulae, and mass analyzed by FD-MS of Intermediates C1 to C9. Interme- Interme- Alcohol intermediate Intermediate Cn diate diate Yield Chemical Structure/ Yield An Bn Chemical Structure (%) Formula/Mass (M.sup.+) (%) A1 B1 86 95 A2 B1 76 87 A1 B2 85 0 91 A1 B3 74 81 A3 B1 83 76 A1 B4 83 95 A1 B5 88 83 A1 B6 62 0 85 A3 B4 88 84

(49) Modifications of Intermediates C1 to C9

(50) In addition to the Intermediates C1 to C9, one person skilled in the art can adopt any intermediate An other than Intermediates A1 to A3 and/or any Intermediate Bn other than Intermediates B1 to B6 to successfully synthesize other desired Intermediate Cn through a reaction mechanism similar to Scheme C1. Applicable modifications of Intermediates C1 to C9 may be, for example, but not limited to, Intermediates C10 to C33 as follows.

(51) ##STR00153## ##STR00154## ##STR00155## ##STR00156## ##STR00157## ##STR00158##

(52) The foresaid Intermediates C6 to C9 and C22 to C33 could be further oxidized to synthesize other Intermediates Cn. Take Intermediates C6 and C7 as examples, the Intermediates C6 and C7 could be oxidized into Intermediates C34 and C35 by methods of Scheme C2 and C3, respectively.

(53) Synthesis of Intermediate C34

(54) ##STR00159##

(55) Trifluoroperacetic acid was prepared by the dropwise addition of 30% aqueous hydrogen peroxide (15.2 ml) to trifluoroacetic acid (75 ml) at 0 C. The ice bath was removed after the completion of the addition of peroxide. Then Intermediate C6 (5 g, 1 eq) was added slowly with stirring to the solution. After the completion of the reaction, the reaction mixture was washed with water, followed by filtering to get solid. The crude mixture was purified by silica-gel column chromatography to obtain Intermediate C34 (3.3 g, yield: 62.5%). The solid product was identified as Intermediate C34 by FD-MS analysis. FD-MS analysis: C.sub.37H.sub.21BrO.sub.2S: theoretical value of 609.53 and observed value of 609.53.

(56) Synthesis of Intermediate C35

(57) ##STR00160##

(58) Intermediate C35 was synthesized in a similar manner as Intermediate C34, except that the Intermediate C6 was replaced by Intermediate C7.

(59) The solid product was identified as intermediate C35 (yield 85%) by FD-MS analysis. FD-MS analysis:C.sub.37H.sub.21BrO.sub.2S: theoretical value of 609.53 and observed value of 609.53.

(60) Modifications of Intermediates C34 and C35

(61) In addition to the Intermediates C34 and C35, one person skilled in the art can adopt other Intermediates Cn including thiofuran group, such as Intermediates C8, C9, C22 to C33 to synthesize other desired Intermediates Cn through a reaction mechanism similar to Scheme C2 or Scheme C3.Applicable modifications of Intermediates C34 and C35 may be, for example, but not limited to, Intermediates C36 to C46 as follows.

(62) ##STR00161## ##STR00162## ##STR00163##

(63) Synthesis of Intermediate Cn-B

(64) 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.

(65) ##STR00164##

(66) 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 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.

(67) 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.

(68) 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.+) 87 93 C.sub.43H.sub.33BO.sub.3/ 608.53 91 98 C.sub.43H.sub.33BO.sub.3/ 608.53 81 0 96 C.sub.43H.sub.33BO.sub.3/ 608.53 95 91 C.sub.43H.sub.33BO.sub.2S/ 624.60 83 91 C.sub.43H.sub.33BO.sub.2S/ 624.60 85 92 C.sub.43H.sub.33BO.sub.2S/ 624.60

(69) Modifications of Intermediate Cn-B

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

(71) ##STR00177## ##STR00178##

(72) Synthesis of Novel Compounds

(73) 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 B34 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.

(74) ##STR00179##

(75) TABLE-US-00005 TABLE 4 chemical structure and CAS No. of Reactants B1 to B34. Reactant No. Reactant B1 Reactant B2 Reactant B3 Reactant B4 Chemical Structure 0 CAS No. [126747-14-6] [1319255-85-0] [181219-01-2] [1260106-29-3] Reactant No. Reactant B5 Reactant B6 Reactant B7 Reactant B8 Chemical Structure CAS No. [29874-83-7] [867044-33-5] [3842-55-5] [29509-91-9] Reactant No. Reactant B9 Reactant B10 Reactant B11 Reactant B12 Chemical Structure 0 CAS No. [916653-46-8] [329214-79-1] [150255-96-2] [406482-73-3] Reactant No. Reactant B13 Reactant B14 Reactant B15 Reactant B16 Chemical Structure CAS No. [952514-79-3] [1588407-97-9] [1300115-09-6] [6484-25-9] Reactant No. Reactant B17 Reactant B18 Reactant B19 Reactant B20 Chemical Structure CAS No. [3114-52-1] [7089-68-1] [1616231-57-2] [1421599-34-9] Reactant No. Reactant B21 Reactant B22 Chemical Structure 00 01 CAS No. [99682-89-0] [170230-28-1] Reactant No. Reactant B23 Reactant B24 Reactant B25 Reactant B26 Chemical Structure 02 03 04 05 Reactant No. Reactant B27 Reactant B28 Chemical Structure 06 07 Reactant No. Reactant B29 Reactant B30 Chemical Structure 08 09 CAS No. [774-53-8] [867044-33-5] Reactant No. Reactant B31 Reactant B32 Chemical Structure 0 Reactant No. Reactant B33 Reactant B34 Chemical Structure CAS No. [1009033-87-7]

(76) A mixture of Intermediate Cn (1.0 eq), Pd(OAc).sub.2(0.01 eq), P(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 12h 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.

(77) Reactant Bn and Intermediate C adopted to synthesize Compounds I to XXVII were listed in Table 5. Compounds I to XXVII were identified by H.sup.1-NMR and FD-MS, and the chemical structure, yield, formula and mass of each of Compounds I to XXVII were also listed in Table 5. According to FIGS. 2 to 28 and the results of FD-MS, the chemical structure of Compounds I to XXVII were identified as follows.

(78) TABLE-US-00006 TABLE 5 reactants and intermediates adopted to prepare Compounds I to XXVII 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 B1 95 C.sub.44H.sub.25NO/ 583.68 C1 B2 97 C.sub.47H.sub.28N.sub.2O/ 636.75 C1 B4 86 C.sub.47H.sub.28N.sub.2O/ 636.74 C1-B B5 72 C.sub.51H.sub.30N.sub.2O/ 686.80 C1-B B7 83 C.sub.51H.sub.31N.sub.3O/ 713.82 C3-B B6 73 C.sub.56H.sub.34N.sub.2O/ 750.88 C3-B B8 0 83 C.sub.53H.sub.32N.sub.2O/ 712.83 C4-B B7 62 C.sub.52H.sub.31N.sub.3O/ 713.82 C2-B B7 81 C.sub.52H.sub.31N.sub.3O/ 713.82 C5 B3 63 C.sub.47H.sub.28N.sub.2O/ 636.74 C6 B1 84 C.sub.44H.sub.25NS/ 599.74 C6 B4 68 C.sub.47H.sub.28N.sub.2S/ 652.81 C6-B B8 88 C.sub.53H.sub.32N.sub.2S/ 728.9 C6-B B9 70 C.sub.49H.sub.28N.sub.2S/ 676.83 C6-B B5 72 C.sub.51H.sub.30N.sub.2S/ 702.86 C6 B10 78 C.sub.42H.sub.25NS/ 575.72 C6 B2 0 78 C.sub.47H.sub.28N.sub.2S/ 652.80 C7-B B6 66 C.sub.56H.sub.34N.sub.2S/ 766.95 C7-B B7 79 C.sub.52H.sub.31N.sub.3S/ 729.89 C8-B B7 66 C.sub.52H.sub.31N.sub.3S/ 729.89 C9 B3 85 C.sub.47H.sub.28N.sub.2S/ 652.80 C34 B1 56 C.sub.44H.sub.25NO.sub.2S/ 631.74 C34-B B8 83 C.sub.53H.sub.32N.sub.2O.sub.2S/ 760.90 C34-B B5 83 C.sub.51H.sub.30N.sub.2O.sub.2S/ 734.86 C34-B B6 71 C.sub.56H.sub.34N.sub.2O.sub.2S/ 798.95 C34-B B7 63 C.sub.52H.sub.31N.sub.3O.sub.2S/ 761.89 C35 B2 0 66 C.sub.47H.sub.28N.sub.2O.sub.2S/ 684.79

(79) Modifications of Compounds I to XXVII

(80) In addition to the Compounds I to XXVII, 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.

(81) Preparation of OLED Devices

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

(83) After that, various organic materials and metal materials were sequentially deposited on the ITO substrate to obtain the OLED device of Examples 1 to 19. 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).

(84) 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 the 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 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.

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

(86) Preparation of Red OLED Devices

(87) 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.

(88) 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 A1 1500

(89) Preparation of Green OLED Devices

(90) 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.

(91) 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 1300 3 HTL-1 HT-1 100 4 HTL-2 HT-2 100 5 GEL GH doped with 10.0 wt % of GD 400 6 ETL Commercial ET/novel compounds 350 doped with 35.0 wt % of Liq 7 EIL Liq 15 8 Cthd A1 1500

(92) Preparation of Blue OLED Devices

(93) 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.

(94) 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 750 3 HTL-1 HT-1 100 4 HTL-2 HT-2 100 5 BEL BH doped with 3.5 wt % of BD 250 6 ETL Commercial ET/novel compounds 250 doped with 35.0 wt % of Liq 7 EIL Liq 15 8 Cthd A1 1500

(95) Performance of OLED Device

(96) 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.

(97) The materials of ETL, color and data of CIE, driving voltage, current efficiency, and external quantum efficiency (EQE) of each of Examples 1 to 19 and Comparative Example 1 to 3 were listed in Table 10.

(98) TABLE-US-00011 TABLE 10 materials of ETL, colors, CIEs, voltages, current efficiencies, and EQE of OLED devices of Examples 1 to 19 and Comparative Examples 1 to 3. Current OLED Material Color, Voltage Efficiency EQE device No. of ETL CIE(x, y) (V) (cd/A) (%) Example 1 Compound B(0.130, 0.149) 4.94 9.46 6.69 XXII Example 2 Compound B(0.129, 0.152) 5.38 10.8 7.75 XXV Example 3 Compound B(0.129, 0.160) 5.49 9.89 7.36 I Example 4 Compound B(0.129, 0.155) 4.68 10.7 7.62 XIX Example 5 Compound B(0.129, 0.154) 4.73 11.5 6.27 XIII Example 6 Compound B(0.129, 0.155) 4.58 10.2 7.54 XXVI Example 7 Compound B(0.130, 0.146) 5.59 8.47 6.05 IV Example 8 Compound B(0.129, 0.158) 4.91 9.86 6.96 XIV Example 9 Compound B(0.129, 0.150) 4.54 10.9 7.67 XXIV Example 10 Compound B(0.129, 0.149) 5.23 9.86 6.88 III Example 11 Compound B(0.129, 0.149) 5.23 9.86 6.88 XVIII Comparative BCP B(0.130, 0.142) 6.71 6.98 4.88 Example 1 Example 12 Compound G(0.311, 0.640) 3.87 72.6 17.27 IX Example 13 Compound G(0.317, 0.637) 4.45 72.0 17.79 XII Example 14 Compound G(0.315, 0.638) 3.75 74.4 17.86 XXIII Example 15 Compound G(0.319, 0.636) 4.52 72.8 17.66 XI Comparative BCP G(0.313, 0.638) 4.67 70.3 16.95 Example 2 Example 16 Compound R(0.661, 0.338) 4.06 26.6 18.19 VII Example 17 Compound R(0.661, 0.338) 3.93 27.0 16.37 XXI Example 18 Compound R(0.660, 0.338) 4.09 24.9 17.41 XV Example 19 Compound R(0.659, 0.339) 3.85 24.5 16.14 X Comparative BCP R(0.659, 0.340) 4.16 24.1 16.05 Example 3

(99) Based on the results, in comparison with the commercial electron transport material (BCP), adopting Compounds I to XXVII 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 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 as well as improved external quantum efficiency.

(100) 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.