Spiro compound and organic electronic device comprising 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.a), multiple (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), multiple (R.sup.b)s are the same or different, and the two (R.sup.b)s are joined together to form a polycyclic aromatic ring.

Claims

1. A compound represented by the following Formula (I): ##STR00179## 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 polycyclic aromatic ring; wherein Z.sup.1 to Z.sup.10 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 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 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 extended from X.sup.3 and X.sup.4 is selected from the group consisting of: 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.

3. The compound as claimed in claim 1, wherein the compound is represented by ##STR00180## ##STR00181## ##STR00182## wherein n1 is a positive integral from 0 to 4, 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 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 or unsubstituted anthracene ring, a substituted or unsubstituted phenanthrene ring, a substituted or unsubstituted flourene 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.

6. The compound as claimed in claim 4, wherein the substituted or unsubstituted 6 to 60-membered carbon ring is a substituted or unsubstituted benzene ring.

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 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.

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: ##STR00183## ##STR00184## ##STR00185## ##STR00186## 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 30 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; 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.2, Z.sup.3, Z.sup.6, and Z.sup.7 in Formula (I) is selected from the group consisting of: ##STR00187## ##STR00188## ##STR00189## ##STR00190## 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; 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; 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, 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: ##STR00191## ##STR00192## ##STR00193## ##STR00194##

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 triazine group substituted 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 and Z.sup.10 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 40 carbon atoms, an alkenyl group having 2 to 40 carbon atoms, an alkynyl group having 2 to 40 carbon atoms, an aryl group having 6 to 60 ring carbon atoms, and a heteroaryl group having 3 to 60 ring carbon atoms.

13. The compound as claimed in claim 1, wherein Z.sup.1, Z.sup.4 to Z.sup.8 are each independently a hydrogen atom or a deuterium atom.

14. The compound as claimed in claim 1, wherein Z.sup.1, Z.sup.2, Z.sup.4, Z.sup.5, Z.sup.7, and Z.sup.8 are each independently a hydrogen atom or a deuterium atom.

15. The compound as claimed in claim 1, wherein the compound is selected from the group consisting of: ##STR00195## ##STR00196## ##STR00197## ##STR00198##

16. 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.

17. The organic electronic device as claimed in claim 16, wherein the organic electronic device is an organic light emitting device.

18. The organic electronic device as claimed in claim 17, 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.

19. The organic electronic device as claimed in claim 17, 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.

20. The organic electronic device as claimed in claim 16, wherein the compound is selected from the group consisting of: ##STR00199## ##STR00200## ##STR00201## ##STR00202##

Description

BRIEF DESCRIPTION OF THE DRAWINGS

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

(2) FIGS. 2 to 19 are respectively .sup.1H nuclear magnetic resonance (NMR) spectra of Compounds I to XVIII.

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) ##STR00058##

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

(8) A mixture of 3-bromodibenzo[a,d]cyclohepten-5-one (1.0 eq), N-bromosuccinimide (2.0 eq), and benzyl peroxide (0.01 eq) in carbon tetrachloride (5 times of starting material) was heated to about 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, then purified by recrystallization. The purified product was concentrated to dryness, whereby a white solid product was obtained in 92.3% yield. FD-MS analysis C.sub.15H.sub.9Br.sub.3O: theoretical value 444.94, observed value 444.94.

(9) Step 2: Synthesis of Intermediate A1

(10) The obtained intermediate A1-1 (1.0 eq) in DMSO, (w/v= to the reactant) 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.

(11) The pale yellow 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.

(12) Synthesis of Intermediate A2

(13) 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.

(14) ##STR00059##

(15) Synthesis of Intermediate A3

(16) 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 Table 1.

(17) ##STR00060##

(18) 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 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

(19) Modifications of Intermediates A1 to A3

(20) 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 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.

(21) ##STR00067## ##STR00068##

(22) Synthesis of Intermediates B1 and B3 to B6

(23) Intermediates B1 and B3 to B6 were synthesized by reacting 1-bromo-2-iodobenzene and aryl boronic acid (Reactant An). 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 A5 as listed in Table 2, and Intermediate Bn may be any one of foresaid Intermediates B1 and B3 to B6.

(24) ##STR00069##

(25) According to the Scheme B-1, each of Intermediates B1 and B3 to B6 was synthesized by the steps as follows.

(26) 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. After the completion of the reaction, the reaction mixture was then cooled to 25 C., and an organic layer was extracted with a saturated aqueous solution of sodium chloride and EA and dried over magnesium sulfate, followed by filtered with silica gel. After a solid prepared by concentrating the filtrate under a reduced pressure was suspended in hexane, the suspension was filtered again and washed with hexane to obtain Intermediate Bn. All intermediates were analyzed by FD-MS analysis, and the results were listed in Table 2.

(27) TABLE-US-00002 TABLE 2 Reactant An used for preparing Intermediates B1 and B3 to B6, and the chemical structures, yields, formulae, and mass analyzed by FD-MS of Intermediates B1 and B3 to B6. Reactant An Intermediate Bn Yield Formula/ Chemical Structure Chemical Structure (%) Mass (M.sup.+) 0 81 C.sub.16H.sub.11Br/ 283.16 85 C.sub.21H.sub.17Br/ 349.26 83 C.sub.20H.sub.13Br/ 333.22 76 C.sub.22H.sub.13Br/ 357.24 80 C.sub.24H.sub.15Br/ 383.28

(28) Synthesis of Intermediates B2

(29) In addition to Scheme B-1, another synthesis pathway for Intermediate B2 was summarized in Scheme B-2.

(30) ##STR00080##

(31) Step 1: Synthesis of Intermediate B2-1

(32) A mixture of dichloro bis-(triphenylphosphine) palladium (0.05 eq) and 2-bromobenzaldehyde (1 eq) in THF (0.13-0.15 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 B2-1 in a yield of 92.4%. The product was identified as Intermediate B2-1 by FD-MS analysis. FD-MS analysis: C.sub.15H.sub.10O: theoretical value of 206.64 and observed value of 206.64.

(33) Step 2: Synthesis of Intermediate B2

(34) A mixture of intermediate B2-1 (1.0 eq) and Cu(OTf).sub.2 (0.05 eq) in 1,2-dichloroethane (5 times of Intermediate B2-1) 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 B2 (yield 80%). The product was identified as intermediate B2 by FD-MS analysis. FD-MS analysis: C.sub.16H.sub.11Br: theoretical value of 283.16 and observed value of 283.16.

(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 aryl boronic acid other than Reactants A1 to A5 to react with 1-bromo-2-iodobenzene to successfully synthesize other desired Intermediate Bn through a reaction mechanism similar to Scheme B-1. Similarly, one person skilled in the art can synthesize other desired Intermediate Bn through a reaction mechanism similar to Scheme B-2. Applicable modifications of Intermediates B1 to B6 may be, for example, but not limited to, Intermediates B7 and B14 as follows.

(37) ##STR00081## ##STR00082##

(38) Synthesis of Intermediates C

(39) The foresaid Intermediates B1 to B14, 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, 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 C9 as listed in Table 3-1 or the like. Intermediates C1 to C9 were each synthesized by the following steps.

(40) ##STR00083##

(41) Step 1: Synthesis of Alcohol Intermediate (Intermediate Cn-1)

(42) Intermediate Bn (1.0 eq) was dissolved in 120 mL of anhydrous THF (0.4M), and cooled to 78 C. n-Butyl lithium (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 normal 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.

(43) 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.

(44) Step 2: synthesis of Intermediate Cn

(45) The foresaid Intermediate Cn-1 (1.0 eq), acetic acid (w/v= to the reactant) 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.

(46) 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.

(47) TABLE-US-00003 TABLE 3-1 Intermediate A and B 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. Alcohol intermediate Intermediate Cn Intermediate Intermediate Yield Chemical Structure/ Yield An Bn Chemical Structure (%) Formula/Mass (M.sup.+) (%) A1 B1 88.5 95.0 A3 B1 85 94 A1 B2 77 90 A1 B3 0 80 88 A1 B4 78 90 A3 B4 90 88 A1 B5 94 70 A1 B6 86 87 A3 B6 00 80 01 92

(48) Modifications of Intermediates C1 to C9

(49) In addition to the Intermediates C1 to C9, one person skilled in the art can adopt any intermediate A other than Intermediates A1 and A3 and any Intermediate B other than Intermediates B1 to B6 to successfully synthesize other desired Intermediate C 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 C21 as follows.

(50) ##STR00102## ##STR00103## ##STR00104##

(51) Synthesis of Intermediate Cn-B

(52) 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.

(53) ##STR00105##

(54) A mixture of bis(pinacolato)diboron (1.2 eq), Intermediate Cn (1.0 eq), 1,1-bis(diphenylphosphino)-ferrocenedichloropalladium (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.

(55) 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.

(56) 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.+) 06 95.0 07 91 C.sub.37H.sub.31BO.sub.2/ 518.45 08 90 09 93 C.sub.37H.sub.31BO.sub.2/ 518.45 0 88 92 C.sub.42H.sub.37BO.sub.2/ 584.55 90 91 C.sub.41H.sub.33BO.sub.2/ 568.51 70 94 C.sub.43H.sub.33BO.sub.2/ 592.53 87 91 C.sub.45H.sub.35BO.sub.2/ 618.57

(57) Modifications of Intermediate Cn-B

(58) 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.

(59) Synthesis of Novel Compounds

(60) Each of the foresaid Intermediates Cn and Cn-B could be reacted with various reactants to synthesis various claimed novel compounds. The general synthesis pathway of the claimed novel compound was summarized in Scheme I. In the following Scheme I, Reactant Bn may be any one of Reactants B1 to B25 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.

(61) ##STR00118##

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

(63) Intermediate Cn (1.0 eq), Reactant Bn (2.1 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), and 3.0M of K.sub.2CO.sub.3 aqueous solution were mixed, followed by stirred at 100 C. for 12 h under nitrogen atmosphere. After completion of the reaction, water and toluene were added to the reaction mass. Subsequently, the organic layer was recovered by solvent extraction and dried over sodium sulfate. The solvent was then removed from the organic layer under a reduced pressure, and the resulting residue was purified by silica gel column chromatography. The obtained residue was recrystallized with toluene to obtain white solids as the claimed novel compound.

(64) Reactant Bn and Intermediate Cn adopted to synthesize Compounds I to XVIII were listed in Table 5. Compounds I to XVIII were identified by H.sup.1-NMR and FD-MS, and the chemical structure, yield, formula and mass of each of Compounds I to XVIII were also listed in Table 5. According to FIGS. 2 to 19 and the results of FD-MS, the chemical structure of Compounds I to XVIII were identified as follows.

(65) TABLE-US-00006 TABLE 5 reactants and intermediates adopted to prepare Compounds I to XVIII and their yields, formulae, and FD-MS data. Claimed Compound Intermediate Reactant Yield Formula/ No. No. Chemical Structure (%) Mass (M.sup.+) C1-B B7 86 C.sub.46H.sub.29N.sub.3/ 623.74 C1 B1 91 C.sub.38H.sub.23N/ 493.60 Cl B12 85 C.sub.44H.sub.27N/ 569.69 C2 B11 84 C.sub.45H.sub.26N.sub.2/ 594.70 Cl-B B10 89 C.sub.46H.sub.19D.sub.10N.sub.3/ 633.80 C3 B8 81 C.sub.50H.sub.32N.sub.2/ 660.80 C3-B B4 0 84 C.sub.43H.sub.26N.sub.2/ 570.68 C8-B B4 86 C.sub.51H.sub.30N.sub.2/ 670.80 C8 B1 82 C.sub.46H.sub.27N/ 593.71 C9 B1 91 C.sub.53H.sub.30N.sub.2/ 694.82 C5-B B5 80 C.sub.49H.sub.30N.sub.2/ 646.78 C5-B B7 82 C.sub.50H.sub.31N.sub.3/ 673.80 C5 B1 66 C.sub.42H.sub.25N/ 543.65 C6 B2 72 C.sub.45H.sub.28N.sub.2/ 596.72 C7-B B7 67 C.sub.52H.sub.31N.sub.3/ 697.82 C7-B B6 68 C.sub.53H.sub.32N.sub.2/ 696.83 C4-B B7 0 71 C.sub.51H.sub.35N.sub.3/ 689.84 C4-B B4 76 C.sub.48H.sub.32N.sub.2/ 636.78

(66) Modifications of Compounds I to XVIII

(67) In addition to the Compounds I to XVIII, one person skilled in the art can react any Intermediate C, for example, but not limited to, 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.

(68) Preparation of OLED devices

(69) A glass substrate coated with 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.

(70) After that, various organic materials and metal materials were sequentially deposited on the ITO substrate to obtain the OLED devices of Examples 1 to 40. 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).

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

(72) TABLE-US-00007 TABLE 6 chemical structures of commercial materials for OLED devices. 0

(73) Preparation of Red OLED Devices

(74) To prepare red OLED devices, multiple organic layers were respectively deposited on the ITO substrate according to the sequence as listed in Table 7 to prepare first red OLED devices and second red OLED devices. The materials and the thicknesses of the organic layers in the first and second red OLED devices were also listed in Table 7. The difference between the first and the second red OLED devices is the materials of HIL-1, HIL-2, HTL-1, and REL as listed in Table 7.

(75) TABLE-US-00008 TABLE 7 coating sequence, materials and thickness of the organic layers in the first and second red OLED devices. Material Coating First red Second red Sequence Layer OLED device OLED device Thickness 1 HIL-1 HAT HI-2 doped with 100 3.0 wt % of HI-D 2 HIL-2 HI-2 doped with HI-2 2100 5.0 wt % of HAT 3 HTL-1 HT-1 HI-2 100 4 HTL-2 HT-2 HT-2 100 5 REL RH-1 doped with RH-2 doped with 300 3.5 wt % of RD 3.5 wt % of RD 6 ETL Commercial Commercial 350 ET/novel ET/novel compounds doped compounds doped with 35.0 wt % of with 35.0 wt % of Liq Liq 7 EIL Liq Liq 15 8 Cthd Al Al 1500

(76) Preparation of Green OLED Devices

(77) To prepare the green OLED devices, multiple organic layers were respectively deposited on the ITO substrate according to the sequence as listed in Table 8 to prepare first green OLED devices and second green OLED devices. The materials and the thicknesses of the organic layers in the first and second green OLED devices were also listed in Table 8. The difference between the first and the second green OLED devices is the materials of HIL-1, HIL-2, HTL-1, and GEL as listed in Table 8.

(78) TABLE-US-00009 TABLE 8 coating sequence, materials and thickness of the layers in the first and second green OLED devices. Material Coating First green Second green Sequence Layer OLED device OLED device Thickness 1 HIL-1 HAT HI-2 doped with 100 3.0 wt % of HI-D 2 HIL-2 HI-2 doped with HI-2 1300 5.0 wt % of HAT 3 HTL-1 HT-1 HI-2 100 4 HTL-2 HT-2 HT-2 100 5 GEL GH-1 doped with GH-2 doped with 300 10.0 wt % of GD 10.0 wt % of GD 6 ETL Commercial Commercial 350 ET/novel ET/novel compounds compounds doped doped with 35.0 wt with 35.0 wt % of % of Liq Liq 7 EIL Liq Liq 15 8 Cthd Al Al 1500

(79) Preparation of Blue OLED Devices

(80) To prepare the blue OLED devices, multiple organic layers were respectively deposited on the ITO substrate according to the sequence as listed in Table 9 to prepare first blue OLED devices and second blue OLED devices. The materials and the thicknesses of the organic layers in the first and second blue OLED devices were also listed in Table 9. The difference between the first and the second blue OLED devices is the materials of HIL-1, HIL-2, HTL-1, and BEL as listed in Table 9.

(81) TABLE-US-00010 TABLE 9 coating sequence, materials and thickness of the layers in the first and second blue OLED device. Material Coating First blue Second blue Sequence Layer OLED device OLED device Thickness 1 HIL-1 HAT HI-2 doped with 100 3.0 wt % of HI-D 2 HIL-2 HI-2 doped with HI-2 750 5.0 wt % of HAT 3 HTL-1 HT-1 HI-2 100 4 HTL-2 HT-2 HT-2 100 5 BEL BH doped with BH doped with 300 3.5 wt % of BD-1 3.5 wt % of BD-2 6 ETL Commercial Commercial 350 ET/novel ET/novel compounds compounds doped doped with 35.0 wt with 35.0 wt % of % of Liq Liq 7 EIL Liq Liq 15 8 Cthd Al Al 1500

(82) Performance of OLED Device

(83) 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.

(84) The materials of ETL, color and data of CIE, driving voltage, and current efficiency of Examples 1 to 40 (E1 to E40) and Comparative Examples 1 to 6 (C1 to C6) were listed in Table 10. As listed in Table 10, the first blue OLED devices were named as B1, and the second blue OLED devices were named as B2. Similarly, the first and second red OLED devices and the first and second green OLED devices were respectively named as R1, R2, G1, and G2.

(85) TABLE-US-00011 TABLE 10 materials of ETL, characteristics and performance of OLED devices of Examples 1 to 40 and Comparative Examples 1 to 6. Ex- OLED Volt- Current ample Device age Efficiency No. Material of ETL No. CIE (x, y) (V) (cd/A) E1 Compound II B1 (0.136, 0.172) 3.7 8.55 E2 Compound III B1 (0.136, 0.189) 3.59 8.97 E3 Compound IV B1 (0.137, 0.191) 4.25 9.1 E4 Compound IX B1 (0.136, 0.175) 3.82 12.5 E5 Compound XIII B1 (0.136, 0.17) 3.63 8.54 E6 Compound I B2 (0.129, 0.164) 4.53 8.08 E7 Compound II B2 (0.103, 0.159) 3.67 7.98 E8 Compound III B2 (0.130, 0.161) 3.64 6.7 E9 Compound V B2 (0.129, 0.165) 4.49 8.21 E10 Compound VI B2 (0.103, 0.155) 4.73 7.67 E11 Compound VIII B2 (0.129, 0.159) 4.31 8.8 E12 Compound X B2 (0.129, 0.168) 4.66 7.22 E13 Compound XI B2 (0.129, 0.156) 4.33 8.83 E14 Compound XII B2 (0.129, 0.16) 4.52 8.17 E15 Compound XIV B2 (0.13, 0.154) 3.72 6.84 E16 Compound XVII B2 (0.129, 0.164) 4.58 8.17 E17 Compound XVIII B2 (0.13, 0.165) 6.15 6.6 C1 BCP B1 (0.130, 0.170) 6.35 7.05 C2 TAZ B2 (0.131, 0.174) 7.84 6.55 E18 Compound II G1 (0.309, 0.640) 3.02 66.2 E19 Compound IV G1 (0.316, 0.638) 3.2 66.1 E20 Compound IX G1 (0.312, 0.64) 3.31 70.3 E21 Compound XIII G1 (0.311, 0.64) 3 66.5 E22 Compound I G2 (0.320, 0.635) 4.22 78.5 E23 Compound III G2 (0.311, 0.64) 3.14 62.4 E24 Compound V G2 (0.331, 0.628) 4.32 76.2 E25 Compound VIII G2 (0.321, 0.634) 4.35 71.2 E26 Compound X G2 (0.325, 0.632) 4.51 68.8 E27 Compound XI G2 (0.319, 0.636) 4.43 74.9 E28 Compound XII G2 (311, 0.64) 3.87 72.8 E29 Compound XIV G2 (0.323, 0.633) 4.04 72.6 E30 Compound XVII G2 (0.327, 0.63) 4.36 73.4 E31 Compound XVIII G2 (0.323, 0.63) 6.11 51.9 C3 BCP G1 (0.313, 0.638) 5.27 65.3 C4 TAZ G2 (0.325, 0.628) 8.36 48.4 E32 Compound II R1 (0.660, 0.339) 3.12 22.4 E33 Compound IV R1 (0.661, 0.337) 3.27 21.4 E34 Compound IX R1 (0.662, 0.337) 3.16 21.1 E35 Compound XIII R1 (0.661, 0.337) 3.16 21.9 E36 Compound I R2 (0.657, 0.341) 3.97 29.2 E37 Compound III R2 (0.657, 0.341) 3.23 22.1 E38 Compound V R2 (0.658, 0.34) 4.01 29.3 E39 Compound XI R2 (0.656, 0.341) 4.26 28.6 E40 Compound XII R2 (0.657, 0.34) 4.04 29.2 C5 BCP R1 (0.659, 0.340) 4.16 20.10 C6 TAZ R2 (0.648, 0.342) 11.38 21.04

(86) Based on the results, in comparison with the commercial electron transport materials (BCP and TAZ), adopting Compounds I to XVIII as the electron transport material can reduce the driving voltage and improve the current 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.

(87) 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 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.