NITROGEN-CONTAINING FUSED HETEROCYCLIC COMPOUND AND APPLICATIONS THEREOF

Abstract

The present invention provides a nitrogen-containing fused heterocyclic compound and applications thereof. When the nitrogen-containing fused heterocyclic compound of the present invention is used as a host material of an emitting layer of an organic light-emitting element, the organic light-emitting element has a lower driving voltage (4.3 V or lower), a higher current efficiency (16 Cd/A or higher) and a longer service life (230 h or higher).

Claims

1. A nitrogen-containing fused heterocyclic compound, characterized in that the nitrogen-containing fused heterocyclic compound has a structure represented by Formula (1): ##STR00073## wherein, Ar and Ar.sup.1 are each independently selected from a substituted or unsubstituted C6-C60 aryl group, and a substituted or unsubstituted C3-C60 heteroaryl group; L and L.sup.1 are each independently selected from a bond, a substituted or unsubstituted C6-C30 arylene group, and a substituted or unsubstituted C3-C30 heteroarylene group; R.sup.1 to R.sup.4 are each independently selected from hydrogen, deuterium, a halo group, a cyano group, a substituted or unsubstituted C1-C30 alkyl group, a substituted or unsubstituted C7-C30 arylalkyl group, a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C3-C30 heteroaryl group, a substituted or unsubstituted C4-C30 heteroarylalkyl group, a substituted or unsubstituted C3-C30 cycloalkyl group, a substituted or unsubstituted C3-C30 heterocycloalkyl group, a substituted or unsubstituted C3-C30 cycloalkenyl group, a substituted or unsubstituted C1-C30 alkoxy group, and a substituted or unsubstituted C6-C30 aryloxy group; R.sup.1 to R.sup.4 are present individually without forming a ring, or any adjacent two of R.sup.1 to R.sup.4 joined to form a ring A, and the ring A is a C6-C30 aromatic ring.

2. The nitrogen-containing fused heterocyclic compound as claimed in claim 1, characterized in that Ar is selected from ##STR00074## and a substituted or unsubstituted C6-C60 aryl group; Y is selected from O and S; R.sup.Y is selected from a substituted or unsubstituted C6-C30 arylene group, and a substituted or unsubstituted C3-C30 heteroarylene group; R.sup.5 to R.sup.12 are each independently selected from hydrogen, deuterium, a halo group, a cyano group, a substituted or unsubstituted C1-C30 alkyl group, a C1-C30 alkyl group in which one or more methylene groups are independently substituted by —O— and/or —S— in a manner that O atom and/or S atom are not adjacent to each other, a substituted or unsubstituted C2-C30 alkenyl group, a C2-C30 alkenyl group in which one or more methylene groups are independently substituted by —O— and/or —S— in a manner that O atom and/or S atom are not adjacent to each other, a substituted or unsubstituted C2-C30 alkynyl group, a substituted or unsubstituted C7-C30 arylalkyl group, a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C3-C30 heteroaryl group, a substituted or unsubstituted C4-C30 heteroarylalkyl group, a substituted or unsubstituted C3-C30 cycloalkyl group, a substituted or unsubstituted C3-C30 heterocycloalkyl group, a substituted or unsubstituted C3-C30 cycloalkenyl group, a substituted or unsubstituted C1-C30 alkoxy group, a substituted or unsubstituted C6-C30 aryloxy group, a substituted or unsubstituted C6-C60 arylamine group, a substituted or unsubstituted C5-C60 heteroarylamine group, and a substituted or unsubstituted C5-C60 arylheteroarylamine group; R.sup.5 to R.sup.12 are present individually without forming a ring, or any adjacent two to four of R.sup.5 to R.sup.12 joined to form a ring B, the ring B is a substituted or unsubstituted C6-C30 aromatic ring, or a substituted or unsubstituted C3-C30 heteroaromatic ring.

3. The nitrogen-containing fused heterocyclic compound as claimed in claim 1, characterized in that Ar is selected from ##STR00075## ##STR00076## ##STR00077## ##STR00078## ##STR00079## ##STR00080## ##STR00081## ##STR00082## ##STR00083##

4. The nitrogen-containing fused heterocyclic compound as claimed in claim 1, characterized in that Ar.sup.1 is selected from a phenyl group, a biphenylyl group, a terphenylyl group, a naphthyl group, a phenylnaphthyl group, a naphthylphenyl group, an anthryl group, a phenanthryl group, a benzophenanthryl group, a pyridyl group, a dibenzofuryl group, a dibenzothiophenyl group, a carbazolyl group, a phenylcarbazolyl group, a pyridylcarbazolyl group, a naphthylcarbazolyl group, a biphenylylcarbazolyl group, a dibenzofurylphenyl group, a dibenzothiophenylphenyl group, a dimethylfluorenyl group, a diphenylfluorenyl group, a spiro-bifluorenyl group, a benzonaphthofuryl group, a benzonaphthothiophenyl group, a benzocarbazolyl group, and a dibenzocarbazolyl group, each of which is substituted or unsubstituted.

5. The nitrogen-containing fused heterocyclic compound as claimed in claim 1, characterized in that the nitrogen-containing fused heterocyclic compound is any one of the following compounds: ##STR00084## ##STR00085## ##STR00086## ##STR00087## ##STR00088## ##STR00089## ##STR00090## ##STR00091## ##STR00092## ##STR00093## ##STR00094## ##STR00095## ##STR00096## ##STR00097## ##STR00098## ##STR00099## ##STR00100## ##STR00101## ##STR00102## ##STR00103## ##STR00104## ##STR00105## ##STR00106## ##STR00107## ##STR00108## ##STR00109## ##STR00110## ##STR00111## ##STR00112## ##STR00113## ##STR00114## ##STR00115## ##STR00116## ##STR00117## ##STR00118## ##STR00119## ##STR00120## ##STR00121## ##STR00122## ##STR00123## ##STR00124##

6. An application of the nitrogen-containing fused heterocyclic compound as claimed in claim 1 in preparation of an optical element.

7. The application as claimed in claim 6, characterized in that the optical element comprises any one of an organic electroluminescence element, an organic field-effect transistor, an organic thin film transistor, an organic light-emitting transistor, an organic integrated circuit, an organic solar cell, an organic field quenching element, a light-emitting electrochemical cell, an organic laser diode, and an organic photoreceptor.

8. An organic electroluminescence element, characterized in that the organic electroluminescence element comprises an anode, a cathode, and an organic layer disposed between the anode and the cathode, and the organic layer comprises one or more the nitrogen-containing fused heterocyclic compounds as claimed in claim 1.

9. The organic electroluminescence element as claimed in claim 8, characterized in that the organic layer comprises a hole injection layer, a hole transport layer, an emitting layer, an electron transport layer and an electron injection layer, which are sequentially layered from a side of the anode to a side of the cathode.

10. An organic electroluminescence device, characterized in that the organic electroluminescence device comprises the organic electroluminescence element as claimed in claim 8.

Description

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0044] Specific embodiments are further illustrated by the following examples to demonstrate the technical approaches of the present invention. Those skilled in the art should understand that the illustrative examples are helpful to understand the present invention, however, they should not be construed as being limiting to the scope of the present invention.

Preparation Example 1

[0045] ##STR00055## ##STR00056##

[0046] (1) Synthesis of 1-B: In a three-necked bottle of 50 milliliters (mL), 1-A (1 millimole (mmol)) and hydrazine hydrate (15 mL) were added, and stirred at 60° C. to react for 2 hours (h). After the reaction ended, the reaction mixture was quenched by water, extracted by methylene dichloride, and solvent was removed by rotary evaporation, to obtain 1-B.

[0047] (2) Synthesis of 1-C: In a three-necked bottle of 50 mL, the product obtained from the step (1), 2-bromobenzaldehyde (1 mmol), ethanol (20 mL) were added, and stirred at 90° C. to react for 5 h. After the reaction ended, the reaction mixture was quenched by water, extracted by methylene dichloride, dried by anhydrous magnesium sulfate, and filtered to obtain an organic phase, and then solvent was removed by rotary evaporation to give a crude product. The crude product was separated by column chromatography (ethyl acetate:n-hexane=1:10 (volume ratio)) to obtain 1-C (0.28 g, 70% yield).

[0048] (3) Synthesis of 1-D: In a three-necked bottle of 50 mL, 1-C (1 mmol), iodobenzene diacetate (2 mmol) and methylene dichloride (20 mL) were added, stirred at room temperature to react for 6 h. After the reaction ended, solvent was removed to give a crude product. The crude product was separated by column chromatography (ethyl acetate:n-hexane=1:10 (volume ratio)), to obtain 1-D (0.26 g, 65% yield).

[0049] (4) Synthesis of 1-E: In a three-necked bottle of 50 mL, 1-D (1 mmol), potassium carbonate (2 mmol) and 1,2-dichlorobenzene (20 mL) were added, and stirred at 190° C. to react for 3 h. After the reaction ended, solvent was removed to give a crude product. The crude product was separated by column chromatography (ethyl acetate:n-hexane=1:10 (volume ratio)), to obtain 1-E (0.31 g, 78% yield).

[0050] (5) Synthesis of Compound 1: In a two-necked round-bottom flask of 50 mL, which was dried and purged with nitrogen gas, 1-E (1 mmol), 1-F (1 mmol), caesium carbonate (0.012 mol), tris(dibenzylideneacetone)dipalladium (Pd.sub.2(dba).sub.3, 0.05 mmol) and 2-dicyclohexylphosphino-2′,4′,6′-triisopropylbiphenyl (X-Phos, 0.055 mmol) were added, then toluene was added, and the mixture was refluxed for 24 h. After reaction, the mixture was cooled to room temperature, and the reaction system was filtered for concentration to give a crude product. The crude product was purified by column chromatography (methylene dichloride:n-hexane=1:10 (volume ratio)), to obtain Compound 1 (0.5 g, 82% yield).

[0051] HRMS-ESI m/z [M+H]+: 612.24.

[0052] Anal. Calcd. for C.sub.43H.sub.25N.sub.5: C, 84.43; H, 4.12; N, 11.45. Found: C, 84.49; H, 4.10; N, 11.41.

Preparation Example 2

[0053] ##STR00057## ##STR00058##

[0054] (1) Synthesis of 2-C: Similar to the synthesis of 1-C, with the difference that 3-bromobenzaldehyde is used to replace 2-bromobenzaldehyde, to obtain 2-C (0.27 g, 68% yield).

[0055] (2) Synthesis of 2-D: Similar to the synthesis of 1-D, with the difference that 2-C is used to replace 1-C, to obtain 2-D (0.27 g, 68% yield).

[0056] (3) Synthesis of 2-E: Similar to the synthesis of 1-E, with the difference that 2-D is used to replace 1-D, to obtain 2-E (0.3 g, 75% yield).

[0057] (4) Synthesis of Compound 2: Similar to the synthesis of Compound 1, with the difference that 2-E is used to replace 1-E, and 2-F is used to replace 1-F, to obtain Compound 2 (0.56 g, 86% yield).

[0058] HRMS-ESI m/z [M+H]+: 654.24.

[0059] Anal. Calcd. for C.sub.44H.sub.27N.sub.7: C, 80.84; H, 4.16; N, 15.00. Found: C, 80.77; H, 4.18; N, 15.05.

Preparation Example 3

[0060] ##STR00059## ##STR00060##

[0061] (1) Synthesis of 3-B: Similar to the synthesis of 1-B, with the difference that 3-A is used to replace 1-A, to obtain 3-B.

[0062] (2) Synthesis of 3-C: Similar to the synthesis of 1-C, with the difference that 3-B is used to replace 1-B, to obtain 3-C (0.33 g, 67% yield).

[0063] (3) Synthesis of 3-D: Similar to the synthesis of 1-D, with the difference that 3-C is used to replace 1-C, to obtain 3-D (0.31 g, 63% yield).

[0064] (4) Synthesis of 3-E: Similar to the synthesis of 1-E, with the difference that 3-D is used to replace 1-D, to obtain 3-E (0.38 g, 78% yield).

[0065] (5) Synthesis of Compound 3: Similar to the synthesis of Compound 1, with the difference that 3-E is used to replace 1-E, to obtain Compound 3 (0.55 g, 78% yield).

[0066] HRMS-ESI m/z [M+H]+: 702.23.

[0067] Anal. Calcd. for C.sub.49H.sub.27N.sub.5O: C, 83.86; H, 3.88; N, 9.98. Found: C, 83.84; H, 3.87; N, 10.01.

Preparation Example 4

[0068] ##STR00061## ##STR00062##

[0069] (1) Synthesis of 4-B: Similar to the synthesis of 1-B, with the difference that 4-A is used to replace 1-A, to obtain 4-B.

[0070] (2) Synthesis of 4-C: Similar to the synthesis of 1-C, with the difference that 4-B is used to replace 1-B, 3-bromobenzaldehyde is used to replace 2-bromobenzaldehyde, to obtain 4-C (0.35 g, 67% yield).

[0071] (3) Synthesis of 4-D: Similar to the synthesis of 1-D, with the difference that 4-C is used to replace 1-C, to obtain 4-D (0.36 g, 69% yield).

[0072] (4) Synthesis of 4-E: Similar to the synthesis of 1-E, with the difference that 4-D is used to replace 1-D, to obtain 4-E (0.40 g, 77% yield).

[0073] (5) Synthesis of Compound 4: Similar to the synthesis of Compound 1, with the difference that 4-E is used to replace 1-E, 4-F is used to replace 1-F, to obtain Compound 4 (0.66 g, 87% yield).

[0074] HRMS-ESI m/z [M+H]+: 760.26.

[0075] Anal. Calcd. for C.sub.52H.sub.33N.sub.5S: C, 82.19; H, 4.38; N, 9.22; S, 4.22. Found: C, 82.21; H, 4.40; N, 9.19; S, 4.20.

Preparation Example 5

[0076] ##STR00063## ##STR00064##

[0077] (1) Synthesis of 5-C: Similar to the synthesis of 1-C, with the difference that 4-bromo-3-methyl-benzaldehyde is used to replace 2-bromobenzaldehyde, to obtain 5-C (0.27 g, 64% yield).

[0078] (2) Synthesis of 5-D: Similar to the synthesis of 1-D, with the difference that 5-C is used to replace 1-C, to obtain 5-D (0.27 g, 65% yield).

[0079] (3) Synthesis of 5-E: Similar to the synthesis of 1-E, with the difference that 5-D is used to replace 1-D, to obtain 5-E (0.33 g, 80% yield).

[0080] (4) Synthesis of Compound 5: Similar to the synthesis of Compound 1, with the difference that 5-E is used to replace 1-E, to obtain Compound 5 (88% yield).

[0081] HRMS-ESI m/z [M+H]+: 626.20.

[0082] Anal. Calcd. for C.sub.44H.sub.27N.sub.5: C, 84.46; H, 4.35; N, 11.19. Found: C, 84.42; H, 4.37; N, 11.21.

Preparation Example 6

[0083] ##STR00065## ##STR00066##

[0084] (1) Synthesis of 6-B: Similar to the synthesis of 1-B, with the difference that 6-A is used to replace 1-A, to obtain 6-B.

[0085] (2) Synthesis of 6-C: Similar to the synthesis of 1-C, with the difference that 6-B is used to replace 1-B, to obtain 6-C (0.3 g, 70% yield).

[0086] (3) Synthesis of 6-D: Similar to the synthesis of 1-D, with the difference that 6-C is used to replace 1-C, to obtain 6-D (0.29 g, 67% yield).

[0087] (4) Synthesis of 6-E: Similar to the synthesis of 1-E, with the difference that 6-D is used to replace 1-D, to obtain 6-E (0.33 g, 77% yield).

[0088] (5) Synthesis of Compound 6: Similar to the synthesis of Compound 1, with the difference that 6-E is used to replace 1-E, to obtain Compound 6 (0.5 g, 78% yield).

[0089] HRMS-ESI m/z [M+H]+: 637.18.

[0090] Anal. Calcd. for C.sub.44H.sub.24N.sub.6: C, 83.00; H, 3.80; N, 13.20. Found: C, 83.03; H, 3.81; N, 13.16.

Preparation Example 7

[0091] ##STR00067##

[0092] Synthesis of Compound 7: In a three-necked bottle of 50 mL, 2-E (1 mmol), a raw material 7-F (1 mmol), potassium carbonate (1.2 mmol), tetrakis(triphenylphosphine)palladium (0.05 mmol), toluene (10 mL) and water (3 mL) were added, to react at 60° C. for 10 h. After the reaction ended, the reaction mixture was cooled to room temperature, quenched by adding 3 mL ice-cold water, extracted by methylene dichloride (10×3 mL), and the extracted solution was dried by magnesium sulfate, filtered, and dried by rotary evaporation to give a crude product. The crude product was purified by column chromatography (ethyl acetate/n-hexane, 1/10 (volume ratio)), to obtain Compound 7 (0.43 g, 69% yield).

[0093] HRMS-ESI m/z [M+H]+: 625.25.

[0094] Anal. Calcd. for C.sub.45H.sub.28N.sub.4: C, 86.51; H, 4.52; N, 8.97. Found: C, 86.47; H, 4.54; N, 8.99.

Preparation Example 8

[0095] ##STR00068##

[0096] Synthesis of Compound 8: Similar to the synthesis of Compound 7, with the difference that 1-E is used to replace 2-E, and 8-F is used to replace 7-F, to obtain Compound 8 (0.48 g, 76% yield).

[0097] HRMS-ESI m/z [M+H]+: 632.21.

[0098] Anal. Calcd. for C.sub.42H.sub.25N.sub.5S: C, 79.85; H, 3.99; N, 11.09; S, 5.07. Found: C, 79.85; H, 3.98; N, 11.12; S, 5.05.

Preparation Example 9

[0099] ##STR00069##

[0100] Synthesis of Compound 9: Similar to the synthesis of Compound 7, with the difference that 4-E is used to replace 2-E, and 9-F is used to replace 7-F, to obtain Compound 9 (0.55 g, 73% yield).

[0101] HRMS-ESI m/z [M+H]+: 753.30.

[0102] Anal. Calcd. for C.sub.55H.sub.36N.sub.4: C, 87.74; H, 4.82; N, 7.44. Found: C, 87.78; H, 4.81; N, 7.41.

Preparation Example 10

[0103] ##STR00070##

[0104] Synthesis of Compound 10: Similar to the synthesis of Compound 1, with the difference that 2-E is used to replace 1-E, and 10-F is used to replace 1-F, to obtain Compound 10 (85% yield).

[0105] HRMS-ESI m/z [M+H]+: 651.19.

[0106] Anal. Calcd. for C.sub.45H.sub.26N.sub.6: C, 83.06; H, 4.03; N, 12.91. Found: C, 83.11; H, 4.03; N, 12.86.

Element Example 1

[0107] The present invention provides an organic electroluminescence element comprising an anode (ITO), a hole injection layer, a hole transport layer, an emitting layer, an electron transport layer, an electron injection layer and a cathode, which were sequentially layered on a substrate, was prepared by the following method:

[0108] (1) Cleaning the substrate: a glass substrate coated with ITO (the anode) was ultrasonicated in an aqueous detergent, washed in deionized water, degreased in an acetone/ethanol mixed solvent (volume ratio=1:1) by ultrasonication, baked in a clear environment until water was completely removed, and washed by ozone under ultraviolet light;

[0109] (2) Depositing the hole injection layer: the glass substrate with an anode layer was placed in a chamber, and the chamber was vacuumized until 1×10.sup.−6 Pascal (Pa) to 2×10.sup.−4 Pa, and NDP-9 was deposited on the anode layer in vacuum to form a first hole injection layer, in which the deposited thickness was 5 nanometers (nm);

[0110] and H was deposited on the hole injection layer to form a second hole injection layer of 10 nm;

[0111] in which the hole injection layer herein comprises the first hole injection layer and the second hole injection layer;

[0112] (3) Depositing the hole transport layer: HT was deposited on the hole injection layer to form a hole transport layer, the deposited thickness was 80 nm;

[0113] (4) Depositing the emitting layer: the Compound 1 of the present invention (host material) and a guest material (piq).sub.2Ir(acac) were co-deposited on the hole transport layer in vacuum, in which the mass ratio of the host material and the guest material was 95:5, and the total deposited thickness was 30 nm;

[0114] (5) Depositing the electron transport layer: ET1 and LiQ (with a mass ratio of 1:1) were co-deposited on the emitting layer in vacuum, in which the total deposited thickness was 30 nm;

[0115] (6) Depositing the electron injection layer: LiQ was deposited on the electron transport layer in vacuum to form an electron injection layer, in which the total deposited thickness was 1 nm;

[0116] (7) Depositing the cathode: Mg:Ag (with a mass ratio of 9:1) were deposited on the electron injection layer to form a cathode, in which the deposited thickness was 20 nm; to obtain the organic electroluminescence element.

Element Examples 2 to 10, Comparative Element Example 1

[0117] An organic electroluminescence element was prepared, with the difference from the Element Example 1 that, the host material in the emitting layer was replaced with the corresponding compounds for Element Examples 2 to 10 and Comparative Element Example 1 listed in Table 1. The Compounds 1 to 10 are described above, and the Comparative Compound is shown below.

[0118] The structures of the materials involved in the above Element Examples and Comparative Element Example are shown as below:

##STR00071## ##STR00072##

[0119] Characteristic Tests:

[0120] The characteristics such as current, voltage, luminance and the like of the organic electroluminescence elements of the above Element Examples 1 to 10 and Comparative Element Example 1 were synchronously tested by PR 650 SpectraScan Colorimeter and Keithley K 2400 SourceMeter;

[0121] Testing conditions for electro-optical properties: with a current density of 10 milliamperes/square centimeter (mA/cm.sup.2) under room temperature;

[0122] Service life test: tested with a current density of 20 mA/cm.sup.2 under room temperature, and the time period recorded when the luminance of the tested element was reduced to 95% of the original luminance (in hour). The test results are shown in Table 1.

TABLE-US-00001 TABLE 1 Host material in Driving Current Service the emitting voltage efficiency life layer (V) (Cd/A) (h) Element Example Compound 1 4.0 20 253 1 Element Example Compound 2 4.2 19 239 2 Element Example Compound 3 4.0 18 260 3 Element Example Compound 4 4.1 19 245 4 Element Example Compound 5 4.1 20 244 5 Element Example Compound 6 4.0 20 249 6 Element Example Compound 7 4.3 17 241 7 Element Example Compound 8 4.2 16 233 8 Element Example Compound 9 4.3 18 230 9 Element Example Compound 10 4.2 19 247 10  Comparative Comparative 4.2 17 187 Element Example Compound 1

[0123] From Table 1, it is clear that the compounds of the present invention make the organic electroluminescence elements have a lower driving voltage (4.3 voltages (V) or lower), a higher current efficiency (16 Candelas/Ampere (Cd/A) or higher) and a longer service life (230 h or higher).

[0124] The applicant claims herein that even though the nitrogen-containing fused heterocyclic compound of the present invention and applications thereof are demonstrated by the above examples, the scope of the present invention is not limited by these examples. That is to say, it does not mean that the present invention has to be carried out based on the above examples. Those skilled in the art should understand that any improvement of the present invention, equivalent replacement of materials, addition of auxiliary components, selection of specific means and the like are all within the scope of protection and disclosure of the present invention.