A compound, an organic electroluminescent device and a display device

Abstract

The disclosure provides a compound, an organic electroluminescent device and a display device. Wherein, the compound has a structure as shown in Formula I. The introduction of a substituent Ar.sup.2 at the 1-position of naphthalene ring can not only adjust the adjacent steric hindrance size, but also effectively regulate the distortion degree of a molecule so as to reduce the crystallinity of the molecule. Secondly, an arylamino group is introduced at the 2-position, and the introduction of a trisubstituted structure on the arylamino group can effectively regulate the stereostructure of the molecule, improve the packing density of the molecule, so that the materials designed can meet the requirements of devices for materials. The compound of the disclosure can improve the luminous efficiency, reduce the starting voltage and prolong the service life of the device when it is applied to the organic electroluminescent device.

Claims

1. A compound, wherein, the compound has a structure as shown in Formula I; ##STR00483## In Formula I, the Ar.sup.1 and Ar.sup.2 are independently selected from the group consisting of a substituted or unsubstituted C6-C30 aryl group or a substituted or unsubstituted C3-C30 heteroaryl group; In Formula I, the L.sup.1 is selected from the group consisting of a substituted or unsubstituted C6-C30 arylene or a substituted or unsubstituted C3-C30 heteroarylene; In Formula I, the L.sup.2 is selected from one of a single bond, a substituted or unsubstituted C6-C30 arylene or a substituted or unsubstituted C3-C30 heteroarylene; In Formula I, the R.sup.1, R.sup.2 and R.sup.3 are independently selected from the group consisting of any one of a substituted or unsubstituted C1-C20 chain alkyl, a substituted or unsubstituted C3-C20 cycloalkyl, a substituted or unsubstituted C1-C20 chain alkoxy, a substituted or unsubstituted C3-C20 cycloalkoxy, a substituted or unsubstituted C2-C10 alkenyl, a substituted or unsubstituted C2-C10 alkynyl, halogen, cyano, nitro, hydroxyl, C1-C20 silyl, amino, a substituted or unsubstituted C6-C30 arylamino, a substituted or unsubstituted C3-C30 heteroarylamino, a substituted or unsubstituted C6-C30 aryl, a substituted or unsubstituted C3-C30 heteroaryl; the R.sup.1, R.sup.2 and R.sup.3 are connected to form a ring or not connected to form a ring; In Formula I, the m is an integer from 0 to 6; In Formula I, the R.sup.4 is independently selected from the group consisting of one of a substituted or unsubstituted C1-C20 chain alkyl, a substituted or unsubstituted C3-C20 cycloalkyl, a substituted or unsubstituted C1-C20 chain alkoxy, a substituted or unsubstituted C3-C20 cycloalkoxy, a substituted or unsubstituted C2-C10 alkenyl, a substituted or unsubstituted C2-C10 alkynyl, halogen, cyano, nitro, hydroxyl, a substituted or unsubstituted C1-C20 silyl, amino, a substituted or unsubstituted C6-C30 arylamino, a substituted or unsubstituted C3-C30 heteroarylamino, a substituted or unsubstituted C6-C30 aryl, a substituted or unsubstituted C3-C30 heteroaryl; In Ar.sup.1, Ar.sup.2, L.sup.1, L.sup.2, R.sup.1, R.sup.2, R.sup.3 and R.sup.4, the substituted groups are each independently selected from the group consisting of one or a combination of at least two of halogen, C1-C10 chain alkyl, C3-C10 cycloalkyl, C1-C10 alkoxy, C1-C10 thioalkoxy, C6-C30 arylamino, C3-C30 heteroarylamino, C6-C30 monocyclic aryl, C10-C30 fused ring aryl, C3-C30 monocyclic heteroaryl, C6-C30 fused ring heteroaryl.

2. The compound according to claim 1, wherein, the L.sup.2 is selected from the group consisting of one of a single bond, a substituted or unsubstituted C6-C20 arylene or a substituted or unsubstituted C3-C20 heteroarylene, preferably a single bond or phenylene.

3. The compound according to claim 1, wherein, the Ar.sup.2 is selected from the group consisting of a substituted or unsubstituted C6-C20 aryl or a substituted or unsubstituted C3-C20 heteroaryl; preferably, the Ar.sup.2 is selected from the group consisting of any of the following substituted or unsubstituted groups: phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, anthracyl, dibenzofuranyl, dibenzothiophenyl, carbazolyl, 9,9 dimethylfluorenyl, 9,9 diphenylfluorenyl, spirofluorenyl, triphenylene, fluoranthenyl, benzo9,9 dimethylfluorenyl, and benzospirofluorenyl; preferably, the Ar.sup.2 is selected from the group consisting of any of the following substituted or unsubstituted groups: ##STR00484## wherein, the dotted line represents a connecting bond of the groups.

4. (canceled)

5. The compound according to claim 1, wherein, the L.sup.2 is a single bond, and the Ar.sup.2 is selected from the group consisting of a substituted or unsubstituted C10-C30 fused ring aryl or a substituted or unsubstituted C6-C30 fused ring heteroaryl; preferably, the L.sup.2 is a single bond, and the Ar.sup.2 is selected from the group consisting of any of the following substituted or unsubstituted groups: naphthyl, phenanthryl, anthracyl, dibenzofuranyl, dibenzothiophenyl, carbazolyl, 9,9dimethylfluorenyl, 9,9diphenylfluorenyl, spirofluorenyl, triphenylene, fluoranthenyl, benzo9,9dimethylfluorenyl, and benzospirofluorenyl; preferably, the L.sup.2 is a single bond, and the Ar.sup.2 is selected from the group consisting of any of the following substituted or unsubstituted groups: ##STR00485## wherein, the dotted line represents a connecting bond of the groups; preferably, the L.sup.2 is the phenylene, and the Ar.sup.2 is selected from the group consisting of a substituted or unsubstituted C6-C30 aryl or a substituted or unsubstituted C3-C30 heteroaryl; preferably, the L.sup.2 is the phenylene, and the Ar.sup.2 is selected from the group consisting of any of the following substituted or unsubstituted groups: phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, anthracyl, dibenzofuranyl, dibenzothiophenyl, carbazolyl, 9,9dimethylfluorenyl, 9,9diphenylfluorenyl, spirofluorenyl, triphenylene, fluoranthenyl, benzo9,9dimethylfluorenyl, and benzospirofluorenyl; preferably, the L.sup.2 is the phenylene, and the Ar.sup.2 is selected from the group consisting of any of the following substituted or unsubstituted groups: ##STR00486## wherein, the dotted line represents a connecting bond of the groups.

6. (canceled)

7. The compound according to claim 1, wherein, the R.sup.1, R.sup.2 and R.sup.3 are independently selected from the group consisting of one of methyl, ethyl, or phenyl; preferably, the R.sup.1, R.sup.2 and R.sup.3 are all methyl; preferably, the L.sup.1 is selected from the group consisting of one of the following substituted or unsubstituted groups: phenylene, biphenylene, naphthylene, dibenzofuranylene, dibenzothiophenylene, and 9,9dimethylfluorenylene; preferably, the L.sup.1 is selected from the group consisting of any of the following substituted or unsubstituted groups: ##STR00487## wherein, the dotted line represents a connecting bond of the groups; preferably, the m is 0.

8. (canceled)

9. (canceled)

10. (canceled)

11. The compound according to claim 1, wherein, the compound has any one of the following structures as shown in P1-P777: ##STR00488## ##STR00489## ##STR00490## ##STR00491## ##STR00492## ##STR00493## ##STR00494## ##STR00495## ##STR00496## ##STR00497## ##STR00498## ##STR00499## ##STR00500## ##STR00501## ##STR00502## ##STR00503## ##STR00504## ##STR00505## ##STR00506## ##STR00507## ##STR00508## ##STR00509## ##STR00510## ##STR00511## ##STR00512## ##STR00513## ##STR00514## ##STR00515## ##STR00516## ##STR00517## ##STR00518## ##STR00519## ##STR00520## ##STR00521## ##STR00522## ##STR00523## ##STR00524## ##STR00525## ##STR00526## ##STR00527## ##STR00528## ##STR00529## ##STR00530## ##STR00531## ##STR00532## ##STR00533## ##STR00534## ##STR00535## ##STR00536## ##STR00537## ##STR00538## ##STR00539## ##STR00540## ##STR00541## ##STR00542## ##STR00543## ##STR00544## ##STR00545## ##STR00546## ##STR00547## ##STR00548## ##STR00549## ##STR00550## ##STR00551## ##STR00552## ##STR00553## ##STR00554## ##STR00555## ##STR00556## ##STR00557## ##STR00558## ##STR00559## ##STR00560## ##STR00561## ##STR00562## ##STR00563## ##STR00564## ##STR00565## ##STR00566## ##STR00567## ##STR00568## ##STR00569## ##STR00570## ##STR00571## ##STR00572## ##STR00573## ##STR00574## ##STR00575## ##STR00576## ##STR00577## ##STR00578## ##STR00579## ##STR00580## ##STR00581## ##STR00582## ##STR00583## ##STR00584## ##STR00585## ##STR00586## ##STR00587## ##STR00588## ##STR00589## ##STR00590## ##STR00591## ##STR00592## ##STR00593## ##STR00594## ##STR00595## ##STR00596## ##STR00597## ##STR00598## ##STR00599## ##STR00600## ##STR00601## ##STR00602## ##STR00603## ##STR00604## ##STR00605## ##STR00606## ##STR00607## ##STR00608## ##STR00609## ##STR00610## ##STR00611## ##STR00612## ##STR00613## ##STR00614## ##STR00615## ##STR00616## ##STR00617## ##STR00618## ##STR00619## ##STR00620## ##STR00621## ##STR00622## ##STR00623## ##STR00624## ##STR00625## ##STR00626## ##STR00627## ##STR00628## ##STR00629## ##STR00630## ##STR00631## ##STR00632## ##STR00633## ##STR00634## ##STR00635## ##STR00636## ##STR00637## ##STR00638## ##STR00639## ##STR00640## ##STR00641## ##STR00642## ##STR00643## ##STR00644## ##STR00645## ##STR00646## ##STR00647## ##STR00648## ##STR00649## ##STR00650## ##STR00651## ##STR00652## ##STR00653## ##STR00654## ##STR00655## ##STR00656## ##STR00657## ##STR00658## ##STR00659## ##STR00660## ##STR00661## ##STR00662## ##STR00663## ##STR00664## ##STR00665## ##STR00666## ##STR00667## ##STR00668## ##STR00669## ##STR00670## ##STR00671## ##STR00672## ##STR00673## ##STR00674## ##STR00675## ##STR00676## ##STR00677## ##STR00678## ##STR00679## ##STR00680## ##STR00681## ##STR00682## ##STR00683## ##STR00684## ##STR00685## ##STR00686## ##STR00687## ##STR00688## ##STR00689## ##STR00690## ##STR00691## ##STR00692## ##STR00693## ##STR00694## ##STR00695## ##STR00696## ##STR00697## ##STR00698## ##STR00699## ##STR00700## ##STR00701## ##STR00702## ##STR00703## ##STR00704## ##STR00705## ##STR00706## ##STR00707## ##STR00708## ##STR00709## ##STR00710## ##STR00711## ##STR00712## ##STR00713## ##STR00714## ##STR00715## ##STR00716## ##STR00717## ##STR00718## ##STR00719## ##STR00720## ##STR00721## ##STR00722## ##STR00723## ##STR00724## ##STR00725## ##STR00726## ##STR00727## ##STR00728## ##STR00729## ##STR00730## ##STR00731## ##STR00732## ##STR00733## ##STR00734## ##STR00735## ##STR00736## ##STR00737## ##STR00738## ##STR00739## ##STR00740## ##STR00741## ##STR00742## ##STR00743## ##STR00744## ##STR00745## ##STR00746## ##STR00747## ##STR00748## ##STR00749## ##STR00750## ##STR00751## ##STR00752## ##STR00753## ##STR00754## ##STR00755## ##STR00756## ##STR00757## ##STR00758## ##STR00759## ##STR00760## ##STR00761## ##STR00762##

12. An organic electroluminescent device, wherein, the organic electroluminescent device comprises a first electrode, a second electrode and at least one organic layer inserted between the first electrode and the second electrode, wherein the organic layer contains at least one compound according to claim 1.

13. The organic electroluminescent device according to claim 12, wherein, the organic layer comprises an electron blocking layer, wherein the electron blocking layer comprises at least one compound according to claim 1.

14. The organic electroluminescent device according to claim 12, wherein, the first electrode is an anode layer, the second electrode is a cathode layer, the organic layer comprises a light emitting layer, and the light emitting layer contains a host material and a doping material; the host material comprises a first host material and a second host material, and the first host material is a compound according to claim 1.

15. The organic electroluminescent device according to claim 14, wherein, In Formula I, the Ar.sup.1 is selected from the group consisting of any of the following substituted or unsubstituted groups: phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, anthracyl, dibenzofuranyl, dibenzothiophenyl, carbazolyl, 9,9dimethylfluorenyl, 9,9diphenylfluorenyl, spirofluorenyl, triphenylene, fluoranthenyl, benzo9,9dimethylfluorenyl, and benzospirofluorenyl; and/or, In Formula I, the Ar.sup.2 is selected from the group consisting of any of the following substituted or unsubstituted groups: phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, anthracyl, dibenzofuranyl, dibenzothiophenyl, carbazolyl, 9,9dimethylfluorenyl, 9,9diphenylfluorenyl, spirofluorenyl, triphenylene, fluoranthenyl, benzo9,9dimethylfluorenyl, benzospirofluorenyl, preferably a substituted or unsubstituted naphthyl; preferably, In Formula I, the R.sup.1, R.sup.2 and R.sup.3 are independently selected from the group consisting of one of methyl, ethyl or phenyl, preferably all are methyl; preferably, the first host material is selected from the group consisting of any one or a combination of at least two of the compounds according to claim 6; preferably, the mass ratio of the first host material to the second host material is 0.01:1-1.5:1, preferably 0.1:1-1:1.

16. (canceled)

17. (canceled)

18. (canceled)

19. The organic electroluminescent device according to claim 14, wherein, the HOMO energy level of the second host material is −5.3 eV to −5.7 eV; and/or, the LUMO energy level of the second host material is −2.3 eV to −2.6 eV; preferably, the HOMO energy level of the second host material is −5.3 eV to −5.7 eV, and the LUMO energy level is −2.3 eV to −2.6 eV; preferably, the second host material is selected from the group consisting of any one or a combination of at least two of the following compound PH-1 to compound PH-85: ##STR00763## ##STR00764## ##STR00765## ##STR00766## ##STR00767## ##STR00768## ##STR00769## ##STR00770## ##STR00771## ##STR00772## ##STR00773## ##STR00774##

20. (canceled)

21. The organic electroluminescent device according to any one of claim 1, wherein, the thickness of the light emitting layer is 10-65 nm, preferably 15-55 nm; preferably, the organic layer further comprises any one or a combination of at least two of a hole injection layer, a hole transporting layer, an electron blocking layer, an electron transporting layer or an electron injection layer, wherein the hole injection layer, the hole transporting layer, the electron blocking layer, the light emitting layer, the electron transporting layer and the electron injection layer are arranged in sequence from the anode layer to the cathode layer.

22. (canceled)

23. The organic electroluminescent device according to claim 12, wherein, the first electrode is an anode layer, the second electrode is a con cathode layer, the organic layer contains compound I and compound II, and the compound I is the compound according to claim 1; the compound II has the structure as shown in Formula (3), ##STR00775## the r is an integer from 0 to 6; the Ar.sup.3 to Ar.sup.5 are independently selected from the group consisting of a substituted or unsubstituted C6-C30 aryl or a substituted or unsubstituted C3-C30 heteroaryl; the L.sup.3 to L.sup.5 are each independently selected from the group consisting of any one of a single bond, a substituted or unsubstituted C6-C30 arylene, and a substituted or unsubstituted C3-C30 heteroarylene; the R.sup.5 are independently selected from the group consisting of any one of a substituted or unsubstituted C1-C20 chain alkyl, a substituted or unsubstituted C3-C20 cycloalkyl, a substituted or unsubstituted C6-C30 aryl, and a substituted or unsubstituted C3-C30 heteroaryl; the y is an integer from 1 to 15, the Rx is a substituent at any substitutable position, and at least one Rx is selected from the group consisting of a substituted or unsubstituted C3-C20 cycloalkyl; In Formula I and Formula (3), in Ar.sup.1 to Ar.sup.5, L.sup.1 to L.sup.5, R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5 and Rx, the substituted groups are independently selected from the group consisting of one or a combination of at least two of halogen, C1-C10 chain alkyl, C3-C10 cycloalkyl, C1-C10 alkoxy, C1-C10 thioalkoxy, C6-C30 arylamino, C3-C30 heteroarylamino, C6-C30 monocyclic aryl, C10-C30 fused ring aryl, C3-C30 monocyclic heteroaryl, and C6-C30 fused ring heteroaryl.

24. The organic electroluminescent device according to claim 23, wherein, the compound I is any of the compounds according to claim 11.

25. The organic electroluminescent device according to claim 23, wherein, the compound II has any one of the structures as shown in A1 to A291: ##STR00776## ##STR00777## ##STR00778## ##STR00779## ##STR00780## ##STR00781## ##STR00782## ##STR00783## ##STR00784## ##STR00785## ##STR00786## ##STR00787## ##STR00788## ##STR00789## ##STR00790## ##STR00791## ##STR00792## ##STR00793## ##STR00794## ##STR00795## ##STR00796## ##STR00797## ##STR00798## ##STR00799## ##STR00800## ##STR00801## ##STR00802## ##STR00803## ##STR00804## ##STR00805## ##STR00806## ##STR00807## ##STR00808## ##STR00809## ##STR00810## ##STR00811## ##STR00812## ##STR00813## ##STR00814## ##STR00815## ##STR00816## ##STR00817## ##STR00818## ##STR00819## ##STR00820## ##STR00821## ##STR00822## ##STR00823## ##STR00824## ##STR00825## ##STR00826## ##STR00827## ##STR00828## ##STR00829## ##STR00830## ##STR00831## ##STR00832## ##STR00833## ##STR00834## ##STR00835## ##STR00836## ##STR00837## ##STR00838## ##STR00839## ##STR00840## ##STR00841## ##STR00842## ##STR00843## ##STR00844## ##STR00845## ##STR00846## ##STR00847## ##STR00848## ##STR00849## ##STR00850## ##STR00851## ##STR00852## ##STR00853## ##STR00854## ##STR00855## ##STR00856## ##STR00857## ##STR00858## ##STR00859## ##STR00860## ##STR00861## ##STR00862## ##STR00863## ##STR00864## ##STR00865## ##STR00866## ##STR00867## ##STR00868## ##STR00869## ##STR00870## ##STR00871## ##STR00872##

26. The organic electroluminescent device according to claim 23, wherein, in the direction from the cathode layer to the anode layer, the organic layer comprises a light emitting layer and an electron blocking layer in sequence, the light emitting layer contains the compound I, and the electron blocking layer contains the compound II; or the light emitting layer contains the compound II, and the electron blocking layer contains the compound I.

27. The organic electroluminescent device according to claim 26, wherein, the light emitting layer contains a first host material, a second host material and a doping material; the first host material is the compound I, the electron blocking layer contains the compound II, or, the first host material is the compound II, and the electron blocking layer contains the compound I; preferably, the mass ratio of the first host material to the second host material is 0.01:1-1.5:1, preferably is 0-1:1-1:1.

28. (canceled)

29. The organic electroluminescent device according to claim 26, wherein, the thickness of the light emitting layer is 10-60 nm, preferably is 20-50 nm; preferably, the thickness of the electron blocking layer is 2-100 nm, preferably is 3-90 nm.

30. (canceled)

31. The organic electroluminescent device according to claim 27, wherein, the organic layer further comprises a hole injection layer, a hole transporting layer, an electron transporting layer and an electron injection layer, and in the direction from the anode layer to the cathode layer, the organic layer comprises the hole injection layer, the hole transporting layer, the electron blocking layer, the light emitting layer, the electron transporting layer and the electron injection layer in sequence.

32. A display device, wherein, the display device comprises the organic electroluminescent device according to claim 1 or according to claim 25.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0220] The accompanying drawings of the description, which form a part of the present application, are used to provide a further understanding of the disclosure. The illustrative examples and their descriptions of the disclosure are used to explain the disclosure, and do not constitute an improper limitation to the disclosure. In the drawings:

[0221] FIG. 1 is a structural representation of the organic electroluminescent device provided in a specific embodiment of the disclosure;

[0222] wherein, 1—a glass substrate with an anode; 2—a hole injection layer; 3—a hole transporting layer; 4—an electron blocking layer; 5—a light emitting layer; 6—an electron transporting layer; 7—an electron injection layer; 8—a cathode layer; 9—an external power supply.

DETAILED DESCRIPTION OF THE EMBODIMENTS

[0223] It should be noted that the embodiments and features in the embodiments in the application can be combined with each other without conflict. The disclosure will be described in detail below with reference to the embodiments.

[0224] The representative synthesis route of compound of Formula I according to the disclosure is as follows:

##STR00462##

[0225] wherein, R.sub.1, R.sup.2, R.sub.3, R.sub.4, L.sup.1, L.sup.2, Ar.sup.1 and Ar.sup.2 have the same meaning as the symbols in Formula I; Pd.sub.2(dba).sub.3 represents tris(dibenzyl acetone) dipalladium(0), IPr.Math.HCl represents 1, bis(2,-diisopropylphenyl)imidazolium chloride, NaOBu-t represents sodium tert-butoxide, and (t-Bu).sub.3P represents tri(tert-butyl)phosphine.

[0226] More specifically, the disclosure provides a specific synthesis method of the representative compounds in the following synthesis examples. Solvents and reagents used in the following synthesis examples, such as for example, 3-bromo-9,9-dimethylfluorene, 1, bis (2, diisopropyl phenyl) imidazolium chloride, tris(dibenzyl acetone) dipalladium(O), toluene, methanol, ethanol, tri(tert-butyl)phosphine, potassium/sodium tert-butoxide, etc., can be purchased or customized from the domestic chemical product market, for example, purchased from Sinopharm Reagent Co., Ltd., SigmaAldrich Co., Ltd., and J&K Scientific Co., Ltd., and Intermediates M1 to M7 were customized through reagent companies. In addition, they can also be synthesized by those skilled in the art through well-known methods.

Synthesis Example 1: Synthesis of Compound P1

[0227] ##STR00463##

[0228] Into a 1000 mL single-necked bottle, 13.5 g (50 mmol) of M1, 13.6 g (50 mmol) of 3-bromo-9,9-dimethylfluorene, 0.9 g (1 mmol) of tris(dibenzylideneacetone)dipalladium (i.e. Pd.sub.2(dba).sub.3), 0.5 g of IPr.Math.HCl, 500 mL of toluene, and 14.4 g (150 mmol) of sodium tert-butoxide (NaOBu-t) were added, vacuumized and replaced with nitrogen for three times, and the reaction was heated up to 90° C. for reacting 5 hours. After the reaction was completed, it was stopped. The reaction was cooled to room temperature, the reaction solution was layered, the organic phase was concentrated and methanol was added and stirred for 1 hour, suction filtered to obtain M1-1 as a light yellow powder.

[0229] Into a 1000 mL single-necked bottle, 23 g (50 mmol) of M1-1, 11 g (50 mmol) of 4-bromo-4′-tert-butylbiphenyl, 0.9 g (1 mmol) of tris(dibenzylideneacetone)dipalladium (i.e. Pd.sub.2(dba).sub.3), 0.5 mL of Tri-tert-butylphosphine ((t-Bu).sub.3P), 500 mL of toluene, and 14.4 g (150 mmol) of sodium tert-butoxide (NaOBu-t) were added, vacuumized and replaced with nitrogen for three times, and the reaction was heated up to 110° C. for reacting 5 hours. After the reaction was completed, it was stopped. The reaction was cooled to room temperature, the reaction solution was layered, the organic phase was concentrated and methanol was added and stirred for 1 hour, suction filtered to obtain P1 as a light yellow powder.

[0230] M/Z theoretical value: 593; ZAB-HS Model Mass Spectrometer (Manufactured by Micromass, British) M/Z found: 594.

Synthesis Example 2: Synthesis of Compound P2

[0231] ##STR00464##

[0232] Into a 1000 mL single-necked bottle, 23 g (50 mmol) of M1-1, 14.4 g (50 mmol) of 4-bromo-4′-tert-butylbiphenyl, 0.9 g (1 mmol) of tris(dibenzylideneacetone)dipalladium (i.e. Pd2(dba)3), 0.5 mL of Ti-tert-butylphosphine((t-Bu)3P), 500 mL of toluene, and 14.4 g (150 mmol) of sodium tert-butoxide(NaOBu-t) were added, vacuumized and replaced with nitrogen for three times, and the reaction was heated up to 110° C. for reacting 5 hours. After the reaction was completed, it was stopped. The reaction was cooled to room temperature, the reaction solution was layered, the organic phase was concentrated and methanol was added and stirred for 1 hour, suction filtered to obtain P2 as a light yellow powder.

[0233] M/Z theoretical value: 669; ZAB-HS Model Mass Spectrometer (Manufactured by Micromass, British) M/Z found: 670.

Synthesis Example 3: Synthesis of Compound P5

[0234] ##STR00465##

[0235] Into a 1000 mL single-necked bottle, 23 g (50 mmol) of M1-1, 14.5 g (50 mmol) of 2-bromo-5-tert-butylbiphenyl, 0.9 g (1 mmol) of tris(dibenzylideneacetone)dipalladium (i.e. Pd.sub.2(dba).sub.3), 0.5 mL of Tri-tert-butylphosphine((t-Bu).sub.3P), 500 mL of toluene, 14.4 g (150 mmol) of sodium tert-butoxide(NaOBu-t) were added, vacuumized and replaced with nitrogen for three times, and the reaction was heated up to 110° C. for reacting 5 hours. After the reaction was completed, it was stopped. The reaction was cooled to room temperature, the reaction solution was layered, the organic phase was concentrated and methanol was added and stirred for 1 hour, suction filtered to obtain P5 as a light yellow powder.

[0236] M/Z theoretical value: 669; ZAB-HS Model Mass Spectrometer (Manufactured by Micromass, British) M/Z found: 670.

Synthesis Example 4: Synthesis of Compound P6

[0237] ##STR00466##

[0238] Into a 1000 mL single-necked bottle, 23 g (50 mmol) of M1-1, 18.5 g (50 mmol) of 4-bromo-3phenyl-4′-tert-butylbiphenyl, 0.9 g (1 mmol) of tris(dibenzylideneacetone)dipalladium (i.e. Pd.sub.2(dba).sub.3), 0.5 mL of Tri-tert-butylphosphine((t-Bu).sub.3P), 500 mL of toluene, and 14.4 g (150 mmol) of sodium tert-butoxide(NaOBu-t) were added, vacuumized and replaced with nitrogen for three times, and the reaction was heated up to 110° C. for reacting 5 hours. After the reaction was completed, it was stopped. The reaction was cooled to room temperature, the reaction solution was layered, the organic phase was concentrated and methanol was added and stirred for 1 hour, suction filtered to obtain P6 as a light yellow powder.

[0239] M/Z theoretical value: 745; ZAB-HS Model Mass Spectrometer (Manufactured by Micromass, British) M/Z found: 746.

Synthesis Example 5: Synthesis of Compound P7

[0240] ##STR00467##

[0241] Into a 1000 mL single-necked bottle, 13.5 g (50 mmol) of M1, 20 g (50 mmol) of 3-bromo-9,9-diphenylfluorene, 0.9 g (1 mmol) of tris(dibenzylideneacetone)dipalladium (i.e. Pd.sub.2(dba).sub.3), 0.5 g of IPr.Math.HCl, 500 mL of toluene, and 14.4 g (150 mmol) of sodium tert-butoxide(NaOBu-t) were added, vacuumized and replaced with nitrogen for three times, and the reaction was heated up to 90° C. for reacting 5 hours. After the reaction was completed, it was stopped. The reaction was cooled to room temperature, the reaction solution was layered, the organic phase was concentrated and methanol was added and stirred for 1 hour, suction filtered to obtain M1-2 as a light yellow powder.

[0242] Into a 1000 mL single-necked bottle, 29 g (50 mmol) of M1-2, 11 g (50 mmol) of 4-bromo-4′-tert-butylbiphenyl, 0.9 g (1 mmol) of tris(dibenzylideneacetone)dipalladium (i.e. Pd.sub.2(dba).sub.3), 0.5 mL of Tri-tert-butylphosphine ((t-Bu).sub.3P), 500 mL of toluene, and 14.4 g (150 mmol) of sodium tert-butoxide (NaOBu-t) were added, vacuumized and replaced with nitrogen for three times, and the reaction was heated up to 110° C. for reacting 5 hours. After the reaction was completed, it was stopped. The reaction was cooled to room temperature, the reaction solution was layered, the organic phase was concentrated and methanol was added and stirred for 1 hour, suction filtered to obtain P7 as a light yellow powder.

[0243] M/Z theoretical value: 717; ZAB-HS Model Mass Spectrometer (Manufactured by Micromass, British) M/Z found: 718.

Synthesis Example 6: Synthesis of Compound P15

[0244] ##STR00468##

[0245] Into a 1000 mL single-necked bottle, 13.5 g (50 mmol) of M1, 16.5 g (50 mmol) of 3-bromo-[6,7]-benzo-9,9-dimethylfluorene, 0.9 g (1 mmol) of tris(dibenzylideneacetone)dipalladium (i.e. Pd.sub.2(dba).sub.3), 0.5 g of IPr.Math.HCl, 500 mL of toluene, and 14.4 g (150 mmol) of sodium tert-butoxide(NaOBu-t) were added, vacuumized and replaced with nitrogen for three times, and the reaction was heated up to 90° C. for reacting 5 hours. After the reaction was completed, it was stopped. The reaction was cooled to room temperature, the reaction solution was layered, the organic phase was concentrated and methanol was added and stirred for 1 hour, suction filtered to obtain M1-3 as a light yellow powder.

[0246] Into a 1000 mL single-necked bottle, 25.5 g (50 mmol) of M1-3, 11 g (50 mmol) of 4-bromo-tert-butylbenzene, 0.9 g (1 mmol) of tris(dibenzylideneacetone)dipalladium (i.e. Pd.sub.2(dba).sub.3), 0.5 mL of Tri-tert-butylphosphine((t-Bu).sub.3P), 500 mL of toluene, and 14.4 g (150 mmol) of sodium tert-butoxide(NaOBu-t) were added, vacuumized and replaced with nitrogen for three times, and the reaction was heated up to 110° C. for reacting 5 hours. After the reaction was completed, it was stopped. The reaction was cooled to room temperature, the reaction solution was layered, the organic phase was concentrated and methanol was added and stirred for 1 hour, suction filtered to obtain P15 as a light yellow powder.

[0247] M/Z theoretical value: 643; ZAB-HS Model Mass Spectrometer (Manufactured by Micromass, British) M/Z found: 644.

Synthesis Example 7: Synthesis of Compound P37

[0248] ##STR00469##

[0249] Into a 1000 mL single-necked bottle, 16 g (50 mmol) of M2, 13.5 g (50 mmol) of 3-bromo-9,9-dimethylfluorene, 0.9 g (1 mmol) of tris(dibenzylideneacetone)dipalladium (i.e. Pd.sub.2(dba).sub.3), 0.5 g of IPr.Math.HCl, 500 mL of toluene, and 14.4 g (150 mmol) of sodium tert-butoxide (NaOBu-t) were added, vacuumized and replaced with nitrogen for three times, and the reaction was heated up to 90° C. for reacting 5 hours. After the reaction was completed, it was stopped. The reaction was cooled to room temperature, the reaction solution was layered, the organic phase was concentrated and methanol was added and stirred for 1 hour, suction filtered to obtain M2-1 as a light yellow powder.

[0250] Into a 1000 mL single-necked bottle, 26 g (50 mmol) of M2-1, 11 g (50 mmol) of 4-bromo-tert-butylbenzene, 0.9 g (1 mmol) of tris(dibenzylideneacetone)dipalladium (i.e. Pd.sub.2(dba).sub.3), 0.5 mL of Tri-tert-butylphosphine((t-Bu).sub.3P), 500 mL of toluene, and 14.4 g (150 mmol) of sodium tert-butoxide(NaOBu-t) were added, vacuumized and replaced with nitrogen for three times, and the reaction was heated up to 110° C. for reacting 5 hours. After the reaction was completed, it was stopped. The reaction was cooled to room temperature, the reaction solution was layered, the organic phase was concentrated and methanol was added and stirred for 1 hour, suction filtered to obtain P37 as a light yellow powder.

[0251] M/Z theoretical value: 649; ZAB-HS Model Mass Spectrometer (Manufactured by Micromass, British) M/Z found: 650.

Synthesis Example 8: Synthesis of Compound P38

[0252] ##STR00470##

[0253] Into a 1000 mL single-necked bottle, 26 g (50 mmol) of M2-1, 14.5 g (50 mmol) of 4-bromo-4′-tert-butylbiphenyl, 0.9 g (1 mmol) of tris(dibenzylideneacetone)dipalladium (i.e. Pd.sub.2(dba).sub.3), 0.5 mL of Tri-tert-butylphosphine((t-Bu).sub.3P), 500 mL of toluene, and 14.4 g (150 mmol) of sodium tert-butoxide(NaOBu-t) were added, vacuumized and replaced with nitrogen for three times, and the reaction was heated up to 110° C. for reacting 5 hours. After the reaction was completed, it was stopped. The reaction was cooled to room temperature, the reaction solution was layered, the organic phase was concentrated and methanol was added and stirred for 1 hour, suction filtered to obtain P38 as a light yellow powder.

[0254] M/Z theoretical value: 725; ZAB-HS Model Mass Spectrometer (Manufactured by Micromass, British) M/Z found: 726.

Synthesis Example 9: Synthesis of Compound P74

[0255] ##STR00471##

[0256] Into a 1000 mL single-necked bottle, 15.5 g (50 mmol) of M3, 13.5 g (50 mmol) of 3-bromo-9,9-dimethylfluorene, 0.9 g (1 mmol) of tris(dibenzylideneacetone)dipalladium (i.e. Pd.sub.2(dba).sub.3), 0.5 g of IPr.Math.HCl, 500 mL of toluene, and 14.4 g (150 mmol) of sodium tert-butoxide (NaOBu-t) were added, vacuumized and replaced with nitrogen for three times, and the reaction was heated up to 90° C. for reacting 5 hours. After the reaction was completed, it was stopped. The reaction was cooled to room temperature, the reaction solution was layered, the organic phase was concentrated and methanol was added and stirred for 1 hour, suction filtered to obtain M3-1 as a light yellow powder.

[0257] Into a 1000 mL single-necked bottle, 25 g (50 mmol) of M3-1, 14.5 g (50 mmol) of 4-bromo-4′-tert-butylbiphenyl, 0.9 g (1 mmol) of tris(dibenzylideneacetone)dipalladium (i.e. Pd.sub.2(dba).sub.3), 0.5 mL of Tri-tert-butylphosphine((t-Bu).sub.3P), 500 mL of toluene, and 14.4 g (150 mmol) of sodium tert-butoxide(NaOBu-t) were added, vacuumized and replaced with nitrogen for three times, and the reaction was heated up to 110° C. for reacting 5 hours. After the reaction was completed, it was stopped. The reaction was cooled to room temperature, the reaction solution was layered, the organic phase was concentrated and methanol was added and stirred for 1 hour, suction filtered to obtain P74 as a light yellow powder.

[0258] M/Z theoretical value: 709; ZAB-HS Model Mass Spectrometer (Manufactured by Micromass, British) M/Z found: 710.

Synthesis Example 10: Synthesis of Compound P253

[0259] ##STR00472##

[0260] Into a 1000 mL single-necked bottle, 16.5 g (50 mmol) of M4, 13.6 g (50 mmol) of 3-bromo-9,9-dimethylfluorene, 0.9 g (1 mmol) of tris(dibenzylideneacetone)dipalladium (i.e. Pd.sub.2(dba).sub.3), 0.5 g of IPr.Math.HCl, 500 mL of toluene, and 14.4 g (150 mmol) of sodium tert-butoxide (NaOBu-t) were added, vacuumized and replaced with nitrogen for three times, and the reaction was heated up to 90° C. for reacting 5 hours. After the reaction was completed, it was stopped. The reaction was cooled to room temperature, the reaction solution was layered, the organic phase was concentrated and methanol was added and stirred for 1 hour, suction filtered to obtain M4-1 as a light yellow powder.

[0261] Into a 1000 mL single-necked bottle, 26.5 g (50 mmol) of M4-1, 11 g (50 mmol) of 4-bromo-4′-tert-butylbiphenyl, 0.9 g (1 mmol) of tris(dibenzylideneacetone)dipalladium (i.e. Pd.sub.2(dba).sub.3), 0.5 mL of Tri-tert-butylphosphine ((t-Bu).sub.3P), 500 mL of toluene, and 14.4 g (150 mmol) of sodium tert-butoxide (NaOBu-t) were added, vacuumized and replaced with nitrogen for three times, and the reaction was heated up to 110° C. for reacting 5 hours. After the reaction was completed, it was stopped. The reaction was cooled to room temperature, the reaction solution was layered, the organic phase was concentrated and methanol was added and stirred for 1 hour, suction filtered to obtain P253 as a light yellow powder.

[0262] M/Z theoretical value: 659; ZAB-HS Model Mass Spectrometer (Manufactured by Micromass, British) M/Z found: 660.

Synthesis Example 11: Synthesis of Compound P284

[0263] ##STR00473##

[0264] Into a 1000 mL single-necked bottle, 26.5 g (50 mmol) of M4-1, 20 g (50 mmol) of 1-(4-bromophenyl)-1,1,1-triphenylmethane, 0.9 g (1 mmol) of tris(dibenzylideneacetone)dipalladium (i.e. Pd.sub.2(dba).sub.3), 0.5 mL of Tri-tert-butylphosphine((t-Bu).sub.3P), 500 mL of toluene, and 14.4 g (150 mmol) of sodium tert-butoxide(NaOBu-t) were added, vacuumized and replaced with nitrogen for three times, and the reaction was heated up to 110° C. for reacting 5 hours. After the reaction was completed, it was stopped. The reaction was cooled to room temperature, the reaction solution was layered, the organic phase was concentrated and methanol was added and stirred for 1 hour, suction filtered to obtain P284 as a light yellow powder.

[0265] M/Z theoretical value: 845; ZAB-HS Model Mass Spectrometer (Manufactured by Micromass, British) M/Z found: 846.

Synthesis Example 12: Synthesis of Compound P375

[0266] ##STR00474##

[0267] Into a 1000 mL single-necked bottle, 15 g (50 mmol) of M5, 13.5 g (50 mmol) of 3-bromo-9,9-dimethylfluorene, 0.9 g (1 mmol) of tris(dibenzylideneacetone)dipalladium (i.e. Pd.sub.2(dba).sub.3), 0.5 g of IPr.Math.HCl, 500 mL of toluene, and 14.4 g (150 mmol) of sodium tert-butoxide (NaOBu-t) were added, vacuumized and replaced with nitrogen for three times, and the reaction was heated up to 90° C. for reacting 5 hours. After the reaction was completed, it was stopped. The reaction was cooled to room temperature, the reaction solution was layered, the organic phase was concentrated and methanol was added and stirred for 1 hour, suction filtered to obtain M5-1 as a light yellow powder.

[0268] Into a 1000 mL single-necked bottle, 25 g (50 mmol) of MS-1, 14.5 g (50 mmol) of 2-phenyl4-bromotert-butylbenzene, 0.9 g (1 mmol) of tris(dibenzylideneacetone)dipalladium (i.e. Pd.sub.2(dba).sub.3), 0.5 mL of Tri-tert-butylphosphine((t-Bu).sub.3P), 500 mL of toluene, and 14.4 g (150 mmol) of sodium tert-butoxide(NaOBu-t) were added, vacuumized and replaced with nitrogen for three times, and the reaction was heated up to 110° C. for reacting 5 hours. After the reaction was completed, it was stopped. The reaction was cooled to room temperature, the reaction solution was layered, the organic phase was concentrated and methanol was added and stirred for 1 hour, suction filtered to obtain P375 as a light yellow powder.

[0269] M/Z theoretical value: 695; ZAB-HS Model Mass Spectrometer (Manufactured by Micromass, British) M/Z found: 696.

Synthesis Example 13: Synthesis of Compound P322

[0270] ##STR00475##

[0271] Into a 1000 mL single-necked bottle, 16.5 g (50 mmol) of M7, 13.5 g (50 mmol) of 3-bromo-9,9-dimethylfluorene, 0.9 g (1 mmol) of tris(dibenzylideneacetone)dipalladium (i.e. Pd.sub.2(dba).sub.3), 0.5 g of IPr.Math.HCl, 500 mL of toluene, and 14.4 g (150 mmol) of sodium tert-butoxide (NaOBu-t) were added, vacuumized and replaced with nitrogen for three times, and the reaction was heated up to 90° C. for reacting 5 hours. After the reaction was completed, it was stopped. The reaction was cooled to room temperature, the reaction solution was layered, the organic phase was concentrated and methanol was added and stirred for 1 hour, suction filtered to obtain M7-1 as a light yellow powder.

[0272] Into a 1000 mL single-necked bottle, 26.5 g (50 mmol) of M7-1, 14 g (50 mmol) of 1-(4-bromophenyl)-1,1-dimethyl-1-phenylmethane, 0.9 g (1 mmol) of tris(dibenzylideneacetone)dipalladium (i.e. Pd.sub.2(dba).sub.3), 0.5 mL of Tri-tert-butylphosphine((t-Bu).sub.3P), 500 mL of toluene, and 14.4 g (150 mmol) of sodium tert-butoxide(NaOBu-t) were added, vacuumized and replaced with nitrogen for three times, and the reaction was heated up to 110° C. for reacting 5 hours. After the reaction was completed, it was stopped. The reaction was cooled to room temperature, the reaction solution was layered, the organic phase was concentrated and methanol was added and stirred for 1 hour, suction filtered to obtain P322 as a light yellow powder.

[0273] M/Z theoretical value: 721; ZAB-HS Model Mass Spectrometer (Manufactured by Micromass, British) M/Z found: 722.

Synthesis Example 14: Synthesis of Compound P323

[0274] ##STR00476##

[0275] Into a 1000 mL single-necked bottle, 16.5 g (50 mmol) of M7, 16.5 g (50 mmol) of 3-bromo-9,9-dimethyl-6,7-benzofluorene, 0.9 g (1 mmol) of tris(dibenzylideneacetone)dipalladium (i.e. Pd.sub.2(dba).sub.3), 0.5 g of IPr.Math.HCl, 500 mL of toluene, and 14.4 g (150 mmol) of sodium tert-butoxide(NaOBu-t) were added, vacuumized and replaced with nitrogen for three times, and the reaction was heated up to 90° C. for reacting 5 hours. After the reaction was completed, it was stopped. The reaction was cooled to room temperature, the reaction solution was layered, the organic phase was concentrated and methanol was added and stirred for 1 hour, suction filtered to obtain M7-2 as a light yellow powder.

[0276] Into a 1000 mL single-necked bottle, 29 g (50 mmol) of M7-2, 12.7 g (50 mmol) of 1-(4-bromophenyl)-1,1,1-triethylmethane, 0.9 g (1 mmol) of tris(dibenzylideneacetone)dipalladium (i.e. Pd.sub.2(dba).sub.3), 0.5 mL of Tri-tert-butylphosphine((t-Bu).sub.3P), 500 mL of toluene, and 14.4 g (150 mmol) of sodium tert-butoxide(NaOBu-t) were added, vacuumized and replaced with nitrogen for three times, and the reaction was heated up to 110° C. for reacting 5 hours. After the reaction was completed, it was stopped. The reaction was cooled to room temperature, the reaction solution was layered, the organic phase was concentrated and methanol was added and stirred for 1 hour, suction filtered to obtain P323 as a light yellow powder.

[0277] M/Z theoretical value: 751; ZAB-HS Model Mass Spectrometer (Manufactured by Micromass, British) M/Z found: 752.

Synthesis Example 15: Synthesis of Compound P20

[0278] ##STR00477##

[0279] Into a 1000 mL single-necked bottle, 25.5 g (50 mmol) of M1-3, 16 g (50 mmol) of 3-bromo-6-tert-butyldibenzothiophene, 0.9 g (1 mmol) of tris(dibenzylideneacetone)dipalladium (i.e. Pd.sub.2(dba).sub.3), 0.5 mL of Tri-tert-butylphosphine((t-Bu).sub.3P), 500 mL of toluene, and 14.4 g (150 mmol) of sodium tert-butoxide(NaOBu-t) were added, vacuumized and replaced with nitrogen for three times, and the reaction was heated up to 110° C. for reacting 5 hours. After the reaction was completed, it was stopped. The reaction was cooled to room temperature, the reaction solution was layered, the organic phase was concentrated and methanol was added and stirred for 1 hour, suction filtered to obtain P20 as a light yellow powder.

[0280] M/Z theoretical value: 749; ZAB-HS Model Mass Spectrometer (Manufactured by Micromass, British) M/Z found: 750.

Synthesis Example 16: Synthesis of Compound P628

[0281] ##STR00478##

[0282] Into a 1000 mL single-necked bottle, 13.5 g (50 mmol) of M1, 16.5 g (50 mmol) of 3-bromo-9,9-dimethyl-5,6-benzofluorene, 0.9 g (1 mmol) of tris(dibenzylideneacetone)dipalladium (i.e. Pd.sub.2(dba).sub.3), 0.5 g of IPr.Math.HCl, 500 mL of toluene, and 14.4 g (150 mmol) of sodium tert-butoxide(NaOBu-t) were added, vacuumized and replaced with nitrogen for three times, and the reaction was heated up to 90° C. for reacting 5 hours. After the reaction was completed, it was stopped. The reaction was cooled to room temperature, the reaction solution was layered, the organic phase was concentrated and methanol was added and stirred for 1 hour, suction filtered to obtain M1-4 as a light yellow powder.

[0283] Into a 1000 mL single-necked bottle, 25.5 g (50 mmol) of M1-4, 14.5 g (50 mmol) of 2-bromo-5-tert-butylbiphenyl, 0.9 g (1 mmol) of tris(dibenzylideneacetone)dipalladium (i.e. Pd.sub.2(dba).sub.3), 0.5 mL of Tri-tert-butylphosphine((t-Bu).sub.3P), 500 mL of toluene, 14.4 g (150 mmol) of sodium tert-butoxide(NaOBu-t) were added, vacuumized and replaced with nitrogen for three times, and the reaction was heated up to 110° C. for reacting 5 hours. After the reaction was completed, it was stopped. The reaction was cooled to room temperature, the reaction solution was layered, the organic phase was concentrated and methanol was added and stirred for 1 hour, suction filtered to obtain P628 as a light yellow powder.

[0284] M/Z theoretical value: 719; ZAB-HS Model Mass Spectrometer (Manufactured by Micromass, British) M/Z found: 720.

Synthesis Example 17: Synthesis of Compound P613

[0285] ##STR00479##

[0286] Into a 1000 mL single-necked bottle, 13.5 g (50 mmol) of M1, 12.3 g (50 mmol) of 3-bromo-dibenzofuran, 0.9 g (1 mmol) of tris(dibenzylideneacetone)dipalladium (i.e. Pd.sub.2(dba).sub.3), 0.5 g of IPr.Math.HCl, 500 mL of toluene, and 14.4 g (150 mmol) of sodium tert-butoxide(NaOBu-t) were added, vacuumized and replaced with nitrogen for three times, and the reaction was heated up to 90° C. for reacting 5 hours. After the reaction was completed, it was stopped. The reaction was cooled to room temperature, the reaction solution was layered, the organic phase was concentrated and methanol was added and stirred for 1 hour, suction filtered to obtain M1-5 as a light yellow powder.

[0287] Into a 1000 mL single-necked bottle, 22 g (50 mmol) of M1-5, 11 g (50 mmol) of 4-bromo-4′-tert-butylbiphenyl, 0.9 g (1 mmol) of tris(dibenzylideneacetone)dipalladium (i.e. Pd.sub.2(dba).sub.3), 0.5 mL of Tri-tert-butylphosphine ((t-Bu).sub.3P), 500 mL of toluene, and 14.4 g (150 mmol) of sodium tert-butoxide (NaOBu-t) were added, vacuumized and replaced with nitrogen for three times, and the reaction was heated up to 110° C. for reacting 5 hours. After the reaction was completed, it was stopped. The reaction was cooled to room temperature, the reaction solution was layered, the organic phase was concentrated and methanol was added and stirred for 1 hour, suction filtered to obtain P613 as a light yellow powder.

[0288] M/Z theoretical value: 567; ZAB-HS Model Mass Spectrometer (Manufactured by Micromass, British) M/Z found: 568.

Synthesis Example 18: Synthesis of Compound P602

[0289] ##STR00480##

[0290] Into a 1000 mL single-necked bottle, 21 g (50 mmol) of M1-5, 14.5 g (50 mmol) of 4-bromo-4′-tert-butylbiphenyl, 0.9 g (1 mmol) of tris(dibenzylideneacetone)dipalladium (i.e. Pd.sub.2(dba).sub.3), 0.5 mL of Tri-tert-butylphosphine((t-Bu).sub.3P), 500 mL of toluene, and 14.4 g (150 mmol) of sodium tert-butoxide(NaOBu-t) were added, vacuumized and replaced with nitrogen for three times, and the reaction was heated up to 110° C. for reacting 5 hours. After the reaction was completed, it was stopped. The reaction was cooled to room temperature, the reaction solution was layered, the organic phase was concentrated and methanol was added and stirred for 1 hour, suction filtered to obtain P602 as a light yellow powder.

[0291] M/Z theoretical value: 629; ZAB-HS Model Mass Spectrometer (Manufactured by Micromass, British) M/Z found: 630.

Example 1

[0292] This example provides an organic electroluminescent device. The specific preparation process is as follows:

[0293] After ultrasonic treatment of the glass plate coated with ITO transparent conductive layer (as anode) in a commercial cleaning agent, it was rinsed in deionized water, the oil was removed by ultrasonic in a mixed solvent of acetone and ethanol, baked in a clean environment until the water was completely removed, cleaned with ultraviolet light and ozone, and the surface was bombarded with a low-energy cation beam;

[0294] the above glass substrate with anode was placed in the vacuum chamber and vacuumized to less than 1×10.sup.−5 Pa, HI-3 was vacuum evaporated on the aforementioned anode layer film as a hole injection layer, the evaporation rate was 0.1 nm/s, and the evaporation film thickness was 10 nm;

[0295] HT-4 was vacuum evaporated on the hole injection layer as the hole transporting layer of the device, the evaporation rate was 0.1 nm/s, and the total evaporation film thickness was 80 nm;

[0296] Compound P1 was vacuum evaporated on the hole transporting layer as the electron blocking layer material of the device, the evaporation rate was 0.1 nm/s, and the total evaporation film thickness was 80 nm.

[0297] A light-emitting layer of the device was vacuum evaporated on the top of the electron blocking layer, the light emitting layer included a host material and a dye material. Using the method of mufti-source co-evaporation, the evaporation rate of the host material GPH-59 was adjusted to 0.1 nm/s, and the evaporation rate of the dye RPD-8 of 3% of the host material was proportionally set, and the total evaporation film thickness was 30 nm;

[0298] the electron transporting layer material ET-46 of the device was vacuum evaporated on the light emitting layer, the evaporation rate thereof was 0.1 nm/s, and the total evaporation film thickness was 30 nm;

[0299] LiF with a thickness of 0.5 nm was vacuum evaporated on the electron transporting layer (ETL) as the electron injection layer, and Al layer with a thickness of 150 nm was used as the cathode of the device.

[0300] In examples 2 to 18, the manufacturing process of the organic electroluminescent devices provided in the comparative examples 1 to 6 is the same as that in example 1, with the difference lying in that the compound P1 of the electron blocking layer material is replaced with the compound as shown in Table 1, respectively.

[0301] The structure of the electron blocking layer material in comparative examples 1 to 6 is as follows:

##STR00481## ##STR00482##

[0302] wherein, see compound 39 and compound 94 in patent application CN109749735A for R-1 and R-2, and see compound P405, P389, P406 and compound P418 in patent application CN110511151A for R-3 to R-6.

[0303] The performance of the organic electroluminescent device prepared by the above mentioned process is measured as follows:

[0304] Under the same brightness, the driving voltage and current efficiency of the organic electroluminescent devices prepared in examples 1 to 18 and comparative examples 1 to 6 were measured with a digital source meter (Keithley 2400), a luminance meter (ST-86LA type luminance meter, Optoelectronic Instrument Factory of Beijing Normal University) and a luminance meter. Specifically, the voltage was increased at a rate of 0.1V per second, the voltage when the brightness of the organic electroluminescent device reached 3000 cd/m.sup.2 was measured, that is, the driving voltage, at which time the current density was measured; and the ratio of brightness to current density was the current efficiency. See Table 1 for the test results.

TABLE-US-00001 TABLE 1 electron blocking current layer material voltage/V efficiency/cd/A Comparative example 1 R-1 5.3 11 Comparative example 2 R-2 5.8 10.1 Comparative example 3 R-3 3.3 19.0 Comparative example 4 R-4 3.1 19.3 Comparative example 5 R-5 3.4 18.5 Comparative example 6 R-6 3.5 17.8 Example 1 P1 3.3 19.5 Example 2 P2 3.2 20.1 Example 3 P5 3.4 19.0 Example 4 P6 3.5 18.2 Example 5 P7 3.4 19.3 Example 6 P15 3.3 19.4 Example 7 P20 3.4 18.7 Example 8 P37 3.2 19.8 Example 9 P38 3.1 20.3 Example 10 P74 3.3 19.6 Example 11 P253 3.2 19.7 Example 12 P284 3.5 19.5 Example 13 P322 3.6 19.4 Example 14 P323 3.6 19.5 Example 15 P375 3.5 20.0 Example 16 P613 3.4 19.9 Example 17 P628 3.3 18.9 Example 18 P602 3.5 18.4

[0305] It can be seen from the data in Table 1 that when the compound of the disclosure is used for the electron blocking layer material of the organic electro luminescent device, when the device brightness reaches 3000 cd/m.sup.2, the driving voltage is as low as 3.8 V or less, and the current efficiency is as high as 18.2 cd/A or more, which can effectively improve the driving voltage and current efficiency, and is an electron blocking layer material with good performance.

[0306] Compared the compound R-1 of comparative example 1 with the compound P602 of example 18, the difference lies in that in the structure of compound R-1, there is no substitution at 1-position of naphthalene and there is a benzene ring substitution at 4-position. When the compound is used as the electron blocking layer material of the organic electroluminescent device, the driving voltage of the devices is 5.3 V and the current efficiency is 11 cd/A. The starting voltage and current efficiency of the compound are lower than those of P602, which may be attributed to the better space packing of compound P602, which improves the hole transporting properties.

[0307] The arylamino group of compound R-2 in comparative example 2 is substituted on the 1-position of the naphthalene ring, and the benzone ring is substituted on the 2-position and the 3-position, without containing the substituents of the tert-butyl structure. When the compound is used as the electron blocking layer material of the organic electroluminescent device, the driving voltage of the device is 5.8V, the current efficiency is 10.1 cd/A, and the effect is significantly worse than that of examples 1 to 18.

[0308] Compared the compound R-3 of comparative example 3 with the compound P1 of example 1, the difference lies in that there is no tert-butyl substitution at the 4-position of the phenyl group connected with N. When the compound is used as the electron blocking layer material of the organic electroluminescent device, the driving voltage of the device is 3.3 V, and the current efficiency is 19 cd/A. The current efficiency of the compound is lower than that of P1, which may be attributed to the fact that the tert-butyl at the 4-position in compound P1 can not only provide strong electron donating ability, but also improve the molecular space packing structure, thus effectively improving the hole transporting performance of the material.

[0309] Compared the compound R-4 of comparative example 4 with the compound P2 of example 2, the difference lies in that there is no tert-butyl substitution at the biphenyl end connected with N in the molecule. When the compound is used as the electron blocking layer material of the organic electroluminescent device, the driving voltage of the device is 3.1V, and the current efficiency is 19.3 cd/A. The current efficiency of the compound is lower than that of P2, which may be attributed to the fact that the tert-butyl at the 4-position in compound P2 can not only provide electron donating ability, but also improve the molecular space packing structure, thus effectively improving the hole transporting performance of the material.

[0310] Compared the compound R-5 of comparative example 5 with the compound P5 of example 3, the difference lies in that there is no tert-butyl substitution at the 4-position of the biphenyl group connected with N. When the compound is used as the electron blocking layer material of the organic electroluminescent device, the driving voltage of the device is 3.4V, and the current efficiency is 18.5 cd/A. The current efficiency of the compound is lower than that of P5, which may be attributed to the fact that the tert-butyl at the 4-position in compound P5 can not only provide strong electron donating ability, but also improve the molecular space packing structure, thus effectively improving the hole transporting performance of the material.

[0311] Compared the compound R-6 of comparative example 6 with the compound P6 of example 4, the difference lies in that there is no tert-butyl substitution at the 2-phenylbiphenyl end connected with N in the molecule. When the compound is used as the electron blocking layer material of the organic electroluminescent device, the driving voltage of the device is 3.5V, and the current efficiency is 17.8 cd/A. The current efficiency of the compound is lower than that of P6, which may be attributed to the fact that the tert-butyl in compound P6 compound can not only provide electron donating ability, but also improve the molecular space packing structure, thus effectively improving the hole transporting performance of the material.

[0312] It can be seen that in the compounds provided by the disclosure, the substituent Ar.sup.2 at 1-position of the naphthalene ring, the substituent arylamino group at 2-position as well as the tert-butyl structure substituent are important factors that enable the compounds to bring excellent performances when applied to the organic electroluminescent devices.

Example 19

[0313] This example provides an organic electroluminescent device, whose structure is as shown in FIG. 1, including a glass substrate 1 with an anode, a hole injection layer 2, a hole transporting layer 3, an electron blocking layer 4, a light emitting layer 5, an electron transporting layer 6, an electron injection layer 7, a cathode layer 8 and an external power supply 9.

[0314] The preparation method of the organic electroluminescent devices is as follows:

[0315] After ultrasonic treatment of the glass plate coated with ITO transparent conductive layer in a commercial cleaning agent, it was rinsed in deionized water, the oil was removed by ultrasonic in a mixed solvent of acetone and ethanol, baked in a clean environment until the water was completely removed, cleaned with ultraviolet light and ozone, and the surface was bombarded with a low-energy cation beam;

[0316] the glass substrate with an anode was placed in the vacuum chamber and vacuumized to less than 1×10.sup.−5 Pa, the HT-4:HI-3 (97/3, w/w) mixture of 10 nm was vacuum hot evaporated on the aforementioned anode layer film as the hole injection layer: 60 nm of compound HT-4 as the hole transporting layer; 5 nm of compound HT-48 as the electron blocking layer; 40 nm of PH-34:P1:RPD-10 (100:30:3, w/w/w) ternary mixture as the light emitting layer; 5 nm of ET-23 as the hole blocking layer, 25 nm of compound ET-69: ET-57 (50/50, w/w) mixture as the electron transporting layer, 1 nm of LiF as the electron injection layer, and 150 nm of the metal aluminum as the cathode in sequence. The total evaporation rate of all organic layers and LiF is controlled at 0.1 nm/s, and the evaporation rate of metal electrode is controlled at 1 nm/s. wherein, “97/3, w/W” represents the mass ratio of 97:3.

[0317] The differences among examples 19-42, comparative examples 7-8 and example 19 are listed in Table 3, respectively, and the parts not mentioned in Table 3 are the same as those in example 19.

[0318] Performance Testing

[0319] (1) The HOMO energy level and LUMO energy level of the second host material used in the previous examples and comparative examples are shown in Table 2 in details.

TABLE-US-00002 TABLE 2 HOMO energy level (eV) LUMO energy level (eV) PH-34 −5.4 eV −2.4 eV PH-27 −5.2 eV −2.2 eV

[0320] (2) Under the same brightness, the current efficiencies of the organic electroluminescent devices prepared in the examples and the comparative examples were measured. Specifically, the voltage was increased at a rate of 0.1 V per second, the current density when the brightness of the organic electroluminescent device reached 3000 cd/m.sup.2 was measured; and the ratio of brightness to current density was the current efficiency. The test results are shown in Table 3.

TABLE-US-00003 TABLE 3 Host materials of the Thickness of light emitting layer the light Required Current and proportions emitting layer brightness efficiency Compound No. (w/w) nm cd/m.sup.2 cd/A Comparative PH-34 40 3000 10.36 example 7 Comparative P1 40 10.11 example 8 Example 19 P1:PH-34 = 30:100 40 17.68 Example 20 P1:PH-34 = 80:100 40 15.73 Example 21 P1:PH-34 = 30:100 50 15.21 Example 22 P1:PH-34 = 1:100 40 15.47 Example 23 P1:PH-34 = 150:100 40 15.08 Example 24 P1:PH-34 = 10:100 40 17.29 Example 25 P1:PH-34 = 100:100 40 17.81 Example 26 P1:PH-34 = 0.9:100 40 11.7 Example 27 P1:PH-34 = 160:100 40 13 Example 28 P1:PH-34 = 30:100 10 15.86 Example 29 P1:PH-34 = 30:100 65 15.47 Example 30 P1:PH-34 = 30:100 15 16.9 Example 31 P1:PH-34 = 30:100 55 17.03 Example 32 P1:PH-34 = 30:100 9 12.74 Example 33 P1:PH-34 = 30:100 66 12.87 Example 34 P1:PH-27 = 30:100 40 14.56 Example 35 P12:PH-34 = 30:100 40 16.38 Example 36 P23:PH-34 = 30:100 40 16.9 Example 37 P25:PH-34 = 30:100 40 15.34 Example 38 P56:PH-34 = 30:100 40 16.64 Example 39 P68:PH-34 = 30:100 40 16.25 Example 40 P107:PH-34 = 30:100 40 15.86 Example 41 P142:PH-34 = 30:100 40 17.03 Example 42 P509:PH-34 = 30:100 40 15.6

[0321] The comparative example 7 is a single host device, where the mass ratio of PH-34 to RPD-10 is 130:3; the comparative example 8 is also a single host device, where the mass ratio of P1 to RPD-10 is 130:3.

[0322] It can be seen from Table 3 that the organic electroluminescent device containing the dual host light emitting layer provided by the disclosure has excellent photoelectric performance, and its current efficiency is 11.7 cd/A or more, most of which can reach 15 cd/A or more, and the maximum can reach 17 cd/A or more. The single host device is adopted for the comparative examples 7 and 8, and the effect is obviously inferior to that of the disclosure.

[0323] By comparing examples 19 and 22-27, it can be seen that when the mass ratio of the first host material to the second host material is 0.01:1-1.5:1 (examples 19, 22-27), the device efficiency can be further improved, where the effect is the best at 0.1:1-1:1 (examples 19, 24 and 25).

[0324] By comparing examples 19 and 28-33, it can be seen that when the thickness of the dual host light emitting layer is 10-65 nm (examples 19, 28-31), the device efficiency can be further improved, where the effect is the best when the thickness is within the range of 15-55 nm (examples 19, 30 and 31).

[0325] It can be seen from the comparison between example 19 and example 34 that when the second host material meets the specific LUMO energy level and HOMO energy level (example 19), it is beneficial to further improve the device efficiency.

[0326] In the following examples, the synthesis method of compound I is as described above. For the synthesis method of compound II, reference can be made to the Chinese patent application with the publication number CN110950762A (application number 201910857132.9).

Example 43

[0327] This example provides an organic electroluminescent device, whose structure is as shown in FIG. 1, including a glass substrate 1 with an anode, a hole injection layer 2, a hole transporting layer 3, an electron blocking layer 4, a light emitting layer 5, an electron transporting layer 6, an electron injection layer 7, a cathode layer 8 and an external power supply 9.

[0328] The preparation method of the organic electroluminescent devices is as follows:

[0329] After ultrasonic treatment of the glass plate coated with ITO transparent conductive laver in a commercial cleaning agent, it was rinsed in deionized water, the oil was removed by ultrasonic in a mixed solvent of acetone and ethanol, baked in a clean environment until the water was completely removed, cleaned with ultraviolet light and ozone, and the surface was bombarded with a low-energy cation beam;

[0330] the glass substrate with an anode was placed in the vacuum chamber and vacuumized to less than 1×10.sup.−5 Pa, the HT-4:HI-3 (97/3, w/w) mixture of 10 nm was vacuum hot evaporated on the aforementioned anode layer film as the hole injection layer; 60 nm of compound HT-4 as the hole transporting layer; 60 nm of compound A1 as the electron blocking layer; 30 nm of compound PH86:P1:RPD-10 (1:0.01:0.05, w/w/w) ternary mixture as the light emitting layer (wherein, PH86 and P1 were the host materials): 25 nm of compound ET-61:ET-57(50/50, w/w) mixture as the electron transporting layer, 1 nm of LiF as the electron injection layer, and 150 nm of the metal aluminum as the cathode in sequence. The total evaporation rate of all organic layers and LiF is controlled at 0.1 nm/s, and the evaporation rate of metal electrode is controlled at 1 nm/s.

[0331] The differences among examples 44-68, comparative examples 9-12 and example 43 are all listed in Table 4, and the parts not mentioned in Table 4 are the same as those in example 43.

[0332] Performance Testing

[0333] Under the same brightness, the external quantum efficiency (EQE, %) of the organic electroluminescent devices prepared in the examples and the comparative examples were measured, the required brightness is 3000 cd/m.sup.2.

TABLE-US-00004 TABLE 4 Thickness of Thickness Light emitting light emitting of electron layer material electron blocking layer blocking layer and proportions layer material (nm) (nm) EQE % Comparative PH86 HT5 30 60 12.76 example 9 Comparative PH86:A1 = 1:0.3 HT5 30 60 11.98 example 10 Comparative PH86:P1 = 1:0.3 HT5 30 60 12.66 example 11 Comparative PH86:HT-10 = 1:0.3 A1 30 60 11.87 example 12 Example 43 PH86:P1 = 1:0.01 A1 30 60 15.33 Example 44 PH86:P1 = 1:0.1 A1 30 60 16.67 Example 45 PH86:P1 = 1:0.3 A1 30 60 19.63 Example 46 PH86:P1 = 1:1 A1 30 60 19.22 Example 47 PH86:P1 = 1:1.5 A1 30 60 18.58 Example 48 PH86:P1 = 1:0.3 A1 10 60 18.96 Example 49 PH86:P1 = 1:0.3 A1 20 60 19.10 Example 50 PH86:P1 = 1:0.3 A1 50 60 18.92 Example 51 PH86:P1 = 1:0.3 A1 60 60 18.23 Example 52 PH86:P1 = 1:0.3 A1 30 2 15.49 Example 53 PH86:P1 = 1:0.3 A1 30 3 16.03 Example 54 PH86:P1 = 1:0.3 A1 30 90 18.85 Example 55 PH86:P1 = 1:0.3 A1 30 100 17.98 Example 56 PH86:A1 = 1:0.3 P1 30 60 18.18 Example 57 P1:RPD-10 = 1:5 A1 30 60 14.42 Example 58 A1:RPD-10 = 0.3:0.05 P1 30 60 14.64 Example 59 PH86:P1 = 1:0.005 A1 30 60 13.28 Example 60 PH86:P1 = 1:1.51 A1 30 60 13.87 Example 61 PH86:P1 = 1:0.3 A1 9 60 14.10 Example 62 PH86:P1 = 1:0.3 A1 61 60 14.55 Example 63 PH86:P1 = 1:0.3 A1 9 1 13.98 Example 64 PH86:P1 = 1:0.3 A1 30 101 13.87 Example 65 PH86:P2 = 1:0.3 A3 30 60 16.28 Example 66 PH86:P5 = 1:0.3 A8 30 60 15.46 Example 67 PH86:P6 = 1:0.3 A35 30 60 15.89 Example 68 PH86:P32 = 1:0.3 A56 30 60 16.00

[0334] It can be seen from Table 4 that compound I and compound II are used in organic electroluminescent devices in the disclosure, which can effectively improve the external quantum efficiency, thereby improving the device performance, and ultimately exhibiting excellent characteristics such as reduced device energy consumption, and improved brightness, etc., they are electron blocking layer and light emitting layer materials with good performances, and the external quantum efficiency of the device can reach 19%.

[0335] The difference between comparative example 10 and example 56 only lies in that the electron blocking layer material is HT5, and its external quantum efficiency is significantly lower than that of example 14; The difference between comparative example 11 and example 45 only lies in that the electron blocking layer material is HT5, and its external quantum efficiency is significantly lower than that of example 45; The difference between comparative example 4 and example 45 only lies in that the host material is PH86 and HT-10, and its external quantum efficiency is significantly reduced relative to example 45; The above results prove that the combination of compound I and compound II in the disclosure can effectively improve the device efficiency, and replacing any one of them will reduce the efficiency.

[0336] By comparing example 45 with example 57, example 56 and example 58, it can be seen that when compound I or compound II is applied to the dual host light emitting layer, the device efficiency can be further improved (example 45, and example 56), and the effect becomes worse when used alone (example 57, and example 58).

[0337] By comparing examples 43-47, 59 and 60, it can be seen that when the mass ratio of the first host material to the second host material is 0.01:1-1.5:1 (examples 43-47), the external quantum efficiency can be further improved. Too low (example 59) or too high (example 60) of the addition amount will reduce the efficiency.

[0338] By comparing examples 45, 48-51, 61, and 62, it can be seen that controlling the thickness of the light emitting layer at 10-60 nm (examples 45, 48-51) can further improve the external quantum efficiency of the device. If the thickness is too small (example 61) or too large (examples 62), the efficiency will be reduced.

[0339] By comparing examples 45, 52-55 and 63, 64, it can be seen that controlling the thickness of the electron blocking layer at 2-100 nm (examples 45, 52-55) can further improve the external quantum efficiency of the device. If the thickness is too small (example 63) or too large (examples 64), the efficiency will be reduced.

[0340] The above descriptions are only the preferred examples of the present invention, and is not intended to limit thereto. For those skilled in the art, various modifications and changes can be made to the present invention. Any modifications, equivalent substitutions, improvements, and the like made within the spirit and principle of the present invention shall be included into the protection scope of the present invention.