A spiro fluorene heteroanthracene compound and application thereof in a light-emitting layer doping material

Abstract

The application provides a spiro fluorene heteroanthracene compound and application thereof in a light-emitting layer doping material. The compound shown in formula I provided by the application takes the groups shown in (I-1) to (I-6) as a basic mother nucleus structure, and is connected with spiro fluorene oxygen heteroanthracene or spiro fluorene sulfur heteroanthracene through N, so as to improve the material performance, so that the organic electroluminescent device prepared by using the compound has higher light-emitting efficiency, lower driving voltage and longer service life. Meanwhile, part of the structure can be used for green light doping material, and the performance is relatively excellent.

Description

TECHNICAL FIELD

[0001] The present application belongs to the field of electroluminescence, and particularly relates to a spirofluorene heteroanthracene compound and application thereof, in particular to a spirofluorene oxygen heteroanthracene compound, a preparation method, an intermediate and an organic electroluminescent device. BACKGROUND

[0002] At present, organic electroluminescence (OLED) display technology has been applied in the field of smart phones, tablet computers and the like, and will further be extended to large-size application fields such as televisions. In the development process in the past 30 years, people have developed various OLED materials with excellent performance, and through different designs of device structures and optimization of device performance such as lifetime and efficiency, the commercialization process of OLEDs has been accelerated, and OLEDs have been widely used in the fields of display and lighting.

[0003] The selection of the hole layer, the light-emitting layer and other organic functional layer materials also has a great influence on the current efficiency, driving voltage and lifetime of the device, and functional layer materials with higher performance are still being explored.

[0004] CN109956961A discloses a nitrogen-containing organic compound and application thereof in an organic electroluminescent device. The compound takes azaspirofluorene as a mother nucleus. The compound has the characteristics of not being easy to crystallize and aggregate between molecules, and good film-forming property due to the strong rigidity of the azaspirofluorene mother nucleus. The azaspirofluorene mother nucleus has strong electron-withdrawing ability, and the branched chain has electron-donating ability. Therefore, the efficiency and lifetime of the OLED device as a doping material are improved.

[0005] CN106008537A discloses a bipolar host organic electroluminescent material containing a 4,5-diazaspirofluorene structure of carbazole and oxygen / sulfur / 9,9-dimethyl heteroanthracene. The organic electroluminescent material has good thermodynamic stability, good film-forming property, suitable triplet energy level and the like, and can be used as a blue / green host material.

[0006] Therefore, in order to meet the higher requirements of people for OLED devices, more kinds and higher performance of OLED materials need to be developed in the field. SUMMARY

[0007] In view of the deficiencies of the prior art, the present application aims to provide a spirofluorene heteroanthracene compound and its application. In particular, a spirofluorene oxygen heteroanthracene compound, a preparation method thereof, an intermediate, and an organic electroluminescent device are provided. The compound of the present application can be used as a light-emitting layer dopant material for an OLED light-emitting device. The obtained organic electroluminescent device has a lower driving voltage and a higher current efficiency. In particular, it can be applied to blue and green light-emitting devices to reduce the driving voltage of the blue and green light-emitting devices and improve the light-emitting efficiency of the light-emitting device.

[0008] To achieve the object of the present application, the following technical solutions are adopted in the present application.

[0009] In a first aspect, the present application provides a spirofluorene heteroanthracene compound, which has the structure shown in the following formula I:

[0010]

[0011] wherein Ar is selected from any one of the following substituted or unsubstituted groups I-1 to I-6, and the groups I-1 to I-6 are connected to the N atom in the compound of formula I through a SP2 hybridized carbon atom.

[0012]

[0013] R 11 , R 12 , R 21 , R 22 are each independently selected from substituted or unsubstituted C1-C20 (e.g., C1, C2, C3, C4, C5, C7, C8, C9, C10, C13, C15, C18, C20, etc.) alkyl, substituted or unsubstituted C6-C40 (e.g., C6, C7, C8, C9, C10, C13, C15, C18, C20, C23, C25, C27, C30, C32, C35, C37, C39, C40, etc.) aryl.

[0014] n is selected from 0 or 1.

[0015] Ar1-Ar4 are each independently selected from substituted or unsubstituted C6-C40 (e.g., C6, C7, C8, C9, C10, C13, C15, C18, C20, C23, C25, C27, C30, C32, C35, C37, C39, C40, etc.) aryl, substituted or unsubstituted X is selected from O or S; and the group II-1 is connected to the N atom in the compound of formula I through a SP2 hybridized carbon atom.

[0016] and at least one of Ar1 to Ar4 is selected from the group consisting of Formula II-1 when n = 1; and at least one of Ar3 or Ar4 is selected from the group consisting of Formula II-1 when n = 0.

[0017] Preferably, the groups shown in I-1 to I-6 can be substituted with at least one R; wherein R is selected from the group consisting of deuterium, F, CN, C1-C20 (e.g., C1, C2, C3, C4, C5, C7, C8, C9, C10, C13, C15, C18, C20, etc.) alkyl, C1-C20 (e.g., C1, C2, C3, C4, C5, C7, C8, C9, C10, C13, C15, C18, C20, etc.) alkoxy, C6-C40 (e.g., C6, C7, C8, C9, C10, C13, C15, C18, C20, C23, C25, C27, C30, C32, C35, C37, C39, C40, etc.) aryl; and R is selected from C6-C40 aryl, which can be substituted with at least one C1-C20 alkyl or at least one C1-C20 alkoxy.

[0018] Preferably, the groups shown in I-1 to I-6 can be substituted with at least one R; wherein R is selected from the group consisting of deuterium, F, CN, C1-C20 (e.g., C1, C2, C3, C4, C5, C7, C8, C9, C10, C13, C15, C18, C20, etc.) alkyl, C1-C20 (e.g., C1, C2, C3, C4, C5, C7, C8, C9, C10, C13, C15, C18, C20, etc.) alkoxy, C6-C40 (e.g., C6, C7, C8, C9, C10, C13, C15, C18, C20, C23, C25, C27, C30, C32, C35, C37, C39, C40, etc.) aryl; and R is selected from C6-C40 aryl, which can be substituted with at least one C1-C20 alkyl or at least one C1-C20 alkoxy.

[0019] Preferably, the groups shown in I-1 to I-6 can be substituted with at least one R; wherein R is selected from the group consisting of deuterium, F, CN, C1-C20 (e.g., C1, C2, C3, C4, C5, C7, C8, C9, C10, C13, C15, C18, C20, etc.) alkyl, C1-C20 (e.g., C1, C2, C3, C4, C5, C7, C8, C9, C10, C13, C15, C18, C20, etc.) alkoxy, C6-C40 (e.g., C6, C7, C8, C9, C10, C13, C15, C18, C20, C23, C25, C27, C30, C32, C35, C37, C39, C40, etc.) aryl; and R is selected from C6-C40 aryl, which can be substituted with at least one C1-C20 alkyl or at least one C1-C20 alkoxy.

[0020] Preferably, the groups shown in I-1 to I-6 can be substituted with at least one R; wherein R is selected from the group consisting of deuterium, F, CN, C1-C20 (e.g., C1, C2, C3, C4, C5, C7, C8, C9, C10, C13, C15, C18, C20, etc.) alkyl, C1-C20 (e.g., C1, C2, C3, C4, C5, C7, C8, C9, C10, C13, C15, C18, C20, etc.) alkoxy, C6-C40 (e.g., C6, C7, C8, C9, C10, C13, C15, C18, C20, C23, C25, C27, C30, C32, C35, C37, C39, C40, etc.) aryl; and R is selected from C6-C40 aryl, which can be substituted with at least one C1-C20 alkyl or at least one C1-C20 alkoxy. 11 and R 12 are connected by a single bond to form a ring, and / or R 21 and R 22 are connected by a single bond to form a ring.

[0021] In the present application, the substituents of the substituted groups represented by formulae I-1 to I-6, the substituted C1 to C20 alkyl group, the substituted C6 to C40 aryl group, and the substituted group represented by formula II-1 are each independently selected from any one of deuterium, fluorine, cyano, C1 to C20 (e.g., C1, C2, C3, C4, C5, C7, C8, C9, C10, C13, C15, C18, C20, etc.) alkyl group, C1 to C20 (e.g., C1, C2, C3, C4, C5, C7, C8, C9, C10, C13, C15, C18, C20, etc.) alkoxy group, or C6 to C40 (e.g., C6, C7, C8, C9, C10, C13, C15, C18, C20, C23, C25, C27, C30, C32, C35, C37, C39, C40, etc.) aryl group.

[0022] Preferably, the C1 to C20 alkyl group is a C1 to C20 straight chain alkyl group or a C1 to C20 branched chain alkyl group.

[0023] Preferably, the C1 to C20 alkyl group is selected from any one of a methyl group, an ethyl group, a n-propyl group, an i-propyl group, a n-butyl group, a t-butyl group, a s-butyl group, an i-butyl group, a n-pentyl group, or a n-hexyl group.

[0024] Preferably, the C1 to C20 alkoxy group is a C1 to C20 straight chain alkoxy group or a C1 to C20 branched chain alkoxy group.

[0025] Preferably, the C1 to C20 alkoxy group is selected from any one of a methoxy group, an ethoxy group, a n-propoxy group, an i-propoxy group, a n-butoxy group, a n-pentoxy group, or a n-hexyloxy group.

[0026] Preferably, the C6 to C40 aryl group is selected from any one of a phenyl group, a naphthyl group, a fluorenyl group, an anthryl group, a spirofluorene group, a phenanthryl group, a pyrenyl group, a perylenyl group, a naphthacene group, a triphenylene group, a fluoranthenyl group, a hydride benzanthracene group, an indenofluorene group, a benzindenofluorene group, a benzofluorene group, a naphthofluorene group, or Preferably, the C6 to C40 aryl group is selected from any one of a phenyl group, a naphthyl group, a fluorenyl group, an anthryl group, a spirofluorene group, a phenanthryl group, a pyrenyl group, a perylenyl group, a naphthacene group, a triphenylene group, a fluoranthenyl group, a hydride benzanthracene group, an indenofluorene group, a benzindenofluorene group, a benzofluorene group, a naphthofluorene group, or

[0027] Preferably, at least one of the Ar1 or Ar2 groups is selected from a phenyl group, at least one of the Ar3 or Ar4 groups is selected from a phenyl group; and the phenyl group can be substituted with at least one C1 to C20 alkyl group or at least one C1 to C20 alkoxy group.

[0028] Preferably, the group represented by formula II-1 is connected at and the N atom:

[0029] Preferably, the spirofluorene heteroanthracene compound is selected from any one of the compounds represented by formulae 1-168:

[0030] Preferably, the spirofluorene heteroanthracene compound is selected from any one of the compounds represented by formulae 1-168:

[0031]

[0032]

[0033]

[0034]

[0035]

[0036]

[0037]

[0038]

[0039]

[0040]

[0041]

[0042]

[0043] The spirofluorene heteroanthracene compound further includes a thio derivative of the spirofluorene oxygen heteroanthracene compound shown in the above formulae 1-168, which is a spirofluorene heteroanthracene compound obtained by replacing O in one or two benzooxygen heteroanthracene groups in the structure shown in formulae 1-168 with S.

[0044] That is, in addition to the structure shown in formulae 1-168, the compound of the present application can also be a compound formed by replacing O in the structure shown in formulae 1-168 with S. Among them, when replacing, O in one or two benzooxygen heteroanthracene groups in the structure shown in formulae 1-168 can be replaced with S, and such a compound is defined as a thio derivative.

[0045] Specifically, the following examples are given:

[0046] The structure of compound 1 is shown below:

[0047]

[0048] When O in one benzooxygen heteroanthracene group in compound 1 is replaced with S, a thio derivative is obtained:

[0049]

[0050] When O in two benzooxygen heteroanthracene groups in compound 1 is replaced with S, a thio derivative is obtained:

[0051]

[0052] In a second aspect, the present application provides a preparation method of the spirofluorene heteroanthracene compound as described in the first aspect, wherein n = 0, and the preparation method comprises the following steps:

[0053] reacting Ar-X and Ar3-NH-Ar4 to obtain the spirofluorene heteroanthracene compound shown in formula I. Wherein, X is selected from Cl, Br, I or OSO2CF3, and Ar, Ar3 and Ar4 each independently has the same range of limitations as described in the first aspect.

[0054] The reaction formula is shown as follows:

[0055]

[0056] In a third aspect, the present application provides an intermediate for preparing the spirofluorene heteroanthracene compound as described in the first aspect, and the intermediate has the structure shown in the following formula M:

[0057]

[0058] Wherein, Ar3 and Ar4 each independently has the same range of limitations as described in the first aspect.

[0059] Preferably, the intermediate shown in formula M is selected from any one of the following compounds:

[0060]

[0061] In a fourth aspect, the present application provides an application of the spirofluorene heteroanthracene compound as described in the first aspect in a light-emitting layer doping material.

[0062] In a fifth aspect, the present application provides an organic electroluminescent device comprising the spirofluorene heteroanthracene compound as described in the first aspect.

[0063] Preferably, the organic electroluminescent device is a blue light-emitting device and / or a green light-emitting device, preferably a blue light-emitting device.

[0064] In a sixth aspect, the present application provides a display device comprising the organic electroluminescent device as described in the fifth aspect.

[0065] Compared with the prior art, the present application has the following beneficial effects:

[0066] The present application provides a compound shown in formula I, which is a basic mother nucleus structure of (I-1)~(I-6) and is connected with spirofluorene oxanthrene or spirofluorene thioxanthrene through N, for improving material performance, so that the organic electroluminescent device prepared by using the compound has higher luminous efficiency, lower driving voltage and longer service life. Meanwhile, part of the structure can be used for green light doping material. BRIEF DESCRIPTION OF DRAWINGS

[0067] Figure 1 The present application provides a compound shown in formula I, which is a basic mother nucleus structure of (I-1)~(I-6) and is connected with spirofluorene oxanthrene or spirofluorene thioxanthrene through N, for improving material performance, so that the organic electroluminescent device prepared by using the compound has higher luminous efficiency, lower driving voltage and longer service life. Meanwhile, part of the structure can be used for green light doping material. DETAILED DESCRIPTION

[0068] The technical solutions of the present application will be further described by specific embodiments. Those skilled in the art should understand that the embodiments are only used to help understand the present application and should not be regarded as specific limitations of the present application.

[0069] Preparation Example 1

[0070] Synthesis of intermediate M-1

[0071]

[0072] A 250 mL three-necked flask was protected by nitrogen, 100 mL of dry toluene was added, 0.93 g (0.01 mol) of aniline, 4.11 g (0.01 mol) of 4'-bromospiro[fluorene-9,9'-oxanthrene], 0.0575 g (0.0001 mol) of Pd(dba)2(bis-benzylideneacetone palladium), 0.4 g (0.0002 mol) of toluene solution containing 10% tri-tert-butyl phosphine, 1.44 g (0.015 mol) of sodium tert-butoxide, heated to 60°C for 8h, cooled, water was added and separated, the organic layer was washed with water until neutral, dried with magnesium sulfate, filtered to remove magnesium sulfate, concentrated to dryness, recrystallized in a mixed solvent of ethanol and toluene, and 3.2 g of intermediate shown in formula M-1 was obtained.

[0073] Mass spectrometry was performed on the intermediate shown in formula M-1, and the molecular m / z was determined to be 423.16.

[0074] Nuclear magnetic resonance was performed on the intermediate shown in formula M-1, and the data analysis is as follows: 1 H-NMR (Switzerland Bruker Company, Avance Ⅱ 400MHz nuclear magnetic resonance spectrometer, CDCl3) δ 7.92 (m, 2H), δ 7.59 (m, 2H), δ 7.45-7.14 (m, 11H), δ 7.06-6.95 (m, 3H), δ 6.88 (m, 1H), δ 6.83 (m, 1H), δ 5.21 (s, 1H).

[0075] Preparation Example 2

[0076] Synthesis of intermediate M-2

[0077]

[0078] The synthesis method refers to the synthesis of M-1, except that the aniline therein is replaced by 3,4-dimethylaniline to obtain M-2.

[0079] The intermediate shown in formula M-2 was subjected to mass spectrometry to determine the molecular m / z as: 451.19.

[0080] Preparation Example 3

[0081] Synthesis of intermediate M-3

[0082]

[0083] The synthesis method refers to the synthesis of M-1, except that the aniline therein is replaced by 4-tert-butylaniline to obtain M-3.

[0084] The intermediate shown in formula M-3 was subjected to mass spectrometry to determine the molecular m / z as: 479.22.

[0085] Preparation Example 4

[0086] Synthesis of intermediate M-4

[0087]

[0088] The synthesis method refers to the synthesis of M-1, except that the aniline therein is replaced by 4-methoxyaniline to obtain M-4.

[0089] The intermediate shown in formula M-4 was subjected to mass spectrometry to determine the molecular m / z as: 453.17.

[0090] Example 1

[0091] Synthesis of compound 1

[0092]

[0093] 500 mL three-necked flask, nitrogen protection, 250 mL dry toluene, 3.36 g (0.01 mol) 9, 10-dibromoanthracene, 9.3 g (0.022 mol) intermediate compound shown in M-1, 0.0575 g (0.0001 mol) Pd (dba) 2 (bisbenzylideneacetone palladium), 0.4 g (0.0002 mol) 10% tri-tert-butyl phosphine in toluene, 2.88 g (0.03 mol) sodium tert-butoxide, heated to reflux for 24 h, cooled, filtered, the obtained solid was washed with water and ethanol to obtain the crude product, the crude product was dissolved by heating with toluene, decolorized by silica gel column, eluted with toluene, the eluent was concentrated to about 60 mL and then stopped, cooled, filtered, the obtained solid was washed with 80 mL acetone by refluxing for 3 h, cooled, filtered and dried to obtain yellow-green solid, compound 1, 7.8 g.

[0094] The compound shown in formula 1 was subjected to mass spectrometry detection, and the molecular m / z was determined to be: 1020.37.

[0095] The compound shown in formula 1 was subjected to nuclear magnetic detection, and the data analysis was as follows: 1 H-NMR (Switzerland Bruker Company, Avance II 400 MHz nuclear magnetic resonance spectrometer, CDCl3), δ 8.11 (m, 4H), δ 7.92 (m, 4H), δ 7.73 (m, 4H), δ 7.52 (m, 4H), δ 7.39-7.14 (m, 18H), δ 7.11-6.96 (m, 10H), δ 6.95-6.82 (m, 4H).

[0096] Example 2

[0097] Synthesis of compound 2

[0098]

[0099] The synthesis method refers to the synthesis of compound 1 in synthesis example 1, except that the compound shown in M-1 is replaced by the compound shown in M-2 to obtain compound 2.

[0100] The compound shown in formula 2 was subjected to mass spectrometry detection, and the molecular m / z was determined to be: 1076.43.

[0101] Example 3

[0102] Synthesis of compound 5

[0103]

[0104] The synthetic method refers to the synthesis of compound 1 in synthesis example 1, except that 9, 10-dibromoanthracene is replaced by 9-phenyl-10-bromoanthracene, the amount of substance of compound M-1 and the amount of substance of 9, 10-dibromoanthracene are the same, and the reaction time is changed to 12 h, to obtain compound 5.

[0105] The mass spectrometry of the compound shown in formula 5 is detected, and the molecular m / z is determined to be: 675.26.

[0106] The nuclear magnetic detection of the compound shown in formula 5 is analyzed as follows: 1H-NMR (Switzerland Bruker Company, Avance Ⅱ 400MHz nuclear magnetic resonance spectrometer, CDCl3), δ 8.24-8.12 (m, 4H), δ 7.91 (m, 2H), δ 7.72 (m, 2H), δ 7.63 (m, 2H), δ 7.53 (m, 2H), δ 7.50-7.13 (m, 14H), δ 7.11-6.96 (m, 5H), δ 6.95-6.83 (m, 2H).

[0107] Example 4

[0108] Synthesis of compound 11

[0109]

[0110] The synthetic method refers to the synthesis of compound 1 in synthesis example 1, except that the corresponding bromide and amine compound are used for reaction, to obtain compound 11.

[0111] The mass spectrometry of the compound shown in formula 11 is detected, and the molecular m / z is determined to be: 1100.43.

[0112] Elemental analysis is performed on compound 11, and the theoretical value is: C: 89.43%, H: 5.13%, N: 2.54%, O: 2.91%, and the measured value is C: 89.44%, H: 5.12%, N: 2.55%.

[0113] Example 5

[0114] Synthesis of compound 13

[0115]

[0116] The synthetic method refers to the synthesis of compound 5 in synthesis example 3, except that the corresponding bromide and amine compound are used for reaction, to obtain compound 13.

[0117] The mass spectrometry of the compound shown in formula 13 is detected, and the molecular m / z is determined to be: 623.22.

[0118] Example 6

[0119] Synthesis of compound 29

[0120]

[0121] The synthesis method refers to the synthesis of compound 1 in synthesis example 1, except that the corresponding bromide and amine compound are used for reaction to obtain compound 29.

[0122] The mass spectrum of the compound shown in formula 29 is detected, and the molecular m / z is determined to be: 1086.42.

[0123] The elemental analysis of the compound shown in formula 29 is carried out, and the theoretical value is C: 89.47%, H: 5.01%, N: 2.58%, O: 2.94%, and the measured value is C: 89.46%, H: 5.00%, N: 2.57%.

[0124] Example 7

[0125] Synthesis of compound 33

[0126]

[0127] The synthesis method refers to the synthesis of compound 5 in synthesis example 3, except that the corresponding bromide and amine compound are used for reaction to obtain compound 33.

[0128] The mass spectrum of the compound shown in formula 33 is detected, and the molecular m / z is determined to be: 665.27.

[0129] Example 8

[0130] Synthesis of compound 57

[0131]

[0132] The synthesis method refers to the synthesis of compound 1 in synthesis example 1, except that the corresponding bromide and amine compound are used for reaction to obtain compound 57.

[0133] The mass spectrum of the compound shown in formula 57 is detected, and the molecular m / z is determined to be: 1152.47.

[0134] Example 9

[0135] Synthesis of compound 81

[0136]

[0137] The synthesis method refers to the synthesis of compound 5 in synthesis example 3, except that the corresponding bromide and amine compound are used for reaction to obtain compound 81.

[0138] The mass spectrum of the compound shown in formula 81 is detected, and the molecular m / z is determined to be: 781.33.

[0139] Example 10

[0140] Synthesis of compound 101

[0141]

[0142] The synthesis method refers to the synthesis of compound 5 in synthesis example 3, except that the corresponding bromide and amine compound are used for reaction to obtain compound 101.

[0143] The compound shown in formula 101 is subjected to mass spectrometry to determine the molecular m / z as: 789.30.

[0144] Example 11

[0145] Synthesis of compound 102

[0146]

[0147] The synthesis method refers to the synthesis of compound 5 in synthesis example 3, except that the corresponding bromide and amine compound are used for reaction to obtain compound 102.

[0148] The compound shown in formula 102 is subjected to mass spectrometry to determine the molecular m / z as: 787.29.

[0149] Example 12

[0150] Synthesis of compound 113

[0151]

[0152] The synthesis method refers to the synthesis of compound 5 in synthesis example 3, except that the corresponding bromide and amine compound are used for reaction to obtain compound 113.

[0153] The compound shown in formula 113 is subjected to mass spectrometry to determine the molecular m / z as: 691.29.

[0154] Example 13

[0155] Synthesis of compound 145

[0156]

[0157] The synthesis method refers to the synthesis of compound 5 in synthesis example 3, except that the corresponding bromide and amine compound are used for reaction to obtain compound 145.

[0158] The compound shown in formula 145 is subjected to mass spectrometry to determine the molecular m / z as: 699.26.

[0159] Example 14

[0160] Synthesis of compound 161

[0161]

[0162] The synthesis method refers to the synthesis of compound 1 in synthesis example 1, except that the corresponding bromide and amine compound are used for reaction to obtain compound 161.

[0163] Mass spectrometry is performed on the compound shown in formula 161 to determine the molecular m / z as: 1252.50.

[0164] The materials used in the following application examples and comparative application examples are as follows:

[0165]

[0166] Application example 1A

[0167] Application example 1A selects compound 11 prepared in example 4 as a light-emitting layer doping material in an organic electroluminescent device.

[0168] The structure of the organic electroluminescent device is: ITO / HIL02(100 nm) / HT(30 nm) / EM1(30 nm): doping material 5% / TPBI(30 nm) / LiF(0.5 nm) / Al(150 nm).

[0169] The preparation process of the organic electroluminescent device is as follows:

[0170] (1) The glass substrate coated with ITO transparent conductive layer (as anode) is treated with ultrasonic in cleaning agent, then washed in deionized water, then ultrasonic deoiled in a mixed solvent of acetone and ethanol, then baked in a clean environment until completely dehydrated, washed with ultraviolet light and ozone, and the surface is bombarded with low-energy cation beam to improve the surface properties and improve the binding ability with the hole injection layer;

[0171] (2) The above glass substrate is placed in a vacuum chamber, vacuumed to 1x10 -5 ~ 1x10 -6 Pa, vacuum evaporates HIL02 as a hole injection layer on the anode, the evaporation rate is 0.1 nm / s, and the evaporation film thickness is 100 nm;

[0172] (3) Vacuum evaporates HT as a hole transport layer on the hole injection layer, the evaporation rate is 0.1 nm / s, and the evaporation film thickness is 30 nm;

[0173] (4) Vacuum evaporate a light-emitting layer on the hole-transporting layer, the evaporation rate is 0.1 nm / s, the total film thickness is 30 nm, the light-emitting layer host material is EM1, and the doping material is compound 11 prepared in Example 4, 5% refers to the doping ratio of the doping material, that is, the volume ratio of the light-emitting layer host material to the doping material is 100:5;

[0174] (5) Vacuum evaporate TPBI as an electron-transporting layer of the organic electroluminescent device on the organic light-emitting layer; the evaporation rate is 0.1 nm / s, and the total film thickness is 30 nm;

[0175] (6) Vacuum evaporate 0.5 nm of LiF and 150 nm of Al as an electron-injecting layer and a cathode on the electron-transporting layer.

[0176] Application Examples 2A-11A

[0177] Application Examples 2A-11A differ from Application Example 1 only in that compound 11 is replaced by compound 13-compound 16 prepared in corresponding Examples 5-14 as shown in Table 1 below, respectively; and the other preparation steps are the same.

[0178] Comparative Application Examples 1A-2A

[0179] Comparative Application Examples 1A-2A differ from Application Example 1 only in that compound 11 is replaced by corresponding D-2-D-3 as shown in Table 1 below, respectively; and the other preparation steps are the same.

[0180] Performance Test 1

[0181] Tested samples: the organic electroluminescent devices provided in Application Examples 1A-11A and the organic electroluminescent devices provided in Comparative Application Examples 1-2; test method: using OLED-1000 multi-channel accelerated aging life and light color performance analysis system produced by Hangzhou Yuanfang; test items: brightness, driving voltage, current efficiency of the organic electroluminescent device.

[0182] The performance of the organic electroluminescent device is shown in Table 1 below:

[0183] Table 1

[0184] Test sample Doping material Requesting brightness cd / m 2 ]]> Driving voltage V Current efficiency cd / A Luminous color Comparative Example 1A D-2 1000 5.06 3.99 Blue Comparative Example 2A D-3 1000 4.77 3.87 Blue Example 1A 11 1000 4.88 4.16 Blue Example 2A 13 1000 4.06 3.71 Blue Example 3A 29 1000 4.92 5.01 Blue Example 4A 33 1000 4.11 3.93 Blue Example 5A 57 1000 4.06 4.06 Blue Example 6A 81 1000 4.55 4.27 Blue Example 7A 101 1000 3.62 3.68 Blue Example 8A 102 1000 4.18 4.69 Blue Example 9A 113 1000 4.09 4.88 Blue Example 10A 145 1000 4.12 3.99 Blue Example 11A 161 1000 4.21 4.56 Blue

[0185] From the test data in Table 1, it can be seen that the spirofused heteroanthracene compound of the present application is used to improve the material performance by N-connection of spirofused oxanthracene or spirofused thioanthracene, so that the organic electroluminescent device prepared by using the compound of the present application, especially the blue light-emitting device, has higher luminous efficiency, lower driving voltage and longer service life. The driving voltage of the organic electroluminescent device prepared by using the spirofused heteroanthracene compound of the present application as a light-emitting layer dopant material can reach below 5V, and the current efficiency can reach above 3.6 cd / A; in particular, according to the preferred technical solution of the present application, the driving voltage of the spirofused heteroanthracene compound can reach below 3.7V, and the current efficiency can reach above 4.6 cd / A.

[0186] Application Example 1B

[0187] Application Example 1B selects the compound 1 prepared in Example 1 as a light-emitting layer dopant material in an organic electroluminescent device.

[0188] The structure of the organic electroluminescent device is: ITO / HIL02 (100 nm) / HT (30 nm) / EM1 (30 nm): 6% of dopant material / TPBI (30 nm) / LiF (0.5 nm) / Al (150 nm).

[0189] The preparation process of the organic electroluminescent device is as follows:

[0190] (1) The glass substrate coated with ITO transparent conductive layer (as anode) is subjected to ultrasonic treatment in a cleaning agent, then washed in deionized water, then ultrasonic oil removal in a mixed solvent of acetone and ethanol, then baked in a clean environment until completely water-free, washed with ultraviolet light and ozone, and the surface is bombarded with low-energy cation beams to improve the surface properties and improve the binding ability with the hole injection layer;

[0191] (2) The above glass substrate is placed in a vacuum chamber, vacuumed to 1×10 -5 ~ 1×10 -6 Pa, and HIL02 is vacuum evaporated on the anode as a hole injection layer, the evaporation rate is 0.1 nm / s, and the evaporation film thickness is 100 nm;

[0192] (3) HT is vacuum evaporated on the hole injection layer as a hole transport layer, the evaporation rate is 0.1 nm / s, and the evaporation film thickness is 30 nm;

[0193] (4) The light-emitting layer is vacuum evaporated on the hole transport layer, the evaporation rate is 0.1 nm / s, the total evaporation film thickness is 30 nm, the main material of the light-emitting layer is EM1, and the dopant materials are respectively the compound 1 prepared in Example 1, and 6% refers to the doping ratio of the dopant material, i.e. the volume ratio of the main material of the light-emitting layer to the dopant material is 100:6;

[0194] (5) Vacuum evaporate TPBI as the electron transport layer of the organic electroluminescent device on the organic light-emitting layer; the evaporation rate is 0.1 nm / s, and the total film thickness is 30 nm;

[0195] (6) Vacuum evaporate 0.5 nm of LiF and 150 nm of Al as the electron injection layer and the cathode on the electron transport layer.

[0196] Application Examples 2B-3B

[0197] Application Examples 2B-3B are different from Application Example 1 only in that the compound 1 is replaced by the compound 2 and the compound 5 prepared in the corresponding Examples 2-3 respectively as shown in Table 2 below; and the other preparation steps are the same.

[0198] Comparative Application Example 1B

[0199] Comparative Application Example 1B is different from Application Example 1 only in that the compound 11 is replaced by the corresponding D-1 respectively as shown in Table 1 below; and the other preparation steps are the same.

[0200] Performance Test 2

[0201] Test sample: the organic electroluminescent devices provided by Application Examples 1B-3B and the organic electroluminescent device provided by Comparative Application Example 1B; test method: using the OLED-1000 multi-channel accelerated aging life and light color performance analysis system produced by Hangzhou Yuanfang to test; test item: the brightness, driving voltage and current efficiency of the organic electroluminescent device.

[0202] The performance of the organic electroluminescent device is shown in Table 2 below:

[0203] Table 2

[0204]

[0205]

[0206] From the test data in Table 2, it can be seen that the spirofluorene heteroanthracene compound of the application is connected to the spirofluorene oxygen heteroanthracene or the spirofluorene sulfur heteroanthracene through N to improve the material performance, so that the organic electroluminescent device prepared by using the compound of the application can be used as a green light doping material. The driving voltage of the organic electroluminescent device prepared by using the spirofluorene heteroanthracene compound as a light-emitting layer doping material can reach below 4V, and the current efficiency can reach above 7.19 cd / A; in particular, as a preferred technical solution of the application, the driving voltage of the spirofluorene heteroanthracene compound can reach below 3.6V, and the current efficiency can reach above 8 cd / A.

[0207] Applicants declare that the process of the present application is illustrated by the above examples, but the present application is not limited to the above process steps, i.e. it does not mean that the present application must rely on the above process steps to be implemented. It should be understood by those skilled in the art that any improvement of the present application, equivalent replacement of the raw materials selected by the present application, addition of auxiliary ingredients, selection of specific modes, etc. fall within the protection scope and disclosure scope of the present application.

Claims

1. A spirofluorene heteroanthracene compound, characterized by, The spirofluorene heteroanthracene compound has the structure shown in the following formula I: Ar is selected from any one of the substituted or unsubstituted groups shown in the following formula I-3 to I-6, and the groups shown in the formula I-3 to I-6 are connected to the N atom in the compound shown in the formula I through SP2 hybridized carbon atom; R 11 , R 12 , R 21 , R 22 are each independently selected from the group consisting of unsubstituted C1-C20alkyl, substituted or unsubstituted C6-C40aryl; n is selected from 0 or 1; Ar1to Ar4are each independently selected from the group consisting of substituted or unsubstituted C6to C40aryl, unsubstituted X is selected from O or S; the group shown in formula II-1 is attached at the the N atom: and when n = 1, at least one of Ar1to Ar4is selected from the group shown in formula II-1 ; when n = 0, at least one of Ar3or Ar4is selected from the group shown in formula II-1 ; The substituents of the substituted groups shown in the formula I-3 to I-6 and the substituted C6-C40 aryl are each independently selected from any one of deuterium, C1-C20 alkyl or C6-C40 aryl; The C1-C20 alkyl is selected from any one of methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, sec-butyl, isobutyl, n-pentyl or n-hexyl; The C6-C40 aryl is selected from phenyl. The following structures and the structures obtained by replacing O in the following structures with S are excluded from the formula I:

2. The spirofused heteroanthracene compound according to claim 1, wherein The groups shown in the formula I-3 to I-6 can be substituted by at least one R; wherein R is selected from deuterium, C1-C20 alkyl, C6-C40 aryl; and when R is selected from C6-C40 aryl, R can be substituted by at least one C1-C20 alkyl; The C1-C20 alkyl is selected from any one of methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, sec-butyl, isobutyl, n-pentyl or n-hexyl; The C6-C40 aryl is selected from phenyl.

3. The spirofused heteroanthracene compound according to claim 1, wherein The Ar1 to Ar4 can be substituted by at least one R; wherein R is selected from deuterium, C1-C20 alkyl, C6-C40 aryl; and when R is selected from C6-C40 aryl, R can be substituted by at least one C1-C20 alkyl; The C1-C20 alkyl is selected from any one of methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, sec-butyl, isobutyl, n-pentyl or n-hexyl; The C6-C40 aryl is selected from phenyl.

4. The spirofused heteroanthracene compound according to claim 1, wherein The Ar can be substituted by C6-C40 aryl; and the C6-C40 aryl is selected from phenyl.

5. The spirofused heteroanthracene compound according to claim 1, wherein said R 11 and R 12 are connected by a single bond to form a ring, and / or said R 21 and R 22 are connected by a single bond to form a ring.

6. The spirofused heteroanthracene compound according to claim 1, wherein At least one of the Ar1 or Ar2 is selected from phenyl, and at least one of the Ar3 or Ar4 is selected from phenyl; and the phenyl can be substituted by at least one C1-C20 alkyl; The C1-C20 alkyl is selected from any one of methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, sec-butyl, isobutyl, n-pentyl or n-hexyl.

7. A spirofluorene heteroanthracene compound, characterized by The spirofluorene heteroanthracene compound is selected from any one of the compounds shown in the following: The spirofluorene heteroanthracene compound further includes the thio compounds of the spirofluorene oxanthracene compounds shown in the above, and the thio compounds are the spirofluorene heteroanthracene compounds obtained by replacing O in one or two of the benzoxanthracene groups shown in the above formula with S.

8. A method for producing the spirofluorene heteroanthracene compound according to any one of claims 1 to 7, characterized by, The n=0, and the preparation method of the spirofluorene heteroanthracene compound includes the following steps: reacting Ar-X and Ar3-NH-Ar4 to obtain the spirofluorene heteroanthracene compound shown in the formula I; X is selected from Cl, Br, I or OSO2CF3, and Ar, Ar3 and Ar4 each independently have the same range of limitations as any one of claims 1 to 7.

9. Use of the spirofluorene heteroanthracene compound according to any one of claims 1 to 7 as a dopant material in a light-emitting layer.

10. An organic electroluminescent device, characterized by comprising The organic electroluminescent device comprises the spirofluorene heteroanthracene compound according to any one of claims 1 to 7.

11. The organic electroluminescent device according to claim 10, wherein The organic electroluminescent device is a blue light-emitting device and / or a green light-emitting device.

12. The organic electroluminescent device according to claim 11, characterized in that, The organic electroluminescent device is a blue light-emitting device.

13. A display device comprising: The display device comprises the organic electroluminescent device according to any one of claims 10 to 12.

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