CN106986814A - A kind of compound as core using dimethyl anthrone and its application on organic electroluminescence device - Google Patents

A kind of compound as core using dimethyl anthrone and its application on organic electroluminescence device Download PDF

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CN106986814A
CN106986814A CN201710196991.9A CN201710196991A CN106986814A CN 106986814 A CN106986814 A CN 106986814A CN 201710196991 A CN201710196991 A CN 201710196991A CN 106986814 A CN106986814 A CN 106986814A
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layer
raw material
compound
substitution
unsubstituted
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李萍
缪康健
张兆超
张小庆
李崇
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Valiant Co Ltd
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Jiangsu Sanyue Optoelectronic Technology Co Ltd
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Abstract

The invention discloses a kind of compound as core using dimethyl anthrone and its application on organic electroluminescence device, the compound using dimethyl anthrone as core, with it is intermolecular be difficult to crystallize, be difficult to assemble, with good filming the characteristics of.The compounds of this invention is as the emitting layer material of organic electroluminescence device in use, the current efficiency of device is greatly improved；Simultaneously for device lifetime lifting clearly.

Description

A kind of compound using dimethyl anthrone as core and its in organic electroluminescence device On application
Technical field
The present invention relates to technical field of semiconductors, more particularly to a kind of compound using dimethyl anthrone as core and its Application on organic electroluminescence device.
Background technology
Organic electroluminescent (OLED:Organic Light Emission Diodes) device technology both can for system New display product is made, can be used for making novel illumination product, be expected to substitute existing liquid crystal display and fluorescent lighting, Application prospect is quite varied.OLED luminescent devices are just as the structure of sandwich, including electrode material film layer and are clipped in different electricity Organic functional material between the film layer of pole, various difference in functionality materials are overlapped mutually according to purposes collectively constitutes OLED hairs together Optical device.OLED luminescent devices are as current device, when applying voltage to its two end electrodes, and pass through electric field action organic layer work( Can be in film layer positive and negative charge when, positive and negative charge is further combined in luminescent layer, that is, produces OLED electroluminescent.
Currently, OLED Display Techniques are in smart mobile phone, and the field such as tablet personal computer is applied, further will also be to electricity Depending on etc. the extension of large scale application field, still, compare, the luminous efficiency of OLED and use with actual products application requirement The performances such as life-span also need to further lifting.Proposing high performance research to OLED luminescent devices at present includes：Reduce the drive of device Dynamic voltage, the luminous efficiency for improving device, the service life for improving device etc..In order to realize that the continuous of performance of OLED carries Rise, not only need the innovation from OLED structure and manufacture craft, with greater need for the constantly research and wound of oled light sulfate ferroelectric functional material Newly, the OLED functional materials of higher performance are formulated out.
Oled light sulfate ferroelectric functional material applied to OLED can be divided into two major classes from purposes, and respectively electric charge injects Transmission material and luminescent material.Further, it can also inject charge into transmission material and be divided into electron injection transmission material, electronic blocking Luminescent material, can also be divided into main body luminescent material and doping material by material, hole injection transmission material and hole barrier materials Material.In order to make high performance OLED luminescent devices, it is desirable to which various organic functional materials possess good photoelectric properties, for example, It is used as charge transport materials, it is desirable to which, with good carrier mobility, high-vitrification conversion temperature etc. is used as the master of luminescent layer Body material has good bipolarity, appropriate HOMO/LUMO energy ranks etc..
Constituting the oled light sulfate ferroelectric functional material film layer of OLED at least includes what is applied in more than two layers structure, industry OLED structure then includes hole injection layer, hole transmission layer, electronic barrier layer, luminescent layer, hole blocking layer, electric transmission A variety of film layers such as layer, electron injecting layer, that is to say, that the photoelectric functional material applied to OLED at least includes hole and injected Material, hole mobile material, luminescent material, electron transport material etc., material type and collocation form have rich and various The characteristics of property.In addition, for the OLED collocation of different structure, used photoelectric functional material has stronger choosing Selecting property, performance of the identical material in different structure device may also be completely totally different.
Therefore, industry application requirement and the difference in functionality film layer of OLED for current OLED, device Photoelectric characteristic demand, it is necessary to which selection is more suitable for, the OLED functional materials or combination of materials that performance is higher, could realize the height of device The overall characteristic of efficiency, long-life and low-voltage.For the actual demand that current OLED shows Lighting Industry, current OLED The development of material is also far from enough, lags behind the requirement of panel manufacturing enterprise, is used as the organic of material enterprise development higher performance Functional material is particularly important.
The content of the invention
In view of the above-mentioned problems existing in the prior art, the applicant provides a kind of chemical combination using dimethyl anthrone as core Thing and its application on organic electroluminescence device.The compounds of this invention is used as luminescent layer material using dimethyl anthrone as core Material is applied to Organic Light Emitting Diode, and the device that the present invention makes has good photoelectric properties, disclosure satisfy that panel manufacture enterprise The requirement of industry.
The applicant provides a kind of compound using dimethyl anthrone as core, the structure such as formula of the compound (1) shown in：
In formula (1), n is 1 or 2；In formula (1), Ar be expressed as substitution or unsubstituted C6-C30 aromatic radical, One kind in substitution or unsubstituted C6-C30 heteroaryls；Ar is also denoted as singly-bound；
In formula (1), R1And R2Independently be expressed as structure shown in hydrogen atom or formula (2), and R1And R2It is different When be hydrogen atom；
In formula (2), R3And R4The C1-C10 alkyl that is expressed as independently replaces or unsubstituted phenyl, C1-C10 Alkyl replace or unsubstituted naphthyl, C1-C10 alkyl substitution or unsubstituted xenyl, C1-C10 alkyl substitution or not Substituted anthryl, the substitution of C1-C10 alkyl or unsubstituted 9,9- dimethyl fluorenyl, the substitution of C1-C10 alkyl are not taken One kind in dibenzofuran group or C1-C10 the alkyl substitution in generation or unsubstituted dibenzothiophenes base.
It is preferred that, described formula (2) is：
In Any one.
It is preferred that, the compound that described formula (1) is represented is：
In one kind.
The applicant additionally provides a kind of method of the compound, and its synthesis step is as follows：
Wherein, Ar1It is expressed as substitution or unsubstituted C6-C30 aromatic radical, substitution or unsubstituted C6-C30 One kind in heteroaryl；R1、R2With n as described in claim 1；
Specifically preparation process is：
React A：Raw material I and raw material II are dissolved in dry toluene, Pd is added after deoxygenation2(dba)3, tri-tert phosphorus and Sodium tert-butoxide, 95~110 DEG C of 10~24 hours of reaction under an inert atmosphere, in course of reaction constantly with TLC monitorings react into Journey, after after raw material reaction completely, filtrate revolving is removed solvent, crude product crosses silicagel column, obtains target chemical combination by cooling, filtering Thing；The toluene consumption is that every gram of raw material I uses 30~50mL toluene, and raw material II and raw material I mol ratio are 1:(1.0~ 2.5), Pd2(dba)3Mol ratio with raw material I is (0.006~0.02):1, tri-butyl phosphine and raw material I mol ratio are (1.5 ~2):1, sodium tert-butoxide and raw material I mol ratio are (1.5~2.5):1；
React B：Raw material I and raw material II I are dissolved in the mixed solution of toluene and ethanol, Pd (PPh are added after deoxygenation3)4 And K2CO3, under an inert atmosphere 95~110 DEG C of 10~24 hours of reaction, constantly reaction process is monitored with TLC in course of reaction, After after raw material reaction completely, filtrate revolving is removed solvent, crude product crosses silicagel column, obtains target compound by cooling, filtering； Described toluene and the consumption of ethanol are that every gram of raw material I uses 30~50mL toluene and 5~10mL ethanol, raw material II I and raw material I Mol ratio be (1.0~2.5):1, Pd (PPh3)4Mol ratio with raw material I is (0.006~0.02):1, K2CO3With raw material I Mol ratio be (1.5~2.5):1.
The applicant additionally provides the application that a kind of described compound is used to prepare organic electroluminescence device.
The applicant additionally provides a kind of organic electroluminescence device, including luminescent layer, the luminescent layer include it is described with Dimethyl anthrone is the compound of core.It is preferred that, the organic electroluminescence device also includes stacking gradually cloth from bottom to up Transparent substrate layer, ito anode layer, hole injection layer, hole transmission layer, electronic barrier layer, the hole blocking layer/electric transmission put Layer, electron injecting layer and negative electrode reflection electrode layer；The luminescent layer is located at electronic barrier layer and hole blocking layer/electron transfer layer Between.
Group comprising electron donor (donor, D) with electron acceptor (acceptor, A) in the compounds of this invention structural molecule Conjunction can increase Orbital Overlap, improve luminous efficiency, while connecting what aromatic heterocycle group was spatially separating to obtain HOMO, LUMO Charge transfer state material, realizes the energy level difference of small S1 states and T1 states, so that reverse intersystem crossing is realized under the conditions of thermostimulation, It can be applied to as emitting layer material in organic electroluminescence device；The compound is using dimethyl anthrone as parent nucleus, connection It is generally rigid radical in aromatic group, the crystallinity of saboteur, it is to avoid intermolecular aggtegation, molecule, with good Film forming and fluorescence quantum efficiency, are suitable as luminescent layer dopant material and use.
The compounds of this invention branch containing alkyl, these branches can significantly improve the physicochemical property of material：1st, draw The chance contacted with each other between material core can be greatly reduced by entering branch, be conducive to improving the fluorescence quantum efficiency of material, together When alleviate the influence of efficiency roll-off, improve device lifetime.2nd, introduce material molecule intermolecular forces after branch to weaken, reduction rises Evaporation temperature prepared by magnificent temperature and device, expands the application widget of industrialization.3rd, introduce branch after material molecule in routine Dissolubility in organic solvent is greatly enhanced, and is reduced the difficulty and cost of material purification, can be obtained high-purity material, it is to avoid Because of the carrier traps of the not high generation of material purity, device lifetime is further improved.
Brief description of the drawings
Fig. 1 is the materials application of the invention provided in the structural representation of OLED；
Wherein, 1 is transparent substrate layer, and 2 be ito anode layer, and 3 be hole injection layer, and 4 be hole transmission layer, and 5 be luminous Layer, 6 be electron transfer layer, and 7 be electron injecting layer, and 8 be negative electrode reflection electrode layer.
Embodiment
Embodiment 1：The synthesis of compound 1
In 500mL there-necked flask, lead under nitrogen protection, add 0.03mol 3,6- dibromo carbazoles, 0.07mol raw materials The stirring mixing of B1,250mL toluene, then adds 0.09mol sodium tert-butoxides, 0.0015mol Pd2(dba)3, the uncles of 0.002mol tri- Butyl phosphine, is heated to 120 DEG C, back flow reaction 24 hours；Room temperature is naturally cooled to, is filtered, filtrate progress vacuum rotary steam (- 0.09MPa, 85 DEG C), neutral silica gel post is crossed, intermediate P1 is obtained；
In 250ml there-necked flask, lead under nitrogen protection, add 0.03mol intermediates P1,0.036mol Isosorbide-5-Nitrae-dibromo Benzene, 150ml toluene, stirring mixing, add 0.09mol sodium tert-butoxides, 0.002molPd2(dba)3, 0.002mol tri-terts Phosphine, is heated with stirring to 115 DEG C, back flow reaction 24 hours, sample point plate, display is remaining without intermediate P1, reaction is complete；Naturally it is cold But to room temperature, filtering, filtrate decompression is rotated to without cut, is crossed neutral silica gel post, is obtained intermediate N1；
In 250ml there-necked flask, lead under nitrogen protection, sequentially add 0.02mol intermediates N1,0.025mol connection boric acid Pinacol ester, 0.04mol potassium acetates, 0.002mol Pd (dppf) Cl2, 100ml Isosorbide-5-Nitraes-dioxane, stirring mixing, heating To 80 DEG C, react 24 hours, sample point plate, display is remaining without intermediate N1, reaction is complete；Room temperature is naturally cooled to, after adding water There is solid precipitation, filter, take filter cake to be dried with vacuum drying chamber, then cross neutral silica gel post, obtain intermediate M1；
In 250ml there-necked flask, lead under nitrogen protection, add 0.01mol raw material A 1,0.012mol intermediate M1, 150ml toluene/50mL ethanol stirring mixing, then adds 20ml wet chemicals (2M), 1 × 10-4molPd(PPh3)4, plus Heat is to 105 DEG C, and back flow reaction 24 hours, sample point plate, display reacts complete without starting material left；Naturally cool to room temperature, mistake Filter, filtrate carries out vacuum rotary steam (- 0.09MPa, 85 DEG C), crosses neutral silica gel post, obtains target product, HPLC purity 99.1%, Yield 71.4%；
Elementary analysis structure (molecular formula C62H51N3O)：Theoretical value C, 87.19；H,6.02；N,4.92；Test value：C, 87.36；H,6.01；N,4.91.MS m/z：855.21[M+H]+, theoretical value：855.10.
Embodiment 2：The synthesis of compound 4
In 500mL there-necked flask, lead under nitrogen protection, add 0.03mol 3,6- dibromo carbazoles, 0.07mol raw materials The stirring mixing of B2,250mL toluene, then adds 0.09mol sodium tert-butoxides, 0.0015mol Pd2(dba)3, the uncles of 0.002mol tri- Butyl phosphine, is heated to 120 DEG C, back flow reaction 24 hours；Room temperature is naturally cooled to, is filtered, filtrate progress vacuum rotary steam (- 0.09MPa, 85 DEG C), neutral silica gel post is crossed, intermediate P2 is obtained；
In 250ml there-necked flask, lead under nitrogen protection, add 0.03mol intermediates P2,0.036mol Isosorbide-5-Nitrae-dibromo Benzene, 150ml toluene, stirring mixing, add 0.09mol sodium tert-butoxides, 0.002molPd2(dba)3, 0.002mol tri-terts Phosphine, is heated with stirring to 115 DEG C, back flow reaction 24 hours, sample point plate, display is remaining without intermediate P2, reaction is complete；Naturally it is cold But to room temperature, filtering, filtrate decompression is rotated to without cut, is crossed neutral silica gel post, is obtained intermediate N2；
In 250ml there-necked flask, lead under nitrogen protection, sequentially add 0.02mol intermediates N2,0.025mol connection boric acid Pinacol ester, 0.04mol potassium acetates, 0.002mol Pd (dppf) Cl2, 100ml Isosorbide-5-Nitraes-dioxane, stirring mixing, heating To 80 DEG C, react 24 hours, sample point plate, display is remaining without intermediate N2, reaction is complete；Room temperature is naturally cooled to, after adding water There is solid precipitation, filter, take filter cake to be dried with vacuum drying chamber, then cross neutral silica gel post, obtain intermediate M2；
In 250ml there-necked flask, lead under nitrogen protection, add 0.01mol raw material A 1,0.012mol intermediate M2, 150ml toluene/50mL ethanol stirring mixing, then adds 20ml wet chemicals (2M), 1 × 10-4molPd(PPh3)4, plus Heat is to 105 DEG C, and back flow reaction 24 hours, sample point plate, display reacts complete without starting material left；Naturally cool to room temperature, mistake Filter, filtrate carries out vacuum rotary steam (- 0.09MPa, 85 DEG C), crosses neutral silica gel post, obtains target product, HPLC purity 99.4%, Yield 68.4%；
Elementary analysis structure (molecular formula C64H55N3O)：Theoretical value C, 87.14；H,6.28；N,4.76；Test value：C, 87.21；H,6.26；N,4.75.MS m/z：883.42[M+H]+, theoretical value：883.15.
Embodiment 3：The synthesis of compound 23
In 500mL there-necked flask, lead under nitrogen protection, add 0.03mol 3,6- dibromo carbazoles, 0.07mol raw materials The stirring mixing of B3,250mL toluene, then adds 0.09mol sodium tert-butoxides, 0.0015mol Pd2(dba)3, the uncles of 0.002mol tri- Butyl phosphine, is heated to 120 DEG C, back flow reaction 24 hours；Room temperature is naturally cooled to, is filtered, filtrate progress vacuum rotary steam (- 0.09MPa, 85 DEG C), neutral silica gel post is crossed, intermediate P3 is obtained；
In 250ml there-necked flask, lead under nitrogen protection, add 0.03mol intermediates P3,0.036mol Isosorbide-5-Nitrae-dibromo Benzene, 150ml toluene, stirring mixing, add 0.09mol sodium tert-butoxides, 0.002molPd2(dba)3, 0.002mol tri-terts Phosphine, is heated with stirring to 115 DEG C, back flow reaction 24 hours, sample point plate, display is remaining without intermediate P3, reaction is complete；Naturally it is cold But to room temperature, filtering, filtrate decompression is rotated to without cut, is crossed neutral silica gel post, is obtained intermediate N3；
In 250ml there-necked flask, lead under nitrogen protection, sequentially add 0.02mol intermediates N3,0.025mol connection boric acid Pinacol ester, 0.04mol potassium acetates, 0.002mol Pd (dppf) Cl2, 100ml Isosorbide-5-Nitraes-dioxane, stirring mixing, heating To 80 DEG C, react 24 hours, sample point plate, display is remaining without intermediate N3, reaction is complete；Room temperature is naturally cooled to, after adding water There is solid precipitation, filter, take filter cake to be dried with vacuum drying chamber, then cross neutral silica gel post, obtain intermediate M3；
In 250ml there-necked flask, lead under nitrogen protection, add 0.01mol raw material A 1,0.012mol intermediate M3, 150ml toluene/50mL ethanol stirring mixing, then adds 20ml wet chemicals (2M), 1 × 10-4molPd(PPh3)4, plus Heat is to 105 DEG C, and back flow reaction 24 hours, sample point plate, display reacts complete without starting material left；Naturally cool to room temperature, mistake Filter, filtrate carries out vacuum rotary steam (- 0.09MPa, 85 DEG C), crosses neutral silica gel post, obtains target product, HPLC purity 99.3%, Yield 65.8%；
Elementary analysis structure (molecular formula C76H59N3O)：Theoretical value C, 88.60；H,5.77；N,4.08；Test value：C, 88.74；H,5.74；N,4.07.MS m/z：1031.95[M+H]+, theoretical value：1031.31.
Embodiment 4：The synthesis of compound 24
In 500mL there-necked flask, lead under nitrogen protection, add 0.03mol 3,6- dibromo carbazoles, 0.07mol raw materials The stirring mixing of B4,250mL toluene, then adds 0.09mol sodium tert-butoxides, 0.0015mol Pd2(dba)3, the uncles of 0.002mol tri- Butyl phosphine, is heated to 120 DEG C, back flow reaction 24 hours；Room temperature is naturally cooled to, is filtered, filtrate progress vacuum rotary steam (- 0.09MPa, 85 DEG C), neutral silica gel post is crossed, intermediate P4 is obtained；
In 250ml there-necked flask, lead under nitrogen protection, add 0.03mol intermediates P4,0.036mol Isosorbide-5-Nitrae-dibromo Benzene, 150ml toluene, stirring mixing, add 0.09mol sodium tert-butoxides, 0.002molPd2(dba)3, 0.002mol tri-terts Phosphine, is heated with stirring to 115 DEG C, back flow reaction 24 hours, sample point plate, display is remaining without intermediate P4, reaction is complete；Naturally it is cold But to room temperature, filtering, filtrate decompression is rotated to without cut, is crossed neutral silica gel post, is obtained intermediate N4；
In 250ml there-necked flask, lead under nitrogen protection, sequentially add 0.02mol intermediates N4,0.025mol connection boric acid Pinacol ester, 0.04mol potassium acetates, 0.002mol Pd (dppf) Cl2, 100ml Isosorbide-5-Nitraes-dioxane, stirring mixing, heating To 80 DEG C, react 24 hours, sample point plate, display is remaining without intermediate N4, reaction is complete；Room temperature is naturally cooled to, after adding water There is solid precipitation, filter, take filter cake to be dried with vacuum drying chamber, then cross neutral silica gel post, obtain intermediate M4；
In 250ml there-necked flask, lead under nitrogen protection, add 0.01mol raw material A 1,0.012mol intermediate M4, 150ml toluene/50mL ethanol stirring mixing, then adds 20ml wet chemicals (2M), 1 × 10-4molPd(PPh3)4, plus Heat is to 105 DEG C, and back flow reaction 24 hours, sample point plate, display reacts complete without starting material left；Naturally cool to room temperature, mistake Filter, filtrate carries out vacuum rotary steam (- 0.09MPa, 85 DEG C), crosses neutral silica gel post, obtains target product, HPLC purity 99.4%, Yield 60.4%；
Elementary analysis structure (molecular formula C78H63N3O)：Theoretical value C, 88.52；H,6.00；N,3.97；Test value：C, 88.63；H,5.98；N,3.97.MS m/z：1059.51[M+H]+, theoretical value：1059.36.
Embodiment 5：The synthesis of compound 34
In 500mL there-necked flask, lead under nitrogen protection, add 0.03mol 3,6- dibromo carbazoles, 0.07mol raw materials The stirring mixing of B5,250mL toluene, then adds 0.09mol sodium tert-butoxides, 0.0015mol Pd2(dba)3, the uncles of 0.002mol tri- Butyl phosphine, is heated to 120 DEG C, back flow reaction 24 hours；Room temperature is naturally cooled to, is filtered, filtrate progress vacuum rotary steam (- 0.09MPa, 85 DEG C), neutral silica gel post is crossed, intermediate P5 is obtained；
In 250ml there-necked flask, lead under nitrogen protection, add 0.03mol intermediates P5,0.036mol Isosorbide-5-Nitrae-dibromo Benzene, 150ml toluene, stirring mixing, add 0.09mol sodium tert-butoxides, 0.002molPd2(dba)3, 0.002mol tri-terts Phosphine, is heated with stirring to 115 DEG C, back flow reaction 24 hours, sample point plate, display is remaining without intermediate P5, reaction is complete；Naturally it is cold But to room temperature, filtering, filtrate decompression is rotated to without cut, is crossed neutral silica gel post, is obtained intermediate N5；
In 250ml there-necked flask, lead under nitrogen protection, sequentially add 0.02mol intermediates N5,0.025mol connection boric acid Pinacol ester, 0.04mol potassium acetates, 0.002mol Pd (dppf) Cl2, 100ml Isosorbide-5-Nitraes-dioxane, stirring mixing, heating To 80 DEG C, react 24 hours, sample point plate, display is remaining without intermediate N5, reaction is complete；Room temperature is naturally cooled to, after adding water There is solid precipitation, filter, take filter cake to be dried with vacuum drying chamber, then cross neutral silica gel post, obtain intermediate M5；
In 250ml there-necked flask, lead under nitrogen protection, add 0.01mol raw material A 1,0.012mol intermediate M5, 150ml toluene/50mL ethanol stirring mixing, then adds 20ml wet chemicals (2M), 1 × 10-4molPd(PPh3)4, plus Heat is to 105 DEG C, and back flow reaction 24 hours, sample point plate, display reacts complete without starting material left；Naturally cool to room temperature, mistake Filter, filtrate carries out vacuum rotary steam (- 0.09MPa, 85 DEG C), crosses neutral silica gel post, obtains target product, HPLC purity 99.3%, Yield 63.5%；
Elementary analysis structure (molecular formula C82H55N3O3)：Theoretical value C, 87.13；H,4.90；N,3.92；Test value：C, 87.26；H,4.87；N,3.91.MS m/z：1131.73[M+H]+, theoretical value：1131.34.
Embodiment 6：The synthesis of compound 38
In 500mL there-necked flask, lead under nitrogen protection, add 0.03mol 3,6- dibromo carbazoles, 0.07mol raw materials The stirring mixing of B6,250mL toluene, then adds 0.09mol sodium tert-butoxides, 0.0015mol Pd2(dba)3, the uncles of 0.002mol tri- Butyl phosphine, is heated to 120 DEG C, back flow reaction 24 hours；Room temperature is naturally cooled to, is filtered, filtrate progress vacuum rotary steam (- 0.09MPa, 85 DEG C), neutral silica gel post is crossed, intermediate P6 is obtained；
In 250ml there-necked flask, lead under nitrogen protection, add 0.03mol intermediates P6,0.036mol Isosorbide-5-Nitrae-dibromo Benzene, 150ml toluene, stirring mixing, add 0.09mol sodium tert-butoxides, 0.002molPd2(dba)3, 0.002mol tri-terts Phosphine, is heated with stirring to 115 DEG C, back flow reaction 24 hours, sample point plate, display is remaining without intermediate P6, reaction is complete；Naturally it is cold But to room temperature, filtering, filtrate decompression is rotated to without cut, is crossed neutral silica gel post, is obtained intermediate N6；
In 250ml there-necked flask, lead under nitrogen protection, sequentially add 0.02mol intermediates N6,0.025mol connection boric acid Pinacol ester, 0.04mol potassium acetates, 0.002mol Pd (dppf) Cl2, 100ml Isosorbide-5-Nitraes-dioxane, stirring mixing, heating To 80 DEG C, react 24 hours, sample point plate, display is remaining without intermediate N6, reaction is complete；Room temperature is naturally cooled to, after adding water There is solid precipitation, filter, take filter cake to be dried with vacuum drying chamber, then cross neutral silica gel post, obtain intermediate M6；
In 250ml there-necked flask, lead under nitrogen protection, add 0.01mol raw material A 1,0.012mol intermediate M6, 150ml toluene/50mL ethanol stirring mixing, then adds 20ml wet chemicals (2M), 1 × 10-4molPd(PPh3)4, plus Heat is to 105 DEG C, and back flow reaction 24 hours, sample point plate, display reacts complete without starting material left；Naturally cool to room temperature, mistake Filter, filtrate carries out vacuum rotary steam (- 0.09MPa, 85 DEG C), crosses neutral silica gel post, obtains target product, HPLC purity 99.3%, Yield 63.5%；
Elementary analysis structure (molecular formula C84H59N3O3)：Theoretical value C, 87.10；H,5.13；N,3.63；Test value：C, 87.21；H,5.10；N,3.61.MS m/z：1159.64[M+H]+, theoretical value：1159.39.
Embodiment 7：The synthesis of compound 57
In 500mL there-necked flask, lead under nitrogen protection, add 0.03mol 3,6- dibromo carbazoles, 0.07mol raw materials The stirring mixing of B7,250mL toluene, then adds 0.09mol sodium tert-butoxides, 0.0015mol Pd2(dba)3, the uncles of 0.002mol tri- Butyl phosphine, is heated to 120 DEG C, back flow reaction 24 hours；Room temperature is naturally cooled to, is filtered, filtrate progress vacuum rotary steam (- 0.09MPa, 85 DEG C), neutral silica gel post is crossed, intermediate P7 is obtained；
In 250ml there-necked flask, lead under nitrogen protection, add 0.03mol intermediates P7,0.036mol 1,3- dibromos Benzene, 150ml toluene, stirring mixing, add 0.09mol sodium tert-butoxides, 0.002molPd2(dba)3, 0.002mol tri-terts Phosphine, is heated with stirring to 115 DEG C, back flow reaction 24 hours, sample point plate, display is remaining without intermediate P7, reaction is complete；Naturally it is cold But to room temperature, filtering, filtrate decompression is rotated to without cut, is crossed neutral silica gel post, is obtained intermediate N7；
In 250ml there-necked flask, lead under nitrogen protection, sequentially add 0.02mol intermediates N7,0.025mol connection boric acid Pinacol ester, 0.04mol potassium acetates, 0.002mol Pd (dppf) Cl2, 100ml Isosorbide-5-Nitraes-dioxane, stirring mixing, heating To 80 DEG C, react 24 hours, sample point plate, display is remaining without intermediate N7, reaction is complete；Room temperature is naturally cooled to, after adding water There is solid precipitation, filter, take filter cake to be dried with vacuum drying chamber, then cross neutral silica gel post, obtain intermediate M7；
In 250ml there-necked flask, lead under nitrogen protection, add 0.01mol raw material A 1,0.012mol intermediate M7, 150ml toluene/50mL ethanol stirring mixing, then adds 20ml wet chemicals (2M), 1 × 10-4molPd(PPh3)4, plus Heat is to 105 DEG C, and back flow reaction 24 hours, sample point plate, display reacts complete without starting material left；Naturally cool to room temperature, mistake Filter, filtrate carries out vacuum rotary steam (- 0.09MPa, 85 DEG C), crosses neutral silica gel post, obtains target product, HPLC purity 99.5%, Yield 68.1%；
Elementary analysis structure (molecular formula C72H55N3O3)：Theoretical value C, 87.10；H,5.13；N,3.63；Test value：C, 87.21；H,5.10；N,3.61.MS m/z：1159.64[M+H]+, theoretical value：1159.39.
Embodiment 8：The synthesis of compound 68
In 250ml there-necked flask, lead under nitrogen protection, add 0.01mol raw material A 2,0.012mol intermediate M1, 150ml toluene/50mL ethanol stirring mixing, then adds 20ml wet chemicals (2M), 1 × 10-4molPd(PPh3)4, plus Heat is to 105 DEG C, and back flow reaction 24 hours, sample point plate, display reacts complete without starting material left；Naturally cool to room temperature, mistake Filter, filtrate carries out vacuum rotary steam (- 0.09MPa, 85 DEG C), crosses neutral silica gel post, obtains target product, HPLC purity 99.5%, Yield 70.2%；
Elementary analysis structure (molecular formula C62H51N3O)：Theoretical value C, 87.19；H,6.02；N,4.92；Test value：C, 87.26；H,6.00；N,4.89.MS m/z：855.25[M+H]+, theoretical value：855.10.
Embodiment 9：The synthesis of compound 83
In 250ml there-necked flask, lead under nitrogen protection, add 0.01mol raw material A 1,0.012mol intermediate N1, The stirring mixing of 150ml toluene, then adds 0.02mol sodium tert-butoxides, 1 × 10-4molPd2(dna)3, 0.02mol tri-terts Phosphine, is heated to 105 DEG C, back flow reaction 24 hours, sample point plate, display reacts complete without starting material left；Naturally cool to room Temperature, filtering, filtrate carries out vacuum rotary steam (- 0.09MPa, 85 DEG C), crosses neutral silica gel post, obtains target product, HPLC purity 99.5%, yield 70.2%；
Elementary analysis structure (molecular formula C56H47N3O)：Theoretical value C, 86.45；H,6.09；N,5.40；Test value：C, 86.57；H,6.05；N,5.38.MS m/z：779.25[M+H]+, theoretical value：779.00.
Embodiment 10：The synthesis of compound 99
In 500mL there-necked flask, lead under nitrogen protection, add 0.03mol 3,6- dibromo carbazoles, 0.07mol raw materials The stirring mixing of B8,250mL toluene, then adds 0.09mol sodium tert-butoxides, 0.0015mol Pd2(dba)3, the uncles of 0.002mol tri- Butyl phosphine, is heated to 120 DEG C, back flow reaction 24 hours；Room temperature is naturally cooled to, is filtered, filtrate progress vacuum rotary steam (- 0.09MPa, 85 DEG C), neutral silica gel post is crossed, intermediate P8 is obtained；
In 250ml there-necked flask, lead under nitrogen protection, add 0.03mol intermediates P8,0.036mol Isosorbide-5-Nitrae-dibromo Benzene, 150ml toluene, stirring mixing, add 0.09mol sodium tert-butoxides, 0.002molPd2(dba)3, 0.002mol tri-terts Phosphine, is heated with stirring to 115 DEG C, back flow reaction 24 hours, sample point plate, display is remaining without intermediate P8, reaction is complete；Naturally it is cold But to room temperature, filtering, filtrate decompression is rotated to without cut, is crossed neutral silica gel post, is obtained intermediate N8；
In 250ml there-necked flask, lead under nitrogen protection, sequentially add 0.02mol intermediates N8,0.025mol connection boric acid Pinacol ester, 0.04mol potassium acetates, 0.002mol Pd (dppf) Cl2, 100ml Isosorbide-5-Nitraes-dioxane, stirring mixing, heating To 80 DEG C, react 24 hours, sample point plate, display is remaining without intermediate N8, reaction is complete；Room temperature is naturally cooled to, after adding water There is solid precipitation, filter, take filter cake to be dried with vacuum drying chamber, then cross neutral silica gel post, obtain intermediate M8；
In 250ml there-necked flask, lead under nitrogen protection, add 0.01mol raw material A 1,0.012mol intermediate M8, 150ml toluene/50mL ethanol stirring mixing, then adds 20ml wet chemicals (2M), 1 × 10-4molPd(PPh3)4, plus Heat is to 105 DEG C, and back flow reaction 24 hours, sample point plate, display reacts complete without starting material left；Naturally cool to room temperature, mistake Filter, filtrate carries out vacuum rotary steam (- 0.09MPa, 85 DEG C), crosses neutral silica gel post, obtains target product, HPLC purity 99.5%, Yield 69.4%；
Elementary analysis structure (molecular formula C74H71N3O)：Theoretical value C, 87.28；H,7.03；N,4.13；Test value：C, 87.21；H,7.00；N,4.12.MS m/z：1019.59[M+H]+, theoretical value：1019.38.
The compounds of this invention can be used as luminescent layer material of main part.To the compounds of this invention, current material CPB difference Heat endurance, cyclic voltammetric stability, △ Est measure are carried out, testing result is as shown in table 1.
Table 1
Compound Tg(℃) △Est(eV) Cyclic voltamogram Function
Compound 1 150 0.1020 It is excellent Material of main part
Compound 4 135 0.0953 It is excellent Material of main part
Compound 23 141 0.0135 It is excellent Material of main part
Compound 24 133 0.0059 It is excellent Material of main part
Compound 34 146 0.1038 It is excellent Material of main part
Compound 57 159 0.1825 It is excellent Material of main part
Compound 99 157 0.1258 It is excellent Material of main part
CBP 113 0.81 Difference Material of main part
Note：△ Est are the fluorescence emission spectrum and phosphorescence emission spectra for first distinguishing test compound, and by fluorescence emission peak Calculated with phosphorescent emissions peak and obtain (test equipment：Using Edinburgh Instruments FLS980 XRFs, Oxford Instruments Optistat DN-V2 cryogenic assemblies)；The DSC-60 heat differentials scanning point of Shimadzu Corporation of Tg Japan Analyzer is measured, nitrogen flow 10mL/min.Cyclic voltammetric stability is to observe the oxidation of material also by cyclic voltammetry Former characteristic is identified；Test condition：It is 2 that test sample, which is dissolved in volume ratio,:1 dichloromethane and acetonitrile mixed solvent is dense 1mg/mL is spent, electrolyte is 0.1M tetrabutyl ammonium tetrafluoroborate or the organic solution of hexafluorophosphate.Reference electrode It is Ag/Ag+ electrodes, is titanium plate to electrode, working electrode is ITO electrode, and cycle-index is 20 times.
From upper table data, the compounds of this invention has a preferable oxidation-reduction stability, higher heat endurance, compared with High T1 energy levels, are suitable as the material of main part of luminescent layer；Meanwhile, the compounds of this invention contain electron donor (donor, D) with Electron acceptor (acceptor, A) so that the OLED electronics of application the compounds of this invention and hole reach poised state, make Obtain device efficiency and the life-span gets a promotion.The compounds of this invention has preferable oxidation-reduction stability, higher Tg, evaporation film It is in stable condition；It has relatively low △ Est, easily realizes high T1→S1State exciton conversion ratio, is suitable as the main body material of luminescent layer Material.
Calculating is carried out by quantum-mechanical effects software ORCA to HOMO, the lumo energy of the compounds of this invention to go forward side by side Row visualization, computational methods use B3LYP hydridization functionals, base group 6-31g (d).Compound 1, compound 4, compound 24, chemical combination Thing 99 and compound CBP visualization HOMO, LUMO distribution map are as shown in table 2；
Table 2
It can see from the spatial distribution of HOMO, LUMO in the molecule, at the HOMO and lumo energy of the compounds of this invention In the state that is spatially separating, HOMO, LUMO degree of overlapping are small, so as to cause singlet-triplet difference small, are conducive to triplet state to swash Son is converted into singlet exciton by thermal excitation, in theory device internal quantum efficiency can be made to reach 100%.
By the following examples 11~20 and comparative example 1~3 describe the compound that synthesizes of the present invention in detail and make in the devices For the application effect of luminescent layer material of main part.Embodiment 12~20 is compared with embodiment 11, and the manufacture craft of the device is complete Identical, and employed identical baseplate material and electrode material, the thickness of electrode material is also consistent, except that Emitting layer material is changed in device.Embodiment 11~20 is compared with comparative example 1~3, device described in comparative example 1~3 Emitting layer material uses existing conventional raw material, and the device emitting layer material of embodiment 11~20 uses of the present inventionization Compound.The structure composition of each embodiment obtained device is as shown in table 3.The performance test results of each device are as shown in table 4.
Embodiment 11
(the molybdenum trioxide MoO of 2/ hole injection layer of transparent substrate layer 1/ITO anode layers 33, thickness 10nm) and/hole transmission layer 4 (compound 1 and GD-19 are according to 100 for (TAPC, thickness 80nm)/luminescent layer 5：5 weight is than blending, thickness 30nm)/electronics biography Defeated layer 6 (TPBI, thickness 40nm)/electron injecting layer 7 (LiF, thickness 1nm)/negative electrode layer 8 (Al).The molecule of associated materials Structural formula is as follows：
Specific preparation process is as follows：
Transparent substrate layer 1 uses transparent material.Ito anode 2 (thickness is 150nm) of layer are washed, i.e., carried out successively Ultraviolet-ozone washing is carried out after neutralizing treatment, pure water, drying again to remove the organic residue on transparent ITO surfaces.
On the ito anode layer 2 after having carried out above-mentioned washing, using vacuum deposition apparatus, evaporation thickness is 10nm's Molybdenum trioxide MoO3Used as hole injection layer 3.And then the TAPC of evaporation 80nm thickness is used as hole transmission layer 4.
After above-mentioned hole mobile material evaporation terminates, the luminescent layer 5 of OLED luminescent devices is made, its structure is sent out including OLED Photosphere 5 uses material compound 1 as material of main part, and GD-19 is as dopant material, and dopant material doping ratio is 5% weight Amount ratio, luminescent layer thickness is 30nm.
After above-mentioned luminescent layer 5, it is TPBI to continue vacuum evaporation electron transport layer materials.The vacuum evaporation coating of the material Thickness is 40nm, and this layer is electron transfer layer 6.On electron transfer layer 6, by vacuum deposition apparatus, the fluorine that thickness is 1nm is made Change lithium (LiF) layer, this layer is electron injecting layer 7.On electron injecting layer 7, by vacuum deposition apparatus, making thickness is 80nm Aluminium (Al) layer, this layer be negative electrode reflection electrode layer 8 use.Complete after OLED luminescent devices, driven with known as described above Dynamic circuit connects anode and negative electrode, the luminous efficiency of measurement device, and the current-voltage of luminescent spectrum and device is special Property.
Embodiment 12
(the molybdenum trioxide MoO of 2/ hole injection layer of transparent substrate layer 1/ITO anode layers 33, thickness 10nm) and/hole transmission layer 4 (compound 4 and GD-19 are according to 100 for (TAPC, thickness 80nm)/luminescent layer 5:5 weight is than blending, thickness 30nm)/electronics biography Defeated layer 6 (TPBI, thickness 40nm)/electron injecting layer 7 (LiF, thickness 1nm)/negative electrode reflection electrode layer 8 (Al).
Embodiment 13
(the molybdenum trioxide MoO of 2/ hole injection layer of transparent substrate layer 1/ITO anode layers 33, thickness 10nm) and/hole transmission layer 4 (compound 23 and GD-19 are according to 100 for (TAPC, thickness 80nm)/luminescent layer 5:5 weight is than blending, thickness 30nm)/electronics biography Defeated layer 6 (TPBI, thickness 40nm)/electron injecting layer 7 (LiF, thickness 1nm)/negative electrode reflection electrode layer 8 (Al).
Embodiment 14
(the molybdenum trioxide MoO of 2/ hole injection layer of transparent substrate layer 1/ITO anode layers 33, thickness 10nm) and/hole transmission layer 4 (compound 24 and Ir (ppy) 3 are according to 100 for (TAPC, thickness 80nm)/luminescent layer 5:10 weight is than blending, thickness 30nm)/electricity Sub- transport layer 6 (TPBI, thickness 40nm)/electron injecting layer 7 (LiF, thickness 1nm)/negative electrode reflection electrode layer 8 (Al).
Embodiment 15
(the molybdenum trioxide MoO of 2/ hole injection layer of transparent substrate layer 1/ITO anode layers 33, thickness 10nm) and/hole transmission layer 4 (compound 34 and Ir (ppy) 3 are according to 100 for (TAPC, thickness 80nm)/luminescent layer 5:10 weight is than blending, thickness 30nm)/electricity Sub- transport layer 6 (TPBI, thickness 40nm)/electron injecting layer 7 (LiF, thickness 1nm)/negative electrode reflection electrode layer 8 (Al).
Embodiment 16
(the molybdenum trioxide MoO of 2/ hole injection layer of transparent substrate layer 1/ITO anode layers 33, thickness 10nm) and/hole transmission layer 4 (compound 38 and Ir (ppy) 3 are according to 100 for (TAPC, thickness 80nm)/luminescent layer 5:10 weight is than blending, thickness 30nm)/electricity Sub- transport layer 6 (TPBI, thickness 40nm)/electron injecting layer 7 (LiF, thickness 1nm)/negative electrode reflection electrode layer 8 (Al).
Embodiment 17
(the molybdenum trioxide MoO of 2/ hole injection layer of transparent substrate layer 1/ITO anode layers 33, thickness 10nm) and/hole transmission layer 4 (compound 57 and GD-PACTZ are according to 100 for (TAPC, thickness 80nm)/luminescent layer 5:5 weight is than blending, thickness 30nm)/electricity Sub- transport layer 6 (TPBI, thickness 40nm)/electron injecting layer 7 (LiF, thickness 1nm)/negative electrode reflection electrode layer 8 (Al).
Embodiment 18
(the molybdenum trioxide MoO of 2/ hole injection layer of transparent substrate layer 1/ITO anode layers 33, thickness 10nm) and/hole transmission layer 4 (compound 68 and GD-PACTZ are according to 100 for (TAPC, thickness 80nm)/luminescent layer 5:5 weight is than blending, thickness 30nm)/electricity Sub- transport layer 6 (TPBI, thickness 40nm)/electron injecting layer 7 (LiF, thickness 1nm)/negative electrode reflection electrode layer 8 (Al).
Embodiment 19
(the molybdenum trioxide MoO of 2/ hole injection layer of transparent substrate layer 1/ITO anode layers 33, thickness 10nm) and/hole transmission layer 4 (compound 83, GH-204 and Ir (ppy) 3 are according to 70 for (TAPC, thickness 80nm)/luminescent layer 5:30:10 weight is thick than blending Spend 30nm)/electron transfer layer 6 (TPBI, thickness 40nm)/electron injecting layer 7 (LiF, thickness 1nm)/negative electrode reflection electrode layer 8 (Al)。
Embodiment 20
(the molybdenum trioxide MoO of 2/ hole injection layer of transparent substrate layer 1/ITO anode layers 33, thickness 10nm) and/hole transmission layer 4 (compound 99, GH-204 and GD-PACTZ are according to 70 for (TAPC, thickness 80nm)/luminescent layer 5:30:5 weight is than blending, thickness 30nm)/electron transfer layer 6 (TPBI, thickness 40nm)/electron injecting layer 7 (LiF, thickness 1nm)/negative electrode reflection electrode layer 8 (Al)。
Comparative example 1
(the molybdenum trioxide MoO of 2/ hole injection layer of transparent substrate layer 1/ITO anode layers 33, thickness 10nm) and/hole transmission layer 4 (CBP and GD-19 are according to 100 for (TAPC, thickness 80nm)/luminescent layer 5:5 weight is than blending, thickness 30nm)/electron transfer layer 6 (TPBI, thickness 40nm)/electron injecting layer 7 (LiF, thickness 1nm)/negative electrode reflection electrode layer 8 (Al).
Comparative example 2
(the molybdenum trioxide MoO of 2/ hole injection layer of transparent substrate layer 1/ITO anode layers 33, thickness 10nm) and/hole transmission layer 4 (CBP and Ir (ppy) 3 are according to 100 for (TAPC, thickness 80nm)/luminescent layer 5:10 weight is than blending, thickness 30nm)/electronics biography Defeated layer 6 (TPBI, thickness 40nm)/electron injecting layer 7 (LiF, thickness 1nm)/negative electrode reflection electrode layer 8 (Al).
Comparative example 3
(the molybdenum trioxide MoO of 2/ hole injection layer of transparent substrate layer 1/ITO anode layers 33, thickness 10nm) and/hole transmission layer 4 (CBP and GD-PACTZ are according to 100 for (TAPC, thickness 80nm)/luminescent layer 5:5 weight is than blending, thickness 30nm)/electric transmission Layer (LiF, thickness the 1nm)/negative electrode layer 8 (Al) of 6 (TPBI, thickness 40nm)/electron injecting layer 7.
The test result of made OLED luminescent devices is shown in Table 4.
Table 3
Table 4
Device code name Current efficiency (cd/A) Color The LT95 life-spans (Hr)
Embodiment 11 8.3 Green glow 5.1
Embodiment 12 8.8 Green glow 6.5
Embodiment 13 9.0 Green glow 5.6
Embodiment 14 24.61 Green glow 6.2
Embodiment 15 26.35 Green glow 8.1
Embodiment 16 27.14 Green glow 6.9
Embodiment 17 28.02 Green glow 6.3
Embodiment 18 29.36 Green glow 8.5
Embodiment 19 27.58 Green glow 11.3
Embodiment 20 30.21 Green glow 10.6
Comparative example 1 6.50 Green glow 3.8
Comparative example 2 24.60 Green glow 4.3
Comparative example 3 25.10 Green glow 7.8
Explanation:The current efficiency of comparative example 1 is 6.5cd/A (@10mA/cm2)；Startup voltage is 4.3V (@1cd/m2), LT95 life time decays are 3.8Hr under 5000nit brightness.The current efficiency of comparative example 2 is 24.6cd/A (@10mA/cm2)； LT95 life time decays are 4.3Hr under 5000nit brightness.The current efficiency of comparative example 3 is 25.1cd/A (@10mA/cm2)；Start Voltage is 3.5V (@1cd/m2), and LT95 life time decays are 7.8Hr under 5000nit brightness.Life-span test system is all for the present invention Weigh people and the OLED life-span tester of Shanghai University's joint research.
The startup voltage of embodiment 11 is 4.1V (@1cd/m2), the startup voltage of embodiment 20 is 3.3V (@1cd/m2)。
The result of table 4 can be seen that compound of the present invention as luminescent layer material of main part can be applied to OLED light Element manufacturing；And compared with comparative example, either efficiency, voltage or life-span obtain and larger change than known OLED material See, the driving life-span of particularly device obtains larger lifting.
Further to embody advantage of the compounds of this invention in commercial application, the present invention is made by embodiment and comparative example Standby device places 24h under the conditions of hot and humid (85 DEG C, RH=85%), and its performance is then tested again, simulates same device Performance change situation of the part structure in hot and humid environment before and after the processing, defines humiture coefficientIt is indicated；
It represents that driving current is 10mA/cm2Under be placed on device under different temperature and humidity conditions, its maximum efficiency μmax, minimum value μminUniformity coefficient between average value,Value is bigger, illustrates efficiency of the hot and humid environment processing to device Influence is bigger, and its practical application effect is poor, and commercial Application window is smaller；Conversely, explanation device performance is by hot and humid environment Influence it is smaller, easily realize industrialized production, product possesses the higher market competitiveness, before good commercial application Scape.
Reference implementation example 11-20 luminescent device method of testing, selection example 11, embodiment 14, embodiment 17 and right Ratio 1~3 carries out hot and humid environment processing, and its test result is as shown in table 5：
Table 5
From the point of view of data above application, the compounds of this invention has well as emitting layer material in OLED luminescent devices Application effect, humiture coefficient is smaller, is influenceed smaller by extraneous application environment, so that with good industrialization prospect.
Although disclosing the present invention by embodiment and preferred embodiment, it should be appreciated that public the invention is not restricted to institute The embodiment opened.On the contrary, it will be understood by those skilled in the art that it is intended to various modifications and similar arrangement.Therefore, institute The scope of attached claim should be consistent with most wide explanation to cover all such modifications and similar arrangement.

Claims (7)

1. a kind of compound using dimethyl anthrone as core, it is characterised in that the structure of the compound such as formula (1) institute Show：
In formula (1), n is 1 or 2；
In formula (1), Ar is expressed as substitution or unsubstituted C6-C30 aromatic radical, substitution or unsubstituted C6-C30 One kind in heteroaryl；Ar is also denoted as singly-bound；
In formula (1), R1And R2Independently be expressed as structure shown in hydrogen atom or formula (2), and R1And R2It is asynchronously Hydrogen atom；
In formula (2), R3And R4The C1-C10 alkyl that is expressed as independently replaces or unsubstituted phenyl, C1-C10 alkyl Substitution or unsubstituted naphthyl, the substitution of C1-C10 alkyl or unsubstituted xenyl, the substitution of C1-C10 alkyl are not taken Anthryl, the substitution of C1-C10 alkyl or the unsubstituted 9,9- dimethyl fluorenyl in generation, the substitution or unsubstituted of C1-C10 alkyl One kind in dibenzofuran group or the substitution of C1-C10 alkyl or unsubstituted dibenzothiophenes base.
2. compound according to claim 1, it is characterised in that described formula (2) is：
In any one.
3. compound according to claim 1, it is characterised in that the compound that described formula (1) is represented is：
In one kind.
4. a kind of method for preparing any one of claims 1 to 3 compound, it is characterised in that its synthesis step is as follows：
Wherein, Ar1It is expressed as substitution or unsubstituted C6-C30 aromatic radical, substitution or unsubstituted C6-C30 heteroaryls One kind in base；R1、R2With n as described in claim 1；
Specifically preparation process is：
React A：Raw material I and raw material II are dissolved in dry toluene, Pd is added after deoxygenation2(dba)3, tri-tert phosphorus and tertiary fourth Sodium alkoxide, 95~110 DEG C are reacted in 10~24 hours, course of reaction constantly with TLC monitoring reaction process under an inert atmosphere, are treated After raw material reaction completely, filtrate revolving is removed solvent, crude product crosses silicagel column, obtains target compound by cooling, filtering；Institute State toluene consumption and use 30~50mL toluene for every gram of raw material I, raw material II and raw material I mol ratio are 1:(1.0~2.5), Pd2 (dba)3Mol ratio with raw material I is (0.006~0.02):1, tri-butyl phosphine and raw material I mol ratio are (1.5~2):1, Sodium tert-butoxide and raw material I mol ratio are (1.5~2.5):1；
React B：Raw material I and raw material II I are dissolved in the mixed solution of toluene and ethanol, Pd (PPh are added after deoxygenation3)4With K2CO3, 95~110 DEG C are reacted in 10~24 hours, course of reaction constantly with TLC monitoring reaction process under an inert atmosphere, are treated After raw material reaction completely, filtrate revolving is removed solvent, crude product crosses silicagel column, obtains target compound by cooling, filtering；Institute The toluene and the consumption of ethanol stated are that every gram of raw material I uses 30~50mL toluene and 5~10mL ethanol, raw material II I and raw material I's Mol ratio is (1.0~2.5):1, Pd (PPh3)4Mol ratio with raw material I is (0.006~0.02):1, K2CO3With raw material I's Mol ratio is (1.5~2.5):1.
5. a kind of compound as described in any one of claims 1 to 3 is used to prepare organic electroluminescence device.
6. a kind of organic electroluminescence device, including luminescent layer, it is characterised in that the luminescent layer is appointed including claims 1 to 3 Compound described in one.
7. organic electroluminescence device according to claim 6, it is characterised in that also including stacking gradually cloth from bottom to up Transparent substrate layer, ito anode layer, hole injection layer, hole transmission layer, electronic barrier layer, the hole blocking layer/electric transmission put Layer, electron injecting layer and negative electrode reflection electrode layer, the luminescent layer are located at electronic barrier layer and hole blocking layer/electron transfer layer Between.
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CN109574908A (en) * 2017-09-28 2019-04-05 江苏三月光电科技有限公司 A kind of compound of the fluorenes of dimethylanthracene containing spiral shell and its application on organic electroluminescence device
CN109912575A (en) * 2017-12-12 2019-06-21 江苏三月光电科技有限公司 Compound with nitrogen-containing five-membered heterocycle as core and application thereof in organic electroluminescent device
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CN110963904A (en) * 2018-09-30 2020-04-07 江苏三月光电科技有限公司 Compound with ketone and fluorene as cores, preparation method and application thereof

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WO2018033087A1 (en) * 2016-08-18 2018-02-22 江苏三月光电科技有限公司 Compound using anthrone as core and applications thereof
CN109574908A (en) * 2017-09-28 2019-04-05 江苏三月光电科技有限公司 A kind of compound of the fluorenes of dimethylanthracene containing spiral shell and its application on organic electroluminescence device
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CN110963904A (en) * 2018-09-30 2020-04-07 江苏三月光电科技有限公司 Compound with ketone and fluorene as cores, preparation method and application thereof

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