CN106977446A - It is a kind of using three benzo cycloheptene ketone as the compound of core and its application in OLED - Google Patents

It is a kind of using three benzo cycloheptene ketone as the compound of core and its application in OLED Download PDF

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CN106977446A
CN106977446A CN201710196612.6A CN201710196612A CN106977446A CN 106977446 A CN106977446 A CN 106977446A CN 201710196612 A CN201710196612 A CN 201710196612A CN 106977446 A CN106977446 A CN 106977446A
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compound
key
aryl
layer
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高晓祥
徐凯
李崇
张小庆
张兆超
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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 with three benzo cycloheptene ketone compounds and its application on organic electroluminescence device, the compound using three benzo cycloheptene ketone 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 luminescent layer material of main part of OLED luminescent devices in use, the current efficiency of device, power efficiency and external quantum efficiency are greatly improved；Simultaneously for device lifetime lifting clearly.

Description

It is a kind of using three benzo cycloheptene ketone as the compound of core and its in OLED Using
Technical field
The present invention relates to technical field of semiconductors, more particularly, to a kind of compound of three benzos cycloheptene ketone, and Its application as luminescent layer material of main part on Organic Light Emitting Diode.
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 just as the structure of sandwich, including electrode material film layer, and be clipped in Different electrodes film layer it Between organic functional material, various difference in functionality materials are overlapped mutually according to purposes collectively constitutes OLED luminescent devices together. As current device, when the two end electrodes to OLED luminescent devices apply voltage, and pass through electric field action organic layer functional material Positive and negative charge in film layer, positive and negative charge is further combined in luminescent layer, that is, produces OLED electroluminescent.
Organic Light Emitting Diode (OLEDs) large-area flat-plate show and illumination in terms of application cause industrial quarters and The extensive concern of art circle.However, traditional organic fluorescence materials can only be lighted using 25% singlet exciton to be formed is electrically excited, device The internal quantum efficiency of part is relatively low (up to 25%).External quantum efficiency is generally less than 5%, also has with the efficiency of phosphorescent devices very big Gap.Although phosphor material enhances intersystem crossing due to the strong SO coupling in heavy atom center, electricity can be effectively utilized The singlet exciton to be formed and Triplet exciton are excited, makes the internal quantum efficiency of device up to 100%.But phosphor material is present Expensive, stability of material is poor, and the problems such as device efficiency tumbles serious limits its application in OLEDs.Hot activation is prolonged Slow fluorescence (TADF) material is the third generation luminous organic material developed after organic fluorescence materials and organic phosphorescent material.Should Class material typically has that small singlet-triplet is poor (△ EST), and triplet excitons can be changed by anti-intersystem crossing It is luminous into singlet exciton.This can make full use of the singlet exciton and triplet excitons that are electrically excited lower formation, device it is interior Quantum efficiency can reach 100%.Meanwhile, material structure is controllable, and property is stable, cheap without precious metal, in OLEDs Field has a extensive future.
In recent years, hot activation delayed fluorescence (TADF) material of main part is carried because of the hole with balance and electronic carrier stream The high combined efficiency of electronics and hole, and then be conducive to strengthening the luminous efficiency of device, reduction efficiency is roll-offed.Meanwhile, it is main There is very strong Intramolecular electron transfer between the donor and acceptor of body material, cause the triplet energy level of material in itself to be drawn It is low, limit its application in industrialized production.
For the actual demand that current OLED shows Lighting Industry, the development of current OLED material is also far from enough, falls After the requirement of panel manufacturing enterprise, it is particularly important as the organic functional material of material enterprise development higher performance.
The content of the invention
In view of the above-mentioned problems existing in the prior art, the applicant provides a kind of compound of three benzos cycloheptene ketone And its application on organic electroluminescence device.The compounds of this invention be based on TADF mechanism, using three benzo cycloheptene ketones as Core, is applied to Organic Light Emitting Diode, the device that the present invention makes has good photo electric as luminescent layer material of main part Can, it disclosure satisfy that the requirement of panel manufacturing enterprise.
Technical scheme is as follows：The applicant provides a kind of chemical combination using three benzo cycloheptene ketone as core Thing, shown in the structure such as formula (1) of the compound：
In formula (1), m is expressed as Ar1Quantity, n is expressed as Ar2Quantity, p is expressed as Ar3Quantity；M, n, p distinguish Independent selection 0 or 1；
In formula (1), Ar1、Ar2、Ar3Expression-Ar-R or-R independently；Ar represents C1-10Alkyl replace or not Substituted aryl；
Wherein, R chooses hydrogen atom, C1-10Alkyl, C1-10The substituted or unsubstituted aryl of alkyl, formula (2) or formula (3) Shown structure, and at least one R chooses structure shown in formula (2) or formula (3)：
In formula (2), X1It is expressed as oxygen atom, sulphur atom, selenium atom, C1-10The alkylidene of straight or branched alkyl substitution, One kind in the tertiary amine groups that alkylidene, the alkyl or aryl of aryl substitution replace；R1、R2Selection hydrogen, C independently1-10Alkane Base, C4-20Aryl, structure shown in formula (4) or formula (5)：
In formula (4), a isWherein X2、X3Independently to be expressed as oxygen atom, sulphur former Son, selenium atom, C1-10The alkylidene of straight or branched alkyl substitution, the alkylidene of aryl substitution, the uncle of alkyl or aryl substitution One kind in amido；A passes through CL1-CL2Key, CL2-CL3Key, CL3-CL4Key, CL4-CL5Key, CL‘1-CL’2Key, CL‘2-CL’3Key, CL‘3- CL’4Key or CL‘4-CL’5Key is connected on formula (2)；
In formula (5), Ar4、Ar5Independently be expressed as C5-20Aryl, or C5-20Heteroaryl；
In formula (3), R3、R4Selection hydrogen, C independently1-10Alkyl, C4-20Aryl, formula (6) or formula (7) Shown structure：
In formula (6), b isWherein X2、X3Respectively oxygen atom, sulphur atom, selenium atom, C1-10One in the tertiary amine groups that alkylidene, the alkylidene of aryl substitution, the alkyl or aryl of straight or branched alkyl substitution replace Kind；B passes through CL1-CL2Key, CL2-CL3Key, CL3-CL4Key, CL‘1-CL’2Key, CL‘2-CL’3Key or CL‘3-CL’4Key is connected to formula (3) On；
In formula (7), Ar6、Ar7Independently be expressed as C5-20Aryl, or C5-20Heteroaryl.
It is preferred that, R concrete structure formula includes and is not limited in the formula (1)：
Any of.
It is preferred that, the concrete structure formula of the compound includes and is not limited to：
Any of.
The applicant additionally provides a kind of organic electroluminescence device for including the compound, and the compound is used as hair The material of main part of photosphere, for making OLED.
The applicant additionally provides the reaction equation occurred in a kind of method for preparing the compound, preparation process For：
In reaction equation 1, Y1, Y2 independently be expressed as chlorine atom, bromine atoms or iodine atom；
Wherein, the specific reactions steps of reaction equation 1 are as follows：The halogenated compound and RH of three benzo cycloheptene ketone are taken, is used Toluene dissolves；Add Pd2(dba)3, tri-butyl phosphine, sodium tert-butoxide；Under an inert atmosphere, it is the mixing of above-mentioned reactant is molten Liquid reacts 10~24 hours in 95~100 DEG C of reaction temperature, cooling, filtering reacting solution, filtrate revolving, crosses silicagel column, obtains Target product；
The halogenated compound of the three benzos cycloheptene ketone and RH mol ratio are 1:1.0~4.0；Pd2(dba)3With triphen And the mol ratio of the halogenated compound of cycloheptyl ketenes is 0.006~0.02:1, the halogen of tri-butyl phosphine and three benzo cycloheptene ketone Mol ratio for compound is 0.006~0.02:1, the mol ratio of the halogenated compound of sodium tert-butoxide and three benzo cycloheptene ketone For 1.0~3.0:1.
The present invention is beneficial to be had technical effect that：
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 as to realize reverse intersystem crossing under the conditions of thermostimulation. The compounds of this invention reconnects aromatic heterocycle group, possesses very strong rigidity, destroy point using three benzo cycloheptene ketone as parent nucleus Sub- symmetry, so that the crystallinity of saboteur, it is to avoid intermolecular aggtegation.
The compound structure intramolecular, as electron acceptor (acceptor, A), is conducive to comprising three benzo cycloheptene ketone Transmission of the electronics in luminescent layer.The heterocyclic group of connection is electron donor (donor, D), and it is conducive to hole in luminescent layer Transmission.Oxygen atom inside azepine xanthone is saturation atom, and it not only has very strong rigidity, also advantageously improves mother The combination of nuclear compound triplet energy level, electron donor and electron acceptor can improve the mobility in electronics and hole, reduction and open Dynamic voltage, improves the combined efficiency of exciton, improves device performance.
In summary, the compounds of this invention has high triplet energy level, while reducing the △ Est of molecule, makes chemical combination Thing triplet exciton is confined in luminescent layer, improves luminous efficiency, therefore the compounds of this invention is suitable as luminous layer main body material Material is used.Compound of the present invention can make as emitting layer material applied to OLED luminescent devices, be used as luminous layer main body Material can obtain good device performance, and the current efficiency of device, power efficiency and external quantum efficiency are greatly improved； Simultaneously for device lifetime lifting clearly.Compound-material of the present invention has good in OLED luminescent devices Application effect, with good industrialization prospect.
Brief description of the drawings
Fig. 1 is the structural representation of the organic electroluminescence device prepared using the compounds of this invention；
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
With reference to the accompanying drawings and examples, the present invention is specifically described.
Embodiment 1：The synthesis of R structures (shown in formula 3)
The preparation method of R structures (shown in formula 3)：
Weigh the adjacent bromine nitro compounds of raw material I, raw material II boric acid, be 2 with volume ratio:1 toluene alcohol mixed solvent is molten Solution, under an inert atmosphere, adds wet chemical, Pd (PPh3)4, react 10~24 hours, be cooled at 95~110 DEG C And filtering reacting solution, filtrate revolving, silicagel column is crossed, target product is obtained；Adjacent bromine nitro compound is with boric acid molar ratio 1:1.0~3.0；The mol ratio of adjacent bromine nitro compound and potassium carbonate is 1:1.0~3.0；Adjacent bromine nitro compound and Pd (PPh3)4Mol ratio be 1:0.006~0.02；
The product of previous step is weighed, is dissolved with o-dichlorohenzene, PPh is added3, under an inert atmosphere, by above-mentioned reactant Mixed solution in being reacted 10~15 hours at 160~180 DEG C of reaction temperature, cool down and filtering reacting solution, filtrate revolving, mistake Silicagel column, obtains target product；The nitro compound and PPh3Mol ratio be 1:1.0~3.0.
With the reaction intermediate D of compound 21Exemplified by：
500ml three-necked flask, under the atmosphere of nitrogen, adds the bromo- 2- nitros dibenzofurans of 0.04mol 1-, 0.10mol 4- dibenzofurans boric acid, 150ml toluene：Ethanol volume ratio is 2:1 mixed solvent, adds 0.12mol's Wet chemical, 0.0004mol Pd (PPh3)4, it is heated to reflux 24 hours, sample point plate, is shown without bromo-derivative at 120 DEG C Residue, reaction is complete；Room temperature is naturally cooled to, is filtered, filtrate carries out vacuum rotary steam (- 0.09MPa, 85 DEG C), neutral silica gel is crossed Post, obtains target product, purity 95%, yield 79.2%；250ml three-necked flask is separately taken, by 0.04mol obtained in the previous step Nitro compound is dissolved in 60ml o-dichlorohenzenes, adds 0.1mol PPh3, reacted 12 hours at 180 DEG C, sample point plate, Display is remaining without bromo-derivative, and reaction is complete；Room temperature is naturally cooled to, is filtered, filtrate carries out vacuum rotary steam, neutral silica gel post is crossed, Obtain target product, purity 96.8%, yield 70.6%.HRMS(m/z)：[M+H]+, theoretical value 348.1025, measured value 348.0942.It is as shown in table 1 with the product structure formula that above-mentioned synthetic method is prepared.
Table 1
Embodiment 2：The synthesis of R structures (shown in formula 2)
Reaction equation 3-1 preparation method is：Weigh the corresponding o-aminophenol of raw material 1, the ortho-nitrophenol of raw material 2, iodine, using molten Agent diethylene glycol (DEG) stirring and dissolving, is heated to reacting 12~24 hours at 250~270 DEG C under an inert atmosphere, sample point plate, question response After end, room temperature is naturally cooled to, there is solid precipitation, is filtered, is taken filter cake to cross neutral silica gel post, obtain intermediate E n；The neighbour The mol ratio of nitrophenols and o-aminophenol is 1:0.8~2.0；The mol ratio of the ortho-nitrophenol and iodine is 1:0.05~0.1；
Reaction equation 3-2 preparation method is：Corresponding bromo-derivative and the arylamine with methyl formate are weighed, is added Pd2(dba)3, tri-butyl phosphine, sodium tert-butoxide；Under an inert atmosphere, by the mixed solution of above-mentioned reactant in reaction temperature 95 ~110 DEG C, react 10~24 hours, cool down and filtering reacting solution, filtrate revolving crosses silicagel column, obtains target product；It is described The mol ratio of bromo-derivative and ester group compound is 1:0.8~2.0:0.8~2.0, Pd2(dba)3Mol ratio with bromo-derivative is 0.006~0.02:1, the mol ratio of tri-butyl phosphine and bromo-derivative is 0.006~0.02:1, sodium tert-butoxide and bromo-derivative rub You are than being 1.0~3.0:1；
Product obtained in the previous step is dissolved in THF, temperature THF is at -10~0 DEG C for control, and R- is slowly added dropwise thereto MgCl grignard reagent, is reacted at room temperature 10~24 hours, sample point plate, after question response terminates, filtering, filtrate decompression revolving, mistake Neutral silica gel post, obtains target product；The mol ratio of the grignard reagent and ester group compound is 2.0~3.0:1；
Under an inert atmosphere, alcohol obtained in the previous step is added into H at a temperature of -10~0 DEG C3PO4In, risen after completion of dropping To room temperature and insulation reaction 4~12 hours, sample point plate adds the NaOH aqueous solution and is neutralized to pH=7, add to reacting complete DCM (50ml × 3) is extracted, and takes organic phase, is filtered, and filtrate carries out vacuum rotary steam, is crossed neutral silica gel post, is obtained intermediate E n.
Reaction equation 3-2 specific implementation steps：With the reaction intermediate E of compound 321Exemplified by：
500ml there-necked flask, under the atmosphere for being passed through nitrogen, adds 0.04mol 2- bromine dibenzofurans, 0.06mol is adjacent Methyl anthranilate, 0.12mol sodium tert-butoxides, 4 × 10-4mol Pd2(dba)3, 4 × 10-4Mol tri-butyl phosphines, 250ml Toluene, is heated to reflux 24 hours, sample point plate, and reaction is complete, natural cooling, filtering, filtrate revolving, crosses silicagel column, obtains mesh Mark product, purity 97.36%, yield 75.8%；
500ml there-necked flask is separately taken, is led under nitrogen protection, 0.04mol previous step products, 100mlTHF, control is sequentially added The THF solution of the grignard reagent of methyl-magnesium-chloride containing 0.1mol is slowly added dropwise in temperature processed at -10~0 DEG C, reacts at room temperature 12 hours, Sample point plate, display is remaining without 2- bromobenzofurans, and reaction is complete；Filtering, filtrate carries out vacuum rotary steam, crosses neutral silica gel post, Obtain 2- (2- (dibenzo [b, d] furans -3- bases amino) phenyl) propan-2-ol, HPLC purity 99.1%, yield 75.9%；
500ml there-necked flask is taken again, is led under nitrogen protection, is added H3PO4200ml, is added at a temperature of -10~0 DEG C It is warmed to room temperature and is incubated anti-after 0.04mol2- (2- (dibenzo [b, d] furans -3- bases amino) phenyl) propan-2-ol, completion of dropping Answer 6 hours, sample point plate, display is remaining without (2- (dibenzo [b, d] furans -3- bases amino) phenyl) benzohydrol, reaction Completely；Add the NaOH aqueous solution and be neutralized to pH=7, add DCM (50ml × 3) extractions, take organic phase, filter, filtrate is subtracted Pressure revolving, crosses neutral silica gel post, obtains compound E1, HPLC purity 99.2%, yield 75.5%；HRMS(m/z)：[M+H]+, Theoretical value 300.1388, measured value 300.1329.
Reaction equation 3-1 specific implementation steps：With the reaction intermediate E of compound 332Exemplified by：
In 250ml there-necked flask, lead under nitrogen protection, sequentially add 0.05mol1- amino -9,9- dimethyl -9H- Fluorenes -2- alcohol, 0.06mol Ortho-Aminophenols, 0.005mol iodine, 60ml diethylene glycol (DEG)s, stirring and dissolving is heated to 270 DEG C and warm herein Degree is lower to protect 0 reaction 24 hours；Sample point plate, display is remaining without 1- amino -9,9- dimethyl -9H- fluorenes -2- alcohol, and reaction is complete；Instead After should terminating, room temperature is naturally cooled to, there is solid precipitation, is filtered, is taken filter cake to cross neutral silica gel post, obtain intermediate E 2, HPLC Purity 99.1%, yield 58.5%；HRMS(m/z)：[M+H]+, theoretical value 300.1388, measured value 300.1319.
Embodiment 3：The synthesis of the halogenated compound of three benzo cycloheptene ketone
Reaction equation 4-1 specific implementation steps：
Weigh three benzo cycloheptene ketone to be dissolved in acetic acid, 0 DEG C is cooled to ice salt bath；Bromine is weighed to be dissolved in glacial acetic acid, And be slowly added dropwise into the acetic acid solution containing three benzo cycloheptene ketone, after completion of dropwise addition, it is warmed to room temperature, stirring reaction is until anti- Should be complete；After reaction terminates, alkali lye neutralization is added into reaction solution, is extracted with dichloromethane, is layered, takes organic phase to filter, is filtered Liquid vacuum rotary steam crosses neutral silica gel post, obtains intermediate A n to without cut；The mol ratio of the three benzos cycloheptene ketone and bromine Example is 1:0.5~2；
Reaction equation 4-2 specific implementation steps：
Weigh raw material A n and starting boronic acid, dissolved with toluene, under an inert atmosphere, add potassium carbonate, four triphenyl phosphorus palladiums, Ethanol and water mixed liquid, stirring are warming up to 110~120 DEG C, react 10~24 hours；After reaction terminates, room temperature is cooled to, point Layer, organic phase is rotated to without cut, is crossed neutral silica gel post, is obtained intermediate B n.In above-mentioned reaction, raw material A n and starting boronic acid Mol ratio is 1:1~2；The mol ratio of raw material A n and potassium carbonate is 1:1~3；Raw material A n and four triphenyl phosphorus palladiums mol ratio is 1:0.01~0.05.
Embodiment 4：The synthesis of compound 1
In 250ml there-necked flask, the benzo cycloheptene ketone of 0.04mol tri-, 100ml acetic acid stirring and dissolvings, Ran Houyong are added Ice salt bath is cooled to 0 DEG C；By 0.06mol Br2It is dissolved in 50ml acetic acid, the acetic acid solution of bromine is slowly added dropwise to above-mentioned reaction In system, after completion of dropwise addition, 20-25 DEG C of stirring reaction of temperature control 12 hours；Sample point plate, display is remained without three benzo cycloheptene ketone It is remaining；After reaction terminates, NaOH aqueous solution neutralization reaction liquid is added dropwise, dichloromethane extraction is added, layering takes organic phase to filter, filtered Liquid vacuum distillation crosses neutral silica gel post, obtains intermediate A 1, HPLC purity 98.5%, yield 18.9% to without cut；
250ml four-hole bottle, under the atmosphere for being passed through nitrogen, adds 0.01mol A1,0.030mol carbazoles, 0.03mol Sodium tert-butoxide, 1 × 10-4mol Pd2(dba)3, 1 × 10-4Mol tri-butyl phosphines, 150ml toluene is heated to reflux 24 hours, taken Sampling point plate, reaction is complete, natural cooling, filtering, filtrate revolving, crosses silicagel column, obtains target product, purity 98.8%, yield 59.70%.HRMS(m/z)：[M+H]+, theoretical value 587.2123, measured value 587.2135.
Embodiment 5：The synthesis of compound 2
In 250ml there-necked flask, the benzo cycloheptene ketone of 0.04mol tri-, 100ml acetic acid stirring and dissolvings, Ran Houyong are added Ice salt bath is cooled to 0 DEG C；By 0.04mol Br2It is dissolved in 50ml acetic acid, the acetic acid solution of bromine is slowly added dropwise to above-mentioned reaction In system, after completion of dropwise addition, 20-25 DEG C of stirring reaction of temperature control 12 hours；Sample point plate, display is remained without three benzo cycloheptene ketone It is remaining；After reaction terminates, NaOH aqueous solution neutralization reaction liquid is added dropwise, dichloromethane extraction is added, layering takes organic phase to filter, filtered Liquid vacuum distillation crosses neutral silica gel post, obtains intermediate A 2, HPLC purity 97.2%, yield 23.8% to without cut；
500ml four-hole bottle, under the atmosphere for being passed through nitrogen, adds 0.01molA2,0.011mol is used bromobenzeneboronic acid Mixed solvent dissolves (180ml toluene, 90ml ethanol), then adds 0.03mol Na2CO3The aqueous solution (2M), is then added 0.0001mol Pd(PPh3)4, it is heated to reflux 24 hours, sample point plate, reaction is complete.Natural cooling, filtering, filtrate revolving, mistake Silicagel column, obtains intermediate product B2, HPLC purity 99.10%, yield 35.60%.
250ml four-hole bottle, under the atmosphere for being passed through nitrogen, adds 0.01mol intermediate Bs 2,0.015mol intermediates D1,0.03mol sodium tert-butoxide, 1 × 10-4mol Pd2(dba)3, 1 × 10-4Mol tri-butyl phosphines, 150ml toluene, are heated to reflux 24 hours, sample point plate, reaction was complete, natural cooling, filtering, filtrate revolving, crosses silicagel column, obtains target product, purity 98.60%, yield 57.30%.HRMS(m/z)：[M+H]+, theoretical value 678.2069, measured value 678.2057.
Embodiment 6：The synthesis of compound 3
250ml four-hole bottle, under the atmosphere for being passed through nitrogen, adds 0.01mol intermediate Bs 2,0.015mol 3,6- bis- Phenyl -9- hydrogen carbazoles, 0.03mol sodium tert-butoxides, 1 × 10-4mol Pd2(dba)3, 1 × 10-4Mol tri-butyl phosphines, 150ml first Benzene, is heated to reflux 24 hours, sample point plate, and reaction is complete, natural cooling, filtering, filtrate revolving, crosses silicagel column, obtains target Product, purity 99.60%, yield 70.50%.HRMS(m/z)：[M+H]+, theoretical value 650.2484, measured value 650.2487。
Embodiment 7：The synthesis of compound 5
In 250ml there-necked flask, the benzo cycloheptene ketone of 0.04mol tri-, 100ml acetic acid stirring and dissolvings, Ran Houyong are added Ice salt bath is cooled to 0 DEG C；By 0.04mol Br2It is dissolved in 50ml acetic acid, the acetic acid solution of bromine is slowly added dropwise to above-mentioned reaction In system, after completion of dropwise addition, 20-25 DEG C of stirring reaction of temperature control 12 hours；Sample point plate, display is remained without three benzo cycloheptene ketone It is remaining；After reaction terminates, NaOH aqueous solution neutralization reaction liquid is added dropwise, dichloromethane extraction is added, layering takes organic phase to filter, filtered Liquid vacuum distillation crosses neutral silica gel post, obtains intermediate A 3, HPLC purity 98.3%, yield 24.2% to without cut；
500ml four-hole bottle, under the atmosphere for being passed through nitrogen, adds 0.01molA3,0.011mol is used bromobenzeneboronic acid Mixed solvent dissolves (180ml toluene, 90ml ethanol), then adds 0.03mol Na2CO3The aqueous solution (2M), is then added 0.0001mol Pd(PPh3)4, it is heated to reflux 24 hours, sample point plate, reaction is complete.Natural cooling, filtering, filtrate revolving, mistake Silicagel column, obtains intermediate product B3, HPLC purity 99.50%, yield 41.50%.
250ml four-hole bottle, under the atmosphere for being passed through nitrogen, adds 0.01mol intermediate Bs 3,0.015mol 10H- spiral shells [acridine -9,9'- fluorenes], 0.03mol sodium tert-butoxides, 1 × 10-4mol Pd2(dba)3, 1 × 10-4Mol tri-butyl phosphines, 150ml Toluene, is heated to reflux 24 hours, sample point plate, and reaction is complete, natural cooling, filtering, filtrate revolving, crosses silicagel column, obtains mesh Mark product, purity 99.10%, yield 52.70%.HRMS(m/z)：[M+H]+, theoretical value 662.2484, measured value 662.2470。
Embodiment 8：The synthesis of compound 24
250ml four-hole bottle, under the atmosphere for being passed through nitrogen, adds 0.01mol intermediate Bs 3,0.015mol intermediates E1,0.03mol sodium tert-butoxide, 1 × 10-4mol Pd2(dba)3, 1 × 10-4Mol tri-butyl phosphines, 150ml toluene, are heated to reflux 24 hours, sample point plate, reaction was complete, natural cooling, filtering, filtrate revolving, crosses silicagel column, obtains target product, purity 98.80%, yield 62.00%.HRMS(m/z)：[M+H]+, theoretical value 630.2433, measured value 630.2445.
Embodiment 9：The synthesis of compound 31
250ml four-hole bottle, under the atmosphere for being passed through nitrogen, adds 0.01mol intermediate Bs 3,0.015mol intermediates E2,0.03mol sodium tert-butoxide, 1 × 10-4mol Pd2(dba)3, 1 × 10-4Mol tri-butyl phosphines, 150ml toluene, are heated to reflux 24 hours, sample point plate, reaction was complete, natural cooling, filtering, filtrate revolving, crosses silicagel column, obtains target product, purity 98.90%, yield 48.10%.HRMS(m/z)：[M+H]+, theoretical value 630.2433, measured value 630.2459.
Embodiment 10：The synthesis of compound 63
250ml four-hole bottle, under the atmosphere for being passed through nitrogen, adds 0.01mol intermediate Bs 3,0.015mol intermediates D3,0.03mol sodium tert-butoxide, 1 × 10-4mol Pd2(dba)3, 1 × 10-4Mol tri-butyl phosphines, 150ml toluene, are heated to reflux 24 hours, sample point plate, reaction was complete, natural cooling, filtering, filtrate revolving, crosses silicagel column, obtains target product, purity 97.90%, yield 59.80%.HRMS(m/z)：[M+H]+, theoretical value 614.2484, measured value 614.2475.
Embodiment 11：The synthesis of compound 68
250ml four-hole bottle, under the atmosphere for being passed through nitrogen, adds 0.01mol intermediate Bs 3,0.015mol intermediates D4,0.03mol sodium tert-butoxide, 1 × 10-4mol Pd2(dba)3, 1 × 10-4Mol tri-butyl phosphines, 150ml toluene, are heated to reflux 24 hours, sample point plate, reaction was complete, natural cooling, filtering, filtrate revolving, crosses silicagel column, obtains target product, purity 98.80%, yield 58.50%.HRMS(m/z)：[M+H]+, theoretical value 663.2436, measured value 663.2427.
Embodiment 12：The synthesis of compound 72
250ml four-hole bottle, under the atmosphere for being passed through nitrogen, adds 0.01mol intermediate Bs 3,0.015mol intermediates D2,0.03mol sodium tert-butoxide, 1 × 10-4mol Pd2(dba)3, 1 × 10-4Mol tri-butyl phosphines, 150ml toluene, are heated to reflux 24 hours, sample point plate, reaction was complete, natural cooling, filtering, filtrate revolving, crosses silicagel column, obtains target product, purity 99.50%, yield 68.00%.HRMS(m/z)：[M+H]+, theoretical value 663.2436, measured value 663.2447.
Embodiment 13：The synthesis of compound 77
250ml four-hole bottle, under the atmosphere for being passed through nitrogen, adds 0.01mol intermediate Bs 2,0.015mol intermediates D5,0.03mol sodium tert-butoxide, 1 × 10-4mol Pd2(dba)3, 1 × 10-4Mol tri-butyl phosphines, 150ml toluene, are heated to reflux 24 hours, sample point plate, reaction was complete, natural cooling, filtering, filtrate revolving, crosses silicagel column, obtains target product, purity 99.40%, yield 46.20%.HRMS(m/z)：[M+H]+, theoretical value 663.2436, measured value 663.2423.
Embodiment 14：The synthesis of compound 80
500ml four-hole bottle, under the atmosphere for being passed through nitrogen, adds 0.01molA3,0.011mol4'- bromo biphenyl -4- bases Boric acid, (180ml toluene, 90ml ethanol) is dissolved with mixed solvent, then adds 0.03mol Na2CO3The aqueous solution (2M), then Add 0.0001mol Pd (PPh3)4, it is heated to reflux 24 hours, sample point plate, reaction is complete.Natural cooling, filtering, filtrate rotation Steam, cross silicagel column, obtain intermediate product B4, HPLC purity 98.20%, yield 47.80%.
250ml four-hole bottle, under the atmosphere for being passed through nitrogen, adds 0.01mol intermediate Bs 4,0.015mol intermediates D3,0.03mol sodium tert-butoxide, 1 × 10-4mol Pd2(dba)3, 1 × 10-4Mol tri-butyl phosphines, 150ml toluene, are heated to reflux 24 hours, sample point plate, reaction was complete, natural cooling, filtering, filtrate revolving, crosses silicagel column, obtains target product, purity 98.50%, yield 53.10%.HRMS(m/z)：[M+H]+, theoretical value 690.2797, measured value 690.2802.
Embodiment 15：The synthesis of compound 92
250ml four-hole bottle, under the atmosphere for being passed through nitrogen, adds 0.01mol intermediate Bs 3,0.015mol intermediates D6,0.03mol sodium tert-butoxide, 1 × 10-4mol Pd2(dba)3, 1 × 10-4Mol tri-butyl phosphines, 150ml toluene, are heated to reflux 24 hours, sample point plate, reaction was complete, natural cooling, filtering, filtrate revolving, crosses silicagel column, obtains target product, purity 98.80%, yield 62.40%.HRMS(m/z)：[M+H]+, theoretical value 755.2699, measured value 755.2705.
Embodiment 16：The synthesis of compound 101
250ml four-hole bottle, under the atmosphere for being passed through nitrogen, adds 0.01mol intermediate Bs 3,0.015mol intermediates D8,0.03mol sodium tert-butoxide, 1 × 10-4mol Pd2(dba)3, 1 × 10-4Mol tri-butyl phosphines, 150ml toluene, are heated to reflux 24 hours, sample point plate, reaction was complete, natural cooling, filtering, filtrate revolving, crosses silicagel column, obtains target product, purity 98.90%, yield 63.40%.HRMS(m/z)：[M+H]+, theoretical value 781.3219, measured value 781.3210.
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 2.
Table 2
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.
From the data in table 2, it can be seen that the compounds of this invention has preferable oxidation-reduction stability, higher Tg is deposited membranaceous State is stable；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 3, compound 24, compound 68, change Compound 80 and compound CBP visualization HOMO, LUMO distribution map are as shown in table 3；
Table 3
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 17~27 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 18~27 is compared with embodiment 17, 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 17~27 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 17~27 uses of the present inventionization Compound.The structure composition of each embodiment obtained device is as shown in table 5.The performance test results of each device are as shown in table 6.
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 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 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 5 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 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 63 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 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 92 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 21
(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 3 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 22
(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 23
(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 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 24
(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 31 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 25
(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 77 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 26
(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 3, GH-204 and Ir (ppy) 3 are according to 70 for (TAPC, thickness 80nm)/luminescent layer 5:30:10 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)。
Embodiment 27
(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 77, 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 4
Table 5
Device code name Current efficiency (cd/A) Color The LT95 life-spans (Hr)
Embodiment 17 7.1 Green glow 4.2
Embodiment 18 8.9 Green glow 5.8
Embodiment 19 9.2 Green glow 5.2
Embodiment 20 8.2 Green glow 5.6
Embodiment 21 25.70 Green glow 7.0
Embodiment 22 26.90 Green glow 6.1
Embodiment 23 26.10 Green glow 5.5
Embodiment 24 28.40 Green glow 7.9
Embodiment 25 26.80 Green glow 9.5
Embodiment 26 29.10 Green glow 9.5
Embodiment 27 29.80 Green glow 10.5
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 17 is 4.1V (@1cd/m2), the startup voltage of embodiment 24 is 3.3V (@1cd/m2)。
The result of table 5 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 μ Uniformity coefficient between max, minimum value and average value,Value is bigger, illustrates that hot and humid environment processing influences on the efficiency of device Bigger, its practical application effect is poor, and commercial Application window is smaller；Conversely, shadow of the explanation device performance by hot and humid environment Sound is smaller, industrialized production is easily realized, product possesses the higher market competitiveness, with good commercial application prospect.
The luminescent device method of testing of reference implementation example 17~27, selection example 18, embodiment 24, embodiment 30 and right Ratio 1~3 carries out hot and humid environment processing, and its test result is as shown in table 6：
Table 6
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 (5)

1. a kind of compound using three benzo cycloheptene ketone as core, it is characterised in that the structure of the compound such as formula (1) It is shown：
In formula (1), m is expressed as Ar1Quantity, n is expressed as Ar2Quantity, p is expressed as Ar3Quantity；M, n, p are independently Selection 0 or 1；
In formula (1), Ar1、Ar2、Ar3Expression-Ar-R or-R independently；Ar represents C1-10Alkyl is substituted or unsubstituted Aryl；
Wherein, R chooses hydrogen atom, C1-10Alkyl, C1-10Shown in the substituted or unsubstituted aryl of alkyl, formula (2) or formula (3) Structure, and at least one R chooses structure shown in formula (2) or formula (3)：
In formula (2), X1It is expressed as oxygen atom, sulphur atom, selenium atom, C1-10Alkylidene, the aryl of straight or branched alkyl substitution One kind in substituted alkylidene, the tertiary amine groups of alkyl or aryl substitution；R1、R2Selection hydrogen, C independently1-10Alkyl, C4-20Aryl, structure shown in formula (4) or formula (5)：
In formula (4), a isWherein X2、X3Independently be expressed as oxygen atom, sulphur atom, selenium Atom, C1-10In the tertiary amine groups that alkylidene, the alkylidene of aryl substitution, the alkyl or aryl of straight or branched alkyl substitution replace One kind；A passes through CL1-CL2Key, CL2-CL3Key, CL3-CL4Key, CL4-CL5Key, CL‘1-CL’2Key, CL‘2-CL’3Key, CL‘3-CL’4Key Or CL‘4-CL’5Key is connected on formula (2)；
In formula (5), Ar4、Ar5Independently be expressed as C5-20Aryl, or C5-20Heteroaryl；
In formula (3), R3、R4Selection hydrogen, C independently1-10Alkyl, C4-20Aryl, shown in formula (6) or formula (7) Structure：
In formula (6), b isWherein X2、X3Respectively oxygen atom, sulphur atom, selenium atom, C1-10Directly One kind in chain or the alkylidene of branched alkyl substitution, the alkylidene of aryl substitution, the tertiary amine groups of alkyl or aryl substitution；B leads to Cross CL1-CL2Key, CL2-CL3Key, CL3-CL4Key, CL‘1-CL’2Key, CL‘2-CL’3Key or CL‘3-CL’4Key is connected on formula (3)；
In formula (7), Ar6、Ar7Independently be expressed as C5-20Aryl, or C5-20Heteroaryl.
2. compound according to claim 1, it is characterised in that in the formula (1) R concrete structure formula include and It is not limited to：
Any of.
3. compound according to claim 1, it is characterised in that the concrete structure formula of the compound includes and do not limited In：
Any of.
4. a kind of organic electroluminescence device for including any one of the claims 1 to 3 compound, it is characterised in that describedization Compound as luminescent layer material of main part, for making OLED.
5. a kind of method for preparing any one of claims 1 to 3 compound, it is characterised in that what is occurred in preparation process is anti- The equation is answered to be：
In reaction equation 1, Y1, Y2 independently be expressed as chlorine atom, bromine atoms or iodine atom；
Wherein, the specific reactions steps of reaction equation 1 are as follows：The halogenated compound and RH of three benzo cycloheptene ketone are taken, toluene is used Dissolving；Add Pd2(dba)3, tri-butyl phosphine, sodium tert-butoxide；Under an inert atmosphere, by the mixed solution of above-mentioned reactant in 95~100 DEG C of reaction temperature, reacts 10~24 hours, cooling, filtering reacting solution, filtrate revolving, crosses silicagel column, obtains target Product；
The halogenated compound of the three benzos cycloheptene ketone and RH mol ratio are 1:1.0~4.0；Pd2(dba)3With three benzo rings The mol ratio of the halogenated compound of heptenone is 0.006~0.02:1, tri-butyl phosphine is Halogenated with three benzo cycloheptene ketone The mol ratio of compound is 0.006~0.02:1, the mol ratio of the halogenated compound of sodium tert-butoxide and three benzo cycloheptene ketone is 1.0 ~3.0:1.
CN201710196612.6A 2017-03-29 2017-03-29 It is a kind of using three benzo cycloheptene ketone as the compound of core and its application in OLED Pending CN106977446A (en)

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JP2021050203A (en) * 2017-01-25 2021-04-01 四川知本快車創新科技研究院有限公司Ｓｉｃｈｕａｎ Ｋｎｏｗｌｅｄｇｅ Ｅｘｐｒｅｓｓ Ｉｎｓｔｉｔｕｔｅ Ｆｏｒ Ｉｎｎｏｖａｔｉｖｅ Ｔｅｃｈｎｏｌｏｇｉｅｓ Ｃｏ， Ｌｔｄ． Organic molecules for direct singlet capture in short emission decay time, and process of manufacturing optoelectronic products utilizing those organic molecules
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CN115304499A (en) * 2017-06-20 2022-11-08 三星显示有限公司 Condensed cyclic compound and organic light-emitting device including the same
CN107502343A (en) * 2017-09-05 2017-12-22 中节能万润股份有限公司 A kind of electroluminescent organic material and application
CN109574930A (en) * 2017-09-28 2019-04-05 江苏三月光电科技有限公司 A kind of compound of nitrogen-containing hetero heptatomic ring derivative, preparation method and applications
CN109575037A (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
CN109575038A (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 xanthene containing spiral shell and its application on organic electroluminescence device
CN110655438A (en) * 2018-06-29 2020-01-07 江苏三月光电科技有限公司 Cycloheptene-based compound and application thereof in organic electroluminescent device
CN116332828A (en) * 2021-12-10 2023-06-27 四川大学 Dibenzocycloheptanone derivatives and application thereof in OLED (organic light emitting diode) device

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