CN108530454A - A kind of fused-polycyclic compounds and its preparation method and application - Google Patents
A kind of fused-polycyclic compounds and its preparation method and application Download PDFInfo
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Abstract
The invention discloses a kind of fused-polycyclic compounds, have the structure as shown in formula (I) or formula (II).Above-mentioned fused-polycyclic compounds have high triplet and glass transition temperature, can ensure efficient transmission of the energy to guest materials as luminescent layer material of main part, and be not easy to crystallize, and are conducive to the luminous efficiency for improving device.The substituent group for adjusting fused-polycyclic compounds, makes it have electron-transport and hole transport performance concurrently, reduces its singlet and triplet is poor, widened the recombination region of carrier, prevented triplet excitons from burying in oblivion.The invention also discloses a kind of organic electroluminescence devices, contain above-mentioned fused-polycyclic compounds at least one functional layer, material of main part of the fused-polycyclic compounds as luminescent layer, with adjacent carrier blocking layers level-density parameter, while improving device light emitting efficiency, the driving voltage for reducing device is advantageously implemented the long-acting use of organic electroluminescence device.
Description
Technical field
The invention belongs to display technology fields, and in particular to a kind of fused-polycyclic compounds and its preparation method and application.
Background technology
Pope et al. is found that the Electroluminescence Properties of monocrystalline anthracene in nineteen sixty-five for the first time, this is the first electricity of organic compound
Photoluminescence phenomenon；1987, Tang of U.S.'s Kodak Company etc. succeeded in developing low electricity using Organic micromolecular semiconductor material
The Organic Light Emitting Diode (Organic Light-Emitting Diode, OLED) of pressure, high brightness.Two pole of organic electroluminescent
(Organic Light-Emitting Diode, OLED) is managed as a kind of novel display technology, there is self-luminous, width to regard
Angle, many advantages, such as low energy consumption, rich in color, corresponding speed is fast, Applicable temperature range is wide and can realize Flexible Displays, aobvious
Show has great application prospect with lighting area, is increasingly valued by people.
OLED mostly uses sandwich structure, i.e., organic luminous layer is clipped between two lateral electrodes.Luminescence mechanism is:In the external world
Under the driving of electric field, electrons and holes are injected into organic electron transport layer and hole transmission layer by cathode and anode respectively, and
Composition generation exciton in organic luminous layer, exciton radiation transistion return to ground state and shine.During electroluminescent, singlet swashs
Son and triplet excitons generate simultaneously, are speculated according to electron spin statistical law, the ratio of singlet exciton and triplet excitons
It is 1:3, ground state is returned in singlet exciton transition, and material fluoresces, and ground state is returned in triplet excitons transition, then material is phosphorescent.
Fluorescent material is electroluminescent organic material (the Organic Electroluminescent applied earliest
Materials), type is various, cheap, but is prohibited by electron spin and limited the singlet exciton that can only utilize 25%
It shines, internal quantum efficiency is relatively low, limits the efficiency of device.For phosphor material, acted on using the spin coupling of heavy atom,
The energy of singlet exciton is transferred to by intersystem crossing (ISC) in triplet excitons, and then sends out phosphorescence by triplet excitons,
It can theoretically realize 100% internal quantum efficiency.However, generally existing concentration quenching and triplet state-triplet state in phosphorescent devices
Bury in oblivion phenomenon, the luminous efficiency of device is made to be affected.
The OLED device made of doping way has advantage in the luminous efficiency of device, therefore emitting layer material is normal
It is formed using material of main part doping guest materials, wherein material of main part is the weight of the luminous efficiency and performance that influence OLED device
Want factor.4,4'-Bis (9H-carbazol-9-yl) biphenyl (CBP) are a kind of widely applied material of main parts, are had good
Good hole transporting property, but CBP as material of main part in use, the glass transition temperature due to CBP is low, be easy to tie again
Crystalline substance causes the performance of OLED device and luminous efficiency to reduce；On the other hand, the triplet energy state of CBP is adulterated less than blue light
Material, results in low to the efficiency of guest materials energy transfer from material of main part, reduces device efficiency.
Invention content
Therefore, the technical problem to be solved in the present invention is to overcome the triplet state of the material of main part of luminescent layer in the prior art
Energy level is low, easy crystallization, and the energy of material of main part cannot efficiently be transferred to guest materials, lead to the luminous efficiency and photism of device
The low defect of energy.
The present invention provides a kind of fused-polycyclic compounds, have the structure as shown in formula (I) or formula (II)：
Wherein, ring A separately indicates substituted or unsubstituted following radicals：Phenyl ring, 3 yuan to 7 yuan of saturation or portion
Divide undersaturated carbocyclic ring, the undersaturated heterocycle of 3 yuan to 7 yuan of saturation or part, the fused aromatic rings or C3~C30 of C6~C30
Annelated heterocycles；The ring A forms the condensed ring on shared one side with adjoining phenyl；
R1-R10 independently indicates hydrogen, halogen, cyano, alkyl, alkenyl, alkynyl, naphthenic base, alkoxy, silylation, virtue
Base or heteroaryl；
L is singly-bound, the substituted or unsubstituted aliphatic group of C1~C10, the substituted or unsubstituted aryl of C6~C60,
Or the substituted or unsubstituted heteroaryl of C3~C30；
Ar is hydrogen, halogen, cyano, alkyl, alkenyl, alkynyl, naphthenic base, alkoxy, silylation, aryl or heteroaryl；
The heterocycle, the annelated heterocycles and the heteroaryl separately have it is at least one independently selected from nitrogen,
The hetero atom of sulphur, oxygen, phosphorus, boron or silicon.
Preferably, above-mentioned fused-polycyclic compounds, the R1-R10 independently indicate hydrogen, halogen, cyano, C1~
The substituted or unsubstituted alkyl of C30, the substituted or unsubstituted alkenyl of C2~C30, the substituted or unsubstituted alkynes of C2~C30
Base, the substituted or unsubstituted naphthenic base of C3~C30, the substituted or unsubstituted alkoxy of C1-C30, the substitution of C1-C30 or
Unsubstituted silylation, the substituted or unsubstituted aryl of C6~C60 or the substituted or unsubstituted heteroaryl of C3~C30；
The Ar is hydrogen, halogen, cyano, and the substituted or unsubstituted alkyl of C1~C30 or does not take the substitution of C2~C30
The alkenyl in generation, the substituted or unsubstituted alkynyl of C2~C30, the substituted or unsubstituted naphthenic base of C3~C30, C1-C30's takes
Generation or unsubstituted alkoxy, the substituted or unsubstituted silylation of C1-C30, the substituted or unsubstituted aryl of C6~C60,
Or the substituted or unsubstituted heteroaryl of C3~C30.
Preferably, above-mentioned fused-polycyclic compounds, the ring A are selected from substituted or unsubstituted following radicals：
Phenyl ring, naphthalene nucleus, anthracene nucleus, phenanthrene ring, pyrene ring, ring, fluoranthene ring, pyridine ring, pyrrole ring, pyridine ring, pyrimidine ring, pyridazine
Ring, triazine ring, iso-indoles ring, indazole ring, fluorenyl ring, fluorenes and carbazole ring, purine ring, isoquinolin ring, imidazole ring, naphthyridines ring, phthalein
Piperazine ring, quinazoline ring, quinoxaline ring, cinnolines ring, quinoline ring, pteridine ring, phenanthridines ring, acridine ring, pah phenazine ring, phenanthroline ring, pheno
Piperazine ring, carboline ring, indole ring, carbazole ring, indolocarbazole ring, pyranoid ring, furan nucleus, dibenzofurans Huan , oxazole rings, thiazole
Basic ring, Thiadiazole, azepine dibenzofurans ring, imidazole ring, triaromatic amine, two aromatic amines, have 1~2 independently selected from
The heteroatomic pentamethylene of nitrogen, oxygen or sulphur has 1~3 heteroatomic hexamethylene independently selected from nitrogen, oxygen or sulphur, or
Condensed ring, loop coil or the connection ring being made of above-mentioned group；
The substituent group is selected from the alkyl of C1~C10, and the undersaturated carbocyclic ring of 3 yuan to 8 yuan of saturation or part has 1~3
A heteroatomic 3 yuan independently selected from nitrogen, oxygen or sulphur to 7 circle heterocyclic rings, the condensed-nuclei aromatics base of C6~C30 or C6~C30's
Condensed hetero ring base；
The condensed hetero ring base has at least one hetero atom independently selected from nitrogen, oxygen or sulphur.
Preferably, above-mentioned fused-polycyclic compounds, the Ar are selected from following any groups, and the R1-R10 is independently
Ground is selected from hydrogen or following any groups：
Wherein, X is nitrogen, oxygen or sulphur, and Y is each independently nitrogen or carbon；It is describedIn, the Y is at least
There are one be nitrogen；
N be 0~5 integer, m be 0~7 integer, p be 0~6 integer, q be 0~8 integer, t be 0~7 it is whole
Number；For separate room or double bond；
R11 is each independently hydrogen or the substituted or unsubstituted aryl of C6~C54；
Ar2It is each independently hydrogen, phenyl, pentalene base, indenyl, naphthalene, azulenyl, fluorenyl, heptalene base, pungent takes alkene
Base, two indenyl of benzo, acenaphthylene base, that non-alkenyl, phenanthryl, anthryl, three indenyls, fluoranthene base, vinegar phenanthryl, aceanthrene alkenyl, 9,10- benzene
And phenanthryl, pyrenyl, 1,2- benzos phenanthryl, butylbenzene base, naphthacene base, seven days of the week alkenyl, Pi base, base, five phenyl, pentacene, Asia
Tetraphenyl, cholanthrene base, helicene base, hexaphene base, rubicene base, coronene base, trinaphthylene base, heptaphene base, pyranthrene base, ovalene base, the heart
Cycloalkenyl group, anthanthrene base, trimeric indenyl, pyranose, benzopyranyl, furyl, benzofuranyl, isobenzofuran-base, oxygen
Miscellaneous anthryl, oxazolinyls, compel xanthene and xanthyl, thienyl, thioxanthene base, thianthrene group, phenoxathiin groups, sulphur at dibenzofuran group
Indenyl, isothianaphthene base, bithiophene base, aphthothiophenes base, dibenzothiophene, pyrrole radicals, pyrazolyl, tellurium oxazolyl, selenazoles base, thiophene
Oxazolyl, isothiazolyl, oxazolyls, furazanyl, pyridyl group, pyrazinyl, pyrimidine radicals, pyridazinyl, triazine radical, indolizine base, indyl,
Isoindolyl, indazolyl, purine radicals, quinazinyl, isoquinolyl, carbazyl, fluorenes and carbazyl, indolocarbazole base, imidazole radicals,
Naphthyridines base, phthalazinyl, quinazolyl, Benzodiazepine base, quinoxalinyl, cinnoline base, quinolyl, pteridyl, phenanthridinyl, acridine
Base, pah piperidinyl, phenanthroline, phenazinyl, carboline base, pheno tellurium piperazine base, phenoselenazine base, phenothiazinyl, phenoxazine groups, two thiophene of triphen
Piperazine base, azepine dibenzofuran group, triphendioxazine base, anthracene azine, benzothiazolyl, benzimidazolyl, benzoxazolyl,
Benzoxazine or benzisothia oxazolyl.
Preferably, above-mentioned fused-polycyclic compounds, the R1-R10 and the Ar include at least one electron-withdrawing group
Group.
Preferably, above-mentioned fused-polycyclic compounds have the molecular structure as shown in formula D-1~formula D-23.
The present invention provides a kind of preparation method of above-mentioned condensed compounds,
The synthesis step of compound shown in the formula (I) is as follows：
Using formula (A) compound represented and formula (C) compound represented as starting material, intermediate is obtained through coupling reaction
1；Intermediate 1 obtains intermediate 2 through cyclized condensation reaction；Intermediate 2 and R5, R6- magnesium bromides under the action of catalyst, are substituted
Intermediate 3 is obtained by the reaction；Intermediate 3, under the action of catalyst through coupling reaction, obtains intermediate with formula (B) compound represented
4；After the nitro of intermediate 4 is reduced, Cyclization intermediate 5；Intermediate 5 and compound Q-L-Ar under the action of catalyst,
It is substituted or coupling reaction, obtains formula (I) compound represented；
The synthesis path of compound shown in the formula (I) is as follows：
The synthesis step of compound shown in the formula (II) is as follows：
Using formula (D) compound represented and formula (E) compound represented as starting material, intermediate is obtained through coupling reaction
6；Intermediate 6 obtains intermediate 7 through cyclized condensation reaction；Intermediate 7 and R5, R6- magnesium bromides under the action of catalyst, are substituted
Intermediate 8 is obtained by the reaction；Intermediate 8 under the action of catalyst, intermediate is obtained through coupling reaction with formula (B) compound represented
9；After the nitro of intermediate 9 is reduced, Cyclization intermediate 10；Intermediate 10 and compound Q-L-Ar is in catalyst action
Under, it is substituted or coupling reaction, obtains formula (II) compound represented；
The synthesis path of compound shown in the formula (II) is as follows：
Wherein, Q is each independently fluorine, chlorine, bromine or iodine.
A kind of purposes the present invention provides above-mentioned fused-polycyclic compounds as electroluminescent organic material.
The present invention provides a kind of organic electroluminescence device, at least one function of the organic electroluminescence device
Contain above-mentioned fused-polycyclic compounds in layer.
Preferably, above-mentioned organic electroluminescence device, the functional layer are luminescent layer.
Preferably, above-mentioned organic electroluminescence device, the emitting layer material include that material of main part and object shine and contaminate
Material, the material of main part are the fused-polycyclic compounds.
Technical solution of the present invention has the following advantages that：
1, fused-polycyclic compounds provided by the invention have the structure as shown in formula (I) or formula (II).Above-mentioned is condensed
Polycyclic compound is using chromene and carbazole is as molecule parent nucleus, has obtained a kind of new electroluminescent organic material, material point
Son has high triplet state (T1) energy level and high glass transition temperature.Above-mentioned fused-polycyclic compounds are as luminescent layer master
When body material, due to its triplet height, material of main part can be promoted to the effective energy transmission of guest materials, reduce energy
Passback, improves the luminous efficiency of OLED device.The HOMO energy levels of fused-polycyclic compounds are high, the fermi level with hole injection layer
Matching is promoted, and then the hole injection efficiency of material molecule is made to get a promotion, to promote the luminous efficiency of device.
The glass transition temperature of fused-polycyclic compounds is high, and thermal stability and morphology stability are high, and filming performance is excellent
It is different, it is not easy to crystallize as luminescent layer material of main part, is conducive to the performance and luminous efficiency that promote OLED device.
2, fused-polycyclic compounds provided by the invention can be in substituent group by adjusting R1~R10 and Ar substituent groups
Electron-withdrawing group (pyridine, pyrimidine, triazine, pyrazine, oxadiazoles, thiadiazoles, quinazoline, imidazoles, quinoxaline, quinoline are introduced in group
Etc.), simultaneously the connection of carbazole work forms a kind of new quadripole material to electron-withdrawing group with the chromene with electron performance
Material, HOMO energy levels are distributed in electron donating group, and lumo energy is distributed in electron-withdrawing group, can realize HOMO energy levels and LUMO energy
Grade efficiently separates, and both has good hole transport performance, it may have good electronic transmission performance can realize balance
Charge transmits；Above-mentioned fused ring compound can expand hole and electronics is complex as exciton as electroluminescent organic material
Region, the exciton concentration of dilution unit volume prevent the concentration that triplet excitons cause due to high concentration from burying in oblivion or triplet state-
Triplet excitons are buried in oblivion.
(compound shown in Fig. 1 is the fused-polycyclic compounds described in D-5) as shown in Figure 1, fused-polycyclic compounds are logical
It crosses and HOMO and LUMO is distributed on differently electron donating group and electron-withdrawing group, by adjusting electron donating group and electrophilic
Group is adjusted HOMO and lumo energy distribution, the HOMO of compound is made to improve, and lumo energy reduces, and is improving material
While triplet, reduce material molecule singlet and triplet difference △ Est (<0.6eV), be conducive to three lines
State exciton promotes material of main part to guest materials to the anti-intersystem crossing of singlet excitonEnergy transfer reduces energy
Measure the loss in transmittance process.
By setting electron-donating group and electron-withdrawing group and its spatial position, the molecular configuration of torsion rigidity is realized, and
Intermolecular conjugated degree is adjusted, the triplet of material molecule is further increased, obtains small △ Est.Another party
Face, by the way that L and Ar is arranged, to adjust for the spacing distance between electron-withdrawing group and electron donating group and electron-withdrawing group,
So that lumo energy or HOMO energy levels is more evenly distributed on electron-withdrawing group or electron-donating group, advanced optimizes HOMO
And lumo energy.
2, the preparation method of fused-polycyclic compounds provided by the invention, starting material are easily obtained, and reaction condition is mild,
Operating procedure is simple, and a kind of simple, preparation side for being easily achieved is provided for the large-scale production of above-mentioned fused-polycyclic compounds
Method.
3, organic electroluminescent (OLED) device provided by the invention, containing above-mentioned condensed at least one functional layer
Polycyclic compound, wherein the functional layer is luminescent layer.
Above-mentioned fused-polycyclic compounds have high triplet, in the luminescent layer material of main part as OLED device
When, energy transmission of the material of main part to guest materials is may advantageously facilitate, prevents energy from returning.Meanwhile fused-polycyclic compounds
High glass transition temperature can prevent emitting layer material molecular crystalline, promote the performance and luminous efficiency of OLED device.
By adjusting substituent group, makes fused-polycyclic compounds while there is the quadripole of electrons and holes transmission performance
Property, emitting layer material more balances the transmission of charge and hole, can expand hole and electronics in luminescent layer and be complex as electronics
Region, reduce exciton concentration, prevent the triplet state-triplet state annihilation of device, improve device efficiency；And carrier can be made to answer
Adjacent interfaces of the region of conjunction far from luminescent layer and hole or electron transfer layer, improve the excitation purity of OLED device, while energy
Passback of the exciton to transport layer is enough prevented, device efficiency is further increased.
Above-mentioned fused-polycyclic compounds adjust the HOMO energy levels of material molecule using electron-donating group and electron-withdrawing group
And lumo energy, make the HOMO/LUMO energy levels and adjacent hole transmission layer, the energy level of electron transfer layer of luminescent layer material of main part
Match, be conducive to the injection of carrier, reduces the driving voltage of OLED device.
Above-mentioned fused-polycyclic compounds have small △ Est, triplet state converts anti-to singlet as material of main part
(RISC) rate height is passed through between system, can inhibit the dexter energy transfer (DET) from material of main part to luminescent dye, is promotedEnergy transfer improves singlet exciton ratio, while inhibiting triplet excitons, to greatly reduce dexter energy
The exciton loss of amount transfer (DET), effectively reduces the efficiency roll-off of organic electroluminescence device, the external quantum efficiency of device carries
It is high.
Description of the drawings
It, below will be to specific in order to illustrate more clearly of the specific embodiment of the invention or technical solution in the prior art
Embodiment or attached drawing needed to be used in the description of the prior art are briefly described, it should be apparent that, in being described below
Attached drawing is some embodiments of the present invention, for those of ordinary skill in the art, before not making the creative labor
It puts, other drawings may also be obtained based on these drawings.
Fig. 1 be the HOMO energy levels of fused-polycyclic compounds, LOMO energy levels shown in D-5 prepared by the embodiment of the present invention 1 and
The schematic diagram of △ Est；
Fig. 2 is the structure of organic electroluminescence device in 5~embodiment of the embodiment of the present invention 8, comparative example 1 and comparative example 2
Schematic diagram；
Reference sign：
1- anodes, 2- hole injection layers, 3- hole transmission layers, 4- luminescent layers, 5- electron transfer layers, 6- electron injecting layers,
7- cathodes.
Specific implementation mode
Technical scheme of the present invention is clearly and completely described below in conjunction with attached drawing, it is clear that described implementation
Example is a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, ordinary skill
The every other embodiment that personnel are obtained without making creative work, shall fall within the protection scope of the present invention.
In the description of the present invention, it should be noted that term " first ", " second ", " third " are used for description purposes only,
It is not understood to indicate or imply relative importance.
The present invention can be embodied in many different forms, and should not be construed as limited to embodiment set forth herein.
On the contrary, providing these embodiments so that the disclosure will be thorough and complete, and the design of the present invention will be fully conveyed to
Those skilled in the art, the present invention will only be defined by the appended claims.In the accompanying drawings, for clarity, the areas Ceng He can be exaggerated
The size and relative size in domain.It should be understood that when element such as layer is referred to as " being formed in " or " setting exists " another element
When "upper", which can be arranged directly on another element, or there may also be intermediary elements.On the contrary, working as element
When referred to as on " being formed directly into " or " being set up directly on " another element, intermediary element is not present.
Embodiment 1
The present embodiment provides a kind of fused-polycyclic compounds, have structure shown in following formula D-5：
The synthesis path of fused-polycyclic compounds shown in formula D-5 is as follows：
The preparation method of fused-polycyclic compounds shown in formula D-5 specifically includes following steps：
(1) synthetic intermediate 1-1
Under nitrogen protection, into two mouthfuls of reaction bulbs of 500mL, be added lithium hydroxide 1.6g, addition N-Methyl pyrrolidone and
7.44g formulas (A-1) compound represented and 7.6g formulas (C-1) compound represented is added in each 100mL of water, and stirring is lower to add people three
Two palladium chloroform adducts of acetylacetone,2,4-pentanedione.Then continue stirring 18 hours at 65 DEG C.After the completion of reaction, hydrochloric acid acidification is added, uses
Methyl tertiary butyl ether(MTBE) extracts, and after organic liquid phase is distilled off, crosses silicagel column and obtains 6.8g solid intermediate 1-1 (yields：70%)
(2) synthetic intermediate 2-1
Under nitrogen protection, 6.5g intermediates 1-1,100mL water, 100mL acetonitriles, 14.5g are added into the two-mouth bottle of 500mL
Sodium thiosulfate, mixing flow back 18 hours at 50 DEG C.It is cooled to room temperature, saturated sodium bicarbonate aqueous solution is added, with acetic acid second
Ester extracts, and revolving removes solvent, crosses silicagel column and obtains 3.3g solid intermediate 2-1 (yields：50%).
(3) synthetic intermediate 3-1
Under nitrogen protection, in the three-necked flask of 250mL, the tetrahydrochysene of the intermediate 2-1,100mL of 3.25g (10mmol) is added
Furans, is added 22mL (1M) methyl magnesium bromide solution at -20 DEG C, mixing, after room temperature reaction 6 hours, adds water quenching to go out reaction, with two
After chloromethanes extraction three times, revolving removes solvent, and obtained solid is transferred in 250mL three-necked flasks, and 120mL toluene, 1g is added
P-methyl benzenesulfonic acid, 2 hours postcoolings of heating reflux reaction to room temperature, revolving removes solvent after being extracted with toluene, crosses silicagel column
Obtain 2.8g solid intermediate 3-1 (yields：83%).
(4) synthetic intermediate 4-1
Under nitrogen protection, in 100mL three-necked flasks, 2.7g intermediates 3-1 (8mmol), 1.4g (8.2mmol) are weighed respectively
2- nitrophenyl boronic acids (that is, formula B compounds represented), 0.44g (0.4mmol) tetra-triphenylphosphine palladium, 2.0g sodium carbonate,
30mL toluene, 9mL ethyl alcohol, 9mL deionized waters, mixing are heated to 110 DEG C, after reacting 6 hours, are cooled to room temperature, reaction solution
Solvent is removed with revolving after being extracted with toluene, silicagel column is crossed and obtains 2.2g solid intermediates 4-1 (yield 70%).
(5) synthetic intermediate 5-1
Under nitrogen protection, in 100mL reaction bulbs, 2.1g solid intermediates 4-1 (5.5mmol), triphenylphosphine 3.6g is added
(13.5mmol), ortho-xylene 40mL, 180 DEG C are reacted 12 hours, and after vacuum distillation removes solvent, crossing silicagel column, to obtain 1.3g solid
Body intermediate 5-1 (yields：68%).
(6) synthesis fused-polycyclic compounds D-5
Under nitrogen protection, 1.2g intermediates 5-1 (3.34mmol), 1.06g compounds is added
(4.4mmol), 1.1g cesium carbonates (3.34mmol), 0.2g 4-dimethylaminopyridine (1.64mmol), dimethyl sulfoxide (DMSO) 20mL,
100 DEG C are reacted 3 hours, and after being cooled to room temperature, toluene extraction, revolving removes solvent, and crossing silicagel column, to obtain 1.5g solids condensed more
Cycle compound D-5 (yield 81%).
Elemental analysis：(C39H27N3O) theoretical value：C,84.61；H,4.92；N,7.59；O,2.89；Measured value：C,
84.59；H,4.94；N,7.55；O, 2.93, HRMS (ESI) m/z (M+)：Theoretical value：553.22；Measured value：553.56.
Embodiment 2
The present embodiment provides a kind of fused-polycyclic compounds, have structure shown in following formula D-4：
The synthesis path of fused-polycyclic compounds shown in formula D-4 is as follows：
The preparation method of fused-polycyclic compounds shown in formula D-4 specifically includes following steps：
(1) with synthetic method shown in embodiment 1, synthetic intermediate 5-1.
(2) synthesis fused-polycyclic compounds D-4
Under nitrogen protection, 1.2g intermediates 5-1 (3.34mmol), 22mg palladiums (0.1mmol), tri- tertiary fourths of 74mg is added
Base phosphine (0.4mmol), 1.32g compounds(3.34mmol), 0.9g sodium tert-butoxides, toluene
50mL, mixing, 110 DEG C are reacted 12 hours, and after being cooled to room temperature, chloroform extraction, revolving removes solvent, crosses silicagel column and obtains 1.8g
Solid fused-polycyclic compounds D-4 (yield 81%).
Elemental analysis：(C46H32N4O) theoretical value：C,84.12；H,4.91；N,8.53；O,2.44；Measured value：C,
84.09；H,4.95；N,8.51；O, 2.48, HRMS (ESI) m/z (M+)：Theoretical value：656.26；Measured value：656.47.
Embodiment 3
The present embodiment provides a kind of fused-polycyclic compounds, have structure shown in following formula D-12：
The synthesis path of fused-polycyclic compounds shown in formula D-12 is as follows：
(1) synthetic intermediate 1-2
Under nitrogen protection, into two mouthfuls of reaction bulbs of 500mL, be added lithium hydroxide 1.6g, addition N-Methyl pyrrolidone and
7.44g formulas (A-1) compound represented and 7.6g formulas (C-2) compound represented is added in each 100mL of water, and stirring is lower to add people three
Two palladium chloroform adducts of acetylacetone,2,4-pentanedione.Then continue stirring 18 hours at 65 DEG C.After the completion of reaction, hydrochloric acid acidification is added, uses
Methyl tertiary butyl ether(MTBE) extracts, and after organic liquid phase is distilled off, crosses silicagel column and obtains 6.8g solid intermediate 1-2 (yields：70%).
(2) synthetic intermediate 2-2
Under nitrogen protection, 6.5g intermediates 1-2,100mL water, 100mL acetonitriles, 14.5g are added into the two-mouth bottle of 500mL
Sodium thiosulfate, mixing flow back 18 hours at 50 DEG C.It is cooled to room temperature, saturated sodium bicarbonate aqueous solution is added, with acetic acid second
Ester extracts, and revolving removes solvent, crosses silicagel column and obtains 3.3g solid intermediate 2-2 (yields：50%).
(3) synthetic intermediate 3-2
Under nitrogen protection, in the three-necked flask of 250mL, the tetrahydrochysene of the intermediate 2-2,100mL of 3.25g (10mmol) is added
Furans, is added 22mL (1M) methyl magnesium bromide solution at -20 DEG C, mixing, after room temperature reaction 6 hours, adds water quenching to go out reaction, with two
After chloromethanes extraction three times, revolving removes solvent, and obtained solid is transferred in 250mL three-necked flasks, and 120mL toluene, 1g is added
P-methyl benzenesulfonic acid, 2 hours postcoolings of heating reflux reaction to room temperature, revolving removes solvent after being extracted with toluene, crosses silicagel column
Obtain 2.8g solid intermediate 3-2 (yields：83%).
(4) synthetic intermediate 4-2
Under nitrogen protection, in 100mL three-necked flasks, 2.7g intermediates 3-2 (8mmol), 1.4g (8.2mmol) are weighed respectively
2- nitrophenyl boronic acids (that is, formula B compounds represented), 0.44g (0.4mmol) tetra-triphenylphosphine palladium, 2.0g sodium carbonate,
30mL toluene, 9mL ethyl alcohol, 9mL deionized waters, mixing are heated to 110 DEG C, after reacting 6 hours, are cooled to room temperature, reaction solution
Solvent is removed with revolving after being extracted with toluene, silicagel column is crossed and obtains 2.2g solid intermediates 4-2 (yield 70%).
(5) synthetic intermediate 5-2
Under nitrogen protection, in 100mL reaction bulbs, 2.1g solid intermediates 4-2 (5.5mmol), triphenylphosphine 3.6g is added
(13.5mmol), ortho-xylene 40mL, 180 DEG C are reacted 12 hours, and after vacuum distillation removes solvent, crossing silicagel column, to obtain 1.3g solid
Body intermediate 5-2 (yields：68%).
(6) synthesis fused-polycyclic compounds D-12
Under nitrogen protection, 1.2g intermediates 5-2 (3.34mmol), 1.06g compounds is added
(4.4mmol), 1.1g cesium carbonates (3.34mmol), 0.2g 4-dimethylaminopyridine (1.64mmol), dimethyl sulfoxide (DMSO) 20mL,
100 DEG C are reacted 3 hours, and after being cooled to room temperature, toluene extraction, revolving removes solvent, and crossing silicagel column, to obtain 1.5g solids condensed more
Cycle compound D-12 (yield 81%).
Elemental analysis：(C41H27N3O2) theoretical value：C,82.95；H,4.58；N,7.08；O,5.39；Measured value：C,
82.91；H,4.62；N,7.07；O, 5.43, HRMS (ESI) m/z (M+)：Theoretical value：593.21；Measured value：593.37.
Embodiment 4
The present embodiment provides a kind of fused-polycyclic compounds, have structure shown in following formula D-13：
The synthesis path of fused-polycyclic compounds shown in formula D-13 is as follows：
(1) synthetic intermediate 1-3
Under nitrogen protection, into two mouthfuls of reaction bulbs of 500mL, be added lithium hydroxide 1.6g, addition N-Methyl pyrrolidone and
7.44g formulas (A-1) compound represented and 7.6g formulas (C-3) compound represented is added in each 100mL of water, and stirring is lower to add people three
Two palladium chloroform adducts of acetylacetone,2,4-pentanedione.Then continue stirring 18 hours at 65 DEG C.After the completion of reaction, hydrochloric acid acidification is added, uses
Methyl tertiary butyl ether(MTBE) extracts, and after organic liquid phase is distilled off, crosses silicagel column and obtains 6.8g solid intermediate 1-3 (yields：70%).
(2) synthetic intermediate 2-3
Under nitrogen protection, 6.5g intermediates 1-3,100mL water, 100mL acetonitriles, 14.5g are added into the two-mouth bottle of 500mL
Sodium thiosulfate, mixing flow back 18 hours at 50 DEG C.It is cooled to room temperature, saturated sodium bicarbonate aqueous solution is added, with acetic acid second
Ester extracts, and revolving removes solvent, crosses silicagel column and obtains 3.3g solid intermediate 2-3 (yields：50%).
(3) synthetic intermediate 3-3
Under nitrogen protection, in the three-necked flask of 250mL, the tetrahydrochysene of the intermediate 2-2,100mL of 3.25g (10mmol) is added
Furans, is added 22mL (1M) methyl magnesium bromide solution at -20 DEG C, mixing, after room temperature reaction 6 hours, adds water quenching to go out reaction, with two
After chloromethanes extraction three times, revolving removes solvent, and obtained solid is transferred in 250mL three-necked flasks, and 120mL toluene, 1g is added
P-methyl benzenesulfonic acid, 2 hours postcoolings of heating reflux reaction to room temperature, revolving removes solvent after being extracted with toluene, crosses silicagel column
Obtain 2.8g solid intermediate 3-3 (yields：83%).
(4) synthetic intermediate 4-3
Under nitrogen protection, in 100mL three-necked flasks, 2.7g intermediates 3-3 (8mmol), 1.4g (8.2mmol) are weighed respectively
2- nitrophenyl boronic acids (that is, formula B compounds represented), 0.44g (0.4mmol) tetra-triphenylphosphine palladium, 2.0g sodium carbonate,
30mL toluene, 9mL ethyl alcohol, 9mL deionized waters, mixing are heated to 110 DEG C, after reacting 6 hours, are cooled to room temperature, reaction solution
Solvent is removed with revolving after being extracted with toluene, silicagel column is crossed and obtains 2.2g solid intermediates 4-3 (yield 70%).
(5) synthetic intermediate 5-3
Under nitrogen protection, in 100mL reaction bulbs, 2.1g solid intermediates 4-3 (5.5mmol), triphenylphosphine 3.6g is added
(13.5mmol), ortho-xylene 40mL, 180 DEG C are reacted 12 hours, and after vacuum distillation removes solvent, crossing silicagel column, to obtain 1.3g solid
Body intermediate 5-3 (yields：68%).
(6) synthesis fused-polycyclic compounds D-13
Under nitrogen protection, 1.2g intermediates 5-3 (3.34mmol), 1.06g compounds is added
(4.4mmol), 1.1g cesium carbonates (3.34mmol), 0.2g 4-dimethylaminopyridine (1.64mmol), dimethyl sulfoxide (DMSO) 20mL,
100 DEG C are reacted 3 hours, and after being cooled to room temperature, toluene extraction, revolving removes solvent, and crossing silicagel column, to obtain 1.5g solids condensed more
Cycle compound D-13 (yield 81%).
Elemental analysis：(C41H27N3OS) theoretical value：C,80.76；H,4.46；N,6.89；O,2.62；S,5.26；Actual measurement
Value：C,80.76；H,4.48；N,6.87；O,2.66；S, 5.23, HRMS (ESI) m/z (M+)：Theoretical value：609.19；Measured value：
609.39。
Embodiment 5
The present embodiment provides a kind of organic electroluminescence devices, as shown in Fig. 2, including being cascading from bottom to top
Anode 1, hole injection layer 2, hole transmission layer 3, luminescent layer 4, electron transfer layer 5, electron injecting layer 6 and cathode 7.
Organic electroluminescence device Anodic selects ITO materials；Cathode 7 selects metal Al；
2 material selection HAT (CN) 6, HAT (CN) 6 of hole injection layer has chemical constitution as follows：
The compound of 3 material selection of hole transmission layer structure as described below：
The compound of 5 material selection of electron transfer layer structure as described below：
6 material of electron injecting layer is adulterated with electron injection material LiF by the compound of following shown structures and is formed：
Luminescent layer 32 is formed with material of main part and object luminescent dye codope in organic electroluminescence device, wherein main
Body material selection fused-polycyclic compounds D-5, guest materials select compound R D, the quality of material of main part and guest materials doping
Than being 100:5.Organic electroluminescent device is set to form following concrete structure：ITO/ hole injection layers (HIL)/hole transmission layer
(HTL)/organic luminous layer (fused-polycyclic compounds D-5 doped compound RD)/electron transfer layer (ETL)/electron injecting layer
(EIL/LiF)/cathode (Al).Fused-polycyclic compounds D-5, the chemical constitution of compound R D are as follows：
Material of main part in luminescent layer selects condensed heterocyclic compouds shown in formula D-5, have high triplet and
Glass transition temperature can ensure that energy is effectively transmitted from material of main part to guest materials, and prevent emitting layer material molecule
Crystallization.Meanwhile the compound has quadripole, the HOMO energy levels and lumo energy of material of main part are respectively positioned in different confessions
On electron group (chromene and carbazole) and electron-withdrawing group (quinazoline), the balance of charge and hole transport in material of main part
Property it is good, expand the region that hole and electronics in luminescent layer are complex as electronics, reduce exciton concentration, prevent the triplet state-of device
Triplet state is buried in oblivion, and device efficiency is improved；The region of Carrier recombination is passed far from luminescent layer and hole or electronics in material of main part
The adjacent interfaces of defeated layer improve the excitation purity of OLED device, while can prevent passback of the exciton to transport layer, further increase
Device efficiency.
The HOMO energy levels and lumo energy of condensed heterocyclic compouds D-5 and adjacent hole transmission layer, electron transfer layer phase
Matching makes OLED device have small driving voltage.
Condensed heterocyclic compouds D-5 singlets energy level is high, can ensure that material of main part is passed to the effective energy of guest materials
It passs, there is small poor (the Δ E of singlet and tripletST), promote anti-intersystem crossing of the triplet excitons to singlet exciton；
On the other hand, passing through (RISC) rate between the anti-system of height that material of main part triplet state T1 is converted to singlet S1 can inhibit from main body
Material promotes to the dexter energy transfer (DET) of luminescent dyeEnergy transfer reduces dexter energy and turns
The exciton loss for moving (DET) avoids the efficiency roll-off effect of organic electroluminescence device, the external quantum efficiency of device from improving, from
And realize high device efficiency.
Embodiment 6
The present embodiment provides the areas that organic electroluminescence device is provided in a kind of organic electroluminescence device, with embodiment 8
It is not only that：Luminescent layer material of main part selects the condensed heterocyclic compouds of following shown structures：
Embodiment 7
The present embodiment provides the areas that organic electroluminescence device is provided in a kind of organic electroluminescence device, with embodiment 8
It is not only that：Luminescent layer material of main part selects the condensed heterocyclic compouds of following shown structures：
Embodiment 8
The present embodiment provides the areas that organic electroluminescence device is provided in a kind of organic electroluminescence device, with embodiment 8
It is not only that：Luminescent layer material of main part selects the condensed heterocyclic compouds of following shown structures：
Comparative example 1
This comparative example provides a kind of organic electroluminescence device, with the area for providing organic electroluminescence device in embodiment 8
It is not only that：Luminescent layer material of main part selects 4,4'- bis- (9- carbazoles) biphenyl (referred to as：CBP).
Comparative example 2
This comparative example provides a kind of organic electroluminescence device, with the area for providing organic electroluminescence device in embodiment 8
It is not only that：Luminescent layer material of main part selects following compound：
Test case 1
1, glass transition temperature is measured
Glass transition temperature is carried out to this patent material to test, test model using differential scanning calorimeter (DSC)
Peripheral cell's temperature is to 400 DEG C, 10 DEG C/min of heating rate, under nitrogen atmosphere.
2, the toluene solution (substance withdrawl syndrome of condensed heterocyclic compouds is measured at a temperature of 298K and 77K respectively：
10-5Mol/L fluorescence) and phosphorescence spectrum, and according to calculation formula E=1240/ λ calculate corresponding singlet (S1) and
Triplet state (T1) energy level, and then the singlet-triplet for obtaining condensed heterocyclic compouds is poor.Wherein, annelated heterocycles chemical combination
The energy level difference of object is as shown in table 1 below：
Table 1
| Condensed heterocyclic compouds | Formula D-5 | Formula D-4 | Formula D-12 | Formula D-13 |
| Glass transition temperature (DEG C) | 161 | 168 | 165 | 167 |
| T1(eV) | 2.71 | 2.682.48 | 2.702.50 | 2.692.49 |
| S1-T1(eV) | 0.25 | 0.17 | 0.20 | 0.21 |
Test case 2
The characteristics such as electric current, voltage, brightness, the luminescent spectrum of device use 650 spectral scan luminance meters of PR and Keithley
2400 digital sourcemeter system synchronizations of K are tested.To the organic electroluminescence hair provided in embodiment 5-8 and comparative example 1, comparative example 2
Optical device is tested, and the results are shown in Table 2：
Table 2
The organic electroluminescence device provided in comparative example 5-8 and comparative example 1, comparative example 2 is tested, knot
Fruit is as shown in table 2, and the luminous efficiency of the OLED device provided in embodiment 5-8 drives electricity higher than the device in comparative example 1
The OLED device in comparative example 1 is forced down, illustrates that the condensed heterocyclic compouds provided using in the present invention shine as OLED device
The material of main part of layer can effectively improve the luminous efficiency of device, reduce the driving voltage of device.
Obviously, the above embodiments are merely examples for clarifying the description, and does not limit the embodiments.It is right
For those of ordinary skill in the art, can also make on the basis of the above description it is other it is various forms of variation or
It changes.There is no necessity and possibility to exhaust all the enbodiments.And it is extended from this it is obvious variation or
It changes still within the protection scope of the invention.
Claims (11)
1. a kind of fused-polycyclic compounds, which is characterized in that have the structure as shown in formula (I) or formula (II)：
Wherein, ring A separately indicates substituted or unsubstituted following radicals：Phenyl ring, 3 yuan to 7 yuan of saturation or part are not
The carbocyclic ring of saturation, the undersaturated heterocycle of 3 yuan to 7 yuan of saturation or part, the fused aromatic rings of C6~C30 or C3~C30's is thick
Close heterocycle；The ring A forms the condensed ring on shared one side with adjoining phenyl；
R1-R10 independently indicates hydrogen, halogen, cyano, alkyl, alkenyl, alkynyl, naphthenic base, alkoxy, silylation, aryl or
Heteroaryl；
L is singly-bound, the substituted or unsubstituted aliphatic group of C1~C10, the substituted or unsubstituted aryl of C6~C60, or
The substituted or unsubstituted heteroaryl of C3~C30；
Ar is hydrogen, halogen, cyano, alkyl, alkenyl, alkynyl, naphthenic base, alkoxy, silylation, aryl or heteroaryl；
The heterocycle, the annelated heterocycles and the heteroaryl separately have it is at least one independently selected from nitrogen, sulphur,
The hetero atom of oxygen, phosphorus, boron or silicon.
2. fused-polycyclic compounds according to claim 1, which is characterized in that
The R1-R10 independently indicates hydrogen, halogen, cyano, the substituted or unsubstituted alkyl of C1~C30, C2~C30's
Substituted or unsubstituted alkenyl, the substituted or unsubstituted alkynyl of C2~C30, the substituted or unsubstituted naphthenic base of C3~C30,
The substituted or unsubstituted alkoxy of C1-C30, the substituted or unsubstituted silylation of C1-C30 or do not take the substitution of C6~C60
The aryl in generation or the substituted or unsubstituted heteroaryl of C3~C30；
The Ar is hydrogen, and halogen, cyano, the substituted or unsubstituted alkyl of C1~C30, C2~C30's is substituted or unsubstituted
Alkenyl, the substituted or unsubstituted alkynyl of C2~C30, the substituted or unsubstituted naphthenic base of C3~C30, the substitution of C1-C30 or
Unsubstituted alkoxy, the substituted or unsubstituted silylation of C1-C30, the substituted or unsubstituted aryl of C6~C60, or
The substituted or unsubstituted heteroaryl of C3~C30.
3. according to fused-polycyclic compounds according to claim 1 or 2, which is characterized in that the ring A is selected from substitution or not
Substituted following radicals：
Phenyl ring, naphthalene nucleus, anthracene nucleus, phenanthrene ring, pyrene ring, ring, fluoranthene ring, pyridine ring, pyrrole ring, pyridine ring, pyrimidine ring, pyridazine ring,
Triazine ring, iso-indoles ring, indazole ring, fluorenyl ring, fluorenes and carbazole ring, purine ring, isoquinolin ring, imidazole ring, naphthyridines ring, phthalazines
Ring, quinazoline ring, quinoxaline ring, cinnolines ring, quinoline ring, pteridine ring, phenanthridines ring, acridine ring, pah phenazine ring, phenanthroline ring, azophenlyene
Ring, carboline ring, indole ring, carbazole ring, indolocarbazole ring, pyranoid ring, furan nucleus, dibenzofurans Huan , oxazole rings, thiazolyl
Ring, Thiadiazole, azepine dibenzofurans ring, imidazole ring, triaromatic amine, two aromatic amines, have 1~2 independently selected from nitrogen,
The heteroatomic pentamethylene of oxygen or sulphur has 1~3 heteroatomic hexamethylene independently selected from nitrogen, oxygen or sulphur, or by upper
State the condensed ring, loop coil or connection ring of group composition；
The substituent group is selected from the alkyl of C1~C10, and the undersaturated carbocyclic ring of 3 yuan to 8 yuan of saturation or part is only with 1~3
On the spot be selected from nitrogen, heteroatomic 3 yuan of oxygen or sulphur to 7 circle heterocyclic rings, the condensed-nuclei aromatics base of C6~C30 or C6~C30's is thick miscellaneous
Ring group；
The condensed hetero ring base has at least one hetero atom independently selected from nitrogen, oxygen or sulphur.
4. according to claim 1-3 any one of them fused-polycyclic compounds, which is characterized in that the Ar is selected from following any
Group, the R1-R10 are separately selected from hydrogen or following any groups：
Wherein, X is nitrogen, oxygen or sulphur, and Y is each independently nitrogen or carbon；It is describedIn, the Y at least one be
Nitrogen；
The integer that n is 0~5, the integer that m is 0~7, the integer that p is 0~6, the integer that q is 0~8, the integer that t is 0~7；For separate room or double bond；
R11 is each independently hydrogen or the substituted or unsubstituted aryl of C6~C54；
Ar2It is each independently hydrogen, phenyl, pentalene base, indenyl, naphthalene, azulenyl, fluorenyl, heptalene base, pungent takes alkenyl, benzo
Two indenyls, acenaphthylene base, that non-alkenyl, phenanthryl, anthryl, three indenyls, fluoranthene base, vinegar phenanthryl, aceanthrene alkenyl, 9,10- benzos phenanthryl,
Pyrenyl, 1,2- benzos phenanthryl, butylbenzene base, naphthacene base, seven days of the week alkenyl, Pi base, base, five phenyl, pentacene, tetraphenylene,
Cholanthrene base, helicene base, hexaphene base, rubicene base, coronene base, trinaphthylene base, heptaphene base, pyranthrene base, ovalene base, thimble alkenyl,
Anthanthrene base, trimeric indenyl, pyranose, benzopyranyl, furyl, benzofuranyl, isobenzofuran-base, oxa- anthryl,
Oxazolinyl, dibenzofuran group compel xanthene and xanthyl, are thienyl, thioxanthene base, thianthrene group, phenoxathiin groups, thianaphthenyl, different
It is thianaphthenyl, bithiophene base, aphthothiophenes base, dibenzothiophene, pyrrole radicals, pyrazolyl, tellurium oxazolyl, selenazoles base, thiazolyl, different
Thiazolyl, oxazolyls, furazanyl, pyridyl group, pyrazinyl, pyrimidine radicals, pyridazinyl, triazine radical, indolizine base, indyl, iso-indoles
Base, indazolyl, purine radicals, quinazinyl, isoquinolyl, carbazyl, fluorenes and carbazyl, indolocarbazole base, imidazole radicals, naphthyridines
Base, phthalazinyl, quinazolyl, Benzodiazepine base, quinoxalinyl, cinnoline base, quinolyl, pteridyl, phenanthridinyl, acridinyl, pah
Piperidinyl, phenanthroline, phenazinyl, carboline base, pheno tellurium piperazine base, phenoselenazine base, phenothiazinyl, phenoxazine groups, triphen dithiazine base,
Azepine dibenzofuran group, triphendioxazine base, anthracene azine, benzothiazolyl, benzimidazolyl, benzoxazolyl, benzo
Isoxazolyl or benzisothia oxazolyl.
5. according to claim 1-4 any one of them fused-polycyclic compounds, which is characterized in that the R1-R10 and Ar
It include at least one electron-withdrawing group.
6. according to claim 1-4 any one of them fused-polycyclic compounds, which is characterized in that have molecule knot as follows
Structure：
7. a kind of preparation method of the fused-polycyclic compounds as described in claim any one of 1-6, which is characterized in that
The synthesis step of compound shown in the formula (I) is as follows：
Using formula (A) compound represented and formula (C) compound represented as starting material, intermediate 1 is obtained through coupling reaction；In
Mesosome 1 obtains intermediate 2 through cyclized condensation reaction；Intermediate 2 and R5, R6- magnesium bromides under the action of catalyst, are substituted reaction
Obtain intermediate 3；Intermediate 3, under the action of catalyst through coupling reaction, obtains intermediate 4 with formula (B) compound represented；In
After the nitro of mesosome 4 is reduced, Cyclization intermediate 5；Intermediate 5 and compound Q-L-Ar under the action of catalyst, through taking
Generation or coupling reaction, obtain formula (I) compound represented；
The synthesis path of compound shown in the formula (I) is as follows：
The synthesis step of compound shown in the formula (II) is as follows：
Using formula (D) compound represented and formula (E) compound represented as starting material, intermediate 6 is obtained through coupling reaction；In
Mesosome 6 obtains intermediate 7 through cyclized condensation reaction；Intermediate 7 and R5, R6- magnesium bromides under the action of catalyst, are substituted reaction
Obtain intermediate 8；Intermediate 8 under the action of catalyst, intermediate 9 is obtained through coupling reaction with formula (B) compound represented；In
After the nitro of mesosome 9 is reduced, Cyclization intermediate 10；Intermediate 10 and compound Q-L-Ar under the action of catalyst, is passed through
Substitution or coupling reaction, obtain formula (II) compound represented；
The synthesis path of compound shown in the formula (II) is as follows：
Wherein, Q is each independently fluorine, chlorine, bromine or iodine.
8. a kind of purposes of claim 1-6 any one of them fused-polycyclic compounds as electroluminescent organic material.
9. a kind of organic electroluminescence device, which is characterized in that at least one functional layer of the organic electroluminescence device
In contain claim 1-6 any one of them fused-polycyclic compounds.
10. organic electroluminescence device according to claim 9, which is characterized in that the functional layer is luminescent layer.
11. organic electroluminescence device according to claim 10, which is characterized in that the emitting layer material includes main body
Material and object luminescent dye, the material of main part are the fused-polycyclic compounds.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110078692A (en) * | 2019-05-14 | 2019-08-02 | 河北德隆泰化工有限公司 | Organic Nan dian Yao fused ring compound, preparation method and its organic electroluminescence device |
| CN111499656A (en) * | 2020-04-08 | 2020-08-07 | 中山大学 | Nitrogen-sulfur hetero-fused ring hexacene compound and preparation method and application thereof |
| CN112961165A (en) * | 2021-02-18 | 2021-06-15 | 同济大学 | Preparation and application of novel carbazole benzopyran compound |
| CN113493450A (en) * | 2020-04-07 | 2021-10-12 | 中国科学院福建物质结构研究所 | Ligand compound, preparation method thereof and application thereof in asymmetric reaction |
| CN113912616A (en) * | 2021-10-13 | 2022-01-11 | 武汉华星光电半导体显示技术有限公司 | Organic compound, preparation method thereof and light-emitting device |
| CN114773323A (en) * | 2022-02-28 | 2022-07-22 | 陕西莱特光电材料股份有限公司 | Organic compound, organic electroluminescent device, and electronic device |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105916963A (en) * | 2014-01-17 | 2016-08-31 | 默克专利有限公司 | Materials for organic electroluminescent devices |
| CN107200746A (en) * | 2016-03-16 | 2017-09-26 | 德山新勒克斯有限公司 | Organic electronic element compound, uses the organic electronic element and its electronic installation of the compound |
-
2018
- 2018-05-25 CN CN201810516365.8A patent/CN108530454B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105916963A (en) * | 2014-01-17 | 2016-08-31 | 默克专利有限公司 | Materials for organic electroluminescent devices |
| CN107200746A (en) * | 2016-03-16 | 2017-09-26 | 德山新勒克斯有限公司 | Organic electronic element compound, uses the organic electronic element and its electronic installation of the compound |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110078692A (en) * | 2019-05-14 | 2019-08-02 | 河北德隆泰化工有限公司 | Organic Nan dian Yao fused ring compound, preparation method and its organic electroluminescence device |
| CN113493450A (en) * | 2020-04-07 | 2021-10-12 | 中国科学院福建物质结构研究所 | Ligand compound, preparation method thereof and application thereof in asymmetric reaction |
| CN111499656A (en) * | 2020-04-08 | 2020-08-07 | 中山大学 | Nitrogen-sulfur hetero-fused ring hexacene compound and preparation method and application thereof |
| CN112961165A (en) * | 2021-02-18 | 2021-06-15 | 同济大学 | Preparation and application of novel carbazole benzopyran compound |
| CN113912616A (en) * | 2021-10-13 | 2022-01-11 | 武汉华星光电半导体显示技术有限公司 | Organic compound, preparation method thereof and light-emitting device |
| CN114773323A (en) * | 2022-02-28 | 2022-07-22 | 陕西莱特光电材料股份有限公司 | Organic compound, organic electroluminescent device, and electronic device |
| CN114773323B (en) * | 2022-02-28 | 2023-05-16 | 陕西莱特光电材料股份有限公司 | Organic compound, organic electroluminescent device and electronic apparatus |
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