CN107915648A - Compounds and the organic luminescent device for including it - Google Patents

Compounds and the organic luminescent device for including it Download PDF

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Publication number
CN107915648A
CN107915648A CN201710941051.8A CN201710941051A CN107915648A CN 107915648 A CN107915648 A CN 107915648A CN 201710941051 A CN201710941051 A CN 201710941051A CN 107915648 A CN107915648 A CN 107915648A
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integer
compound
layer
hydrogen
substituted
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咸昊完
安贤哲
姜京敏
裴惟珍
金东骏
闵丙哲
金槿泰
李萤振
林东焕
林大喆
权桐热
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Dongjin Semichem Co Ltd
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Dongjin Semichem Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C07C211/57—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings being part of condensed ring systems of the carbon skeleton
    • C07C211/61—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings being part of condensed ring systems of the carbon skeleton with at least one of the condensed ring systems formed by three or more rings
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
    • H10K85/633—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine comprising polycyclic condensed aromatic hydrocarbons as substituents on the nitrogen atom
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H10K85/626—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing more than one polycyclic condensed aromatic rings, e.g. bis-anthracene

Abstract

The present invention relates to compounds and include its organic luminescent device.

Description

Compounds and the organic luminescent device for including it
Technical field
The present invention relates to compounds and include its organic luminescent device.
Background technology
In Organic Light Emitting Diode, the material as organic matter layer can be broadly dassified into luminescent material, sky according to function Hole injection material, hole transporting material, electron transport materials, electron injection material etc..Also, above-mentioned luminescent material can according to point Son amount is categorized as macromolecule and low molecule, and the phosphor of the singlet excited state from electronics can be categorized as according to luminescence mechanism The phosphor material of material and tri-state excited state from electronics, luminescent material can be categorized as blue, green, red according to illuminant colour Yellow and orange light emitting materials needed for color luminescent material and the more preferable natural colour of embodiment.Also, in order to increase excitation purity, and lead to Energy transfer increase luminous efficiency is crossed, main body/dopant class can be used as luminescent substance.If its principle is that will be sent out with main composition The main body of photosphere is compared, and the dopant that band gap is small and luminous efficiency is outstanding is mixed in luminescent layer on a small quantity, then is produced in main body Raw exciton is conveyed to dopant, so as to send efficient light.At this time, the wavelength of main body is moved to the wavelength band of dopant, The light of wavelength that thus can be according to needed for obtaining the species of the dopant and main body utilized.
So far, it is well-known to have multiple compounds as the material for being used in this organic luminescent device, but utilizing So far in the case of the organic luminescent device of well-known material, due to high driving voltage, low efficiency and short life, hold It is continuous to require to develop new material.Therefore, ongoing effort using the material with outstanding characteristic come develop with low voltage drive, High brightness and the organic luminescent device of long-life.
Prior art literature
Patent document
Japanese Laid-Open Patent 10-2015-530735
The content of the invention
The present invention provides novel organic compound and preparation method thereof and includes its organic luminescent device.
But problem to be solved by this invention is not limited to problem described above, the technical field of the invention Those of ordinary skill can be clearly understood that the other problems not described according to following contents.
The first embodiment of the present invention, there is provided the compound represented by formula 1 below.
Chemical formula 1
In above-mentioned chemical formula 1, R1And R2It is separately hydrogen, heavy hydrogen or C1-C6Alkyl, R3To R5It is separately Hydrogen, heavy hydrogen, C6-C30Aryl, C1-C6Alkyl, Ar1And Ar2It is separately substituted or unsubstituted C6-C30Aryl or substitution Or unsubstituted C6-C30Heteroaryl, Ar3For substituted or unsubstituted C6-C24Aryl or substituted or unsubstituted C6-C24Heteroaryl Base, L1And L2It is separately direct-coupling, C6-C30Arlydene or C6-C30Heteroarylidene, l are 1 to 4 integer, and m is 1 to 3 Integer, o be 1 to 4 integer.
Second embodiment of the present invention, there is provided the organic luminescent device of the compound comprising the present invention.
It is easy that the present invention forms dialkyl fluorene that arylamine key substitute suitable for phenyl and the second place of diaryl fluorene Injection and the highest occupied molecular orbital(HOMO) (HOMO) in conveying hole, and remain by substituted diaryl fluorenes portion high and minimum do not account for There is molecular orbit (LUMO), easily to obstruct electronics, therefore high efficiency is realized by being effectively formed in luminescent layer exciton Organic luminescent device.Also, substituted by the phenyl of dimethyl fluorene to expand conjugation, therefore the film of molecule and interface arrangement are excellent Show, so as to suppress phenomenon of roll-offing by quick hole flow (hole mobil ity), and realizes long lived devices, And in compared with low molecule, high Tg can be also maintained, the recrystallization of film is thus prevented to add driving stability.
The compound of the present invention has the effect of high luminous efficiency, high excitation purity etc., so as to be suitable for organic light emission Device, solar power generation organic optical device etc., thus can greatly contribute to organic hair of flexible display, lighting apparatus etc. Optical diode (OLED) industry.
Brief description of the drawings
Fig. 1 shows the schematic diagram of the organic luminescent device of an example of the invention.
The explanation of reference numeral
100：Base material
200：Hole injection layer
300：Hole transporting layer
400：Luminescent layer
500：Electron supplying layer
600：Electron injecting layer
1000：Anode
2000：Cathode
Embodiment
Hereinafter, referring to the drawings, the example and embodiment that the present invention will be described in detail so that the technical field of the invention it is general Logical technical staff can easily implement.
But the present invention can by it is a variety of it is different in the form of realize, and be not limited to example described herein and embodiment. Also, in figure, in order to clearly state the present invention, the part unrelated with explanation is eliminated, in the specification, for similar Part, be labelled with similar reference numeral.
In description of the invention full text, when a component be located at another component " on " when, not only including a component with The situation that another component is in contact, further includes and there is a situation where miscellaneous part between the two elements.
In description of the invention full text, when one structural element of a part " comprising ", unless there are especially opposite Record, then mean to may also include other structures key element, rather than exclude other structures key element.In description of the invention full text The term " about " that uses, " substantial " when prompting intrinsic preparation and material tolerance in mentioned implication with its numerical value or Implication close to its numerical value uses, and is undeservedly utilized with the infringer for preventing against one's conscience and is referred to help to understand the present invention The disclosure of accurate or absolute numerical value.Description of the invention full term "~() step " used herein or "~ Step " does not mean that " be used for~the step of ".
In description of the invention full text, in the performance of Markush (Markush) form contained " these combination " this One term means one or more of group that described multiple structural elements in the performance by Markush form form Mixing or combination, it is meant that including selected from one or more of group being made of above-mentioned multiple structural elements.
In description of the invention full text, " A and/or B " this record mean " A or B, or A and B ".
In description of the invention full text, term " aryl " means to include C5-30Aromatic cyclic hydrocarbon group, for example, benzyl Base, phenyl, naphthyl, xenyl, terphenyl, fluorenyl, phenanthryl, triphenyl alkenyl, phenylakenyl, Qu Ji, fluorane thenyl, Benzo fluorenyl, benzo triphenyl alkenyl, benzo bend the aromatic ring of base, anthryl, stilbenyl, pyrenyl etc., " heteroaryl " As the aromatic ring for including at least one miscellaneous element, such as, it is meant that include pyrrolinyl, pyrazinyl, pyridine radicals, indoles Base, isoindolyl, furyl, benzofuranyl, isobenzofuran-base, dibenzofuran group, aisaa benzothiophenyl, hexichol acene sulphur Base, quinolyl, isoquinolyl, quinoxalinyl, carbazyl, luxuriant and rich with fragrance cry base, acridinyl, phenanthroline, thienyl and by pyridine ring, pyrrole Piperazine ring, pyrimidine ring, pyridazine ring, triazine ring, indole ring, quinoline ring, acridine ring, pyrrolidine ring, dioxanes ring, piperidine ring, morpholine Ring, piperazine ring, carbazole ring, furan nucleus, thiphene ring, oxazole ring, oxadiazoles ring, benzoxazoles ring, thiazole ring, thiadiazole ring, benzene And the aromatic heterocycle that thiazole ring, triazole ring, imidazole ring, benzimidazole ring, pyranoid ring, dibenzofurans ring are formed.
In description of the invention full text, term " alkyl " can include the saturation of straight or branched or undersaturated C1-C6Alkane Base, for example, methyl, ethyl, propyl group, butyl, amyl group, hexyl or these possible all isomers can be included, but have can Can be not limited to this.
In description of the invention full text, in term " substituted or unsubstituted ", " substitution " mean can by selected from by Heavy hydrogen, halogen, amino, itrile group, nitro or C1~C20Alkyl, C2~C20Alkenyl, C1~C20Alkoxy, C3~C20Ring Alkyl, C3~C20Heterocyclylalkyl, C6~C30Aryl and C5~C30The base of one or more of group of heteroaryl composition take Generation.
Also, in description of the invention full text, referred to unless there are special, identical mark can then have identical contain Justice.
The first embodiment of the present invention, there is provided the compound represented by formula 1 below.
Chemical formula 1
R1And R2It is separately hydrogen, heavy hydrogen or C1-C6Alkyl, R3To R5It is separately hydrogen, heavy hydrogen, C6-C30Virtue Base, C1-C6Alkyl, Ar1And Ar2It is separately substituted or unsubstituted C6-C30Aryl or substituted or unsubstituted C6-C30 Heteroaryl, Ar3For substituted or unsubstituted C6-C24Aryl or substituted or unsubstituted C6-C24Heteroaryl, L1And L2Independently Ground is direct-coupling, C6-C30Arlydene or C6-C30Heteroarylidene, l are 1 to 4 integer, and m is 1 to 3 integer, and o is 1 to 4 Integer.
In the example of the present invention, the compound of above-mentioned chemical formula 1 can be included by 3 table of formula 2 below or chemical formula The compound shown.
Chemical formula 2
Chemical formula 3
In multiple above-mentioned chemical formulas, R1And R2It is separately hydrogen, heavy hydrogen or C1-C6Alkyl, R3To R7Independently Ground is hydrogen, heavy hydrogen, C6-C30Aryl, C1-C6Alkyl, Ar3For substituted or unsubstituted C6-C24Aryl is substituted or unsubstituted C6-C24Heteroaryl, L1And L2It is separately C6-C30Aryl or C6-C30Heteroaryl, l are 1 to 4 integer, and m and n are 1 to 3 Integer, o is 1 to 4 integer, and p and q are 1 to 5 integer.
In the example of the present invention, above-claimed cpd can include the chemical combination represented by formula 4 below or chemical formula 5 Thing.
Chemical formula 4
Chemical formula 5
In multiple above-mentioned chemical formulas, R1To R7、Ar3, m, n, o, p and q as defined in chemical formula 1 to 3, r is 0 to 3 Integer.
In the example of the present invention, above-claimed cpd can include the compound of formula 6 below.
Chemical formula 6
In multiple above-mentioned chemical formulas, R1To R7、Ar3, m, n, o, p and q be as defined in chemical formula 1 to 3.Specifically, The N of arylamine is attached in the second place of dialkyl fluorene, in this case, can have the HOMO for being suitable for hole transporting layer, Thus can be conducive to improve driving voltage.
For the example of the present invention, in above-mentioned chemical formula 1 to 6, Ar3Optional free phenyl, xenyl, three In the group that phenyl, fluorenyl, naphthyl, dimethyl fluorene and combinations thereof form, for example, it may be phenyl, xenyl or terphenyl Base.Also, above-mentioned phenyl, xenyl, terphenyl, fluorenyl, naphthyl or dimethyl fluorene can be by C6-C30Aryl substitutes, such as by Phenyl substitutes.In this case, especially maintain electronics to obstruct easy LUMO, when process is deposited, can with low temperature into Row control.
For the example of the present invention, in above-mentioned chemical formula 1 to 6, R1And R2Separately can be hydrogen or C1-C6Alkyl, R3To R7Can be hydrogen.
For the example of the present invention, in above-mentioned chemical formula 1 to 6, work as R1And R2It is separately C1-C6Alkane During base, substituted phenyl is attached to first to fourth position of dialkyl fluorene, such as is attached to second or the third place.
For the example of the present invention, in above-mentioned chemical formula 1 to 6, work as R1And R2It is separately C1-C6Alkane During base, arylamine can be coupling in the second place of dialkyl fluorene.
In the example of the present invention, the compound of above-mentioned chemical formula 1 can be prepared by formulas below 1, but have can Can be not limited to this.
Reaction equation 1
In the example of the present invention, above-mentioned organic luminescent compounds can include following compound, it is likely that not limiting to In this.
In above-mentioned particular compound, following compound can be more suitable in N direct-couplings at least two fluorenyls to have In the HOMO of hole transporting layer, and there can be faster hole flow.Thus, driving voltage can be more reduced, and more improves effect Rate and service life.
Second embodiment of the present invention, there is provided include the organic luminescent device of the compound represented by above-mentioned chemical formula 1. Above-mentioned organic luminescent device can include having for more than one layer containing the compounds of this invention between first electrode and second electrode Machine nitride layer.
In the example of the present invention, above-mentioned organic matter layer can be hole injection layer, hole transporting layer and the auxiliary that shines More than one layer in layer, it is likely that not limited to this, at this time, compound of the invention can be used alone or with it is known organic Luminophor is used together.
The present invention an example in, above-mentioned organic luminescent device may include the organic matter layer containing cavity conveying material and Organic matter layer containing the compound represented by above-mentioned chemical formula 1, it is likely that not limited to this.
Above-mentioned organic luminescent device can include more than one hole between anode (anode) and cathode (cathod) and note Enter having for layer (HIL), hole transporting layer (HTL), luminescent layer (E ML), electron supplying layer (ETL), electron injecting layer (EIL) etc. Machine nitride layer.
For example, above-mentioned organic luminescent device can be prepared according to structure described in Fig. 1.Organic luminescent device is extremely The electricity of anode (hole injecting electrode 1000)/200/ hole transporting layer of hole injection layer, 300/ luminescent layer 400/ is stacked gradually on down Sub- 500/ electron injecting layer of transfer layer, 600/ cathode (electron injection electrode 2000).
In Fig. 1, the substrate for organic luminescent device can be used in substrate 100, can be mechanical strength, hot steady especially Qualitative, transparent, surface smoothness, ease of handling and the outstanding transparent glass substrate or flexible plastic base of water proofing property Plate.
Hole injecting electrode 1000 is used as the anode for being used to be injected with the hole of machine luminescent device.In order to which hole can be injected, , can be by tin indium oxide (ITO), indium zinc oxide (IZO), graphene (graphene) etc using the material with low work function Transparent material formed.
By vacuum deposition method, spin-coating method, casting, LB (Langmuir-Blodgett) method etc. come in above-mentioned anode electricity Pole overburden hole injection layer material, thus can form hole injection layer 200.Sky is being formed by above-mentioned vacuum deposition method In the case of the implanted layer of cave, its sedimentary condition because the material as hole injection layer 200 compound, needed for hole injection layer Structure and thermal characteristics etc. and it is different, but usually can 50-500 DEG C depositing temperature, 10-8To 10-3The vacuum of tor r, 0.01 ExtremelyDeposition velocity,Suitably made choice in the range of to 5 μm of layer thickness.
Then, by vacuum deposition method, spin-coating method, casting, LB methods etc. come in above-mentioned 200 overburden of hole injection layer Hole transporting layer material, thus can form hole transporting layer 300.Hole transporting layer is being formed by above-mentioned vacuum deposition method In the case of, its sedimentary condition is different because of the compound used, but typically it will be preferred to, in the formation with hole injection layer almost Made choice in identical condition and range.Afterwards, by vacuum deposition method, spin-coating method, casting, LB methods etc. come in above-mentioned hole Transfer layer overburden luminescent layer material, thus can form luminescent layer 400.Luminescent layer is being formed by above-mentioned vacuum deposition method In the case of, its sedimentary condition is different because of the compound used, but typically it will be preferred to, it is several in the formation with hole injection layer Made choice in identical condition and range.Also, known compound can be used as main body or doping by above-mentioned emitting layer material Agent.
Also, in luminescent layer, in the case of being used together with phosphorescent dopants, in order to prevent triplet excitons or hole to The phenomenon of electron supplying layer diffusion, can also be laminated hole by vacuum deposition method or spin-coating method and suppress material (HBL).It can make at this time Hole inhibiting substances are not particularly limited, but can select any thing from the known material for suppressing material as hole Matter utilizes.For example, oxadiazole derivatives or triazole derivative, phenanthroline derivative or Japanese Unexamined Patent Publication 11- can be enumerated Described hole suppresses material etc. in 329734 (A1), typically, can be used Balq (double (8- hydroxy-2-methylquinolines)- Aluminium biphenyl phenates), phenanthroline (phe nanthrolines) class compound (such as：BCP (the B of general purpose display (UDC) company Asso Coupoline)) etc..
On 400 top of luminescent layer as formed above formed with electron supplying layer 500, at this time, above-mentioned electron supplying layer can lead to The methods of crossing vacuum deposition method, spin-coating method, casting is formed.Also, the sedimentary condition of above-mentioned electron supplying layer is because using Compound and it is different, but typically it will be preferred to, made choice in the almost identical condition and range of the formation with hole injection layer.
Afterwards, electron injecting layer 600 can be formed in above-mentioned 500 overburden electron injecting layer material of electron supplying layer, At this time, above-mentioned electron supplying layer can form conventional electron injection by the method for vacuum deposition method, spin-coating method, casting etc. Layer material.
This can be used in hole injection layer 200, hole transporting layer 300, luminescent layer 400, the electron supplying layer 500 of above-mentioned device The compound of invention or following material, alternatively, the compound of the present invention and known material can be used together.
The moon for being used for injecting electronics is formed on electron injecting layer 600 by the method for vacuum deposition method or sputtering method etc. Pole 2000.As cathode, various metals can be used.Concrete example has the material of aluminium, gold, silver etc..
The organic luminescent device of the present invention can not only use anode, hole injection layer, hole transporting layer, luminescent layer, electricity Sub- transfer layer, electron injecting layer, the organic luminescent device of cathode construction, can also use the knot of the organic luminescent device of various structures Structure, as needed, can also form the intermediate layer of one or two layers.
As described above, the thickness of each organic matter layer formed according to the present invention can be adjusted according to required degree Section, it is preferable that it is specially 10 to 1000nm, more specifically 20 to 150nm.
Also, the organic matter layer in the present invention, comprising the compound represented by above-mentioned chemical formula 1 can be by organic matter layer Thickness is adjusted to molecular unit, thus has the advantages that surface is uniform and morphological stability protrudes.
For the organic luminescent compounds of present embodiment, what the applicable first embodiment for the present invention was recorded Content, it is likely that not limited to this.
Hereinafter, more specific description is carried out by the embodiment of the present invention, the scope of the present invention is not limited to the present embodiment.
Embodiment
Preparation example 1
The synthesis of IM
In order to synthesize purpose compound, synthesized by above-mentioned steps, to prepare IM.
The synthetic method of following IM1 is as follows.
In round-bottomed flask, in Isosorbide-5-Nitrae-dioxanes of 200ml dissolve 15.0g bromo- 9, the 9- dimethyl -9H- fluorenes of 2- and The phenylboric acid of 7.4g, and it is put into the K of 80ml2CO3Pd (the PPh of (2M) and 1.9g3)4Afterwards, it is refluxed.By thin Layer chromatography (TLC) confirms reaction, and after adding water, reaction was completed.Organic layer is extracted with dichloromethane (MC), and depressurized After filter, column purification is carried out to obtain the intermediate compound I M1-1 of 10.69g (yield 72%).
In round-bottomed flask, in the dimethylformamide (DMF) of 100ml after the above-mentioned IM1-1 of dissolving 10.0g, slowly The solution for the DMF that the NBS of 6.6g is dissolved in 50ml is instilled, when stirring 6 is small.Confirm to react by thin-layered chromatography (TLC), add After adding water, reaction was completed.After being filtered under diminished pressure, recrystallized to obtain the IM1 of 8.7g (yield 67%).
Using the method for such as above-mentioned IM1, change initial substance to have synthesized following IM2 to I M4.
The synthesis of OP
In order to synthesize purpose compound, synthesized by above-mentioned steps, to prepare OP.
The synthetic method of following OP1 is as follows.
In round-bottomed flask, bromo- 9, the 9- diphenyl -9H- fluorenes of 2-, the benzene of 2.6g of 10.0g are dissolved in the toluene of 130ml Amine, 3.6g t-BuONa, 0.9g Pd2(dba)3And (t-Bu) of 1.1ml3After P, it is refluxed.Pass through thin layer color Spectrometry confirms to react, and after adding water, reaction was completed.Organic layer is extracted with dichloromethane (MC), and carries out being filtered under diminished pressure it Afterwards, column purification and recrystallization are carried out, so as to obtain the OP1 of 7.22g (yield 70%).
Using the method for such as above-mentioned OP1, change initial substance, so as to synthesize following OP2 to OP7.
Synthesis example 1：The synthesis of compound 1
In round-bottomed flask, in the toluene of 110ml dissolve 5.0g IM1,6.5g OP1,2.0g t-BuONa, The Pd of 0.5g2(dba)3And (t-Bu) of 0.65ml3After P, it is refluxed.Confirm to react by thin-layered chromatography, add After adding water, reaction was completed.Organic layer is extracted with dichloromethane (MC), and after being filtered under diminished pressure, carry out column purification and again Crystallization, so as to obtain the compound 1 of 7.08g (yield 73%).
m/z：677.31 (100.0%), 678.31 (57.1%), 679.31 (15.7%), 680.32 (2.9%)
Synthesis example 2：The synthesis of compound 2
IM1 is replaced using IM2, so as to synthesize compound 2 (yield 69%) by the method for such as synthesis example 1.
m/z：677.31 (100.0%), 678.31 (57.1%), 679.31 (15.7%), 680.32 (2.9%)
Synthesis example 3：The synthesis of compound 3
IM1 is replaced using IM3, so as to synthesize compound 3 (yield 70%) by the method for such as synthesis example 1.
m/z：677.31 (100.0%), 678.31 (57.1%), 679.31 (15.7%), 680.32 (2.9%)
Synthesis example 4：The synthesis of compound 4
IM1 is replaced using IM4, so as to synthesize compound 4 (yield 65%) by the method for such as synthesis example 1.
m/z：677.31 (100.0%), 678.31 (57.1%), 679.31 (15.7%), 680.32 (2.9%)
Synthesis example 5：The synthesis of compound 5
OP1 is replaced using OP2, so as to synthesize compound 5 (yield 65%) by the method for such as synthesis example 1.
m/z：727.32 (100.0%), 728.33 (61.0%), 729.33 (18.3%), 730.33 (3.6%)
Synthesis example 6：The synthesis of compound 6
OP1 is replaced using OP3, so as to synthesize compound 6 (yield 70%) by the method for such as synthesis example 1.
m/z：727.32 (100.0%), 728.33 (61.0%), 729.33 (18.3%), 730.33 (3.6%)
Synthesis example 7：The synthesis of compound 7
OP1 is replaced using OP4, so as to synthesize compound 7 (yield 74%) by the method for such as synthesis example 1.
m/z：753.34 (100.0%), 754.34 (63.1%), 755.35 (19.6%), 756.35 (4.0%)
Synthesis example 8：The synthesis of compound 8
OP1 is replaced using OP5, so as to synthesize compound 8 (yield 68%) by the method for such as synthesis example 1.
m/z：753.34 (100.0%), 754.34 (63.1%), 755.35 (19.6%), 756.35 (4.0%)
Synthesis example 9：The synthesis of compound 9
OP1 is replaced using OP6, so as to synthesize compound 9 (yield 70%) by the method for such as synthesis example 1.
m/z：753.34 (100.0%), 754.34 (63.1%), 755.35 (19.6%), 756.35 (4.0%)
Synthesis example 10：The synthesis of compound 10
OP1 is replaced using OP7, so as to synthesize compound 10 (yield 66%) by the method for such as synthesis example 1.
m/z：829.37 (100.0%), 830.37 (69.6%), 831.38 (24.0%), 832.38 (5.4%)
Synthesis example 11：The synthesis of compound 11
OP1 is replaced using OP8, so as to synthesize compound 11 (yield 62%) by the method for such as synthesis example 1.
m/z：793.37 (100.0%), 794.37 (66.3%), 795.38 (21.8%), 796.38 (4.7%)
Synthesis example 12：The synthesis of compound 12
OP1 is replaced using OP9, so as to synthesize compound 12 (yield 60%) by the method for such as synthesis example 1.
m/z：793.37 (100.0%), 794.37 (66.3%), 795.38 (21.8%), 796.38 (4.7%)
Synthesis example 13：The synthesis of compound 13
In round-bottomed flask, bromo- 9, the 9- dimethyl -9H- of 3,6- bis- of 10.0g are dissolved in Isosorbide-5-Nitrae-dioxanes of 120ml The phenylboric acid of fluorenes and 2.1g, and it is put into the K of 40ml2CO3Pd (the PPh of (2M) and 1.0g3)4Afterwards, it is refluxed.It is logical Cross thin-layered chromatography (TLC) and confirm reaction, after adding water, reaction was completed.Organic layer is extracted with dichloromethane (MC), and is subtracted After press filtration, column purification is carried out to obtain the intermediate compound I M5 of 5.06g (yield 51%).Using above-mentioned intermediate compound I M5 come Instead of IM1, so as to synthesize compound 13 (yield 60%) by the method for such as synthesis example 1.
m/z：677.31 (100.0%), 678.31 (57.1%), 679.31 (15.7%), 680.32 (2.9%)
Synthesis example 14：The synthesis of compound 14
OP1 is replaced using OP10, so that (yield is to have synthesized compound 14 by the method for such as synthesis example 1 70%).
m/z：753.34 (100.0%), 754.34 (63.1%), 755.35 (19.6%), 756.35 (4.0%)
Synthesis example 15：The synthesis of compound 15
In round-bottomed flask, double (connection pinacols of the IM1 and 9.45g of 10.0g are dissolved in Isosorbide-5-Nitrae-dioxanes of 200ml Base) two boron, and it is put into Pd (dppf) Cl of the KOAc and 0.1g of 8.5ml2Afterwards, it is refluxed.Pass through thin-layered chromatography (TLC) reaction is confirmed, after adding water, reaction was completed.Organic layer is extracted with dichloromethane (MC), and after being filtered under diminished pressure, Column purification is carried out to obtain the intermediate compound I M6-1 of 9.1g (yield 80%).In round-bottomed flask, in the Isosorbide-5-Nitrae-two of 200ml The bromo- 4- iodobenzenes of 1- of the IM6-1 and 7.1g of 9.0g are dissolved in oxane, and are put into the K of 35ml2CO3The Pd of (2M) and 0.8g (PPh3)4Afterwards, it is refluxed.Confirm to react by thin-layered chromatography (TLC), after adding water, reaction was completed.Use dichloro Methane (MC) extracts organic layer, and after being filtered under diminished pressure, carries out column purification to obtain in 5.12g (yield 53%) Mesosome IM6.Afterwards, IM1 is replaced using above-mentioned intermediate compound I M6, so as to synthesize compound by the method for such as synthesis example 1 15 (yields 67%).
m/z：753.34 (100.0%), 754.34 (63.1%), 755.35 (19.6%), 756.35 (4.0%)
Preparation example 2：The preparation of organic luminescent device
To by distilled water ultrasonic wave withThickness tin indium oxide (ITO) is applied as to the glass substrate of film Washed.If distillation water washing terminates, ultrasonic washing is carried out using the solvent of isopropanol, acetone, methanol etc., is gone forward side by side After row is dry, plasma cleaner is transferred to, after then aforesaid substrate is cleaned 5 minutes using oxygen plasma, in oxygen Change indium tinbase plate top and utilize thermal vacuum depositor (thermal evaporator), will as hole injection layer's HI01 is filmed, willHATCN be filmed, as hole transporting layer willCompound 1 it is filmed Afterwards, the BH01 as above-mentioned luminescent layer doping 3%：BD01, withIt is filmed.Then, will as electron supplying layer ET01：Liq(1：1), will after being filmedLiF,Aluminium (Al) be filmed, and should Device sealing (Encapsulation) is in glove box, so as to be prepared for organic luminescent device (embodiment 1).
Chemical combination is replaced using compound 2 to compound 15 (embodiment 2 to embodiment 15) by mode as described above Thing 1, so as to be prepared for organic luminescent device.
Comparative example
Compound 1 is replaced using following Ref.1 to Ref.11 (comparative example 1 to comparative example 11), it is in addition, and above-mentioned Preparation example 2 is prepared for organic luminescent device in the same manner.
Experimental example 1：The performance evaluation of organic luminescent device
Apply electricity using 2400 source measuring unit of Keithley (Kiethley 2400source measurement unit) Press to inject electronics and hole, measured using Konica Minolta (Konica Minolta) spectroradiometer (CS-2000) Brightness when shining, thus under atmospheric conditions, measures for applying alive current density and brightness, so as to have rated reality The performance of the organic luminescent device of example and comparative example is applied, and the results are shown in table 1.
Table 1
As shown in Table 1 above, it is seen that in embodiments of the invention, compared with comparative example 1 to comparative example 10, present Improve efficiency and extend the result in service life.If comparing the embodiment of the present invention, it is known as below：1) with comparative example 2,3,7,10 Compare, there is diphenylfluorene component, 2) compared with comparative example 2, comparative example 6, by the dimethyl fluorene portion for substituting tabular Phenyl expands the situation of conjugation, 3) compared with comparative example 4, comparative example 5, easy barrier electronics is maintained by substituted-phenyl The situation of lowest unocccupied molecular orbital, 4) compared with comparative example 8, comparative example 9, comparative example 10, pass through the fast hexichol of mobility The second place coupling of base fluorenes, has a case that easy HOMO is injected in hole, and 5) compared with comparative example 11, Ar3 is included The situation of the more unit of tabular is maintained, in the compound of the invention of consideration case above, the driving of organic luminescent device Voltage is low, and substantially improves efficiency and service life.
The being illustrative for property of explanation of the invention described above, general technical staff of the technical field of the invention can manage Solution can be easily deformed in other specific ways in the case where not changing the technological thought of the present invention or essential feature.Therefore, It should be understood that various embodiments described above is illustrative in all respects, rather than it is limited.For example, said with single type Bright each structural element is implemented dispersiblely, and equally, illustrating also can be in a manner of combination for scattered multiple structural elements Implement.
Range Representation, rather than above-mentioned detailed description, patent is claimed by appended patented invention in the scope of the present invention The implication and scope of the claimed scope of invention and the mode that has altered or deform as derived from its equivalents should be by It is construed to be included within the scope of the present invention.

Claims (13)

  1. A kind of 1. compound, it is characterised in that represented by formula 1 below,
    Chemical formula 1
    In above-mentioned chemical formula 1,
    R1And R2It is separately hydrogen, heavy hydrogen or C1-C6Alkyl,
    R3To R5It is separately hydrogen, heavy hydrogen, C6-C30Aryl, C1-C6Alkyl,
    Ar1And Ar2It is separately substituted or unsubstituted C6-C30Aryl or substituted or unsubstituted C6-C30Heteroaryl,
    Ar3For substituted or unsubstituted C6-C24Aryl or substituted or unsubstituted C6-C24Heteroaryl,
    L1And L2It is separately direct-coupling, C6-C30Arlydene or C6-C30Heteroarylidene,
    L is 1 to 4 integer, and m is 1 to 3 integer, and o is 1 to 4 integer.
  2. 2. compound according to claim 1, it is characterised in that
    Above-claimed cpd includes the compound represented by formula 2 below or chemical formula 3,
    Chemical formula 2
    Chemical formula 3
    In multiple above-mentioned chemical formulas,
    R1And R2It is separately hydrogen, heavy hydrogen or C1-C6Alkyl,
    R3To R7It is separately hydrogen, heavy hydrogen, C6-C30Aryl, C1-C6Alkyl,
    Ar3For substituted or unsubstituted C6-C24Aryl or substituted or unsubstituted C6-C24Heteroaryl,
    L1And L2It is separately C6-C30Aryl or C6-C30Heteroaryl,
    L is 1 to 4 integer, m and the integer that n is 1 to 3, and o is 1 to 4 integer, p and the integer that q is 1 to 5.
  3. 3. compound according to claim 1, it is characterised in that
    Above-claimed cpd includes the compound represented by formula 4 below or chemical formula 5,
    Chemical formula 4
    Chemical formula 5
    In multiple above-mentioned chemical formulas,
    R1And R2It is separately hydrogen, heavy hydrogen or C1-C6Alkyl,
    R3To R7It is separately hydrogen, heavy hydrogen, C6-C30Aryl, C1-C6Alkyl,
    Ar3For substituted or unsubstituted C6-C24Aryl or substituted or unsubstituted C6-C24Heteroaryl,
    M and n is 1 to 3 integer, and o is 1 to 4 integer, p and the integer that q is 1 to 5, and r is 0 to 3 integer.
  4. 4. compound according to claim 1, it is characterised in that
    Above-claimed cpd includes the compound represented by chemical formula 6,
    Chemical formula 6
    In multiple above-mentioned chemical formulas,
    R1And R2It is separately hydrogen, heavy hydrogen or C1-C6Alkyl,
    R3To R7It is separately hydrogen, heavy hydrogen, C6-C30Aryl, C1-C6Alkyl,
    Ar3For substituted or unsubstituted C6-C24Aryl or substituted or unsubstituted C6-C24Heteroaryl,
    M and n is 1 to 3 integer, and o is 1 to 4 integer, p and the integer that q is 1 to 5.
  5. 5. compound according to any one of claim 1 to 4, it is characterised in that Ar3Select free phenyl, xenyl, three In the group that xenyl, fluorenyl, naphthyl, dimethyl fluorene and combinations thereof form.
  6. 6. compound according to any one of claim 1 to 4, it is characterised in that Ar3For phenyl, xenyl or terphenyl Base.
  7. 7. compound according to any one of claim 1 to 4, it is characterised in that R1And R2Separately for hydrogen or C1-C6Alkyl, R3To R7For hydrogen.
  8. 8. compound according to any one of claim 1 to 4, it is characterised in that work as R1And R2Respectively C1-C6Alkyl When, substituted phenyl is connected to second or the third place.
  9. 9. compound according to any one of claim 1 to 4, it is characterised in that work as R1And R2Respectively C1-C6Alkyl When, arylamine is coupling in the second place of dialkyl fluorene.
  10. 10. compound according to any one of claim 1 to 4, it is characterised in that the N of above-mentioned arylamine is connected to dioxane The second place of base fluorenes.
  11. 11. compound according to claim 1, it is characterised in that above-claimed cpd is one kind in following compound,
  12. 12. a kind of organic luminescent device, it is characterised in that include containing claim 1 between first electrode and second electrode More than one layer of organic matter layer of the compound.
  13. 13. organic luminescent device according to claim 12, it is characterised in that above-mentioned organic matter layer for hole injection layer, More than one layer in hole transporting layer and luminous auxiliary layer.
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CN107963973A (en) * 2016-10-20 2018-04-27 东进世美肯株式会社 Compounds and the organic luminescent device for including it
CN109400487A (en) * 2018-11-12 2019-03-01 长春海谱润斯科技有限公司 A kind of fluorene kind derivative and its organic electroluminescence device
CN110551087A (en) * 2018-05-31 2019-12-10 东进世美肯株式会社 Novel compound and organic light emitting device comprising the same
CN110903276A (en) * 2018-09-17 2020-03-24 北京鼎材科技有限公司 Organic compound and organic electroluminescent device
CN111211235A (en) * 2018-11-22 2020-05-29 固安鼎材科技有限公司 Organic electroluminescent device
CN113233987A (en) * 2021-04-21 2021-08-10 陕西莱特迈思光电材料有限公司 Nitrogen-containing compound, electronic element comprising same and electronic device
CN113287211A (en) * 2019-01-18 2021-08-20 株式会社Lg化学 Organic light emitting device
CN115466184A (en) * 2022-09-20 2022-12-13 北京八亿时空液晶科技股份有限公司 Organic compound and application thereof
CN116554039A (en) * 2023-07-10 2023-08-08 吉林奥来德光电材料股份有限公司 Organic light-emitting auxiliary material and preparation method and application thereof

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CN104583176A (en) * 2012-08-31 2015-04-29 出光兴产株式会社 Aromatic amine derivative and organic electroluminescent element using same
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CN107963973A (en) * 2016-10-20 2018-04-27 东进世美肯株式会社 Compounds and the organic luminescent device for including it
CN107963973B (en) * 2016-10-20 2023-07-25 东进世美肯株式会社 Novel compound and organic light emitting device comprising the same
CN110551087A (en) * 2018-05-31 2019-12-10 东进世美肯株式会社 Novel compound and organic light emitting device comprising the same
CN110903276A (en) * 2018-09-17 2020-03-24 北京鼎材科技有限公司 Organic compound and organic electroluminescent device
CN109400487A (en) * 2018-11-12 2019-03-01 长春海谱润斯科技有限公司 A kind of fluorene kind derivative and its organic electroluminescence device
CN111211235A (en) * 2018-11-22 2020-05-29 固安鼎材科技有限公司 Organic electroluminescent device
CN111211235B (en) * 2018-11-22 2023-08-08 固安鼎材科技有限公司 Organic electroluminescent device
CN113287211A (en) * 2019-01-18 2021-08-20 株式会社Lg化学 Organic light emitting device
CN113233987A (en) * 2021-04-21 2021-08-10 陕西莱特迈思光电材料有限公司 Nitrogen-containing compound, electronic element comprising same and electronic device
WO2022222737A1 (en) * 2021-04-21 2022-10-27 陕西莱特迈思光电材料有限公司 Nitrogen-containing compound, and electronic element and electronic device comprising same
CN115466184A (en) * 2022-09-20 2022-12-13 北京八亿时空液晶科技股份有限公司 Organic compound and application thereof
CN116554039A (en) * 2023-07-10 2023-08-08 吉林奥来德光电材料股份有限公司 Organic light-emitting auxiliary material and preparation method and application thereof
CN116554039B (en) * 2023-07-10 2023-09-19 吉林奥来德光电材料股份有限公司 Organic light-emitting auxiliary material and preparation method and application thereof

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