CN109206325A - Compounds and organic luminescent device comprising it - Google Patents

Compounds and organic luminescent device comprising it Download PDF

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Publication number
CN109206325A
CN109206325A CN201810695694.3A CN201810695694A CN109206325A CN 109206325 A CN109206325 A CN 109206325A CN 201810695694 A CN201810695694 A CN 201810695694A CN 109206325 A CN109206325 A CN 109206325A
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compound
chemical formula
unsubstituted
substituted
layer
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咸昊完
安贤哲
姜京敏
金熙宙
金东骏
闵丙哲
文锺勋
李萤振
林东焕
林大喆
金昇好
权桐热
李成圭
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Dongjin Semichem Co Ltd
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Abstract

This application involves compounds and comprising its organic luminescent device, the compounds of an example of the invention are suitable for organic luminescent device, it can be ensured that high efficiency, long-life, low driving voltage and the driving stability of organic luminescent device.

Description

Compounds and organic luminescent device comprising it
Technical field
The present invention relates to compounds and include its organic luminescent device.
Background technique
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 classified as macromolecule and low molecule, and the phosphor of the singlet excited state from electronics can be classified as according to luminescence mechanism Material and the triplet excitation state from electronics phosphor material, luminescent material can be classified as according to illuminant colour blue, green, Yellow and orange light emitting materials needed for red illuminating material and the better natural colour of embodiment.Also, in order to increase excitation purity, and Increase luminous efficiency by energy transfer, main body/dopant class can be used as luminescent substance.If its principle is will be with main composition The main body of luminescent layer is compared, and the dopant that band gap is small and luminous efficiency is outstanding is mixed in auxiliary layer on a small quantity, then in main body The exciton of generation is conveyed to dopant, to issue high-efficient light.At this point, the wavelength of main body is moved to the wavelength band of dopant It is dynamic, thus the light of required wavelength can be obtained according to the type of the dopant and main body utilized.
So far, as the substance for being used in this organic luminescent device, well-known there are many compounds, but are utilizing So far it in the case where the organic luminescent device of well-known substance, due to high driving voltage, low efficiency and short life, holds It is continuous to require to develop new material.Therefore, ongoing effort developed using the substance with outstanding characteristic with low voltage drive, High brightness and the organic luminescent device of long-life.
Existing technical literature
Patent document
(patent document 1) KR published patent 10-2015-0086721
Summary of the invention
The present invention provides compounds, preparation method and the organic luminescent device comprising it.
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 contents below.
First embodiment of the invention provides the compound indicated by following formula 1:
Chemical formula 1
In above-mentioned chemical formula 1,
Ar、Ar’、Ar1And Ar2It is each independently substituted or unsubstituted C6~C30Aryl or substituted or unsubstituted C3~C30Heteroaryl,
L1And L2It is each independently Direct Bonding, substituted or unsubstituted C6~C18Arlydene or substituted or unsubstituted C3~C30Heteroarylidene,
R1To R4, R and R ' be each independently hydrogen, heavy hydrogen, substituted or unsubstituted C1~C30Alkyl, replace or do not take The C in generation1~C30Alkoxy, substituted or unsubstituted C2~C30Alkenyl, substituted or unsubstituted C6~C30Aryl or Substituted or unsubstituted C3~C30Heteroaryl, the R and R ' can connect and form ring or do not form ring,
The integer that l is 0 or 1 to 4, m, n and o are each independently 0 or integer of 1 to 3.
It includes containing chemical combination of the invention that second embodiment of the present invention, which is provided between first electrode and second electrode, The organic luminescent device of the organic matter layer of object.
The compound of an example of the invention, imports fluorenes linker between diaryl fluorene and arylamine, and maintenance is easy defeated High lumo energy is maintained while sending the HOMO energy level in hole, is easy to block electronics.It is effectively formed in luminescent layer as a result, sharp Thus son can realize low-voltage and efficient organic luminescent device.
Also, since by fluorenes linker, increase is pi-conjugated, therefore has quick hole flow (hole Mobility), because of the diaryl fluorene of end, pi accumulation between inducing molecule, arranging the film of molecule becomes outstanding, can improve thin Mobility on film can inhibit phenomenon of roll-offing, it can be achieved that long lived devices.
Detailed description of the invention
Fig. 1 shows the schematic diagrams of the organic luminescent device of an example of the invention.
The explanation of appended drawing reference
100: substrate
200: hole injection layer
300: hole transporting layer
400: luminescent layer
500: electron supplying layer
600: electron injecting layer
1000: anode
2000: cathode
Specific embodiment
Hereinafter, referring to attached drawing, the example and embodiment that the present invention will be described in detail, so that the technical field of the invention is general Logical technical staff can be easy to 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 and embodiment described herein. Also, the part unrelated with explanation is omitted, in the specification, for similar in the figure in order to clearly state the present invention Part, be labelled with similar appended drawing reference.
In the full text of description of the invention, when a component is located at another component "upper", not only include component with The case where another component is in contact, include thes case where there is other component between the two parts.
In the full text of description of the invention, when one structural element of a part " comprising ", unless there are especially opposite It records, then means to may also include other structures element, rather than exclude other structures element.In the full text of description of the invention The term " about " that uses, " substantial " etc. when prompting intrinsic preparation and substance tolerance in mentioned meaning with its numerical value or Meaning 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.Term "~() step " used in the full text of description of the invention or "~ Step " do not mean that " for~the step of ".
In the full text of description of the invention, " their combination " contained in the performance of Markush (Markush) form this One term means one or more of the group that documented multiple structural elements form in the performance by Markush form Mixing or combination, it is meant that including selected from one or more of the group that is made of above-mentioned multiple structural elements.
In the full text of description of the invention, " A and/or B " this record means " A or B or A and B ".
In the full text of description of the invention, term " aryl " means comprising C5-30Aromatic cyclic hydrocarbon group, for example, benzene Base, benzyl, naphthalene, xenyl, terphenyl, fluorenyl, phenanthryl, triphenyl alkenyl, phenylakenyl,Base, fluorane thenyl, Benzo fluorenyl, benzo triphenyl alkenyl, benzoThe aromatic ring of base, anthryl, stilbenyl, pyrenyl etc., " heteroaryl " As the C comprising at least one miscellaneous element3-30Aromatic ring, such as, it is meant that comprising from pyrrolinyl, pyrazinyl, pyridine Base, indyl, isoindolyl, furyl, benzofuranyl, isobenzofuran-base, dibenzofuran group, aisaa benzothiophenyl, two Aisaa benzothiophenyl, quinolyl, isoquinolyl, quinoxalinyl, carbazyl, luxuriant and rich with fragrance cry base, acridinyl, phenanthroline, thienyl and by Pyridine ring, pyridine ring, pyrimidine ring, pyridazine ring, triazine ring, indole ring, quinoline ring, acridine ring, pyrrolidine ring, dioxanes ring, piperazine Phenazine ring, morpholine ring, piperazine ring, carbazole ring, furan nucleus, thiphene ring, oxazole ring, oxadiazoles ring, benzoxazoles ring, thiazole ring, thiophene The aromatic series that diazonium ring, benzothiazole ring, triazole ring, imidazole ring, benzimidazole ring, pyranoid ring, dibenzofurans ring are formed is miscellaneous Ring group.
In the full text of description of the invention, term " substituted or unsubstituted " refer to selected from by heavy hydrogen, halogen, amino, Itrile group, nitro or C1~C20Alkyl, C2~C20Alkenyl, C1~C20Alkoxy, C3~C20Naphthenic base, C3~C20's Heterocyclylalkyl, C6~C30Aryl and C3~C30Heteroaryl composition one or more of group base it is substituted or unsubstituted.And And in description of the invention full text, identical appended drawing reference can have equivalent as long as no the special content referred to.
In the full text of description of the invention, term " fluorenes " may include hydrogen in conjunction with the 9th carbon by substituted or unsubstituted C1-20Alkyl, substituted or unsubstituted C5-30Aryl or substituted or unsubstituted C3-30Heteroaryl replace feelings Condition.
First embodiment of the invention provides the compound indicated by following formula 1:
Chemical formula 1
In above-mentioned chemical formula 1,
Ar、Ar’、Ar1And Ar2It is each independently substituted or unsubstituted C6~C30Aryl or substituted or unsubstituted C3~C30Heteroaryl,
L1And L2It is each independently Direct Bonding, substituted or unsubstituted C6~C18Arlydene or substituted or unsubstituted C3~C30Heteroarylidene,
R1To R4, R and R ' be each independently hydrogen, heavy hydrogen, substituted or unsubstituted C1~C30Alkyl, replace or do not take The C in generation1~C30Alkoxy, substituted or unsubstituted C2~C30Alkenyl, substituted or unsubstituted C6~C30Aryl or Substituted or unsubstituted C3~C30Heteroaryl, the R and R ' can connect and form ring or do not form ring,
The integer that l is 0 or 1 to 4, m, n and o are each independently 0 or integer of 1 to 3.
In the compound of above-mentioned chemical formula 1, fluorenes linker maintains to be easy conveying sky between diaryl fluorene and arylamine The HOMO energy level in cave, while high lumo energy is maintained, it is easy barrier electronics.Exciton is effectively formed in luminescent layer as a result, it can Realize low-voltage and efficient organic luminescent device.
Also, since by fluorenes linker, increase is pi-conjugated, therefore has quick hole flow (hole Mobility), because of the diaryl fluorene of end, pi accumulation between inducing molecule can improve so that the film arrangement of molecule becomes outstanding Mobility on film can inhibit phenomenon of roll-offing, it can be achieved that long lived devices.
Also, in an example of the invention, in above-mentioned chemical formula 1, above-mentioned Ar1And Ar2Can be selected from each independently by In the group that phenyl, xenyl, triphenyl, naphthalene, fluorenes, dibenzofurans, dibenzothiophenes and their combination form.
Also, in an example of the invention, above compound can be indicated by following formula 2.
Chemical formula 2
In above-mentioned chemical formula 2,
Ar1、Ar2、R1To R4、R、R’、L1、L2, l, m, n and o as defined in above-mentioned chemical formula 1,
R5To R6It is each independently hydrogen, heavy hydrogen, substituted or unsubstituted C1~C24Alkyl, substituted or unsubstituted C1 ~C24Alkoxy, substituted or unsubstituted C2~C24Alkenyl, substituted or unsubstituted C6~C24Aryl or substitution or Unsubstituted C3~C24Heteroaryl,
P and q is each independently 0 or 1 to 5 integer.
The compound indicated by above-mentioned chemical formula 2 has diphenylfluorene in end, makes the huge characteristic of molecule as a result, most Smallization, intermolecular accumulation is outstanding, thus can have quick hole flow (hole mobility).
In an example of the invention, above compound can be indicated by following formula 3 or chemical formula 4.
Chemical formula 3
Chemical formula 4
In above-mentioned chemical formula 3 and chemical formula 4,
Ar1、Ar2、R1To R6、R、R’、L1、L2, for example above-mentioned chemical formula 2 of l, m, n, o, p and q defined.
The compound indicated by above-mentioned chemical formula 3 or chemical formula 4 is compared with the case where all having linker L1 and L2, molecule Amount is relatively low, and vapor deposition temperature is likely to decrease.Thus when manufacturing organic luminescent device, there can be thermal stability.
In an example of the invention, in above-mentioned chemical formula 1 into chemical formula 4, L1And L2Direct key can be each independently Conjunction or phenylene.
In an example of the invention, above compound can be indicated by following formula 5.
Chemical formula 5
In above-mentioned chemical formula 5,
Ar1、Ar2、R1To R6, R, R ', for example above-mentioned chemical formula 2 of l, m, n, o, p and q defined.
In the compound indicated by above-mentioned chemical formula 5, fluorenes and arylamine and diaryl fluorene Direct Bonding can be maintained high Thus LUMO can be easier to block electronics.
In an example of the invention, above compound can be indicated by one of following formula 6 to chemical formula 8.
Chemical formula 6
Chemical formula 7
Chemical formula 8
In above-mentioned chemical formula 6 into chemical formula 8,
Ar1、Ar2、R1To R6、R、R’、L1And L2As above-mentioned chemical formula 2 defines.
In an example of the invention, in above-mentioned chemical formula 7 and chemical formula 8, L1And L2Direct key can be each independently Conjunction or phenylene.In this case, exciton barrier effect can be made to maximize by maintaining high T1, thus can manufactures height Efficiency organic luminescent device.
The compound indicated by above-mentioned chemical formula 6 to chemical formula 8 is combined in the second position of the fluorenes as intermediate linker Thus arylamine can reduce driving voltage to form the HOMO for being suitable for hole transporting layer.
In an example of the invention, above compound can be indicated by following formula 9.
Chemical formula 9
In above-mentioned chemical formula 9,
Ar1、Ar2、R1To R6, R and R ' such as above-mentioned chemical formula 2 define.
In the compound indicated by above-mentioned chemical formula 9, the of arylamine and diaryl fluorene and the fluorenes as intermediate linker Two and the 7th position combines, and remains linear on the whole, so that molecules align is become outstanding, thus can have quick hole flow Property (hole mobility).
In an example of the invention, above compound can be indicated by following formula 10 or chemical formula 11.
Chemical formula 10
Chemical formula 11
In above-mentioned chemical formula 10 or chemical formula 11,
Ar1、Ar2、R1To R6If above-mentioned chemical formula 2 defines,
R7And R8It is each independently substituted or unsubstituted C1~C30Alkyl,
Ar3And Ar4It is each independently substituted or unsubstituted C6~C30Aryl or substituted or unsubstituted C3~ C30Heteroaryl.
In an example of the invention, above-mentioned Ar3And Ar4It can be each independently selected from by phenyl, xenyl, triphenyl, naphthalene In the group of base, fluorenes and their combination composition.
The compound indicated by above-mentioned chemical formula 10 or chemical formula 11 has as the dialkyl fluorene of intermediate linker or two Thus aryl fluorenes can induce outstanding intermolecular accumulation.
In an example of the invention, in above-mentioned chemical formula 2 to 11, Ar1And Ar2Can be each independently selected from by phenyl, In the group that xenyl, triphenyl, naphthalene, fluorenes, dibenzofurans, dibenzothiophenes and their combination form.
An example according to the present invention can be in following compound by the compound that above-mentioned chemical formula 1 to 11 indicates It is a kind of, it is possible to not limited to this:
In an example of the invention, the compound indicated by above-mentioned chemical formula 1, more specifically, can be above-mentioned chemical combination Compound number 1~19,21~26,101~104,130~141,159~162,191~194,201,206 in object~ 351~369,371~376,451~454,480~491,509~512,541~544,551,556~558,701 208 ,~ 719,721~726,801~804,830~841,859~862,891~894,901,906~908,1051~1069,1071 Any of~1076,1151~1154,1180~1191,1209~1212,1241~1244,1251,1256~1258. These compounds reduce excessive conjugation, can minimize molecular weight, thus maintain to have while HOMO appropriate higher LUMO and T1 can inhibit the thermal decomposition phenomenon of compound when process is deposited.
An example according to the present invention, the compound indicated by above-mentioned chemical formula 1 can be closed by following reaction equation At, it is possible to it is not limited to this.
In above-mentioned reaction equation, h is halogen, other symbols are such as above-mentioned chemical formula 1.
It includes having for the compound indicated by any of above-mentioned chemical formula 1 to 11 that second embodiment of the present invention, which provides, Machine luminescent device.Above-mentioned organic luminescent device can include 1 containing the compounds of this invention between first electrode and second electrode Layer or more organic matter layer.
In an example of the invention, above-mentioned organic matter layer can be hole injection layer, hole transporting layer and the auxiliary that shines Layer, it is likely that being not limited except as.Also, the compound of the present invention can be used alone when forming organic layer or have with well known Machine luminophor is used together.
In an example of the invention, above-mentioned organic luminescent device may include the organic matter layer containing cavity conveying substance and Organic matter layer containing the compound indicated by above-mentioned chemical formula 1, it is likely that being not limited except as.According to the present invention one is real Example, as described above, the compound of above-mentioned chemical formula 1 can be indicated by any of chemical formula 2 to 11.
Above-mentioned organic luminescent device can include that 1 layer or more of hole is infused between anode (anode) and cathode (cathode) Enter the organic of layer (HIL), hole transporting layer (HTL), luminescent layer (EML), electron supplying layer (ETL), electron injecting layer (EIL) etc. Nitride layer.
For example, above-mentioned organic luminescent device can be prepared according to structure documented in Fig. 1.Organic luminescent device can To it is lower and on stack gradually anode (hole injecting electrode 1000)/200/ hole transporting layer of hole injection layer, 300/ luminescent layer 400/ 500/ electron injecting layer of electron supplying layer, 600/ cathode (electron injection electrode 2000).
In Fig. 1, the substrate for organic luminescent device is can be used in substrate 100, in particular, can be steady for mechanical strength, heat Qualitative, transparent, surface smoothness, ease of handling and the outstanding transparent glass substrate or flexible plastic base of waterproofness Plate.
Hole injecting electrode 1000 is used as the anode for being injected with the hole of machine luminescent device.In order to which hole can be injected, It, can be by tin indium oxide (ITO), indium zinc oxide (IZO), graphene (graphene) etc using the substance 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 substance, thus can form hole injection layer 200.Sky is being formed by above-mentioned vacuum deposition method In the case where the implanted layer of cave, the compound of material of the sedimentary condition because being used as hole injection layer 200, 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 degree of torr (support), 0.01 toDeposition velocity,It is suitably selected in 5 μm of layer thickness range.
Then, by vacuum deposition method, spin-coating method, casting, LB method etc. come in above-mentioned 200 overburden of hole injection layer Thus hole transporting layer substance can form hole transporting layer 300.Hole transporting layer is being formed by above-mentioned vacuum deposition method In the case of, sedimentary condition is different due to the compound used, but typically it will be preferred to, the formation with hole injection layer almost It is selected in identical condition and range.
The compound of the present invention can be used in above-mentioned hole transporting layer 300, as described above, the chemical combination of the invention that can be used alone Object is used together with well known compound.Also, an example according to the present invention, hole transporting layer 300 can be 1 layer with On, and can together include the hole transporting layer only formed by well known substance.An also, example according to the present invention, above-mentioned Luminous auxiliary layer can be formed on hole transporting layer 300.
By the methods of vacuum deposition method, spin-coating method, casting, LB method, in above-mentioned hole transporting layer 300 or the auxiliary that shines Layer overburden luminescent layer substance, thus can form luminescent layer 400.In the feelings for forming luminescent layer by above-mentioned vacuum deposition method Under condition, sedimentary condition is different due to the compound used, but typically it will be preferred to, in the almost phase of the formation with hole injection layer It is selected in same condition and range.Also, well known compound can be used as main body or dopant by above-mentioned emitting layer material.
Also, in the case where being used together in luminescent layer with phosphorescent dopants, triplet exciton or hole in order to prevent The phenomenon that spreading to electron supplying layer can also be laminated hole by vacuum deposition method or spin-coating method and inhibit material (HBL).At this time may be used The hole inhibiting substances used are not particularly limited, but selection in the well known substance of material can be inhibited any from hole is used as Substance utilizes.For example, oxadiazole derivatives or triazole derivative, phenanthroline derivative or Japanese Unexamined Patent Publication 11- can be enumerated Documented hole inhibits material etc. in 329734 (A1), typically, can be used Balq (bis- (8- hydroxy-2-methylquinolines)- Aluminium biphenyl phenates), phenanthroline (phe nanthrolines) class compound (such as BCP (Basso of general purpose display (UDC) company Coupoline)) etc..
It is formed with electron supplying layer 500 on 400 top of luminescent layer as formed above, at this point, above-mentioned electron supplying layer can lead to The methods of vacuum deposition method, spin-coating method, casting are crossed to be 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, selected in the condition and range almost the same with the formation of hole injection layer.
Later, electron injecting layer 600 can be formed in above-mentioned 500 overburden electron injecting layer substance of electron supplying layer, At this point, above-mentioned electron supplying layer can form conventional electron injection by the method for vacuum deposition method, spin-coating method, casting etc. Layer substance.
Hole injection layer 200, hole transporting layer 300, luminescent layer 400, the electron supplying layer 500 of above-mentioned organic luminescent device The compound of the present invention or following substance can be used, alternatively, the compound of the present invention and well known substance can be used together.
The yin 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 substance of aluminium, gold, silver etc..
Organic luminescent device of the invention can not only use anode, hole injection layer, hole transporting layer, luminescent layer, electricity Sub- transfer layer, electron injecting layer, cathode construction organic luminescent device, the knot of the organic luminescent device of various structures also can be used Structure can also form the middle layer of one or two layers as needed.
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 be specially 1 to 1000nm, more specifically 5 to 200nm.
Also, the organic matter layer in the present invention, comprising the compound indicated 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 is prominent.
It is applicable that first embodiment of the invention recorded for the organic luminescent compounds of present embodiment Content, it is likely that being not limited except as.
Hereinafter, embodiment through the invention carries out more specific description, the scope of the present invention is not limited to the present embodiment.
Embodiment
The synthesis of intermediate
In order to synthesize purpose compound, following synthetic intermediate IM.
Preparation example 1: intermediate (IM1) synthesis
In round-bottomed flask, by (9,9- diphenyl -9H- fluorenes -2- base) boric acid (9,9-diphenyl-9H- of 5.1g Fluoren-2-yl) boronic acid), the bromo- 9,9- dimethyl -9H- fluorenes (2,7-dibromo-9,9- of 2,7- bis- of 10.0g Dimethyl-9H-fluorene it) is dissolved in Isosorbide-5-Nitrae-dioxanes (Isosorbide-5-Nitrae-dioxan) of 200ml, is put into K2CO3(2M) 40ml and After the Pd (PPh3) 4 of 1.0g, return stirring.Reaction is confirmed using thin-layered chromatography (TLC), and after adding water, terminate Reaction.Organic layer is extracted using methylcellulose (MC), and after being filtered under diminished pressure, carries out column purification to obtain The IM1 of 11.9g (yield 71%).
Using method identical with above-mentioned IM1, specifically, as shown in the following Table 1, using different parent materials, synthesis Following IM2 to IM8.
Table 1
Compound synthesis
Using above-mentioned intermediate IM1 to IM8, purpose compound 1 to 20 is synthesized.
The synthesis of compound 1
In round-bottomed flask, by N- phenyl-[1,1'- the xenyl] -4- amine (N-phenyl- of IM1,1.25g of 3.0g [1,1'-biphenyl] -4-amine), the Pd of t-BuONa, 0.2g of 0.7g2(dba)3, 0.2ml (t-Bu)3P is dissolved in After the toluene of 80ml, return stirring.Reaction is confirmed using thin-layered chromatography (TLC), and after adding water, reaction was completed. Organic layer is extracted using methylcellulose (MC), and after being filtered under diminished pressure, carries out column purification and recrystallization to obtain The compound 1 of 2.69g (yield 70%).M/z:753.34 (100.0%), 754.34 (63.1%), 755.35 (19.6%), 756.35 (4.0%)
The synthesis of compound 2
It is replaced using 4- (naphthalene -1- base)-N- phenylaniline (4- (naphthalen-1-yl)-N-phenylaniline) N- phenyl-[1,1'- xenyl] -4- amine (N-phenyl- [1,1'-biphenyl] -4-amine), by identical as compound 1 Method synthesize compound 2.(yield 65%) m/z:803.36 (100.0%), 804.36 (67.6%), 805.36 (22.7%), 806.37 (4.9%)
The synthesis of compound 3
N- benzene is replaced using two ([1,1'- biphenyl] -4- base) amine (di ([1,1'-biphenyl] -4-yl) amine) Base-[1,1'- xenyl] -4- amine (N-phenyl- [1,1'-biphenyl] -4-amine), passes through side identical with compound 1 Method synthesizes compound 3.(yield 70%) m/z:829.37 (100.0%), 830.37 (69.6%), 831.38 (24.0%), The synthesis of 832.38 (5.4%) compounds 4
Utilize 4- (dibenzo [b, d] furans -4- base)-N- phenylaniline (4- (dibenzo [b, d] furan-4-yl)-N- Phenylanilin) N- phenyl-[1,1'- xenyl] -4- amine (N-phenyl- [1,1'-biphenyl] -4- is replaced Amine), by synthesizing compound 4 with the identical method of compound 1.(yield 60%) m/z:843.35 (100.0%), 844.35 (69.6%), 845.36 (24.0%), 846.36 (5.5%)
The synthesis of compound 5
Utilize 9,9- dimethyl-N-phenyl -9H- fluorenes -2- amine (9,9-dimethyl-N-phenyl-9H-fluoren-2- Amine it) replaces N- phenyl-[1,1'- xenyl] -4- amine (N-phenyl- [1,1'-biphenyl] -4-amine), passes through Compound 5 is synthesized with the identical method of compound 1.(yield 63%) m/z:793.37 (100.0%), 794.37 (66.3%), 795.38 (21.8%), 796.38 (4.7%)
The synthesis of compound 6
IM1 is replaced using IM3, by synthesizing compound 6 with the identical method of compound 1.(yield 67%) m/z: 753.34 (100.0%), 754.34 (63.1%), 755.35 (19.6%), 756.35 (4.0%)
The synthesis of compound 7
Utilize IM3 and 9,9- dimethyl-N-phenyl -9H- fluorenes -2- amine (9,9-dimethyl-N-phenyl-9H- Fluoren-2-amine) IM1 and N- phenyl-[1,1'- xenyl] -4- amine (N-phenyl- [1,1'- is replaced Biphenyl] -4-amine), by synthesizing compound 7 with the identical method of compound 1.(yield 63%) m/z:793.37 (100.0%), 794.37 (66.3%), 795.38 (21.8%), 796.38 (4.7%)
The synthesis of compound 8
Utilize IM5 and 9,9- dimethyl-N-phenyl -9H- fluorenes -2- amine (9,9-dimethyl-N-phenyl-9H- Fluoren-2-amine) IM1 and N- phenyl-[1,1'- xenyl] -4- amine (N-phenyl- [1,1'- is replaced Biphenyl] -4-amine), by synthesizing compound 8 with the identical method of compound 1.(yield 70%) m/z:793.37 (100.0%), 794.37 (66.3%), 795.38 (21.8%), 796.38 (4.7%)
The synthesis of compound 9
Utilize IM5 and N- ([1,1'- biphenyl] -4- base) -9,9- dimethyl -9H- fluorenes -2- amine (N- ([1,1'- Biphenyl] -4-yl) -9,9-dimethyl-9H-fluoren-2-amine) replace IM1 and N- phenyl-[1,1'- biphenyl Base] -4- amine (N-phenyl- [1,1'-biphenyl] -4-amine), by synthesizing compound with the identical method of compound 1 9.(yield 71%) m/z:869.40 (100.0%), 870.41 (73.1%), 871.41 (26.3%), 872.41 (6.2%), 873.42 (1.1%)
The synthesis of compound 10
Utilize IM7 and 9,9- dimethyl-N-phenyl -9H- fluorenes -2- amine (9,9-dimethyl-N-phenyl-9H- Fluoren-2-amine) IM1 and N- phenyl-[1,1'- xenyl] -4- amine (N-phenyl- [1,1'- is replaced Biphenyl] -4-amine), by synthesizing compound 10 with the identical method of compound 1.(yield 60%) m/z:793.37 (100.0%), 794.37 (66.3%), 795.38 (21.8%), 796.38 (4.7%)
The synthesis of compound 11
IM1 and N- phenyl-[1,1'- xenyl] -4- amine is replaced using IM2 and diphenylamine (diphenylamine) (N-phenyl- [1,1'-biphenyl] -4-amine), by synthesizing compound 11 with the identical method of compound 1.(yield 63%) m/z:801.34 (100.0%), 802.34 (67.4%), 803.35 (22.5%), 804.35 (4.9%)
The synthesis of compound 12
IM1 is replaced using IM2, by synthesizing compound 12 with the identical method of compound 1.(yield 65%) m/z: 877.37 (100.0%), 878.37 (73.9%), 879.38 (27.0%), 880.38 (6.5%), 881.38 (1.1%)
The synthesis of compound 13
Utilize IM3 and N- ([1,1'- biphenyl] -4- base)-[1,1'- biphenyl] -2- amine (N- ([1,1'-biphenyl] -4- Yl)-[1,1'-biphenyl] -2-amine) come replace IM1 and N- phenyl-[1,1'- xenyl] -4- amine (N-phenyl- [1, 1'-biphenyl] -4-amine), by synthesizing compound 13 with the identical method of compound 1.(yield 65%) m/z: 829.37 (100.0%), 830.37 (69.6%), 831.38 (24.0%), 832.38 (5.4%)
The synthesis of compound 14
IM1 and N- phenyl-[1,1'- xenyl] -4- amine is replaced using IM4 and diphenylamine (diphenylamine) (N-phenyl- [1,1'-biphenyl] -4-amine), by synthesizing compound 14 with the identical method of compound 1.(yield 67%) m/z:801.34 (100.0%), 802.34 (67.4%), 803.35 (22.5%), 804.35 (4.9%)
The synthesis of compound 15
IM1 is replaced using IM4, by synthesizing compound 15 with the identical method of compound 1.(yield 73%) m/z: 877.37 (100.0%), 878.37 (73.9%), 879.38 (27.0%), 880.38 (6.5%), 881.38 (1.1%)
The synthesis of compound 16
IM1 is replaced using IM5, by synthesizing compound 16 with the identical method of compound 1.(yield 66%) m/z: 753.34 (100.0%), 754.34 (63.1%), 755.35 (19.6%), 756.35 (4.0%)
The synthesis of compound 17
IM1 and N- phenyl-[1,1'- xenyl] -4- amine is replaced using IM6 and diphenylamine (diphenylamine) (N-phenyl- [1,1'-biphenyl] -4-amine), by synthesizing compound 17 with the identical method of compound 1.(yield 65%) m/z:801.34 (100.0%), 802.34 (67.4%), 803.35 (22.5%), 804.35 (4.9%)
The synthesis of compound 18
IM1 is replaced using IM6, by synthesizing compound 18 with the identical method of compound 1.(yield 68%) m/z: 877.37 (100.0%), 878.37 (73.9%), 879.38 (27.0%), 880.38 (6.5%), 881.38 (1.1%)
The synthesis of compound 19
It utilizes IM7 and N- phenyl-[1,1'- xenyl] -2- amine (N-phenyl- [1,1'-biphenyl] -2-amine) Replace IM1 and N- phenyl-[1,1'- xenyl] -4- amine (N-phenyl- [1,1'-biphenyl] -4-amine), by with The identical method of compound 1 synthesizes compound 19.(yield 62%) m/z:753.34 (100.0%), 754.34 (63.1%), 755.35 (19.6%), 756.35 (4.0%)
The synthesis of compound 20
IM1 and N- phenyl-[1,1'- xenyl] -4- amine is replaced using IM8 and diphenylamine (diphenylamine) (N-phenyl- [1,1'-biphenyl] -4-amine), by synthesizing compound 20 with the identical method of compound 1.(yield 60%) m/z:801.34 (100.0%), 802.34 (67.4%), 803.35 (22.5%), 804.35 (4.9%)
The preparation of organic luminescent device
Embodiment 1 (hole transporting layer)
By distilled water ultrasonic wave toThickness tin indium oxide (ITO) is applied as to the glass substrate of film It is 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, it is transferred to plasma cleaner, after then cleaning aforesaid substrate 5 minutes using oxygen plasma, in oxygen Change indium tinbase plate top and utilizes thermal vacuum depositor (thermal evaporator), it will as hole injection layer's (H101) it is filmed, it willHATCN be filmed, as hole transporting layer willCompound 1 be filmed Later, the BH01:BD01 as above-mentioned luminescent layer doping 3%, withIt is filmed.It then, will as electron supplying layer ET01:Liq (1:1) be filmed after, willLiF,Aluminium (Al) be filmed, and should Device is sealed (Encapsulation) in glove box, to be prepared for organic luminescent device.
Embodiment 2 is to embodiment 10
By method same as Example 1, manufacture is replaced compound 1 using compound 2 to 10 and is film-made organic Luminescent device.
Comparative example 1-1 to comparative example 1-8
By method same as Example 1, manufacture is replaced compound 1 using Ref.1 to Ref.8 and is film-made organic Luminescent device.
Embodiment 11 (luminous auxiliary layer)
By distilled water ultrasonic wave toThickness by tin indium oxide (ITO) be applied as the glass substrate of film into Row washing.If distillation water washing terminates, ultrasonic washing is carried out using the solvent of isopropanol, acetone, methanol etc., and carry out After drying, it is transferred to plasma cleaner, after then being cleaned aforesaid substrate 5 minutes using oxygen plasma, is being aoxidized Indium tinbase plate top utilizes thermal vacuum depositor (thermal evaporator), will as hole injection layer's (H101) it is filmed, it willHATCN be filmed, as hole transporting layer willBPA be filmed, as Shining auxiliary layer willCompound 11 be filmed after, as above-mentioned luminescent layer doping 7% main body PH01:PH02 (5:5) and dopant Ir (ppy)3, withIt is filmed.It then, will as electron supplying layerET01:Liq It, will after (1:1) is filmedLiF, Aluminium (Al) be filmed, and by the device in glove box into Row sealing (Enca psulation), to be prepared for organic luminescent device.
Embodiment 12 is to embodiment 20
By method identical with embodiment 11, manufacture replaces compound 11 using compound 12 to 20 and what is be film-made have Machine luminescent device.
Comparative example 2-1 to comparative example 2-8
By method identical with embodiment 11, manufacture is replaced compound 11 using above-mentioned Ref.1 to Ref.8 and is film-made Organic luminescent device.
The performance evaluation of organic luminescent device
Apply electricity using 2400 source measuring unit of Keithley (Kiethley 2400source measureme nt unit) Pressure is measured to inject electronics and hole using Konica Minolta (Konica Minolta) spectroradiometer (CS-2000) Thus under atmospheric conditions brightness when shining is measured for applying alive current density and brightness, 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 2 (hole transporting layer embodiment) and (hair of table 3 Light auxiliary layer embodiment) in.
Table 2
Op.V mA/cm2 Cd/A QE (%) CIEx CIEy LT95
Embodiment 1 3.86 10 7.20 6.14 0.140 0.109 125
Embodiment 2 3.85 10 7.23 6.10 0.140 0.110 120
Embodiment 3 3.84 10 7.30 6.13 0.141 0.110 130
Embodiment 4 3.85 10 7.20 6.12 0.140 0.110 110
Embodiment 5 3.84 10 7.25 6.10 0.141 0.110 116
Embodiment 6 3.81 10 7.30 6.25 0.140 0.110 120
Embodiment 7 3.83 10 7.33 6.27 0.140 0.110 123
Embodiment 8 3.80 10 7.22 6.20 0.140 0.111 140
Embodiment 9 3.84 10 7.20 6.20 0.139 0.111 133
Embodiment 10 3.82 10 7.25 6.24 0.141 0.110 120
Comparative example 1-1 4.22 10 6.05 4.90 0.14 0.114 20
Comparative example 1-2 4.07 10 6.77 5.56 0.143 0.111 40
Comparative example 1-3 4.08 10 6.80 5.70 0.141 0.110 45
Comparative example 1-4 4.10 10 6.39 5.25 0.141 0.112 33
Comparative example 1-5 4.10 10 7.00 6.03 0.141 0.111 70
Comparative example 1-6 4.07 10 6.95 5.84 0.142 0.112 80
Comparative example 1-7 4.00 10 7.05 6.03 0.141 0.110 95
Comparative example 1-8 4.15 10 7.06 5.98 0.140 0.111 87
Table 3
Op.V mA/cm2 Cd/A QE (%) CIEx CIEy LT95
Embodiment 11 4.71 10 57.60 16.50 0.301 0.620 180
Embodiment 12 4.70 105 57.66 16.50 0.299 0.619 191
Embodiment 13 4.73 10 57.64 16.51 0.298 0.619 170
Embodiment 14 4.76 10 57.65 16.55 0.300 0.620 202
Embodiment 15 4.77 10 57.70 16.57 0.298 0.619 197
Embodiment 16 4.81 10 57.71 16.60 0.298 0.619 182
Embodiment 17 4.80 10 57.65 16.58 0.297 0.618 190
Embodiment 18 4.80 10 57.63 16.50 0.302 0.620 210
Embodiment 19 4.81 10 57.60 16.55 0.300 0.620 175
Embodiment 20 4.80 10 57.70 16.57 0.299 0.622 191
Comparative example 2-1 5.40 10 38.20 12.10 0.301 0.644 32
Comparative example 2-2 5.10 10 46.91 14.77 0.299 0.629 76
Comparative example 2-3 5.12 10 49.05 14.90 0.298 0.630 83
Comparative example 2-4 5.00 10 46.63 14.50 0.300 0.631 62
Comparative example 2-5 5.03 10 41.10 13.11 0.298 0.629 115
Comparative example 2-6 5.13 10 50.95 15.00 0.298 0.629 110
Comparative example 2-7 5.05 10 43.85 14.55 0.297 0.630 100
Comparative example 2-8 5.10 10 41.00 14.10 0.302 0.633 91
As shown in above-mentioned table 2 and table 3, it is seen that the embodiment of the present invention is compared with comparative example 1 to comparative example 8, driving voltage Improved, and efficiency improves and service life extended result.
More specifically, with the Comparative Examples 1 and 2 without diaryl fluorene substituent group, 3,4, the comparative example without fluorenes linker 5,6, do not have the comparative example 7 of diaryl fluorene in end, in end there is the comparative example 8 of huge spiro fluorene to compare, it is of the invention Embodiment has diaryl fluorene substituent group, to form the HOMO for being suitable for hole transporting layer, and has fluorenes linker, passes through increasing Add it is pi-conjugated, have quick hole flow, end have diaryl fluorene, thus pi accumulation between inducing molecule, makes molecule Film arrangement becomes outstanding, can improve the mobility on film, has rotatable diaryl fluorene huge to replace in end Mobility can be improved in spiro fluorene.The compound of the present invention as a result, can reduce the driving voltage of organic luminescent device, and can change significantly Kind efficiency and service life.
The explanation of aforementioned present invention is for illustrative, and 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 technical idea or essential feature of the invention.Therefore, It should be understood that various embodiments described above be in all respects it is illustrative, without being restrictive.For example, being said with single type Bright each structural element is implemented dispersiblely, and equally, illustrating also can be in a manner of combination for multiple structural elements of dispersion Implement.
Range Representation, rather than above-mentioned detailed description, patent is claimed by appended patented invention in the scope of the present invention The meaning and range and the mode for having altered or deforming as derived from its equivalents for inventing claimed range should be by It is construed to be included within the scope of the present invention.

Claims (12)

1. a kind of compound, which is characterized in that indicated by following formula 1:
Chemical formula 1
In the chemical formula 1,
Ar、Ar’、Ar1And Ar2It is each independently substituted or unsubstituted C6~C30Aryl or substituted or unsubstituted C3 ~C30Heteroaryl,
L1And L2It is each independently Direct Bonding, substituted or unsubstituted C6~C18Arlydene or substituted or unsubstituted C3 ~C30Heteroarylidene,
R1To R4, R and R ' be each independently hydrogen, heavy hydrogen, substituted or unsubstituted C1~C30Alkyl, substituted or unsubstituted C1~C30Alkoxy, substituted or unsubstituted C2~C30Alkenyl, substituted or unsubstituted C6~C30Aryl or substitution Or unsubstituted C3~C30Heteroaryl, the R and R ' can connect and form ring or do not form ring,
The integer that l is 0 or 1 to 4, m, n and o are each independently 0 or integer of 1 to 3.
2. compound according to claim 1, which is characterized in that the compound is indicated by following formula 2:
Chemical formula 2
In the chemical formula 2,
R5To R6It is each independently hydrogen, heavy hydrogen, substituted or unsubstituted C1~C24Alkyl, substituted or unsubstituted C1~C24 Alkoxy, substituted or unsubstituted C2~C24Alkenyl, substituted or unsubstituted C6~C24Aryl or substitution or do not take The C in generation3~C24Heteroaryl,
P and q is each independently 0 or 1 to 5 integer.
3. compound according to claim 2, which is characterized in that the compound is by 4 table of following formula 3 or chemical formula Show:
Chemical formula 3
Chemical formula 4
4. compound according to claim 2, which is characterized in that the compound is indicated by following formula 5:
Chemical formula 5
5. compound according to claim 2, which is characterized in that the compound is by following formula 6 into chemical formula 8 A kind of expression:
Chemical formula 6
Chemical formula 7
Chemical formula 8
6. compound according to claim 2, which is characterized in that the compound is indicated by following formula 9:
Chemical formula 9
7. compound according to claim 2, which is characterized in that the compound is by following formula 10 or chemical formula 11 It indicates:
Chemical formula 10
Chemical formula 11
In the chemical formula 10 or chemical formula 11,
R7And R8It is each independently substituted or unsubstituted C1~C30Alkyl,
Ar3And Ar4It is each independently substituted or unsubstituted C6~C30Aryl or substituted or unsubstituted C3~C30's Heteroaryl.
8. compound according to any one of claim 1 to 7, which is characterized in that the Ar1And Ar2It is each independently In the group be made of phenyl, xenyl, triphenyl, naphthalene, fluorenes, dibenzofurans, dibenzothiophenes and their combination.
9. compound described in any one of according to claim 1 to 3 and 5, which is characterized in that the L1And L2Each independently For Direct Bonding or phenylene.
10. compound according to claim 1, which is characterized in that the compound is one of following compound:
11. a kind of organic luminescent device, which is characterized in that include containing claim 1 between first electrode and second electrode To the organic matter layer of compound described in any one of 10.
12. organic luminescent device according to claim 11, which is characterized in that the organic matter layer be hole injection layer, 1 layer or more in hole transporting layer and luminous auxiliary layer.
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