CN109485637A - The manufacture and its application of 4,4 '-bipyridyliums derivatives - Google Patents

The manufacture and its application of 4,4 '-bipyridyliums derivatives Download PDF

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CN109485637A
CN109485637A CN201710826771.XA CN201710826771A CN109485637A CN 109485637 A CN109485637 A CN 109485637A CN 201710826771 A CN201710826771 A CN 201710826771A CN 109485637 A CN109485637 A CN 109485637A
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phenyl
group
logical formula
bipyridine
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李之洋
邢其锋
张向慧
任雪艳
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Beijing Eternal Material Technology Co Ltd
Guan Eternal Material Technology Co Ltd
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Beijing Eternal Material Technology Co Ltd
Guan Eternal Material Technology Co Ltd
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Abstract

The present invention relates to 4,4'-Bipyridine analog derivative and the organic electroluminescence device for having used it, in particular to the high organic electroluminescence device of service life length, high-luminous-efficiency, excitation purity and its 4,4'-Bipyridine analog derivative is realized.

Description

The manufacture and its application of 4,4'-Bipyridine analog derivative
Technical field
The present invention relates to 4,4'-Bipyridine analog derivative and the organic electroluminescence devices for having used it, in particular to longevity The high organic electroluminescence device of life length, high-luminous-efficiency, excitation purity and the 4,4'-Bipyridine analog derivative for realizing it.
Background technique
The organic electroluminescence device (OLED) of electroluminescent organic material, can be used for the panchromatic colour display screen of solid luminescence type Show and the fields such as solid-state white illumination, is known as next-generation novel display and lighting engineering.Usual OLED device contains luminous Layer and a pair of of the opposite electrode for clamping this layer.When device applies electric field between two electrodes, electronics is injected from cathode side, from anode-side Hole is injected, electronics, with hole-recombination, forms excited state, when excited state is restored to ground state, energy is with light in luminescent layer Form release.
Most of material of main part of preliminary stage report is hole-transporting type material of main part or electron-transporting type material of main part, Due to the imbalance of carrier transmission performance, this unipolar material of main part unfavorable narrow recombination region easy to form.It is logical Often when using hole-transporting type material of main part, charge recombination zone can be generated in luminescent layer and electron-transport bed boundary, and is worked as When using electron-transporting type material of main part, charge recombination zone can be generated in luminescent layer and hole transport bed boundary, however it is weak Unbalanced charge is unfavorable to the luminous efficiency of organic luminescent device in carrier mobility and luminescent layer, while organic electroluminescence phosphorus This narrow charge recombination zone of optical device can accelerate T-T annihilation process, so as to cause luminous efficiency decline, especially It is under current density condition in order to avoid this effect, and the strategy generallyd use is using two luminescent layers, wherein one layer Using hole-transporting type material of main part, another luminescent layer uses electron-transporting type material of main part, by hole-transporting type and electronics The mixing of mode transmission material of main part is placed in single luminescent layer, however both strategies make the preparation of device become complicated, and mixed The material of main part of conjunction will lead to the problem of mutually separating, and therefore, in order to reach efficient electroluminescence, needs to develop to have and put down The material of main part of the carrier transmission performance of weighing apparatus, that is, so-called bipolar host material, to widen charge recombination zone.Separately On the one hand, the service life of the stability strong influence luminescent device of material of main part itself, improves the service life of device It is the target that this field is pursued always.
Summary of the invention
The present invention is in order to solve the problems, such as above to carry out in the prior art.The purpose of the present invention is to provide one kind with excellent The high material of main part of good life characteristic and luminous efficiency and the organic electroluminescence device for having used it.
The present inventor has made intensive studies to achieve the above object, as a result, it has been found that, when using with the following general formula (1) institute When light emitting host material of the 4,4'-Bipyridine analog derivative shown as organic electroluminescence device, it can obtain that the service life is long, hair The high organic electroluminescence device of light efficiency.
Specifically, lead in formula (I),
L1、L2、L3And L4It independently is C6~C30Aryl, C4~C30Heteroaryl or be singly-bound；L1、L2、L3And L4It is identical Or it is different；
Ar1、Ar2、Ar3And Ar4It independently is in the substituent group selected from structure shown in hydrogen atom, phenyl or logical formula (II) It is any number of, also, Ar1And Ar4At least one of for structure shown in logical formula (II) substituent group, Ar2And Ar3In at least one A substituent group for structure shown in logical formula (II), substituent group shown in two logical formula (II)s is identical, described identical to refer to structure It is identical；Preferably, the identical further finger connection site of substituent group shown in the logical formula (II) is identical；
Work as Ar1、Ar2、Ar3Or Ar4When to lead to substituent group shown in formula (II), L1、L2、L3Or L4With the connection of logical formula (II) Site is located on the phenyl ring of logical formula (II) or X1；
In logical formula (II),
X1Selected from N, NR2、CRa、CRbRcOr X1It is not present；Work as X1In the absence of, in formula (II) with X1Two connected carbon Atom single bonds are connected；X2Selected from O, S, NR3、CRdReOr X2It is not present；Work as X2In the absence of, in formula (II) with X2Connected two A carbon atom singly-bound is connected；Also, X1And X2It will not be not present simultaneously；
Wherein R2、R3、Ra、Rb、Rc、Rd、ReIndependently selected from H, C1~C4Alkyl, phenyl, xenyl, terphenyl, naphthalene Base, thienyl, phenothiazinyl, phenoxazine base, carbazyl, furyl, azepine carbazyl；
Two phenyl ring in formula (II) are optionally independently by 0,1,2,3,4 independently selected from C1~C4Alkyl, phenyl, Xenyl, terphenyl, naphthalene, triphenylene, fluorenyl, furyl, benzofuranyl, dibenzofuran group, thienyl, benzo Group in thienyl, dibenzothiophene, phenothiazinyl, phenoxazine base, the group of carbazyl and its composed group replaces；
Optionally, the phenyl ring in formula (II) and other aromatic groups form condensed aromatic ring, other aromatic series bases Group is selected from phenyl, naphthalene, furyl, carbazyl；The condensed aromatic ring is optionally by 0,1,2,3,4 independently selected from C1~ C4Alkyl, substituted or unsubstituted phenyl group replaced.
In above-mentioned the compound of the present invention, L1-Ar1、L2-Ar2、L3-Ar3And L4-Ar4The atomic group collectively constituted is excellent It is selected as the atomic group of rich electrical property, the inventors discovered that, replaced on 4,4'-Bipyridine by rich electrical atomic group, it should Compound as phosphorescence light emitting device material of main part in use, compare existing material of main part, can increase substantially luminous Efficiency.Because material of main part used at present is mostly the mixture of electron type main body and cavity type main body, and the compounds of this invention There is the mother nucleus structure of electron deficient and substituted electron rich group simultaneously, so that it has both been suitble to transmission electronics or be suitble to transmission sky Cave, so as to the material of main part of the carrier transmission performance effectively balanced, so as to widen charge recombination zone, in turn It is presented as reduction operation voltage, improves the technical effect of luminous efficiency.
In the present invention, as long as L1-Ar1、L2-Ar2、L3-Ar3And L4-Ar4The atomic group collectively constituted is rich electrically former Son group.But from reaction easiness, raw material it is ready availability from the aspect of, L1~L4Preferably singly-bound, or selected from phenyl, connection Phenyl, terphenyl, naphthalene, triphenylene, fluorenyl, furyl, benzofuranyl, dibenzofuran group, thienyl, benzo thiophene Group in pheno base, dibenzothiophene, leading to substituent group shown in formula (II) is preferably group represented by following formula.
Wherein, X3Selected from N, N (C1~C4) alkyl, N- phenyl or X3It is not present；Work as X3In the absence of, in formula (II) With X3Two connected carbon atom singly-bounds are connected；L1、L2、L3Or L4It is located at the phenyl ring of logical formula (II) with the connection site of logical formula (II) Upper or X3,
X4Selected from O, S, N (C1~C4) alkyl, N- phenyl or X4It is not present；Work as X4In the absence of, in formula (II) with X4 Two connected carbon atom singly-bounds are connected；Also, X3And X4It will not be not present simultaneously.
These groups can be by 0,1,2,3,4 independently selected from C1~C4Alkyl, substituted or unsubstituted phenyl base Replaced group；Wherein * indicates connection site, the not specific original in following structural formula, in connection site and following structural formula When son connection, expression can be attached with any attachable site in structural formula.
From reaction easiness, raw material it is ready availability from the aspect of, further preferably L1And L2For singly-bound, and Ar1、Ar2It independently is hydrogen Atom, i.e., on each pyridine ring of the parent nucleus of 4,4'-Bipyridine respectively with a rich electrical substituent group (in logical formula (I)- L3-Ar3,-L4-Ar4).Such compound can greatly simplify preparation section.
It is the pyridine derivate of 2-2 ' structure in addition, having been reported that a small amount of Bipyridine compound derivative with the prior art, Experiment proves that the service life of device is not so good as the parent nucleus of our 4,4'-Bipyridines, the possible reason is the position of two N of bipyridyl When distance is too close, some metals or other groups may be coordinated between two N elements, device lifetime is caused to decline.
L3And L4It can be the same or different, from the aspect of synthesis easiness, preferably L3And L4It is identical.Ar3And Ar4 It can be the same or different, from the aspect of synthesis easiness, preferably Ar3And Ar4It is identical.In addition, the inventors discovered that ,- L3-Ar3With-L4-Ar4Identical compound can be realized good hair when being used as the material of main part of organic electroluminescence device Light efficiency.The compound of the present invention can be realized better device efficiency.Its reason is unclear, thus it is speculated that and reason may be, when- L3-Ar3With-L4-Ar4When identical, electron cloud arrangement is more advantageous to the efficiency of transmission for improving carrier, and molecule is stretching, extension Centrosymmetric structure can form a film as better lattice arrangement, in the vapor deposition process for preparing device to obtain structure and electricity The more stable luminous tunic of gas performance, to bring better device efficiency.
In the 4,4'-Bipyridine analog derivative of the invention, as L3And L4Preference, singly-bound can be enumerated, or Person be selected from phenyl, xenyl, terphenyl, naphthalene, triphenylene, fluorenyl, furyl, benzofuranyl, dibenzofuran group, Thienyl, benzothienyl, the group in dibenzothiophene, these groups are optionally by phenyl or C1~C4Alkyl replace； As Ar3And Ar4Preference, can enumerate hydrogen atom or selected from carbazyl, phenothiazinyl, phenoxazine base, acridan base, Dibenzofuran group, naphtho- benzofuranyl, dibenzothiophene, the group in naphtho- benzothienyl, these groups are optional Ground is by phenyl or C1~C4Alkyl replace.
As the preference of formula of of the present invention (I) compound, the change that following structural formula Al to A35 is represented can be enumerated Close object.
The invention further relates to organic electroluminescence devices.Organic electroluminescence device and existing organic light emission of the invention Device has no difference in structure, all includes cathode, anode and organic layer, which is characterized in that include in the organic layer 4,4'-Bipyridine analog derivative shown in above-mentioned logical formula (I).The organic layer of the organic electroluminescence device includes hole injection Layer, hole transmission layer, luminescent layer, electron transfer layer and electron injecting layer, the luminescent layer include material of main part and guest materials, The present invention leads to the material of main part use that 4,4'-Bipyridine analog derivative shown in formula (I) can be used as luminescent layer.
It is bright in terms of the luminous efficiency and driving voltage of organic electroluminescence device in luminescent layer comprising the compounds of this invention It is aobvious to give out light device better than existing organic electroluminescence, and pass through the specific symmetrical compound in the selection present invention, Ke Yishi Now better life characteristic.
It should be noted that in the present invention, the expression way of Ca~Cb represents the carbon atom number that the group has as a~b, Unless specifically indicated, it is however generally that the carbon atom number does not include the carbon atom number of substituent group.
In the present invention, the statement for chemical element includes the concept of chemical property identical isotope, such as " hydrogen " Statement also includes the concept of chemical property identical " deuterium ", " tritium ".
Hetero atom in the present invention is often referred to selected from B, N, O, S, P, P (=O), Si and atom or atomic group in Se.
Specific embodiment
Compound in above-mentioned logical formula (I) can be, but not limited to be used as emitting layer material in organic electroluminescence device.
The specific preparation method of the compound of the present invention, but the present invention will be described in detail by taking multiple synthetic examples as an example below Preparation method be not limited to this multiple synthetic example, those skilled in the art can not depart from the present invention on its basis Any modification, equivalent substitution, improvement and etc. are carried out under the premise of principle, and this method is expanded into claims of the present invention and is wanted Within the scope of the technical solution for asking protection.
The present invention is more specifically described referring to the following examples, but the invention is not limited to these embodiments.
The compound for the synthetic method that do not mention in the present invention is all the raw produce being obtained through commercial channels.Implement Various chemicals used in example chemical products can be commercially available at home.
Parent nucleus synthesis general formula for sharing in the general formula of the present invention (1) of organic electroluminescence device is as follows:
Under argon gas stream, put into 500mL eggplant type flaskThe chloro- 4- pyridine boronic acid of 2-(15.7g, 0.1mol), 2- chlorine 4- Bromopyridine (19.2g, 0.1mol), tetrakis triphenylphosphine palladium 0.6g, potassium carbonate (27.6g, 0.2mol), dioxane 200mL, water 50ml, back flow reaction 3 hours.After cooling, water is added and is extracted with dichloromethane, organic phase is concentrated to give brown solid, ethanol washing Obtain yellow solid M1=20.5g, yield 91.1%.1H NMR (500MHz, Chloroform) δ 8.93 (s, 1H), 8.90 (s, 1H), 8.70 (d, J=2.9Hz, 1H), 8.67 (d, J=2.9Hz, 1H), 7.93 (d, J=3.1Hz, 2H)
Under argon gas stream, put into 500mL eggplant type flaskM1(20g, 0.089mol), connection pinacol borate (67.7g, 0.267mol), Pd2(DBA)30.6g, S-Phos1.2g, sodium tert-butoxide (19.6g, 0.2mol), dimethylbenzene 300ml, Back flow reaction 3 hours.After cooling, water is added and is extracted with dichloromethane, organic phase is concentrated to give brown solid, and it is white that ethanol washing obtains class Color solid M2=28.5g, yield 78.6%.1H NMR (500MHz, Chloroform) δ 8.71 (d, J=15.0Hz, 2H), 8.40 (dd, J=15.0,2.9Hz, 2H), 7.72 (d, J=2.9Hz, 2H), 1.14 (s, 24H)
Main compound synthetic example
Synthetic example 1.
The synthesis of A1
Under argon gas stream, M2 (4.1g, 0.01mol), 3- bromine-N-phenylcarbazole are put into 500mL eggplant type flask (8.5g, 0.025mol), tetrakis triphenylphosphine palladium 0.1g, potassium carbonate (5.5g, 0.04mol), dioxane 100mL, water 10ml, Back flow reaction 6 hours.It after cooling, directly filters, filter cake recrystallizes to obtain white solid Al=4.6g, yield with dimethylbenzene 72.7%.1H NMR (500MHz, Chloroform) δ 8.68 (d, J=15.0Hz, 2H), 8.60 (d, J=2.9Hz, 2H), 8.58-8.49 (m, 3H), 8.30-8.14 (m, 2H), 8.00 (dd, J=14.9,3.0Hz, 2H), 7.89 (dd, J=14.9, 3.0Hz, 1H), 7.70 (t, J=10.1Hz, 1H), 7.67-7.56 (m, 7H), 7.56-7.45 (m, 5H), 7.44-7.33 (m, 1H), 7.25-7.05 (m, 4H)
Synthetic example 2~30
With synthetic example 1, difference is to replace with 3- bromine-N-phenylcarbazole the synthetic method of chemical combination listed in Table The corresponding raw material of equivalent, wherein raw materials used can be bought by Chemical market, shown in table 1 specific as follows:
Table 1
Synthetic example 31
The synthesis of A10
Under argon gas stream, in 500mL eggplant type flask put into M1 (22.5g, 0.1mol), carbazole (18.3g, 0.1mol), Pd2(dba)30.6g, sodium tert-butoxide (27.6g, 0.2mol), tri-tert-butylphosphine, dimethylbenzene 500mL, back flow reaction 4 hours.It is cold But it after, directly filters, filter cake recrystallizes to obtain white solid A10=36g, yield 74.6% with dimethylbenzene.1H NMR (500MHz, Chloroform) δ 8.89-8.80 (m, 2H), 8.55 (dd, J=14.2,3.7Hz, 2H), 8.41-8.32 (m, 4H), 8.25- 8.12 (m, 2H), 7.52 (dd, J=14.2,3.9Hz, 2H), 7.45-7.33 (m, 2H), 7.27-7.02 (m, 8H)
Synthetic example 32~35
With synthetic example 31, difference is to replace with parent nucleus and raw material etc. works as the synthetic method of compound listed in Table The corresponding raw material of amount, wherein raw materials used can be bought by Chemical market, shown in table 2 specific as follows:
Table 2
3 synthetic example characterization of compound data of table
Device embodiments
The structure of organic electroluminescence device in device embodiments of the present invention are as follows: according to " anode/hole is injected on substrate Layer (HIL)/hole transmission layer (HTL)/luminescent layer (EL)/electron transfer layer (ETL)/electron injecting layer (EIL)/cathode " it is suitable Sequence stacking, each layer are made of following material；
ITO/2-TNATA (30nm)/NPB (20nm)/general formula (1) derivative: Ir (ppy)3(5%) (20nm)/BPhen (50nm)/LiF(1nm)/Al。
Emitting layer material uses green phosphorescent coloring Ir (ppy)3Dyestuff, main body general formula (1) derivative of arranging in pairs or groups.Each functional layer material Expect that molecular structure is as follows:
1. compound A1 of device embodiments is as light emitting host material
Organic electroluminescence device preparation process is as follows in the present embodiment:
The glass substrate that surface is coated with transparent conductive film is cleaned by ultrasonic in cleaning solution, in deionized water Ultrasonic treatment, in acetone: ultrasonic oil removing in alcohol mixed solvent (volume ratio 1: 1) mixed solution is baked under clean environment Moisture is completely removed, is performed etching with ultraviolet lamp and ozone treatment, and with low energy cation beam bombarded surface；
The above-mentioned glass substrate with anode is placed in vacuum chamber, is evacuated to 1 × 10-5~9 × 10-3Pa, above-mentioned Vacuum evaporation 2-TNATA is as hole injection layer on anode tunic, and evaporation rate 0.1nm/s, vapor deposition total film thickness is 40nm；So Hole transmission layer NPB, evaporation rate 0.1nm/s are deposited afterwards, vapor deposition film thickness is 10nm；
Luminescent layer of the vacuum evaporation EML as device on hole transmission layer, EML include material of main part and dyestuff material A2 as luminous layer main body is placed in the cell of vacuum phase deposition equipment, will be made by material, the method steamed altogether using multi-source For (ppy) of dopant3Ir is placed in another room of vacuum phase deposition equipment, is adjusted material of main part A1 evaporation rate and is The concentration of 0.1nm/s, Ir (ppy) 3 is 10%, and vapor deposition total film thickness is 20nm；
Vacuum evaporation Bphen forms the electron transfer layer that film thickness is 50nm, evaporation rate 0.1nm/ on the light-emitting layer s；
On the electron transport layer successively vacuum evaporation with a thickness of 1nm LiF as electron injecting layer, with a thickness of 150nm's The Al layers of cathode as device.
2. the compounds of this invention A4 of device embodiments is as light emitting host material
Organic electroluminescence device is prepared using method same as Example 1, difference is, by compound A1ization It closes object and replaces with compound A-13.
3. the compounds of this invention A7 of device embodiments is as light emitting host material
Organic electroluminescence device is prepared using method same as Example 1, difference is, compound A1 is replaced It is changed to compound A22.
4. the compounds of this invention A12 of device embodiments is as light emitting host material
Organic electroluminescence device is prepared using method same as Example 1, difference is, compound A1 is replaced It is changed to compound A24.
5. the compounds of this invention A16 of device embodiments is as light emitting host material
Organic electroluminescence device is prepared using method same as Example 1, difference is, compound A1 is replaced It is changed to compound B-11.
6. the compounds of this invention A20 of device embodiments is as light emitting host material
Organic electroluminescence device is prepared using method same as Example 1, difference is, compound A1 is replaced It is changed to compound B3.
7. the compounds of this invention A29 of device embodiments is as light emitting host material
Organic electroluminescence device is prepared using method same as Example 1, difference is, by compound A1ization It closes object and replaces with compound B22.
8. the compounds of this invention A31 of device embodiments is as light emitting host material
Organic electroluminescence device is prepared using method same as Example 1, difference is, compound A1 is replaced It is changed to compound B24.
Device comparative example 1.CPB is as light emitting host material
Organic electroluminescence device is prepared using method same as Example 1, difference is, compound A1 is replaced It is changed to compound CPB.
Device comparative example 2.CC1 is as light emitting host material
Organic electroluminescence device is prepared using method same as Example 1, difference is, compound A1 is replaced It is changed to compound CC1.
Device comparative example 3.CC2 is as light emitting host material
Organic electroluminescence device is prepared using method same as Example 1, difference is, compound A1 is replaced It is changed to compound CC2.
Device comparative example 4.CC3 is as light emitting host material
Organic electroluminescence device is prepared using method same as Example 1, difference is, compound A1 is replaced It is changed to compound CC3.
Under same brightness, using in digital sourcemeter and luminance meter measurement device embodiments 1-8 and device comparative example 1-4 The driving voltage and current efficiency of the organic electroluminescence device being prepared and the service life of device, specially with 0.1V per second Rate promoted voltage, when brightness reaches 10000cd/m2When current density also measure simultaneously, the ratio of brightness and current density Value is efficiency；The life test of T90 is using luminance meter in 10000cd/m2Under brightness, it is bright to measure its for the electric current kept constant Degree is reduced to 9000cd/m2Time.
It the results are shown in Table 2.
Concrete preferred structure compound disclosed in device embodiments of the present invention is applied in organic electroluminescence device Device performance detection data is detailed in the following table 4:
Table 4
The device performance data of the device embodiments 1-8 as disclosed in table 4 are as it can be seen that in organic electroluminescence device structure In the identical situation of other materials, the adjustment of EML material in the devices, compare device comparative example 1-4, can increase substantially The luminous efficiency of device and the service life of device.
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above Detail within the scope of the technical concept of the present invention can be with various simple variants of the technical solution of the present invention are made, this A little simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance In the case where shield, can be combined in any appropriate way, in order to avoid unnecessary repetition, the present invention to it is various can No further explanation will be given for the combination of energy.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally The thought of invention, it should also be regarded as the disclosure of the present invention.

Claims (9)

1. the 4,4'-Bipyridine analog derivative as shown in logical formula (I):
In logical formula (I),
L1、L2、L3And L4It independently is C6~C30Aryl, C4~C30Heteroaryl or be singly-bound；L1、L2、L3And L4It is identical or It is different；
Ar1、Ar2、Ar3And Ar4It independently is any in the substituent group selected from structure shown in hydrogen atom, phenyl or logical formula (II) Kind, also, Ar1And Ar4At least one of for structure shown in logical formula (II) substituent group, Ar2And Ar3At least one of be The substituent group of structure shown in logical formula (II), substituent group shown in two logical formula (II)s is identical, described identical to refer to that structure is identical； Preferably, the identical further finger connection site of substituent group shown in the logical formula (II) is identical；
Work as Ar1、Ar2、Ar3Or Ar4When to lead to substituent group shown in formula (II), L1、L2、L3Or L4With the connection site of logical formula (II) On the phenyl ring of logical formula (II) or X1；
In logical formula (II),
X1Selected from N, NR2、CRa、CRbRcOr X1It is not present；Work as X1In the absence of, in formula (II) with X1Two connected carbon atoms Singly-bound is connected；X2Selected from O, S, NR3、CRdReOr X2It is not present；Work as X2In the absence of, in formula (II) with X2Two connected carbon Atom single bonds are connected；Also, X1And X2It will not be not present simultaneously；
Wherein R2、R3、Ra、Rb、Rc、Rd、ReIndependently selected from H, C1~C4Alkyl, phenyl, xenyl, terphenyl, naphthalene, Thienyl, phenothiazinyl, phenoxazine base, carbazyl, furyl, azepine carbazyl；
Two phenyl ring in formula (II) are optionally independently by 0,1,2,3,4 independently selected from C1~C4Alkyl, phenyl, biphenyl Base, terphenyl, naphthalene, triphenylene, fluorenyl, furyl, benzofuranyl, dibenzofuran group, thienyl, benzothiophene Group in base, dibenzothiophene, phenothiazinyl, phenoxazine base, the group of carbazyl and its composed group replaces；
Optionally, the phenyl ring in formula (II) and other aromatic groups form condensed aromatic ring, other aromatic group choosings From phenyl, naphthalene, furyl, carbazyl；The condensed aromatic ring is optionally by 0,1,2,3,4 independently selected from C1~C4's Alkyl, substituted or unsubstituted phenyl group replaced.
2. 4,4'-Bipyridine analog derivative according to claim 1, which is characterized in that substituent group shown in logical formula (II) For group represented by following formula, following formula group it is optional by 0,1,2,3,4 independently selected from C1~C4Alkyl, replace or not Replaced the group of substituted phenyl；Wherein * indicates connection site, in following structural formula, when connection site and following structures When not specific atoms in formula connect, expression can be attached with any attachable site in structural formula:
Wherein, X3Selected from N, N (C1~C4) alkyl, N- phenyl or X3It is not present；Work as X3In the absence of, in formula (II) with X3 Two connected carbon atom singly-bounds are connected；L1、L2、L3Or L4It is located on the phenyl ring of logical formula (II) with the connection site of logical formula (II) Or X3,
X4Selected from O, S, N (C1~C4) alkyl, N- phenyl or X4It is not present；Work as X4In the absence of, in formula (II) with X4It is connected Two carbon atom singly-bounds be connected；Also, X3And X4It will not be not present simultaneously.
3. 4,4'-Bipyridine analog derivative according to claim 1 or 2, which is characterized in that L1And L2For singly-bound, and Ar1、 Ar2It independently is hydrogen atom.
4. 4,4'-Bipyridine analog derivative according to claim 1 or 2, which is characterized in that L3And L4Singly-bound independently is, Or it is selected from phenyl, xenyl, terphenyl, naphthalene, triphenylene, fluorenyl, furyl, benzofuranyl, dibenzofurans Base, thienyl, benzothienyl, the group in dibenzothiophene, these groups are optionally by phenyl or C1~C4Alkyl take Generation；L3And L4It is same or different, it is preferable that L3And L4It is identical；Ar3And Ar4Independently be hydrogen atom or selected from carbazyl, Phenothiazinyl, phenoxazine base, acridan base, dibenzofuran group, naphtho- benzofuranyl, dibenzothiophene, naphtho- benzene Group in bithiophene base, these groups are optionally by phenyl or C1~C4Alkyl replace；Ar3And Ar4It is same or different, Preferably, Ar3And Ar4It is identical.
5. 4,4'-Bipyridine analog derivative according to claim 4, wherein L3And L4It is respectively positioned on N in 4,4'-Bipyridine Ortho position.
6. 4,4'-Bipyridine analog derivative according to claim 1, which is characterized in that the compound is with flowering structure One of the compound that formula A1 to A35 is represented:
7. 4,4'-Bipyridine analog derivative shown in logical formula (I) according to any one of claims 1 to 6 is sent out in organic electroluminescence Application in optical device.
8. a kind of organic electroluminescence device comprising cathode, anode and organic layer, the organic layer include claim 1 4,4'-Bipyridine analog derivative shown in logical formula (I) described in any one of~7.
9. organic electroluminescence device according to claim 8, organic layer include hole injection layer, hole transmission layer, Luminescent layer, electron transfer layer and electron injecting layer, the luminescent layer include that 4,4'-Bipyridine class shown in the logical formula (I) is spread out Material of main part of the biology as luminescent layer.
CN201710826771.XA 2017-09-13 2017-09-13 The manufacture and its application of 4,4 '-bipyridyliums derivatives Pending CN109485637A (en)

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JP2013131518A (en) * 2011-12-20 2013-07-04 Konica Minolta Inc Material for organic electroluminescent element, organic electroluminescent element, display device and lighting system
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000186066A (en) * 1998-12-22 2000-07-04 Minolta Co Ltd New amino compound, its production and use thereof
CN1643105A (en) * 2002-03-15 2005-07-20 出光兴产株式会社 Material for organic electroluminescent device and organic electroluminescent device prepared using the same
JP2013131518A (en) * 2011-12-20 2013-07-04 Konica Minolta Inc Material for organic electroluminescent element, organic electroluminescent element, display device and lighting system
CN106715420A (en) * 2014-09-25 2017-05-24 西诺拉股份有限公司 Crosslinkable host materials

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