CN110452239A - Nitrogen-containing heterocycle compound and its application and organic electroluminescence device - Google Patents
Nitrogen-containing heterocycle compound and its application and organic electroluminescence device Download PDFInfo
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- C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
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Abstract
This disclosure relates to a kind of nitrogen-containing heterocycle compound, which has the structure as shown in following formula (1):
Description
Technical field
This disclosure relates to field of organic electroluminescent materials, and in particular, to a kind of nitrogen-containing heterocycle compound and its application
And organic electroluminescence device.
Background technique
The research of electroluminescent organic material and device starts from the 1960s.According to principle of luminosity difference, Organic Electricity
Photoluminescence can be divided into electroluminescent fluorescent and electroluminescent phosphorescence two major classes.The triplet exciton of fluorescent material is acted on by spin forbidden, only
Ground state can be returned to unirradiated form and generates photon, and the internal quantum efficiency of electroluminescent fluorescent is caused to be limited within 25%.And it is electric
Photo-phosphorescence is because the energy of singlet excitons and triplet exciton can be made full use of, the theoretically interior quantum of phosphorescent devices
Efficiency can achieve 100%.1998, Hong Kong University Ma etc. and Princeton university Forrest etc. were reported respectively
Theoretical internal quantum efficiency up to 100% electromechanical phosphorescent material and device.These important research work have greatly pushed
The development of organic electroluminescence devices, so that the research of organic electroluminescent becomes international hot spot.
The fluorescence OLED device for being able to achieve the internal quantum efficiency limitation for breaking through 25% mainly uses thermal activation delayed fluorescence
(TADF:Thermally Activated Delayed Fluorescence) mechanism.TADF mechanism is using with smaller list
Weight poor (the Δ E of state-triplet energy levelST) organic small molecule material, triplet exciton can be by anti-in the case where absorbing environment thermal energy
To intersystem crossing (RISC), this process is converted into singlet excitons, and theoretically its device internal quantum efficiency can reach 100%.But
Efficiency roll-off (roll-off) is larger under high illumination for the TADF material reported at present, and the service life is shorter, limits it panchromatic aobvious
Show and the application in white-light illuminating.Currently, improving the super quick fluorophor of exciton utilization rate using TADF material as material of main part
System becomes the hot spot of everybody concern.In thermal activation delayed fluorescence luminescence system, the thermal activation delay as material of main part is glimmering
The triplet state of light (TADF) material returns to singlet by reversed intersystem crossing (RISC) process, and then transfers energy to object
Complete energy transmission can be realized in material emission at low concentrations in this way, so as to reduce concentration quenching, reduce device
Part cost.
But current thermal activation delayed fluorescence (TADF) material there are cavity transmission ability and electron transport abilities not
The case where matching, reversed intersystem crossing rate (kRISC) lower, triplet state-polaron buries in oblivion the problems such as (TPA) is more serious.
In addition, cave transmittability is often better than electron transport ability in electroluminescent organic material, lead to electricity in this way
Son and hole transport are unbalanced, influence the luminous efficiency of electroluminescent device.
Summary of the invention
The purpose of the disclosure is the driving voltage for reducing organic electroluminescence device, improves luminous efficiency.
To achieve the goals above, disclosure first aspect provides a kind of nitrogen-containing heterocycle compound, heterocyclic compound tool
Just like structure shown in following formula (1):
Wherein, Z1、Z2、Z3、Z4、Z5And Z6It is respectively selected from C atom, CR9At least one of with N atom, and Z1、Z2、
Z3、Z4、Z5And Z6The number of middle N atom is 0,1 or 2；
X1、X2、X3And X4It is respectively selected from CR9’Or N atom, and X1、X2、X3And X4In at least one be N atom；
R1、R2、R3、R4、R5、R6、R7、R8、R1’、R2’、R3’、R4’、R9And R9’It is each independently selected from hydrogen atom, C1~C10
Alkyl, C1~C10Naphthenic base, substituted or unsubstituted C6~C30Aryl and substituted or unsubstituted C3~C30In heteroaryl extremely
Few one kind；
L is respectively and independently selected from singly-bound, substituted or unsubstituted C6~C30Arlydene, substituted or unsubstituted C3~C30's
At least one of inferior heteroaryl, m 0,1 or 2；
Work as Z1、Z2、Z3、Z4、Z5And Z6When middle N atomicity is 0, Ar is selected from one of structure shown in S2~S6；Z1、Z2、
Z3、Z4、Z5And Z6When middle N atomicity is 1 or 2, Ar is selected from one of structure shown in S1~S6, and wherein * is connection site；
The substituted C6~C30Arlydene, substituted C3~C30Inferior heteroaryl, substituted C6~C30Aryl, substituted C3
~C30Substituent group in heteroaryl is each independently selected from halogen, C1~C10Alkyl, C3~C10Naphthenic base, C2~C6Alkene
Base, C2~C6Cycloalkenyl, C1~C6Alkoxy, C1~C6Thio alkoxy, C6~C30Aryl and C3~C30Heteroaryl
At least one of base.
Disclosure second aspect provides nitrogen-containing heterocycle compound described in disclosure first aspect and is preparing organic electroluminescence hair
Application in optical device.
The disclosure third aspect provides a kind of organic electroluminescence device, including substrate, anode layer, cathode layer, Yi Jijie
At least one layer of organic layer between anode layer and cathode layer, the organic layer includes hole injection layer, hole transmission layer, organic
Luminescent layer, electron transfer layer and electron injecting layer, the organic luminous layer contain nitrogen-containing hetero described in disclosure first aspect
Cycle compound.
Through the above technical solutions, the nitrogen-containing heterocycle compound of the disclosure include have preferable electron transfer capabilities carboline and
Carbazole group with excellent cavity transmission ability, this unsymmetric structure make molecule be provided simultaneously with excellent hole and electronics
Transmission performance；Since cavity transmission ability is often better than its electron transport ability in organic electroluminescent molecule, the disclosure contains
The electron-withdrawing groups such as N heterocycle and triazine, benzene cyano, pyrazine, the pyridine cyano of bridging are introduced in nitrogen heterocyclic molecular structure
Group, facilitates the promotion of molecular electronic transmittability.The nitrogen-containing heterocycle compound has excellent bipolar transmission ability, can
Charge recombination zone is widened, efficiency roll-off is reduced；And by the introducing of carboline group not of the same race, and to carbazole group and/
Or carboline group can regulate and control the energy level of compound with respect to the change of the position of substitution, so that screening has different energy levels
Material, be easy to device material selection collocation.
Other feature and advantage of the disclosure will the following detailed description will be given in the detailed implementation section.
Specific embodiment
The specific embodiment of the disclosure is described in detail below.It should be understood that described herein specific
Embodiment is only used for describing and explaining the disclosure, is not limited to the disclosure.
Disclosure first aspect provides a kind of nitrogen-containing heterocycle compound, which has as shown in following formula (1)
Structure:
Wherein, Z1、Z2、Z3、Z4、Z5And Z6It is respectively selected from C atom, CR9At least one of with N atom, and Z1、Z2、
Z3、Z4、Z5And Z6The number of middle N atom is 0,1 or 2；
X1、X2、X3And X4It is respectively selected from CR9’Or N atom, and X1、X2、X3And X4In at least one be N atom；
R1、R2、R3、R4、R5、R6、R7、R8、R1’、R2’、R3’、R4’、R9And R9’It is each independently selected from hydrogen atom, C1~C10
Alkyl, C1~C10Naphthenic base, substituted or unsubstituted C6~C30Aryl and substituted or unsubstituted C3~C30In heteroaryl extremely
Few one kind；
L is respectively and independently selected from singly-bound, substituted or unsubstituted C6~C30Arlydene, substituted or unsubstituted C3~C30's
At least one of inferior heteroaryl, m 0,1 or 2；
Work as Z1、Z2、Z3、Z4、Z5And Z6When middle N atomicity is 0, Ar is selected from one of structure shown in S2~S6；Z1、Z2、
Z3、Z4、Z5And Z6When middle N atomicity is 1 or 2, Ar is selected from one of structure shown in S1~S6, and wherein * is connection site；
The substituted C6~C30Arlydene, substituted C3~C30Inferior heteroaryl, substituted C6~C30Aryl, substituted C3
~C30Substituent group in heteroaryl is each independently selected from halogen, C1~C10Alkyl, C3~C10Naphthenic base, C2~C6Alkene
Base, C2~C6Cycloalkenyl, C1~C6Alkoxy, C1~C6Thio alkoxy, C6~C30Aryl and C3~C30Heteroaryl
At least one of base.
The innovation of the invention consists in that:
Carbazole has excellent cavity transmission ability, while carboline has preferable cavity transmission ability, it may have compared with
Strong electron transfer capabilities asymmetricly include both groups in the nitrogen-containing heterocycle compound molecular structure of the disclosure, so that
Molecule is provided simultaneously with excellent hole and electronic transmission performance；
Since cavity transmission ability is often better than its electron transport ability in organic electroluminescent molecule, the disclosure it is nitrogenous
The electron-withdrawing groups such as N heterocycle and triazine, benzene cyano, pyrazine, the pyridine cyano of bridging are introduced in heterocyclic compound molecule, are helped
In the promotion of molecular electronic transmittability, to make compound that there is excellent bipolar transmission ability, it is multiple that charge can be widened
Region is closed, efficiency roll-off is reduced；
And pass through the introducing of carboline group not of the same race, and the change to carbazole carboline group with respect to the position of substitution, it takes
Replace structure with asymmetrical carbazole carboline, the energy level of compound can be regulated and controled, so that screening has different energy levels
Material is easy to device material selection collocation.
In an embodiment of the present disclosure, in the nitrogen-containing heterocycle compound of structure shown in formula (1), Z1、Z2、Z3、Z4、Z5
And Z6Middle N atomicity can be 0, i.e. Z1、Z2、Z3、Z4、Z5And Z6It is respectively selected from C atom or CR9, the nitrogen-containing heterocycle compound at this time
It can have structure shown in formula (2):
Wherein, Ar can be selected from one of structure shown in S2~S6, L, m, X1、X2、X3、X4、R1、R2、R3、R4、R5、R6、
R7、R8、R1’、R2’、R3’、R4’、R9And R9’It can have range of choice same as described above.
In another embodiment, in the nitrogen-containing heterocycle compound of structure shown in formula (1), Z1、Z2、Z3、Z4、Z5And Z6In
N atomicity can be 1, i.e. Z1、Z2、Z3、Z4、Z5And Z6One of them is N atom, remaining each is selected from C atom or CR9, at this time
The nitrogen-containing heterocycle compound can have structure shown in formula (3):
Wherein, Ar can be selected from one of structure shown in S1~S6, L, m, X1、X2、X3、X4、R1、R2、R3、R4、R5、R6、
R7、R8、R1’、R2’、R3’、R4’、R9And R9’It can have range of choice same as described above.
In the third embodiment, in the nitrogen-containing heterocycle compound of structure shown in formula (1), Z1、Z2、Z3、Z4、Z5And Z6In
N atomicity can be 2, i.e. Z1、Z2、Z3、Z4、Z5And Z6In there are two N atom, remaining each is selected from C atom or CR9, at this time should
Nitrogen-containing heterocycle compound can have structure shown in formula (4):
Wherein, Ar can be selected from one of structure shown in S1~S6, L, m, X1、X2、X3、X4、R1、R2、R3、R4、R5、R6、
R7、R8、R1’、R2’、R3’、R4’、R9And R9’It can have range of choice same as described above.
According to the disclosure, the X1、X2、X3And X4The number of middle N atom can be 1~3, preferably 1~2.In order to
The electron transport ability for further increasing heterocyclic compound, in a kind of most preferred embodiment of the disclosure, X1、X2、X3With
X4One of them can be N atom, remaining can be identical or different, and can respectively stand alone as CR9’, R9’Can have with it is above-mentioned
Identical definition is selected from hydrogen atom, C1~C10Alkyl, C1~C10Naphthenic base, substituted or unsubstituted C6~C30It aryl and takes
Generation or unsubstituted C3~C30At least one of heteroaryl.
It is further preferred that R9’It can be H, i.e. X1、X2、X3And X4One of them is N atom, remaining is CH, this time-division
Carboline ring is formed in minor structure, electron transport ability significantly improves, and carboline ring unsubstituted steric hindrance is small, easily prepared.
In another specific embodiment of the disclosure, X1And/or X4It can be N atom, X2And X3It can be respectively independent
For CR9’, X2And X3Can be identical or different, R9’Hydrogen atom, C can be each independently selected from1~C10Alkyl, C1~C10Naphthenic base,
Substituted or unsubstituted C6~C30Aryl and substituted or unsubstituted C3~C30At least one of heteroaryl, wherein X2And X3It can
It is connected with each other cyclization.
According to the disclosure, in structure shown in formula (1)The position of three connection sites is not important on ring
It asks, can be such as 1,3,5 three connections, 1,2,3 three connections or 1,2,4 three connect, preferably 1,3,5 three connections or 1, and 2,4 three
Connection preferably has structure shown in formula (5) or formula (6):
Wherein, * is connection site.
According to the disclosure, above-mentioned C6~C30Arlydene, C3~C30Inferior heteroaryl, C6~C30Aryl or C3~C30Heteroaryl
When respectively having substituent group, their substituent group is respectively independently preferably halogen, C1~C4Alkyl, C3~C6Naphthenic base, C1
~C4At least one of alkoxy, phenyl, xenyl and pyridyl group；Wherein, halogen can be in-F ,-Cl ,-Br ,-I
At least one, C1~C4Alkyl be preferably in methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group and tert-butyl extremely
Few one kind, C1~C4Alkoxy be preferably methoxyl group, ethyoxyl, positive propoxy, isopropoxy, at least one in n-butoxy
Kind, C3~C6Naphthenic base be preferably cyclopenta or cyclohexyl.Wherein, substituent group can be further substituted, such as substituent group is
When phenyl or pyridyl group, phenyl or pyridyl group can be further by halogen or C1~C4The groups such as alkyl replace.
According to the disclosure, C6~C30Aryl be it is well-known to those skilled in the art, that is, have 6~30 skeleton carbon originals
Son aryl, preferably with 6~15 backbone carbon atoms aryl, such as can for selected from phenyl, xenyl, terphenyl,
Naphthalene, anthryl, phenanthryl, indenyl, fluorenyl, benzo fluorenyl, 9,9 '-dialkyl fluorenyls, 9,9 '-spiral shell, two fluorenyl, indeno fluorenyl, fluoranthene
Base, triphenylene, pyrenyl, base,Base and aphthacene baseAt least one of base；Wherein, xenyl may include being selected from
2- xenyl, 3- xenyl and 4- xenyl；Terphenyl may include p- terphenyl -4- base, p- terphenyl -3-
In base, p- terphenyl -2- base, m- terphenyl -4- base, m- terphenyl -3- base and m- terphenyl -2- base extremely
Few one kind, naphthalene may include 1- naphthalene or 2- naphthalene, and anthryl may include at least one in 1- anthryl, 2- anthryl and 9- anthryl
Kind, pyrenyl may include selected from least one of 1- pyrenyl, 2- pyrenyl and 4- pyrenyl.According to the disclosure, C6~C30Arlydene
Be it is well-known to those skilled in the art, i.e., with 6~30 backbone carbon atoms arlydene, it is possible to further for by upper
State the C of type6~C30Aryl lose the arlydene of hydrogen atom formation, preferably phenylene.
According to the disclosure, heteroaryl refers to at least one hetero atom and with the monocycle of certain amount ring skeleton atom
Or polycyclic aromatic group, hetero atom may include one or more hetero atoms selected from B, N, O, S, P (=O), Si and P；It is preferred that
Ground, hetero atom may include one or more hetero atoms for being selected from O, S and N.C3~C30Heteroaryl has 3~30 skeleton carbon originals
Son preferably has 3~15 backbone carbon atoms, such as can be for selected from thienyl, furyl, dibenzofuran group, azepine two
Benzofuranyl, azepine dibenzothiophene, dibenzothiophene, dibenzo selenophen base, carbazyl, carboline base, pyrrole radicals, miaow
Oxazolyl, benzimidazolyl, indyl, pyridyl group, oxazolyl, oxadiazoles base, benzoxazolyl, triazine radical, pyrimidine radicals, quinazoline
At least one of base, quinoxalinyl, naphthyridines base, phenazinyl, ferrosin base, benzimidazolyl and indolocarbazole base；It is preferred that
For at least one of pyridyl group, bipyridyl, phenylpyridyl.According to the disclosure, C3~C30Inferior heteroaryl is this field skill
Known to art personnel, i.e., with the inferior heteroaryl of 3~30 backbone carbon atoms, it is possible to further for by mentioned kind
C3~C30Inferior heteroaryl loses the inferior heteroaryl of hydrogen atom formation, preferably phenylene, sub-pyridyl group.
According to the disclosure, C1~C10Alkyl be it is well-known to those skilled in the art, i.e., with 1~10 carbon atom
Aliphatic alkyl, can in methyl, ethyl, propyl, butyl, amyl, hexyl, heptyl, octyl, nonyl and decyl extremely
Few one kind, wherein alkyl can be direct-connected alkyl or the alkyl with branch, further preferably methyl, ethyl, n-propyl, different
In propyl, normal-butyl, isobutyl group, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl and positive decyl at least
It is a kind of.
According to the disclosure, C1~C6Alkoxy be it is well-known to those skilled in the art, i.e., with 1~6 carbon atom
Alkoxy, can for selected from methoxyl group, ethyoxyl, positive propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy,
At least one of n-pentyloxy, positive hexyloxy.
According to the disclosure, the C3~C10Naphthenic base be it is well-known to those skilled in the art, that is, have 3~10 carbon
The naphthenic base of atom, preferably cyclopenta or cyclohexyl.
According to the disclosure, C2~C6Alkenyl be it is well-known to those skilled in the art, i.e., with 2~6 carbon atoms alkene
Base may include mono alkenyl or the group that polyenoid is formed, such as can be selected from vinyl, acrylic, cyclobutenyl, 1,3- fourth two
One of alkenyl.
According to the disclosure, C1~C6Thio alkoxy be it is well-known to those skilled in the art, that is, have 1~6 carbon original
The thio alkoxy of son, the group after being substituted for the oxygen atom in alkoxy by sulphur atom, such as selected from methyl mercapto or second
Sulfenyl.
According to the disclosure, the number of substituent group is unlimited on carboline group, in order to further increase the electronics of heterocyclic compound
Transmittability, substituent group can be 0~4 on carboline group, preferably 0~1, i.e., in a preferred embodiment, R5、
R6、R7And R8One of them can be C1~C10Alkyl, substituted or unsubstituted C6~C30Aryl and substituted or unsubstituted C3~
C30One of heteroaryl, remaining is hydrogen atom.In another preferred embodiment, unsubstituted on carboline group,
That is R5、R6、R7And R8It is hydrogen atom.
According to the disclosure, the number of substituent group is also unlimited on carbazole group, in order to further increase the sky of heterocyclic compound
Cave transmittability, substituent group can be 0~8, preferably 0~6 on carbazole group.Two benzene ring substituents of carbazole group
Number and type can be identical or different, and preferably number identical type is identical.In disclosure preferred embodiment, in order into
The cavity transmission ability and electron transport ability of one step equilibrium compound, can be unsubstituted on two phenyl ring of carbazole group
Base, i.e. R1、R2、R3、R4、R1’、R2’、R3’And R4’It is hydrogen atom.
In another embodiment, there can be 2 substituent groups on carbazole group, substituting group position is unlimited, and preferably two
Substituent group is located on two phenyl ring of carbazole group, and the position of substitution is symmetrical；Further, R2And R2’It can be respectively selected from
C1~C10Alkyl, substituted or unsubstituted C6~C30Aryl and substituted or unsubstituted C3~C30One of heteroaryl, preferably
For at least one of methyl, isopropyl and tert-butyl, R1、R3、R4、R1’、R3’And R4’Can divide is hydrogen atom；Alternatively, R3
And R3’C can be respectively selected from1~C10Alkyl, substituted or unsubstituted C6~C30Aryl and substituted or unsubstituted C3~C30Heteroaryl
At least one of one of base, preferably methyl, isopropyl and tert-butyl, R1、R2、R4、R1’、R2’And R4’It can divide and be
Hydrogen atom.
Further, in order to improve the disclosure heterocyclic compound electronic transmission performance and meanwhile be convenient for synthesizing, carbazyl
Group and carboline group do not include substituent group, i.e. R1、R2、R3、R4、R5、R6、R7、R8、R1’、R2’、R3’And R4’It is hydrogen atom.
According to the disclosure, in structure shown in formula (1), when m is 2, group represented by L can be identical or different, preferably
Ground, L are each independently singly-bound, substituted or unsubstituted C6~C15Arlydene, substituted or unsubstituted C3~C15Asia it is miscellaneous
One of aryl, further preferably singly-bound, phenylene, sub-pyridyl group, biphenyl subunit, phenanthrylene, naphthylene and anthrylene；
Wherein phenylene may include one of 1,2- phenylene, 1,3- phenylene, Isosorbide-5-Nitrae-phenylene, and naphthylene may include Isosorbide-5-Nitrae-
Naphthylene or 1,5- naphthylene, anthrylene may include 9,10- anthrylene.
It is described that one of following structural formula can be selected from based on nitrogen-containing heterocycle compound according to the disclosure:
Disclosure second aspect provides nitrogen-containing heterocycle compound described in disclosure first aspect and is preparing organic electroluminescence hair
Application in optical device.
According to the disclosure, the nitrogen-containing heterocycle compound has preferable electronic transmission performance and suitable energy level, can be with
Luminescent layer material of main part and/or guest materials as the organic electroluminescence device.
The disclosure third aspect provides a kind of organic electroluminescence device, including substrate, anode layer, cathode layer, Yi Jijie
At least one layer of organic layer between anode layer and cathode layer, the organic layer includes hole injection layer, hole transmission layer, organic
Luminescent layer, electron transfer layer and electron injecting layer, the hole injection layer, hole transmission layer, organic luminous layer, electronics pass
Defeated layer and electron injecting layer are sequentially formed on the anode layer, the material of main part and/or object of the organic luminous layer
Material contains nitrogen-containing heterocycle compound described in first aspect, preferably comprises at least one of compound P1~P138.
Excellent properties of the organic electroluminescence device of the disclosure based on disclosure compound can reduce device and open electricity
Pressure improves luminous efficiency, reduces efficiency roll-off.
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 such as petroleum ether, ethyl acetate, N,N-dimethylformamide, toluene, dioxane, dichloromethane used in example
Alkane, 2,5- difluoro bromobenzene, CuI, connection boric acid pinacol ester, sodium carbonate, potassium phosphate, 4- bromine m-dicyanobenzene, potassium acetate, [1,1'- is bis-
(diphenylphosphino) ferrocene] palladium chloride, tetrakis triphenylphosphine palladium, carbazole, 3,6- di-t-butyl carbazole, the bromo- 2,6- bis- of 4-
The basic chemical industries raw materials such as the bromo- 1,3- benzene dinitrile of fluorine pyridine, 5-, tri- Bromopyrimidine of 2,4,6-, hydrogenation receive, α-carboline and B-carboline
Chemical products are commercially available at home.
The bromo- 2- methyl naphthalene of sodium tert-butoxide, 1-, o-dibromobenzene, butyl lithium, Bromofume, o-dibromobenzene, N- bromo succinyl
Imines, methoxyl methyl San Jia Ji phosphonium chloride.
The analysis detection of intermediate and compound in the present invention uses ABSCIEX mass spectrograph (4000QTRAP) He Bulu
Gram Nuclear Magnetic Resonance (400M Hz).
The above synthetic route is illustrated below with reference to synthetic example 1-10.
Synthetic example 1: the synthesis of compound P37
The preparation of intermediate M1:
2,5- difluoro bromobenzene 13.5g is added in a 3000mL three-necked flask equipped with magnetic agitation at room temperature
(70mmol, 1eq), connection boric acid pinacol ester 35.4g (140mmol, 2eq), potassium acetate 68g (697mmol, 20%eq), [1,
Bis- (diphenylphosphino) ferrocene of 1'-] palladium chloride 6.1g (8.4mmol, 12%eq), solvent dioxane 1000mL, it finishes,
Displacement nitrogen 3 times.Oil bath is warming up to 100 DEG C, and reaction is overnight.(PE:EA=10:1, product Rf=0.5,2,5- difluoro bromobenzene Rf
=1.0)
Reaction solution is down to room temperature, is extracted with ethyl acetate, upper layer is taken, reaction solution is spin-dried for, PE:EA=30:1 carries out column
Chromatography, obtains white solid, intermediate M1,13g.
The preparation of intermediate M2:
Toluene 500mL, intermediate M1 20g is added in a 1000mL single-necked flask equipped with magnetic agitation at room temperature
(83.3mmol, 1.2eq), 4- bromine m-dicyanobenzene 14.3g (70mmol, 1eq), aqueous sodium carbonate (sodium carbonate 22.3g,
210mmol, 3eq, water 105mL, 2M), tetra-triphenylphosphine palladium 4.04g (3.5mmol, 0.05eq) opens stirring, replaces nitrogen 3
It is secondary, 100 DEG C are warming up to, reaction is overnight.(PE:DCM=20:1, product Rf=0.7, intermediate M1Rf=0.2)
Reaction solution is down to room temperature, is extracted with ethyl acetate, upper layer is taken, reaction solution is spin-dried for, PE:DCM=30:1 crosses column
Son obtains white solid, intermediate M1,16g.
The preparation of intermediate M3:
N,N-Dimethylformamide 100mL is added in a 500mL single-necked flask equipped with magnetic agitation at room temperature, adds
Enter the NaH (60% content) of 1.2g (30mmol, 0.8eq), α-carboline 5.2g (30mmol, 0.8eq), it is small that half is reacted under zero degree
When after be added instill dissolved with intermediate M2 9g (37.5mmol, 1eq) n,N-Dimethylformamide solution 20mL, open stirring,
Displacement nitrogen 3 times reacts at room temperature 1h.Ethyl alcohol quenching reaction is added into reaction solution, is spin-dried for rear PE:AE=1:1 and crosses silicagel column, obtain
To 7g white solid M3.
The preparation of compound P37:
N,N-Dimethylformamide 100mL, click is added in a 500mL single-necked flask equipped with magnetic agitation at room temperature
Azoles 4.5g (27mmol, 1.5eq) instills the N dissolved with intermediate M3 7g (18mmol, 1eq), N- dimethyl after reacting half an hour
Formamide solution 20mL opens stirring, replaces nitrogen 3 times, is warming up to 80 DEG C, reaction is overnight.Reaction solution is down to room temperature, to anti-
Addition ethyl alcohol quenching reaction in liquid is answered, rear PE:AE=1:2 is spin-dried for and crosses silicagel column, obtain 8g white solid P37.It is again that product is complete
Fully dissolved does eluent with toluene and crosses silicagel column in toluene；Washout decontamination, which is boiled, with ethyl alcohol obtains crude product, purity
99.1%；Gained crude product again with toluene is boiled and is washed, 6.2g white solid is finally obtained.
Mass spectroscopy molecular amount theoretical value 535.6, molecular weight detection value 535.3.Elemental Analysis theory C, 82.97%；H,
3.95%；N, 13.08%, elemental analysis detected value C, 82.77%；H, 3.98%；N, 13.18%.
Synthetic example 2
The synthesis of compound P66:
The preparation of intermediate M4:
Reaction condition is consistent with intermediate M1 is prepared, and is substituted using bromo- 2, the 6- difluoro pyridine 13.6g (70mmol, 1eq) of 4-
2,5- difluoro bromobenzene 13.5g (70mmol, 1eq).After contact plate detects bromo- 2, the 6- difluoro pyridine fully reacting of 4-, stop reaction.
(bromo- 2, the 6- difluoro pyridine Rf=0.7 of PE:EA=5:1, product Rf=0.5,4-)
Reaction solution is down to room temperature, is extracted with ethyl acetate, upper layer is taken, reaction solution is spin-dried for, PE:EA=10:1 carries out column
Chromatography, obtains white solid intermediate M4,11g.
The preparation of intermediate M5:
Reaction condition is consistent with intermediate M2 is prepared, and uses chloro- 4, the 6- diphenyl -1,3,5-triazines 18.7g of 2-
(70mmol, 1eq) substitutes 4- bromine m-dicyanobenzene.Intermediate M1 is substituted using intermediate M4 20.2g (83.3mmol, 1.2eq),
After detecting fully reacting, stop reaction.(chloro- 4, the 6- diphenyl -1,3,5-triazines Rf of PE:EA=3:1, product Rf=0.5,2-
=1)
Reaction solution is down to room temperature, is extracted with ethyl acetate, upper layer is taken, reaction solution is spin-dried for, PE:EA=5:1 crosses pillar,
Obtain white solid intermediate M5,17.3g.
The preparation of intermediate M6:
N,N-Dimethylformamide 100mL is added in a 500mL single-necked flask equipped with magnetic agitation at room temperature, adds
Enter NaH (60% content), the carbazole 5g (30mmol, 0.8eq) of 1.2g (30mmol, 0.8eq), instillation is added after reacting half an hour
Dissolved with the n,N-Dimethylformamide solution 20mL of intermediate M5 13g (37.5mmol, 1eq), stirring is opened, replaces nitrogen 3
It is secondary, react at room temperature 1h.Ethyl alcohol quenching reaction is added into reaction solution, is spin-dried for rear DCM:AE=1:1 and crosses silicagel column, it is white to obtain 9.2g
Color solid M6.
The preparation of compound P66:
N,N-Dimethylformamide 100mL, β-is added in a 500mL single-necked flask equipped with magnetic agitation at room temperature
Carboline 4.5g (27mmol, 1.5eq) instills N, N- bis- dissolved with intermediate M3 8.9g (18mmol, 1eq) after reacting half an hour
Methylformamide solution 20mL opens stirring, replaces nitrogen 3 times, is warming up to 90 DEG C, reaction is overnight.Reaction solution is down to room temperature,
Ethyl alcohol quenching reaction is added into reaction solution, is spin-dried for rear DCM:AE=1:2 and crosses silicagel column.Product is boiled into washout impurity elimination with ethyl alcohol again
Matter obtains crude product, and gained crude product again with toluene is boiled and is washed, and finally obtains 7.1g white solid P66, purity 99.7%；
Mass spectroscopy molecular amount theoretical value 641.7, molecular weight detection value 641.2.Elemental Analysis theory C, 80.48%；H,
4.24%；N, 15.28%, elemental analysis detected value C, 80.57%；H, 4.33%；N, 14.98%.
Synthetic example 3
The synthesis of compound P83:
The preparation of intermediate M7:
Reaction condition is consistent with intermediate M1 is prepared, and substitutes 2 using bromo- 1, the 3- benzene dinitrile 14.5g (70mmol, 1eq) of 5-,
5- difluoro bromobenzene 13.5g (70mmol, 1eq).After contact plate detects bromo- 1, the 3- benzene dinitrile fully reacting of 5-, stop reaction.(PE:EA
Bromo- 1, the 3- benzene dinitrile Rf=0.8 of=10:1, product Rf=0.4,5-)
Reaction solution is down to room temperature, is extracted with dichloromethane, lower layer is taken, reaction solution is spin-dried for, PE:EA=15:1 carries out column
Chromatography, obtains white solid 12.2g M7.
The preparation of intermediate M8:
Reaction condition is consistent with intermediate M2 is prepared, and substitutes 4- using 2,4,6- tri- Bromopyrimidine 22.1g (70mmol, 1eq)
Bromine m-dicyanobenzene.Intermediate M1 is substituted using intermediate M7 21.1g (37.5mmol, 1.2eq), after detecting fully reacting, is stopped
Reaction.(PE:EA=6:1, product Rf=0.6,2,4,6- tri- Bromopyrimidine Rf=0.9)
Reaction solution is down to room temperature, is extracted with ethyl acetate, upper layer is taken, reaction solution is spin-dried for, PE:EA=3:1 crosses pillar,
Obtain white solid 18.8g M8.
The preparation of intermediate M9:
Dimethylbenzene 400mL, intermediate M8 is added in a 1000mL single-necked flask equipped with magnetic agitation at room temperature
10.85g (30mmol, 1eq), carbazole 4g (24mmol, 0.8eq), cuprous iodide 5.36g (30mmol, 1eq), cesium carbonate 29.3g
(90mmol, 3eq), ethylenediamine 1.75g (30mmol, 1eq) open stirring, replace nitrogen 3 times, are warming up to reflux, reaction is for 24 hours.
Reaction solution is down to room temperature, filters, takes filtrate to be spin-dried for, PE:DCM=1:1 crosses silicagel column, obtains 7.2g pale solid M9.
The preparation of compound P83:
Dimethylbenzene 400mL, intermediate M9 is added in a 1000mL single-necked flask equipped with magnetic agitation at room temperature
6.75g (15mmol, 1eq), B-carboline 4.5g (27mmol, 1.8eq), cuprous iodide 5.36g (30mmol, 2eq), cesium carbonate
29.3g (90mmol, 6eq), ethylenediamine 1.75g (30mmol, 2eq) open stirring, replace nitrogen 3 times, are warming up to reflux, react
24h.Reaction solution is down to room temperature, filters, takes filtrate to be spin-dried for, DCM:AE=1:1 crosses silicagel column, obtains 6.3g pale solid.
Product is boiled into washout decontamination with ethyl alcohol again and obtains crude product, gained crude product again with toluene is boiled and is washed, it is white to finally obtain 5.5g
Color solid P83, purity 98.6%；
Mass spectroscopy molecular amount theoretical value 537.5, molecular weight detection value 537.2.Elemental Analysis theory C, 78.20%；H,
3.56%；N, 18.24%, elemental analysis detected value C, 78.57%；H, 3.33%；N, 18.28%.
It should be noted that the compounds of this invention can be obtained by above-mentioned synthetic method, but it is not limited to these methods.This
Field technical staff can also choose known to other methods, such as Stille coupling method, Grignard Reagent method, Kumada-Tamao etc.
Method, any equivalent synthetic method can be selected as needed using the purpose for being able to achieve target compound preparation.
The luminescent layer and organic electroluminescence device of organic electroluminescence device of the invention are illustrated below.
The luminescent layer of organic electroluminescence device of the invention, including material of main part and dyestuff.The compound of the present invention was both
Can be used as material of main part come using, can also be used as dyestuff come using.
Organic Light Emitting Diode includes the first electrode and second electrode on substrate, and having between electrode
Machine material includes hole transmission layer, luminescent layer, electron transfer layer between first electrode and second electrode.
Substrate using substrate used in organic light emitting display, such as: glass, polymer material and have TFT member device
Glass and polymer material of part etc..
The functional layer may include hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, the sky
Cave implanted layer is formed on the anode layer, and the hole transmission layer is formed on the hole injection layer, described
Cathode layer is formed on the electron transfer layer, is luminous between the hole transmission layer and the electron transfer layer
Layer；The luminescent layer is the luminescent layer of the organic electroluminescence device of aforementioned present invention.
Specifically, anode material can use indium tin oxygen (ITO), indium zinc oxygen (IZO), stannic oxide (SnO2), zinc oxide
(ZnO) etc. transparent conductive materials are also possible to the metal materials such as silver and its alloy, aluminium and its alloy, and being also possible to PEDOT etc. has
The multilayered structure of machine conductive material and above-mentioned material.
Hole injection layer material may include at least one of following compound HI-1~HI-3:
Hole transport layer material may include at least one of compound HT-1~HT-31:
Device luminescent layer material of main part may include at least one of compound TDH1-TDH24.
Luminescent layer dye materials may include at least one of F-1~F-24:
Electron transport layer materials may include at least one of compound ET-1~ET-57:
It can also include the electron injecting layer between electron transfer layer and cathode, electron injecting layer material packet in device
It includes but is not limited to the following one or more combinations enumerated:
LiQ, LiF, NaCl, CsF, Li2O, Cs2CO3, BaO, Na, Li, Ca.
Cathode may include metals, metal mixture, the oxides such as magnesium silver mixture, LiF/Al, ITO.
Dyestuff of the device embodiments 1~7 using the nitrogen-containing heterocycle compound of the disclosure as organic electroluminescence device.
Device embodiments 1:
Device architecture is as follows:
ITO (150nm)/HI-2 (10nm)/HT-2 (40nm)/TDH10:30%P8 (30nm)/ET34 (20nm)/LiF
(0.5nm)/Al(150nm).(wherein 30% expression P8 is 30% relative to the weight ratio of TDH10, and following embodiment also presses this side
Formula expression)
Organic electroluminescence device preparation process is as follows: the glass plate for being coated with transparent conductive layer is cleaned in commercialization
It is ultrasonically treated in agent, rinses in deionized water, in acetone: ultrasonic oil removing in alcohol mixed solvent is toasted under clean environment
To completely removing moisture content, with ultraviolet light and ozone clean, and with low energy cation beam bombarded surface；
The above-mentioned glass substrate with anode is placed in vacuum chamber, is vacuumized less than 10-5Pa, on above-mentioned anode tunic
Vacuum evaporation HI-2 is 10nm as hole injection layer, evaporation rate 0.1nm/s, vapor deposition film thickness；
Hole transmission layer of the vacuum evaporation HT-2 as device on hole injection layer, evaporation rate 0.1nm/s steam
Plating total film thickness is 80nm；
The luminescent layer of vacuum evaporation device on hole transmission layer, luminescent layer include material of main part and dye materials, benefit
The method steamed altogether with multi-source, adjusting material of main part TDH10 evaporation rate are 0.1nm/s, and 30% ratio of dyestuff P8 evaporation rate is set
Fixed, vapor deposition total film thickness is 30nm；
The electron transport layer materials ET-34 of vacuum evaporation device, evaporation rate 0.1nm/s on luminescent layer steam
Plating total film thickness is 20nm；
On electron transfer layer (ETL) vacuum evaporation with a thickness of the LiF of 0.5nm as electron injecting layer, with a thickness of 150nm
Cathode of the Al layer as device.
Device embodiments 2~7: using the method for device embodiments 1, difference is respectively to replace material of main part compound P8
It is changed to P28, P82, P12, P66, P83 and P99.
Device embodiments 2:
ITO (150nm)/HI-2 (10nm)/HT-2 (40nm)/TDH10:30%P28 (30nm)/ET-34 (20nm)/LiF
(0.5nm)/Al(150nm)。
Device embodiments 3:
ITO (150nm)/HI-2 (10nm)/HT-2 (40nm)/TDH10:30%P82 (30nm)/ET-34 (20nm)/LiF
(0.5nm)/Al(150nm)。
Device embodiments 4:
ITO (150nm)/HI-2 (10nm)/HT-2 (40nm)/TDH10:30%P12 (30nm)/ET-34 (20nm)/LiF
(0.5nm)/Al(150nm)。
Device embodiments 5:
ITO (150nm)/HI-2 (10nm)/HT-2 (40nm)/TDH10:30%P66 (30nm)/ET-34 (20nm)/LiF
(0.5nm)/Al(150nm)。
Device embodiments 6:
ITO (150nm)/HI-2 (10nm)/HT-2 (40nm)/TDH10:30%P83 (30nm)/ET-34 (20nm)/LiF
(0.5nm)/Al(150nm)。
Device embodiments 7:
ITO (150nm)/HI-2 (10nm)/HT-2 (40nm)/TDH10:30%P99 (30nm)/ET-34 (20nm)/LiF
(0.5nm)/Al(150nm)。
Device embodiments 8:
ITO (150nm)/HI-2 (10nm)/HT-2 (40nm)/TDH10:30%P120 (30nm)/ET-34 (20nm)/LiF
(0.5nm)/Al(150nm)。
Device comparative example 1: the dyestuff using the material different from the disclosure as organic electroluminescence device.
Using the method for device embodiments 1, difference is guest dye replacing with A129.
Its device architecture are as follows: ITO (150nm)/HI-2 (10nm)/HT-2 (40nm)/TDH10:30%A129 (30nm)/
ET-34(20nm)/LiF(0.5nm)/Al(150nm)。
Device comparative example 2:
Using the method for device embodiments 1, difference is to replace with guest dye into A130, device architecture are as follows:
ITO (150nm)/HI-2 (10nm)/HT-2 (40nm)/TDH10:30%A130 (30nm)/ET-34 (20nm)/LiF
(0.5nm)/Al(150nm)。
Following performance measurement is carried out to the organic electroluminescence device prepared by the above process:
Under same brightness, digital sourcemeter and luminance meter measurement device Examples 1 to 7 and device comparative example 1~2 are used
In the driving voltage of organic electroluminescence device being prepared and current efficiency and device service life.Specifically, with every
The rate of second 0.1V promotes voltage, and measurement reaches 1000cd/m when the brightness of organic electroluminescence device2When voltage driving
Voltage, while measuring current density at this time；The ratio of brightness and current density is current efficiency, is as a result listed in table 1 respectively
In table 2.
Table 1
| Embodiment number | Dyestuff | It is required that brightness (cd/m2) | Operating voltage (V) | Current efficiency (cd/A) |
| Device embodiments 1 | P8 | 1000 | 6.2 | 15.1 |
| Device embodiments 2 | P28 | 1000 | 6.4 | 14.2 |
| Device embodiments 3 | P82 | 1000 | 5.9 | 15.9 |
| Device embodiments 4 | P12 | 1000 | 6.0 | 15.8 |
| Device embodiments 5 | P66 | 1000 | 6.3 | 16.3 |
| Device embodiments 6 | P83 | 1000 | 6.1 | 13.4 |
| Device embodiments 7 | P99 | 1000 | 6.3 | 14.3 |
| Device embodiments 8 | P120 | 1000 | 6.7 | 12.5 |
| Device comparative example 1 | A129 | 1000 | 7.2 | 11.2 |
| Device comparative example 2 | A130 | 1000 | 7.0 | 12.2 |
It can be seen that by upper table data
Embodiment 2 using the compounds of this invention P28 as the OLED organic electroluminescent performance of dyestuff be better than relative to
For comparative example 1 using OLED organic electroluminescent performance of the A129 as dyestuff, P28 obtains higher current efficiency and lower
Driving voltage；Asymmetrical carbazole carboline group introducing dyestuff is prepared organic electroluminescence device by this explanation, can obviously be dropped
Low driving voltage and the advantage for improving luminous efficiency.
Embodiment 5 is better than phase as the OLED organic electroluminescent performance of dyestuff using the compounds of this invention P66 simultaneously
OLED organic electroluminescent performance for comparative example 2 using A130 as dyestuff, P66 equally obtain higher current efficiency
With lower driving voltage；The pyridine groups of carboline group and bridging are introduced into molecule by this explanation, can be substantially reduced driving
Voltage and the advantage for improving luminous efficiency.
The above result shows that new organic materials of the invention are used for organic electroluminescence device, can effectively reduce
Landing voltage improves current efficiency, and energy with good stability, is blue light dye materials of good performance.
Device embodiments 9~12 are using the nitrogen-containing heterocycle compound of the disclosure as organic electroluminescence device luminescent layer
Material of main part.
Device embodiments 9:
Organic electroluminescence device preparation process is as follows in the present embodiment:
The glass plate for being coated with transparent conductive layer is ultrasonically treated in commercial detergent, is rinsed in deionized water,
In acetone: ultrasonic oil removing in alcohol mixed solvent is baked under clean environment and completely removes moisture content, clear with ultraviolet light and ozone
It washes, and with low energy cation beam bombarded surface；
The above-mentioned glass substrate with anode is placed in vacuum chamber, is evacuated to less than 10-5Pa, in above-mentioned anode tunic
Upper vacuum evaporation HI-2 is 10nm as hole injection layer, evaporation rate 0.1nm/s, vapor deposition film thickness；
Hole transmission layer of the vacuum evaporation HT-2 as device on hole injection layer, evaporation rate 0.1nm/s steam
Plating total film thickness is 80nm；
The luminescent layer of vacuum evaporation device on hole transmission layer, luminescent layer include material of main part and dye materials, benefit
The method steamed altogether with multi-source, adjusting material of main part P8 evaporation rate are 0.1nm/s, and 30% ratio of dyestuff F8 evaporation rate is set,
Vapor deposition total film thickness is 30nm；
The electron transport layer materials ET-34 of vacuum evaporation device, evaporation rate 0.1nm/s on luminescent layer steam
Plating total film thickness is 20nm；
On electron transfer layer (ETL) vacuum evaporation with a thickness of the LiF of 0.5nm as electron injecting layer, with a thickness of 150nm
Cathode of the Al layer as device.
Method as described above prepares following device, makes it have with flowering structure:
ITO (150nm)/HI-2 (10nm)/HT-2 (40nm)/P8:30%F8 (30nm)/ET-34 (20nm)/LiF
(0.5nm)/Al(150nm)。
Wherein 30% expression P8 is 20% relative to the weight ratio of TDH10, and following embodiment is also expressed in this way.
Device embodiments 10:
ITO (150nm)/HI-2 (10nm)/HT-2 (40nm)/P28:30%F8 (30nm)/ET-34 (20nm)/LiF
(0.5nm)/Al(150nm)。
Device embodiments 11:
ITO (150nm)/HI-2 (10nm)/HT-2 (40nm)/P82:30%F8 (30nm)/ET-34 (20nm)/LiF
(0.5nm)/Al(150nm)。
Device embodiments 12:
ITO (150nm)/HI-2 (10nm)/HT-2 (40nm)/P12:30%F8 (30nm)/ET-34 (20nm)/LiF
(0.5nm)/Al(150nm)。
Device comparative example 3: the dyestuff using the material different from the disclosure as organic electroluminescence device.
Using the method for device embodiments 9, difference is material of main part replacing with CBP.
Its device architecture are as follows: ITO (150nm)/HI-2 (10nm)/HT-2 (40nm)/CBP:30%F8 (30nm)/ET-34
(20nm)/LiF(0.5nm)/Al(150nm)。
Following performance measurement is carried out to the organic electroluminescence device prepared by the above process:
Under same brightness, is measured in embodiment 9~18 and comparative example 3 and be prepared using digital sourcemeter and luminance meter
Organic electroluminescence device driving voltage and current efficiency and device service life.Specifically, with the speed of 0.1V per second
Rate promotes voltage, and measurement reaches 10000cd/m when the brightness of organic electroluminescence device2When voltage, that is, driving voltage, simultaneously
Measure current density at this time；The ratio of brightness and current density is current efficiency, the results are shown in Table 1.
Table 2
| Embodiment number | Material of main part | It is required that brightness (cd/m2) | Operating voltage (V) | Current efficiency (cd/A) |
| Device embodiments 9 | P8 | 10000 | 5.1 | 48.8 |
| Device embodiments 10 | P28 | 10000 | 5.5 | 39.1 |
| Device embodiments 11 | P82 | 10000 | 5.2 | 49.1 |
| Device embodiments 12 | P12 | 10000 | 4.9 | 53.4 |
| Device comparative example 3 | CBP | 10000 | 6.6 | 23.5 |
It can be seen that by upper table data
Embodiment 9 is better than as the OLED organic electroluminescent performance of main body relative to right using the compounds of this invention P8
Ratio 3 uses OLED organic electroluminescent performance of the CBP as main body, and the device in embodiment 9 obtains higher electric current effect
Rate and lower driving voltage；This material of explanation based on asymmetrical carbazole carboline group is sent out as subject preparation organic electroluminescence
Optical device can equally be substantially reduced driving voltage and improve the advantage of luminous efficiency.
Embodiment 11 is better than phase as the OLED organic electroluminescent performance of dyestuff using the compounds of this invention P82 simultaneously
For embodiment 9 using OLED organic electroluminescent performance of the P8 as main body, P82 obtains higher current efficiency and lower
Driving voltage；This illustrates that driving voltage can be substantially reduced when pyridine groups of the material of main part using bridging and improves the effect that shines
The advantage of rate.
The above result shows that when new organic materials of the invention are used for the main body of organic electroluminescence device, Ke Yiyou
The reduction landing voltage of effect improves current efficiency, and energy with good stability.
The preferred embodiment of the disclosure is described in detail above, still, during the disclosure is not limited to the above embodiment
Detail a variety of simple variants can be carried out to the technical solution of the disclosure in the range of the technology design of the disclosure, this
A little simple variants belong to the protection scope of the disclosure.
It is further to note that specific technical features described in the above specific embodiments, in not lance
In the case where shield, it can be combined in any appropriate way.In order to avoid unnecessary repetition, the disclosure to it is various can
No further explanation will be given for the combination of energy.
In addition, any combination can also be carried out between a variety of different embodiments of the disclosure, as long as it is without prejudice to originally
Disclosed thought equally should be considered as disclosure disclosure of that.
Claims (13)
1. a kind of nitrogen-containing heterocycle compound, which is characterized in that the heterocyclic compound has the structure as shown in following formula (1):
Wherein, Z1、Z2、Z3、Z4、Z5And Z6It is respectively selected from C atom, CR9At least one of with N atom, and Z1、Z2、Z3、Z4、
Z5And Z6The number of middle N atom is 0,1 or 2；
X1、X2、X3And X4It is respectively selected from CR9’Or N atom, and X1、X2、X3And X4In at least one be N atom；
R1、R2、R3、R4、R5、R6、R7、R8、R1’、R2’、R3’、R4’、R9And R9’It is each independently selected from hydrogen atom, C1~C10Alkyl,
C1~C10Naphthenic base, substituted or unsubstituted C6~C30Aryl and substituted or unsubstituted C3~C30At least one in heteroaryl
Kind；
L is respectively and independently selected from singly-bound, substituted or unsubstituted C6~C30Arlydene, substituted or unsubstituted C3~C30Asia it is miscellaneous
At least one of aryl, m 0,1 or 2；
Work as Z1、Z2、Z3、Z4、Z5And Z6When middle N atomicity is 0, Ar is selected from one of structure shown in S2~S6；Z1、Z2、Z3、Z4、
Z5And Z6When middle N atomicity is 1 or 2, Ar is selected from one of structure shown in S1~S6, and wherein * is connection site；
The substituted C6~C30Arlydene, substituted C3~C30Inferior heteroaryl, substituted C6~C30Aryl, substituted C3~C30
Substituent group in heteroaryl is each independently selected from halogen, C1~C10Alkyl, C3~C10Naphthenic base, C2~C6Alkenyl, C2
~C6Cycloalkenyl, C1~C6Alkoxy, C1~C6Thio alkoxy, C6~C30Aryl and C3~C30Heteroaryl in
It is at least one.
2. nitrogen-containing heterocycle compound according to claim 1, which is characterized in that the heterocyclic compound has such as following formula (2)
Shown structure:
Wherein, Ar is selected from one of structure shown in S2~S6, L, m, X1、X2、X3、X4、R1、R2、R3、R4、R5、R6、R7、R8、R1’、
R2’、R3’、R4’、R9And R9’With definition identical with claim 1.
3. nitrogen-containing heterocycle compound according to claim 1, which is characterized in that the heterocyclic compound has such as following formula (3)
Or structure shown in formula (4):
Wherein, Ar is selected from one of structure shown in S1~S6, L, m, X1、X2、X3、X4、R1、R2、R3、R4、R5、R6、R7、R8、R1’、
R2’、R3’、R4’、R9And R9’With definition identical with claim 1.
4. nitrogen-containing heterocycle compound according to any one of claims 1 to 3, which is characterized in that X1、X2、X3And X4Its
One of be N atom, remaining is CR9’, R9’With definition identical with claim 1.
5. nitrogen-containing heterocycle compound according to any one of claims 1 to 3, which is characterized in that X1And/or X4For N original
Son, X2And X3Respectively stand alone as CR9’, R9’It is each independently selected from hydrogen atom, C1~C10Alkyl, C1~C10Naphthenic base, substitution or not
Substituted C6~C30Aryl and substituted or unsubstituted C3~C30At least one of heteroaryl, X2And X3Cyclization can be connected with each other.
6. nitrogen-containing heterocycle compound according to any one of claims 1 to 3, which is characterized in that the C6~C30Virtue
Base is selected from phenyl, xenyl, terphenyl, naphthalene, anthryl, phenanthryl, indenyl, fluorenyl, benzo fluorenyl, 9,9 '-dialkyl fluorenes
Base, 9,9 '-spiral shell, two fluorenyl, indeno fluorenyl, fluoranthene base, triphenylene, pyrenyl, base,Base and aphthacene baseIn base extremely
Few one kind；
The C3~C30Heteroaryl is selected from thienyl, furyl, dibenzofuran group, azepine dibenzofuran group, azepine two
Benzothienyl, dibenzothiophene, dibenzo selenophen base, carbazyl, carboline base, pyrrole radicals, imidazole radicals, benzimidazolyl,
Indyl, pyridyl group, oxazolyl, oxadiazoles base, benzoxazolyl, triazine radical, pyrimidine radicals, quinazolyl, quinoxalinyl, naphthyridines
At least one of base, phenazinyl, ferrosin base, benzimidazolyl and indolocarbazole base；
The C1~C10Alkyl be selected from methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, tert-butyl, n-pentyl,
At least one of n-hexyl, n-heptyl, n-octyl, n-nonyl and positive decyl；
The C3~C10Naphthenic base be selected from cyclopenta or cyclohexyl.
7. nitrogen-containing heterocycle compound according to any one of claims 1 to 3, which is characterized in that R2And R2’It selects respectively
From C1~C10Alkyl, substituted or unsubstituted C6~C30Aryl and substituted or unsubstituted C3~C30One of heteroaryl, R1、
R3、R4、R1’、R3’And R4’It is hydrogen atom；Alternatively, R3And R3’It is respectively selected from C1~C10Alkyl, substituted or unsubstituted C6~C30
Aryl and substituted or unsubstituted C3~C30One of heteroaryl, R1、R2、R4、R1’、R2’And R4’It is hydrogen atom.
8. nitrogen-containing heterocycle compound according to any one of claims 1 to 3, which is characterized in that L is selected from singly-bound, Asia
One of phenyl, sub-pyridyl group, biphenyl subunit, phenanthrylene, naphthylene and anthrylene.
9. nitrogen-containing heterocycle compound according to claim 1, which is characterized in that the heterocyclic compound is selected from following structural formula
One of:
10. application of the nitrogen-containing heterocycle compound described in any one of claim 1~9 in organic electroluminescence device.
11. application according to claim 10, which is characterized in that the nitrogen-containing heterocycle compound is used as the organic electroluminescence
The luminescent layer material of main part and/or guest materials of luminescent device.
12. a kind of organic electroluminescence device, including substrate, anode layer, cathode layer and between anode layer and cathode layer
At least one layer of organic layer, the organic layer include hole injection layer, hole transmission layer, organic luminous layer, electron transfer layer with
And electron injecting layer, which is characterized in that the organic luminous layer contains nitrogen-containing heterocycle according to any one of claims 1 to 9
Compound.
13. organic electroluminescence device according to claim 12, which is characterized in that the main body material of the organic luminous layer
Material and/or guest materials contain nitrogen-containing heterocycle compound according to any one of claims 1 to 9.
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| CN109651364A (en) * | 2019-01-29 | 2019-04-19 | 北京诚志永华显示科技有限公司 | New compound, electroluminescent organic material, organic electroluminescence device, electronic equipment |
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| KR102396694B1 (en) | 2019-12-30 | 2022-05-12 | 산시 라이트 옵토일렉스로닉스 머터리얼 코포레이션 리미티드 | Organic compound, use thereof, and organic electroluminescent device using same |
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