CN110818642A - Heterocyclic arylamine compound and application thereof in organic electronic device - Google Patents

Heterocyclic arylamine compound and application thereof in organic electronic device Download PDF

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CN110818642A
CN110818642A CN201911126961.6A CN201911126961A CN110818642A CN 110818642 A CN110818642 A CN 110818642A CN 201911126961 A CN201911126961 A CN 201911126961A CN 110818642 A CN110818642 A CN 110818642A
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atoms
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heterocyclic
aromatic
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CN110818642B (en
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杨曦
李涛
龙芷君
李们在
李先杰
王煦
张月
潘君友
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Guangzhou Chinaray Optoelectronic Materials Ltd
Wuhan China Star Optoelectronics Semiconductor Display Technology Co Ltd
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Guangzhou Chinaray Optoelectronic Materials Ltd
Wuhan China Star Optoelectronics Semiconductor Display Technology Co Ltd
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Abstract

The invention relates to the technical field of organic electroluminescence, in particular to a heterocyclic arylamine compound and application thereof in electronic devices, in particular to application thereof in organic light-emitting diodes. The compound of the invention has proper energy level, higher extinction coefficient in an ultraviolet region and higher refractive index in a visible light region, and can be used as a light extraction layer in a device. The organic electroluminescent display device can reduce the damage of external high-energy light to internal materials of the organic electroluminescent display device, improve the light extraction rate and improve the luminous efficiency of devices.

Description

Heterocyclic arylamine compound and application thereof in organic electronic device
The present application claims priority from the chinese patent application entitled "a heterocyclic arylamine compound and its use in organic electronic devices" filed by the chinese patent office on 2018, 12, month 10, application number 201811503262.4, the entire contents of which are incorporated herein by reference.
Technical Field
The invention relates to the technical field of organic electroluminescence, in particular to a heterocyclic arylamine compound and a composition thereof, and application thereof in an organic electronic device, especially in an electroluminescent device.
Background
Organic electroluminescent display devices are self-luminous display devices that generate excitons by transfer and recombination of carriers between functional layers and emit light by means of organic compounds or metal complexes having high quantum efficiency. The LED lamp has the characteristics of self-luminescence, high brightness, high efficiency, high contrast, high responsiveness and the like.
In recent years, the luminous efficiency of organic electroluminescent diodes (OLEDs) has been greatly improved, but the internal quantum efficiency thereof has approached the theoretical limit. Therefore, improvement of light extraction efficiency is an effective means for further improving device stability and current efficiency (e.g., deposition of metal complexes in the emission layer, matching of refractive indices between functional layers, etc.). In 2001, Hung et al covered a layer of organic or inorganic compound of about 50nm on the surface of a metal cathode to improve the performance of the device by controlling the thickness and refractive index. In 2003, Riel et al have attempted to evaporate ZnSe, an inorganic compound having a high refractive index (n ═ 2.6), on a cathode, and improve light extraction efficiency by using the difference in refractive index between functional layers, but such compounds have not been much used in organic electroluminescent devices due to the high evaporation temperature and slow evaporation rate of inorganic materials.
In view of the above, it is possible to attempt to use an organic compound having a higher refractive index in an electroluminescent device to improve light extraction efficiency. Such compounds need to satisfy the following conditions: the extinction coefficient is high in an ultraviolet band (less than 400nm), and adverse effects of harmful light on device materials are avoided; the extinction coefficient is close to 0 in the visible light range (>430nm), the visible light has higher transmittance, and the influence on the light extraction efficiency of the equipment is reduced; the high-refractive-index optical material has high refractive index and small difference in a visible light range, and has the characteristics of improving light output and optimizing device structures and the like; has higher glass transition temperature and improves the thermal stability of the compound.
Therefore, a new class of materials for improving light extraction efficiency of organic electroluminescent devices needs to be further developed.
Disclosure of Invention
In view of the above-mentioned deficiencies of the prior art, it is a primary object of the present invention to provide novel heterocyclic arylamine compounds and their use in organic electronic devices. The invention further provides a novel light extraction layer material which is covered on the surface of the cathode of the device and is used for improving the light extraction efficiency of the device.
The technical scheme of the invention is as follows:
a heterocyclic arylamine compound having a structure represented by the general formula (1):
Figure BDA0002277142350000011
wherein:
when Ar is1When selected from the general formula (A-1), n is selected from 1 or 2, Ar3Selected from the structure
Figure BDA0002277142350000012
Or
Figure BDA0002277142350000013
When Ar is1When selected from the general formulae (A-2) to (A-8), n is selected from an integer of 0 to 2, Ar3Selected from substituted or unsubstituted aromatic or heteroaromatic groups having 5 to 60 ring atoms; or a non-aromatic ring system having 3 to 25 ring atoms which may be substituted or unsubstituted;
(A-1) to (A-8) are selected from the following groups:
Figure BDA0002277142350000021
X1、X2multiple occurrences of the same or different compound are independently selected from O, S, SO2、NR3、CR3R4、SiR3R4、C(＝O)；
Y、Y1～Y11Are the same or different when occurring multiple times and are respectively and independently selected from N or CR5And Y is1～Y3At least two of which are N, Y4～Y7At least one of which is N;
L1selected from a single bond, an alkenyl group, an alkynyl group, an acyl group, an amide group, a carbonyl group, a sulfone group, a substituted or unsubstituted alkyl group having 1 to 60 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 60 carbon atoms, a substituted or unsubstituted aromatic group or heteroaromatic group having 5 to 60 ring atoms;
Ar2、Ar4～Ar7each independently selected from substituted or unsubstituted aromatic or heteroaromatic groups having 5 to 60 ring atoms; or a non-aromatic ring system having 3 to 25 ring atoms which may be substituted or unsubstituted, or an arylamine group;
R1～R5are identical or different on multiple occurrence and are each independently selected from hydrogen, or D, or a straight-chain alkyl group having 1 to 20C atoms, an alkoxy group having 1 to 20C atoms, or a thioalkoxy group having 1 to 20C atoms, or a branched-chain alkyl group having 3 to 20C atoms, or a cycloalkyl group having 3 to 20C atoms, an alkoxy group having 3 to 20C atoms, or a thioalkoxy group having 3 to 20C atoms, or a silyl group, or a keto group having 1 to 20C atoms, or an alkoxycarbonyl group having 2 to 20C atoms, or an aryloxycarbonyl group having 7 to 20C atoms, a cyano group (-CN), a carbamoyl group (-C (═ O) NH2) Haloformyl, formyl (-C (═ O) -H), isocyano, isocyanate, thiocyanate or isothiocyanate, hydroxy, nitro, CF3Cl, Br, F, crosslinkable groups, orA substituted or unsubstituted aromatic or heteroaromatic group having 5 to 60 ring atoms, or an aryloxy or heteroaryloxy group having 5 to 60 ring atoms, or a combination thereof; wherein two or more adjacent radicals may optionally form a mono-or polycyclic, aliphatic, aromatic or heteroaromatic ring system with one another;
dotted line represents Ar1And L1An attached key.
A composition comprises at least one heterocyclic arylamine compound and at least one organic solvent.
A light extraction layer material contains the heterocyclic arylamine compound.
An organic electronic device, characterized in that it comprises the heterocyclic arylamine compound.
An organic electronic device comprising two electrodes, one or more organic functional layers between the two electrodes, and a light extraction layer on the surface of one of the electrodes remote from the organic functional layer, wherein the light extraction layer comprises the arylamine compound.
Advantageous effects
The heterocyclic arylamine compound has high thermal stability. And has high extinction coefficient in ultraviolet band, small extinction coefficient in visible light range and high refractive index. When used as a light extraction layer of an electronic device, the adverse effect of harmful light on the internal material of the device can be avoided and the visible light extraction efficiency can be improved.
Drawings
FIG. 1 is a schematic diagram of a device embodiment. Fig. 1 is a view showing a structure of a preferred light emitting device according to the present invention, in which 1 is a substrate, 2 is an anode, 3a is a Hole Injection Layer (HIL), 3b is a Hole Transport Layer (HTL), 3c is a light emitting layer, 3d is an Electron Transport Layer (ETL), 3e is an Electron Injection Layer (EIL), 4 is a cathode, and 5 is a light extraction layer.
FIG. 2 is an ultraviolet-visible absorption spectrum of a solution of Synthesis example C-3 at a concentration of 10mg/L in methylene chloride.
FIG. 3 is an ultraviolet-visible absorption spectrum of a synthesis example C-6 at a concentration of 10mg/L in a dichloromethane solution.
Detailed Description
The invention provides a heterocyclic arylamine compound and application thereof in an organic electroluminescent device, in particular application of the heterocyclic arylamine compound as a light extraction layer material of the organic electroluminescent device. In order to make the objects, technical solutions and effects of the present invention clearer and clearer, the present invention is described in further detail below. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
In the present invention, "substituted" means that a hydrogen atom in a substituent is substituted by a substituent.
In the present invention, the "number of ring atoms" represents the number of atoms among atoms constituting the ring itself of a structural compound (for example, a monocyclic compound, a condensed ring compound, a crosslinked compound, a carbocyclic compound, and a heterocyclic compound) in which atoms are bonded in a ring shape. When the ring is substituted with a substituent, the atoms contained in the substituent are not included in the ring-forming atoms. The "number of ring atoms" described below is the same unless otherwise specified. For example, the number of ring atoms of the benzene ring is 6, the number of ring atoms of the naphthalene ring is 10, and the number of ring atoms of the thienyl group is 5.
In the present invention, "adjacent groups" means that these groups are bonded to the same carbon atom or bonded to adjacent carbon atoms. These definitions apply correspondingly to "adjacent substituents".
An aromatic group refers to a hydrocarbon group containing at least one aromatic ring. A heteroaromatic group refers to an aromatic hydrocarbon group that contains at least one heteroatom. The heteroatoms are preferably selected from Si, N, P, O, S and/or Ge, particularly preferably from Si, N, P, O and/or S. By fused ring aromatic group is meant that the rings of the aromatic group may have two or more rings in which two carbon atoms are shared by two adjacent rings, i.e., fused rings. The fused heterocyclic aromatic group means a fused ring aromatic hydrocarbon group containing at least one hetero atom. For the purposes of the present invention, aromatic or heteroaromatic radicals include not only aromatic ring systems but also non-aromatic ring systems. Thus, for example, systems such as pyridine, thiophene, pyrrole, pyrazole, triazole, imidazole, oxazole, oxadiazole, thiazole, tetrazole, pyrazine, pyridazine, pyrimidine, triazine, carbene, and the like, are also considered aromatic or heterocyclic aromatic groups for the purposes of this invention. For the purposes of the present invention, fused-ring aromatic or fused-heterocyclic aromatic ring systems include not only systems of aromatic or heteroaromatic groups, but also systems in which a plurality of aromatic or heterocyclic aromatic groups may also be interrupted by short non-aromatic units (< 10% of non-H atoms, preferably less than 5% of non-H atoms, such as C, N or O atoms). Thus, for example, systems such as 9, 9' -spirobifluorene, 9, 9-diarylfluorene, triarylamines, diaryl ethers, etc., are also considered fused aromatic ring systems for the purposes of this invention.
The invention relates to a heterocyclic arylamine compound, which has a structure shown as a general formula (1):
Figure BDA0002277142350000031
wherein:
when Ar is1When selected from the general formula (A-1), n is selected from 1 or 2, Ar3Selected from the structure
Figure BDA0002277142350000032
Or
Figure BDA0002277142350000033
When Ar is1When selected from the general formulae (A-2) to (A-8), n is selected from an integer of 0 to 2, Ar3Selected from substituted or unsubstituted aromatic or heteroaromatic groups having 5 to 60 ring atoms; or a non-aromatic ring system having 3 to 25 ring atoms which may be substituted or unsubstituted;
(A-1) to (A-8) are selected from the following groups:
Figure BDA0002277142350000034
X1、X2multiple occurrences of the same or different compound are independently selected from O, S, SO2、NR3、CR3R4、SiR3R4、C(＝O)(ii) a Preferably, X1、X2Each independently selected from O, S, SO2、NR3、CR3R4(ii) a More preferably, X1、X2Are each independently selected from NR3Or CR3R4；
Y、Y1～Y11Are the same or different when occurring multiple times and are respectively and independently selected from N or CR5And Y is1～Y3At least two of which are N, Y4～Y7At least one of which is N; in certain embodiments, Y1～Y3All are selected from N, Y4～Y7At least one of which is N; in other embodiments, Y1～Y3At least two of which are N, Y4And Y7At least one of which is N; in other embodiments, Y1～Y3At least two of which are N, Y4And Y7Are all selected from N. In other embodiments, Y1Is N or CR5，Y2Is N, Y3Is N.
Because of Y4～Y7The number of the N atoms influences the electron-withdrawing ability of the group, the N atoms can enhance the electron-withdrawing ability of the group, improve the electron push-pull of the whole molecule, regulate and control the energy level and dipole moment of the molecule, and improve the ultraviolet absorption of the molecule below 400nm in wavelength and the refractive index of the molecule.
L1Selected from a single bond, an alkenyl group, an alkynyl group, an acyl group, an amide group, a carbonyl group, a sulfone group, a substituted or unsubstituted alkyl group having 1 to 60 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 60 carbon atoms, a substituted or unsubstituted aromatic group or heteroaromatic group having 5 to 60 ring atoms;
Ar2、Ar4～Ar7each independently selected from substituted or unsubstituted aromatic or heteroaromatic groups having 5 to 60 ring atoms; or a non-aromatic ring system having 3 to 25 ring atoms which may be substituted or unsubstituted, or an arylamine group;
R1～R5are the same or different at multiple occurrences and are each independently selected from hydrogen, or D, or a straight chain alkyl group having 1 to 20C atoms,Alkoxy having 1 to 20C atoms, or thioalkoxy having 1 to 20C atoms, or branched alkyl having 3 to 20C atoms, or cycloalkyl having 3 to 20C atoms, alkoxy having 3 to 20C atoms, or thioalkoxy having 3 to 20C atoms, or silyl, or keto having 1 to 20C atoms, or alkoxycarbonyl having 2 to 20C atoms, or aryloxycarbonyl having 7 to 20C atoms, cyano (-CN), carbamoyl (-C (═ O) NH2) Haloformyl, formyl (-C (═ O) -H), isocyano, isocyanate, thiocyanate or isothiocyanate, hydroxy, nitro, CF3Cl, Br, F, a crosslinkable group, or a substituted or unsubstituted aromatic or heteroaromatic group having 5 to 60 ring atoms, or an aryloxy group having 5 to 60 ring atoms, or a heteroaryloxy group having 5 to 60 ring atoms, or a combination thereof; wherein two or more adjacent radicals may optionally form a mono-or polycyclic, aliphatic, aromatic or heteroaromatic ring system with one another;
dotted line represents Ar1And L1An attached key.
In a preferred embodiment, Ar1Is selected from the general formula (A-1), preferably, the general formula (A-1) is selected from the following groups:
Figure BDA0002277142350000041
wherein: h atoms in the structure may be further substituted, X1The meaning is the same as above.
In other preferred embodiments, the compound according to the invention, Ar1Selected from the formulae (A-2) to (A-8), preferably the formulae (A-2) to (A-8) are selected from the following groups:
Figure BDA0002277142350000042
wherein: r1And R2The meaning is as described above, the H atom in the structure may be further substituted.
In a preferred embodimentIn Ar1Selected from the group consisting of general formula (A-2), (A-5) and (A-7).
According to the compound as described above, it can be selected from any one of the structures as represented by general formulae (2-1) to (2-4):
Figure BDA0002277142350000051
wherein: n1 is selected from an integer of 1-2; n2 is selected from an integer of 0-2; x1、Y、Y1～Y11、Ar2、Ar4～Ar7、L1、R1The meaning is as described above.
In one embodiment, the compound according to the present invention, Ar2、Ar4、Ar5Can be selected from one or a combination of the following groups:
Figure BDA0002277142350000052
wherein: each occurrence of W is independently selected from N or CR7；
X3Multiple occurrences of the same or different compound are independently selected from O, S, SO2、NR7、CR6R7、SiR6R7、C(＝O)；
R6、R7Are identical or different on multiple occurrence and are each independently selected from hydrogen, or D, or a straight-chain alkyl group having 1 to 20C atoms, an alkoxy group having 1 to 20C atoms, or a thioalkoxy group having 1 to 20C atoms, or a branched-chain alkyl group having 3 to 20C atoms, or a cycloalkyl group having 3 to 20C atoms, or an alkoxy group having 3 to 20C atoms, or a thioalkoxy group having 3 to 20C atoms, or a silyl group, or a keto group having 1 to 20C atoms, or an alkoxycarbonyl group having 2 to 20C atoms, or an aryloxycarbonyl group having 7 to 20C atoms, a cyano group, a carbamoyl group, a haloformyl group, an isocyano group, an isocyanate, a thiocyanate or isothiocyanate, a hydroxyl group, a nitro group, a CF group, or an isocyanate3Cl, Br, F, crosslinkable groups, or having from 5 to 60A substituted or unsubstituted aromatic or heteroaromatic group of one ring atom, or an aryloxy group of 5 to 60 ring atoms or a heteroaryloxy group of 5 to 60 ring atoms, or a combination of the above; wherein two or more adjacent radicals may optionally form a mono-or polycyclic, aliphatic, aromatic or heteroaromatic ring system with one another.
In one embodiment, each occurrence of W is independently selected from CR7. In one embodiment, W is CH.
In a preferred embodiment, Ar2Selected from the following groups:
Figure BDA0002277142350000053
more preferably, Ar2Selected from the following groups:
Figure BDA0002277142350000054
further, Ar2Is selected from
Figure BDA0002277142350000055
In a preferred embodiment, Ar4、Ar5May be selected from the following groups:
Figure BDA0002277142350000056
more preferably, Ar4、Ar5May be selected from the following groups:
Figure BDA0002277142350000057
further, Ar4、Ar5Can be selected from
Figure BDA0002277142350000058
In a preferred embodiment, Ar is2、Ar4、Ar5Can be selected from one or a combination of the following groups:
Figure BDA0002277142350000061
wherein: l is2Selected from a single bond, an alkenyl group, an alkynyl group, an acyl group, an amide group, a carbonyl group, a sulfone group, a substituted or unsubstituted alkyl group having 1 to 60 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 60 carbon atoms, a substituted or unsubstituted aromatic group or heteroaromatic group having 5 to 60 ring atoms;
the H atoms in the structure may be further substituted.
In certain embodiments, L2Selected from a single bond, a substituted or unsubstituted alkyl group having 1 to 60 carbon atoms, a substituted or unsubstituted aromatic group or heteroaromatic group having 5 to 60 ring atoms;
in certain embodiments, L2Selected from a single bond, or a substituted or unsubstituted phenyl group.
In certain embodiments, the compounds of the present invention are represented by formula I1-Ar1And Ar2Selected from the same group.
In certain preferred embodiments, -L1-Ar1And Ar2Each independently selected from: a substituted or unsubstituted carbazole, fluorene, dibenzofuran, or dibenzothiophene group;
in certain embodiments, Ar1Selected from any one of the general formulae (A-2) to (A-8), Ar2Selected from substituted or unsubstituted carbazole, fluorene, dibenzofuran or dibenzothiophene groups.
Preferably, the compound according to the present invention may be selected from any one of the structures of general formulae (3-1) to (3-9):
Figure BDA0002277142350000062
Figure BDA0002277142350000071
wherein: n1 is selected from an integer of 1-2; n2 is selected from an integer of 0 to 2.
In some embodiments, a compound according to the present invention, Ar4、Ar5May be selected from the same group; in certain embodiments, Ar4、Ar5Selected from substituted or unsubstituted benzene, biphenyl, naphthalene, 4-pyridylphenyl, carbazole, fluorene, dibenzofuran, dibenzothiophene groups or any one of the groups of the general formulae (A-2) to (A-8); in certain embodiments, Ar4、Ar5Selected from substituted or unsubstituted phenyl, carbazole, fluorene, dibenzofuran or dibenzothiophene groups. In certain embodiments, Ar4And Ar5And the same are selected from substituted or unsubstituted phenyl.
In certain embodiments, Ar1、Ar2And Ar4Selected from the same group; in certain embodiments, Ar1、Ar2And Ar4、Ar5Selected from the same group.
In certain embodiments, Ar4And Ar5Is phenyl, Y is CR5，Y1Is N or CR5，Y2Is N, Y3Is N.
In certain embodiments, a compound according to the invention, L1And L2Selected from a single bond or one or a combination of the following groups:
Figure BDA0002277142350000072
wherein:
each occurrence of W is independently selected from N or CR7；
X3Multiple occurrences of the same or different compound are independently selected from O, S, SO2、NR7、CR6R7、SiR6R7、C(＝O)；
R6、R7The multiple occurrences of which are the same or different, are independently selected from hydrogen, or D, or a straight chain alkyl group having 1 to 20C atoms, an alkane having 1 to 20C atomsOxy, or thioalkoxy having 1 to 20C atoms, or branched alkyl having 3 to 20C atoms, or cycloalkyl having 3 to 20C atoms, or alkoxy having 3 to 20C atoms, or thioalkoxy having 3 to 20C atoms, or silyl, or keto having 1 to 20C atoms, or alkoxycarbonyl having 2 to 20C atoms, or aryloxycarbonyl having 7 to 20C atoms, cyano, carbamoyl, haloformyl, formyl, isocyano, isocyanate, thiocyanate or isothiocyanate, hydroxy, nitro, CF, or a salt thereof3Cl, Br, F, a crosslinkable group, or a substituted or unsubstituted aromatic or heteroaromatic group having 5 to 60 ring atoms, or an aryloxy group having 5 to 60 ring atoms or a heteroaryloxy group having 5 to 60 ring atoms, or a combination thereof; wherein two or more adjacent radicals may optionally form a mono-or polycyclic, aliphatic, aromatic or heteroaromatic ring system with one another.
In certain embodiments, L1And L2Each independently selected from a single bond or one or a combination of the following groups:
Figure BDA0002277142350000073
Figure BDA0002277142350000081
wherein: the H atoms on the ring may be further substituted.
In certain embodiments, L2And L1The same is true. In certain embodiments, L2And L1Selected from a single bond or substituted or unsubstituted phenyl.
In certain embodiments, L1And L2Selected from single bonds; in certain embodiments, L1And L2Is selected from phenyl; w is CH;
X3selected from O, NR3Or CR3R4；R3And R4Each independently selected from hydrogen, or D, or phenyl, or a straight chain alkyl group having 1 to 20C atoms, or a C atom having 3 to 20Branched alkyl of a subgroup, or cycloalkyl having 3 to 20C atoms;
in one embodiment, the heterocyclic arylamine compound is selected from any one of the structures of general formulas (4-1) to (4-3):
Figure BDA0002277142350000082
wherein: ar in formulas (4-1) - (4-2)1Selected from the general formulae (A-1) to (A-8); ar in formula (4-3)1Selected from the general formulae (A-2) to (A-8). Preferably, in formulae (4-1) to (4-2), Ar1And Ar2Are selected from the same group, preferably, simultaneously from the group (A-1); more preferably, Ar1And Ar2Simultaneously selected from carbazole, fluorene, dibenzofuran, dibenzothiophene and derivatives thereof;
preferably, in formulae (4-1) to (4-2), Ar1And Ar2Are selected from the same group, preferably, are simultaneously selected from any one of groups (A-2) to (A-8).
Preferably, in formula (4-3), Ar1And Ar2Are selected from the same group, preferably, are simultaneously selected from any one of groups (A-2) to (A-8).
Specifically, examples of compounds of the present invention are selected from the following structural formulae, but are not limited thereto:
Figure BDA0002277142350000083
Figure BDA0002277142350000091
Figure BDA0002277142350000101
Figure BDA0002277142350000111
Figure BDA0002277142350000121
the examples of the heterocyclic arylamine compounds of the present invention listed above, wherein H in the structural formula may be further optionally substituted, particularly deuterated.
The compounds according to the invention require a higher glass transition temperature in order to achieve better thermal stability. In certain preferred embodiments, the glass transition temperature TgIn a preferred embodiment, T is not less than 100 DEG Cg120 ℃ or more, in a more preferred embodiment, Tg140 ℃ or more, in a more preferred embodiment, Tg160 ℃ or more, and in a most preferred embodiment, Tg≥180℃。
In certain embodiments, the compounds according to the present invention have a refractive index greater than 1.7 at a wavelength of 630 nm; preferably, greater than 1.78; more preferably, greater than 1.83.
In certain embodiments, compounds according to the present invention have a singlet energy (S1) of greater than or equal to 2.7 eV; preferably, greater than 2.8 eV; more preferably, greater than 2.85 eV.
In other embodiments, compounds according to the present invention have a singlet energy (S1) of less than or equal to 3.1 eV; preferably, less than or equal to 3.0 eV.
The compounds according to the invention require a low extinction coefficient, less than 0.1 at a wavelength of 430 nm; preferably, less than 0.003; more preferably, less than 0.001. The light-emitting diode has higher transmittance on visible light, and the influence on the light-emitting efficiency of equipment is reduced.
In certain preferred embodiments, the arylamine compounds according to the invention have a relatively large extinction coefficient in the wavelength range of ≦ 400 nm; preferentially, the extinction coefficient is more than or equal to 0.3 when the wavelength is 350 nm; it is preferably not less than 0.5, more preferably not less than 0.7, most preferably not less than 1.0.
It is an object of the present invention to provide a material solution for evaporation type OLEDs.
In certain embodiments, the compounds according to the invention have a molecular weight of 1200g/mol or less, preferably 1100g/mol or less, very preferably 1000g/mol or less, more preferably 950g/mol or less, and most preferably 900g/mol or less.
It is another object of the present invention to provide a material solution for printing OLEDs.
In certain embodiments, the compounds according to the invention have a molecular weight of 800g/mol or more, preferably 900g/mol or more, very preferably 1000g/mol or more, more preferably 1100g/mol or more, most preferably 1200g/mol or more.
In other embodiments, the compounds according to the invention have a solubility in toluene of 2mg/ml or more, preferably 3mg/ml or more, more preferably 4mg/ml or more, most preferably 5mg/ml or more at 25 ℃.
The invention also relates to a composition comprising at least one compound as described above, and at least one organic solvent; the at least one organic solvent is selected from aromatic or heteroaromatic, ester, aromatic ketone or aromatic ether, aliphatic ketone or aliphatic ether, alicyclic or olefinic compound, or boric acid ester or phosphoric acid ester compound, or a mixture of two or more solvents.
In some embodiments, the composition according to the invention, said at least one organic solvent is chosen from aromatic or heteroaromatic-based solvents, in particular aliphatic chain/ring-substituted aromatic solvents, or aromatic ketone solvents, or aromatic ether solvents.
Examples of solvents suitable for the present invention are, but not limited to: aromatic or heteroaromatic-based solvents p-diisopropylbenzene, pentylbenzene, tetrahydronaphthalene, cyclohexylbenzene, chloronaphthalene, 1, 4-dimethylnaphthalene, 3-isopropylbiphenyl, p-methylisopropylbenzene, dipentylbenzene, tripentylbenzene, pentyltoluene, o-xylene, m-xylene, p-xylene, o-diethylbenzene, m-diethylbenzene, p-diethylbenzene, 1, 2, 3, 4-tetramethylbenzene, 1, 2, 3, 5-tetramethylbenzene, 1, 2, 4, 5-tetramethylbenzene, butylbenzene, dodecylbenzene, dihexylbenzene, dibutylbenzene, p-diisopropylbenzene, 1-methoxynaphthalene, cyclohexylbenzene, dimethylnaphthalene, 3-isopropylbiphenyl, p-methylisopropylbenzene, 1-methylnaphthalene, 1, 2, 4-trichlorobenzene, 1, 3-dipropoxybenzene, 4-difluorodiphenylmethane, 1, 2-dimethoxy-4- (1-propenyl) benzene, 1, 4-dimethoxynaphthalene, Diphenylmethane, 2-phenylpyridine, 3-phenylpyridine, N-methyldiphenylamine, 4-isopropylbiphenyl, 4- (3-phenylpropyl) pyridine, benzyl benzoate, 1-bis (3, 4-dimethylphenyl) ethane, 2-isopropylnaphthalene, dibenzyl ether, and the like; ketone-based solvents 1-tetralone, 2- (phenylepoxy) tetralone, 6- (methoxy) tetralone, acetophenone, propiophenone, benzophenone, and derivatives thereof, such as 4-methylacetophenone, 3-methylacetophenone, 2-methylacetophenone, 4-methylpropiophenone, 3-methylpropiophenone, 2-methylpropiophenone, isophorone, 2, 6, 8-trimethyl-4-nonanone, fenchyne, 2-nonanone, 3-nonanone, 5-nonanone, 2-decanone, 2, 5-hexanedione, phorone, di-n-amyl ketone; aromatic ether solvent: 3-phenoxytoluene, butoxybenzene, benzylbutylbenzene, p-anisaldehyde dimethylacetal, tetrahydro-2-phenoxy-2H-pyran, 1, 2-dimethoxy-4- (1-propenyl) benzene, 1, 4-benzodioxane, 1, 3-dipropylbenzene, 2, 5-dimethoxytoluene, 4-ethylbenylether, 1, 2, 4-trimethoxybenzene, 4- (1-propenyl) -1, 2-dimethoxybenzene, 1, 3-dimethoxybenzene, glycidylphenyl ether, dibenzyl ether, 4-t-butylanisole, trans-p-propenylanisole, 1, 2-dimethoxybenzene, 1-methoxynaphthalene, diphenyl ether, 2-phenoxymethyl ether, 2-phenoxytetrahydrofuran, and the like, Ethyl-2-naphthyl ether, amyl ether c-hexyl ether, dioctyl ether, ethylene glycol dibutyl ether, diethylene glycol diethyl ether, diethylene glycol butyl methyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, triethylene glycol ethyl methyl ether, triethylene glycol butyl methyl ether, tripropylene glycol dimethyl ether, tetraethylene glycol dimethyl ether; ester solvent: alkyl octanoates, alkyl sebacates, alkyl stearates, alkyl benzoates, alkyl phenylacetates, alkyl cinnamates, alkyl oxalates, alkyl maleates, alkyl lactones, alkyl oleates, and the like.
Further, according to the ink of the present invention, the at least one organic solvent may be selected from: aliphatic ketones such as 2-nonanone, 3-nonanone, 5-nonanone, 2-decanone, 2, 5-hexanedione, 2, 6, 8-trimethyl-4-nonanone, phorone, di-n-amyl ketone and the like; or aliphatic ethers such as amyl ether, hexyl ether, dioctyl ether, ethylene glycol dibutyl ether, diethylene glycol diethyl ether, diethylene glycol butyl methyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, triethylene glycol ethyl methyl ether, triethylene glycol butyl methyl ether, tripropylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, and the like.
In other embodiments, the printing ink further comprises another organic solvent. Examples of another organic solvent include (but are not limited to): methanol, ethanol, 2-methoxyethanol, methylene chloride, chloroform, chlorobenzene, o-dichlorobenzene, tetrahydrofuran, anisole, morpholine, toluene, o-xylene, m-xylene, p-xylene, 1, 4-dioxane, acetone, methyl ethyl ketone, 1, 2-dichloroethane, 3-phenoxytoluene, 1, 1, 1-trichloroethane, 1, 1, 2, 2-tetrachloroethane, ethyl acetate, butyl acetate, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, tetrahydronaphthalene, decalin, indene, and/or mixtures thereof.
In a preferred embodiment, the composition according to the invention is a solution.
In another preferred embodiment, the composition according to the invention is a suspension.
The compositions of the embodiments of the present invention may contain 0.01 to 20 wt% of the organic compound according to the present invention, preferably 0.1 to 15 wt%, more preferably 0.2 to 10 wt%, and most preferably 0.25 to 5 wt% of the organic compound.
The invention also relates to the use of said composition as a coating or printing ink for the production of organic electronic devices, particularly preferably by a printing or coating production process.
Suitable printing or coating techniques include, but are not limited to, ink jet printing, spray printing (Nozleprinting), letterpress printing, screen printing, dip coating, spin coating, doctor blade coating, roll printing, twist roll printing, lithographic printing, flexographic printing, rotary printing, spray coating, brush or pad printing, slot die coating, and the like. Gravure printing, jet printing and ink jet printing are preferred. The solution or suspension may additionally include one or more components such as surface active compounds, lubricants, wetting agents, dispersants, hydrophobing agents, binders, and the like, for adjusting viscosity, film forming properties, enhancing adhesion, and the like. For details on the printing technology and its requirements concerning the solutions, such as solvent and concentration, viscosity, etc., reference is made to the Handbook of Print Media, technology and production Methods, published by Helmut Kipphan, ISBN 3-540-67326-1.
The invention also provides a light extraction layer material which comprises the heterocyclic arylamine compound.
The present invention also provides an organic electronic device comprising at least one heterocyclic arylamine compound as described above. The organic electronic device can be selected from, but not limited to, an Organic Light Emitting Diode (OLED), an organic photovoltaic cell, an organic light emitting cell, an organic field effect transistor, an organic light emitting field effect transistor, an organic laser, an organic spintronic device, an organic sensor, an organic plasmon emitting diode and the like, and is particularly preferably an OLED. Preferably, the compound of the present invention may be used in a hole transport layer or a light emitting layer or a light extraction layer of an organic electronic device.
Further, the organic electronic device according to the present invention comprises two electrodes, one or more organic functional layers between the two electrodes, and a light extraction layer on a surface of one electrode and on a side away from the organic functional layer, wherein the light extraction layer comprises the arylamine compound.
Specifically, the light extraction layer contains a compound represented by structural formula (1).
Figure BDA0002277142350000141
Wherein:
when Ar is1When selected from the general formula (A-1), n is selected from 1 or 2, Ar3Selected from the structure
Figure BDA0002277142350000142
Or
Figure BDA0002277142350000143
When Ar is1When selected from the general formulae (A-2) to (A-8), n is selected from an integer of 0 to 2, Ar3Selected from substituted or unsubstituted aromatic or heteroaromatic groups having 5 to 60 ring atoms; or a non-aromatic ring system having 3 to 25 ring atoms which may be substituted or unsubstituted;
(A-1) to (A-8) are selected from the following groups:
Figure BDA0002277142350000144
X1、X2multiple occurrences of the same or different compound are independently selected from O, S, SO2、NR3、CR3R4、SiR3R4、C(＝O)；
Y、Y1～Y11Are the same or different when occurring multiple times and are respectively and independently selected from N or CR5And Y is1～Y3At least two of which are N, Y4～Y7At least one of which is N;
L1selected from a single bond, an alkenyl group, an alkynyl group, an acyl group, an amide group, a carbonyl group, a sulfone group, a substituted or unsubstituted alkyl group having 1 to 60 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 60 carbon atoms, a substituted or unsubstituted aromatic group or heteroaromatic group having 5 to 60 ring atoms;
Ar2、Ar4～Ar7each independently selected from substituted or unsubstituted aromatic or heteroaromatic groups having 5 to 60 ring atoms; or a non-aromatic ring system having 3 to 25 ring atoms which may be substituted or unsubstituted, or an arylamine group;
R1～R5are identical or different on multiple occurrence and are each independently selected from hydrogen, or D, or a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 20C atoms, or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 20C atoms, or a silyl group, or a keto group having 1 to 20C atoms, or an alkoxycarbonyl group having 2 to 20C atoms, or an aryloxycarbonyl group having 7 to 20C atoms, a cyano group (-CN), a carbamoyl group (-C (═ O) NH2) Haloformyl, formyl (-C (═ O) -H), isocyano, isocyanate, thiocyanate or isothiocyanateHydroxy, nitro, CF3Cl, Br, F, a crosslinkable group, or a substituted or unsubstituted aromatic or heteroaromatic group having 5 to 60 ring atoms, or an aryloxy or heteroaryloxy group having 5 to 60 ring atoms, or a combination of these systems; wherein two or more adjacent radicals may optionally form a mono-or polycyclic, aliphatic, aromatic or heteroaromatic ring system with one another;
dotted line represents Ar1And L1An attached key.
In a preferred embodiment, the organic electronic device is an organic light emitting diode device comprising an anode, and a cathode and an organic functional layer disposed between the anode and the cathode; in one embodiment, the light extraction layer is located on the side of the cathode surface away from the organic functional layer; in other embodiments, the light extraction layer is located on a side of the anode surface remote from the organic functional layer.
In a preferred embodiment, the light extraction layer of the organic electronic device comprises any one of the compounds described above.
Preferably, the light extraction layer of the organic electronic device includes compounds represented by structural formulae (2-1) to (2-4).
In other preferred embodiments, the light extraction layer of the organic electronic device includes compounds represented by structural formulae (3-1) to (3-9).
In other preferred embodiments, the light extraction layer of the organic electronic device includes compounds represented by structural formulae (4-1) to (4-3).
According to the organic electronic device, the light extraction layer contains the compound which needs higher glass transition temperature, and the thermal stability of the compound is improved. In certain preferred embodiments, the glass transition temperature TgIn a preferred embodiment, T is not less than 100 DEG Cg120 ℃ or more, in a more preferred embodiment, Tg140 ℃ or more, in a more preferred embodiment, Tg160 ℃ or more, and in a most preferred embodiment, Tg≥180℃。
According to the organic electronic device of the present invention, the light extraction layer has a high refractive index, and thus may contribute to the improvement of the light efficiency of the organic light emitting device, particularly to the improvement of the external light emitting efficiency, and the refractive index at the wavelength of 630nm is required to be greater than 1.7; preferably, greater than 1.78; more preferably, greater than 1.83.
In some preferred embodiments, in accordance with the organic electronic device of the present invention, the light extraction layer comprises a singlet energy (S1) of greater than or equal to 2.7 eV; preferably, greater than or equal to 2.8 eV; more preferably, greater than or equal to 2.85 eV.
In other preferred embodiments, the organic electronic device according to the present invention, wherein the light extraction layer comprises a singlet energy (S1) of less than or equal to 3.1 eV; preferably, less than or equal to 3.0 eV.
According to the organic electronic device of the present invention, the light extraction layer contains a compound requiring a small extinction coefficient, the extinction coefficient at a wavelength of 430nm being less than 0.1; preferably, less than 0.003; more preferably, less than 0.001. The light-emitting diode has higher transmittance on visible light, and the influence on the light-emitting efficiency of equipment is reduced.
In a preferred embodiment, the organic electronic device according to the invention is an electroluminescent device comprising one or more organic functional layers comprising one or more of an electron injection layer, an electron transport layer, a hole injection layer, a hole transport layer and a light emitting layer, and comprising at least one light emitting layer.
The organic electroluminescent device according to the invention is preferably selected from the group consisting of organic light-emitting diodes (OLEDs), organic light-emitting cells (OLEECs), Organic Field Effect Transistors (OFETs), organic light-emitting field effect transistors.
The device structure of the electroluminescent device, the cathode, the anode and the light extraction layer, will be described below, but not limited thereto.
The anode may comprise a conductive metal or metal oxide, or a conductive polymer. The anode can easily inject holes into a Hole Injection Layer (HIL) or a Hole Transport Layer (HTL) or an emission layer. In one embodiment, the absolute value of the difference between the work function of the anode and the HOMO level or valence band level of the emitter in the light emitting layer or the p-type semiconductor material acting as a HIL or HTL or Electron Blocking Layer (EBL) is less than 0.5eV, preferably less than 0.3eV, most preferably less than 0.2 eV. Examples of anode materials include, but are not limited to: al, Cu, Au, Ag, Mg, Fe, Co, Ni, Mn, Pd, Pt, ITO, aluminum-doped zinc oxide (AZO), and the like. Other suitable anode materials are known and can be readily selected for use by one of ordinary skill in the art. The anode material may be deposited using any suitable technique, such as a suitable physical vapor deposition method, including radio frequency magnetron sputtering, vacuum thermal evaporation, electron beam (e-beam), and the like. In certain embodiments, the anode is pattern structured. Patterned ITO conductive substrates are commercially available and can be used to prepare devices according to the present invention.
The cathode may comprise a conductive metal or metal oxide. The cathode can easily inject electrons into the EIL or ETL or directly into the light emitting layer. In one embodiment, the absolute value of the difference between the work function of the cathode and the LUMO level or conduction band level of the emitter in the light emitting layer or the n-type semiconductor material as Electron Injection Layer (EIL) or Electron Transport Layer (ETL) or Hole Blocking Layer (HBL) is less than 0.5eV, preferably less than 0.3eV, most preferably less than 0.2 eV. In principle, all materials which can be used as cathodes in OLEDs are possible as cathode materials for the device according to the invention. Examples of cathode materials include, but are not limited to: al, Au, Ag, Ca, Ba, Mg, LiF/Al, MgAg alloy, BaF2Al, Cu, Fe, Co, Ni, Mn, Pd, Pt, ITO, etc. The cathode material may be deposited using any suitable technique, such as a suitable physical vapor deposition method, including radio frequency magnetron sputtering, vacuum thermal evaporation, electron beam (e-beam), and the like.
The light extraction layer has a proper energy level structure, the region with the wavelength less than 400nm has strong absorption, and the visible light with the wavelength more than 400nm has weak or near zero absorption, so that the damage of the internal material of the device caused by the irradiation of high-energy light in the subsequent process is avoided. Meanwhile, the light extraction layer has a higher refractive index, so that the emission of visible light can be beneficially led out, and the luminous efficiency of the organic electronic light-emitting device is improved. Since the influence of light interference is large when the reflectance of the interface between the light extraction layer and the adjacent electrode is large, the refractive index of the material constituting the light extraction layer is preferably larger than the refractive index of the adjacent electrode, and the refractive index at 630nm may be 1.50 or more, more preferably 1.70 or more, and particularly preferably 1.80 or more.
According to the organic electroluminescent element of the present invention, the organic compound of the light extraction layer has a thickness of generally 10nm to 200nm, preferably 20nm to 150nm, more preferably 30nm to 100nm, most preferably 40nm to 90 nm.
The invention also relates to the use of the electroluminescent device according to the invention in various electronic devices, including, but not limited to, display devices, lighting devices, light sources, sensors, etc.
The present invention will be described in connection with preferred embodiments, but the present invention is not limited to the following embodiments, and it should be understood that the appended claims outline the scope of the present invention and those skilled in the art, guided by the inventive concept, will appreciate that certain changes may be made to the embodiments of the invention, which are intended to be covered by the spirit and scope of the appended claims.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
The synthesis of the compounds according to the invention is illustrated, but the invention is not limited to the following examples.
Figure BDA0002277142350000161
Figure BDA0002277142350000171
Synthesis of Compound C-1:
Figure BDA0002277142350000172
magnesium (1.49g, 62mmol) and iodine were weighed into a 250mL three-necked flask, 25mL of anhydrous tetrahydrofuran was added, nitrogen gas was replaced, 4-bromotriphenylamine (10g, 31mmol) was added, and the mixture was heated to initiate a reaction, and allowed to react at 65 ℃ for 2 hours. And cooling the reaction liquid to room temperature to obtain the Grignard reagent. Cyanuric chloride (5.67g, 31mmol) was weighed into a 250mL flask and about 80mL of tetrahydrofuran was added. After nitrogen exchange, the Grignard reagent was added slowly and stirred at room temperature overnight. After the reaction is completed, water is added for quenching, ethyl acetate is used for extraction, anhydrous sodium sulfate is used for drying, and after silica gel is mixed with a sample, column chromatography purification is carried out to obtain 4.85g of intermediate yellow solid, wherein the yield is 40%.
Figure BDA0002277142350000173
I-1(2g, 5.1mmol), 9, 9-dimethylfluorene-2-boronic acid (3g, 12.5mmol), palladium tetratriphenylphosphine (0.29g, 0.25mmol), potassium carbonate (3.4g, 25mmol) were weighed into a 250mL two-neck flask, about 60mL of toluene and 15mL of methanol were added, vacuum-pumped and charged with nitrogen five times, the temperature was raised to 70 ℃, the reaction was stirred overnight, the reaction was stopped, the temperature was lowered to room temperature, quenched with water, the organic layer was separated, extracted with dichloromethane, the organic phases were combined and dried over sodium sulfate, and concentrated under reduced pressure to remove the organic solvent. Column chromatography purification was performed to give 2.5g of a solid in 70% yield.
Synthesis of Compound C-2:
Figure BDA0002277142350000181
i-1(2g, 5.1mmol), 4-biphenylboronic acid (1g, 5mmol), tetrakistriphenylphosphine palladium (0.17g, 0.15mmol), potassium carbonate (2.1g, 15.3mmol) were weighed into a 250mL two-neck flask, about 60mL of toluene and 10mL of methanol were added, vacuum was applied and nitrogen was charged five times, the temperature was raised to 50 ℃, the reaction was stirred overnight, the reaction was stopped, the temperature was lowered to room temperature, water was quenched, the organic layer was separated, then extracted with dichloromethane, the combined organic layers were dried over sodium sulfate and concentrated under reduced pressure to remove the organic solvent. Column chromatography purification was performed to give 1.35g of a solid in 52% yield.
I-2(1.35g, 2.65mmol), 9, 9-dimethylfluorene-2-boronic acid (0.71g, 3mmol), palladium tetratriphenylphosphine (92mg, 0.08mol), potassium carbonate (1.1g, 8mmol) were weighed into a 250mL two-neck flask, about 60mL of toluene and 20mL of methanol were added, vacuum-pumped and charged with nitrogen five times, the temperature was raised to 70 ℃, the reaction was stirred overnight, the reaction was stopped, the temperature was lowered to room temperature, quenched with water, the organic layer was separated, extracted with dichloromethane, the organic phases were combined and dried over sodium sulfate, and concentrated under reduced pressure to remove the organic solvent. Column chromatography purification was performed to obtain 1.3g of a solid in 74% yield.
Synthesis of Compound C-3:
Figure BDA0002277142350000183
i-1(2g, 5.1mmol), N-phenyl-3-carbazolboronic acid (3.4g, 12mmol), palladium acetate (56mg, 0.25mmol) and potassium phosphate (3.2g, 15mmol) were weighed into a 250mL two-necked flask, about 100mL dioxane and 20mL water were added, vacuum was evacuated and charged with nitrogen five times, the temperature was raised to 60 ℃, the reaction was stirred overnight, the reaction was stopped, the temperature was lowered to room temperature, the organic solvent was removed by rotary evaporation, dichloromethane was extracted, the organic phases were combined and dried over sodium sulfate, and the organic solvent was removed by concentration under reduced pressure. Column chromatography purification was performed to give 2.26g of a solid in 55% yield.
Synthesis of Compound C-4:
Figure BDA0002277142350000191
i-2(1.5g, 3mmol), N-phenyl-3-carbazolboronic acid (0.95g, 3.3mmol), palladium acetate (34mg, 0.15mmol) and potassium phosphate (1.9g, 9mmol) were weighed into a 250mL two-neck flask, about 80mL dioxane and 20mL water were added, vacuum was charged with nitrogen five times, the temperature was raised to 60 ℃, the reaction was stirred overnight, the reaction was stopped, the temperature was lowered to room temperature, the organic solvent was removed by rotary evaporation, then dichloromethane was used for extraction, the organic phases were combined and dried over sodium sulfate, and the organic solvent was removed by concentration under reduced pressure. Column chromatography purification was performed to give 1.05g of a solid in 50% yield.
Synthesis of Compound C-5:
Figure BDA0002277142350000192
i-1(2g, 5.1mmol), I-3(3.5g, 12mmol), palladium tetratriphenylphosphine (0.29g, 0.25mmol) and potassium carbonate (2.1g, 15mmol) were weighed into a 250mL two-neck flask, about 80mL of toluene and 20mL of methanol were added, vacuum was applied and nitrogen was charged five times, the temperature was raised to 70 ℃, the reaction was stirred overnight, the reaction was stopped, the temperature was reduced to room temperature, water was quenched, the organic layer was separated, then extracted with dichloromethane, the combined organic phases were dried over sodium sulfate and concentrated under reduced pressure to remove the organic solvent. Column chromatography purification was performed to give 2.68g of a solid in 65% yield.
Synthesis of Compound C-6:
Figure BDA0002277142350000193
i-4(8g, 29.3mmol), pinacol diboron (8.4g, 33mmol), [1, 1' -bis (diphenylphosphino) ferrocene ] dichloropalladium (0.65g, 0.88mmol), potassium acetate (8.8g, 0.09mol) were weighed into a 250mL two-necked flask, about 130mL of tetrahydrofuran was added, vacuum was applied and nitrogen was charged five times, the temperature was increased to 80 ℃, the reaction was stirred overnight, the reaction was stopped, the temperature was decreased to room temperature, quenched with water, the organic layers were separated, extracted with dichloromethane, the organic phases were combined and dried over sodium sulfate, and concentrated under reduced pressure to remove the organic solvent. Column chromatography purification was performed to obtain 6.1g of a solid in 74% yield.
Figure BDA0002277142350000201
I-6(2g, 6.3mmol), I-5(4.5g, 14mmol), tetrakistriphenylphosphine palladium (0.37g, 0.32mol), potassium carbonate (4.1g, 30mmol), tetrabutylammonium bromide (0.42g, 1.3mmol) were weighed into a 250mL two-necked flask, about 80mL dioxane and 20mL water were added, vacuum was applied and nitrogen was charged five times, the temperature was increased to 70 ℃, the reaction was stirred overnight, the reaction was stopped, the temperature was decreased to room temperature, V was extracted with dichloromethane, the organic phases were combined and dried over sodium sulfate, concentrated under reduced pressure to remove the organic solvent and purified by column chromatography to give 2.3g of a solid in 58% yield.
Synthesis of Compound C-7:
Figure BDA0002277142350000202
i-7(7g, 25.7mmol), pinacol diboron (7.4g, 29mmol), [1, 1' -bis (diphenylphosphino) ferrocene ] dichloropalladium (0.6g, 0.8mmol), potassium acetate (7.5g, 80mmol) were weighed into a 250mL two-necked flask, about 120mL of tetrahydrofuran was added, vacuum was applied and nitrogen was charged five times, the temperature was raised to 80 ℃, the reaction was stirred overnight, the reaction was stopped, the temperature was lowered to room temperature, quenched with water, the organic layer was separated, extracted with dichloromethane, the organic phases were combined and dried over sodium sulfate, concentrated under reduced pressure to remove the organic solvent. Column chromatography purification was performed to give 6.4g of a solid in 78% yield.
The synthetic procedure was analogous to C-6, column chromatography purification gave 2.1g of solid in 52% yield.
Synthesis of Compound C-8:
Figure BDA0002277142350000204
i-6(2g, 5.1mmol), I-9(3g, 12mmol), palladium acetate (56mg, 0.25mmol), potassium phosphate (3.2g, 15mmol) were weighed into a 250mL two-necked flask, about 90mL dioxane and 20mL water were added, vacuum was applied and nitrogen was applied five times, the temperature was raised to 60 ℃, the reaction was stirred overnight to stop the reaction, the temperature was lowered to room temperature, the organic solvent was removed by rotary evaporation, dichloromethane was extracted, the organic phases were combined and dried over sodium sulfate, and the organic solvent was removed by concentration under reduced pressure. Column chromatography purification was performed to give 2g of a solid with a yield of 65%.
Figure BDA0002277142350000211
I-10(2g, 5.1mmol), 2, 3-dichloropyrazine (0.83g, 5.6mmol), palladium acetate (56mg, 0.25mmol), cesium carbonate (3.9g, 12mmol), 4, 5-bis-diphenylphosphine-9, 9-dimethylxanthene (0.29g, 0.5mmol) were weighed into a 250mL two-neck flask, about 90mL dioxane was added, vacuum was applied and nitrogen was charged five times, the temperature was raised to 100 deg.C, the reaction was stirred overnight, the reaction was stopped, the temperature was lowered to room temperature, the organic solvent was removed by rotary evaporation, dichloromethane was extracted, the organic phases were combined and dried over sodium sulfate, and concentrated under reduced pressure to remove the organic solvent. Column chromatography purification was performed to obtain 1.3g of a solid with a yield of 50%.
Synthesis of Compound C-9:
Figure BDA0002277142350000212
the synthetic procedure was analogous to C-1, 40% yield, 1.6 g.
Energy structure of organic compounds
The energy level of the organic material can be obtained by quantum calculation, for example, by Gaussian09W (Gaussian Inc.) by using TD-DFT (including time density functional theory), and a specific simulation method can be found in WO 2011141110. Firstly, a semi-empirical method of 'group State/DFT/Default Spin/B3LYP/6-31G (d)' (Charge 0/Spin Singlet) is used for optimizing the molecular geometrical structure, and then the energy structure of the organic molecules is calculated by a TD-DFT (including time density functional theory) method to obtain 'TD-SCF/DFT/Default Spin/B3PW 91' and a base group of '6-31G (d)' (Charge 0/Spin Singlet).
The compound is evaporated on the monocrystalline silicon by a vacuum evaporation mode to form a 50nm thin film, the monocrystalline silicon is placed on a sample stage of an ellipsometer (ES-01), the incident angle is 70 degrees, the test is in an atmospheric environment, and the test result of the extinction coefficient (k) and the refractive index (n) of the compound is obtained by the ellipsometer.
Wherein CBP is 4,4' -bis (9-carbazole) biphenyl.
The results are shown in table 1:
TABLE 1
Figure BDA0002277142350000213
As can be seen from Table 1, the compounds C-1 to C-9 all have larger refractive indexes (larger than 1.7), and the higher refractive index can ensure better light extraction effect; the singlet energy of the above compounds is high, so that absorption can be concentrated in the ultraviolet region; FIG. 2 is an ultraviolet-visible absorption spectrum of a compound C-3 at a concentration of 10mg/L in a dichloromethane solution, and FIG. 3 is an ultraviolet-visible absorption spectrum of a compound C-6 at a concentration of 10mg/L in a dichloromethane solution, and it can be seen that the compound has high absorption in an ultraviolet band and weak absorption in a visible band, and can resist damage of external high-energy light to the inside of a device.
Preparation and characterization of OLED device
The following describes in detail the preparation process of the OLED device using the above embodiments, and the structure of the OLED device is as follows: ITO/Ag/ITO (anode)/HATCN/SFNFB/m-CP Ir (p-ppy)3/NaTzF2Ag/light extraction layer/LiF/Mg, the preparation steps are as follows:
and cleaning the ITO conductive glass anode layer, ultrasonically cleaning the ITO conductive glass anode layer for 15 minutes by using deionized water, acetone and isopropanol, and then treating the ITO conductive glass anode layer in a plasma cleaner for 5 minutes to improve the work function of the electrode. Evaporating a hole injection layer material HATCN on the ITO anode layer by a vacuum evaporation mode, wherein the thickness is 5nm, and the evaporation rate is high
Figure BDA0002277142350000222
On the hole injection layer, a hole transport material SFNFB was deposited by vacuum evaporation to a thickness of 80 nm. Depositing a light emitting layer on the hole transport layer, m-CP as a host material, Ir (p-ppy)3As doping material, Ir (p-ppy)3And m-CP in a mass ratio of 1:9 and a thickness of 30 nm. Depositing electron transport material NaTzF on the luminescent layer by vacuum evaporation2And the thickness is 30 nm. On the electron transport layer, an electron injection layer LiF with a thickness of 1nm was vacuum-evaporated, which was an electron injection layer 7. And (3) vacuum evaporating a cathode Mg-Ag layer on the electron injection layer, wherein the doping ratio of Mg to Ag is 9:1, and the thickness is 15 nm. A light extraction layer compound C-1 was deposited on the cathode layer by vacuum deposition to a thickness of 60 nm.
Device example 2: the compound of the light extraction layer of the organic electroluminescent device was changed to C-3.
Device example 3: the compound of the light extraction layer of the organic electroluminescent device was changed to C-5.
Device example 4: the compound of the light extraction layer of the organic electroluminescent device was changed to C-6.
Device example 5: the compound of the light extraction layer of the organic electroluminescent device was changed to C-8.
Device comparative example 1: the light extraction layer compound of the organic electroluminescent device becomes CBP.
The structures of the compounds involved in the devices are as follows:
Figure BDA0002277142350000221
TABLE 2
Device embodiments Light extraction layer compound Luminous efficiency (cd/A)
1 C-1 102
2 C-3 107
3 C-5 110
4 C-6 115
5 C-8 114
6 CBP 87
In Table 2, the luminous efficiency is a current density of 10mA/cm2The data obtained. It can be seen from table 2 that the compounds of the present invention can effectively improve the light emitting efficiency of the organic electroluminescent device as a light extraction layer in comparison with the comparative ratio.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.

Claims (14)

1. A heterocyclic arylamine compound having a structure represented by the general formula (1):
Figure FDA0002277142340000011
wherein:
when Ar is1When selected from the general formula (A-1), n is selected from 1 or 2, Ar3Selected from the structure
Figure FDA0002277142340000012
Or
Figure FDA0002277142340000013
When Ar is1When selected from the general formulae (A-2) to (A-8), n is selected from an integer of 0 to 2, Ar3Selected from substituted or unsubstitutedAn aromatic group or a heteroaromatic group having 5 to 60 ring atoms; or a non-aromatic ring system having 3 to 25 ring atoms which may be substituted or unsubstituted;
(A-1) to (A-8) are selected from the following groups:
Figure FDA0002277142340000014
X1、X2multiple occurrences of the same or different compound are independently selected from O, S, SO2、NR3、CR3R4、SiR3R4、C(＝O)；
Y、Y1～Y11Are the same or different when occurring multiple times and are respectively and independently selected from N or CR5And Y is1～Y3At least two of which are N, Y4～Y7At least one of which is N;
L1selected from a single bond, an alkenyl group, an alkynyl group, an acyl group, an amide group, a carbonyl group, a sulfone group, a substituted or unsubstituted alkyl group having 1 to 60 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 60 carbon atoms, a substituted or unsubstituted aromatic group or heteroaromatic group having 5 to 60 ring atoms;
Ar2、Ar4～Ar7each independently selected from substituted or unsubstituted aromatic or heteroaromatic groups having 5 to 60 ring atoms; or a non-aromatic ring system having 3 to 25 ring atoms which may be substituted or unsubstituted, or an arylamine group;
R1～R5are identical or different on multiple occurrence and are each independently selected from hydrogen, or D, or a straight-chain alkyl group having 1 to 20C atoms, an alkoxy group having 1 to 20C atoms, or a thioalkoxy group having 1 to 20C atoms, or a branched-chain alkyl group having 3 to 20C atoms, or a cycloalkyl group having 3 to 20C atoms, or an alkoxy group having 3 to 20C atoms, or a thioalkoxy group having 3 to 20C atoms, or a silyl group, or a keto group having 1 to 20C atoms, or an alkoxycarbonyl group having 2 to 20C atoms, or an aryloxycarbonyl group having 7 to 20C atoms, a cyano group, a carbamoyl group, a haloformyl groupFormyl, isocyano, isocyanate, thiocyanate or isothiocyanate, hydroxy, nitro, CF3Cl, Br, F, a crosslinkable group, or a substituted or unsubstituted aromatic or heteroaromatic group having 5 to 60 ring atoms, or an aryloxy group having 5 to 60 ring atoms or a heteroaryloxy group having 5 to 60 ring atoms, or a combination thereof; wherein two or more adjacent radicals may optionally form a mono-or polycyclic, aliphatic, aromatic or heteroaromatic ring system with one another;
dotted line represents Ar1And L1An attached key.
2. A heterocyclic arylamine compound according to claim 1, wherein (a-2) to (a-8) are selected from the group consisting of:
Figure FDA0002277142340000021
wherein: the H atoms in the structure may be further substituted.
3. A heterocyclic aromatic amine compound according to claim 1, wherein the heterocyclic aromatic amine compound is selected from any one of the structures of the general formulae (2-1) to (2-4):
Figure FDA0002277142340000022
wherein: n1 is selected from an integer of 1-2; n2 is selected from an integer of 0 to 2.
4. A heterocyclic arylamine compound according to claim 1, characterized in that Ar is Ar2、Ar4、Ar5Each independently selected from one or a combination of the following groups:
Figure FDA0002277142340000023
wherein: each time W appears, it is selected independentlyFrom N or CR7；
X3Multiple occurrences of the same or different compound are independently selected from O, S, SO2、NR7、CR6R7、SiR6R7、C(＝O)；
R6、R7Are identical or different on multiple occurrence and are each independently selected from hydrogen, or D, or a straight-chain alkyl group having 1 to 20C atoms, an alkoxy group having 1 to 20C atoms, or a thioalkoxy group having 1 to 20C atoms, or a branched-chain alkyl group having 3 to 20C atoms, or a cycloalkyl group having 3 to 20C atoms, or an alkoxy group having 3 to 20C atoms, or a thioalkoxy group having 3 to 20C atoms, or a silyl group, or a keto group having 1 to 20C atoms, or an alkoxycarbonyl group having 2 to 20C atoms, or an aryloxycarbonyl group having 7 to 20C atoms, a cyano group, a carbamoyl group, a haloformyl group, an isocyano group, an isocyanate, a thiocyanate or isothiocyanate, a hydroxyl group, a nitro group, a CF group, or an isocyanate3Cl, Br, F, a crosslinkable group, or a substituted or unsubstituted aromatic or heteroaromatic group having 5 to 60 ring atoms, or an aryloxy group having 5 to 60 ring atoms or a heteroaryloxy group having 5 to 60 ring atoms, or a combination thereof; wherein two or more adjacent radicals may optionally form a mono-or polycyclic, aliphatic, aromatic or heteroaromatic ring system with one another.
5. A heterocyclic arylamine compound according to claim 4, characterized in that Ar2、Ar4、Ar5Each independently selected from one or a combination of the following groups:
Figure FDA0002277142340000031
wherein:
L2selected from single bond, alkenyl, alkynyl, acyl, amido, carbonyl, sulfuryl, substituted or unsubstituted alkyl with 1 to 60 carbon atoms, substituted or unsubstituted alkoxy with 1 to 60 carbon atoms, substituted or unsubstitutedAn unsubstituted aromatic or heteroaromatic group having 5 to 60 ring atoms;
the H atoms in the structure may be further substituted.
6. A heterocyclic aromatic amine compound according to claim 4, characterized in that the heterocyclic aromatic amine compound is selected from any one of the structures as defined in general formulae (3-1) to (3-9):
Figure FDA0002277142340000032
Figure FDA0002277142340000041
wherein:
n1 is selected from an integer of 1-2; n2 is selected from an integer of 0 to 2.
7. A heterocyclic arylamine compound according to claim 6, characterized in that Ar is4And Ar5Each independently selected from substituted or unsubstituted benzene, biphenyl, naphthalene, 4-pyridylphenyl, carbazole, fluorene, dibenzofuran, dibenzothiophene groups or any one of the groups of general formulae (A-2) to (A-8).
8. A heterocyclic arylamine compound according to claim 6 wherein L is1And L2Each independently selected from a single bond or a combination of one or more of the following groups:
Figure FDA0002277142340000042
wherein:
each occurrence of W is independently selected from N or CR7；
X3Multiple occurrences of the same or different compound are independently selected from O, S, SO2、NR7、CR6R7、SiR6R7、C(＝O)；
R6、R7Are identical or different on multiple occurrence and are each independently selected from hydrogen, or D, or a straight-chain alkyl group having 1 to 20C atoms, an alkoxy group having 1 to 20C atoms, or a thioalkoxy group having 1 to 20C atoms, or a branched-chain alkyl group having 3 to 20C atoms, or a cycloalkyl group having 3 to 20C atoms, or an alkoxy group having 3 to 20C atoms, or a thioalkoxy group having 3 to 20C atoms, or a silyl group, or a keto group having 1 to 20C atoms, or an alkoxycarbonyl group having 2 to 20C atoms, or an aryloxycarbonyl group having 7 to 20C atoms, a cyano group, a carbamoyl group, a haloformyl group, an isocyano group, an isocyanate, a thiocyanate or isothiocyanate, a hydroxyl group, a nitro group, a CF group, or an isocyanate3Cl, Br, F, a crosslinkable group, or a substituted or unsubstituted aromatic or heteroaromatic group having 5 to 60 ring atoms, or an aryloxy group having 5 to 60 ring atoms or a heteroaryloxy group having 5 to 60 ring atoms, or a combination thereof; wherein two or more adjacent radicals may optionally form a mono-or polycyclic, aliphatic, aromatic or heteroaromatic ring system with one another.
9. A heterocyclic aromatic amine compound according to claim 1, wherein the heterocyclic aromatic amine compound is selected from any one of the structures of the general formulae (4-1) to (4-3):
Figure FDA0002277142340000043
wherein: ar in formulas (4-1) - (4-2)1Selected from the general formulae (A-1) to (A-8); ar in formula (4-3)1Selected from the general formulae (A-2) to (A-8).
10. A heterocyclic aromatic amine compound according to any of claims 1 to 10 wherein the refractive index of the heterocyclic aromatic amine compound at a wavelength of 630nm is greater than 1.7; and/or
The singlet energy of the heterocyclic arylamine compound is greater than or equal to 2.7 eV; and/or
The extinction coefficient of the heterocyclic arylamine compound at the wavelength of 430nm is less than 0.1.
11. A composition comprising a heterocyclic arylamine compound according to any one of claims 1 to 10 and an organic solvent.
12. A light extraction layer material comprising the heterocyclic aromatic amine compound according to any one of claims 1 to 10.
13. An organic electronic device comprising the heterocyclic arylamine compound according to any one of claims 1 to 10.
14. The organic electronic device according to claim 13, comprising two electrodes, one or more organic functional layers disposed between the two electrodes, and a light extraction layer disposed on a surface of one of the electrodes remote from the organic functional layer, wherein the light extraction layer comprises the arylamine compound according to any one of claims 1 to 10.
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