CN111848590B - Compound, high polymer, mixture, composition and organic electronic device - Google Patents

Compound, high polymer, mixture, composition and organic electronic device Download PDF

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CN111848590B
CN111848590B CN202010711708.3A CN202010711708A CN111848590B CN 111848590 B CN111848590 B CN 111848590B CN 202010711708 A CN202010711708 A CN 202010711708A CN 111848590 B CN111848590 B CN 111848590B
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CN111848590A (en
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何锐锋
黄宏
吴灿洁
宋晶尧
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Guangzhou Chinaray Optoelectronic Materials Ltd
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Guangzhou Chinaray Optoelectronic Materials Ltd
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Abstract

The invention discloses compounds, polymers, mixtures, compositions and organic electronic devices. The compound is represented by the general formula (1), and can be facilitated by connecting triphenylene condensed ring and nitrogen-containing heterocyclic unit to aromatic ring substituted by ortho-groupThe molecular dispersion of the compound reduces the quenching of excitons, thereby being beneficial to improving the device performance and stability of the compound and providing an effective scheme for improving the performance and the service life of organic electronic devices, particularly OLEDs.

Description

Compound, high polymer, mixture, composition and organic electronic device
The present application claims priority from the chinese patent application filed on 24/07/2019 under the name "a class of compounds, mixtures, compositions and uses thereof" by the chinese patent office under application number 201910670969.2, the entire contents of which are incorporated herein by reference.
Technical Field
The invention relates to the technical field of organic and photoelectric performance materials, in particular to a compound, a high polymer, a mixture, a composition and an organic electronic device.
Background
The organic semiconductor material has the characteristics of structural diversity, relatively low manufacturing cost, excellent photoelectric performance and the like, and has great potential in the application of photoelectric devices (such as flat panel displays and illumination) such as Organic Light Emitting Diodes (OLEDs).
In order to improve the light emitting performance of the organic light emitting diode and to advance the large-scale industrialization process of the organic light emitting diode, various organic photoelectric performance material systems have been widely developed. However, the performance, especially the lifetime, of OLEDs is still to be further improved.
Two of the important factors affecting OLED device performance are material stability and exciton kinetics. The stability of the material comprises thermal stability, chemical stability, electrical stability, air stability and the like, the stability of the OLED device depends on the stability of the material, and a larger rigid skeleton group is arranged in the structure of the material, so that the thermal stability of the material is improved; has moderate HOMO and LUMO energy levels, and is favorable for improving the chemical stability, the electrical stability and the air stability of the material. The close packing of molecules easily leads to quenching of excitons, and a steric hindrance structural unit is properly introduced into a molecular structure, so that the close packing among molecules can be effectively prevented, the function of exciton dispersion is achieved, the quenching probability of excitons is reduced, the performance, particularly the efficiency, of the OLED is improved, and the efficiency roll-off under high brightness is reduced.
In the prior art, the electron transport type (N-type) compound has a structure containing a large number of aromatic condensed rings and a generally deep HOMO level by combining various factors affecting stability, and as described in patents US2018277767, WO2016051977, and the like, good device performance can be obtained by constructing a compound by combining an aromatic condensed ring and an electron-deficient group. However, such materials are prone to exciton quenching, which affects device stability and lifetime improvement. Therefore, new material systems are still in need of further development.
Disclosure of Invention
In view of the above-mentioned shortcomings of the prior art, the present invention aims to provide a compound with a novel structure, which aims to solve the problems of low performance, low device stability and low lifetime of the existing organic electronic element.
The technical scheme of the invention is as follows:
a compound represented by the general formula (1):
Figure RE-GDA0002654810390000011
wherein each occurrence of V is independently selected from: n atom or CR 1 ；
L 1 、L 2 At each occurrence, is independently selected from: a substituted or unsubstituted aromatic or heteroaromatic group having 5 to 60 ring atoms;
Ar 1 selected from: a substituted or unsubstituted aromatic ring having 5 to 30 ring atomsA group or a heteroaromatic group, and Ar 1 And A is at L 2 The upper ortho position is connected;
a is selected from electron deficient groups;
R 1 at each occurrence, is independently selected from: hydrogen, deuterium, fluorine, cyano, alkenyl, alkynyl, nitrile group, amino group, nitro group, acyl group, alkoxy group, carbonyl group, sulfone group, substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, and substituted or unsubstituted aromatic group or heteroaromatic group having 5 to 60 ring atoms; two or more adjacent R 1 Optionally forming with each other an aliphatic, aromatic or heteroaromatic ring system;
n is any integer of 0 to 6.
A high polymer comprising at least one repeating unit comprising a structural unit represented by the general formula (1).
A mixture comprises an organic functional material H1, wherein H1 is selected from a compound or a high polymer as described above, and at least another organic functional material H2, and H2 is selected from a hole injection material, a hole transport material, an electron injection material, an electron blocking material, a hole blocking material, a light emitter, a host material or an organic dye.
A composition comprising a compound or polymer or mixture as described above and at least one organic solvent.
An organic electronic device comprising at least one compound or polymer or mixture as described above. Wherein the organic electronic device is an electroluminescent device comprising a light-emitting layer comprising a compound or polymer or mixture as described above.
Has the advantages that:
the compound of the invention is used in OLED, especially as a luminescent layer material, and can improve the luminous efficiency and the service life of a device. The reason is as follows, but not limited to, the compound of the invention can effectively prevent the close packing between molecules, improve the dispersion of molecules and excitons, reduce the quenching of excitons by properly introducing steric hindrance groups on the basis of the molecular structure of the combination of the triphenylene condensed rings and the electron-deficient groups, further improve the exciton stability on the basis of the material stability, simultaneously improve the performance, especially the efficiency, of the OLED, reduce the efficiency roll-off under high brightness, and comprehensively improve the stability and the service life of the device.
Detailed Description
The invention provides a compound, a high polymer, a mixture, a composition and an organic electronic 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, "substituted or unsubstituted" means that the defined group may or may not be substituted. When a defined group is substituted, it is understood that it is optionally substituted with art-acceptable groups including, but not limited to: c 1-30 An alkyl group, a cycloalkyl group having 3 to 20 ring atoms, a heterocyclic group having 3 to 20 ring atoms, an aryl group having 5 to 20 ring atoms, a heteroaryl group having 5 to 20 ring atoms, a silane group, a carbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, a haloformyl group, a formyl group, -NRR', a cyano group, an isocyano group, an isocyanate group, a thiocyanate group, an isothiocyanate group, a hydroxyl group, a trifluoromethyl group, a nitro group or a halogen, and the above groups may be further substituted by a substituent acceptable in the art; it is understood that R and R 'in-NRR' are each independently substituted with art-acceptable groups including, but not limited to, H, C 1-6 An alkyl group, a cycloalkyl group having 3 to 8 ring atoms, a heterocyclic group having 3 to 8 ring atoms, an aryl group having 5 to 20 ring atoms or a heteroaryl group having 5 to 10 ring atoms; said C1-6 alkyl, cycloalkyl containing 3-8 ring atoms, heterocyclyl containing 3-8 ring atoms, aryl containing 5-20 ring atoms, or heteroaryl containing 5-10 ring atoms is optionally further substituted with one or moreThe following groups are substituted: c 1-6 Alkyl, cycloalkyl having 3 to 8 ring atoms, heterocyclyl having 3 to 8 ring atoms, halogen, hydroxy, nitro or amino.
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 adjacent carbon atoms. These definitions apply correspondingly to "adjacent substituents".
In the embodiment of the invention, the energy level structure of the organic material, the triplet state energy level E T1 The highest occupied orbital level HOMO and the lowest unoccupied orbital level LUMO play a key role. The determination of these energy levels is described below.
The HOMO and LUMO energy levels can be measured by the photoelectric effect, for example XPS (X-ray photoelectron spectroscopy) and UPS (ultraviolet photoelectron spectroscopy) or by cyclic voltammetry (hereinafter referred to as CV). Recently, quantum chemical methods, such as the density functional theory (hereinafter abbreviated as DFT), have become effective methods for calculating the molecular orbital level.
Triplet energy level E of organic material T1 Can be measured by low temperature Time resolved luminescence spectroscopy, or can be obtained by quantum simulation calculations (e.g., by Time-dependent DFT), such as by commercial software Gaussian09W (Gaussian Inc.), specific simulation methods can be found in WO2011141110 or as described in the examples below.
Note that HOMO, LUMO, E T1 Depending on the measurement or calculation method used, even for the same method, different methods of evaluation, e.g. starting point and peak point on the CV curve, may give different HOMO/LUMO value. Thus, a reasonably meaningful comparison should be made with the same measurement method and the same evaluation method. In the description of the embodiments of the present invention, HOMO, LUMO, E T1 Is based on the simulation of the Time-dependent DFT but does not affect the application of other measurement or calculation methods.
The invention relates to a compound, which is shown as a general formula (1):
Figure RE-GDA0002654810390000021
wherein each occurrence of V is independently selected from: n atom or CR 1 (ii) a In one embodiment, each occurrence of V is independently selected from CR 1 ；
L 1 、L 2 At each occurrence, is independently selected from: a substituted or unsubstituted aromatic or heteroaromatic group having 5 to 60 ring atoms;
Ar 1 selected from: a substituted or unsubstituted aromatic or heteroaromatic group having 5 to 30 ring atoms, and Ar 1 And A is at L 2 The upper ortho position is connected;
a is selected from electron deficient groups;
R 1 at each occurrence, is independently selected from: hydrogen, deuterium, fluorine, cyano, alkenyl, alkynyl, nitrile group, amino, nitro, acyl, alkoxy, carbonyl, sulfone group, substituted or unsubstituted alkyl group having 1-30 carbon atoms, substituted or unsubstituted cycloalkyl group having 3-30 carbon atoms, and substituted or unsubstituted aromatic group or heteroaromatic group having 5-60 ring atoms; two or more adjacent R 1 Optionally forming with each other an aliphatic, aromatic or heteroaromatic ring system;
n is selected from any integer of 0-6.
In a preferred embodiment, the compound is selected from one of the general formulae (2-1) or (2-2):
Figure RE-GDA0002654810390000031
wherein, V, A, L 1 、L 2 、Ar 1 N has the same meaning as described above.
In a preferred embodiment, the electron deficient group a of the compound is selected from one or a combination of the following structures:
Figure RE-GDA0002654810390000032
wherein, each occurrence of X is independently selected from: n atom or CR 4 And at least one X is an N atom;
Y 1 at each occurrence, is independently selected from CR 2 R 3 O, S or NR 2 ；
Ar 2 、Ar 3 Each independently selected from: a substituted or unsubstituted aromatic or heteroaromatic group having 5 to 60 ring atoms, Ar 2 、Ar 3 With or without formation of aliphatic, aromatic or heteroaromatic ring systems with adjacent radicals;
R 2 ～R 4 each occurrence is independently selected from hydrogen, deuterium, fluorine, cyano, alkenyl, alkynyl, nitrile group, amido, nitro, acyl, alkoxy, carbonyl, sulfuryl, substituted or unsubstituted alkyl with 1-30 carbon atoms, substituted or unsubstituted cycloalkyl with 3-30 carbon atoms, and substituted or unsubstituted aromatic group or heteroaromatic group with 5-60 ring atoms; two or more adjacent R 4 Optionally forming with each other an aliphatic, aromatic or heteroaromatic ring system;
n1 is selected from any integer of 0-4;
are attachment sites.
In a more preferred embodiment, the electron deficient group a of the compound is selected from one of the following structures:
Figure RE-GDA0002654810390000033
n1 is selected from any one of 0-4An integer number; x, Y 1 、Ar 2 、Ar 3 、R 2 ～R 4 The meaning is the same as above.
In one embodiment, the electron deficient group A is selected from
Figure RE-GDA0002654810390000034
Further, the electron-deficient group A is selected from
Figure RE-GDA0002654810390000035
Figure RE-GDA0002654810390000036
In one embodiment, the electron deficient group A is selected from
Figure RE-GDA0002654810390000041
Further, the electron-deficient group A is selected from
Figure RE-GDA0002654810390000042
In one embodiment, the electron deficient group A of the compound is selected from
Figure RE-GDA0002654810390000043
Further, the electron deficient group a is selected from:
Figure RE-GDA0002654810390000044
in one embodiment, L in the formula 1 At each occurrence, independently selected from one or a combination of the following structures:
Figure RE-GDA0002654810390000045
wherein R is 5 ～R 6 Is a substituent independently selected for each occurrence from: deuterium, fluorine, cyano, alkenyl, alkynyl, nitrile group, amino group, nitro group, acyl group, alkoxy group, carbonyl group, sulfone group, substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, and the likeA substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted aromatic group or heteroaromatic group having 5 to 60 ring atoms;
n1 is selected from any integer of 0-4; n2 is selected from any integer of 0-3; are attachment sites.
In one embodiment, L 1 Is composed of
Figure RE-GDA0002654810390000046
In certain preferred embodiments, L in the formula 2 At each occurrence, independently selected from one or a combination of the following structures:
Figure RE-GDA0002654810390000047
wherein, Y 2 At each occurrence, each is independently selected from: CR 7 R 8 O, S or NR 7 ；
R 7 ～R 8 At each occurrence, is independently selected from: hydrogen, deuterium, fluorine, cyano, alkenyl, alkynyl, nitrile group, amino group, nitro group, acyl group, alkoxy group, carbonyl group, sulfone group, substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, substituted or unsubstituted aromatic group or heteroaromatic group having 5 to 60 ring atoms, R 7 ～R 8 Directly form a ring system with each other or not;
n1 is selected from any integer of 0-4; n2 is selected from any integer of 0-3; n3 is selected from any integer of 0-5; n4 is selected from any integer of 0-2;
are attachment sites.
In some preferred embodiments, the compound according to the present invention may be selected from one of the general formulae (3-1) or (3-6), wherein the H atom on the ring may be substituted:
Figure RE-GDA0002654810390000051
wherein:V、L 1 、Ar 1 、A、n、Y 2 the meaning is the same as above.
In one embodiment, the compounds according to the present invention may be selected from the following general formula:
Figure RE-GDA0002654810390000052
in certain embodiments, Ar as described in general formula (VII a) 1 One or a combination of the following structures:
Figure RE-GDA0002654810390000053
wherein, Y 3 At each occurrence, is independently selected from CR 9 R 10 O, S or NR 9 ；
R 9 ～R 11 Is a substituent independently selected for each occurrence from: deuterium, fluorine, cyano, alkenyl, alkynyl, nitrile group, amino group, nitro group, acyl group, alkoxy group, carbonyl group, sulfone group, substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, substituted or unsubstituted aromatic group or heteroaromatic group having 5 to 60 ring atoms, R 9 ～R 11 With or without formation of aliphatic, aromatic or heteroaromatic ring systems with adjacent radicals; n1 is selected from any integer of 0-4; n2 is selected from any integer of 0-3; n3 is selected from any integer of 0-5; n4 is selected from any integer of 0-2;
are attachment sites.
More preferably, Ar 1 One or a combination of the following structures:
Figure RE-GDA0002654810390000054
wherein: y is 3 The meaning is the same as above; denotes the attachment site.
In some more preferred embodiments, the compound according to the present invention may be selected from one of the following formulae, wherein the H atom on the ring may be substituted:
Figure RE-GDA0002654810390000055
Figure RE-GDA0002654810390000061
wherein: l is 1 、n、Y 2 、Y 3 And A is as defined above.
In certain embodiments, n referred to in the formula is selected from 0; in other preferred embodiments, n is selected from 1.
In some embodiments, R 1 ～R 8 Preferably H, D, alkyl groups, benzene, naphthalene, fluorene or carbazole.
In some embodiments, the compound, group V, L 1 、L 2 And Ar 1 At least contains one or more deuterium atoms; preferably, the group V contains at least one deuterium atom or group Ar 1 Contains at least one deuterium atom; more preferably, the group V and the group Ar 1 Each containing at least one deuterium atom; most preferably, the group V or the group Ar 1 All H atoms in (a) are deuterated.
In the present invention, "aromatic group" means a hydrocarbon group containing at least one aromatic ring, and includes monocyclic groups and polycyclic ring systems. "heteroaromatic group" refers to a hydrocarbon group (containing heteroatoms) containing at least one aromatic heterocyclic ring, including monocyclic groups and polycyclic ring systems. These polycyclic rings may have two or more rings in which two carbon atoms are shared by two adjacent rings, i.e., fused rings. At least one of these rings of the polycyclic ring system is aromatic or heteroaromatic. For the purposes of the present invention, aromatic or heteroaromatic ring systems include not only aromatic or heteroaromatic systems, but also systems in which a plurality of aromatic or heteroaromatic groups may also be interrupted by short nonaromatic units, for example by C, N, O, Si, S or P atoms. Thus, for example, systems such as 9, 9' -spirobifluorene, 9, 9-diarylfluorene, triarylamines, diaryl ethers, etc., are likewise considered aromatic ring systems for the purposes of the present invention.
Specifically, examples of the aromatic group are: benzene, naphthalene, anthracene, phenanthrene, perylene, tetracene, pyrene, benzopyrene, triphenylene, acenaphthene, fluorene, and derivatives thereof.
Specifically, examples of heteroaromatic groups are: furan, benzofuran, thiophene, benzothiophene, pyrrole, pyrazole, triazole, imidazole, oxazole, oxadiazole, thiazole, tetrazole, indole, carbazole, pyrroloimidazole, pyrrolopyrrole, thienopyrrole, thienothiophene, furopyrrole, furofuran, thienofuran, benzisoxazole, benzisothiazole, benzimidazole, pyridine, pyrazine, pyridazine, pyrimidine, triazine, quinoline, isoquinoline, phthalazine, quinoxaline, phenanthridine, primadine, quinazoline, quinazolinone, and derivatives thereof.
Specifically, the compound is selected from the following structures but is not limited to:
Figure RE-GDA0002654810390000062
Figure RE-GDA0002654810390000071
Figure RE-GDA0002654810390000081
Figure RE-GDA0002654810390000091
Figure RE-GDA0002654810390000101
in certain preferred embodiments, the compound of formula (1), T thereof 1 Not less than 2.2eV, preferablyIs T 1 More preferably not less than 2.4eV, still more preferably T 1 More than or equal to 2.5eV, preferably T 1 ≥2.6eV。
In certain preferred embodiments, the compounds of the present invention have a glass transition temperature T g In a preferred embodiment, T is not less than 100 DEG C g 120 ℃ or more, in a more preferred embodiment, T g 140 ℃ or more, in a more preferred embodiment, T g 160 ℃ or more, and in a most preferred embodiment, T g ≥180℃。
The compounds according to the invention can be used as functional materials in organic electronic devices. The organic functional material may be classified into a Hole Injection Material (HIM), a Hole Transport Material (HTM), an Electron Transport Material (ETM), an Electron Injection Material (EIM), an Electron Blocking Material (EBM), a Hole Blocking Material (HBM), an Emitter (Emitter), and a Host material (Host). In a preferred embodiment, the compounds according to the invention can be used as host materials or electron transport materials.
The present invention also relates to a polymer comprising at least one repeating unit comprising a structural unit represented by the general formula (1).
In a preferred embodiment, the polymer is synthesized by a method selected from the group consisting of SUZUKI-, YAMAMOTO-, STILLE-, NIGESHI-, KUMADA-, HECK-, SONOGASHIRA-, HIYAMA-, FUKUYAMA-, HARTWIG-BUCHWALD-, and ULLMAN.
In a preferred embodiment, the polymers according to the invention have a glass transition temperature (Tg) of 100 ℃ or more, preferably 120 ℃ or more, more preferably 140 ℃ or more, more preferably 160 ℃ or more, most preferably 180 ℃ or more.
In a preferred embodiment, the polymer according to the invention preferably has a molecular weight distribution (PDI) in the range of 1 to 5; more preferably 1 to 4; more preferably 1 to 3, more preferably 1 to 2, and most preferably 1 to 1.5.
In a preferred embodiment, the polymers according to the invention preferably have a weight-average molecular weight (Mw) ranging from 1 to 100 ten thousand; more preferably 5 to 50 ten thousand; more preferably from 10 to 40 ten thousand, even more preferably from 15 to 30 ten thousand, and most preferably from 20 to 25 ten thousand.
The invention also relates to a mixture, which comprises an organic functional material H1, H1 is selected from the compounds or high polymers, and at least another organic functional material H2, wherein H2 is selected from a hole injection material, a hole transport material, an electron injection material, an electron blocking material, a hole blocking material, a light emitter, a host material or an organic dye. Various organic functional materials are described in detail, for example, in WO2010135519a1, US20090134784a1 and WO2011110277a1, the entire contents of this 3 patent document being hereby incorporated by reference. The organic functional material can be small molecule and high polymer material.
In a preferred embodiment, the organic mixture wherein the molar ratio of H1 to H2 is from 2: 8 to 8: 2; preferred molar ratios are 3:7 to 7: 3; more preferred molar ratios are 4:6 to 6: 4; the most preferred molar ratio is 4.5:5.5 to 5.5: 4.5.
In a preferred embodiment, the organic mixture wherein the difference between the molecular weights of H1 and H2 is no more than 100Dalton, preferably no more than 50Dalton, and most preferably no more than 30 Dalton.
In another preferred embodiment, the organic mixture wherein the difference between the sublimation temperatures of H1 and H2 is no more than 50K; more preferably the difference in sublimation temperatures does not exceed 30K; more preferably, the difference in sublimation temperature does not exceed 20K; most preferably the difference in sublimation temperatures does not exceed 10K.
In a more preferred embodiment, the mixture comprises at least one compound or polymer according to the invention and a luminescent material selected from singlet emitters, triplet emitters or TADF emitters.
In certain embodiments, the mixture comprises at least one compound or polymer according to the invention and a singlet emitter. The mixtures according to the invention can be used as fluorescent host materials in which the singlet emitters are present in a proportion by weight of less than or equal to 10%, preferably less than or equal to 9%, more preferably less than or equal to 8%, particularly preferably less than or equal to 7%, most preferably less than or equal to 5%.
In a particularly preferred embodiment, the mixture comprises at least one compound or polymer according to the invention and a triplet emitter. The mixtures according to the invention can be used as phosphorescent host materials in which the triplet emitters are present in amounts of < 25% by weight, preferably < 20% by weight and more preferably < 15% by weight.
In certain embodiments, the mixture comprises a compound or polymer according to the present invention, and another TADF material.
In a further preferred embodiment, the mixture comprises at least one compound or polymer according to the invention, a triplet emitter and a host material. In such embodiments, the compounds according to the invention can be used as auxiliary luminescent materials in a weight ratio to the triplet emitter of from 1:2 to 2: 1.
In a very preferred embodiment, the mixture comprises one compound according to the invention and another host material. The compounds according to the invention can be used here as second bodies, the percentage by weight of which can be between 30% and 70%.
In certain preferred embodiments, the mixture, the further organic functional material H2 comprises a hole transport unit of formula (4):
Figure RE-GDA0002654810390000111
wherein Ar is 4 Is an aromatic group or a heteroaromatic group with 6-180 ring atoms; d is a hole transport unit; m is an integer from 1 to 6.
It will be appreciated that when more than 2D's are present, each D's may be linked to each other by a single bond and then to Ar 4 Or directly attached to Ar 4 Or both of the above two connection modes.
In a preferred embodiment, the hole transport unit D comprises any one of the following groups:
Figure RE-GDA0002654810390000112
wherein M represents an aromatic group or a heteroaromatic group having 6 to 40 ring atoms;
Z 1 ～Z 2 each occurrence is independently selected from: single bond, N (R) 12 )、C(R 12 R 13 )、Si(R 12 R 13 )、O、S、C＝N(R 12 )、C＝C(R 12 R 13 ) Or P (R) 12 )；
R 12 ～R 13 Each occurrence is independently selected from: an alkyl group, an alkoxy group, a cycloalkyl group, a substituted or unsubstituted aromatic group or heteroaromatic group having 5 to 60 ring atoms;
are attachment sites.
In a preferred embodiment, the Ar is 4 Contains any one of the following groups, wherein the H atom on the ring may be further substituted:
Figure RE-GDA0002654810390000113
wherein: y is 3 The meaning is the same as above.
In one embodiment, the H2 is selected from one of the following formulas:
Figure RE-GDA0002654810390000114
wherein: l is 3 Selected from substituted or unsubstituted aromatic or heteroaromatic groups with 5-180 ring atoms; ar (Ar) 5 、Ar 6 Is selected from aromatic groups or heteroaromatic groups with 5-60 ring atoms.
The following are examples of the specific structure of compound H2, but are not limited thereto:
Figure RE-GDA0002654810390000121
Figure RE-GDA0002654810390000131
Figure RE-GDA0002654810390000141
Figure RE-GDA0002654810390000151
some more detailed descriptions of singlet emitters, triplet emitters, and TADF materials are provided below (but not limited thereto)
1. Singlet state luminophor (Singlet Emitter)
Singlet emitters tend to have longer conjugated pi-electron systems. To date, there have been many examples such as styrylamine and its derivatives disclosed in JP2913116B and WO2001021729a1, indenofluorene and its derivatives disclosed in WO2008/006449 and WO2007/140847, and triarylamine derivatives of pyrene disclosed in US7233019, KR 2006-0006760.
In a preferred embodiment, the singlet emitters may be selected from the group consisting of monostyrenes, distyrenes, tristyrenes, tetrastyrenes, styrylphosphines, styryl ethers, and arylamines.
A monostyrene amine is a compound comprising an unsubstituted or substituted styryl group and at least one amine, preferably an aromatic amine. A distyrene amine refers to a compound comprising two unsubstituted or substituted styryl groups and at least one amine, preferably an aromatic amine. A tristyrenylamine refers to a compound comprising three unsubstituted or substituted styrene groups and at least one amine, preferably an aromatic amine. A tetrastyrene amine refers to a compound comprising four unsubstituted or substituted styrene groups and at least one amine, preferably an aromatic amine. One preferred styrene is stilbene, which may be further substituted. The corresponding phosphines and ethers are defined analogously to the amines. Arylamine or aromatic amine refers to a compound comprising three unsubstituted or substituted aromatic rings or heterocyclic systems directly linked to nitrogen. At least one of these aromatic or heterocyclic ring systems is preferably a fused ring system and preferably has at least 14 aromatic ring atoms. Among them, preferred examples are aromatic anthracenamines, aromatic anthracenediamines, aromatic pyrenediamines, aromatic chrysenamines and aromatic chrysenediamines. An aromatic anthracylamine refers to a compound in which a diarylamine group is attached directly to the anthracene, preferably at the 9 position. An aromatic anthracenediamine refers to a compound in which two diarylamine groups are attached directly to the anthracene, preferably at the 9,10 positions. Aromatic pyrene amines, aromatic pyrenediamines, aromatic chrysenes and aromatic chrysenes are similarly defined, wherein preferably the diarylamine groups are attached to the 1 or 1,6 position of pyrene.
Examples, which are also preferred, of singlet emitters based on vinylamines and arylamines can be found in the following patent documents: WO2006/000388, WO2006/058737, WO2006/000389, WO2007/065549, WO2007/115610, US7250532B2, DE102005058557A1, CN1583691A, JP08053397A, US6251531B1, US2006/210830A, EP1957606A1 and US2008/0113101A1 the entire contents of the patent documents listed above are hereby incorporated by reference.
An example of singlet emitters based on stilbene and its derivatives is US 5121029.
Further preferred singlet emitters may be selected from indenofluorene-amines and indenofluorene-diamines, as disclosed in WO2006/122630, benzindenofluorene-amines and benzindenofluorene-diamines, as disclosed in WO2008/006449, dibenzoindenofluorene-amines and dibenzoindenofluorene-diamines, as disclosed in WO 2007/140847.
Further preferred singlet emitters may be selected from fluorene based fused ring systems as disclosed in US2015333277a1, US2016099411a1, US2016204355a 1.
More preferred singlet emitters may be selected from pyrene derivatives, such as the structures disclosed in US2013175509a 1; triarylamine derivatives of pyrene, such as pyrene triarylamine derivatives containing dibenzofuran units as disclosed in CN 102232068B; other triarylamine derivatives of pyrene having specific structures are disclosed in CN105085334A, CN 105037173A. Other materials which can be used as singlet emitters are polycyclic aromatic compounds, in particular derivatives of the following compounds: anthracenes, such as 9, 10-bis (2-naphthoanthracene), naphthalene, tetraphenyl, xanthene, phenanthrene, pyrene (such as 2,5,8, 11-tetra-t-butylperylene), indenopyrene, phenylenes, such as (4,4 '-bis (9-ethyl-3-carbazolylethenyl) -1, 1' -biphenyl), diindenopyrene, decacycloalkene, coronene, fluorene, spirobifluorene, arylpyrene (such as US20060222886), aryleneethylene (such as US5121029, US5130603), cyclopentadiene, such as tetraphenylcyclopentadiene, rubrene, coumarin, rhodamine, quinacridone, pyrans, such as 4 (dicyanomethylene) -6- (4-p-dimethylaminostyryl-2-methyl) -4H-pyran (DCM), thiopyran, bis (azinyl) imine boron compounds (US2007/0092753A1), Bis (azinyl) methylene compounds, carbostyryl compounds, oxazinones, benzoxazoles, benzothiazoles, benzimidazoles, and pyrrolopyrrolediones. Some singlet emitter materials can be found in the following patent documents: US20070252517A1, US4769292, US6020078, US2007/0252517A1, US2007/0252517A 1. The entire contents of the above listed patent documents are hereby incorporated by reference.
Some examples of suitable singlet emitters are listed below:
Figure RE-GDA0002654810390000161
2. thermally activated delayed fluorescence luminescent material (TADF):
the traditional organic fluorescent material can only emit light by utilizing 25% singlet excitons formed by electric excitation, and the internal quantum efficiency of the device is low (up to 25%). Although the phosphorescence material enhances the intersystem crossing due to the strong spin-orbit coupling of the heavy atom center, the singlet excitons and the triplet excitons formed by the electric excitation can be effectively used for emitting light, so that the internal quantum efficiency of the device reaches 100 percent. However, the application of the phosphorescent material in the OLED is limited by the problems of high price, poor material stability, serious efficiency roll-off of the device and the like. The thermally activated delayed fluorescence luminescent material is organic fluorescenceOptical materials and organic phosphorescent materials the third generation of organic light emitting materials developed after. Such materials typically have a small singlet-triplet energy level difference (Δ E) st ) The triplet excitons may be converted to singlet excitons by intersystem crossing to emit light. This can make full use of singlet excitons and triplet excitons formed upon electrical excitation. The quantum efficiency in the device can reach 100%. Meanwhile, the material has controllable structure, stable property, low price and no need of noble metal, and has wide application prospect in the field of OLED.
TADF materials need to have a small singlet-triplet level difference, preferably Δ Est <0.3eV, less preferably Δ Est <0.25eV, more preferably Δ Est <0.20eV, and most preferably Δ Est <0.1 eV. In a preferred embodiment, the TADF material has a relatively small Δ Est, and in another preferred embodiment, the TADF has a good fluorescence quantum efficiency. Some TADF luminescent materials can be found in the following patent documents: CN103483332(a), TW201309696(a), TW201309778(a), TW201343874(a), TW201350558(a), US20120217869(a1), WO2013133359(a1), WO2013154064(a1), Adachi, et al adv.adv.mater, 21,2009,4802, Adachi, et al.appl.lett, 98,2011,083302, Adachi, et al.appl.phys.lett, 101,2012,093306, Adachi, et al chem.commu. 48,2012,11392, Adachi, et al.nature photomonics, 6,2012,253, Adachi, et al.nature,492, Adachi, 234, Adachi, et al.j.chem.c, Adachi 52, Adachi, et al.3842, adachi.t.2012, et al.492, 492, 73, Adachi, et al.27, chem.t.t.t.t.t.t.t.t.t.t, t.t.t.t.t.t.t.t.7, et al, et al.t.t.t.t.t.t.t.t.t.t.t.t.t.t. 7, et al, et al.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.32, et al, et.
Some examples of suitable TADF phosphors are listed below:
Figure RE-GDA0002654810390000171
3. triplet Emitter (Triplet Emitter)
Triplet emitters are also known as phosphorescent emitters. In a preferred embodiment, the triplet emitter is a metal complex of the general formula M (L) n, where M is a metal atom, L, which may be the same or different at each occurrence, is an organic ligand which is bonded or coordinately bound to the metal atom M via one or more positions, and n is an integer from 1 to 6. Preferably, the triplet emitter comprises a chelating ligand, i.e. a ligand, which coordinates to the metal via at least two binding sites, particularly preferably the triplet emitter comprises two or three identical or different bidentate or polydentate ligands. Chelating ligands are advantageous for increasing the stability of the metal complex. In a preferred embodiment, the metal complexes which can be used as triplet emitters are of the form:
Figure RE-GDA0002654810390000172
the metal atom M is selected from the transition metals, lanthanides or actinides, preferably Ir, Pt, Pd, Au, Rh, Ru, Os, Re, Cu, Ag, Ni, Co, W or Eu, particularly preferably Ir, Au, Pt, W or Os.
Ar 1 、Ar 2 May be the same or different at each occurrence and is a cyclic group wherein Ar 1 Contains at least one donor atom, i.e. an atom having a lone pair of electrons, such as nitrogen, which is coordinately bound to the metal via its cyclic group; wherein Ar is 2 Contains at least one carbon atom through which the cyclic group is attached to the metal; ar (Ar) 1 And Ar 2 Linked together by a covalent bond, which may each carry one or more substituent groups, which may in turn be linked together by substituent groups; l', which may be the same or different at each occurrence, is a bidentate chelating ancillary ligand, preferably a monoanionic bidentate chelating ligand; q1 may be 0, 1,2 or 3, preferably 2 or 3; q2 may be 0, 1,2 or 3, preferably 1 or 0. Examples of organic ligands may be selected from phenylpyridine derivatives or 7, 8-benzoquinolinesAnd (3) derivatives. All of these organic ligands may be substituted, for example, with alkyl or fluorine or silicon. The ancillary ligand may preferably be selected from acetone acetate or picric acid.
Examples of the extreme use of some triplet emitter materials can be found in the following patent documents and literature: WO200070655, WO200141512, WO200202714, WO200215645, WO2005033244, WO2005019373, US20050258742, US20070087219, US20070252517, US2008027220, WO2009146770, US20090061681, WO2009118087, WO2010015307, WO2010054731, WO2011157339, WO2012007087, WO201200708, WO2013107487, WO 2019430620, WO2013174471, WO 2014031977, WO 2014112450, WO2014007565, WO 2014024131, Baldo et al nature (2000),750, Adachi et al.appl.phys.leys et al (2001),1622, Kido et al.appl. phys lett et al (1994),2124, wright et al.j.am.em.1998 et al.chett et al (1998), gold et al.1978, moral.s et al (1994). The entire contents of the above listed patent documents and literature are hereby incorporated by reference. Some examples of suitable triplet emitters are listed below:
Figure RE-GDA0002654810390000181
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 or polymer or mixture as described above, and at least one organic solvent. In a preferred embodiment, the at least one organic solvent is selected from aromatic or heteroaromatic, ester, aromatic ketone or ether, aliphatic ketone or ether, alicyclic or olefinic compound, or borate or phosphate compound, or a mixture of two or more solvents.
In a preferred embodiment, according to a composition of the invention, said at least one organic solvent is chosen from aromatic or heteroaromatic-based solvents.
Examples of aromatic or heteroaromatic based solvents suitable for the present invention are, but not limited to: p-diisopropylbenzene, pentylbenzene, tetrahydronaphthalene, cyclohexylbenzene, chloronaphthalene, 1, 4-dimethylnaphthalene, 3-isopropylbiphenyl, p-methylisopropylbenzene, dipentylbenzene, tripentylbenzene, pentyltoluene, 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, cyclohexylbenzene, benzylbutylbenzene, dimethylnaphthalene, 3-isopropylbiphenyl, p-methylisopropylbenzene, 1-methylnaphthalene, 1,2, 4-trichlorobenzene, 4-difluorodiphenylmethane, 1, 2-dimethoxy-4- (1-propenyl) benzene, diphenylmethane, 2-phenylpyridine, 3-phenylpyridine, N-methyldiphenylamine, 4-isopropylbiphenyl, α -dichlorodiphenylmethane, 4- (3-phenylpropyl) pyridine, benzyl benzoate, 1-bis (3, 4-dimethylphenyl) ethane, 2-isopropylnaphthalene, quinoline, isoquinoline, methyl 2-furancarboxylate, ethyl 2-furancarboxylate, and the like;
examples of aromatic ketone-based solvents suitable for the present invention are, but not limited to: 1-tetralone, 2- (phenylepoxy) tetralone, 6- (methoxy) tetralone, acetophenone, propiophenone, benzophenone and their derivatives such as 4-methylacetophenone, 3-methylacetophenone, 2-methylacetophenone, 4-methylacetophenone, 3-methylacetophenone, 2-methylacetophenone and the like;
examples of aromatic ether-based solvents suitable for the present invention are, but not limited to: 3-phenoxytoluene, butoxybenzene, p-anisaldehyde dimethylacetal, tetrahydro-2-phenoxy-2H-pyran, 1, 2-dimethoxy-4- (1-propenyl) benzene, 1, 4-benzodioxan, 1, 3-dipropylbenzene, 2, 5-dimethoxytoluene, 4-ethylphenetole, 1, 3-dipropoxybenzene, 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, methyl ether, 2-phenoxytetrahydrofuran, ethyl-2-naphthyl ether.
In some preferred embodiments, 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, fenchylone, phorone, isophorone, di-n-amyl ketone, etc.; 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 preferred embodiments, the at least one organic solvent may be selected from ester-based solvents: alkyl octanoates, alkyl sebacates, alkyl stearates, alkyl benzoates, alkyl phenylacetates, alkyl cinnamates, alkyl oxalates, alkyl maleates, alkyl lactones, alkyl oleates, and the like. Octyl octanoate, diethyl sebacate, diallyl phthalate, isononyl isononanoate are particularly preferred.
The solvents mentioned may be used alone or as a mixture of two or more organic solvents.
In certain preferred embodiments, a composition according to the present invention comprises at least one compound or polymer or mixture as described above and at least one organic solvent, and may further comprise 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, dimethylsulfoxide, tetrahydronaphthalene, decalin, indene, and/or mixtures thereof.
In some preferred embodiments, particularly suitable solvents for the present invention are those having Hansen (Hansen) solubility parameters within the following ranges:
δ d (dispersion force) of 17.0 to 23.2MPa 1/2 In particular in the range of 18.5 to 21.0MPa 1/2 A range of (d);
δ p (polar force) is 0.2 to 12.5MPa 1/2 In particular in the range of 2.0 to 6.0MPa 1/2 A range of (d);
δ h (hydrogen bonding force) of 0.9 to 14.2MPa 1/2 In particular in the range of 2.0 to 6.0MPa 1/2 In (c) is used.
The compositions according to the invention, in which the organic solvent is selected taking into account its boiling point parameter. In the invention, the boiling point of the organic solvent is more than or equal to 150 ℃; preferably equal to or more than 180 ℃; more preferably more than or equal to 200 ℃; more preferably not less than 250 ℃; most preferably more than or equal to 275 ℃ or more than or equal to 300 ℃. Boiling points in these ranges are beneficial for preventing nozzle clogging in inkjet print heads. The organic solvent may be evaporated from the solvent system to form a thin film comprising the functional material.
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 10 wt% of the compound or polymer or mixture according to the present invention, preferably 0.1 to 15 wt%, more preferably 0.2 to 5 wt%, and most preferably 0.25 to 3 wt%.
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, letterpress, screen Printing, dip coating, spin coating, doctor blade coating, roll Printing, twist roll Printing, offset 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, improving adhesion, and the like. The printing technology and the requirements related to the solution, such as solvent and concentration, viscosity, etc.
The present invention also provides the use of a compound, polymer, mixture or composition as described above in an organic electronic device selected from, but not limited to: organic Light Emitting Diodes (OLEDs), Organic photovoltaic cells (OPVs), Organic light Emitting cells (OLEECs), Organic Field Effect Transistors (OFETs), Organic light Emitting field effect transistors (efets), Organic lasers, Organic spintronics, Organic sensors, and Organic Plasmon Emitting diodes (Organic plasma Emitting diodes), etc., with OLEDs being particularly preferred. In the embodiment of the present invention, the compound or the high polymer is preferably used for a light emitting layer of an OLED device.
The invention further relates to an organic electronic device comprising at least one compound, polymer or mixture as described above. Generally, such organic electronic devices comprise at least a cathode, an anode and a functional layer located between the cathode and the anode, wherein the functional layer comprises at least one compound as described above. The organic electronic device may be selected from, but is not limited to: organic Light Emitting Diodes (OLEDs), Organic photovoltaic cells (OPVs), Organic light Emitting cells (OLEECs), Organic Field Effect Transistors (OFETs), Organic light Emitting field effect transistors (efets), Organic lasers, Organic spintronic devices, Organic sensors, Organic Plasmon Emitting diodes (Organic plasma Emitting diodes), and the like, with Organic electroluminescent devices such as OLEDs, OLEECs, Organic light Emitting field effect transistors being particularly preferred.
In certain preferred embodiments, the organic electroluminescent device comprises a light-emitting layer comprising a compound or mixture or polymer as described above.
In certain preferred embodiments, the organic electroluminescent device comprises a light-emitting layer comprising a compound as described above, or comprising a compound as described above and a phosphorescent light-emitting material, or comprising a compound as described above and a fluorescent light-emitting material, or comprising a compound as described above and a TADF material.
In the above-described organic electroluminescent device, in particular an OLED, it comprises a substrate, an anode, at least one light-emitting layer and a cathode.
The substrate may be opaque or transparent. A transparent substrate may be used to fabricate a transparent light emitting device. See, for example, Bulovic et al Nature 1996,380, p29, and Gu et al, appl.Phys.Lett.1996,68, p 2606. The substrate may be rigid or flexible. The substrate may be plastic, metal, semiconductor wafer or glass. Preferably, the substrate has a smooth surface. A substrate free of surface defects is a particularly desirable choice. In a preferred embodiment, the substrate is flexible, and may be selected from polymeric films or plastics having a glass transition temperature Tg of 150 deg.C or greater, preferably greater than 200 deg.C, more preferably greater than 250 deg.C, and most preferably greater than 300 deg.C. Examples of suitable flexible substrates are poly (ethylene terephthalate) (PET) and polyethylene glycol (2, 6-naphthalene) (PEN).
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 of 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, BaF 2 Al, 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 OLED may also comprise further functional layers, such as a Hole Injection Layer (HIL), a Hole Transport Layer (HTL), an Electron Blocking Layer (EBL), an Electron Injection Layer (EIL), an Electron Transport Layer (ETL), a Hole Blocking Layer (HBL). Suitable materials for use in these functional layers are described in detail above and in WO2010135519a1, US20090134784a1 and WO2011110277a1, the entire contents of these 3 patent documents being hereby incorporated by reference.
The light-emitting device according to the present invention emits light at a wavelength of 300 to 1200nm, preferably 350 to 1000nm, and more preferably 400 to 900 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.
Example 1
Synthesis of Compound (1-3):
Figure RE-GDA0002654810390000211
the synthetic route is as follows:
Figure RE-GDA0002654810390000212
1) synthesis of intermediates 1-3-3: under a nitrogen atmosphere, compound 1-3-1 (27.2g,100mmol), compound 1-3-2 (31.7g,100mmol), and tetrakis (triphenylphosphine) palladium (6.9g,6mmol), (5.2g,16mmol) tetrabutylammonium bromide, (4g,100mmol) sodium hydroxide, (40mL) water, and (250mL) toluene were added to a 500mL three-necked flask, the mixture was heated to 80 ℃ and stirred for 12 hours to complete the reaction, the reaction solution was rotary evaporated to remove most of the solvent, washed with dichloromethane-dissolved water 3 times, and the organic phase-mixed silica gel was collected and purified by column chromatography in 80% yield.
2) Synthesis of intermediates 1-3-4: adding (25.1g,60mmol) of compound 1-3-3 and 150mL of anhydrous tetrahydrofuran into a 250mL three-necked bottle under a nitrogen environment, cooling to-78 ℃, slowly dropwise adding 65mmol of n-butyllithium, reacting for 2 hours, injecting 70mmol of trimethyl borate at one time, naturally heating the reaction to room temperature, continuing to react for 12 hours, adding purified water to quench the reaction, removing most of solvent by rotation, extracting with dichloromethane and washing with water for 3 times, collecting an organic phase, drying by rotation, recrystallizing, and obtaining the yield of 85%.
3) Synthesis of intermediates 1-3-6: according to the synthesis method of the compound 1-3-3, the compound 1-3-4 (15.3g,40mmol) and the compound 1-3-5 (10.7 g,40mmol) were substituted for the compound 1-3-1 and the compound 1-3-2 in a yield of 75%.
4) Synthesis of Compounds 1-3: according to the synthesis method of the compound 1-3-3, the compound 1-3-7 (11.4g,20mmol) and the compound 1-3-6 (10.7 g,20mmol) were substituted for the compound 1-3-1 and the compound 1-3-2 in a yield of 70%.
Example 2
Synthesis of Compounds (1-20):
Figure RE-GDA0002654810390000213
the synthetic route is as follows:
Figure RE-GDA0002654810390000214
1) synthesis of intermediates 1-20-2: according to the synthesis method of the compound 1-3-3, the compound 1-3-4 (15.3g,40mmol) and the compound 1-20-1 (10.4 g,40mmol) were substituted for the compound 1-3-1 and the compound 1-3-2 in a yield of 75%.
2) Synthesis of Compounds 1-20: according to the synthesis method of the compound 1-3-3, the compound 1-20-3 (2.56g,20mmol) and the compound 1-20-2 (10.3g, 20mmol) were substituted for the compound 1-3-1 and the compound 1-3-2 in a yield of 70%.
Example 3
Synthesis of Compounds (1-23):
Figure RE-GDA0002654810390000221
the synthesis route is as follows:
Figure RE-GDA0002654810390000222
1) synthesis of intermediates 1-23-2: according to the synthesis method of the compound 1-3-3, the compound 1-3-4 (15.3g,40mmol) and the compound 1-23-1 (10.7 g,40mmol) were substituted for the compound 1-3-1 and the compound 1-3-2 in a yield of 75%.
2) Synthesis of Compounds 1-23: according to the synthesis method of the compound 1-3-3, the compound 1-23-3 (2.44g,20mmol) and the compound 1-23-2 (11.4g,20mmol) were substituted for the compound 1-3-1 and the compound 1-3-2 in a yield of 75%.
Example 4
Synthesis of Compounds (1-26):
Figure RE-GDA0002654810390000223
the synthetic route is as follows:
Figure RE-GDA0002654810390000224
1) synthesis of intermediates 1-26-2: according to the synthesis method of the compound 1-3-3, the compound 1-23-3 (12.2g,100mmol) and the compound 1-26-1 (25.5g,100mmol) were substituted for the compound 1-3-1 and the compound 1-3-2 in a yield of 75%.
2) Synthesis of intermediates 1-26-3: according to the synthesis method of the compound 1-3-3, the compound 1-3-4 (15.3g,40mmol) and the compound 1-26-2 (11.9 g,40mmol) were substituted for the compound 1-3-1 and the compound 1-3-2 in a yield of 70%.
3) Synthesis of Compounds 1-26: according to the synthesis method of the compound 1-3-3, the compound 1-23-3 (2.44g,20mmol) and the compound 1-26-3 (12.0 g,20mmol) were substituted for the compound 1-3-1 and the compound 1-3-2 in a yield of 75%.
Example 5
Synthesis of Compounds (1-29):
Figure RE-GDA0002654810390000225
Figure RE-GDA0002654810390000231
1) synthesis of intermediates 1-29-3: according to the synthesis method of the compound 1-3-3, the compound 1-29-1 (34.8g,100mmol) and the compound 1-29-2 (31.6g,100mmol) were substituted for the compound 1-3-1 and the compound 1-3-2 in a yield of 75%.
2) Synthesis of intermediates 1-29-4: according to the synthesis method of the compound 1-3-4, the compound 1-29-3 (29.6g,60mmol) was substituted for the compound 1-3-3 in 80% yield.
3) Synthesis of intermediates 1-29-5: according to the synthesis method of the compound 1-3-3, the compound 1-29-4 (18.4g,40mmol) and the compound 1-3-5 (10.7 g,40mmol) were substituted for the compound 1-3-1 and the compound 1-3-2 in a yield of 75%.
4) Synthesis of Compounds 1-29: according to the synthesis method of the compound 1-3-3, the compound 1-23-3 (2.4g,20mmol) and the compound 1-29-5 (12.9 g,20mmol) were substituted for the compound 1-3-1 and the compound 1-3-2 in a yield of 75%.
Example 6
Synthesis of Compounds (1-30):
Figure RE-GDA0002654810390000232
1) synthesis of intermediates 1-30-2: according to the synthesis method of the compound 1-3-3, the compound 1-3-1 (27.2g,100mmol) and the compound 1-30-1 (28.6 g,100mmol) were substituted for the compound 1-3-1 and the compound 1-3-2 in a yield of 75%.
2) Synthesis of intermediates 1-29-3: according to the synthesis method of the compound 1-3-4, the compound 1-30-2 (25.2g,60mmol) was substituted for the compound 1-3-3 in 80% yield.
3) Synthesis of intermediates 1-30-4: according to the synthesis method of the compound 1-3-3, the compound 1-30-3 (15.6g,40mmol) was substituted for the compound 1-3-1 and the compound 1-3-2 in a yield of 70%.
4) Synthesis of intermediates 1-30-5: according to the synthesis method of the compound 1-3-4, the compound 1-30-4 (10.9g,20mmol) was substituted for the compound 1-3-3 in 80% yield.
5) Synthesis of intermediates 1-30-6: according to the synthesis method of the compound 1-3-3, the compound 1-30-5 (5.08g,10mmol) and the compound 1-26-2 (2.68 g,100mmol) were substituted for the compound 1-3-1 and the compound 1-3-2 in a yield of 75%.
6) Synthesis of Compounds 1-30: according to the synthesis method of the compound 1-3-3, the compound 1-23-3 (0.61g,5mmol) and the compound 1-30-6 (3.63 g,5mmol) were substituted for the compound 1-3-1 and the compound 1-3-2 in a yield of 75%.
Example 7
Synthesis of Compounds (1-35):
Figure RE-GDA0002654810390000241
the synthetic route is as follows:
Figure RE-GDA0002654810390000242
1) synthesis of intermediates 1-35-2: according to the synthesis method of the compound 1-3-3, the compound 1-3-4 (15.3g,40mmol) and the compound 1-35-1 (12.4 g,40mmol) were substituted for the compound 1-3-1 and the compound 1-3-2 in a yield of 75%.
2) Synthesis of Compounds 1-35: according to the synthesis method of the compound 1-3-3, the compound 1-23-3 (2.44g,20mmol) and the compound 1-35-2 (11.4g,20mmol) were substituted for the compound 1-3-1 and the compound 1-3-2 in a yield of 75%.
Example 8
Synthesis of Compounds (1-38):
Figure RE-GDA0002654810390000243
the synthetic route is as follows:
Figure RE-GDA0002654810390000244
1) synthesis of intermediates 1-38-2: according to the synthesis method of the compound 1-3-3, the compound 1-23-3 (12.2g,100mmol) and the compound 1-38-1 (22.5g,100mmol) were substituted for the compound 1-3-1 and the compound 1-3-2 in a yield of 75%.
2) Synthesis of intermediates 1-38-3: according to the synthesis method of the compound 1-3-3, the compound 1-3-4 (15.3g,40mmol) and the compound 1-38-2 (10.7 g,40mmol) were substituted for the compound 1-3-1 and the compound 1-3-2 in a yield of 70%.
3) Synthesis of Compounds 1-38: according to the synthesis method of the compound 1-3-3, the compound 1-38-4 (2.46g,20mmol) and the compound 1-38-3 (11.3 g,20mmol) were substituted for the compound 1-3-1 and the compound 1-3-2 in a yield of 75%.
Example 9
Synthesis of Compounds (1-51):
Figure RE-GDA0002654810390000245
the synthetic route is as follows:
Figure RE-GDA0002654810390000251
1) synthesis of intermediates 1-51-2: according to the synthesis method of compound 1-3-3, compound 1-51-1 (27.2g,100mmol) was substituted for compound 1-3-1 in 75% yield.
2) Synthesis of intermediates 1-51-3: according to the synthesis method of the compound 1-3-4, the compound 1-51-2 (25.1g,60mmol) was substituted for the compound 1-3-3 in 80% yield.
3) Synthesis of intermediates 1-51-5: according to the synthesis method of the compound 1-3-3, the compound 1-51-3 (15.3g,40mmol) and the compound 1-51-4 (9.6 g,40mmol) were substituted for the compound 1-3-1 and the compound 1-3-2 in a yield of 75%.
4) Synthesis of Compounds 1-51: according to the synthesis method of the compound 1-3-3, the compound 1-51-6 (3.44g,20mmol) and the compound 1-51-5 (10.9g,20mmol) were substituted for the compound 1-3-1 and the compound 1-3-2 in a yield of 75%.
Example 10
Synthesis of Compounds (1-86):
Figure RE-GDA0002654810390000252
the synthetic route is as follows:
Figure RE-GDA0002654810390000253
1) synthesis of intermediates 1-86-3: according to the synthesis method of the compound 1-3-3, the compound 1-86-1 (34.8g,100mmol) and the compound 1-86-2 (25.6g,100mmol) were substituted for the compound 1-3-1 and the compound 1-3-2 in a yield of 75%.
2) Synthesis of intermediates 1-86-4: under nitrogen atmosphere, adding (28.8g,60mmol) of compound 1-86-3 and 80mL of acetic acid into a 150mL three-necked bottle, slowly adding (10.3g,100mmol) of n-butyl nitrite under ice bath, reacting for 0.5 hour, adding (11.4g, 80mmol) of cuprous bromide in one step, heating the reaction to 60 ℃, continuing to react for 12 hours, after the reaction is finished, removing most of solvent by spinning, dissolving with dichloromethane and washing with water for 3 times, collecting the organic phase, and recrystallizing after spinning, wherein the yield is 85%.
3) Synthesis of intermediates 1-86-5: according to the synthesis method of the compound 1-3-3, the compound 1-23-3 (4.9g,40mmol) and the compound 1-86-4 (21.8g, 40mmol) were substituted for the compound 1-3-1 and the compound 1-3-2 in a yield of 85%.
4) Synthesis of intermediates 1-86-6: under a nitrogen atmosphere, compound 1-86-5 (16.2g, 30mmol), (7.6g, 30mmol) pinacol diboron, (4.9g, 50mmol) potassium acetate, (1.32g, 1.8mmol) Pd (dppf) Cl 2 Adding 60mL of 1, 4-dioxane as a solvent into a 250mL three-necked bottle, heating to 110 ℃ for reaction for 12 hours, cooling the reaction solution to room temperature after the reaction is finished, carrying out suction filtration on the filtrate, carrying out rotary evaporation to remove most of the solvent, dissolving and washing for 3 times by using dichloromethane, collecting an organic phase, mixing with silica gel, and carrying out column chromatography for purification, wherein the yield is 70%.
5) Synthesis of Compounds 1-86: according to the synthesis method of the compound 1-3-3, the compound 1-86-6 (34.8g,100mmol) and the compound 1-26-2 (25.6g,100mmol) were substituted for the compound 1-3-1 and the compound 1-3-2 in a yield of 75%.
Example 11
Synthesis of Compounds (1-92):
Figure RE-GDA0002654810390000261
the synthetic route is as follows:
Figure RE-GDA0002654810390000262
1) synthesis of intermediate 1-92-1: according to the synthesis method of the compound 1-3-3, the compound 1-86-2 (25.6g,100mmol) was substituted for the compound 1-3-2 in a yield of 75%.
2) Synthesis of intermediates 1-92-2: according to the synthesis method of compound 1-86-4, compound 1-92-1 (24.2g,60mmol) was substituted for compound 1-86-3 in 80% yield.
3) Synthesis of intermediates 1-92-3: according to the synthesis method of the compound 1-3-3, the compound 1-51-6 (6.9g,40mmol) and the compound 1-92-2 (18.7 g,40mmol) were substituted for the compound 1-3-1 and the compound 1-3-2 in a yield of 80%.
4) Synthesis of intermediates 1-92-4: according to the synthesis method of the compound 1-86-6, the compound 1-92-3 (15.5g,30mmol) was substituted for the compound 1-86-5 in a yield of 75%.
5) Synthesis of intermediates 1-92-6: according to the synthesis method of the compound 1-3-3, the compound 1-51-6 (10.3g,60mmol) and the compound 1-92-5 (12.0 g,60mmol) were substituted for the compound 1-3-1 and the compound 1-3-2 in a yield of 75%.
6) Synthesis of Compounds 1-92: according to the synthesis method of the compound 1-3-3, the compound 1-92-4 (12.1g,20mmol) and the compound 1-92-6 (5.8 g,20mmol) were substituted for the compound 1-3-1 and the compound 1-3-2 in a yield of 70%.
Example 12
Synthesis of Compounds (1-100):
Figure RE-GDA0002654810390000271
the synthetic route is as follows:
Figure RE-GDA0002654810390000272
1) synthesis of intermediates 1-100-2: according to the synthesis method of compound 1-3-3, compound 1-100-1 (25.6g,100mmol) was substituted for compound 1-3-2 in a yield of 75%.
2) Synthesis of intermediates 1-100-3: according to the synthesis method of the compound 1-3-3, the compound 1-23-3 (7.3g,60mmol) and the compound 1-100-2 (24.2g,60mmol) were substituted for the compound 1-3-1 and the compound 1-3-2 in a yield of 70%.
3) Synthesis of intermediates 1-100-4: according to the synthesis method of the compound 1-86-4, the compound 1-100-3 (17.8g,40mmol) was substituted for the compound 1-86-3 in 85% yield.
4) Synthesis of intermediates 1-100-5: according to the synthesis method of compound 1-86-6, compound 1-100-4 (15.3g,30mmol) was substituted for compound 1-86-5 in 75% yield.
5) Synthesis of intermediates 1 to 100: according to the synthesis method of the compound 1-3-3, the compound 1-100-5 (11.1g,20mmol) and the compound 1-23-1 (5.2g, 20mmol) were substituted for the compound 1-3-1 and the compound 1-3-2 in a yield of 70%.
Example 13
Synthesis of Compounds (1-120):
Figure RE-GDA0002654810390000273
1) synthesis of intermediates 1-120-2: according to the synthesis method of the compound 1-3-3, the compound 1-23-3 (12.2g,100mmol) and the compound 1-120-1 (28.2g,100mmol) were substituted for the compound 1-3-1 and the compound 1-3-2 in a yield of 80%.
2) Synthesis of intermediates 1-120-3: according to the synthesis method of the compound 1-86-6, the compound 1-120-2 (19.5g,70mmol) was substituted for the compound 1-86-5 in a yield of 75%.
3) Synthesis of intermediates 1-120-4: according to the synthesis method of the compound 1-3-3, the compound 1-120-3 (18.5g,50mmol) and the compound 1-23-1 (13.4g,50mmol) were substituted for the compound 1-3-1 and the compound 1-3-2 in a yield of 70%.
4) Synthesis of intermediates 1-120-5: according to the synthesis method of the compound 1-3-4, the compound 1-120-4 (14.3g,30mmol) was substituted for the compound 1-3-3 in 80% yield.
5) Synthesis of Compounds 1-120: according to the synthesis method of the compound 1-3-3, the compound 1-120-5 (10.0g,20mmol) and the compound 1-120-6 (6.1 g,20mmol) were substituted for the compound 1-3-1 and the compound 1-3-2 in a yield of 80%.
Example 14
Synthesis of Compounds (1-123):
Figure RE-GDA0002654810390000281
1) synthesis of intermediates 1-123-3: according to the synthesis method of the compound 1-3-3, the compound 1-123-3 (17.2g,100mmol) and the compound 1-123-2 (29.8g,100mmol) were substituted for the compound 1-3-1 and the compound 1-3-2 in a yield of 80%.
2) Synthesis of intermediates 1-123-4: according to the synthesis method of the compounds 1-86-6, the compound 1-123-3 (24.2g,70mmol) was substituted for the compound 1-86-5 in a yield of 70%.
3) Synthesis of intermediates 1-123-6: according to the synthesis method of the compound 1-3-3, the compound 1-123-4 (21.8g,50mmol) and the compound 1-123-5 (14.0g,50mmol) were substituted for the compound 1-3-1 and the compound 1-3-2 in a yield of 60%.
4) Synthesis of intermediates 1-123-7: according to the synthesis method of the compound 1-3-4, the compound 1-123-6 (16.7g,30mmol) was substituted for the compound 1-3-3 in a yield of 70%.
5) Synthesis of Compounds 1-123: according to the synthesis method of the compound 1-3-3, the compound 1-123-7 (11.0g,20mmol) and the compound 1-120-6 (6.1 g,20mmol) were substituted for the compound 1-3-1 and the compound 1-3-2 in a yield of 80%.
Example 15
Synthesis of Compounds (1-128):
Figure RE-GDA0002654810390000282
the synthetic route is as follows:
Figure RE-GDA0002654810390000291
1) synthesis of intermediates 1-128-3: according to the synthesis method of the compound 1-3-3, the compound 1-128-1 (16.7g,100mmol) and the compound 1-128-2 (43.8g,100mmol) were substituted for the compound 1-3-1 and the compound 1-3-2 in a yield of 70%.
2) Synthesis of intermediates 1-128-5: according to the synthesis method of the compound 1-3-3, the compound 1-128-4 (16.4g,60mmol) and the compound 1-128-3 (26.0g,60mmol) were substituted for the compound 1-3-1 and the compound 1-3-2 in a yield of 70%.
3) Synthesis of intermediates 1-128-6: according to the synthesis method of the compounds 1-86-6, the compound 1-128-5 (23.3g,40mmol) was substituted for the compound 1-86-5 in a yield of 75%.
4) Synthesis of intermediates 1-128-7: according to the synthesis method of the compound 1-3-3, the compound 1-128-6 (18.9g,30mmol) and the compound 1-3-5 (8.0g,30mmol) were substituted for the compound 1-3-1 and the compound 1-3-2 in a yield of 75%.
5) Synthesis of intermediates 1-128-8: compound 1-128-7 (14.6g,20mmol) and 50mL triethyl phosphite were added to a 150mL three-necked flask under nitrogen, heated to 160 ℃ and reacted for 12 hours. The reaction was stopped, and the liquid in the reaction solution was distilled off by a vacuum distillation apparatus. The remaining solid was recrystallized from a solution of dichloromethane and ethanol, and the yield was about 80%.
6) Synthesis of Compounds 1-128: under nitrogen atmosphere, adding (10.5g, 15mmol) compounds 1-128-8, (3.1g, 15mmol) iodobenzene, (1.9g, 10mmol) cuprous iodide, (1.15g, 10mmol) trans-cyclohexanediamine, (6.3g, 20mmol) potassium phosphate and 60mL toluene into a 150mL three-necked flask, heating and stirring to 110 ℃ for reaction for 12 hours, ending the reaction, cooling to room temperature, performing suction filtration on the filtrate, performing rotary evaporation to remove most of the solvent, dissolving and washing with dichloromethane for 3 times, collecting the organic phase, mixing with silica gel, and purifying with a column with a yield of 80%.
Example 16
Synthesis of Compounds (1-139):
Figure RE-GDA0002654810390000292
1) synthesis of intermediates 1-139-2: under nitrogen atmosphere, compound 1-139-1 (30.7g, 100mmol) and 100mL deuterated benzene-d 6 were added to a 250mL three-necked flask, heated under stirring and refluxed for 12 hours to complete the reaction, cooled to room temperature, and rotary evaporated most of the solvent, recrystallized from dichloromethane and ethanol in 90% yield.
2) Synthesis of intermediates 1-139-3: according to the synthesis method of compound 1-3-4, compound 1-139-2 (25.4g,80mmol) was substituted for compound 1-3-3 in 80% yield.
3) Synthesis of intermediates 1-139-4: according to the synthesis method of compound 1-3-3, compound 1-139-3 (17.0g,60mmol) was substituted for compound 1-3-1 in 75% yield.
4) Synthesis of intermediates 1-139-5: according to the synthesis method of compound 1-3-4, compound 1-139-4 (25.7g,40mmol) was substituted for compound 1-3-3 in 80% yield.
5) Synthesis of intermediates 1-139-6: according to the synthesis method of the compound 1-3-3, the compound 1-139-5 (11.8g,30mmol) and the compound 1-23-1 (8.0g,30mmol) were substituted for the compound 1-3-1 and the compound 1-3-2 in a yield of 75%.
6) Synthesis of Compounds 1-139: according to the synthesis method of the compound 1-3-3, the compound 1-23-3 (2.44g,20mmol) and the compound 1-139-7 (11.6 g,20mmol) were substituted for the compound 1-3-1 and the compound 1-3-2 in a yield of 70%.
Example 17
Synthesis of Compounds (1-140):
Figure RE-GDA0002654810390000301
1) synthesis of Compounds 1-140: according to the synthesis method of the compound 1-3-3, the compound 1-140-1 (2.54g,20mmol) and the compound 1-26-3 (12 g,20mmol) were substituted for the compound 1-3-1 and the compound 1-3-2 in a yield of 75%.
Example 18
Synthesis of Compound (4-1):
Figure RE-GDA0002654810390000302
the synthetic route is as follows:
Figure RE-GDA0002654810390000303
1) synthesis of intermediate 4-1-2: according to the synthesis method of the compound 1-3-3, the compound 4-1-1 (31.2g,100mmol) was substituted for the compound 1-3-2 in a yield of 80%.
2) Synthesis of Compound 4-1: according to the synthesis method of the compound 1-3-3, the compound 4-1-3 (17.3g,60mmol) and the compound 4-1-2 (27.5 g,60mmol) were substituted for the compound 1-3-1 and the compound 1-3-2 in a yield of 80%.
Example 19
Synthesis of Compounds (4-12):
Figure RE-GDA0002654810390000311
the synthetic route is as follows:
Figure RE-GDA0002654810390000312
1) synthesis of intermediate 4-12-3: according to the synthesis method of the compounds 1 to 128, the compounds 4-12-1 (10.3g,60mmol) and the compound 4-12-2 (33.6 g,120mmol) were substituted for the compounds 1 to 128-8 and iodobenzene in a yield of 75%.
2) Synthesis of Compounds 4-12: according to the synthesis method of the compound 1-3-3, the compound 4-12-4 (14.8g,40mmol) and the compound 4-12-3 (19.0 g,40mmol) were substituted for the compound 1-3-1 and the compound 1-3-2 in a yield of 80%.
Example 20
Synthesis of Compounds (4-46):
Figure RE-GDA0002654810390000313
1) synthesis of Compounds 4-46: according to the synthesis method of the compound 1-3-3, the compound 4-46-1 (44.5g,100mmol) and the compound 4-46-2 (39.8 g,100mmol) were substituted for the compound 1-3-1 and the compound 1-3-2 in a yield of 85%.
Example 21
Synthesis of Compounds (4-89):
Figure RE-GDA0002654810390000314
Figure RE-GDA0002654810390000321
1) synthesis of intermediates 4-89-3: according to the synthesis method of the compound 1-3-3, the compound 4-89-1 (44.5g,100mmol) and the compound 4-89-2 (20.2g,100mmol) were substituted for the compound 1-3-1 and the compound 1-3-2 in a yield of 80%.
2) Synthesis of intermediates 4-89-4: according to the synthesis method of the compounds 1-128-8, the compound 4-89-3 (26.4g,60mmol) was substituted for the compound 1-128-7 in a yield of 70%.
3) Synthesis of Compounds 4-89: according to the synthesis method of the compounds 1 to 128, the compounds 4 to 89-4 (16.3g,40mmol) and the compound 4 to 12-2 (11.2 g,40mmol) were substituted for the compounds 1 to 128-8 and iodobenzene in a yield of 75%.
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 a molecular geometrical structure, and then the energy structure of the organic molecule 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 HOMO and LUMO energy levels were calculated according to the following calibration formula, and S1 and T1 were used directly.
HOMO(eV)＝((HOMO(G)×27.212)-0.9899)/1.1206
LUMO(eV)＝((LUMO(G)×27.212)-2.0041)/1.385
Where HOMO (G) and LUMO (G) are direct calculations of Gaussian 03W in Hartree.
The comparative materials were as follows:
Figure RE-GDA0002654810390000322
among them, Ref-1 and Ref-2 are referred to patent TW 201509915A.
The results are shown in table 1:
TABLE 1
Figure RE-GDA0002654810390000323
Figure RE-GDA0002654810390000331
Preparation and characterization of OLED device
In the present example, in the green device, the compounds (1-3), (1-20), (1-23), (1-26), (1-29), (1-35), (1-38), (1-86), (1-120), (1-123), (1-128), (1-139) and (1-140) were used as the single host material, or the mixtures (1-3), (4-89), (1-23), (4-46), (1-26), (4-1), (1-29), (4-46), (1-38), (4-12) and (1-123), (4-46), (1-139), (4-46) and (1-140), (4-1) were used as the host material, respectively, Emitter-G shown below as a light emitting material, HATCN as a hole injecting material, HTL as a hole transporting material, ETM as an electron transporting material, and Liq as an electron injecting material were constructed as an electroluminescent device having a device structure of ITO/HATCN/HTL/host material, Emitter-G (10%)/ETM: Liq/Liq/Al.
Figure RE-GDA0002654810390000332
The materials HATCN, HTL, Emitter, ETM, Liq mentioned above are all commercially available, such as gillin alder (Jilin OLED Material Tech co., Ltd, www.jl-OLED. com), or their synthesis methods are all prior art, see references in the prior art for details, and are not repeated here.
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/HATCN/HTL/host material: Emitter/ETM Liq/Liq/Al, the preparation steps are as follows:
a. cleaning an ITO (indium tin oxide) conductive glass substrate: washing with various solvents (such as one or more of chloroform, acetone or isopropanol), and performing ultraviolet ozone treatment;
b. HATCN (30nm), HTL (50nm), host material Emitter (40nm), ETM Liq (30nm), Liq (1nm) and Al (100 nm) in sequence under high vacuum (1X 10 nm) -6 Millibar) hot evaporation;
c. packaging: the devices were encapsulated with uv curable resin in a nitrogen glove box.
The current-voltage (J-V) characteristics of the organic light emitting diodes of the green devices of examples 1 to 21 and comparative examples 1 to 5 were tested using a characterization apparatus, while important parameters such as efficiency, lifetime (see table 2) and external quantum efficiency were recorded. In table 2, all external quantum efficiencies and lifetimes are relative values with respect to the organic light emitting diode of comparative example 1. It can be seen that the external quantum efficiency and lifetime of the devices, whether in a single host or in a mixed host, are improved to some extent in the embodiments based on the present invention over the comparative examples, wherein the external quantum efficiency and lifetime of the dual host-based embodiments are higher than those of the single host-based embodiments, and the light-emitting efficiency and lifetime of the device of example 20 based on the mixture are the highest among the same types of devices. Therefore, the green device prepared on the basis of the compound and the mixture of the invention has greatly improved efficiency and service life,the main reason may be that in the embodiment of the present invention, Ar 1 The group A and the electron-deficient group are connected through an ortho position, so that on one hand, certain steric hindrance can be provided, and quenching of excitons caused by close packing among molecules is prevented; on the other hand, the ortho-position connection of the substituent group can inhibit the interaction between the electron-deficient A group and the adjacent molecule to a great extent to form other energy state structures which can damage the luminescence stability; in addition, deuteration of the compound can reduce chemical and environmental activity of the compound and improve stability of the compound, thereby being further beneficial to improving performance and stability of compound devices.
TABLE 2
OLED device Host material EQE T90@1000nits
Example 1 (1-3) 1.49 1.60
Example 2 (1-20) 1.41 1.52
Example 3 (1-23) 1.60 1.68
Example 4 (1-26) 1.56 1.64
Example 5 (1-29) 1.57 1.66
Example 6 (1-35) 1.36 1.48
Example 7 (1-38) 1.53 1.57
Example 8 (1-86) 1.45 1.56
Example 9 (1-120) 1.38 1.50
Example 10 (1-123) 1.36 1.45
Example 11 (1-128) 1.52 1.61
Example 12 (1-139) 1.64 1.75
Example 13 (1-140) 1.58 1.67
Example 14 (1-3) (4-89) ═ 5:5 (mass ratio) 1.72 1.95
Example 15 (1-23) (4-46) ═ 5:5 (mass ratio) 1.88 2.25
Example 16 (1-26) (4-1) ═ 5:5 (mass ratio) 1.80 2.16
Example 17 (1-29) (4-46) ═ 5:5 (mass ratio) 1.84 2.20
Example 18 (1-38) (4-12) ═ 5:5 (mass ratio) 1.75 2.04
Example 19 (1-123): (4-46) ═ 5:5 (mass ratio) 1.74 1.80
Example 20 (1-139) (4-46) ═ 5:5 (mass ratio) 1.93 2.32
Example 21 (1-140) (4-1) ═ 5:5 (mass ratio) 1.85 2.24
Comparative example 1 Ref-1 1 1
Comparative example 2 Ref-2 1.1 1.22
Comparative example 3 Ref-3 0.76 0.88
Comparative example 4 Ref-1 (4-46) ═ 5:5 (mass ratio) 1.2 1.36
Comparative example 5 Ref-2 (4-46) ═ 5:5 (mass ratio) 1.25 1.39
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
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 should be subject to the appended claims.

Claims (12)

1. A compound represented by the general formula (1):
Figure FDA0003635721650000011
wherein each occurrence of V is independently selected from: n atom or CR 1 ；
Ar 1 And A is at L 2 The upper ortho position is connected;
a is selected from one of the following structures:
Figure FDA0003635721650000012
wherein, each occurrence of X is independently selected from: n atom or CR 4 And at least one X is an N atom;
Y 1 each occurrence is independently selected from O, S;
Ar 2 、Ar 3 each independently selected from: an aromatic group having 5 to 60 ring atoms;
R 4 each occurrence of the aromatic group is independently selected from hydrogen, deuterium and an aromatic group with 5-60 ring atoms;
n1 is selected from 0;
R 1 at each occurrence, is independently selected from: hydrogen, deuterium;
n is selected from 0 or 1;
L 1 at each occurrence, independently selected from one or a combination of the following structures:
Figure FDA0003635721650000013
wherein R is 5 ～R 6 Is a substituent independently selected for each occurrence from: deuterium;
n1 is selected from any integer of 0-4; n2 is selected from any integer of 0-3;
L 2 one or a combination of the following structures:
Figure FDA0003635721650000014
wherein, Y 2 At each occurrence, is independently selected from: CR 7 R 8 O, S or NR 7 ；
R 7 ～R 8 At each occurrence, is independently selected from: hydrogen, deuterium;
n1 is selected from any integer of 0-4; n2 is selected from any integer of 0-3; n3 is selected from any integer of 0-5; n4 is selected from any integer of 0-2;
Ar 1 one or a combination of the following structures:
Figure FDA0003635721650000021
wherein, Y 3 At each occurrence, is independently selected from CR 9 R 10 O, S or NR 9 ；
R 9 ～R 11 Is a substituent independently selected for each occurrence from: deuterium;
n1 is selected from any integer of 0-4; n2 is selected from any integer of 0-3; n3 is selected from any integer of 0-5; n4 is selected from any integer of 0-2;
are attachment sites.
2. The compound of claim 1, wherein the compound is selected from one of the general formulae (2-1) or (2-2):
Figure FDA0003635721650000022
wherein, V, A, L 1 、L 2 、Ar 1 N has the same meaning as in claim 1.
3. The compound of claim 1, wherein a is selected from one or a combination of the following structures:
Figure FDA0003635721650000023
4. the compound of claim 1 or 2, wherein: the compound is selected from any one of general formulas (3-1) to (3-6), wherein the H atom on the ring may be substituted:
Figure FDA0003635721650000024
wherein:
Y 2 at each occurrence, is independently selected from: CR 7 R 8 O, S or NR 7 ；
R 7 ～R 8 At each occurrence, is independently selected from: hydrogen, deuterium.
5. A compound according to claim 1 or 2, characterized in that V, L 1 、L 2 And Ar 1 At least one of which contains one or more deuterium atoms.
6. A polymer comprising at least one repeating unit comprising a structural unit represented by a compound according to any one of claims 1 to 5.
7. A mixture comprising an organic functional material H1, H1 being selected from a compound according to any one of claims 1 to 5 or a polymer according to claim 6, and at least one further organic functional material H2, wherein H2 is selected from a hole injecting material, a hole transporting material, an electron injecting material, an electron blocking material, a hole blocking material, a light emitter, a host material or an organic dye.
8. A mixture according to claim 7, wherein H2 comprises at least one hole transporting unit according to formula (4):
Figure FDA0003635721650000031
wherein Ar is 4 Is a ringAn aromatic group or heteroaromatic group having 6 to 180 atoms; d is a hole transport unit; m is an integer from 1 to 6.
9. The mixture of claim 8, wherein H2 is selected from one of the following formulas:
Figure FDA0003635721650000032
wherein: l is 3 Selected from substituted or unsubstituted aromatic or heteroaromatic groups with 5-180 ring atoms;
Ar 5 、Ar 6 is selected from aromatic group or heteroaromatic group with 5-60 ring atoms.
10. A composition comprising a compound according to any one of claims 1 to 5 or a polymer according to claim 6 or a mixture according to any one of claims 7 to 9 and at least one organic solvent.
11. An organic electronic device, characterized in that it comprises at least one compound according to any one of claims 1 to 5 or a polymer according to claim 6 or a mixture according to any one of claims 7 to 9.
12. The organic electronic device according to claim 11, which is an electroluminescent device, characterized in that the electroluminescent device comprises a light-emitting layer comprising a compound according to any one of claims 1 to 5 or a polymer according to claim 6 or a mixture according to any one of claims 7 to 9.
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