CN111278795B - Organic mixtures and their use in organic electronic devices - Google Patents

Organic mixtures and their use in organic electronic devices Download PDF

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CN111278795B
CN111278795B CN201880069696.XA CN201880069696A CN111278795B CN 111278795 B CN111278795 B CN 111278795B CN 201880069696 A CN201880069696 A CN 201880069696A CN 111278795 B CN111278795 B CN 111278795B
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谭甲辉
何锐锋
潘君友
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Guangzhou Chinaray Optoelectronic Materials Ltd
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Abstract

The present invention relates to an organic mixture and its use in organic electronic devices. The organic mixture comprises organic materials H1 and H2, H1 is a compound shown in the following general formula (1), S1 (H2) -T1 (H2) of H2 is less than or equal to 0.3eV, wherein S1 (H2), and T1 (H2) are a singlet state energy level and a triplet state energy level of H2 respectively. The mixture according to the invention comprising the organic materials H1 and H2 is applied as host material toIn the organic electronic device, taking the electroluminescent device as an example, higher luminous efficiency and longer service life of the device can be provided.
Figure DDA0002465890270000011

Description

Organic mixtures and their use in organic electronic devices
The present application claims priority from chinese patent office, application number 2017113945046, entitled "an organic mixture and its use in organic electronic devices," filed on date 21, 12, 2017, the entire contents of which are incorporated herein by reference.
Technical Field
The invention relates to the field of organic electronic devices, in particular to an organic mixture. The invention also relates to the use of said organic mixture in an organic electronic device.
Background
Organic Light Emitting Diodes (OLEDs) have light weight, active light emission, wide viewing angle, high contrast, high light emission efficiency, low energy consumption, easy fabrication of flexible and large-sized panels, etc., and are considered as devices for next generation display and illumination in the industry.
In order to advance the large-scale industrialization process of the organic light emitting diode, further improving the light emitting performance and the service life of the organic light emitting diode is a major problem to be solved urgently at present, wherein the development of high-performance organic photoelectric performance materials is a key to solve the problem.
The organic light emitting diode is a device for converting electric energy into light energy, and in order to further improve the light emitting efficiency of the organic light emitting diode, the energy conversion efficiency is improved as much as possible, and the energy loss is reduced. For luminescent materials, according to the statistical rule of electron spin, singlet and triplet excitons are generated in a ratio of 1:3, so that the energy utilization rate of the conventional fluorescent luminescent materials is only 25% at maximum, while the phosphorescent luminescent materials enhance the spin orbit coupling on the triplet state due to the heavy atom effect, so that the triplet state of the original spin forbidden is relieved, and the singlet and triplet excitons can emit light, wherein the energy utilization rate can reach 100% theoretically.
The use of host materials is an indispensable component for improving the device lifetime and stability of organic light emitting diodes in order to better achieve energy level matching and transport, preventing exciton aggregation quenching. The conventional host material is easily influenced by triplet state-triplet state exciton quenching and triplet state-polaron quenching, so that the efficiency roll-off of the device is serious, and the service life and the stability of the device are influenced. Currently, there are reports (e.g., adv. Funct. Mater.,2014,23,3551) of the use of singlet and triplet level differences (delta.) S1-T1 ) On one hand, the host material is favorable for electron and hole injection and transmission due to the bipolar transmission groups, and effectively reduces the working voltage of the device; on the other hand, the difference between the singlet and triplet energy levels (Δ S1-T1 ) And the triplet state excitons are easy to cross to the singlet state through the intersystem, so that the concentration of the triplet state excitons is reduced, quenching of the triplet state excitons is effectively avoided, the roll-off of the device efficiency is reduced, and the service life and the stability of the device are further improved.
Delta in further optimizing device efficiency and lifetime S1-T1 Smaller doubleThe polar main body is introduced into another co-main body molecule due to the limitation of the group, so that the functions of charge transmission balance and exciton dispersion are easier to realize. In the prior art, delta is used in many cases S1-T1 The smaller bipolar main body and the hole-transporting main body are matched to be used as a co-main body, as described in patent WO2016158363A1, WO2016158191A1 and the like, carbazole p-type molecules are used as a mixture, so that charge transport of the device is balanced, the working voltage of the device is further reduced, and the luminous efficiency and the service life of the device are effectively improved. However, such mixtures should have a large space for improvement in exciton dispersion if the material structure is designed and optimized.
Disclosure of Invention
Based on this, it is an object of the present application to provide an organic mixture. It is a further object of the present application to provide the use of the organic mixture according to the invention for the preparation of an organic electronic device.
An organic mixture comprising organic materials H1 and H2, H1 being a compound of the following formula (1):
Figure GDA0002465890330000011
wherein, the liquid crystal display device comprises a liquid crystal display device,
L 1 is a single bond, a substituted or unsubstituted aromatic hydrocarbon group having 5 to 30 ring atoms or an aromatic heterocyclic group having 5 to 30 ring atoms, L 1 The connection position of (2) can be any carbon atom on the benzene ring;
X 1 represents a single bond, N (R), C (R) 5 R 6 )、Si(R 5 R 6 )、O、C＝N(R)、C＝C(R 5 R 6 ) P (R), P (=o) R, S, S =o or SO 2 ；
X 2 Represents N (R), C (R) 5 R 6 )、Si(R 5 R 6 )、O、C＝N(R)、C＝C(R 5 R 6 ) P (R), P (=o) R, S, S =o or SO 2 ；
R 1 、R 2 、R 3 、R 4 Are substituents, eachIndependently selected from H, D, F, CN, alkenyl, alkynyl, nitrile, amino, nitro, acyl, alkoxy, carbonyl, sulfonyl, substituted or unsubstituted alkyl with 1 to 30 carbon atoms, substituted or unsubstituted cycloalkyl with 3 to 30 carbon atoms, substituted or unsubstituted aromatic hydrocarbon with 5 to 60 ring atoms or substituted or unsubstituted aromatic heterocyclic with 5 to 60 ring atoms, R 1 、R 2 、R 3 、R 4 May be at any one or more carbon atoms on the fused ring;
R、R 5 、R 6 Each independently represents H, D, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group having 5 to 60 ring atoms or a substituted or unsubstituted aromatic heterocyclic group having 5 to 60 ring atoms, R 5 And R is 6 Bonding or non-bonding to form a saturated or unsaturated ring structure;
h2 is another organic functional material, S1 (H2) -T1 (H2). Ltoreq.0.3 eV, wherein S1 (H2), T1 (H2) are the singlet energy level and the triplet energy level of H2 respectively.
A composition comprising one of said organic mixtures, and at least one organic solvent.
Use of said organic mixture in an organic electronic device.
An organic electronic device, the functional layer of which comprises at least one of said organic mixtures.
Compared with the prior art, the application has the following beneficial effects:
the organic mixture containing the organic materials H1 and H2 is used as a main material applied to an organic electronic device, and an electroluminescent device is taken as an example, so that higher luminous efficiency and longer service life of the device can be provided. The possible reasons for this are, but not limited to, that the organic material H1 is a spiro-ring aromatic compound having a vertically crossed spatial structure, which can effectively prevent close packing between molecules and reduce the concentration of excitons; h2 is an organic functional material, S1 (H2) -T1 (H2) is less than or equal to 0.3eV, is a bipolar molecule with smaller delta S1-T1, and is matched with the bipolar molecule in one aspect, and the main material is beneficial to electron and hole injection and transmission due to the inclusion of bipolar transmission groups, so that the working voltage of a device is effectively reduced; on the other hand, the difference (delta S1-T1) between the singlet state and the triplet state of the host material is small, the triplet state excitons can easily cross to the singlet state through the intersystem, the concentration of the triplet state excitons is further reduced, quenching of the triplet state excitons is avoided, the roll-off of the device efficiency is reduced, and the service life and the stability of the device are further improved.
Drawings
Fig. 1 is a diagram of a semiconductor heterojunction structure in an embodiment showing two types (types I and II) of possible relative positions of energy levels according to the Highest Occupied Molecular Orbital (HOMO) and the Lowest Unoccupied Molecular Orbital (LUMO) when two organic semiconductor materials H1 and H2 are in contact, wherein the semiconductor heterojunction structure of type I is the energy level structure of an organic mixture according to the present invention.
Detailed Description
The invention provides a class of organic mixtures and their use in organic electronic devices. The present invention will be described in further detail below in order to make the objects, technical solutions and effects of the present invention more clear and distinct. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
In the present invention, the Host material, matrix material, host or Matrix material have the same meaning, and they are interchangeable with each other.
In the present invention, the metal-organic complex, and the organometallic complex have the same meaning and are interchangeable.
In the present invention, "substituted" in the expression "substituted or unsubstituted" means that a hydrogen atom in a substituent is substituted by a substituent, and "unsubstituted" means that a hydrogen atom on a group is not substituted by a substituent. Wherein the substituents may be selected from the group consisting of: D. f, CN, alkenyl, alkynyl, nitrile, amine, nitro, acyl, alkoxy, carbonyl, sulfone, boron-containing group, silicon-containing group, alkyl group having 1 to 50 carbon atoms (preferably 1 to 18, more preferably 1 to 8), cycloalkyl group having 3 to 50 ring atoms (preferably 3 to 10, more preferably 3 to 8, more preferably 5 or 6), aromatic hydrocarbon group or aromatic heterocyclic group having 3 to 50 ring atoms (preferably 3 to 25, more preferably 3 to 18).
In the present invention, the "number of ring atoms" means 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, a heterocyclic compound) in which atoms are bonded to form a ring. When the ring is substituted with a substituent, the atoms contained in the substituent are not included in the ring-forming atoms. The same applies to the "number of ring atoms" described below, 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, "aromatic hydrocarbon group" means a hydrocarbon group containing at least one aromatic ring, and includes monocyclic groups and polycyclic ring systems. "aromatic heterocyclic group" refers to a hydrocarbon group (containing a heteroatom) 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. Polycyclic, these cyclic species, at least one of which 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 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-diaryl fluorene, triarylamine, diaryl ether, etc., are likewise considered aromatic ring systems for the purposes of this invention.
Specifically, examples of the aromatic hydrocarbon group are: benzene, naphthalene, anthracene, phenanthrene, perylene, naphthacene, pyrene, benzopyrene, triphenylene, acenaphthene, fluorene, and derivatives thereof.
Specifically, examples of the aromatic heterocyclic group 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, naphthyridine, quinoxaline, phenanthridine, primary pyridine, quinazoline, quinazolinone, and derivatives thereof.
In the embodiment of the invention, the energy level structure of the organic material and the triplet energy level ET, HOMO, LUMO play a key role. The determination of these energy levels is described below.
HOMO and LUMO energy levels can be measured by photoelectric effects such as XPS (X-ray photoelectron spectroscopy) and UPS (ultraviolet electron spectroscopy) or by cyclic voltammetry (hereinafter referred to as CV). Recently, quantum chemical methods, such as density functional theory (hereinafter abbreviated as DFT), have also become effective methods for calculating molecular orbital energy levels.
The triplet energy level ET of an organic material can be measured by low temperature Time resolved luminescence spectroscopy, or obtained by quantum simulation calculations (e.g. by Time-dependent DFT), such as by commercial software Gaussian 03W (Gaussian inc.), specific simulation methods can be seen in WO2011141110 or as described in the examples below.
It should be noted that the absolute value of HOMO, LUMO, ET depends on the measurement or calculation method used and even for the same method, different evaluation methods, e.g. starting and peak points on the CV curve may give different HOMO/LUMO values. Thus, a reasonable and 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, the value of HOMO, LUMO, ET is based on a simulation of the Time-dependent DFT, but does not affect the application of other measurement or calculation methods.
In the invention, (HOMO-1) is defined as the second highest occupied orbital level, (HOMO-2) is the third highest occupied orbital level, and so on. (lumo+1) is defined as the second lowest unoccupied orbital level, (lumo+2) is the third lowest occupied orbital level, and so on.
The invention provides an organic mixture comprising two organic materials (H1 and H2), H1 being a compound represented by the following general formula (1):
Figure GDA0002465890330000031
Wherein L is 1 Is a single bond, a substituted or unsubstituted aromatic hydrocarbon group having 5 to 30 ring atoms or an aromatic heterocyclic group having 5 to 30 ring atoms, L 1 The connection position of (2) can be any carbon atom on the benzene ring;
X 1 represents a single bond, N (R), C (R) 5 R 6 )、Si(R 5 R 6 )、O、C＝N(R)、C＝C(R 5 R 6 ) P (R), P (=o) R, S, S =o or SO 2 ；
X 2 Represents N (R), C (R) 5 R 6 )、Si(R 5 R 6 )、O、C＝N(R)、C＝C(R 5 R 6 ) P (R), P (=o) R, S, S =o or SO 2 ；
R 1 、R 2 、R 3 、R 4 Is a substituent independently selected from H, D, F, CN, alkenyl, alkynyl, nitrile, amino, nitro, acyl, alkoxy, carbonyl, sulfonyl, substituted or unsubstituted alkyl with 1 to 30 carbon atoms, substituted or unsubstituted cycloalkyl with 3 to 30 carbon atoms, substituted or unsubstituted aromatic hydrocarbon with 5 to 60 ring atoms or substituted or unsubstituted aromatic heterocyclic with 5 to 60 ring atoms, R 1 、R 2 、R 3 、R 4 May be at any one or more carbon atoms on the fused ring;
R、R 5 、R 6 each independently represents H, D, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group having 5 to 60 ring atoms or a substituted or unsubstituted aromatic heterocyclic group having 5 to 60 ring atoms, R 5 And R is 6 Bonding or non-bonding to form a saturated or unsaturated ring structure;
H2 is another organic functional material, S1 (H2) -T1 (H2). Ltoreq.0.3 eV, wherein S1 (H2), T1 (H2) are the singlet energy level and the triplet energy level of H2 respectively.
In a preferred embodiment, the organic mixture wherein H1 and H2 form a semiconductor heterojunction structure of type I, i.e., the highest occupied orbital level (HOMO) of H1 is lower than the HOMO of H2, and the lowest unoccupied orbital Level (LUMO) of H1 is higher than the LUMO of H2. In certain embodiments, the energy gap of H1 is less than H2. In certain particularly preferred embodiments, the energy gap of H1 is greater than H2.
In a preferred embodiment, the mixture according to the invention, wherein H2 has thermally-excited delayed fluorescence (TADF) properties.
According to the principle of thermally excited delayed fluorescence TADF material (see Adachi et al, nature Vol 492,234, (2012)), when the (S1-T1) of an organic compound is sufficiently small, triplet excitons of the organic compound can be internally converted into singlet excitons by inversion, thereby achieving efficient light emission. Generally, TADF materials are obtained by linking electron donating (Donor) groups to electron withdrawing or electron withdrawing (acceptors) groups, either directly or through other groups, i.e., have a pronounced D-a structure.
The mixture according to the invention has a smaller H2 content (S1-T1), generally (S1-T1) of 0.30eV or less, preferably 0.25eV or less, more preferably 0.20eV or less, even more preferably 0.15eV or less, most preferably 0.10eV or less.
In certain embodiments, the mixture according to the invention has H2 comprising at least one electron donating group and/or at least one electron withdrawing group.
Examples of suitable groups having electron withdrawing properties are shown below, but are not limited thereto, and may be further optionally substituted:
Figure GDA0002465890330000041
examples of suitable groups having electron donating properties are shown below, but are not limited thereto, and may be further optionally substituted:
Figure GDA0002465890330000042
Figure GDA0002465890330000051
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further electron donating groups can be selected from structures comprising:
Figure GDA0002465890330000052
the further electron withdrawing group may be selected from F, cyano or a group comprising one or more of the following groups:
Figure GDA0002465890330000053
wherein n is an integer from 1 to 3; x is X 2 -X 9 Selected from CR or N, and at least one of which is N, Z 1 、Z 2 Z3 independently represents N (R) and C (R) 2 、Si(R) 2 、O、C＝N(R)、C＝C(R) 2 、P(R)、P(＝O)R、S、S＝O、SO 2 Or none, but at least one is not none; wherein R is selected from the following groups: hydrogen, alkyl, alkoxy, amino, alkene, alkyne, aralkyl, heteroalkyl, aryl, and heteroaryl.
In some particularly preferred embodiments, the electron-deficient group is selected from CN or a group formed by one or more of the structures shown below:
Figure GDA0002465890330000054
further suitable materials which can emit light as TADF for H2 can be found in the following patent or article documents: CN103483332 (a), TW201309696 (a), TW201309778 (a), TW201343874 (a), TW201350558 (a), US20120217869 (A1), WO2013133359 (A1), WO2013154064 (A1), adachi, et.al.Adv.Mater.,21,2009,4802,Adachi,et.al.Appl.Phys.Lett, 98,2011,083302, adachi, et al.appl. Phys. Lett, 101,2012,093306, adachi, et al.chem. Commun, 48,2012,11392,Adachi,et.al.Nature Photonics,6,2012,253,Adachi,et.al.Nature,492,2012,234,Adachi,et.al.J.Am.Chem.Soc,134,2012,14706,Adachi,et.al.Angew.Chem.Int.Ed,51,2012,11311,Adachi,et.al.Chem.Commun, 48,2012,9580, adachi, et al.chem. Commun, 48,2013,10385, adachi, et al.adv. Mater, 25,2013,3319, adachi, et al adv. Mate, 25,2013,3707, adachi, et al chem. Mate, 25,2013,3038, adachi, et al chem. Mate, 25,2013,3766, adachi, et al j. Mate. Chem. C.,1,2013,4599, adachi, et al j. Phys. Chem. A.,117,2013,5607, the entire contents of the above listed patent or article documents are hereby incorporated by reference.
In a preferred embodiment, the mixture according to the invention, wherein H2 is a compound of one of the following formulae (2) to (5):
Figure GDA0002465890330000061
wherein, the liquid crystal display device comprises a liquid crystal display device,
L 2 each independently represents a substituted or unsubstituted aromatic hydrocarbon group or aromatic heterocyclic group having 5 to 30 ring atoms;
L 3 represents a single bond, a substituted or unsubstituted aromatic hydrocarbon group having 5 to 30 ring atoms or a substituted or unsubstituted aromatic heterocyclic group having 5 to 30 ring atoms, L 3 The connection position of (2) can be any carbon atom on the ring;
Ar 1 、Ar 2 、Ar 3 、Ar 4 、Ar 5 、Ar 6 each independently represents a substituted or unsubstituted aromatic hydrocarbon group having 5 to 30 ring atoms or a substituted or unsubstituted aromatic heterocyclic group having 5 to 30 ring atoms;
X 3 、X 4 、X 5 、X 6 、X 7 、X 8 、X 9 、X 10 、X 11 respectively and independently represent a single bond, N (R), C (R) 5 R 6 )、Si(R 5 R 6 )、O、C＝N(R)、C＝C(R 5 R 6 ) P (R), P (=o) R, S, S =o or SO 2 And X is 4 And X 5 Not simultaneously being single bonds, X 6 And X 7 Not simultaneously being single bonds, X 8 And X 9 Not simultaneously being single bonds, X 10 And X 11 Are not single bonds at the same time;
R、R 5 、R 6 the meaning of (2) is as indicated above;
substituent R 7 、R 8 Each independently selected from H, D, F, CN, alkenyl, alkynyl, nitrile, amino, nitro, acyl, alkoxy, carbonyl, sulfonyl, substituted or unsubstituted alkyl having 1 to 30 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 30 carbon atoms, substituted or unsubstituted aromatic hydrocarbon having 5 to 60 ring atoms, and substituted or unsubstituted aromatic heterocyclic having 5 to 60 ring atoms, R 7 、R 8 May be at any one or more carbon atoms on the fused ring; n represents an integer of 1 to 6.
In certain preferred embodiments, X is represented by the general formulae (1) to (5) 1 、X 3 、X 4 、X 5 、X 6 、X 7 、X 8 、X 9 、X 10 、X 11 Are respectively and independently represented as single bond, N (R), C (R) 5 R 6 )、Si(R 5 R 6 ) O, S or SO 2 The method comprises the steps of carrying out a first treatment on the surface of the In a more preferred embodiment, X 1 、X 3 、X 4 、X 5 、X 6 、X 7 、X 8 、X 9 、X 10 、X 11 Are respectively and independently represented as single bond, N (R), C (R) 5 R 6 ) O or S; in the most preferred embodiment, X 1 、X 3 、X 4 、X 5 、X 6 、X 7 、X 8 、X 9 、X 10 、X 11 Each independently represents a single bond or N (R).
In certain preferred embodiments, X is represented by formula (1) 2 Is N (R), C (R) 5 R 6 )、Si(R 5 R 6 ) O, S or SO 2 The method comprises the steps of carrying out a first treatment on the surface of the In a more preferred embodimentIn the example, X 2 Are respectively and independently represented as N (R), C (R) 5 R 6 ) O or S; in the most preferred embodiment, X 2 Are respectively and independently represented as N (R), C (R) 5 R 6 )。
In certain preferred embodiments, the substituent R 1 、R 2 、R 3 、R 4 、R 7 、R 8 Each independently selected from H, D, CN, nitrile, substituted or unsubstituted straight-chain or substituted or unsubstituted branched alkyl having 1 to 18 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 18 carbon atoms, substituted or unsubstituted aromatic hydrocarbon having 5 to 30 ring atoms or substituted or unsubstituted aromatic heterocyclic having 5 to 30 ring atoms; in a more preferred embodiment, R 1 、R 2 、R 3 、R 4 、R 7 、R 8 Each independently represents H, D, a substituted or unsubstituted straight-chain or substituted or unsubstituted branched alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group having 5 to 20 ring atoms or a substituted or unsubstituted aromatic heterocyclic group having 5 to 20 ring atoms; in the most preferred embodiment, R 1 、R 2 、R 3 、R 4 、R 7 、R 8 Each independently represents H, D, a substituted or unsubstituted straight-chain or substituted or unsubstituted branched alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group having 5 to 15 ring atoms, or a substituted or unsubstituted aromatic heterocyclic group having 5 to 15 ring atoms.
In certain preferred embodiments R, R 5 、R 6 Each independently represents a substituted or unsubstituted straight-chain or substituted or unsubstituted branched alkyl group having 1 to 18 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 18 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group having 5 to 30 ring atoms or a substituted or unsubstituted aromatic heterocyclic group having 5 to 30 ring atoms; in the most preferred embodiment R, R 5 、R 6 Each independently represents a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 12 carbon atoms,A substituted or unsubstituted aromatic hydrocarbon group having 5 to 20 ring atoms or a substituted or unsubstituted aromatic heterocyclic group having 5 to 20 ring atoms; in the most preferred embodiment R, R 5 、R 6 Each independently represents a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 6 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group having 5 to 15 ring atoms, or a substituted or unsubstituted aromatic heterocyclic group having 5 to 15 ring atoms.
In a preferred embodiment R, R 5 、R 6 Preferably, each of them is: methyl, benzene, biphenyl, naphthalene, anthracene, phenanthrene, pyrene, pyridine, pyrimidine, triazine, fluorene, dibenzothiophene, silafluorene, carbazole, thiophene, furan, thiazole, triphenylamine, triphenylphosphine oxide, tetraphenylsilicon, spirofluorene, spirosilafluorene and other groups, more preferably benzene, biphenyl, pyridine, pyrimidine, triazine, carbazole and other groups. In a particularly preferred embodiment, R 5 And R is 6 Bonding forms a saturated or unsaturated ring structure.
In some preferred embodiments, ar represented by the general formulae (2) to (5) 1 、Ar 2 、Ar 3 、Ar 4 、Ar 5 、Ar 6 Each independently represents a substituted or unsubstituted aromatic group having 5 to 25 ring atoms or a substituted or unsubstituted aromatic hetero group having 5 to 25 ring atoms; in a more preferred embodiment, ar 1 、Ar 2 、Ar 3 、Ar 4 、Ar 5 、Ar 6 Each independently represents an aromatic group having 5 to 20 ring atoms which is substituted or unsubstituted or an aromatic hetero group having 5 to 20 ring atoms which is substituted or unsubstituted; in the most preferred embodiment, ar 1 、Ar 2 、Ar 3 、Ar 4 、Ar 5 、Ar 6 Each independently represents a substituted or unsubstituted aromatic group having 5 to 15 ring atoms or a substituted or unsubstituted aromatic hetero group having 5 to 15 ring atoms.
In some preferred embodiments, ar in formulas (2) - (5) 1 、Ar 2 、Ar 3 、Ar 4 、Ar 5 、Ar 6 May comprise one of the following structural groupsOne or more groups:
Figure GDA0002465890330000071
wherein A is 1 、A 2 、A 3 、A 4 、A 5 、A 6 、A 7 、A 8 Respectively and independently represent CR 7 Or N;
Y 1 、Y 2 are independently selected from C (R) 5 R 6 )、Si(R 5 R 6 )、NR 3 C (=o), S or O;
R 3 、R 5 、R 6 、R 7 the meaning of (2) is as indicated above.
In a more preferred embodiment, ar in formulas (2) - (5) 1 、Ar 2 、Ar 3 、Ar 4 、Ar 5 、Ar 6 Comprising one of the following structural groups, wherein the H in the ring may be optionally substituted:
Figure GDA0002465890330000072
in certain preferred embodiments, n in formulas (2), (4) represents an integer from 1 to 4; in a more preferred embodiment, n is 1 to 3; in the most preferred embodiment, n is 1 to 2.
In certain preferred embodiments, L is represented by the general formulae (1), (3), (5) 1 、L 3 Each independently represents a single bond, a substituted or unsubstituted aromatic hydrocarbon group having 5 to 25 ring atoms, or a substituted or unsubstituted aromatic hetero group having 5 to 25 ring atoms; in a more preferred embodiment, L 1 、L 3 Each independently represents a single bond, a substituted or unsubstituted aromatic group having 5 to 20 ring atoms, or a substituted or unsubstituted heteroaromatic group having 5 to 20 ring atoms; in the most preferred embodiment, L 1 、L 3 Each independently represents a single bond, a substituted or unsubstituted ring member having 5 to 15 ring atomsAn aromatic group or a substituted or unsubstituted aromatic hetero group having 5 to 15 ring atoms.
In certain preferred embodiments, L represented by the general formulae (2), (4) 2 An aromatic hydrocarbon group having 5 to 25 ring atoms which is substituted or unsubstituted or an aromatic hetero group having 5 to 25 ring atoms which is substituted or unsubstituted; in a more preferred embodiment, L 2 Is a substituted or unsubstituted aromatic group having 5 to 20 ring atoms or a substituted or unsubstituted heteroaromatic group having 5 to 20 ring atoms; in the most preferred embodiment, L 2 Is a substituted or unsubstituted aromatic group having 5 to 15 ring atoms or a substituted or unsubstituted heteroaromatic group having 5 to 15 ring atoms.
In some preferred embodiments, L in formulas (1) - (5) 1 、L 3 Can be a single bond, or L 1 、L 2 、L 3 A group which is independently selected from one or more of the following groups, which may be further substituted or unsubstituted:
Figure GDA0002465890330000081
wherein X is 12 、X 13 、X 14 Respectively and independently represent N (R), C (R) 5 R 6 )、Si(R 5 R 6 )、O、C＝N(R)、C＝C(R 5 R 6 )、P(R)、P(＝O)R、S、S＝O、SO 2 Or X 13 、X 14 One of them may be a single bond or none.
In certain embodiments, L in formulas (1) - (5) 1 、L 2 、L 3 In multiple occurrences, the following structural units, or combinations thereof, may be contained identically or differently:
Figure GDA0002465890330000082
wherein n is 1 or 2 or 3 or 4.
In some preferred embodiments, the organic mixture according to the invention, wherein H1 is selected from one of the following formulae:
Figure GDA0002465890330000091
Wherein L is 1 、X 1 、X 2 、R 1 、R 2 、R 3 、R 4 And R has the meaning indicated above.
In some preferred embodiments, the organic mixture according to the invention, wherein H2 is selected from one of the following formulae:
Figure GDA0002465890330000092
wherein Ar is 1 、Ar 2 、R 7 、R 8 、L 2 The meaning of n is as described above.
In other preferred embodiments, the organic mixture according to the invention, wherein H2 is selected from one of the following formulae:
Figure GDA0002465890330000093
wherein Ar is 1 、Ar 5 、X 4 、X 5 、X 6 、X 7 、R 7 、R 8 The meaning of (2) is as described above.
In other preferred embodiments, the organic mixture according to the invention, wherein H2 is selected from one of the following formulae:
Figure GDA0002465890330000101
wherein Ar is 2 、Ar 3 、X 3 、X 4 、X 5 、R 7 、R 8 、L 2 The meaning of n is as described above.
In other preferred embodiments, the organic mixture according to the invention, wherein H2 is selected from one of the following formulae:
Figure GDA0002465890330000102
wherein Ar is 1 、Ar 2 、Ar 5 、Ar 6 、X 4 、X 5 、X 6 、X 7 、X 8 、X 9 、X 10 、X 11 、R 7 、R 8 The meaning of (2) is as described above.
In a very preferred embodiment, the organic mixture is used for a light-emitting layer in an organic electroluminescent device. There are sometimes special requirements for H1 and H2 for stability or process considerations.
In a preferred embodiment, the organic mixture according to the invention, wherein at least one of H1 and H2 ((LUMO+1) -LUMO) is not less than 0.1eV, preferably not less than 0.15eV, more preferably not less than 0.20eV, even more preferably not less than 0.25eV, most preferably not less than 0.30eV.
In another preferred embodiment, the organic mixture according to the invention, wherein at least one of H1 and H2 has a value (HOMO- (HOMO-1)). Gtoreq.0.2 eV, preferably. Gtoreq.0.25 eV, more preferably. Gtoreq.0.30 eV, even more preferably. Gtoreq.0.35 eV, most preferably. Gtoreq.0.40 eV.
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 preferably the molar ratio is from 4:6 to 6:4.
In a preferred embodiment, the H1 and H2 in the organic mixture according to the invention have at least one of their glass transition temperatures T g Not less than 100℃and in a preferred embodiment at least one of them T g Not less than 120℃and in a preferred embodiment at least one of them T g 140℃or more, in a more preferred embodiment, at least one of them T g Not less than 160 ℃, in a most preferred solid stateIn an embodiment, at least one of them T g ≥180℃。
In a preferred embodiment, at least one of H1 and H2 in the organic mixture according to the invention is partially deuterated, preferably 10% H, more preferably 20% H, most preferably 30% H, most preferably 40% H.
In a preferred embodiment, in the organic mixture according to the invention, both H1 and H2 are a small molecule material.
It is an object of the present invention to provide a material solution for an evaporated OLED.
In a preferred embodiment, the organic mixture according to the invention is used in an evaporative OLED device. For this purpose, the molecular weights of H1 and H2 in the organic mixture according to the invention are 1000g/mol or less, preferably 900g/mol or less, very preferably 850g/mol or less, more preferably 800g/mol or less, most preferably 700g/mol or less.
In a preferred embodiment, the organic mixture wherein the difference in molecular weight between H1 and H2 is no more than 100Dalton; preferably the difference in molecular weight does not exceed 60 daltons; more preferably, the difference in molecular weight is not more than 30 daltons.
In another preferred embodiment, the organic mixture, wherein the difference in sublimation temperatures of H1 and H2 is no more than 30K; preferably the difference in sublimation temperature does not exceed 20K; more preferably, the difference in sublimation temperature does not exceed 10K.
It is another object of the invention to provide a material solution for printed OLEDs.
For this purpose, at least one, preferably both, of the H1 and H2 in the organic mixture according to the invention has a molecular weight of not less than 700g/mol, preferably not less than 800g/mol, very preferably not less than 900g/mol, more preferably not less than 1000g/mol, most preferably not less than 1100g/mol.
In the co-host in the form of Premix in vapor-deposited OLEDs, two host materials are required to have similar chemical properties or physical properties, such as molecular weight, sublimation temperature. The present inventors have found that in solution processed OLEDs, two host materials with different properties may improve film forming properties, thereby improving the performance of the device. The properties may be other than molecular weight, sublimation temperature, such as glass transition temperature, different molecular volumes, etc. Thus printing the OLED, preferred embodiments of the organic mixture according to the invention are:
1) The difference in molecular weight between H1 and H2 is not less than 120g/mol, preferably not less than 140g/mol, more preferably not less than 160g/mol, most preferably not less than 180g/mol.
2) The difference in sublimation temperature between H1 and H2 is not less than 60K, preferably not less than 70K, more preferably not less than 75K, and most preferably not less than 80K.
3) The difference in glass transition temperature between H1 and H2 is not less than 20K, preferably not less than 30K, more preferably not less than 40K, most preferably not less than 45K.
4) The difference in molecular volumes of H1 and H2 is not less than 20%, preferably not less than 30%, more preferably not less than 40%, most preferably not less than 45%.
In other embodiments, at least one, and preferably both, of H1 and H2 in the mixture 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 term "small molecule" as defined herein refers to a molecule that is not a polymer, oligomer, dendrimer, or blend. In particular, there is no repeating structure in small molecules. The molecular weight of the small molecules is less than or equal to 3000 g/mol, preferably less than or equal to 2000 g/mol, and most preferably less than or equal to 1500 g/mol.
Polymers, i.e., polymers, include homopolymers, copolymers, and block copolymers. In addition, in the present invention, the polymer also includes dendrimers (dendrimers), and for synthesis and use of dendrimers, see [ Dendrimers and Dendrons, wiley-VCH Verlag GmbH & Co.KGaA,2002,Ed.George R.Newkome,Charles N.Moorefield,Fritz Vogtle ].
Conjugated polymers (conjugated polymer) are polymers whose backbone backbond is composed mainly of sp2 hybridized orbitals of C atoms, well-known examples being: polyacetylene and poly (phenylene vinylene), whose main chain may also be substituted with other non-C atoms, are still considered conjugated polymers when the sp2 hybridization on the main chain is interrupted by some natural defect. In addition, the conjugated polymer of the present invention includes aryl amine (aryl amine), aryl phosphine (aryl phosphine), other heterocyclic aromatic hydrocarbon (heteroaromolics), organometallic complex (organometallic complexes) and the like.
In certain preferred embodiments, the organic mixture wherein H1 and H2 form a type I heterojunction structure and H1 has an energy gap greater than H2, i.e., HOMO of H1) lower than HOMO of H2, H1 has a (LUMO) higher than LUMO of H1, i.e., HOMO (H1) < HOMO (H2), LUMO (H1) > LUMO (H2).
In a preferred embodiment, the organic mixture has a HOMO (H1) < HOMO (H2) +0.05eV, a LUMO (H1) > LUMO (H2) -0.05eV.
In a preferred embodiment, the organic mixture has a HOMO (H1) < HOMO (H2) +0.1eV, a LUMO (H1) > LUMO (H2) -0.1eV.
In a more preferred embodiment, the organic mixture has a HOMO (H1) < HOMO (H2) +0.15eV, a LUMO (H1) > LUMO (H2) -0.15eV.
In a most preferred embodiment, the organic mixture has a HOMO (H1) < HOMO (H2) +0.2eV, a LUMO (H1) > LUMO (H2) -0.2eV.
Specific examples of the compounds represented by the general formula (1) are shown below, but are not limited thereto:
Figure GDA0002465890330000121
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Figure GDA0002465890330000131
/>
Figure GDA0002465890330000141
/>
Figure GDA0002465890330000151
specific examples of the compounds represented by the general formula (2) are shown below, but are not limited thereto:
Figure GDA0002465890330000152
/>
Figure GDA0002465890330000161
specific examples of the compounds represented by the general formula (3) are shown below, but are not limited thereto:
Figure GDA0002465890330000162
/>
Figure GDA0002465890330000171
specific examples of the compounds represented by the general formula (4) are shown below, but are not limited thereto:
Figure GDA0002465890330000181
/>
Figure GDA0002465890330000191
/>
Figure GDA0002465890330000201
Specific examples of the compounds represented by the general formula (5) are shown below, but are not limited thereto:
Figure GDA0002465890330000202
examples of suitable characteristics of TADF as H2 are set forth in the following table:
Figure GDA0002465890330000203
/>
Figure GDA0002465890330000211
/>
Figure GDA0002465890330000221
in a particularly preferred embodiment, the organic mixture further comprises another organic functional material. The other organic functional materials include hole (also called hole) injecting or transporting materials (HIM/HTM), hole Blocking Materials (HBM), electron injecting or transporting materials (EIM/ETM), electron Blocking Materials (EBM), organic Host materials (Host), singlet state light emitters (fluorescent light emitters), singlet state light emitters (phosphorescent light emitters), organic thermally excited delayed fluorescent materials (TADF materials), especially luminescent organometallic complexes. Various organic functional materials are described in detail in, for example, WO2010135519A1, US20090134784A1 and WO2011110277A1, the entire contents of which 3 patent documents are hereby incorporated by reference. The organic functional material may be small molecule and high polymer materials. In certain preferred embodiments, the organic mixture further comprises a luminescent material selected from the group consisting of fluorescent, phosphorescent, and TADF materials.
In a preferred embodiment, the organic mixture comprises H1 and H2, and a phosphorescent emitter. Wherein the weight percentage of the phosphorescent light-emitting body is less than or equal to 30wt%, preferably less than or equal to 25wt%, more preferably less than or equal to 20wt%.
In another preferred embodiment, the organic mixture comprises H1 and H2, and a fluorescent emitter. Wherein the weight percentage of the fluorescent light-emitting body is less than or equal to 15wt%, preferably less than or equal to 10wt%, and more preferably less than or equal to 8wt%.
In another preferred embodiment, the organic mixture comprises H1 and H2, and a TADF luminescent material. Wherein the weight percentage of the TADF luminescent material is less than or equal to 15 percent, preferably less than or equal to 10 percent, more preferably less than or equal to 8 percent.
Some more detailed descriptions of fluorescent light-emitting materials or singlet light-emitting materials, phosphorescent light-emitting materials or triplet light-emitting materials are provided below (but are not limited thereto).
1. Singlet illuminant (Singlet Emitter)
Singlet emitters tend to have longer conjugated pi electron systems. Heretofore, there have been many examples such as styrylamine and its derivatives disclosed in JP2913116B and WO2001021729A1, and indenofluorene and its derivatives disclosed in WO2008/006449 and WO 2007/140847.
In a preferred embodiment, the singlet light emitters may be selected from the group consisting of monobasic styrenes, dibasic styrenes, tribasic styrenes, quaternary styrenes, styrenes phosphines, styrenes ethers and aromatic amines.
A monostyramine is a compound which comprises an unsubstituted or substituted styryl group and at least one amine, preferably an aromatic amine. A binary styrylamine is a compound comprising two unsubstituted or substituted styryl groups and at least one amine, preferably an aromatic amine. A ternary styrylamine is a compound which comprises three unsubstituted or substituted styryl groups and at least one amine, preferably an aromatic amine. A quaternary styrylamine is a compound comprising four unsubstituted or substituted styryl groups and at least one amine, preferably an aromatic amine. One preferred styrene is stilbene, which may be further substituted. The definition of the corresponding phosphines and ethers is similar to that of the amines. Aryl amine or aromatic amine refers to a compound comprising three unsubstituted or substituted aromatic or heterocyclic ring 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 anthraceneamines, aromatic anthracenediamines, aromatic pyrenamines, aromatic pyrenediamines, aromatic droxylamines and aromatic Qu Eran. An aromatic anthraceneamine is a compound in which a biaryl amine group is attached directly to the anthracene, preferably in the 9 position. An aromatic anthracenediamine is a compound in which two biaryl amine groups are attached directly to the anthracene, preferably in the 9, 10 position. Aromatic pyrenamines, aromatic flexoamines and aromatic flexodiamines are defined similarly, with the biaryl amine groups preferably attached to the 1 or 1,6 positions of pyrene.
Examples of singlet emitters based on vinylamines and arylamines are also preferred and can be found in WO2006/000388, WO2006/058737, WO2006/000389, WO2007/065549, WO2007/115610,US7250532 B2,DE102005058557 A1,CN1583691 A,JP08053397 A,US6251531 B1,US2006/210830 A,EP1957606 A1 and US 2008/0110101 A1, the entire contents of which are hereby incorporated by reference.
An example of a singlet light emitter based on stilbene and its derivatives is US5121029.
Further preferred singlet emitters may be selected from indenofluorene-amines and indenofluorene-diamines, as disclosed in WO2006/122630, benzoindenofluorene-amines and benzoindenofluorene-diamines, as disclosed in WO 2008/006449, dibenzoindenofluorene-amines and dibenzoindenofluorene-diamines, as disclosed in WO 2007/140847.
Other materials which can be used as singlet emitters are polycyclic aromatic compounds, in particular derivatives of the following compounds: anthracene such as 9, 10-bis (2-naphthacene), naphthalene, tetraphenyl, xanthene, phenanthrene, pyrene (e.g., 2,5,8, 11-tetra-t-butylperylene), indenopyrene, phenylene such as (4, 4 '-bis (9-ethyl-3-carbazolyl) -1,1' -biphenyl), bisindenopyrene, decacyclic olefin, hexabenzobenzene, fluorene, spirobifluorene, arylpyrene (e.g., US 20060222886), arylene ethylene (e.g., US5121029, US 5130603), 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 compound (US 2007/0075753 A1), bis (azinyl) methylene compound, carboyryl compound, stzinone, benzoxazole, benzothiazole, benzimidazole and pyrrolodiketone. Some materials for singlet emitters can be found in US20070252517 A1, US4769292, US6020078, US2007/0252517 A1,US2007/0252517 A1. The entire contents of the above listed patent documents are hereby incorporated by reference.
Examples of some suitable singlet emitters are set forth in the following table:
Figure GDA0002465890330000231
Figure GDA0002465890330000241
2. triplet Emitter (Triplet Emitter)
Triplet emitters are also known as phosphorescent emitters. In a preferred embodiment, the triplet emitter is of the formula M (L) n Wherein M is a metal atom, L, which may be the same or different at each occurrence, is an organic ligand bonded or coordinately bound to metal atom M at one or more positions, and n is an integer greater than 1, preferably 1,2,3,4,5 or 6. Optionally, the metal complexes are attached to a polymer via one or more positions, preferably via organic ligands.
In a preferred embodiment, the metal atom M is selected from the group consisting of transition metal elements or lanthanoids or actinoids, preferably Ir, pt, pd, au, rh, ru, os, sm, eu, gd, tb, dy, re, cu or Ag, particularly preferably Os, ir, ru, rh, re, pd or Pt.
Preferably, the triplet emitter comprises a chelating ligand, i.e. a ligand, coordinated to the metal via at least two binding sites, it being particularly preferred to consider that the triplet emitter comprises two or three identical or different bidentate or polydentate ligands. Chelating ligands are beneficial for improving the stability of metal complexes.
Examples of organic ligands may be selected from phenylpyridine derivatives, 7, 8-benzoquinoline derivatives, 2 (2-thienyl) pyridine derivatives, 2 (1-naphthyl) pyridine derivatives, or 2-phenylquinoline derivatives. All of these organic ligands may be substituted, for example by fluorine or trifluoromethyl. The auxiliary ligand may preferably be selected from acetone acetate or picric acid.
In a preferred embodiment, the metal complexes useful as triplet emitters are of the form:
Figure GDA0002465890330000242
wherein M is a metal selected from the group consisting of transition metal elements or lanthanides or actinides;
Ar 1 each occurrence, which may be the same or different, is a cyclic group containing at least one donor atom, i.e., an atom having a lone pair of electrons, such as nitrogen or phosphorus, through which the cyclic group is coordinately bound to the metal; ar (Ar) 2 Each occurrence, which may be the same or different, is a cyclic group containing at least one C atom through which the cyclic group is attached to the metal; ar (Ar) 1 And Ar is a group 2 Are linked together by covalent bonds, may each carry one or more substituent groups, and may be linked together again by substituent groups; l, which may be the same or different for each occurrence, is a ancillary ligand, preferably a bidentate chelating ligand, preferably a monoanionic bidentate chelating ligand; m is 1,2 or 3, preferably 2 or 3, particularly preferably 3; n is 0,1 or 2, preferably 0 or 1, particularly preferably 0;
Examples of materials and applications of some triplet emitters can be found in the following patent documents and literature: WO 200070655,WO 200141512,WO 200202714,WO 200215645,EP 1191613,EP 1191612,EP 1191614,WO 2005033244,WO 2005019373,US 2005/0258742,WO 2009146770,WO 2010015307,WO 2010031485,WO 2010054731,WO 2010054728,WO 2010086089,WO 2010099852,WO 2010102709,US 20070087219 A1,US 20090061681A1,US 20010053462A1,Baldo,Thompson et al.Nature 403, (2000), 750-753,US 20090061681A1,US 20090061681A1,Adachi et al.Appl.Phys.Lett.78 (2001), 1622-1624,J.Kido et al.Appl.Phys.Lett.65 (1994), 2124,Kido et al.Chem.Lett.657, 1990,US 2007/0252517 A1,Johnson et al, JACS 105, 1983, 1795,Wrighton,JACS 96, 1974, 998, ma et al, synth.metals 94, 1998, 245,US 6824895,US 7029766,US 6835469,US 6830828,US 20010053462A1,WO 2007095118 A1,US 2012004407A1,WO 2012007088A1,WO2012007087A1,WO 2012007086A1,US 2008027220A1,WO 2011157339A1,CN 102282150A,WO 2009118087A1. The entire contents of the above listed patent documents and literature are hereby incorporated by reference.
Examples of some suitable triplet emitters are set forth in the following table:
Figure GDA0002465890330000251
/>
Figure GDA0002465890330000261
in certain embodiments, the organic mixture according to the invention has a solubility in toluene of 10mg/ml or more, preferably 15mg/ml or more, most preferably 20mg/ml or more at 25 ℃.
The invention further relates to a composition or ink comprising an organic mixture as described above and at least one organic solvent.
When used in the printing process, the viscosity and surface tension of the ink are important parameters. The surface tension parameters of a suitable ink are suitable for a particular substrate and a particular printing method.
In a preferred embodiment, the ink according to the invention has a surface tension in the range of about 19dyne/cm to 50dyne/cm at an operating temperature or at 25 ℃; more preferably in the range of 22dyne/cm to 35 dyne/cm; preferably in the range of 25dyne/cm to 33 dyne/cm.
In another preferred embodiment, the ink according to the present invention has a viscosity in the range of about 1cps to 100cps at the operating temperature or 25 ℃; preferably in the range of 1cps to 50 cps; more preferably in the range of 1.5cps to 20 cps; and preferably in the range of 4.0cps to 20 cps. The composition so formulated will facilitate ink jet printing.
The viscosity can be adjusted by different methods, such as by appropriate solvent selection and concentration of functional material in the ink. The inks according to the invention comprising said organic mixtures can be conveniently adjusted to the printing process used in the printing ink in the appropriate range. Generally, the composition according to the invention comprises functional materials in a weight ratio ranging from 0.3% to 30% by weight, preferably ranging from 0.5% to 20% by weight, more preferably ranging from 0.5% to 15% by weight, even more preferably ranging from 0.5% to 10% by weight, most preferably ranging from 1% to 5% by weight.
In some embodiments, the at least one organic solvent is selected from aromatic or heteroaromatic based solvents, particularly aliphatic chain/ring substituted aromatic solvents, or aromatic ketone solvents, or aromatic ether solvents, in accordance with the inks of the present invention.
Examples of solvents suitable for the present invention are, but are not limited to: aromatic or heteroaromatic-based solvents such as p-diisopropylbenzene, pentylbenzene, tetrahydronaphthalene, cyclohexylbenzene, chloronaphthalene, 1, 4-dimethylnaphthalene, 3-isopropylbiphenyl, p-methylcumene, dipentylbenzene, tripentylbenzene, pentyltoluenes, 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-methylcumene, 1-methylnaphthalene, 1,2, 4-trichlorobenzene, 1, 3-dipropoxybenzene, 4-difluorodiphenylmethane, 1, 2-dimethoxy-4- (1-propenyl) benzene, diphenylmethane, 2-phenylpyridine, 3-phenylpyridine, N-methyldiphenylamine, 4-isopropylbiphenyl, dichlorodiphenylmethane, 4- (3-phenylpyridine) and (1, 3-diphenylethane, 3-dibenzyl) benzyl ether; ketone-based solvents such as 1-tetralone, 2- (phenylepoxy) tetralone, 6- (methoxy) tetralone, acetophenone, propiophenone, benzophenone, and derivatives thereof, e.g., 4-methylacetophenone, 3-methylacetophenone, 2-methylacetophenone, 4-methylbenzophenone, 3-methylbenzophenone, 2-methylbenzophenone, isophorone, 2,6, 8-trimethyl-4-nonone, fenchyl ketone, 2-nonone, 3-nonone, 5-nonone, 2-decanone, 2, 5-hexanedione, isophorone, di-n-amyl ketone; aromatic ether solvent: 3-phenoxytoluene, butoxybenzene, benzylbutylbenzene, p-anisaldehyde dimethyl acetal, tetrahydro-2-phenoxy-2H-pyran, 1, 2-dimethoxy-4- (1-propenyl) benzene, 1, 4-benzodioxane, 1, 3-dipropylbenzene, 2, 5-dimethoxytoluene, 4-ethylben-ther, 1,2, 4-trimethoxybenzene, 4- (1-propenyl) -1, 2-dimethoxybenzene, 1, 3-dimethoxybenzene, glycidyl phenyl ether, dibenzyl ether, 4-t-butyl anisole, trans-p-propenyl anisole, 1, 2-dimethoxybenzene, 1-methoxynaphthalene, diphenyl ether, 2-phenoxymethyl ether, 2-phenoxytetrahydrofuran, 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, the at least one solvent according to the ink of the present invention may be selected from: aliphatic ketones such as 2-nonene, 3-nonene, 5-nonene, 2-decanone, 2, 5-hexanedione, 2,6, 8-trimethyl-4-nonene, 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 ink further comprises another organic solvent. Examples of other organic solvents 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-trichloroethane, 1, 2-tetrachloroethane, ethyl acetate, butyl acetate, dimethylformamide, dimethylacetamide, dimethylsulfoxide, 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 according to embodiments of the invention may comprise from 0.01 to 20% by weight of the organic mixture according to the invention, preferably from 0.1 to 15% by weight, more preferably from 0.2 to 10% by weight, most preferably from 0.25 to 5% by weight of the organic mixture.
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 printing or coating.
Suitable Printing or coating techniques include, but are not limited to, ink jet Printing, spray Printing (nozle Printing), letterpress Printing, screen Printing, dip coating, spin coating, doctor blade coating, roller Printing, twist roller Printing, lithographic Printing, flexography, rotary Printing, spray coating, brush or pad Printing, slot die coating, and the like. Gravure printing, inkjet printing and inkjet 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, etc., for adjusting viscosity, film forming properties, improving adhesion, etc. For details on printing techniques and their associated requirements for solutions, such as solvent and concentration, viscosity, etc., see the handbook of printing media, techniques and methods of manufacture, by Helmut Kipphan (Handbook of Print Media: technologies and Production Methods), ISBN 3-540-67326-1.
Based on the organic mixture, the invention also provides an application of the organic mixture to an organic electronic device, wherein the organic electronic device can be selected from Organic Light Emitting Diodes (OLED), organic photovoltaic cells (OPV), organic light emitting cells (OLEEC), organic Field Effect Transistors (OFET), organic light emitting field effect transistors, organic lasers, organic spintronic devices, or organic sensors, organic plasmon emitting diodes (Organic Plasmon Emitting Diode), and the like, and particularly OLED. In embodiments of the present invention, the organic mixture is preferably used for the light emitting layer of an OLED device.
The invention further provides an organic electronic device comprising at least one mixture as described above.
In some preferred embodiments, the organic electronic device is an Organic Light Emitting Diode (OLED), an organic photovoltaic cell (OPV), an organic light emitting cell (OLEEC), an Organic Field Effect Transistor (OFET), an organic light emitting field effect transistor, an organic sensor, or an organic plasmon emitting diode (Organic Plasmon Emitting Diode).
In some more preferred embodiments, the organic electronic device is an electroluminescent device comprising a substrate, an anode, at least one light-emitting layer, a cathode, optionally further comprising a hole transport layer or an electron transport layer. In certain embodiments, an organic mixture according to the present invention is included in the hole transport layer. In a preferred embodiment, an organic mixture according to the invention is contained in the light-emitting layer, more preferably a mixture according to the invention, and at least one light-emitting material, which may preferably be a fluorescent, phosphorescent or TADF material, is contained in the light-emitting layer.
The device structure of the electroluminescent device is described below, but is not limited thereto.
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, p2606. The substrate may be rigid or elastic. The substrate may be plastic, metal, semiconductor wafer or glass. Preferably, the substrate has a smooth surface. Substrates without surface defects are a particularly desirable choice. In a preferred embodiment, the substrate is flexible, optionally in the form of a polymer film or plastic, having a glass transition temperature Tg of 150℃or higher, preferably over 200℃and more preferably over 250℃and most preferably over 300 ℃. 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 a light emitting 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 of the p-type semiconductor material as HIL or HTL or Electron Blocking Layer (EBL) is less than 0.5eV, preferably less than 0.3eV, most preferably less than 0.2eV. 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 patterned. 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 or conduction band level of the emitter in the light emitting layer or of the n-type semiconductor material as an Electron Injection Layer (EIL) or Electron Transport Layer (ETL) or Hole Blocking Layer (HBL) is less than 0.5eV, preferably less than 0.3eV, and most preferably less than 0.2eV. In principle, all materials which can be used as cathode of an OLED 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, baF2/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 further include other 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). Materials suitable for use in these functional layers are described in detail above and in WO2010135519A1, US20090134784A1 and WO2011110277A1, the entire contents of which 3 patent documents are hereby incorporated by reference.
In a preferred embodiment, the electroluminescent device according to the invention comprises a light-emitting layer comprising the organic mixture according to the invention.
In another preferred embodiment, the electroluminescent device, wherein the light emitting layer may be formed by one of the following two methods: (1) The mixture comprising H1 and H2 is deposited as a source; (2) H1 and H2 were evaporated as separate two sources.
In a further preferred embodiment, the electron transport layer of the electroluminescent device according to the invention comprises the organic mixture according to the invention.
The light emitting device according to the present invention has a light emitting wavelength of 300 to 1000nm, preferably 350 to 900nm, more preferably 400 to 800 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 invention will be described in connection with the preferred embodiments, but the invention is not limited thereto, and it will be appreciated that the appended claims summarize the scope of the invention and those skilled in the art who have the benefit of this disclosure will recognize certain changes that may be made to the embodiments of the invention and that are intended to be covered by the spirit and scope of the appended claims.
1. The synthetic methods of the compounds according to the present invention are exemplified, but the present invention is not limited to the following examples.
(1) Synthesis of Compound (1-1):
Figure GDA0002465890330000291
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1)
Figure GDA0002465890330000292
under the nitrogen environment, adding (31.2 g,100 mmol) of compound 1-1 and (250 mL) anhydrous tetrahydrofuran into a 500mL three-port bottle, cooling to-78 ℃, slowly dropwise adding 100mmol of n-butyllithium, reacting for 1.5 hours, then adding (18 g,100 mmol) of compound 1-1-2 at one time, naturally heating the reaction to room temperature, continuing the reaction for 12 hours, adding pure water for quenching reaction, extracting with dichloromethane and washing 3 times after most of solvent is removed, collecting an organic phase, and performing column chromatography purification after spin drying, wherein the yield is 85%.
2)
Figure GDA0002465890330000293
The (28.9 g,70 mmol) of compound 1-1-3, (150 mL) acetic acid and (10 mL) hydrochloric acid were added into a 250mL three-necked flask, the reaction was heated and refluxed for 4 hours, after the reaction was completed, the reaction was allowed to cool to room temperature, the pure water was added to quench the reaction, the extraction and washing with methylene chloride were performed for 3 times, the organic phase was collected, and after spinning dry, recrystallization was performed, the yield was 90%.
3)
Figure GDA0002465890330000301
Under the nitrogen environment, adding (19.8 g,50 mmol) of compound 1-1-4 and 200mL of anhydrous tetrahydrofuran into a 500mL three-port bottle, cooling to-78 ℃, slowly dropwise adding 55mmol of n-butyllithium, reacting for 1.5 hours, injecting 60mmol of isopropanol pinacol borate at one time, naturally heating the reaction to room temperature, continuing the reaction for 12 hours, adding pure water for quenching reaction, extracting and washing with dichloromethane for 3 times after most of solvent is removed, collecting an organic phase, and performing column chromatography purification after spin drying, wherein the yield is 85%.
4)
Figure GDA0002465890330000302
Under nitrogen atmosphere, (11.9 g,30 mmol) of compound 1-1-4 and (13.3 g,30 mmol) of compound 1-1-5, (1.73 g,1.5 mmol) of tetra (triphenylphosphine) palladium, (1.3 g,4 mmol) of tetrabutylammonium bromide, (1.6 g,40 mmol) of sodium hydroxide, (10 mL) of water and (60 mL) of toluene were added to a 150mL three-necked flask, the reaction was stirred at 80℃for 12 hours, the reaction was ended, most of the solvent was rotationally evaporated, the mixture was washed with dichloromethane for 3 times, and the organic solution was collected and purified by passing through a silica gel column in 85% yield.
(2) Synthesis of Compound (1-4):
Figure GDA0002465890330000303
1)
Figure GDA0002465890330000304
under the nitrogen environment, adding (23.3 g,100 mmol) of compound 1-4-1 and (250 mL) of anhydrous tetrahydrofuran into a 500mL three-port bottle, cooling to-78 ℃, slowly dropwise adding 100mmol of n-butyllithium, reacting for 1.5 hours, then adding (25.9 g,100 mmol) of compound 1-4-2 at one time, naturally heating to room temperature, continuing reacting for 12 hours, adding pure water for quenching reaction, screwing most of solvent, extracting with dichloromethane and washing 3 times, collecting an organic phase, and performing column chromatography purification after spin drying, wherein the yield is 85%.
2)
Figure GDA0002465890330000305
The (28.9 g,70 mmol) of compound 1-4-3, (150 mL) acetic acid and (10 mL) hydrochloric acid were added into a 250mL three-necked flask, the reaction was heated and refluxed for 4 hours, after the reaction was completed, the reaction was allowed to cool to room temperature, the pure water was added to quench the reaction, the extraction and washing with methylene chloride were performed for 3 times, the organic phase was collected, and after spinning dry, recrystallization was performed, the yield was 90%.
3)
Figure GDA0002465890330000311
Under the nitrogen environment, adding (19.8 g,50 mmol) of compound 1-4 and 200mL of anhydrous tetrahydrofuran into a 500mL three-port bottle, cooling to-78 ℃, slowly dropwise adding 55mmol of n-butyllithium, reacting for 1.5 hours, injecting 60mmol of isopropanol pinacol borate at one time, naturally heating the reaction to room temperature, continuing the reaction for 12 hours, adding pure water for quenching reaction, extracting and washing with dichloromethane for 3 times after most of solvent is removed, collecting an organic phase, and performing column chromatography purification after spin drying, wherein the yield is 85%.
4)
Figure GDA0002465890330000312
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Under nitrogen atmosphere, (11.9 g,30 mmol) of compound 1-4-4 and (13.3 g,30 mmol) of compound 1-4-5, (1.73 g,1.5 mmol) of tetra (triphenylphosphine) palladium, (1.3 g,4 mmol) of tetrabutylammonium bromide, (1.6 g,40 mmol) of sodium hydroxide, (10 mL) of water and (60 mL) of toluene were added to a 150mL three-necked flask, the reaction was stirred at 80℃for 12 hours, the reaction was ended, most of the solvent was rotationally evaporated, the mixture was washed with dichloromethane for 3 times, and the organic solution was collected and purified by passing through a silica gel column in 85% yield.
(3) Synthesis of Compound (1-6):
Figure GDA0002465890330000313
1)
Figure GDA0002465890330000314
under the nitrogen environment, adding (23.3 g,100 mmol) of compound 1-4-1 and (250 mL) of anhydrous tetrahydrofuran into a 500mL three-port bottle, cooling to-78 ℃, slowly dropwise adding 100mmol of n-butyllithium, reacting for 1.5 hours, then adding (25.8 g,100 mmol) of compound 1-6-1 at one time, naturally heating to room temperature, continuing reacting for 12 hours, adding pure water for quenching reaction, screwing most of solvent, extracting with dichloromethane and washing 3 times, collecting an organic phase, and performing column chromatography purification after spinning to obtain the product with 85 percent of yield.
2)
Figure GDA0002465890330000315
The (28.9 g,70 mmol) of compound 1-6-2, (150 mL) acetic acid and (10 mL) hydrochloric acid were added into a 250mL three-necked flask, the reaction was heated and refluxed for 4 hours, after the reaction was completed, the reaction was allowed to cool to room temperature, the pure water was added to quench the reaction, the extraction and washing with methylene chloride were performed for 3 times, the organic phase was collected, and after spinning dry, recrystallization was performed, the yield was 90%.
3)
Figure GDA0002465890330000321
Under the nitrogen environment, adding (19.8 g,50 mmol) of compound 1-6-3 and 200mL of anhydrous tetrahydrofuran into a 500mL three-port bottle, cooling to-78 ℃, slowly dropwise adding 55mmol of n-butyllithium, reacting for 1.5 hours, injecting 60mmol of isopropanol pinacol borate at one time, naturally heating the reaction to room temperature, continuing the reaction for 12 hours, adding pure water for quenching reaction, extracting and washing with dichloromethane for 3 times after most of solvent is removed, collecting an organic phase, and performing column chromatography purification after spin drying, wherein the yield is 85%.
4)
Figure GDA0002465890330000322
Under nitrogen atmosphere, (11.9 g,30 mmol) of compound 1-6-3 and (13.3 g,30 mmol) of compound 1-6-4, (1.73 g,1.5 mmol) of tetra (triphenylphosphine) palladium, (1.3 g,4 mmol) of tetrabutylammonium bromide, (1.6 g,40 mmol) of sodium hydroxide, (10 mL) of water and (60 mL) of toluene were added to a 150mL three-necked flask, the reaction was stirred at 80℃for 12 hours, the reaction was ended, most of the solvent was rotationally evaporated, the mixture was washed with dichloromethane for 3 times, and the organic solution was collected and purified by passing through a silica gel column in 85% yield.
(4) Synthesis of Compound (1-10):
Figure GDA0002465890330000323
1)
Figure GDA0002465890330000324
under the nitrogen environment, adding (24.8 g,100 mmol) of compound 1-10-1 and (250 mL) of anhydrous tetrahydrofuran into a 500mL three-port bottle, cooling to-78 ℃, slowly dropwise adding 100mmol of n-butyllithium, reacting for 1.5 hours, then adding (25.8 g,100 mmol) of compound 1-10-2 at one time, naturally heating to room temperature, continuing reacting for 12 hours, adding pure water for quenching reaction, screwing most of solvent, extracting with dichloromethane and washing 3 times, collecting an organic phase, and performing column chromatography purification after spin drying, wherein the yield is 85%.
2)
Figure GDA0002465890330000325
The (30.0 g,70 mmol) of compound 1-10-3, (150 mL) acetic acid and (10 mL) hydrochloric acid are added into a three-necked flask of 250mL, the mixture is heated and refluxed for 4 hours, after the reaction is completed, the reaction is cooled to normal temperature, pure water is added for quenching reaction, dichloromethane is used for extraction and washing for 3 times, an organic phase is collected, and recrystallization is carried out after spin drying, so that the yield is 90%.
3)
Figure GDA0002465890330000331
Under nitrogen atmosphere, (12.3 g,30 mmol) of compound 1-10-4 and (13.3 g,30 mmol) of compound 1-1-5, (1.73 g,1.5 mmol) of tetra (triphenylphosphine) palladium, (1.3 g,4 mmol) of tetrabutylammonium bromide, (1.6 g,40 mmol) of sodium hydroxide, (10 mL) of water and (60 mL) of toluene were added to a 150mL three-necked flask, the reaction was stirred at 80℃for 12 hours, the reaction was ended, most of the solvent was rotationally evaporated, the mixture was washed with dichloromethane for 3 times, and the organic solution was collected and purified by passing through a silica gel column in 85% yield.
(5) Synthesis of Compound (1-14):
Figure GDA0002465890330000332
1)
Figure GDA0002465890330000333
under the nitrogen environment, adding (31.2 g,100 mmol) of compound 1-14-1 and (250 mL) of anhydrous tetrahydrofuran into a 500mL three-port bottle, cooling to-78 ℃, slowly dropwise adding 100mmol of n-butyllithium, reacting for 1.5 hours, then adding (34.4 g,100 mmol) of compound 1-14-2 at one time, naturally heating to room temperature, continuing reacting for 12 hours, adding pure water for quenching reaction, screwing most of solvent, extracting with dichloromethane and washing 3 times, collecting an organic phase, and performing column chromatography purification after spin drying to obtain the product with the yield of 80%.
2)
Figure GDA0002465890330000334
The (40.4 g,70 mmol) of compound 1-14-3, (150 mL) acetic acid and (10 mL) hydrochloric acid are added into a three-necked flask of 250mL, the mixture is heated and refluxed for 4 hours, after the reaction is completed, the reaction is cooled to normal temperature, pure water is added for quenching reaction, dichloromethane is used for extraction and washing for 3 times, an organic phase is collected, and recrystallization is carried out after spin drying, so that the yield is 90%.
3)
Figure GDA0002465890330000335
Under nitrogen atmosphere, (16.8 g,30 mmol) of compound 1-14-4 and (13.3 g,30 mmol) of compound 1-1-5, (1.73 g,1.5 mmol) of tetra (triphenylphosphine) palladium, (1.3 g,4 mmol) of tetrabutylammonium bromide, (1.6 g,40 mmol) of sodium hydroxide, (10 mL) of water and (60 mL) of toluene were added to a 150mL three-necked flask, the reaction was stirred at 80℃for 12 hours, the reaction was ended, most of the solvent was rotationally evaporated, the mixture was washed with dichloromethane for 3 times, and the organic solution was collected and purified by passing through a silica gel column in 85% yield.
(6) Synthesis of Compound (1-40):
Figure GDA0002465890330000341
1)
Figure GDA0002465890330000342
under nitrogen atmosphere, (11.9 g,30 mmol) of compound 1-40-1 and (13.3 g,30 mmol) of compound 1-4-5, (1.73 g,1.5 mmol) of tetra (triphenylphosphine) palladium, (1.3 g,4 mmol) of tetrabutylammonium bromide, (1.6 g,40 mmol) of sodium hydroxide, (10 mL) of water and (60 mL) of toluene were added to a 150mL three-necked flask, the reaction was stirred at 80℃for 12 hours, the reaction was ended, most of the solvent was rotationally evaporated, the mixture was washed with dichloromethane for 3 times, and the organic solution was collected and purified by passing through a silica gel column in 80% yield.
(7) Synthesis of Compound (1-68):
Figure GDA0002465890330000343
1)
Figure GDA0002465890330000344
under nitrogen atmosphere, (23.7 g,60 mmol) of compound 1-1-4 and (5.0 g,30 mmol) of compound 1-68-1, (1.73 g,1.5 mmol) of tetra (triphenylphosphine) palladium, (1.3 g,4 mmol) of tetrabutylammonium bromide, (1.6 g,40 mmol) of sodium hydroxide, (10 mL) of water and (60 mL) of toluene were added to a 150mL three-necked flask, the reaction was stirred at 80℃for 12 hours, the reaction was ended, most of the solvent was rotationally evaporated, the mixture was washed with dichloromethane for 3 times, and the organic solution was collected and purified by passing through a silica gel column in 80% yield.
(8) Synthesis of Compound (1-131):
Figure GDA0002465890330000345
1)
Figure GDA0002465890330000346
under the nitrogen environment, adding (26.4 g,100 mmol) of compound 1-10-1 and (250 mL) of anhydrous tetrahydrofuran into a 500mL three-port bottle, cooling to-78 ℃, slowly dropwise adding 100mmol of n-butyllithium, reacting for 1.5 hours, then adding (25.8 g,100 mmol) of compound 1-10-2 at one time, naturally heating to room temperature, continuing reacting for 12 hours, adding pure water for quenching reaction, screwing most of solvent, extracting with dichloromethane and washing 3 times, collecting an organic phase, and performing column chromatography purification after spin drying, wherein the yield is 85%.
2)
Figure GDA0002465890330000351
Compound 1-131-2 (31.1 g,70 mmol), acetic acid (150 mL) and hydrochloric acid (10 mL) were added into a three-necked flask of 250mL, and heated and refluxed for 4 hours, after the reaction was completed, the reaction was allowed to cool to room temperature, and then purified water was added for quenching reaction, extracted with dichloromethane and washed 3 times, the organic phase was collected, and recrystallized after spin-drying to yield 90%.
3)
Figure GDA0002465890330000352
Under the nitrogen environment, adding (21.3 g,50 mmol) of compound 1-131-3 and 200mL of anhydrous tetrahydrofuran into a 500mL three-port bottle, cooling to-78 ℃, slowly dropwise adding 55mmol of n-butyllithium, reacting for 1.5 hours, injecting 60mmol of isopropanol pinacol borate at one time, naturally heating the reaction to room temperature, continuing the reaction for 12 hours, adding pure water for quenching reaction, extracting and washing with dichloromethane for 3 times after most of solvent is removed, collecting an organic phase, and performing column chromatography purification after spin drying, wherein the yield is 85%.
4)
Figure GDA0002465890330000353
Under nitrogen atmosphere, (12.8 g,30 mmol) of compound 1-131-3 and (14.2 g,30 mmol) of compound 1-131-4, (1.73 g,1.5 mmol) of tetra (triphenylphosphine) palladium, (1.3 g,4 mmol) of tetrabutylammonium bromide, (1.6 g,40 mmol) of sodium hydroxide, (10 mL) of water and (60 mL) of toluene were added to a 150mL three-necked flask, the reaction was stirred at 80℃for 12 hours, the reaction was ended, most of the solvent was rotationally evaporated, the mixture was washed with dichloromethane for 3 times, and the organic solution was collected and purified by passing through a silica gel column in 80% yield.
(9) Synthesis of Compound (2-1):
Figure GDA0002465890330000354
1)
Figure GDA0002465890330000361
under nitrogen atmosphere, (11.9 g,60 mmol) of compound 2-1-1 and (13.6 g,60 mmol) of compound 2-1-2, (1.73 g,1.5 mmol) of tetrakis (triphenylphosphine) palladium, (1.3 g,4 mmol) of tetrabutylammonium bromide, (1.6 g,40 mmol) of sodium hydroxide, (10 mL) of water and (60 mL) of toluene were added to a 150mL three-necked flask, the reaction was stirred at 80℃for 12 hours, the reaction was ended, most of the solvent was rotationally evaporated, the mixture was washed with dichloromethane for 3 times, and the organic solution was collected and purified by passing through a silica gel column in 80% yield.
2)
Figure GDA0002465890330000362
Under nitrogen, (10.3 g,30 mmol) of Compound 2-1-3, (19.9 g,30 mmol) of Compound 2-1-4, (0.86 g,1.5 mmol) Pd (dba) was reacted under nitrogen 2 (2.9 g,30 mmol) of sodium tert-butoxide and (150 mL) of anhydrous toluene were added to a 300mL two-necked flask, the reaction was completed by stirring at 100℃for 12 hours, most of the solvent was distilled off under reduced pressure, the mixture was washed with methylene chloride-dissolved water for 3 times, and the organic solution was collected and purified by passing through a column with a yield of 70%.
(10) Synthesis of Compound (2-15):
Figure GDA0002465890330000363
1)
Figure GDA0002465890330000364
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(16.7 g,100 mmol) of compound 2-15-1, (7.1 g,50 mmol) of compound 2-15-2, (32.6 g,100 mmol) of cesium carbonate and 250mL of 1-methyl-2-pyrrolidone were added to a 500mL single-port bottle, heated to 200℃and stirred for reaction for 12 hours, the reaction was terminated, the reaction solution was poured into 1000mL of water, suction filtration was performed, and the residue was recrystallized in 90% yield.
2)
Figure GDA0002465890330000365
Under nitrogen atmosphere, (9.69 g,50 mmol) of compound 2-15-3, (9.69 g,100 mmol) of compound 2-15-4, (9.69 g,100 mmol) of cesium carbonate and 150mL of dimethyl sulfoxide are added into a 300mL three-necked flask, the reaction is completed after heating to 90 ℃ for 12 hours, the reaction solution is poured into 1000mL of water, suction filtration is carried out, and the filter residue is recrystallized, thus obtaining 90% yield.
(11) Synthesis of Compound (3-3):
Figure GDA0002465890330000371
1)
Figure GDA0002465890330000372
under nitrogen atmosphere, (11.9 g,60 mmol) of compound 3-3-1 and (13.6 g,60 mmol) of compound 3-3-2, (1.73 g,1.5 mmol) of tetrakis (triphenylphosphine) palladium, (1.3 g,4 mmol) of tetrabutylammonium bromide, (1.6 g,40 mmol) of sodium hydroxide, (10 mL) of water and (60 mL) of toluene were added to a 150mL three-necked flask, the reaction was stirred at 80℃for 12 hours, the reaction was ended, most of the solvent was rotationally evaporated, the mixture was washed with dichloromethane for 3 times, and the organic solution was collected and purified by passing through a silica gel column in 75% yield.
2)
Figure GDA0002465890330000373
Under nitrogen, (10.3 g,30 mmol) of Compound 3-3-3, (12.3 g,30 mmol) of Compound 3-3-4, (0.86 g,1.5 mmol) Pd (dba) was reacted under nitrogen 2 (2.9 g,30 mmol) of sodium tert-butoxide and (150 mL) of anhydrous toluene were added to a 300mL two-necked flask, the reaction was completed by stirring at 100℃for 12 hours, most of the solvent was distilled off under reduced pressure, the mixture was washed 3 times with methylene chloride and the organic solution was collected and purified by passing through a column with a yield of 75%.
(12) Synthesis of Compound (4-3):
Figure GDA0002465890330000374
1)
Figure GDA0002465890330000375
under nitrogen, (10.3 g,30 mmol) of Compound 4-3-1, (10 g,30 mmol) of Compound 4-3-2, (0.86 g,1.5 mmol) Pd (dba) was reacted under nitrogen 2 (2.9 g,30 mmol) of sodium tert-butoxide and (150 mL) of anhydrous toluene were added to a 300mL two-necked flask, the reaction was completed by stirring at 100℃for 12 hours, most of the solvent was distilled off under reduced pressure, the mixture was washed with methylene chloride-dissolved water for 3 times, and the organic solution was collected and purified by passing through a column with a yield of 70%.
(13) Synthesis of Compound (4-52):
Figure GDA0002465890330000381
1)
Figure GDA0002465890330000382
under nitrogen atmosphere, (16.4 g,60 mmol) of compound 4-52-1 and (13.6 g,60 mmol) of compound 3-3-2, (1.73 g,1.5 mmol) of tetrakis (triphenylphosphine) palladium, (1.3 g,4 mmol) of tetrabutylammonium bromide, (1.6 g,40 mmol) of sodium hydroxide, (10 mL) of water and (60 mL) of toluene were added to a 150mL three-necked flask, the reaction was stirred at 80℃for 12 hours, the reaction was ended, most of the solvent was rotationally evaporated, the mixture was washed with dichloromethane for 3 times, and the organic solution was collected and purified by passing through a silica gel column in 80% yield.
2)
Figure GDA0002465890330000383
Under the nitrogen environment, adding (21.9 g,50 mmol) of compound 4-52-3 and 200mL of anhydrous tetrahydrofuran into a 500mL three-port bottle, cooling to-78 ℃, slowly dropwise adding 55mmol of n-butyllithium, reacting for 1.5 hours, injecting 60mmol of isopropanol pinacol borate at one time, naturally heating the reaction to room temperature, continuing the reaction for 12 hours, adding pure water for quenching reaction, extracting and washing with dichloromethane for 3 times after most of solvent is removed, collecting an organic phase, and performing column chromatography purification after spin drying, wherein the yield is 80%.
3)
Figure GDA0002465890330000384
Under nitrogen atmosphere, (12.6 g,30 mmol) of compound 452-2 and (14.6 g,30 mmol) of compound 4-52-4, (1.73 g,1.5 mmol) of tetra (triphenylphosphine) palladium, (1.3 g,4 mmol) of tetrabutylammonium bromide, (1.6 g,40 mmol) of sodium hydroxide, (10 mL) of water and (60 mL) of toluene were added to a 150mL three-necked flask, the reaction was ended by heating at 80℃and stirring for 12 hours, most of the solvent was rotationally evaporated, the mixture was washed 3 times with dichloromethane, and the organic solution was collected and purified by passing through a silica gel column in 80% yield.
(14) Synthesis of Compound (5-2):
Figure GDA0002465890330000385
1)
Figure GDA0002465890330000391
under nitrogen, (14.3 g,50 mmol) of Compound 5-2-1, (16.6 g,50 mmol) of Compound 5-2-2, (0.86 g,1.5 mmol) Pd (dba) was reacted under nitrogen 2 (2.9 g,30 mmol) of sodium tert-butoxide and (150 mL) of anhydrous toluene were added to a 300mL two-necked flask, the reaction was completed by stirring at 100℃for 12 hours, most of the solvent was distilled off under reduced pressure, the mixture was washed with methylene chloride-dissolved water for 3 times, and the organic solution was collected and purified by passing through a column with a yield of 70%.
2)
Figure GDA0002465890330000392
(16.7 g,30 mmol) of compound 5-2-3 and (150 mL) of 1, 4-dioxane are added into a 300mL two-port bottle, N-bromosuccinimide (5.4 g,30 mmol) is slowly added dropwise under ice bath, the reaction is carried out for 4 hours, after the reaction is finished, the reaction solution is inverted into 800mL of purified water, suction filtration is carried out, and filter residues are recrystallized and purified, so that the yield is 90%.
3)
Figure GDA0002465890330000393
Under nitrogen, (12.9 g,20 mmol) of Compound 5-2-4, (6.4 g,25 mmol) of the bisboronate, (0.73 g,1 mmol) of Pd (dppf) Cl 2 (2.9 g,30 mmol) of potassium acetate and (100 mL) of 1, 4-dioxane were added to a 250mL three-necked flask, the reaction was completed by heating at 110℃and stirring, most of the solvent was distilled off under reduced pressure, the solvent was washed 3 times with methylene chloride solution and the organic solution was collected and purified by passing through a column with a yield of 85%.
4)
Figure GDA0002465890330000394
Under nitrogen atmosphere, (19.3 g,30 mmol) of compound 5-2-4 and (20.7 g,30 mmol) of compound 5-2-5, (1.73 g,1.5 mmol) of tetra (triphenylphosphine) palladium, (1.3 g,4 mmol) of tetrabutylammonium bromide, (1.6 g,40 mmol) of sodium hydroxide, (10 mL) of water and (60 mL) of toluene were added to a 150mL three-necked flask, the reaction was stirred at 80℃for 12 hours, the reaction was ended, most of the solvent was rotationally evaporated, the mixture was washed with dichloromethane for 3 times, and the organic solution was collected and purified by passing through a silica gel column in 85% yield.
2. Energy structure of organic compound
The energy level of the organic material can be obtained by quantum computation, for example by means of a Gaussian03W (Gaussian inc.) using a TD-DFT (time-dependent density functional theory), and a specific simulation method can be seen in WO2011141110. The molecular geometry is optimized by a semi-empirical method of "group State/DFT/Default Spin/B3LYP" and a basic group of "6-31G (d)" (Charge 0/Spin single), and then the energy structure of the organic molecule is calculated by a TD-DFT (time Density functional theory) method to obtain "TD-SCF/DFT/Default Spin/B3PW91" and a basic group of "6-31G (d)" (Charge 0/Spin single). The HOMO and LUMO energy levels are calculated according to the following calibration formula, and S1 and T1 are used directly.
HOMO(eV)＝((HOMO(G)×27.212)-0.9899)/1.1206
LUMO(eV)＝((LUMO(G)×27.212)-2.0041)/1.385
Wherein HOMO (G) and LUMO (G) are direct calculations of Gaussian 09W in Hartree. The results are shown in Table 1:
TABLE 1
Figure GDA0002465890330000401
Preparation and characterization of OLED devices
In this example, compounds (1-1), (1-4), (1-40), (1-68) and (1-131) were used as the first host H1 and (2-1), (3-3) and (4-3) were used as the second host H2 as a mixture at 1:1 (mass ratio), ir (p-ppy) in the following figures 3 As a light-emitting material, HATCN as a hole injection material, SFNFB as a hole transport material, naTzF 2 As electron transportThe material, liq is used as an electron injection material, and is constructed into a device structure of ITO/HATCN/HTL/main material: ir (p-ppy) 3 (10％)/NaTzF 2 Liq/Liq/Al electroluminescent devices.
Figure GDA0002465890330000402
HATCN, SFNFB, ir (p-ppy) of the above-mentioned material 3 、NaTzF 2 Liq is commercially available, such as Jilin Orede (Jilin OLED Material Tech Co., ltd., www.jl-oled. Com), or methods for synthesizing the same are known in the art, and are described in detail in the prior art references and are not described in detail herein.
The following describes in detail the preparation process of the OLED device by using the above embodiment, and the OLED device (e.g. table 2) has the following structure: ITO/HATCN/SFNFB/host material Ir (p-ppy) 3 (10％)/NaTzF 2 Liq/Liq/Al, the preparation steps are as follows:
a. Cleaning an ITO (indium tin oxide) conductive glass substrate: cleaning with various solvents (such as chloroform, acetone or isopropanol, or both), and performing ultraviolet ozone treatment;
b. HATCN (30 nm), SFNFB (50 nm), bulk material 10% Ir (p-ppy) 3 (40nm)，NaTzF 2 Liq (30 nm), liq (1 nm), al (100 nm) under high vacuum (1×10) -6 Millibar) by thermal evaporation;
c. encapsulation the device was encapsulated with an ultraviolet curable resin in a nitrogen glove box.
TABLE 2
Figure GDA0002465890330000411
The current-voltage (J-V) characteristics of each OLED device were characterized by a characterization apparatus while recording important parameters such as efficiency, lifetime (as in table 2) and external quantum efficiency. In table 2, all device lifetime data are relative values with OLED 16. Wherein H1 and H2 are significantly longer device lifetime as co-hosts than single hosts. The device lifetime based on the device OLED3 is highest in the same type of device, wherein the device lifetime based on the OLED3 is about twice that of the single body device OLED11 and about 20 times that of the OLED 16. Therefore, the service life of the OLED device prepared by the organic mixture is greatly prolonged.
4. Preparation and characterization of solution processed OLED device
Figure GDA0002465890330000421
1) Cleaning an ITO transparent electrode (anode) glass substrate: ultrasonic treatment is carried out for 30 minutes by using an aqueous solution of 5% Decon90 cleaning liquid, then deionized water is used for ultrasonic cleaning for a plurality of times, then isopropanol is used for ultrasonic cleaning, and nitrogen is used for blow-drying; treating for 5 minutes under oxygen plasma to clean the ITO surface and increase the work function of the ITO electrode;
2) Hole transport layer preparation: spin-coating a PEDOT: PSS solution on the glass substrate subjected to the oxygen plasma treatment to obtain a film of 80nm, annealing at 150℃for 20 minutes in air after the spin-coating is completed, and then spin-coating a 20nm Poly-TFB film (CAS: 223569-31-1, available from Lumtec. Corp;5mg/mL toluene solution) on the PEDOT: PSS layer, followed by treatment on a hot plate of 180℃for 60 minutes;
3) Preparing a light-emitting layer: the host material for the light-emitting layer was dissolved in toluene at various ratios with a solid content of 18mg/mL, and the ratio of guest doping (PD-1, the synthesis of which is referred to in patent CN 102668152) was generally 20% (i.e., 80% of the host material in the light-emitting layer solution), and this solution was spin-coated in a nitrogen glove box to give a 40nm thin film, which was then annealed at 150 ℃ for 10 minutes.
4) Electron transport layer and cathode preparation: placing the spin-coated device into a vacuum evaporation cavity, and placing ET (NaTzF 2 ) And LiQ are placed in different evaporation units, so that the LiQ and LiQ are respectively co-deposited in a proportion of 50 weight percent, a 40nm electron transport layer is formed on the light-emitting layer, and then 100nm aluminum is evaporated to serve as a cathode to complete the light-emitting device.
5) And packaging the light-emitting device in a nitrogen glove box by adopting ultraviolet curing resin and a glass cover plate.
Wherein:
the solid mixtures of the light-emitting layers of the OLED18 are (1-1), respectively: (4-52): PD-1 = 40:40:20, a step of;
the solid mixtures of the light-emitting layers of the OLED19 are (1-1), respectively: (5-2): PD-1 = 40:40:20, a step of;
the solid mixtures of the light-emitting layers of the OLED20 are (4-52), respectively: PD-1 = 80:20, a step of;
the solid mixtures of the light-emitting layers of the OLED21 are (5-2), respectively: PD-1 = 80:20, a step of;
TABLE 3 Table 3
Figure GDA0002465890330000422
The lifetime of each OLED device is shown in table 3, where t90@1000nits is the value relative to OLED 21. According to detection, the luminous life of the organic mixed device is 2-5 times higher than that of the OLED21, and the current efficiency at 1000 brightness is 20% -60% higher than that of the OLED 21. Therefore, the service life and the current efficiency of the OLED device prepared by the organic mixture are greatly improved.
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description. The above examples illustrate only a few embodiments of the invention, which are described in detail and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.

Claims (10)

1. An organic mixture comprising organic materials H1 and H2, H1 being a compound of the general formula (1-1), (1-4), (1-6), (1-10), (1-14), (1-40), (1-68) and (1-131):
Figure FDA0004118151470000011
h2 is a compound represented by the following general formula (2-1), (2-15), (3-3), (4-52) and (5-2):
Figure FDA0004118151470000012
s1 (H2) -T1 (H2) of H2 is less than or equal to 0.3eV, wherein S1 (H2), and T1 (H2) are a singlet state energy level and a triplet state energy level of H2 respectively.
2. The organic mixture of claim 1, wherein H1 and H2 form a semiconductor heterojunction structure of type I.
3. The organic mixture according to claim 1, wherein the difference in molecular weight of H1 and H2 is not more than 100Dalton, and/or the difference in sublimation temperature of H1 and H2 is not more than 50K.
4. An organic mixture according to any one of claims 1 to 3, further comprising a luminescent material selected from the group consisting of fluorescent, phosphorescent and TADF materials.
5. A composition comprising an organic mixture according to any one of claims 1 to 4, and at least one organic solvent.
6. Use of the organic mixture according to any of claims 1 to 4 in an organic electronic device.
7. An organic electronic device, characterized in that its functional layer comprises at least one organic mixture according to any one of claims 1 to 4.
8. The organic electronic device of claim 7, wherein the organic electronic device is an organic light emitting diode, an organic photovoltaic cell, an organic light emitting cell, an organic field effect transistor, an organic light emitting field effect transistor, an organic sensor, or an organic plasmon emitting diode.
9. The organic electronic device of claim 8, wherein the organic electronic device is an organic light emitting diode comprising at least one light emitting layer comprising an organic mixture according to any one of claims 1 to 4.
10. The organic electronic device according to claim 9, wherein the light-emitting layer is formed by one of the following methods (1) to (3):
(1) The organic mixture containing H1 and H2 is deposited as a source by a vacuum evaporation method;
(2) H1 and H2 are deposited by vacuum evaporation as separate two sources;
(3) Deposited by solution processing using the composition of claim 5.
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