CN110669048A

CN110669048A - Organic compound based on nitrogen-containing fused ring and application thereof

Info

Publication number: CN110669048A
Application number: CN201911040146.8A
Authority: CN
Inventors: 张晨; 潘君友
Original assignee: Guangzhou Hua Rui Photoelectric Material Co Ltd
Current assignee: Guangzhou Hua Rui Photoelectric Material Co Ltd
Priority date: 2018-12-06
Filing date: 2019-10-29
Publication date: 2020-01-10

Abstract

The invention relates to the field of electroluminescent materials, in particular to an organic compound based on nitrogen-containing condensed rings and application thereof. The organic compound hasThe structure of the structural formula (1). The organic compound can be matched with a proper main material, so that the luminous efficiency and the service life of the organic photoelectric material are improved, and the problems of high cost, high efficiency roll-off speed under high brightness and short service life of the conventional phosphorescent luminous material are solved.

Description

Organic compound based on nitrogen-containing fused ring and application thereof

The present application claims priority from the chinese patent application entitled "a material based on nitrogen-containing fused rings and uses thereof" filed by the chinese patent office on 2018, 12 and 06, 8 and having application number 2018114842272, the entire contents of which are incorporated herein by reference.

Technical Field

The invention relates to the field of electroluminescent materials, in particular to an organic compound based on nitrogen-containing condensed rings and application thereof.

Background

The organic photoelectric material has diversity in synthesis, relatively low manufacturing cost and excellent optical and electrical properties. Organic Light Emitting Diodes (OLEDs) have the advantages of wide viewing angle, fast response time, low operating voltage, thin panel thickness, etc., in the application of optoelectronic devices, such as flat panel displays and lighting, and thus have a wide potential for development.

In order to improve the light emitting efficiency of the organic light emitting diode, various fluorescent and phosphorescent-based light emitting material systems have been developed. The organic light emitting diode using a fluorescent material has a characteristic of high reliability, but its internal electroluminescence quantum efficiency under electric field excitation is limited to 25% because the branching ratio of the singlet excited state and the triplet excited state of excitons is 1: 3. In contrast, the organic light emitting diode using the phosphorescent material has achieved almost 100% internal electroluminescence quantum efficiency. However, phosphorescent OLEDs have a significant problem, namely the Roll-off effect, i.e. the luminous efficiency decreases rapidly with increasing current or brightness, which is particularly disadvantageous for high brightness applications.

The phosphorescent materials which have been put to practical use to date are iridium and platinum complexes, which are rare and expensive as raw materials, and the synthesis of the complexes is complicated and therefore the cost is relatively high. To overcome the inherent drawbacks of phosphorescent guests, Adachi et al have made a series of advances in metal complex-free high efficiency light emitting diodes by using combinations of materials to achieve complex excited states (exiplex) and to design new guest materials free of rare metals, see Adachi et al, Nature Photonics, Vol 6, p253 (2012); adachi et al, Nature, Vol 492,234, (2012). The existing red and green light guest materials without noble metals have achieved certain results in many aspects of performance after a period of development, but compared with phosphorescent light emitting materials, the performance of the red and green light guest materials has certain gap in terms of efficiency and service life.

Disclosure of Invention

Based on the organic compound based on the nitrogen-containing condensed ring and the application thereof, the organic compound based on the nitrogen-containing condensed ring is needed to be provided to improve the luminous efficiency and the service life of the organic photoelectric material and solve the problems of high cost, fast efficiency roll-off and short service life of the existing phosphorescent luminous material.

The technical scheme of the invention is as follows:

an organic compound having a structure represented by structural formula (1):

wherein:

each Z₁Is independently selected from CR₁Or N;

a is selected from substituted or unsubstituted aromatic groups or heteroaromatic groups with 5-60 ring atoms;

R、R₁independently selected from H, D, F, Cl, Br, CF₃A hydroxyl group, a nitro group, a cyano group, an isocyano group, a formyl group, a carbamoyl group, a haloformyl group, an isocyanate group, a thiocyanate group, an isothiocyanate group, a silyl group, a linear alkyl group, an alkoxy group or a thioalkoxy group having 1 to 20 carbon atoms, a branched alkyl group, an alkoxy group or a thioalkoxy group having 3 to 20 carbon atoms, a cyclic alkyl group, an alkoxy group or a thioalkoxy group having 3 to 20 carbon atoms, a ketone group having 1 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms, a carbo group having 2 to 20 carbon atoms7-20 of aryloxycarbonyl, crosslinkable group, substituted or unsubstituted aryl or heteroaryl with 5-60 ring atoms, and aryloxy or heteroaryloxy with 5-60 ring atoms;

two or more adjacent R₁Aliphatic, aromatic or heteroaromatic rings which may optionally form a single ring or multiple rings with one another.

A polymer comprising at least one repeat unit comprising an organic compound as described in any of the above embodiments.

A mixture comprising an organic compound as described in any of the above embodiments or a high polymer as described above, and at least one organic functional material H2, said organic functional material H2 being selected from the group consisting of hole injection materials, hole transport materials, electron injection materials, electron blocking materials, hole blocking materials, light emitters, host materials.

A composition comprising an organic compound as described in any one of the preceding embodiments or a polymer as described above or a mixture as described in any one of the preceding embodiments, and at least one organic solvent.

An organic electronic device comprising an organic compound as described in any preceding embodiment or a polymer as described above or a mixture as described in any preceding embodiment.

Has the advantages that:

the organic compound based on the nitrogen-containing condensed ring can be used as a guest material, has smaller delta Est, and can improve the luminous efficiency and the service life of an electroluminescent device by being matched with a proper host material; the problems of high cost, high efficiency roll-off speed under high brightness and short service life of the existing phosphorescent material are solved; a solution for a light emitting device with low manufacturing cost, high efficiency, long lifetime, and low roll-off is provided.

Detailed Description

In order that the invention may be more fully understood, reference will now be made to the accompanying examples. The present invention is given by way of preferred embodiments only. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.

The invention provides an organic compound based on nitrogen-containing condensed rings and application thereof in an organic electroluminescent device, and the invention is further described in detail below in order to make the purpose, technical scheme and effect of the invention clearer and clearer. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.

In the present invention, the Host material, the matrix material and the Host material have the same meaning and may be interchanged.

In the present invention, singlet state and singlet state have the same meaning and may be interchanged.

In the present invention, the triplet state and the triplet state have the same meaning and are interchangeable.

In the present invention, "substituted" means that a hydrogen atom in a substituted group is substituted with a substituent.

In the present invention, the "number of ring atoms" represents the number of atoms among atoms constituting the ring itself of a structural compound (for example, a monocyclic compound, a condensed ring compound, a crosslinked compound, a carbocyclic compound, and a heterocyclic compound) in which atoms are bonded in a ring shape. When the ring is substituted with a substituent, the atoms contained in the substituent are not included in the ring-forming atoms. The "number of ring atoms" described below is the same unless otherwise specified. For example, the number of ring atoms of the benzene ring is 6, the number of ring atoms of the naphthalene ring is 10, and the number of ring atoms of the thienyl group is 5.

In the present invention, "adjacent groups" means that these groups are bonded to the same carbon atom or bonded to adjacent carbon atoms. These definitions apply correspondingly to "adjacent substituents".

In the embodiment of the present invention, the energy level structure of the organic material, the triplet state energy level E_T1The highest occupied orbital level HOMO and the lowest unoccupied orbital level LUMO play a key role. The determination of these energy levels is described below.

The HOMO and LUMO energy levels can be measured by the photoelectric effect, for example XPS (X-ray photoelectron spectroscopy) and UPS (ultraviolet photoelectron spectroscopy) or by cyclic voltammetry (hereinafter referred to as CV). Recently, quantum chemical methods, such as the density functional theory (hereinafter abbreviated as DFT), have become effective methods for calculating the molecular orbital level.

Triplet energy level E of organic material_T1Can be measured by low temperature Time resolved luminescence spectroscopy, or can be obtained by quantum simulation calculations (e.g., by Time-dependent DFT), such as by commercial software Gaussian09W (Gaussian Inc.), specific simulation methods can be found in WO2011141110 or as described in the examples below.

Note that HOMO, LUMO, E_T1The absolute value of (c) depends on the measurement method or calculation method used, and even for the same method, different methods of evaluation, for example starting point and peak point on the CV curve, can give different HOMO/LUMO values. Thus, a reasonably meaningful comparison should be made with the same measurement method and the same evaluation method. In the description of the embodiments of the present invention, HOMO, LUMO, E_T1Is based on the simulation of the Time-dependent DFT but does not affect the application of other measurement or calculation methods.

One embodiment of the present invention relates to an organic compound having a structure represented by the following structural formula (1)

Wherein:

each Z₁Is independently selected from CR₁Or N;

R、R₁independently selected from H, D, F, Cl, Br, CF₃One or more of hydroxyl, nitro, cyano, isocyano, formyl, carbamoyl, haloformyl, isocyanate, thiocyanate, isothiocyanate, silyl, C1-20 linear alkyl or alkoxy or thioalkoxy, C3-20 branched alkyl or alkoxy or thioalkoxy, C3-20 cyclic alkyl or alkoxy or thioalkoxy, C1-20 ketone, C2-20 alkoxycarbonyl, C7-20 aryloxycarbonyl, crosslinkable group, substituted or unsubstituted aryl or heteroaryl having 5-60 ring atoms, and C5-60 aryloxy or heteroaryloxy; preferably, R is selected from H or methyl;

In a preferred embodiment, A is selected from substituted or unsubstituted heteroaromatic groups with 5-40 ring atoms; more preferably, A is selected from substituted or unsubstituted N-containing heteroaromatic groups with 5-40 ring atoms.

In a certain preferred embodiment, at least two adjacent Z₁Is independently selected from CR₁And at least two adjacent R₁Form a monocyclic or polycyclic aromatic or heteroaromatic ring with one another.

In a preferred embodiment, the structural formula (1) is selected from any one of the following structural formulae (2-1) to (2-8):

wherein: each B₁Independently selected from substituted or unsubstituted aromatic groups or heteroaromatic groups with 5-25 ring atoms and non-aromatic rings with 3-25 ring atoms.

In a certain preferred embodiment, each Z₁Is independently selected from CR₁(ii) a Structural formula (1) is selected from the following structural formulae:

in a certain preferred embodiment, each Z₁Is independently selected from CR₁And at least two adjacent R₁Aromatic or heteroaromatic rings forming a single or multiple ring with each other; structural formula (1) is selected from any one of the following structural formulae:

wherein: r, R₁、A、B₁The meaning is as described above.

In a preferred embodiment, each B₁The group is independently selected from one or more of the following structures:

wherein:

each X is independently selected from N or CR₂；

Each Y is independently selected from the group consisting of a single bond, CR₂R₃、C＝C(R₂R₃)、Si R₂R₃、NR₂C (═ O), S (═ O), or O; in a certain preferred embodiment, Y is independently selected from CR₂R₃、NR₂S or O; in a certain preferred embodiment, Y is independently selected from CR₂R₃Or NR₂；

R₂、R₃Independently selected from H, D, F, Cl, Br, CF₃A hydroxyl group, a nitro group, a cyano group, an isocyano group, a formyl group, a carbamoyl group, a haloformyl group, an isocyanate group, a thiocyanate group, an isothiocyanate group, a silyl group, a linear alkyl group having 1 to 20 carbon atoms, an alkoxy group or a thioalkoxy group, a branched chain having 3 to 20 carbon atomsThe group is one or more of alkyl, alkoxy or thioalkoxy, alkyl, alkoxy or thioalkoxy with a ring having 3-20 carbon atoms, ketone group having 1-20 carbon atoms, alkoxycarbonyl having 2-20 carbon atoms, aryloxycarbonyl having 7-20 carbon atoms, a crosslinkable group, substituted or unsubstituted aryl or heteroaryl having 5-60 ring atoms, and aryloxy or heteroaryloxy having 5-60 ring atoms.

wherein H on the ring may be further substituted.

in a preferred embodiment, the structural formula (1) may be selected from any one of the following structural formulae (3-1) to (3-16):

in a preferred embodiment, Z in the formulae are each selected from CR₂(ii) a More preferably, Z in the formula are all selected from CR₂And each Z₁Is independently selected from CR₁。

Preferably, the structural formula (1) may be selected from any one of the following structural formulae (4-1) to (4-17):

in a preferred embodiment, a is selected from the group consisting of one or more of the following structures:

wherein:

each Z is independently selected from N or CR₄(ii) a Preferably, at least one Z is selected from N;

each Y is independently selected from the group consisting of a single bond, CR₂R₃、C＝C(R₂R₃)、Si R₂R₃、NR₂C (═ O), S (═ O), or O;

R₂、R₃、R₄independently selected from H, D, F, Cl, Br, CF₃The compound is characterized by comprising one or more of hydroxyl, nitryl, cyano, isocyano, formyl, carbamoyl, haloformyl, isocyanate, thiocyanate, isothiocyanate, silyl, straight-chain alkyl or alkoxy or thioalkoxy with the carbon number of 1-20, branched-chain alkyl or alkoxy or thioalkoxy with the carbon number of 3-20, alkyl or alkoxy or thioalkoxy with the ring with the carbon number of 3-20, ketone group with the carbon number of 1-20, alkoxycarbonyl with the carbon number of 2-20, aryloxycarbonyl with the carbon number of 7-20, a crosslinkable group, substituted or unsubstituted aryl or heteroaryl with the ring number of 5-60, and aryloxy or heteroaryloxy with the ring number of 5-60.

wherein:

Ar₁、Ar₂independently selected from substituted or unsubstitutedA substituted aryl or heteroaryl group having 5 to 40 ring atoms, or a substituted or unsubstituted non-aromatic cyclic group having 5 to 40 ring atoms; h in the structural formula of a may be further substituted.

An aromatic group refers to a hydrocarbon group containing at least one aromatic ring. A heteroaromatic group refers to an aromatic hydrocarbon group that contains at least one heteroatom. The heteroatoms are preferably selected from Si, N, P, O, S and/or Ge, particularly preferably from Si, N, P, O and/or S. By fused ring aromatic group is meant that the rings of the aromatic group may have two or more rings in which two carbon atoms are shared by two adjacent rings, i.e., fused rings. The fused heterocyclic aromatic group means a fused ring aromatic hydrocarbon group containing at least one hetero atom. For the purposes of the present invention, aromatic or heteroaromatic radicals include not only aromatic ring systems but also non-aromatic ring systems. Thus, for example, systems such as pyridine, thiophene, pyrrole, pyrazole, triazole, imidazole, oxazole, oxadiazole, thiazole, tetrazole, pyrazine, pyridazine, pyrimidine, triazine, carbene, and the like, are also considered aromatic or heterocyclic aromatic groups for the purposes of this invention. For the purposes of the present invention, fused-ring aromatic or fused-heterocyclic aromatic ring systems include not only systems of aromatic or heteroaromatic groups, but also systems in which a plurality of aromatic or heterocyclic aromatic groups may also be interrupted by short non-aromatic units (< 10% of non-H atoms, preferably less than 5% of non-H atoms, such as C, N or O atoms). Thus, for example, systems such as 9,9' -spirobifluorene, 9, 9-diarylfluorene, triarylamines, diaryl ethers, etc., are also considered fused aromatic ring systems for the purposes of this invention.

Specifically, examples of the condensed ring aromatic group are: naphthalene, anthracene, fluoranthene, phenanthrene, triphenylene, perylene, tetracene, pyrene, benzopyrene, acenaphthene, fluorene, and derivatives thereof.

Specifically, examples of the fused heterocyclic aromatic group are: benzofuran, benzothiophene, indole, carbazole, pyrroloimidazole, pyrrolopyrrole, thienopyrrole, thienothiophene, furopyrrole, furofuran, thienofuran, benzisoxazole, benzisothiazole, benzimidazole, quinoline, isoquinoline, phthalazine, quinoxaline, phenanthridine, primadine, quinazoline, quinazolinone, and derivatives thereof.

In particular, the organic compounds according to the invention. Selected from the following structures but not limited to:

in a preferred embodiment, Δ Est ≦ 0.3eV, Δ Est represents a compound singlet-triplet energy level difference. The organic compound as a TADF material needs smaller singlet state-triplet state energy level difference delta Est which is less than or equal to 0.3 eV; preferably, Delta Est is less than or equal to 0.2 eV; more preferably,. DELTA.Est.ltoreq.0.10 eV.

In a preferred embodiment, f (S)₁)≥0.015，f(S₁) Representing the resonance factor. The organic compound according to the present invention needs to have a relatively suitable resonance factor f (S) as a TADF material₁) (ii) a Preferably f (S)₁) Not less than 0.001; more preferably f (S)₁) Not less than 0.010; preferably f (S)₁)≥0.021。

In certain preferred embodiments, the organic compounds according to the invention preferably have a Δ HOMO, ((HOMO- (HOMO-1)) of ≧ 0.23eV, more preferably ≧ 0.43eV, and most preferably ≧ 0.6 eV.

In certain preferred embodiments, the organic compounds according to the invention preferably have a Δ LUMO, i.e., ((LUMO +1) -LUMO), of ≧ 0.05 eV; more preferably not less than 0.3 eV; more preferably, it is not less than 0.59 eV.

In some embodiments, the organic compounds according to the present invention have a light emitting function with a light emitting wavelength between 300nm and 1000 nm; preferably between 350nm and 900 nm; more preferably between 400nm and 800 nm. Luminescence as used herein refers to photoluminescence or electroluminescence.

The organic compounds according to the invention can be used as functional materials in organic electronic devices. Organic functional materials can be classified into Hole Injection Materials (HIM), Hole Transport Materials (HTM), Electron Transport Materials (ETM), Electron Injection Materials (EIM), Electron Blocking Materials (EBM), Hole Blocking Materials (HBM), emitters (Emitter), and Host materials (Host). In a preferred embodiment, the compounds according to the invention can be used as host materials, or electron-transport materials, or hole-transport materials, or guest materials. In a more preferred embodiment, the compounds according to the invention are used as delayed fluorescence guest materials.

An embodiment of the present invention is also directed to a polymer comprising at least one repeating unit comprising an organic compound of any of the embodiments above.

In a preferred embodiment, the polymer is synthesized by a method selected from the group consisting of SUZUKI-, YAMAMOTO-, STILLE-, NIGESHI-, KUMADA-, HECK-, SONOGASHIRA-, HIYAMA-, FUKUYAMA-, HARTWIG-BUCHWALD-and ULLMAN.

In a preferred embodiment, the polymers according to the invention have a glass transition temperature (Tg) of 100 ℃ or more; preferably equal to or more than 120 ℃; more preferably not less than 140 ℃; more preferably more than or equal to 160 ℃; most preferably greater than or equal to 180 ℃.

In a preferred embodiment, the molecular weight distribution (PDI) of the polymer according to the present invention is preferably in the range of 1 to 5; more preferably 1 to 4; more preferably 1 to 3; more preferably 1 to 2; most preferably 1 to 1.5.

In a preferred embodiment, the polymers according to the invention preferably have a weight average molecular weight (Mw) ranging from 1 to 100 ten thousand; more preferably 5 to 50 ten thousand; more preferably 10 to 40 ten thousand; more preferably 15 to 30 ten thousand; most preferably 20 to 25 ten thousand.

An embodiment of the present invention further relates to a mixture, which includes the organic compound or the polymer in any one of the above embodiments, and at least one organic functional material H2. The organic compound or polymer is designated as H1. Wherein the organic functional material H2 is selected from Hole Injection Material (HIM), Hole Transport Material (HTM), Electron Transport Material (ETM), Electron Injection Material (EIM), Electron Blocking Material (EBM), Hole Blocking Material (HBM), luminophor (Emitter), and Host material (Host).

Preferably, H2 is selected from singlet emitters (fluorescent emitters), singlet emitters (phosphorescent emitters), in particular light-emitting organometallic complexes and organic thermally excited delayed fluorescence materials (TADF materials). Various organic functional materials are described in detail, for example, in WO2010135519a1, US20090134784a1 and WO2011110277a1, the entire contents of this 3 patent document being hereby incorporated by reference. The organic functional material can be small molecule and high polymer material.

In certain preferred embodiments, the mixtures according to the invention, wherein at least one of H1 and H2 has a Δ LUMO ≧ 0.05 eV; preferably not less than 0.2 eV; more preferably not less than 0.4 eV; more preferably, it is not less than 0.6 eV.

In a more preferred embodiment, the mixtures according to the invention, where Δ LUMO of H1 is ≧ 0.05 eV; preferably not less than 0.2 eV; more preferably not less than 0.4 eV; more preferably, it is not less than 0.6 eV.

In certain preferred embodiments, the mixtures according to the invention, wherein at least one of H1 and H2 has a Δ HOMO ≧ 0.2 eV; preferably not less than 0.4 eV; more preferably, it is not less than 0.6 eV.

In a more preferred embodiment, the organic mixture according to the invention, where H2 has a. DELTA. HOMO ≧ 0.2 eV; preferably not less than 0.4 eV; more preferably, it is not less than 0.6 eV.

In certain preferred embodiments, mixtures according to the invention in which min ((LUMO (H1) -HOMO (H2), LUMO (H2) -HOMO (H1)) ≦ min (ET (H1), ET (H2)) +0.1eV are used, in which LUMO (H1), HOMO (H1) and ET (H1) are respectively the lowest unoccupied orbital, the highest occupied orbital, the energy level of the triplet state of H1, LUMO (H2), HOMO (H2) and ET (H2) are respectively the lowest unoccupied orbital, the highest occupied orbital, the energy level of the triplet state of H2, more preferably min ((LUMO (H1) -HOMO (H2), LUMO (H2) -HOMO (H1)) ≦ min (ET (H1), 686ET (H9)); still more preferably ((min ((LUMO (H5962) -HOMO (HOMO 56), LUMO (H828653)) ≦ HOMO (H828653)_T(H1),E_T(H2))-0.1eV。

In certain more preferred embodiments, the mixtures according to the invention, wherein 1) Δ E (S1-T1) of H1 is ≦ 0.30 eV; preferably less than or equal to 0.2 eV; more preferably not more than 0.15 eV; more preferably less than or equal to 0.10 eV; and/or, 2) the LUMO of H2 is higher than the LUMO of H1, and the HOMO of H2 is lower than the HOMO of H1.

In a preferred embodiment, the mixture according to the invention, wherein the molar ratio of H1 and H2 is from 2: 8 to 8: 2; preferred molar ratios are 3:7 to 7: 3; more preferred molar ratios are 4:6 to 6: 4; the most preferred molar ratio is 4.5:5.5 to 5.5: 4.5.

In a preferred embodiment, the mixture according to the invention, wherein the difference between the molecular weights of H1 and H2 does not exceed 100 Dalton; preferably not more than 80 Dalton; more preferably not more than 70 Dalton; more preferably not more than 60 Dalton; very preferably not more than 40 Dalton; preferably not more than 30 daltons.

In another preferred embodiment, the mixture according to the invention, wherein the difference between the sublimation temperatures of H1 and H2 does not exceed 50K; more preferably the difference in sublimation temperatures does not exceed 30K; more preferably, the difference in sublimation temperature does not exceed 20K; most preferably the difference in sublimation temperatures does not exceed 10K.

In a preferred embodiment, the mixtures according to the invention have at least one of the glass transition temperatures Tg of H1 and H2 of 100 ℃ or more; in a preferred embodiment, at least one of the polymers has a Tg of 120 ℃ or higher; in a more preferred embodiment, at least one of the polymers has a Tg of 140 ℃ or higher; in a more preferred embodiment, at least one of the polymers has a Tg of 160 ℃ or higher; in a most preferred embodiment, at least one of the polymers has a Tg of 180 ℃ or higher.

In a preferred embodiment, the organic functional material is selected from compounds represented by structural formula (5):

wherein:

each R₅Independently selected from the group shown in the structural formula (6), H, D, F, Cl, Br, CF₃Hydroxy, nitro, cyano, isocyanoOne or more of formyl group, carbamoyl group, haloformyl group, isocyanate group, thiocyanate group, isothiocyanate group, silyl group, linear alkyl or alkoxy or thioalkoxy group with the carbon number of 1-20, branched alkyl or alkoxy or thioalkoxy group with the carbon number of 3-20, alkyl or alkoxy or thioalkoxy group with the carbon number of 3-20 and ring, ketone group with the carbon number of 1-20, alkoxycarbonyl group with the carbon number of 2-20, aryloxycarbonyl group with the carbon number of 7-20, crosslinkable group, substituted or unsubstituted aryl or heteroaryl group with the ring number of 5-60, and aryloxy or heteroaryloxy group with the ring number of 5-60; two or more adjacent R₅Aliphatic, aromatic or heteroaromatic rings which may optionally form a single ring or multiple rings with one another;

at least one R₅Selected from the group represented by the structural formula (6); ar in the structural formula (6)₃、Ar₄Independently selected from substituted or unsubstituted aryl or heteroaryl with 5-30 ring atoms and substituted or unsubstituted non-aromatic ring group with 5-30 ring atoms; l is₁Selected from substituted or unsubstituted aryl or heteroaryl with 5-30 ring atoms and substituted or unsubstituted non-aromatic ring group with 5-30 ring atoms; ar (Ar)₃、Ar₄、L₁Any two of which may be interconnected to form a ring.

Preferably, examples of the organic functional material H2 according to structural formula (5) are selected from the following structures, but not limited thereto, wherein H in the structures may be further optionally substituted.

In a more preferred embodiment, said mixture comprises at least one organic compound or polymer according to the invention and a host material selected from the group consisting of singlet host material, triplet host material or TADF material.

In certain embodiments, the mixture comprises at least one organic compound or polymer according to the present invention and a host material. The mixtures according to the invention can be used here as delayed-fluorescence guest materials, where the weight percentage of fluorescence guest is 10 wt.% or less; preferably less than or equal to 9 wt%; more preferably less than or equal to 8 wt%; particularly preferably not more than 7 wt%; more preferably not more than 5 wt%.

Some more detailed descriptions (but not limited to) of TADF materials, singlet host materials and triplet host materials follow.

1. Singlet Host material (Singlet Host):

examples of the singlet host material are not particularly limited, and any organic compound may be used as the host as long as the singlet energy thereof is higher than that of the light emitter, particularly, the singlet light emitter or the fluorescent light emitter.

Examples of the organic compound used as the singlet host material may be selected from the group consisting of cyclic aromatic hydrocarbon-containing compounds such as benzene, biphenyl, triphenyl, benzo, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene, chrysene, perylene, azulene; aromatic heterocyclic compounds, such as dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridine indole, pyrrole bipyridine, pyrazole, imidazole, triazole, isoxazole, thiazole, oxadiazole, oxatriazole, bisoxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indazole, indolizine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthalene, phthalein, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzofuran pyridine, furan bipyridine, benzothiophene pyridine, thiophene bipyridine, benzoselenophene pyridine, and selenophene bipyridine; groups having 2 to 10 ring structures, which may be the same or different types of cyclic aromatic hydrocarbon groups or aromatic heterocyclic groups, are bonded to each other directly or through at least one group selected from the group consisting of an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, a phosphorus atom, a boron atom, a chain structural unit and an alicyclic group.

In a preferred embodiment, the singlet host material may be selected from compounds comprising at least one of the following groups:

x, Y has the same meaning as above, R¹At each occurrence, is independently selected from the group consisting of: hydrogen, deuterium, halogen atoms (F, Cl, Br, I), cyano, alkyl, alkoxy, amino, alkenyl, alkynyl, aralkyl, heteroalkyl, aryl and heteroaryl groups, n being selected from an integer from 1 to 20.

In some preferred embodiments, the singlet hosts are selected from derivatives of anthracene, as disclosed in patents CN 102224614B, CN 100471827C, CN 1914293B, WO2015033559a1, US2014246657a1, WO2016117848a1, WO2016117861a1, WO2016171429a2, CN102369256B, CN102428158B, and the like.

Some examples of anthracene-based singlet host materials are listed below:

in some more preferred embodiments, the anthracene-based singlet host material is deuterated, i.e., the host material contains at least one or more deuterium atoms in its molecule, as disclosed in patent documents CN102369256B, CN102428158B, CN102639671B, US2015021586a1, etc., and specific examples are:

2. triplet Host material (Triplet Host):

examples of the triplet host material are not particularly limited, and any metal complex or organic compound may be used as the host as long as the triplet energy level thereof is higher than that of a light emitter, particularly a triplet light emitter or a phosphorescent light emitter.

Examples of metal complexes that can be used as triplet hosts (Host) include, but are not limited to, the following general structures:

m is a metal; (Y)³-Y⁴) Is a bidentate ligand, Y³And Y⁴Independently selected from C, N, O, P or S; l is an ancillary ligand; m is an integer having a value from 1 to the maximum coordination number of the metal; in a preferred embodiment, the metal complexes useful as triplet hosts are of the form:

(O-N) is a bidentate ligand in which the metal is coordinated to both the O and N atoms. m is an integer having a value from 1 up to the maximum coordination number of the metal.

In one embodiment, M may be selected from Ir and Pt.

Examples of the organic compound which can be a triplet host are selected from compounds containing a cyclic aromatic hydrocarbon group such as benzene, biphenyl, triphenylbenzene, benzofluorene; compounds containing aromatic heterocyclic groups, such as dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, dibenzocarbazole, indolocarbazole, pyridine indole, pyrrole bipyridine, pyrazole, imidazole, triazoles, oxazole, thiazole, oxadiazole, bisoxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indazole, oxazole, dibenzooxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, phthalazine, quinazoline, quinoxaline, naphthalene, phthalein, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzofuran pyridine, furopyridine, benzothiophene pyridine, thiophene pyridine, benzoselenophene pyridine, and selenophene benzodipyridine; groups having 2 to 10 ring structures, which may be the same or different types of cyclic aromatic hydrocarbon groups or aromatic heterocyclic groups, are bonded to each other directly or through at least one group selected from the group consisting of an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, a phosphorus atom, a boron atom, a chain structural unit and an alicyclic group. Wherein each Ar may be further substituted, and the substituents may be selected from the group consisting of hydrogen, deuterium, cyano, halogen, alkyl, alkoxy, amino, alkene, alkyne, aralkyl, heteroalkyl, aryl and heteroaryl.

In a preferred embodiment, the triplet host material may be selected from compounds comprising at least one of the following groups:

wherein: x and Y have the same meanings as above, Ar¹～Ar³Selected from aryl or heteroaryl, R¹Groups which can be selected from: hydrogen, deuterium, a halogen atom (F, Cl, Br, I), cyano, alkyl, alkoxy, amino, alkenyl, alkynyl, aralkyl, heteroalkyl, aryl or heteroaryl, and n is selected from an integer of 1 to 20.

Examples of suitable triplet host materials are listed below but are not limited to:

3. thermally activated delayed fluorescence luminescent material (TADF):

the traditional organic fluorescent material can only emit light by utilizing 25% singlet excitons formed by electric excitation, and the internal quantum efficiency of the device is low (up to 25%). Although the phosphorescence material enhances the intersystem crossing due to the strong spin-orbit coupling of the heavy atom center, the singlet excitons and the triplet excitons formed by the electric excitation can be effectively used for emitting light, so that the internal quantum efficiency of the device reaches 100 percent. However, the application of the phosphorescent material in the OLED is limited by the problems of high price, poor material stability, serious efficiency roll-off of the device and the like. The thermally activated delayed fluorescence emitting material is a third generation organic emitting material developed after organic fluorescent materials and organic phosphorescent materials. Such materials generally have a small singlet-triplet energy level difference (Δ Est), and triplet excitons may be converted to singlet excitons for emission by intersystem crossing. This can make full use of singlet excitons and triplet excitons formed upon electrical excitation. The quantum efficiency in the device can reach 100%. Meanwhile, the material has controllable structure, stable property, low price and no need of noble metal, and has wide application prospect in the field of OLED.

TADF materials are required to have a small singlet-triplet level difference, preferably Δ Est < 0.3eV, less preferably Δ Est < 0.25eV, still more preferably Δ Est < 0.20eV, and most preferably Δ Est < 0.1 eV. In a preferred embodiment, the TADF material has a relatively small Δ Est, and in another preferred embodiment, the TADF has a good fluorescence quantum efficiency. Some TADF luminescent materials may be found in CN103483332(a), TW201309696(a), TW201309778(a), TW201343874(a), TW201350558(a), US20120217869(a1), WO2013133359(a1), WO2013154064(a1), Adachi, et.al.nature Photonics,6,2012,253, Adachi, et.al.nature,492,2012,234, Adachi, et.al.adv.mater, 25,2013,3707, Adachi, et.al.chem.mater, 25,2013,3038, Adachi, et.al.chem.mater, 25,2013,3766, j.y.lee, et.203al.adv.mater, 2018,1800255, t.yasuda, adv.chem.mater, 2018, t.t.t.2018, et.2889, see patent document No. et al.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.

Some examples of suitable TADF phosphors are listed in the following table:

it is an object of the present invention to provide a material solution for evaporation type OLEDs.

In certain embodiments, the organic compounds according to the present invention have a molecular weight of 1200g/mol or less; preferably 1100g/mol or less; very preferably 1000g/mol or less; more preferably 950g/mol or less; most preferably 900g/mol or less.

It is another object of the present invention to provide a material solution for printing OLEDs.

In certain embodiments, the organic compounds according to the invention have a molecular weight of 800g/mol or more, preferably 900g/mol or more; very preferably not less than 1000 g/mol; more preferably 1100g/mol or more; most preferably 1200g/mol or more.

In other embodiments, the organic compounds according to the invention have a solubility in toluene of 2mg/ml or more at 25 ℃; preferably more than or equal to 3 mg/ml; more preferably not less than 4 mg/ml; most preferably ≥ 5 mg/ml.

An embodiment of the present invention further relates to a composition comprising the organic compound or the polymer or the mixture of any of the above embodiments, and at least one organic solvent.

In a preferred embodiment, the organic solvent is selected from aromatic or heteroaromatic, ester, aromatic ketone or ether, aliphatic ketone or ether, alicyclic or olefinic compound, or borate or phosphate compound, or a mixture of two or more solvents.

Preferably, the organic solvent is selected from aromatic or heteroaromatic based solvents.

Examples of aromatic or heteroaromatic based solvents suitable for the present invention are, but not limited to: p-diisopropylbenzene, pentylbenzene, tetrahydronaphthalene, cyclohexylbenzene, chloronaphthalene, 1, 4-dimethylnaphthalene, 3-isopropylbiphenyl, p-methylisopropylbenzene, dipentylbenzene, tripentylbenzene, pentyltoluene, o-diethylbenzene, m-diethylbenzene, p-diethylbenzene, 1,2,3, 4-tetramethylbenzene, 1,2,3, 5-tetramethylbenzene, 1,2,4, 5-tetramethylbenzene, butylbenzene, dodecylbenzene, dihexylbenzene, dibutylbenzene, p-diisopropylbenzene, cyclohexylbenzene, benzylbutylbenzene, dimethylnaphthalene, 3-isopropylbiphenyl, p-methylisopropylbenzene, 1-methylnaphthalene, 1,2, 4-trichlorobenzene, 4-difluorodiphenylmethane, 1, 2-dimethoxy-4- (1-propenyl) benzene, diphenylmethane, 2-phenylpyridine, 3-phenylpyridine, N-methyldiphenylamine, 4-isopropylbiphenyl, α -dichlorodiphenylmethane, 4- (3-phenylpropyl) pyridine, benzyl benzoate, 1-bis (3, 4-dimethylphenyl) ethane, 2-isopropylnaphthalene, quinoline, isoquinoline, methyl 2-furancarboxylate, ethyl 2-furancarboxylate, and the like.

Examples of aromatic ketone-based solvents suitable for the present invention are, but not limited to: 1-tetralone, 2- (phenylepoxy) tetralone, 6- (methoxy) tetralone, acetophenone, propiophenone, benzophenone, and derivatives thereof, such as 4-methylacetophenone, 3-methylacetophenone, 2-methylacetophenone, 4-methylpropiophenone, 3-methylpropiophenone, 2-methylpropiophenone, and the like.

Examples of aromatic ether-based solvents suitable for the present invention are, but not limited to: 3-phenoxytoluene, butoxybenzene, p-anisaldehyde dimethylacetal, tetrahydro-2-phenoxy-2H-pyran, 1, 2-dimethoxy-4- (1-propenyl) benzene, 1, 4-benzodioxan, 1, 3-dipropylbenzene, 2, 5-dimethoxytoluene, 4-ethylphenetole, 1, 3-dipropoxybenzene, 1,2, 4-trimethoxybenzene, 4- (1-propenyl) -1, 2-dimethoxybenzene, 1, 3-dimethoxybenzene, glycidylphenyl ether, dibenzyl ether, 4-t-butylanisole, trans-p-propenylanisole, 1, 2-dimethoxybenzene, 1-methoxynaphthalene, diphenyl ether, 2-phenoxymethyl ether, methyl ether, 2-phenoxytetrahydrofuran, ethyl-2-naphthyl ether.

Further, the organic solvent may be selected from: aliphatic ketones such as 2-nonanone, 3-nonanone, 5-nonanone, 2-decanone, 2, 5-hexanedione, 2,6, 8-trimethyl-4-nonanone, fenchylone, phorone, isophorone, di-n-amyl ketone, etc.; or aliphatic ethers such as amyl ether, hexyl ether, dioctyl ether, ethylene glycol dibutyl ether, diethylene glycol diethyl ether, diethylene glycol butyl methyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, triethylene glycol ethyl methyl ether, triethylene glycol butyl methyl ether, tripropylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, and the like.

In other preferred embodiments, the organic solvent may be selected from ester-based solvents: alkyl octanoates, alkyl sebacates, alkyl stearates, alkyl benzoates, alkyl phenylacetates, alkyl cinnamates, alkyl oxalates, alkyl maleates, alkyl lactones, alkyl oleates, and the like. Octyl octanoate, diethyl sebacate, diallyl phthalate, isononyl isononanoate are particularly preferred.

The organic solvent may be used alone or as a mixture of two or more organic solvents.

In certain preferred embodiments, a composition according to the present invention comprises at least one organic compound or polymer or mixture as described above and at least one organic solvent, and may further comprise another organic solvent. Examples of another organic solvent include (but are not limited to): methanol, ethanol, 2-methoxyethanol, methylene chloride, chloroform, chlorobenzene, o-dichlorobenzene, tetrahydrofuran, anisole, morpholine, toluene, o-xylene, m-xylene, p-xylene, 1, 4-dioxane, acetone, methyl ethyl ketone, 1, 2-dichloroethane, 3-phenoxytoluene, 1,1, 1-trichloroethane, 1,1,2, 2-tetrachloroethane, ethyl acetate, butyl acetate, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, tetrahydronaphthalene, decalin, indene, and/or mixtures thereof.

In some preferred embodiments, particularly suitable solvents for the present invention are those having Hansen (Hansen) solubility parameters within the following ranges:

δ_d(dispersion force) of 17.0 to 23.2MPa^1/2In particular in the range of 18.5 to 21.0MPa^1/2A range of (d);

δ_p(polar force) is 0.2 to 12.5MPa^1/2In particular in the range of 2.0 to 6.0MPa^1/2A range of (d);

δ_h(hydrogen bonding force) of 0.9 to 14.2MPa^1/2In particular in the range of 2.0 to 6.0MPa^1/2The range of (1).

The compositions according to the invention, in which the organic solvent is selected taking into account its boiling point parameter. In the invention, the boiling point of the organic solvent is more than or equal to 150 ℃; preferably equal to or more than 180 ℃; more preferably more than or equal to 200 ℃; more preferably more than or equal to 250 ℃; most preferably more than or equal to 275 ℃ or more than or equal to 300 ℃. Boiling points in these ranges are beneficial for preventing nozzle clogging in inkjet print heads. The organic solvent may be evaporated from the solvent system to form a thin film comprising the functional material.

In a preferred embodiment, the composition according to the invention is a solution.

In another preferred embodiment, the composition according to the invention is a suspension.

The composition of the embodiments of the present invention may contain 0.01 to 10 wt% of the organometallic complex or polymer or mixture according to the present invention, preferably 0.1 to 15 wt%, more preferably 0.2 to 5 wt%, most preferably 0.25 to 3 wt%.

The invention also relates to the use of said composition as a coating or printing ink for the production of organic electronic devices, particularly preferably by a printing or coating production process.

Suitable printing or coating techniques include, but are not limited to, ink jet printing, spray printing (Nozleprinting), letterpress printing, screen printing, dip coating, spin coating, doctor blade coating, roll printing, twist roll printing, lithographic printing, flexographic printing, rotary printing, spray coating, brush or pad printing, slot die coating, and the like. Gravure printing, jet printing and ink jet printing are preferred. The solution or suspension may additionally include one or more components such as surface active compounds, lubricants, wetting agents, dispersants, hydrophobing agents, binders, and the like, for adjusting viscosity, film forming properties, enhancing adhesion, and the like. For details on the printing technology and its requirements concerning the solutions, such as solvent and concentration, viscosity, etc., reference is made to the Handbook of Print Media, technology and production Methods, published by Helmut Kipphan, ISBN 3-540-67326-1.

An embodiment of the invention also relates to an organic electronic device comprising the organic compound or the polymer or the mixture of any of the above embodiments.

In a preferred embodiment, the organic electronic device is an electroluminescent device comprising a light-emitting layer comprising an organic compound according to any of the above embodiments or a polymer according to any of the above embodiments or a mixture according to any of the above embodiments.

In a preferred embodiment, the Organic electronic device is selected from the group consisting of 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 laser, an Organic spintronic device, an Organic sensor, or an Organic Plasmon emitting diode (Organic plasma emitting diode).

Preferably, the organic electronic device is an OLED. Further, the above organic compound or high polymer or mixture is used for a light emitting layer of an OLED.

In general, an organic electronic device comprises at least a cathode, an anode and a functional layer located between the cathode and the anode, wherein the functional layer comprises at least one organic compound as described above. The Organic electronic device can be selected from, but not limited to, Organic Light Emitting Diodes (OLEDs), Organic photovoltaic cells (OPVs), Organic light Emitting cells (OLEECs), Organic Field Effect Transistors (OFETs), Organic light Emitting field effect transistors (fets), Organic lasers, Organic spintronic devices, Organic sensors, Organic Plasmon Emitting diodes (Organic Plasmon Emitting diodes), and the like, and particularly preferred are Organic electroluminescent devices such as OLEDs, OLEECs, Organic light Emitting field effect transistors.

In certain particularly preferred embodiments, the electroluminescent device comprises a light-emitting layer comprising one of the above-mentioned organic compounds or polymers or mixtures thereof.

In the above-mentioned light emitting device, especially an OLED, it comprises a substrate, an anode, at least one light emitting layer, and a cathode.

The substrate may be opaque or transparent. A transparent substrate may be used to fabricate a transparent light emitting device. See, for example, Bulovic et al Nature 1996,380, p29, and Gu et al, appl.Phys.Lett.1996,68, p 2606. The substrate may be rigid or flexible. The substrate may be plastic, metal, semiconductor wafer or glass. Preferably, the substrate has a smooth surface. A substrate free of surface defects is a particularly desirable choice. In a preferred embodiment, the substrate is flexible, and may be selected from polymeric films or plastics having a glass transition temperature Tg of 150 deg.C or greater, preferably greater than 200 deg.C, more preferably greater than 250 deg.C, and most preferably greater than 300 deg.C. Examples of suitable flexible substrates are poly (ethylene terephthalate) (PET) and polyethylene glycol (2, 6-naphthalene) (PEN).

The anode may comprise a conductive metal or metal oxide, or a conductive polymer. The anode can easily inject holes into a Hole Injection Layer (HIL) or a Hole Transport Layer (HTL) or an emission layer. In one embodiment, the absolute value of the difference between the work function of the anode and the HOMO level or valence band level of the emitter in the light emitting layer or the p-type semiconductor material acting as a HIL or HTL or Electron Blocking Layer (EBL) is less than 0.5eV, preferably less than 0.3eV, most preferably less than 0.2 eV. Examples of anode materials include, but are not limited to: al, Cu, Au, Ag, Mg, Fe, Co, Ni, Mn, Pd, Pt, ITO, aluminum-doped zinc oxide (AZO), and the like. Other suitable anode materials are known and can be readily selected for use by one of ordinary skill in the art. The anode material may be deposited using any suitable technique, such as a suitable physical vapor deposition method including radio frequency magnetron sputtering, vacuum thermal evaporation, electron beam (e-beam), and the like. In certain embodiments, the anode is pattern structured. Patterned ITO conductive substrates are commercially available and can be used to prepare devices according to the present invention.

The cathode may comprise a conductive metal or metal oxide. The cathode can easily inject electrons into the EIL or ETL or directly into the light emitting layer. In one embodiment, the absolute value of the difference between the work function of the cathode and the LUMO level or conduction band level of the emitter in the light-emitting layer or of the n-type semiconductor material as Electron Injection Layer (EIL) or Electron Transport Layer (ETL) or Hole Blocking Layer (HBL) is less than 0.5eV, preferably less than 0.3eV, most preferably less than 0.2 eV. In principle, all materials which can be used as cathodes in OLEDs are possible as cathode materials for the device according to the invention. Examples of cathode materials include, but are not limited to: al, Au, Ag, Ca, Ba, Mg, LiF/Al, MgAg alloy, BaF₂Al, Cu, Fe, Co, Ni, Mn, Pd, Pt, ITO, etc. The cathode material may be deposited using any suitable technique, such as a suitable physical vapor deposition method, including radio frequency magnetron sputtering, vacuum thermal evaporation, electron beam (e-beam), and the like.

The OLED may also comprise further functional layers, such as a Hole Injection Layer (HIL), a Hole Transport Layer (HTL), an Electron Blocking Layer (EBL), an Electron Injection Layer (EIL), an Electron Transport Layer (ETL), a Hole Blocking Layer (HBL). Suitable materials for use in these functional layers are described in detail above and in WO2010135519a1, US20090134784a1 and WO2011110277a1, the entire contents of these 3 patent documents being hereby incorporated by reference.

The light-emitting device according to the present invention emits light having a wavelength of 300nm to 1200 nm; preferably between 350nm and 1000 nm; more preferably between 400nm and 900 nm.

The invention also relates to the use of the electroluminescent device according to the invention in various electronic devices, including, but not limited to, display devices, lighting devices, light sources, sensors, etc.

The present invention will be described in connection with preferred embodiments, but the present invention is not limited to the following embodiments, and it should be understood that the appended claims outline the scope of the present invention and those skilled in the art, guided by the inventive concept, will appreciate that certain changes may be made to the embodiments of the invention, which are intended to be covered by the spirit and scope of the appended claims.

Provided is a concrete embodiment.

1. Synthesis of organic compounds

Example 1

Synthesis of D1-1: in a flask, indole (30.0g), 2-fluoronitrobenzene (36.2g), NaH (6.15g) and 500ml of dry THF were added and reacted at 50 ℃ for 12 hours under a nitrogen atmosphere. And cooling the reaction solution, pouring the reaction solution into water, extracting by ethyl acetate, washing the separated liquid by water, and performing column chromatography to obtain D1-1. MS (ASAP) 238.25.

Synthesis of D1-2: in a flask, D1-1(25.0g) was added and 400ml triethyl phosphite was added, heated to 140 ℃ and reacted for 6 h. The solvent was removed by distillation under the reduced pressure, and the concentrated reaction solution was subjected to column chromatography to give D1-2. MS (ASAP) 206.25.

Synthesis of D1-3: in a flask, D1-2(20.0g), NaH (4.6g) and 500ml of dry THF were added and reacted at 75 ℃ for 1h under a nitrogen atmosphere; then, 2-fluoronitrobenzene (13.7g) was added and reacted at 50 ℃ for 6 hours. And cooling the reaction solution, pouring the reaction solution into water, extracting by ethyl acetate, washing the separated liquid by water, and performing column chromatography to obtain D1-3. MS (ASAP) 327.24.

Synthesis of D1-4: in a flask, D1-3(20.0g) was added and 400ml triethyl phosphite was added, heated to 140 ℃ and reacted for 6 h. The solvent was removed by distillation under the reduced pressure, and the concentrated reaction solution was subjected to column chromatography to give D1-4. MS (ASAP) 295.35.

Synthesis of D1: in a flask, D1-4(15.0g), cesium carbonate (33.1g) and 300ml of DMF were charged and reacted at 75 ℃ for 1 hour under a nitrogen atmosphere, followed by addition of 2-chloro-4, 6-diphenyl-1, 3, 5-triazine (13.6g) and reaction at 130 ℃ for 12 hours. After cooling, the filtrate was filtered and taken, poured into excess water, extracted and the liquid separated by washing with water. After the organic phase was spin dried, it was recrystallized to yield D1. MS (ASAP) 526.60.

Example 2

Synthesis of D2-4: synthesis of D2-4 reference was made to the synthesis of D1-4 in example 1, except that indole was replaced with 3-methylindole. MS (ASAP) 309.37.

Synthesis of D2: d2-4, 2- (4-bromophenyl) -4-phenylquinazoline, palladium acetate, tri-tert-butylphosphine, sodium tert-butoxide and toluene were added to the flask and refluxed for 12h under a nitrogen atmosphere. After cooling, the filtrate was filtered, the toluene was removed by rotary evaporation, extracted with dichloromethane and the liquid separated by washing with water, and column chromatography gave D2. MS (ASAP) 589.70.

Example 3

Synthesis of D3: in a flask, D2-4(15.0g), NaH (1.6g) and 200ml DMF were added and reacted at 75 ℃ for 1h under a nitrogen atmosphere, then D3-1(18.8g) was added and the temperature was raised to 130 ℃ for 12h. After cooling, the reaction solution was poured into excess water, extracted and the separated liquid was washed with water. After the organic phase was spin dried, it was recrystallized to yield D3. MS (ASAP) 735.87.

Example 4

Synthesis of D4: reference is made to the synthesis of D2 in example 2, except that 2- (4-bromophenyl) -4-phenylquinazoline is replaced with 2- (4-bromophenyl) -4, 6-diphenyl-1, 3, 5-triazine. MS (ASAP) 616.73

Example 5

Synthesis of D5-2: in a flask, D2-2(20.0g), NaH (4.6g) and 500ml of dry THF were added and reacted at 75 ℃ for 1h under a nitrogen atmosphere; d5-1(29.4g) was then added and reacted at 80 ℃ for 6 h. And cooling the reaction solution, pouring the reaction solution into water, extracting by ethyl acetate, washing the separated liquid by water, and performing column chromatography to obtain D5-2. MS (ASAP) 523.61.

Synthesis of D5-3 reference was made to the synthesis of D2-4 in example 2, except that D2-3 was replaced with D5-2. Ms (asap): 491.61

Synthesis of D5: d5-3(15.0g) and NaH (1.4g) were dissolved in 400ml dry DMF and stirred at 75 ℃ for 1h under nitrogen atmosphere; then adding 2-chloro-4-phenylquinazoline (7.3g), heating to 120 ℃, reacting for 12h, cooling, pouring into a large amount of water, and extracting and separating liquid; the organic phase was spin dried and recrystallized to yield D5. MS (ASAP) 695.84.

Example 6

Synthesis of D6-5 reference was made to the synthesis of D2-4, except that 3-methylindole was replaced with D6-1. MS (ASAP) 415.51

Synthesis of D6 reference was made to the synthesis of D5, with the exception that D5-3 was replaced by D6-5. MS (ASAP) 619.75.

Example 7

Synthesis of D7-2 reference was made to the synthesis of D1-1 in example 1, except that o-fluoronitrobenzene was changed to D7-1 and indole was changed to 3-methylindole. Ms (asap): 358.42.

synthesis of D7-5 reference was made to the synthesis of D1-4 in example 1, except that D1-1 was changed to D7-2. Ms (asap): 415.51.

synthesis of D7 reference was made to the synthesis of D5, with the exception that D5-3 was replaced by D7-5. MS (ASAP) 619.75.

Example 8

Synthesis of D8-5 reference was made to the synthesis of D1-4, except that indole was replaced with D8-1. MS (ASAP) 460.54

Synthesis of D8 reference was made to the synthesis of D5, with the exception that D5-3 was replaced by D8-5. MS (ASAP) 677.25.

Example 9

Synthesis of D9-3 reference was made to the synthesis of D2-4, except that o-fluoronitrobenzene was changed to D9-1. MS (ASAP) 415.51.

Synthesis of D9: synthesis of D9 reference was made to the synthesis of D5, with the exception that D5-3 was replaced by D9-3. Ms (asap): 619.75.

example 10

Synthesis of D10: synthesis of D10 reference was made to the synthesis of D5, except that 2-chloro-4-phenylquinazoline was replaced with D10-1. Ms (asap): 569.69.

example 11

Synthesis of D11-2 reference was made to the synthesis of D1-3, except that D1-2 was changed to D2-2 and o-fluoronitrobenzene was changed to D11-1. Synthesis of D11-3 reference was made to the synthesis of D1-4, except that D1-3 was replaced by D11-2. MS (ASAP) 359.43 of D11-3

Synthesis of D11 reference was made to the synthesis of D5, with the exception that D5-3 was replaced by D11-3. MS (ASAP) 563.66.

Example 12

Synthesis of D12-5 reference was made to the synthesis of D2-4, except that 3-methylindole was replaced with D12-1. Synthesis of D12 reference was made to the synthesis of D5, with the exception that D5-3 was replaced by D12-5. MS (ASAP) 603.69 of D12.

Example 13

Synthesis of D13-2 reference was made to the synthesis of D1-1 in example 1, except that indole was changed to 3-methylindole and o-fluoronitrobenzene was changed to D13-1. Ms (asap): 358.42.

synthesis of D13-5 reference was made to the synthesis of D1-4 in example 1, except that D1-1 was changed to D13-2. Ms (asap): 415.51.

synthesis of D13 reference was made to the synthesis of D5, with the exception that D5-3 was replaced by D13-5. MS (ASAP) 619.75.

Example 14

Synthesis of D14 reference was made to the synthesis of D9, with the exception that D2-2 was replaced by D14-1 and D9-1 was replaced by D14-4. MS (ASAP) 680.82.

Example 15

Synthesis of D15 reference was made to the synthesis of D13, except that o-fluoronitrobenzene was replaced with D15-1 and 2-chloro-4-phenylquinazoline was replaced with D15-4. MS (ASAP) 710.19.

2. Calculation of energy level Structure of Compound

The energy level of the organic compound material can be obtained by quantum calculation, for example, by using TD-DFT (including time density functional theory) through Gaussian09W (Gaussian Inc.), and a specific simulation method can be seen in WO 2011141110. Firstly, a Semi-empirical method of 'group State/Semi-empirical/Default Spin/AM 1' (Charge 0/Spin Singlet) is used for optimizing the molecular geometrical structure, and then the energy structure of the organic molecules is calculated by a TD-DFT (including time density functional theory) method to obtain 'TD-SCF/DFT/Default Spin/B3PW 91' and a base group of '6-31G (d)' (Charge 0/Spin Singlet). The HOMO and LUMO energy levels were calculated according to the following calibration formula, S1, T1 and resonance factor f (S1) were used directly.

HOMO(eV)＝((HOMO(G)×27.212)-0.9899)/1.1206

LUMO(eV)＝((LUMO(G)×27.212)-2.0041)/1.385

Where HOMO (G) and LUMO (G) are direct calculations of Gaussian09W in Hartree. The results are shown in table 1:

table 1: quantum calculation results of example materials

In Table 1, each of the compounds D1 to D15 has a large Δ HOMO (S) ((R))>0.2eV), the materials other than D1, D4 all have a larger Δ LUMO ((D)>0.5eV), indicating that these compounds are ideal materials for long-life OLED devices; the materials in Table 1 all have suitable Δ E_ST(<0.30eV), particularly D1-D13, have a relatively smaller Δ E_ST(<0.20eV), which shows that these compounds can be used as TADF material, especially D7, D9, D12, D15 have better f (S1) ((S1)>0.015), indicating that these materials are more efficient luminescent materials. Wherein D9 and F-2, D13 and F-1,The mixture of D12 and F-2 meets the condition of min ((LUMO (H1) -HOMO (H2), LUMO (H2) -HOMO (H1)) ≦ min (ET (H1), ET (H2)) +0.1eV, the mixture of D13 and F-2 meets the condition of min ((LUMO (H1) -HOMO (H2), LUMO (H2) -HOMO (H1)) ≦ min (ET (H1), ET (H2)), and the mixtures can form an exciplex with TADF effect and can be used as a high-performance mixed host material.

3. OLED device fabrication

Preparing an OLED device:

example 17 preparation of a material according to the invention as TADF guest Material

The device structure is ITO/HATCN/HTM/host material (F-1) guest material (D1)/ETM Liq/Liq/Al. Wherein the mass ratio of F-1 to guest material is 95: 5. The specific preparation process is as follows:

a. cleaning the conductive glass substrate, namely cleaning the conductive glass substrate by using various solvents such as chloroform, ketone and isopropanol when the conductive glass substrate is used for the first time, and then carrying out ultraviolet ozone plasma treatment;

b. HATCN (30nm), HTM (50nm), host material RD (40nm), ETM Liq (30nm), Liq (1nm), Al (100nm) in high vacuum (1X 10)^-6Millibar) hot evaporation;

c. encapsulation the devices were encapsulated with uv curable resin in a nitrogen glove box.

Example 18 example 33

An OLED device was prepared with reference to example 17, except that compound D1 was changed to the compound shown in table 2.

Table 2: OLED device embodiments and materials used

OLED device	Luminescent material	Color of light emission	Life (T95)
				Example 17	D1	Green	2.9
Example 18	D4	Green	3.2
				Example 19	D9	Green	3.4
Example 20	D7	Green	2.0
				Example 21	D10	Green	2.6
Example 22	D11	Green	2.4
				Example 23	D12	Green	3.5
Example 24	D13	Green	2.9
				Example 25	D14	Green	2.2
Example 26	D15	Green	2.1
				Example 27	Comparative material E1	Green	0.6
Example 28	Comparative material E2	Green	1.0

The current-voltage (J-V) characteristics of each OLED device were characterized by a characterization device, while recording important parameters such as efficiency, lifetime, and external quantum efficiency. The devices shown in the table are all green devices. It was determined that the efficiency and lifetime of green devices using the materials of the present invention are more than 2 times that of examples 28 (comparative material E2) and 27 (comparative material E1) because the materials of the present invention have a larger Δ HOMO (R) ((R) ())>0.2eV) to make the material have a better charge transport propertyGood stability, the lifetime of the green-emitting materials of the invention other than D7 is significantly higher than that of D7, since the materials of the invention other than D7 have a relatively better Δ HOMO (S) ((R))>0.5 eV). The green devices using the materials of the present invention all had external quantum efficiencies more than 2 times that of comparative example 27 (corresponding to E1) and example 28 (corresponding to E2), because the green materials of the present invention have relatively small Δ E_ST(<0.30eV), triplet excitons generated by current in the device can emit light by being changed into singlet excitons through reverse intersystem crossing, thereby improving light emitting efficiency. In particular, the lifetimes of example 18 (corresponding to material D4) and example 19 (corresponding to material D9) were 3 times or more as long as those of comparative example 27 (corresponding to material E1) and example 28 (corresponding to material E2), and the external quantum efficiencies thereof exceeded 10%, because the Δ E's of these two materials_STRelatively smaller (<0.20eV), and f (S1) thereof is relatively large (S1)>0.015), the luminous efficiency and the service life of the object are further improved. The lifetime of example 19 (corresponding material D9) was higher than that of example 18 (corresponding material D4), which is consistent with the Δ LUMO (D9)>0.6eV) is much larger than D4(0.06eV) is consistent. Therefore, the OLED device prepared by the material provided by the invention has the advantages that the light-emitting life and the efficiency are obviously improved.

Example 29 preparation of an OLED device based on the material according to the invention as host material:

device preparation reference was made to example 17, except that the device structure was ITO/HATCN/HTM/host material (D9): RD/ETM: Liq/Liq/Al. Wherein the mass ratio of the host material to RD is 95: 5.

Examples 31 to 35

Device preparation reference was made to example 29, except that D9 was replaced with the host material shown in table 3. In table 3, examples in which the host material is two or more compounds are shown, and the host material is a mixture in which the two materials shown in the table are blended in a mass ratio of 1: 1.

Table 3: OLED device embodiments and materials used

OLED device	Host material	Life (T95)
			Example 29	D9	2.5
Example 30	D13	2.4
			Example 31	D9：F2	3.2
Example 32	D13：F2	3.5
			Example 33	D13:F1	3.3
Example 34	E2	1
			Example 35	E2:F2	1.6

The current-voltage (J-V) characteristics of each OLED device were characterized by a characterization device, while recording important parameters such as efficiency, lifetime, and external quantum efficiency. The devices in the table are all red phosphorescent devices. It was determined that the efficiency and lifetime of OLED phosphorescent devices using the materials or mixtures according to the invention as host material are more than 2 times higher than those of example 34 (comparative E2) and significantly higher than those of comparative example 35 (corresponding to mixture E2: F2). In particular, the lifetime of examples 31, 32 and 33 based on the mixtures according to the invention is significantly higher than that of the devices according to the other examples. This is because the mixture of the present invention can form an exciplex, thereby improving the device lifetime. Therefore, the phosphorescent OLED device prepared by using the material and the mixture as the main body has the advantages that the light-emitting life and the light-emitting efficiency are remarkably improved.

It is to be understood that the invention is not limited to the examples described above, but that modifications and variations may be effected thereto by those of ordinary skill in the art in light of the foregoing description, and that all such modifications and variations are intended to be within the scope of the invention as defined by the appended claims.

The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.

The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.

Claims

1. An organic compound having a structure represented by structural formula (1):

wherein:

each Z₁Is independently selected from CR₁Or N;

R、R₁independently selected from H, D, F, Cl, Br, CF₃One or more of hydroxyl, nitro, cyano, isocyano, formyl, carbamoyl, haloformyl, isocyanate, thiocyanate, isothiocyanate, silyl, C1-20 linear alkyl or alkoxy or thioalkoxy, C3-20 branched alkyl or alkoxy or thioalkoxy, C3-20 cyclic alkyl or alkoxy or thioalkoxy, C1-20 ketone, C2-20 alkoxycarbonyl, C7-20 aryloxycarbonyl, crosslinkable group, substituted or unsubstituted aryl or heteroaryl having 5-60 ring atoms, and C5-60 aryloxy or heteroaryloxy;

2. The organic compound according to claim 1, wherein A is selected from substituted or unsubstituted heteroaromatic groups having 5 to 40 ring atoms.

3. The organic compound according to claim 1, wherein the structural formula (1) is selected from any one of the following structural formulae (2-1) to (2-8):

4. The organic compound of claim 3, wherein each of B is₁The group is independently selected from one or more of the following structures:

wherein:

each X is independently selected from N or CR₂；

R₂、R₃independently selected from H, D, F, Cl, Br, CF₃The compound is characterized by comprising one or more of hydroxyl, nitryl, cyano, isocyano, formyl, carbamoyl, haloformyl, isocyanate, thiocyanate, isothiocyanate, silyl, straight-chain alkyl or alkoxy or thioalkoxy with the carbon number of 1-20, branched-chain alkyl or alkoxy or thioalkoxy with the carbon number of 3-20, alkyl or alkoxy or thioalkoxy with the ring with the carbon number of 3-20, ketone group with the carbon number of 1-20, alkoxycarbonyl with the carbon number of 2-20, aryloxycarbonyl with the carbon number of 7-20, a crosslinkable group, substituted or unsubstituted aryl or heteroaryl with the ring number of 5-60, and aryloxy or heteroaryloxy with the ring number of 5-60.

5. The organic compound according to claim 4, wherein the structural formula (1) is selected from any one of the following structural formulae (3-1) to (3-16):

wherein:

each X is independently selected from N or CR₂；

Each Y is independentSelected from single bond, CR₂R₃、C＝C(R₂R₃)、Si R₂R₃、NR₂C (═ O), S (═ O), or O;

6. The organic compound of any one of claims 1 to 4, wherein A is selected from the group consisting of one or more of the following structures:

wherein:

each Z is independently selected from N or CR₄；

R₂、R₃、R₄independently selected from H, D, F, Cl, Br, CF₃A hydroxyl group, a nitro group, a cyano group, an isocyano group, a formyl group, a carbamoyl group, a haloformyl group, an isocyanate group, a thiocyanate group, an isothiocyanate group, a silyl group, a linear alkyl group having 1 to 20 carbon atoms, an alkoxy group or a thioalkoxy group having 3 to 20 carbon atomsThe group is one or more of alkyl or alkoxy or thioalkoxy with branched chain, alkyl or alkoxy or thioalkoxy with ring with 3-20 carbon atoms, ketone group with 1-20 carbon atoms, alkoxycarbonyl with 2-20 carbon atoms, aryloxycarbonyl with 7-20 carbon atoms, crosslinkable group, aryl or heteroaryl with 5-60 substituted or unsubstituted ring atoms, and aryloxy or heteroaryloxy with 5-60 ring atoms.

7. The organic compound of claim 6, wherein A is selected from the group consisting of one or more of the following structures:

wherein:

Ar₁、Ar₂independently selected from substituted or unsubstituted aryl or heteroaryl with 5-40 ring atoms and substituted or unsubstituted non-aromatic ring group with 5-40 ring atoms; h in the structural formula of A can be further substituted.

8. An organic compound according to any one of claims 1 to 5, 7, wherein Δ Est ≦ 0.3eV, said Δ Est representing a compound singlet-triplet energy level difference.

9. A polymer comprising at least one repeating unit comprising an organic compound according to any one of claims 1 to 8.

10. A mixture comprising an organic compound according to any one of claims 1 to 8 or a high polymer according to claim 9, and at least one organic functional material H2, wherein the organic functional material H2 is selected from the group consisting of hole injection materials, hole transport materials, electron injection materials, electron blocking materials, hole blocking materials, light emitters, and host materials.

11. The mixture according to claim 10, wherein the organic functional material H2 is selected from compounds represented by structural formula (5):

wherein:

each R₅Independently selected from the group shown in the structural formula (6), H, D, F, Cl, Br, CF₃One or more of hydroxyl, nitro, cyano, isocyano, formyl, carbamoyl, haloformyl, isocyanate, thiocyanate, isothiocyanate, silyl, C1-20 linear alkyl or alkoxy or thioalkoxy, C3-20 branched alkyl or alkoxy or thioalkoxy, C3-20 cyclic alkyl or alkoxy or thioalkoxy, C1-20 ketone, C2-20 alkoxycarbonyl, C7-20 aryloxycarbonyl, crosslinkable group, substituted or unsubstituted aryl or heteroaryl having 5-60 ring atoms, and C5-60 aryloxy or heteroaryloxy; two or more adjacent R₅Aliphatic, aromatic or heteroaromatic rings which may optionally form a single ring or multiple rings with one another;

12. A composition comprising an organic compound according to any one of claims 1 to 8 or a polymer according to claim 9 or a mixture according to any one of claims 10 to 11, and at least one organic solvent.

13. An organic electronic device comprising an organic compound according to any one of claims 1 to 8 or a polymer according to claim 9 or a mixture according to any one of claims 10 to 11.