Organic compound containing oxygenated heterocycle and application thereof

文档序号：802002 发布日期：2021-03-26 浏览：61次中文

阅读说明：本技术 含氧化杂环的有机化合物及其应用 (Organic compound containing oxygenated heterocycle and application thereof ) 是由温华文杨曦刘爱香宋晶尧李们在李先杰王煦张月于 2020-09-11 设计创作，主要内容包括：本发明涉及一种含氧化杂环的有机化合物及其应用。该含氧化杂环的有机化合物具有式(1)所示结构,表现出优异的空穴传输性质及稳定性,可作为有机电致发光元件中的空穴注入层材料,也可以作为掺杂剂掺杂在空穴注入层或空穴传输层中,这样既可用低电压驱动,也可提高电致发光效率,延长器件的寿命。(The invention relates to an organic compound containing an oxygenated heterocycle and application thereof. The organic compound containing the oxygenated heterocycle has the structure shown in the formula (1), shows excellent hole transport property and stability, can be used as a hole injection layer material in an organic electroluminescent element, and can also be used as a dopant to be doped in a hole injection layer or a hole transport layer, so that the organic compound can be driven by low voltage, the electroluminescent efficiency can be improved, and the service life of a device can be prolonged.)

1. An organic compound containing an oxygenated heterocycle is characterized in that the structural general formula is shown as a formula (1):

wherein:

a is selected from S or N; OM is selected from O or OH;

n1 is selected from 1 or 2; m1 is selected from any integer from 1 to 3; m2 is selected from any integer from 2 to 4;

ar is selected from a substituted or unsubstituted ring system containing 3 to 6 ring atoms, wherein the number of Ar ring atoms is the sum of m1+ m 2;

when in useWhen selected from C ═ X, each occurrence of X is independently selected from O, S, S (═ O)₂、CR₁R₂、NR₃、SiR₄R₅、PR₆A substituted or unsubstituted aromatic group having 6 to 60C atoms, a substituted or unsubstituted heteroaromatic group having 5 to 60 ring atoms, or a substituted or unsubstituted non-aromatic ring system having 3 to 30 ring atoms; and at least one X is selected from CR₁R₂；

When in useWhen selected from C-X, X is selected from H, D, a straight chain alkyl group having 1 to 20C atoms, an alkoxy or thioalkoxy group having 1 to 20C atoms, a branched or cyclic alkyl group having 3 to 20C atoms, an alkoxy or thioalkoxy group having 3 to 20C atoms, a silyl group, a ketone group having 1 to 20C atoms, an alkoxycarbonyl group having 2 to 20C atoms, an aryloxycarbonyl group having 7 to 20C atoms, a cyano group, a carbamoyl group, a haloformyl group, a formyl group, an isocyano group, an isocyanate group, a thiocyanate group, an isothiocyanate group, a hydroxyl group, a nitro group, CF₃Cl, Br, F, I, a crosslinkable group, a substituted or unsubstituted heteroaromatic group having 5 to 60 ring atoms, a substituted or unsubstituted aromatic group having 6 to 60 ring atoms, a substituted or unsubstituted aryloxy or heteroaryloxy group having 5 to 60 ring atoms, or a combination of these groups;

when in useWhen present, at least one is selected from the group consisting of C ═ X; and all C atoms on the Ar ring have an atomic orbital sp2 hybridized orbital;

R₁-R₆each occurrence is independently selected from H, D, a straight chain alkyl group having 1 to 20C atoms, an alkoxy or thioalkoxy group having 1 to 20C atoms, a branched or cyclic alkyl group having 3 to 20C atoms, an alkoxy or thioalkoxy group having 3 to 20C atoms, a silyl group, a ketone group having 1 to 20C atoms, an alkoxycarbonyl group having 2 to 20C atoms, a carbonyl group having 7 to 20C atomsAryloxycarbonyl, cyano, carbamoyl, haloformyl, formyl, isocyano, isocyanate, thiocyanate, isothiocyanate, hydroxy, nitro, CF of a molecule₃Cl, Br, F, I, a crosslinkable group, a substituted or unsubstituted heteroaromatic group having 5 to 60 ring atoms, a substituted or unsubstituted aromatic group having 6 to 60 ring atoms, a substituted or unsubstituted aryloxy or heteroaryloxy group having 5 to 60 ring atoms, or a combination of these groups;

when Ar is selected from a substituted or unsubstituted ring system having 3 ring atoms, at least one X is selected from CR₁R₂And at least one R₁Selected from cyano, nitro, CF₃A Cl, Br, F or I substituted aromatic or heteroaromatic group;

when Ar is selected from the group consisting of substituted or unsubstituted ring systems having 5 ring atoms, if containing a C-X bond, at least one X is selected from the group consisting of cyano, nitro, CF₃Cl, Br, F or I, or by cyano, nitro, CF₃Cl, Br, F or I substituted aromatic or heteroaromatic groups.

2. The organic compound having an oxygenated heterocycle according to claim 1, wherein the general structural formula of the organic compound is any one selected from the group consisting of formulas (2-1) to (2-12):

3. the organic compound having an oxygenated heterocycle according to claim 1, wherein C ═ X is selected from any one of the following groups:

wherein:

q, E are each independently selected from CR₈R₉、NR₁₀、O、S、SiR₁₁R₁₂、PR₁₃、P(＝O)R₁₄、S＝O、S(＝O)₂Or C ═ O;

R₇-R₁₄each occurrence is independently selected from H, D, a straight chain alkyl group having 1 to 20C atoms, an alkoxy or thioalkoxy group having 1 to 20C atoms, a branched or cyclic alkyl group having 3 to 20C atoms, an alkoxy or thioalkoxy group having 3 to 20C atoms, a silyl group, a ketone group having 1 to 20C atoms, an alkoxycarbonyl group having 2 to 20C atoms, an aryloxycarbonyl group having 7 to 20C atoms, a cyano group, a carbamoyl group, a haloformyl group, a formyl group, an isocyano group, an isocyanate group, a thiocyanate group, an isothiocyanate group, a hydroxyl group, a nitro group, a CF, a hydroxyl group, a cyano group, a haloformyl group, a formyl group, an isocyano group₃Cl, Br, F, I, a crosslinkable group, a substituted or unsubstituted heteroaromatic group having 5 to 60 ring atoms, a substituted or unsubstituted aromatic group having 6 to 60 ring atoms, a substituted or unsubstituted aryloxy or heteroaryloxy group having 5 to 60 ring atoms, or a combination of these groups;

n is selected from any integer from 0 to 4.

4. An oxygenated heterocyclic organic compound according to claim 1, wherein in C ═ X, X is selected from O and CR₁R₂。

5. The organic compound having an oxygenated heterocycle according to claim 4, wherein the general structural formula is any one selected from the group consisting of formulas (3-1) to (3-14):

6. the organic oxygenated heterocyclic compound according to any one of claims 1 to 5, wherein C ═ X is selected from any one of the following groups:

7. the organic compound having an oxygenated heterocycle according to claim 1, whereinWhen selected from C-X, at least one X is selected from cyano, nitro, CF₃Cl, Br, F, I, or by cyano, nitro, CF₃Cl, Br, F or I substituted aromatic or heteroaromatic groups.

8. The oxygenated heterocyclic organic compound according to claim 1,are all selected from C ═ X.

9. The oxygenated heterocyclic organic compound according to claim 1,are all selected from

10. A mixture comprising an organic compound containing an oxidized heterocycle according to any one of claims 1 to 9, and at least one organic functional material selected from at least one of a hole injecting material, a hole transporting material, an electron injecting material, an electron blocking material, a hole blocking material, a light emitting body, a host material and an organic dye.

11. A composition comprising at least one of an oxygenated heterocyclic organic compound of any one of claims 1 to 9 and a mixture of claim 10, and at least one organic solvent.

12. An organic electronic device comprising at least one of the oxygenated heterocyclic organic compound of any one of claims 1 to 9 and the mixture of claim 10 or prepared from the composition of claim 11.

13. The organic electronic device according to claim 12, wherein the organic electronic device comprises at least a hole injection layer or a hole transport layer comprising at least one of the oxygenated heterocyclic organic compound of any one of claims 1 to 9 and the mixture of claim 10 or prepared from the composition of claim 11.

Technical Field

The invention relates to the field of electroluminescent materials, in particular to an organic compound containing an oxygenated heterocycle and application thereof.

Background

Organic Light Emitting Diodes (OLEDs) have great potential for applications in optoelectronic devices such as flat panel displays and lighting due to the versatility of organic semiconductor materials in synthesis, relatively low manufacturing costs, and excellent optical and electrical properties.

The organic electroluminescence phenomenon refers to a phenomenon of converting electric energy into light energy using an organic substance. An organic electroluminescent element utilizing an organic electroluminescent phenomenon generally has a structure including a positive electrode and a negative electrode and an organic layer therebetween. In order to improve the efficiency and lifetime of the organic electroluminescent element, the organic layer has a multi-layer structure, each layer containing a different organic substance. Specifically, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and the like may be included. In such an organic electroluminescent element, when a voltage is applied between the two electrodes, holes are injected from the positive electrode into the organic layer, electrons are injected from the negative electrode into the organic layer, excitons are formed when the injected holes and electrons meet, and light is emitted when the excitons transition back to the ground state. The organic electroluminescent element has the characteristics of self-luminescence, high brightness, high efficiency, low driving voltage, wide viewing angle, high contrast, high responsiveness and the like.

In order to realize an efficient organic electroluminescent device, in addition to the development of a high-performance light emitting material, efficient injection transport of electrons and holes from a cathode and an anode, respectively, is a key among them. It has been known in recent years that the conductivity of organic semiconducting materials can be greatly influenced by doping the materials. For the hole-transporting matrix material, it may be composed of a host compound having good electron donor properties and a dopant compound having good electron acceptor properties. Strong electron acceptors, such as Tetracyanoquinodimethane (TCNQ) or 2,3,5, 6-tetrafluoro-tetracyano-1, 4-benzoquinodimethane (F4TCNQ), are now widely used for doping electron donor Materials (Chemical Science 2018,9(19), 4468-. The action mechanism is mainly that holes are generated through the interaction of an electron acceptor dopant and an electron donor host material, and the number and the mobility of the holes enable the conductivity of the substrate material to be obviously changed.

However, these current doping compounds have a number of drawbacks when used for doping, such as: the operation is unstable in the manufacturing process of the organic light emitting diode, the stability is insufficient when the organic light emitting diode is driven, the life is reduced, or the above compound is diffused in the device to contaminate the device when the organic light emitting diode is manufactured by vacuum deposition.

Therefore, there is an urgent need to develop a new high-performance electron acceptor, i.e., a P-dopant, which can be used for doping of the hole transport layer.

Disclosure of Invention

In view of the defects of the prior art, the invention aims to provide an organic compound containing an oxygenated heterocycle and application thereof, and aims to provide a novel organic photoelectric functional material, and improve the efficiency and the service life of a device.

The technical scheme of the invention is as follows:

an organic compound containing an oxygenated heterocycle has a structure shown in formula (1):

wherein:

represents a single bond or a double bond;

a is selected from S or N; OM is selected from O or OH;

n1 is selected from 1 or 2; m1 is selected from any integer from 1 to 3; m2 is selected from any integer from 2 to 4;

ar is selected from a substituted or unsubstituted ring system containing 3 to 6 ring atoms, wherein the number of Ar ring atoms is the sum of m1+ m 2;

when in useIs selected from the group consisting of X, X is independently selected at each occurrence from O, S, S (═ O)₂、CR₁R₂、NR₃、SiR₄R₅、PR₆A substituted or unsubstituted aromatic group having 6 to 60C atoms, or a substituted or unsubstituted heteroaromatic group having 5 to 60 ring atoms, or a substituted or unsubstituted non-aromatic ring system having 3 to 30 ring atoms; and at least one X is selected from CR₁R₂；

When in useWhen selected from C-X, X is selected from H, D, or a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 20C atoms, or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 20C atoms, or a silyl group, or a ketone group having 1 to 20C atoms, or an alkoxycarbonyl group having 2 to 20C atoms, or an aryloxycarbonyl group having 7 to 20C atoms, a cyano group, a carbamoyl group, a haloformyl group, a formyl group, an isocyano group, an isocyanate group, a thiocyanate group or an isothiocyanate group, a hydroxyl group, a nitro group, a CF group₃Cl, Br, F, I, a crosslinkable group, or a substituted or unsubstituted heteroaromatic group having 5 to 60 ring atoms, or a substituted or unsubstituted aromatic group having 6 to 60 ring atoms, or a substituted or unsubstituted aryloxy or heteroaryloxy group having 5 to 60 ring atoms, or a combination of these groups;

when present, at least one is selected from C ═ X; and all C atoms in the Ar ring have an atomic orbital of sp2 hybrid orbital;

R₁-R₆independently at each occurrence, H, D, or a straight-chain alkyl, alkoxy or thioalkoxy group having from 1 to 20C atoms, or a branched or cyclic alkyl, alkoxy or thioalkoxy group having from 3 to 20C atoms, or a silyl group, or a ketone group having from 1 to 20C atoms, or an alkoxycarbonyl group having from 2 to 20C atoms, or an aryloxycarbonyl group having from 7 to 20C atoms, a cyano group, a carbamoyl group, a haloformyl group, a formyl group, an isocyano group, an isocyanate group, a thiocyanate group or an isothiocyanate group, a hydroxyl group, a nitro group, a CF group₃Cl, Br, F, I, a crosslinkable group, or a substituted or unsubstituted heteroaromatic group having 5 to 60 ring atoms, or a substituted or unsubstituted aromatic group having 6 to 60 ring atoms, or a substituted or unsubstituted aryloxy or heteroaryloxy group having 5 to 60 ring atoms, or a combination of these groups;

when Ar is selected from a substituted or unsubstituted ring system having 3 ring atoms; at least one X is selected from CR₁R₂And at least one R₁Selected from cyano, nitro, CF₃A Cl, Br, F or I substituted aromatic or heteroaromatic group;

The present invention also provides a polymer comprising at least one repeating unit comprising the structural unit represented by the above formula (1).

The invention also provides a mixture, which comprises the organic compound containing the oxygenated heterocycle or the high polymer and at least one organic functional material, wherein the organic functional material is at least one selected from a hole injection material, a hole transport material, an electron injection material, an electron blocking material, a hole blocking material, a light emitting body, a host material and an organic dye.

The invention also provides a composition, which comprises the organic compound containing the oxygenated heterocyclic ring or the high polymer or the mixture and at least one organic solvent.

The invention also provides an organic electronic device, which at least comprises the organic compound containing the oxygenated heterocycle, or the high polymer, or the mixture, or is prepared from the composition.

Compared with the prior art, the invention has the following beneficial effects:

the organic compound containing the oxygenated heterocyclic ring provided by the invention has excellent hole transport property and stability, can be used as a hole injection layer material in an organic electroluminescent element, and can also be doped in a hole injection layer or a hole transport layer as a dopant, so that the organic compound can be driven by low voltage, the electroluminescent efficiency can be improved, and the service life of a device can be prolonged.

Detailed Description

The invention provides an organic compound containing an oxygenated heterocycle and application thereof. The present invention will be described in further detail with reference to specific examples. The present invention may be embodied in many different forms and is not limited to the embodiments described 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.

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

In the present invention, "substituted or unsubstituted" means that the defined group may or may not be substituted. When a defined group is substituted, it is understood to be optionally substituted with art-acceptable groups including, but not limited to: c_1-30An alkyl group, a cycloalkyl group having 3 to 20 ring atoms, a heterocyclic group having 3 to 20 ring atoms, an aryl group having 5 to 20 ring atoms, a heteroaryl group having 5 to 20 ring atoms, a silane group, a carbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, a haloformyl group, a formyl group, -NRR', a cyano group, an isocyano group, an isocyanate group, a thiocyanate group, an isothiocyanate group, a hydroxyl group, a trifluoromethyl group, a nitro group or a halogen, and the above groups may be further substituted with a substituent acceptable in the art; it is understood that R and R 'in-NRR' are each independently substituted with art-acceptable groups including, but not limited to, H, C_1-6An alkyl group, a cycloalkyl group having 3 to 8 ring atoms, a heterocyclic group having 3 to 8 ring atoms, an aryl group having 5 to 20 ring atoms, or a heteroaryl group having 5 to 10 ring atoms; said C is_1-6Alkyl, cycloalkyl containing 3 to 8 ring atoms, heterocyclyl containing 3 to 8 ring atoms, aryl containing 5 to 20 ring atoms or heteroaryl containing 5 to 10 ring atoms are optionally further substituted by one or more of the following: c_1-6Alkyl, cycloalkyl having 3 to 8 ring atoms, heterocyclyl having 3 to 8 ring atoms, halogen, hydroxy, nitro or amino.

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

In the present invention, "sp 2" indicates that hybridization within an atom involving 1 ns orbital and 2 np orbitals is referred to as sp2 hybridization, and 3 formed hybridization orbitals are referred to as sp2 hybridization orbitals. The hybridization of the C atom sp2 means that the C atom contains twoA single bond, a double bond, e.g.Form (a).

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.

In the embodiment of the present invention, the energy level structure of the organic material, the triplet state energy level E_THOMO, LUMO play a key role. These energy levels are 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 used for dredgingThe measurement can be made from a low temperature Time resolved luminescence spectrum, or can be 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 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.

In the present invention, (HOMO-1) is defined as the second highest occupied orbital level, (HOMO-2) is defined as 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 present invention provides a compound represented by the general formula (1):

wherein:

represents a single bond or a double bond;

a is selected from S or N; OM is selected from O or OH;

n1 is selected from 1 or 2; m1 is selected from any integer from 1 to 3; m2 is selected from any integer from 2 to 4;

ar is selected from a substituted or unsubstituted ring system containing 3 to 6 ring atoms, wherein the number of Ar ring atoms is the sum of m1+ m 2;

when in useIs selected from C ═ XEach occurrence of X is independently selected from O, S, S (═ O)₂、CR₁R₂、NR₃、SiR₄R₅、PR₆A substituted or unsubstituted aromatic group having 6 to 60C atoms, a substituted or unsubstituted heteroaromatic group having 5 to 60 ring atoms, or a substituted or unsubstituted non-aromatic ring system having 3 to 30 ring atoms; and at least one X is selected from CR₁R₂；

when occurring multiple times, at least one C ═ X; and all C atoms on the Ar ring have an atomic orbital sp2 hybridized orbital;

R₁-R₆independently at each occurrence H, D, or a straight chain alkyl, alkoxy or thioalkoxy group having 1 to 20C atoms, or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 20C atoms, or a silyl group, or a keto group having 1 to 20C atoms, or an alkoxycarbonyl group having 2 to 20C atoms, or having 7Aryloxycarbonyl of up to 20C atoms, cyano, carbamoyl, haloformyl, formyl, isocyano, isocyanate, thiocyanate or isothiocyanate, hydroxy, nitro, CF₃Cl, Br, F, I, a crosslinkable group, or a substituted or unsubstituted heteroaromatic group having 5 to 60 ring atoms, or a substituted or unsubstituted aromatic group having 6 to 60 ring atoms, or a substituted or unsubstituted aryloxy or heteroaryloxy group having 5 to 60 ring atoms, or a combination of these groups;

when Ar is selected from substituted or unsubstituted groups having 3 ring systems; at least one X is selected from CR₁R₂And at least one R₁Selected from cyano, nitro, CF₃A Cl, Br, F or I substituted aromatic or heteroaromatic group;

In one embodiment, when Ar is selected from substituted or unsubstituted having 3 ring systems;are all selected from C ═ X;

in one embodiment, when Ar is selected from substituted or unsubstituted having 4 ring systems;are all selected from C ═ X.

In a more preferred embodiment, in the formula (1)Selected from S ═ O, or S (═ O)₂Or N-OH, or N-O.

In one embodiment of the present invention, the substrate is,are all selected fromFurther, in the case of a liquid crystal display,are all selected from

In a more preferred embodiment, m1 in formula (1) is selected from 1; in another more preferred embodiment, m1 in formula (1) is selected from 2.

In a more preferred embodiment, formula (1) contains at least two C ═ X bonds; in another more preferred embodiment, formula (1) contains at least three C ═ X bonds; in another more preferred embodiment, formula (1) contains at least four C ═ X bonds; more preferably, in the general formula (1)Are all selected from C ═ X.

In one embodiment, Ar is selected from the following groups:

denotes the attachment site to a or C.

In a more preferred embodiment, the structure of the oxidized heterocycle-containing organic compound is selected from any one of formulas (2-1) to (2-12):

in a more preferred embodiment, in formula (1), C ═ X is selected from any one of the following groups:

wherein:

q, E are each independently selected from CR₈R₉、NR₁₀、O、S、SiR₁₁R₁₂、PR₁₃、P(＝O)R₁₄、S＝O、S(＝O)₂Or C ═ O;

R₇-R₁₄independently at each occurrence, H, D, or a straight-chain alkyl, alkoxy or thioalkoxy group having from 1 to 20C atoms, or a branched or cyclic alkyl, alkoxy or thioalkoxy group having from 3 to 20C atoms, or a silyl group, or a ketone group having from 1 to 20C atoms, or an alkoxycarbonyl group having from 2 to 20C atoms, or an aryloxycarbonyl group having from 7 to 20C atoms, a cyano group, a carbamoyl group, a haloformyl group, a formyl group, an isocyano group, an isocyanate group, a thiocyanate group or an isothiocyanate group, a hydroxyl group, a nitro group, a CF group₃A Cl, Br, F, I crosslinkable group, or a substituted or unsubstituted heteroaromatic group having 5 to 60 ring atoms, or a substituted or unsubstituted aromatic group having 6 to 60 ring atoms, or a substituted or unsubstituted aryloxy or heteroaryloxy group having 5 to 60 ring atoms, or a combination of these groups;

n is selected from any integer of 0-4.

In one embodiment, C ═ X is selected from

In a certain preferred embodiment, at least one X of C ═ X is selected from CR₁R₂；

In one embodiment, R₁And R₂Are all selected from cyano, nitro, CF₃Cl, Br, F or I, or by cyano, nitro, CF₃Cl, Br, F or I substituted aromatic or heteroaromatic groups.

Further, R₁And R₂Are all selected from cyano, nitro, CF₃Cl, Br, F or I, or by cyano, nitro, CF₃、Cl、BrF or I, and at least one R₁Selected from cyano, nitro, CF₃Cl, Br, F or I substituted aromatic or heteroaromatic groups.

More preferably, X in C ═ X is selected from CR₁R₂(ii) a More preferably, at least one R₁Selected from cyano, nitro, CF₃Cl, Br, F or I, or by cyano, nitro, CF₃A Cl, Br, F or I substituted aromatic or heteroaromatic group; particularly preferably, R₁And R₂Are all selected from cyano, nitro, CF₃Cl, Br, F or I, or by cyano, nitro, CF₃A Cl, Br, F or I substituted aromatic or heteroaromatic group;

in a more preferred embodiment, C ═ X is selected from any one of the following groups:

in one embodiment, whenWhen selected from C-X, at least one X in C-X is selected from cyano, nitro, CF₃Cl, Br, F or I, or by cyano, nitro, CF₃A Cl, Br, F or I substituted aromatic or heteroaromatic group; more preferably, X in C-X are all selected from cyano, nitro, CF₃Cl, Br, F or I, or by cyano, nitro, CF₃Cl, Br, F or I substituted aromatic or heteroaromatic group, most preferably C-X is selected from C-F, C-CN, C-Cl or C-CF₃。

In a more preferred embodiment, when Ar is selected from a substituted or unsubstituted ring system having 3 ring atoms, formula (1) is selected from the following formulae:

further, the general formula (1) is selected from structures represented by general formula (3-1):

still further, formula (1) is selected from the following formulae:

wherein: r₁₅Selected from cyano, nitro, CF₃Cl, Br, F or I; n2 is selected from any integer from 1 to 4.

In a certain preferred embodiment, when Ar is selected from a substituted or unsubstituted ring system having 4 ring atoms, formula (1) is selected from the following formulae:

further, the general formula (1) is selected from structures represented by general formulas (3-2) to (3-3):

still further, formula (1) is selected from the following formulae:

in a certain preferred embodiment, when Ar is selected from a substituted or unsubstituted ring system having 5 ring atoms, m1 is selected from 2; in a certain preferred embodiment, m1 is selected from 3;

in a certain preferred embodiment, when Ar is selected from a substituted or unsubstituted ring system having 5 ring atoms, two C ═ X are contained.

In a certain preferred embodiment, when Ar is selected from a substituted or unsubstituted ring system having 5 ring atoms, three C ═ X are contained.

In a certain preferred embodiment, when Ar is selected from a substituted or unsubstituted ring system having 5 ring atoms, m1 is selected from 2 and contains three C ═ X.

In a certain preferred embodiment, when Ar is selected from a substituted or unsubstituted ring system having 5 ring atoms, m1 is selected from 3 and contains two C ═ X.

Preferably, formula (1) is selected from the following formulae:

further, the general formula (1) is selected from any one of structures represented by general formulas (3-5) to (3-9):

preferably, at least one X in the general formula (3-8) or (3-9) is selected from cyano, nitro, CF₃Cl, Br, F or I, or by cyano, nitro, CF₃Cl, Br, F or I substituted aromatic or heteroaromatic groups.

More preferably, X in the general formula (3-8) or (3-9) is selected from cyano, nitro, CF₃Cl, Br, F or I, or by cyano, nitro, CF₃Cl, Br, F or I substituted aromatic or heteroaromatic groups.

In a certain preferred embodiment, when Ar is selected from a substituted or unsubstituted ring system having 6 ring atoms, m1 is selected from 2, andand when multiple occurrences, are selected from the same structure. More preferably still, the first and second liquid crystal compositions are,each occurrence is selected from N-OH, or S ═ O, or S (═ O)₂。

In a certain preferred embodiment, m1 is selected from 3, andwhen present multiple times, are selected from the same structure; more preferably still, the first and second liquid crystal compositions are,each occurrence is selected from N-OH, or S ═ O, or S (═ O)₂。

In a certain preferred embodiment, when Ar is selected from a substituted or unsubstituted ring system having 6 ring atoms, at least two C ═ X; more preferably, at least four C ═ X are contained.

Preferably, formula (1) is selected from the following formulae:

further, the general formula (1) is selected from any one of structures of general formulae (3-10) to (3-13):

preferably, at least one X in the general formula (3-10) or (3-12) is selected from cyano, nitro, CF₃Cl, Br, F or I, or by cyano, nitro, CF₃Cl, Br, F or I substituted aromatic or heteroaromatic groups.

More preferably, X in the general formula (5-1) or (5-3) is selected from cyano, nitro, CF₃Cl, Br, F or I, or by cyano, nitro, CF₃Cl, Br, F or I substituted aromatic or heteroaromatic groups.

In a more preferred embodiment, all H atoms in the formulae referred to in the present invention are substituted by cyano, nitro, CF₃，ClBr, F or I.

Examples of organic compounds according to the invention are listed below, but are not limited to:

the organic compounds according to the invention can be used as functional materials in functional layers of electronic devices. The organic functional layer includes, but is not limited to, a Hole Injection Layer (HIL), a Hole Transport Layer (HTL), an Electron Transport Layer (ETL), an Electron Injection Layer (EIL), an Electron Blocking Layer (EBL), a Hole Blocking Layer (HBL), and an emission layer (EML).

In a particularly preferred embodiment, the organic compounds according to the invention are used in a Hole Injection Layer (HIL) or a Hole Transport Layer (HTL).

In a very preferred embodiment, the organic compounds according to the invention are used as p-type doping materials in Hole Injection Layers (HILs) or Hole Transport Layers (HTLs).

In certain embodiments, the organic compound according to the invention, T thereof₁More preferably, it is not less than 0.3eV, still more preferably not less than 0.6eV, particularly preferably not less than 0.8 eV.

Functional materials require good thermal stability. In general, the organic compounds according to the invention have a glass transition temperature Tg of 100 ℃ or higher, in a preferred embodiment 120 ℃ or higher, in a more preferred embodiment 140 ℃ or higher, in a more preferred embodiment 160 ℃ or higher, and in a most preferred embodiment 180 ℃ or higher.

An appropriate LUMO energy level is necessary as the p-type doping material. In certain embodiments, the organic compounds according to the invention have a LUMO ≦ -5.30eV, more preferably ≦ -5.50eV, and most preferably ≦ -5.60 eV.

In certain preferred embodiments, the organic compound according to the invention, which ((HOMO- (HOMO-1)). gtoreq.0.2 eV, preferably ≧ 0.25eV, more preferably ≧ 0.3eV, more preferably ≧ 0.35eV, very preferably ≧ 0.4eV, most preferably ≧ 0.45 eV.

The present invention also provides a polymer comprising at least one repeating unit comprising the structural unit represented by the above formula (1).

The invention also provides a mixture, which is characterized by comprising at least one organic compound containing the oxidized heterocycle or the high polymer and at least another organic functional material, wherein the at least another organic functional material can be selected from a Hole Injection Material (HIM), a Hole Transport Material (HTM), an Electron Transport Material (ETM), an Electron Injection Material (EIM), an Electron Blocking Material (EBM), a Hole Blocking Material (HBM), a luminescent material (Emitter), a main body material (Host) and an organic dye. Various organic functional materials are described in detail, for example, in WO2010135519a1, US20090134784a1 and WO2011110277a1, the entire contents of this 3 patent document being hereby incorporated by reference.

In some preferred embodiments, the mixture, wherein the another organic functional material is selected from a Hole Injection Material (HIM), a Hole Transport Material (HTM), and a Host material (Host).

In certain preferred embodiments, the mixture wherein the LUMO of the organic compound is equal to or lower than the HOMO +0.2eV of another organic functional material.

In certain preferred embodiments, the mixture wherein the LUMO of the organic compound is equal to or lower than the HOMO +0.1eV of another organic functional material.

In certain particularly preferred embodiments, the mixture wherein the LUMO of the organic compound is equal to or lower than the HOMO of another organic functional material.

In one embodiment, the mixture comprises at least one host material and one dopant, the dopant being an organic compound as described above, preferably the host material is selected from a Hole Injection Material (HIM) or a hole transport material, the molar ratio of dopant to host being from 1:1 to 1: 100000.

Details of HIM/HTM/EBM, and Host (Host material/matrix material) are described in WO2018095395A 1.

In certain embodiments, the compounds according to the invention have a molecular weight of 800g/mol or more, preferably 900g/mol or more, very preferably 1000g/mol or more, more preferably 1100g/mol or more, most preferably 1200g/mol or more.

In other embodiments, the compounds according to the invention have a solubility in toluene of 2mg/ml or more, preferably 3mg/ml or more, more preferably 4mg/ml or more, most preferably 5mg/ml or more at 25 ℃.

The invention also relates to a composition comprising at least one organic compound or polymer or mixture containing oxygenated heterocycles as described above, and at least one organic solvent; the at least one organic solvent is selected from aromatic or heteroaromatic, ester, aromatic ketone or aromatic ether, aliphatic ketone or aliphatic ether, alicyclic or olefinic compound, or boric acid ester or phosphoric acid ester compound, or a mixture of two or more solvents.

In a preferred embodiment, a composition according to the invention is characterized in that said at least one organic solvent is chosen from aromatic or heteroaromatic-based solvents.

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

examples of aromatic ketone-based solvents suitable for the present invention are, but not limited to: 1-tetralone, 2- (phenylepoxy) tetralone, 6- (methoxy) tetralone, acetophenone, propiophenone, benzophenone, and 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;

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

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

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

In certain preferred embodiments, a composition according to the present invention comprises at least one oxygenated heterocyclic containing 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^1/2Range of (1)Especially 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 compositions of the embodiments of the present invention may contain from 0.01 to 10 wt%, preferably from 0.1 to 15 wt%, more preferably from 0.2 to 5 wt%, most preferably from 0.25 to 3 wt%, of the organic compound or polymer or mixture according to the present invention.

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

Suitable Printing or coating techniques include, but are not limited to, ink jet Printing, letterpress, screen Printing, dip coating, spin coating, doctor blade coating, roll Printing, twist roll Printing, 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. The printing technology and the requirements related to the solution, such as solvent and concentration, viscosity, etc.

The present invention also provides a use of the Organic compound, polymer, mixture or composition containing an oxygenated heterocycle as described above in an Organic electronic device, which 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 (efets), Organic lasers, Organic spintronics, Organic sensors, and Organic Plasmon Emitting diodes (Organic Plasmon Emitting diodes), etc., and particularly preferably OLEDs. In the embodiment of the present invention, the organic compound or the high polymer is preferably used for a light emitting layer of an OLED device.

The invention further relates to an organic electronic device comprising at least one oxygenated heterocyclic organic compound or polymer or mixture as described above, or prepared from the above composition. Furthermore, the organic electronic device comprises at least one functional layer comprising a compound or mixture as described above, or prepared from a composition as described above. The functional layer is selected from a Hole Injection Layer (HIL), a Hole Transport Layer (HTL), an emission layer (EML), an Electron Blocking Layer (EBL), an Electron Injection Layer (EIL), an Electron Transport Layer (ETL), and a Hole Blocking Layer (HBL).

In a preferred embodiment, the organic electronic device according to the present invention comprises at least one hole injection layer or hole transport layer, wherein the hole injection layer or hole transport layer comprises an organic compound or polymer or mixture as described above, or is prepared from the above composition.

In general, the organic electronic device of the present invention comprises at least a cathode, an anode and a functional layer disposed 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 some preferred embodiments, the electroluminescent device, the hole injection layer or the hole transport layer comprises an organic compound containing an oxygenated heterocycle, or a polymer or a mixture thereof, or is prepared from the above composition.

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 a preferred 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 acting as 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 at a wavelength of 300 to 1200nm, preferably 350 to 1000nm, and more preferably 400 to 900 nm.

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

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

DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION

The synthesis of the compounds according to the invention is illustrated, but the invention is not limited to the following examples.

1. Compounds and synthetic procedures

Example 1: synthesis of Compound PD-1

(1) Synthesis of intermediate 1-2

Compound 1-1(0.204g, 1mmol), silver tetrafluoroborate (0.583g, 3mmol) and 10mL of dichloromethane were added to a 100mL three-necked flask, stirred in ice bath and added iodine (0.507g, 2mmol) in portions, slowly returned to room temperature, reacted overnight, after the reaction was completed, 100mL of water was added, extracted with dichloromethane, the organic phase was dried over anhydrous sodium sulfate, and separated by dichloromethane/petroleum ether column chromatography to give 243mg of intermediate 1-2 in 78% yield.

(2) Synthesis of intermediates 1 to 3

Compound 1-2(0.31g, 1mmol), cyanobenzonitrile (0.428g, 2mmol), CuI (0.19g, 1mmol), 2-picolinic acid (0.246g, 2mmol), cesium carbonate (1.14g, 3.5mmol) were added sequentially in a 100mL three-necked flask under anhydrous and oxygen-free conditions, anhydrous 1, 4-dioxane (20 mL) was added by syringe, tetraisopropyl titanate (0.85g, 3mmol) was added by syringe, and the reaction was stirred at 40 ℃ for 1 h. Pouring the reaction solution into 200ml of saturated saline solution, extracting by EA for three times, combining organic phases, washing by 50ml of water for three times, drying by anhydrous magnesium sulfate, concentrating under reduced pressure, mixing samples, separating by column chromatography, and eluting by ethyl acetate/petroleum ether to obtain 134mg of intermediate 1-3 with the yield of 28%.

(3) Synthesis of Compound PD-1

30% hydrogen peroxide (0.3mL, 5.35mmol) was added to a 100mL three-necked flask, trifluoroacetic anhydride (0.6mL, 4.25mmol) was added dropwise under ice bath, and stirred for 30min, followed by dropwise addition of 15mL of a dichloromethane solution of intermediate 1-3(168mg, 0.35mmol) and reaction overnight. Slowly pouring the reaction solution into ice water, adjusting the pH value to 9 by using sodium bicarbonate, extracting by using ethyl acetate for 3 times, washing by using water for three times, drying by using anhydrous magnesium sulfate, separating and purifying by adopting a column chromatography mode, wherein an eluent is a mixed solvent of ethyl acetate/petroleum ether (V/V is 5:2), and the yield is 64 percent, and 115mg of PD-1 is obtained.

The compound, formula C, was identified using HPLC-MS₂₀F₈N₄O₂S, detecting value [ M +1 ]]⁺The calculated value is 512, 513.

Example 2: synthesis of Compound PD-2

(1) Synthesis of intermediate 2-2

The compound 2-1(1mmol), trifluoromethyl tetrafluorobenzyl cyanide (1mmol), CuI (1mmol), 2-picolinic acid (2mmol) and cesium carbonate (3.5mmol) are added in sequence to a 100mL three-neck flask under anhydrous and oxygen-free conditions, 20mL of anhydrous 1, 4-dioxane is added by a syringe, tetraisopropyl titanate (3mmol) is added by a syringe, and the reaction is stirred at 40 ℃ for 1 h. Pouring the reaction solution into 200mL of saturated saline solution, extracting by EA for three times, combining organic phases, washing by 50mL of water for three times, drying by anhydrous magnesium sulfate, concentrating under reduced pressure, mixing samples, carrying out column chromatography separation, and eluting by ethyl acetate/petroleum ether to obtain 331mg of intermediate 2-2 with the yield of 71%.

(2) Synthesis of intermediates 2-3

The intermediate 2-2(1mmol), pentafluorobenzyl cyanide (1mmol), CuI (1mmol), 2-picolinic acid (2mmol) and cesium carbonate (3.5mmol) are added in sequence to a 100mL three-necked flask under anhydrous and oxygen-free conditions, 20mL of anhydrous 1, 4-dioxane is added by a syringe, tetraisopropyl titanate (3mmol) is added by a syringe, and the reaction is stirred at 40 ℃ for 1 h. Pouring the reaction solution into 200mL of saturated saline solution, extracting by EA for three times, combining organic phases, washing by 50mL of water for three times, drying by anhydrous magnesium sulfate, concentrating under reduced pressure, mixing samples, separating by column chromatography, and eluting by ethyl acetate/petroleum ether to obtain 2-3 of 453mg of intermediate with the yield of 80%.

(3) Synthesis of Compound PD-2

30% hydrogen peroxide (5.35mmol) was added to a 100mL three-necked flask, trifluoroacetic anhydride (4.25mmol) was added dropwise under ice-cooling, and after stirring for 30min, 15mL of a dichloromethane solution of intermediate 2 to 3(0.35mmol) was added dropwise, and the reaction was allowed to proceed overnight. Slowly pouring the reaction liquid into ice water, adjusting the pH value to 9 by using sodium bicarbonate, extracting by using ethyl acetate for 3 times, washing by using water for three times, drying by using anhydrous magnesium sulfate, separating and purifying by adopting a column chromatography mode, wherein an eluent is a mixed solvent of ethyl acetate/petroleum ether (V/V is 5:2), and 374mg of PD-2 is obtained with the yield of 65%.

The compound, formula C, was identified using HPLC-MS₂₀F₁₂N₂O₃S, detecting value [ M +1 ]]⁺Calculated 577, 576.

Example 3: synthesis of Compound PD-3

(1) Synthesis of intermediate 3-2

Under anhydrous and oxygen-free conditions, adding the intermediate 3-1(1mmol), pentafluorobenzyl cyanide (3mmol), CuI (1mmol), 2-picolinic acid (2mmol) and cesium carbonate (5mmol) in turn into a 100mL three-neck flask, adding 20mL of anhydrous 1, 4-dioxane by using a syringe, adding tetraisopropyl titanate (3mmol) by using a syringe, and stirring for reaction at 40 ℃ for 1 h. Pouring the reaction solution into 200mL of saturated saline solution, extracting by EA for three times, combining organic phases, washing by 50mL of water for three times, drying by anhydrous magnesium sulfate, concentrating under reduced pressure, mixing samples, separating by column chromatography, and eluting by ethyl acetate/petroleum ether to obtain 573mg of intermediate 3-2 with the yield of 84%.

(2) Synthesis of Compound PD-3

30% hydrogen peroxide (5.35mmol) was added to a 100mL three-necked flask, trifluoroacetic anhydride (4.25mmol) was added dropwise under ice-cooling, and after stirring for 30min, 15mL of a dichloromethane solution of intermediate 3-2(0.35mmol) was added dropwise, and the reaction was allowed to proceed overnight. Slowly pouring the reaction liquid into ice water, adjusting the pH value to 9 by using sodium bicarbonate, extracting by using ethyl acetate for 3 times, washing by using water for three times, drying by using anhydrous magnesium sulfate, separating and purifying by adopting a column chromatography mode, wherein an eluent is a mixed solvent of ethyl acetate/petroleum ether (V/V is 5:3), and obtaining 407mg of PD-3 with the yield of 57%.

The compound, formula C, was identified using HPLC-MS₂₇F₁₅N₃O₂S, detecting value [ M +1 ]]⁺The calculated value is 715, 716.

Example 4: synthesis of Compound PD-4

(1) Synthesis of intermediate 4-2

The intermediate 4-1(1mmol), tetrafluoropyridine-4-acetonitrile (2mmol), CuI (1mmol), 2-picolinic acid (2mmol) and cesium carbonate (5mmol) are sequentially added into a 100mL three-neck flask under anhydrous and oxygen-free conditions, 20mL of anhydrous 1, 4-dioxane is added by a syringe, tetraisopropyl titanate (3mmol) is added by a syringe, and the reaction is stirred at 40 ℃ for 1 h. Pouring the reaction solution into 200mL of saturated saline solution, extracting by EA for three times, combining organic phases, washing by 50mL of water for three times, drying by anhydrous magnesium sulfate, concentrating under reduced pressure, mixing samples, separating by column chromatography, and eluting by ethyl acetate/petroleum ether to obtain 352mg of intermediate 4-2 with the yield of 76%.

(2) Synthesis of Compound PD-4

30% hydrogen peroxide (5.35mmol) was added to a 100mL three-necked flask, trifluoroacetic anhydride (4.25mmol) was added dropwise under ice-cooling, and after stirring for 30min, 15mL of a dichloromethane solution of intermediate 4-2(0.35mmol) was added dropwise, and the reaction was allowed to proceed overnight. Slowly pouring the reaction solution into ice water, adjusting the pH value to 9 by using sodium bicarbonate, extracting by using ethyl acetate for 3 times, washing by using water for three times, drying by using anhydrous magnesium sulfate, separating and purifying by adopting a column chromatography mode, wherein an eluent is a mixed solvent of ethyl acetate/petroleum ether (V/V is 10:3), and obtaining 79mg of PD-4 with the yield of 43%.

The compound, formula C, was identified using HPLC-MS₁₆F₈N₄O₄S₂Detection value [ M +1 ]]⁺529, the calculated value is 528.

Example 5: synthesis of Compound PD-5

(1) Synthesis of intermediate 5-2

Compound 5-1(0.5g, 1.26mmol), cyanobenzonitrile (0.6g, 2.80mmol), CuI (0.13g, 0.68mmol), 2-picolinic acid (0.167g, 1.36mmol), cesium carbonate (2.45g, 7.54mmol) were added in this order in a 100mL three-necked flask under anhydrous and oxygen-free conditions, anhydrous 1, 4-dioxane (20 mL) was added by syringe, tetraisopropyl titanate (0.36g, 1.26mmol) was added by syringe, and the reaction was stirred at 40 ℃ for 1 h. Pouring the reaction solution into 200mL of saturated saline solution, extracting by EA for three times, combining organic phases, washing by 50mL of water for three times, drying by anhydrous magnesium sulfate, concentrating under reduced pressure, mixing samples, separating by column chromatography, and eluting by ethyl acetate/petroleum ether to obtain an intermediate 5-2 oily substance 200mg with the yield of 28%.

(2) Synthesis of intermediate 5-3

30% hydrogen peroxide (0.3mL, 5.35mmol) was added to a 100mL three-necked flask, trifluoroacetic anhydride (0.6mL, 4.25mmol) was added dropwise under ice-bath, and stirred for 30min, followed by addition of 15mL of a solution of intermediate 5-2(200mg, 0.35mmol) in dichloromethane and reaction overnight. Slowly pouring the reaction liquid into ice water, adjusting the pH value of sodium bicarbonate to 9, extracting with ethyl acetate for 3 times, washing with water for three times, drying with anhydrous magnesium sulfate, and separating by ethyl acetate/petroleum ether column chromatography to obtain an intermediate 5-3 yellow solid product 50mg with a yield of 23.6%.

(3) Synthesis of Compound PD-5

A100 mL three-neck flask was charged with 5-3(50mg, 0.08mmol) of intermediate, 20mL of anhydrous dichloromethane, 10mL of a solution of boron tribromide (0.1 mL, 1.0mmol) in dichloromethane was added dropwise at-30 ℃ under nitrogen protection, and the mixture was allowed to stir at room temperature for 2 hours. The reaction solution was slowly poured into ice water, the pH value was adjusted to 9 with sodium bicarbonate, dichloromethane was extracted 3 times, washed three times with water, and dried over anhydrous magnesium sulfate to obtain 20mg of PD-5 as a solid product with a yield of 42.5%.

The compound, formula C, was identified using HPLC-MS₂₂F₈N₄O₄S, detecting value [ M +1 ]]⁺When 569, the calculated value is 568.

Example 6: synthesis of Compound PD-6

(1) Synthesis of intermediate 6-2

Compound 6-1(0.40g, 1mmol), cyanobenzonitrile (0.428g, 2mmol), CuI (0.19g, 1mmol), 2-picolinic acid (0.246g, 2mmol), cesium carbonate (1.14g, 3.5mmol) were added sequentially in a 100mL three-necked flask under anhydrous and oxygen-free conditions, anhydrous 1, 4-dioxane (20 mL) was added by syringe, tetraisopropyl titanate (0.85g, 3mmol) was added by syringe, and the reaction was stirred at 40 ℃ for 1 h. Pouring the reaction solution into 200mL of saturated saline solution, extracting by EA for three times, combining organic phases, washing by 50mL of water for three times, drying by anhydrous magnesium sulfate, concentrating under reduced pressure, mixing samples, separating by column chromatography, and eluting by ethyl acetate/petroleum ether to obtain 130mg of an intermediate 6-2 with the yield of 23%.

(2) Synthesis of intermediate 6-3

30% hydrogen peroxide (0.3mL, 5.35mmol) was added to a 100mL three-necked flask, trifluoroacetic anhydride (0.6mL, 4.25mmol) was added dropwise under ice bath, and stirred for 30min, followed by addition of 15mL of a solution of intermediate 6-2(200mg, 0.35mmol) in dichloromethane and reaction overnight. Slowly pouring the reaction liquid into ice water, adjusting the pH value of sodium bicarbonate to 9, extracting with ethyl acetate for 3 times, washing with water for three times, drying with anhydrous magnesium sulfate, and carrying out column chromatography separation on ethyl acetate/petroleum ether to obtain an intermediate 6-3 of 80mg, wherein the yield is 38%.

(3) Synthesis of Compound PD-6

A100 mL three-neck flask was charged with intermediate 6-3(50mg, 0.08mmol), anhydrous dichloromethane 20mL, nitrogen blanketed, and boron tribromide 0.1mL (1.0mmol) in dichloromethane 10mL was added dropwise at-30 deg.C, and the mixture was allowed to cool to room temperature and stirred for 2 h. The reaction solution was slowly poured into ice water, pH was adjusted to 9 with sodium bicarbonate, extracted 3 times with dichloromethane, washed three times with water, and dried over anhydrous magnesium sulfate to give 23mg PD-6 with a yield of 51%.

The compound, formula C, was identified using HPLC-MS₂₂F₈N₄O₄S, detecting value [ M +1 ]]⁺When 569, the calculated value is 568.

Example 7: synthesis of Compound PD-7

(1) Synthesis of intermediate 7-1

To a 100mL three-necked flask, the compound PD-5(1mmol), carbon tetrabromide (2.5mmol) and triphenylphosphine (5mmol) were added in this order under anhydrous conditions, and 20mL of anhydrous toluene was added via a syringe, followed by stirring at 80 ℃ for 24 hours. Filtration at room temperature, slurried and washed solid with toluene to give intermediate 7-1 as a solid 704mg, 80% yield.

(2) Synthesis of Compound PD-7

A100 mL three-necked flask was charged with intermediate 7-1(0.1mmol), dry THF 20mL, and N-butyllithium (0.4mmol) was added dropwise under nitrogen protection at-30 ℃ for reaction with stirring for 30 minutes, then 10mL of a THF solution of N-fluorobisbenzenesulfonamide (0.5mmol) was added, and the mixture was allowed to stand at room temperature and stirred for 2 hours. The reaction was quenched by addition of a small amount of water, THF was removed in vacuo, the residue was extracted with water and EA and the organic phase was spin dried to give 15mg of PD-7 as a solid product in 23% yield.

The compound, formula C, was identified using HPLC-MS₂₄F₁₂N₄O₂S, detecting value [ M +1 ]]⁺637, calculate 636.

Example 8: synthesis of Compound PD-8

(1) Synthesis of intermediate 8-2

Malononitrile (0.066g, 1mmol) and 5mL tetrahydrofuran are added to a 100mL three-necked flask under anhydrous and oxygen-free conditions, n-butyllithium (0.062mL, 1.1mmol, 1.6M n-hexane solution) is added at-78 ℃, after 30 minutes of low temperature reaction, 10mL tetrahydrofuran solution of compound 8-1(0.372g, 1mmol) is added, the mixture is slowly returned to room temperature and reacted overnight, 20mL water is added after the reaction is finished, extraction is performed with dichloromethane, the organic phase is dried with anhydrous sodium sulfate, dichloromethane is used as an eluent, and separation is performed by column chromatography to obtain 72mg of intermediate 8-2 with a yield of 36%.

(2) Synthesis of Compound PD-8

30% hydrogen peroxide (0.3mL, 5.35mmol) was added to a 100mL three-necked flask, trifluoroacetic anhydride (0.6mL, 4.25mmol) was added dropwise under ice bath, and stirred for 30min, followed by addition of 15mL of a solution of intermediate 8-2(71mg, 0.35mmol) in dichloromethane and reaction overnight. Slowly pouring the reaction solution into ice water, adjusting the pH value to 9 by using sodium bicarbonate, extracting by using ethyl acetate for 3 times, washing by using water for three times, drying by using anhydrous magnesium sulfate, separating and purifying by adopting a column chromatography mode, wherein an eluent is a mixed solvent of ethyl acetate/petroleum ether (V/V is 5:2), and 65mg of PD-8 is obtained, and the yield is 70%.

The compound, formula C, was identified using HPLC-MS₆F₂N₂O₄S₂Detection value [ M +1 ]]⁺267, calculated 266.

Example 9: synthesis of Compound PD-9

(1) Synthesis of intermediate 9-2

Under anhydrous and oxygen-free conditions, malononitrile (4mmol) and 10mL of tetrahydrofuran are added into a 100mL three-neck flask, n-butyllithium (4.2mmol, n-hexane solution) is added at the temperature of-78 ℃, after 30 minutes of low-temperature reaction, 10mL of tetrahydrofuran solution of a compound 9-1(1mmol) is added, the mixture is slowly returned to the room temperature for overnight reaction, 20mL of water is added after the reaction is finished, dichloromethane is used for extraction, an organic phase is dried by anhydrous sodium sulfate, and dichloromethane column chromatography separation is carried out to obtain 88mg of an intermediate 9-2 with the yield of 24%.

(2) Synthesis of Compound PD-9

A100 mL three-necked flask was charged with 30% hydrogen peroxide (0.3mL, 5.35mmol), and trifluoroacetic anhydride (0.6mL, 4.25mmol) was added dropwise under ice bath, followed by stirring for 30min, followed by dropwise addition of 15mL of a solution of intermediate 9-2(0.35mmol) in dichloromethane, and the reaction was allowed to proceed overnight. Slowly pouring the reaction liquid into ice water, adjusting the pH value to 9 by sodium bicarbonate, extracting by ethyl acetate for 3 times, washing by water for three times, drying by anhydrous magnesium sulfate, separating and purifying by adopting a column chromatography mode, wherein an eluent is a mixed solvent of ethyl acetate/petroleum ether (V/V is 5:3), and obtaining 98mg of PD-9 with the yield of 65%.

The compound, formula C, was identified using HPLC-MS₁₆N₈O₄S₂Detection value [ M +1 ]]⁺Calculated value is 432, 433.

Example 10: synthesis of Compound PD-10

(1) Synthesis of intermediate 10-2

In a 100mL three-necked flask, compound 10-1(1mmol), pentafluorobenzyl cyanide (2mmol), CuI (1mmol), 2-picolinic acid (2mmol) and cesium carbonate (3.5mmol) were sequentially added under anhydrous and oxygen-free conditions, and 20mL of anhydrous 1, 4-dioxane was added via a syringe, and tetraisopropyl titanate (3mmol) was added via a syringe, followed by stirring at 40 ℃ for 1 hour. Pouring the reaction solution into 200mL of saturated saline solution, extracting by EA for three times, combining organic phases, washing by 50mL of water for three times, drying by anhydrous magnesium sulfate, concentrating under reduced pressure, mixing samples, separating by column chromatography, and eluting by ethyl acetate/petroleum ether to obtain 103mg of an intermediate 10-2 with the yield of 18%.

(2) Synthesis of Compound PD-10

A100 mL three-necked flask was charged with 30% hydrogen peroxide (0.3mL, 5.35mmol), and trifluoroacetic anhydride (0.6mL, 4.25mmol) was added dropwise under ice bath, followed by stirring for 30min, followed by dropwise addition of 15mL of a solution of intermediate 10-2(0.35mmol) in dichloromethane, and the reaction was allowed to proceed overnight. Slowly pouring the reaction liquid into ice water, adjusting the pH value to 9 by using sodium bicarbonate, extracting by using ethyl acetate for 3 times, washing by using water for three times, drying by using anhydrous magnesium sulfate, separating and purifying by adopting a column chromatography mode, wherein an eluent is a mixed solvent of ethyl acetate/petroleum ether (V/V is 5:3), and obtaining a PD-10 solid product 123mg with the yield of 55%.

The compound, formula C, was identified using HPLC-MS₂₂F₁₀N₄O₄S₂Detection value [ M +1 ]]⁺When 639, the calculated value is 638.

Example 11: synthesis of Compound PD-11

(1) Synthesis of intermediate 11-2

In a 100mL three-necked flask, compound 11-1(1mmol), malononitrile (2mmol), CuI (1mmol), 2-picolinic acid (2mmol) and cesium carbonate (3.5mmol) were sequentially added under anhydrous and oxygen-free conditions, and 20mL of anhydrous 1, 4-dioxane was added via a syringe, tetraisopropyl titanate (3mmol) was added via a syringe, and the reaction was stirred at 40 ℃ for 1 hour. Pouring the reaction solution into 200mL of saturated saline solution, extracting by EA for three times, combining organic phases, washing by 50mL of water for three times, drying by anhydrous magnesium sulfate, concentrating and mixing samples under reduced pressure, and separating and purifying by adopting a column chromatography mode, wherein an eluent is a mixed solvent of ethyl acetate/petroleum ether (V/V is 5:1), so that 56mg of intermediate 11-2 is obtained, and the yield is 21%.

(2) Synthesis of Compound PD-11

30% hydrogen peroxide (0.3mL, 5.35mmol) was added to a 100mL three-necked flask, trifluoroacetic anhydride (0.6mL, 4.25mmol) was added dropwise under ice-bath, and stirred for 30min, followed by dropwise addition of 15mL of a dichloromethane solution of intermediate 11-2(0.35mmol) and reaction overnight. Slowly pouring the reaction liquid into ice water, adjusting the pH value to 9 by sodium bicarbonate, extracting by ethyl acetate for 3 times, washing by water for three times, drying by anhydrous magnesium sulfate, separating and purifying by adopting a column chromatography mode, wherein an eluent is a mixed solvent of ethyl acetate/petroleum ether (V/V is 5:1), and obtaining a PD-11 solid product 41mg with the yield of 41%.

The compound, formula C, was identified using HPLC-MS₁₂H₂N₈O₂Detection value [ M +1 ]]⁺291, calculated 290.

Example 12: synthesis of Compound PD-12

(1) Synthesis of intermediate 12-2

Compound 12-1(0.372g, 1mmol), cyanobenzonitrile (0.428g, 2mmol), CuI (0.190g, 1mmol), 2-picolinic acid (0.246g, 2mmol), cesium carbonate (1.14g, 3.5mmol) were added sequentially in a 100mL three-necked flask under anhydrous and oxygen-free conditions, anhydrous 1, 4-dioxane (20 mL) was added by syringe, tetraisopropyl titanate (0.85g, 3mmol) was added by syringe, and the reaction was stirred at 40 ℃ for 1 h. Pouring the reaction solution into 200mL of saturated saline solution, extracting by EA for three times, combining organic phases, washing by 50mL of water for three times, drying by anhydrous magnesium sulfate, concentrating under reduced pressure, mixing samples, separating by column chromatography, and eluting by ethyl acetate/petroleum ether to obtain 114mg of the intermediate 12-2 with the yield of 21%.

(2) Synthesis of Compound PD-12

A100 mL three-necked flask was charged with 30% hydrogen peroxide (0.3mL, 5.35mmol), and trifluoroacetic anhydride (0.6mL, 4.25mmol) was added dropwise under ice bath, followed by stirring for 30min, followed by dropwise addition of 15mL of a solution of intermediate 12-2(190mg, 0.35mmol) in dichloromethane, and reaction overnight. Slowly pouring the reaction liquid into ice water, adjusting the pH value to 9 by using sodium bicarbonate, extracting by using ethyl acetate for 3 times, washing by using water for three times, drying by using anhydrous magnesium sulfate, separating and purifying by adopting a column chromatography mode, wherein an eluent is a mixed solvent of ethyl acetate/petroleum ether (V/V is 5:2), and obtaining a PD-12 solid product 126mg with the yield of 63%.

The compound, formula C, was identified using HPLC-MS₂₂F₁₀N₄O₂S₁Detection value [ M +1 ]]⁺575, the calculated value is 574.

2. Energy level structure of compound

The organic small molecule energy structure 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 calculated above were calculated according to the following calibration formula, and S1 and T1 were used directly.

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

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

Where HOMO (G) and LUMO (G) are direct calculations of Gaussian09W in eV. The results are shown in table 1, where Δ HOMO ═ HOMO- (HOMO-1):

TABLE 1

Comparative Compound 1Comparative Compound 2

3. Preparation method of OLED device

The device structure of the OLED device (OLED-Ref) is as follows: the ITO/HIL (10nm)/HT-1(120nm)/HT-2(10nm)/BH BD (25nm)/ET LiQ (30nm)/LiQ (1nm)/Al (100nm) specifically comprises the following preparation steps:

1) cleaning of an ITO transparent electrode (anode) glass substrate: carrying out ultrasonic treatment for 30 minutes by using an aqueous solution of 5% Decon90 cleaning solution, then carrying out ultrasonic cleaning for several times by using deionized water, then carrying out ultrasonic cleaning by using isopropanol, and carrying out nitrogen blow-drying; processing for 5 minutes under oxygen plasma to clean the ITO surface and improve the work function of an ITO electrode;

2) preparation of HIL (10nm) layer: moving the ITO substrate into a vacuum vapor deposition apparatusUnder high vacuum (1X 10)^-6Millibar), adopting resistance heating evaporation, and forming a 10nm injection layer by HT-1 evaporation;

3) HT-1(120nm), HT-2(10nm), EML (20nm), ETL (30nm), EIL and cathode layer preparation: then, evaporation is sequentially carried out to obtain 120nm HT-1 and 10nm HT-2 layers. Then BH and BD were measured at 97: 3 to form a 25nm light-emitting layer. Then, placing ET and LiQ in different evaporation units, carrying out co-deposition on the ET and the LiQ respectively according to the proportion of 50 weight percent, forming an electron transport layer with the thickness of 30nm on the luminescent layer, then depositing LiQ with the thickness of 1nm on the electron transport layer to be used as an electron injection layer, and finally depositing an Al cathode with the thickness of 100nm on the electron injection layer;

4) all devices were encapsulated in a nitrogen glove box with uv cured resin plus glass cover plate.

The OLED devices (OLED-1 to OLED-12) were prepared as above, but in the case of the HIL layer, with PD-1 to PD-12 and comparative compound 1, respectively, at a ratio of 2: the proportion of 98 was doped with HT-1 to replace the pure HT-1 of OLED-Ref.

The current-voltage (J-V) characteristics of each OLED device were characterized by a characterization instrument while recording important parameters such as efficiency, lifetime and external quantum efficiency, with the results shown in table 2.

TABLE 2

As can be seen from Table 2, compared with OLED-Ref, when the compound of the present invention is used as a doping material of the HIL layer, the service life of the prepared OLED device is at least improved by 5%, and the efficiency is at least improved by 14%; the service life is improved by at least 10 percent; especially when the doping material is selected from PD-1, PD-2, PD-3, PD-5 and PD-7, the efficiency is increased by about 20%; the life is improved by at least 18%. It is possible that the compound containing an oxidized heterocycle according to the present invention has a lower LUMO level because both sulfur atoms and nitrogen atoms in the structure are oxidized, and is more likely to form holes after being combined with a hole transport material, thereby providing a certain contribution to hole injection. Meanwhile, compared with the comparative compounds 1 and 2, the organic electroluminescent device has a molecular weight more suitable for an evaporation process, so that the device effect is better.

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.

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