CN111718338A - Compound, display panel and display device - Google Patents

Compound, display panel and display device Download PDF

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CN111718338A
CN111718338A CN202010610141.0A CN202010610141A CN111718338A CN 111718338 A CN111718338 A CN 111718338A CN 202010610141 A CN202010610141 A CN 202010610141A CN 111718338 A CN111718338 A CN 111718338A
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optionally substituted
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ring
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membered
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冉佺
高威
牛晶华
张磊
代文朋
李侠
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Wuhan Tianma Microelectronics Co Ltd
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Shanghai Tianma AM OLED Co Ltd
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Abstract

The invention discloses a compound, a display panel and a display device. The compounds have the structure shown in formula 1, wherein Aa, Ab, Ac, Y, R and Y are respectively defined as the description. The compound provided by the invention can be used for display panels and display devices.
Figure DDA0002561772320000011

Description

Compound, display panel and display device
Technical Field
The invention belongs to the technical field of organic light emitting, and particularly relates to a compound, a display panel and a display device.
Background
An Organic Light Emitting Diode (OLED) is a self-emitting device that generates electroluminescence by using an organic thin film layer. Specifically, under the drive of an external electric field, the OLED is respectively injected with holes and electrons by an anode and a cathode; the hole and the electron respectively migrate to the light emitting layer and combine in the organic light emitting material to generate an exciton; the excitons in the excited state may release energy in the form of light back to a stable ground state, generating visible light. Different luminescent materials can be selected to generate different colors of emitted light, so that different color requirements can be met.
Generally, a Hole Transport Layer (HTL) including a Hole Transport Material (HTM) and an Electron Transport Layer (ETL) including an Electron Transport Material (ETM) are disposed in an OLED structure to help transport holes and electrons to an emission layer. In the OLED, the electron transport rate and the hole transport rate are balanced, so that the luminous quantum efficiency of the OLED device is improved. However, the commonly used HTM has a high hole transport capability, while the ETM has a much lower electron transport capability, resulting in a larger amount of holes than electrons migrating to the light emitting layer, which makes the electron and hole transport ratio of the whole device unbalanced, and greatly reduces exciton formation efficiency, affecting the light emitting efficiency of the OLED.
Disclosure of Invention
Therefore, the present invention provides a compound capable of improving the light emitting efficiency of an organic light emitting device, and a display panel and a display apparatus including the same.
In a first aspect of the invention, there is provided a compound having a structure represented by formula 1,
Figure BDA0002561772300000011
wherein the content of the first and second substances,
ab represents an optionally substituted benzene ring, an optionally substituted naphthalene ring, an optionally substituted phenanthrene ring, an optionally substituted azabenzene ring, an optionally substituted azanaphthalene ring, or an optionally substituted azaphenanthrene ring,
ab is fused to Aa to form a fusion protein,
y is a number of 0 or 1,
when y is 0, Ab shares a1 and a 3C with Aa,
when y is 1, Ab shares a1 and a2 position C, a2 and a3 position C, or a1, a2 and a3 position C with Aa,
ac represents an optionally substituted 6-to 40-membered aromatic ring or an optionally substituted 5-to 40-membered aromatic heterocycle,
y represents C (Z)1)2、N(Z1)、O、S、Si(Z1)2Or PO (Z)1) Wherein Z is1Independently represent an optionally substituted C1-C20 alkyl group, an optionally substituted C1-C20 alkoxy group, an optionally substituted C1-C20 alkylthio group, an optionally substituted 3-to 20-membered cycloalkyl group, an optionally substituted 6-to 40-membered aryl group, or an optionally substituted 5-to 40-membered heteroaryl group,
r represents an optionally substituted 3-to 20-membered heterocycloalkyl group, an optionally substituted 6-to 40-membered aryl group, an optionally substituted 5-to 30-membered heteroaryl group, -PO (Z)2)2、–PS(Z2)2、–Z2S(＝O)2(Z3)、–Z4–(Z5)nor-Z6–Z7–(Z8)n，
Z2And Z3Each independently represents an optionally substituted 6-to 40-membered aryl group or an optionally substituted 5-to 40-membered heteroaryl group,
Z4、Z6and Z7Independently represent a C2-C10 alkenyl group, a C2-C10 alkynyl group, a 6-to 30-membered aryl group or a 5-to 30-membered heteroaryl group,
Z5and Z8Each independently represents an optionally substituted 3-to 20-membered heterocycloalkyl group, an optionally substituted 6-to 40-membered aryl group, an optionally substituted 5-to 30-membered heteroaryl group, -PO (Z)2)2、–PS(Z2)2or-Z2S(＝O)2(Z3) And n is 1,2 or 3.
A second aspect of the present invention provides a display panel including an organic light emitting device including an anode, a cathode, and an organic thin film layer between the anode and the cathode, the organic thin film layer including a light emitting layer and an electron transport layer; the electron transport layer comprises at least one compound according to the first aspect of the present invention.
A third aspect of the invention provides a display device comprising a display panel as described in the second aspect of the invention.
It has been surprisingly found that the present invention attaches an electron withdrawing group (i.e., R) to the fused rings of Aa and Ab through a phenyl group, respectively
Figure BDA0002561772300000021
The compound has a proper HOMO energy level and a lower LUMO energy level, so that the electron injection and transmission capability can be improved, a lower working voltage can be obtained, holes can be effectively blocked, and a higher exciton utilization rate can be achieved, so that higher luminous efficiency can be obtained. In particular, the compound also has suitable space distortion, can reduce intermolecular stacking, prevent crystallization, and thus has good film-forming property and film stability, thereby being capable of inhibiting the reduction of electron transport property and exciton formation efficiency due to material crystallization, and being beneficial to the improvement of the luminous efficiency and the lifetime of the device. In addition, the compound has better glass transition temperature (Tg) and thermal stability, which can lead the organic light-emitting device adopting the compound to have higher stability and longer service life. The display panel and the display device of the present invention comprise the compound, and thus may have a lower driving voltage, a higher luminous efficiency, and a longer lifespan.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the embodiments of the present invention will be briefly described below, and it is obvious that the drawings described below are only some embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained according to the drawings without creative efforts.
Fig. 1 is a schematic structural diagram of an organic light emitting device according to an embodiment of the present invention.
Fig. 2 is a schematic diagram of a display device according to an embodiment of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantageous technical effects of the present invention more clear, the present invention is further described in detail with reference to the following embodiments. It should be understood that the embodiments described in this specification are only for the purpose of explaining the present invention and are not intended to limit the present invention.
The above summary of the present invention is not intended to describe each disclosed embodiment or every implementation of the present invention. The following description more particularly exemplifies illustrative embodiments. At various points throughout this application, guidance is provided through a list of embodiments that can be used in various combinations. In each instance, the list is merely a representative group and should not be construed as exhaustive.
In the description herein, it is to be noted that, unless otherwise specified, "above" and "below" are inclusive of the present number, and the meaning of "a plurality" or "plural" in "one or plural" is two or more.
The terms "a", "an", "the" each refer to one or more molecules of the compound, and are not limited to a single molecule of the compound. Furthermore, one or more molecules may or may not be the same, provided they fall within the category of the chemical compound.
The term "comprising" and its variants are not to be taken in a limiting sense when these terms appear in the description and claims.
The terms "preferred" and "preferably" refer to embodiments of the invention that may provide certain benefits under certain circumstances. However, other embodiments may also be preferred, under the same or other circumstances. Furthermore, the recitation of one or more preferred embodiments does not imply that other embodiments are not useful, and is not intended to exclude other embodiments from the scope of the disclosure.
Groupings of alternative elements or embodiments disclosed herein are not to be construed as limitations. Each group member may be employed and claimed individually or in any combination with other members of the group or other elements found herein. It is contemplated that one or more members of a group may be included in or deleted from the group for reasons of convenience and/or patentability. When any such inclusion or deletion occurs, the specification is considered herein to contain the modified group and thus satisfy the written description of all markush groups used in the appended claims.
When a compound or a chemical structural feature (e.g., aryl) is referred to as "substituted," the feature may have one or more substituents, unless otherwise specified. The term "substituent" has the broadest meaning known to those of ordinary skill in the art and includes such fragments (moieity): which occupies the position normally occupied by one or more hydrogen atoms attached to the parent compound or chemical structural feature. In some embodiments, the substituent may be a common organic moiety known in the art, which may have a molecular weight (e.g., the sum of the atomic masses of the atoms of the substituent) of 15 to 50g/mol, 15 to 100g/mol, 15 to 200g/mol, or 15 to 500 g/mol. Some substituents include F, Cl, Br, I, NO2、C1-12H3-25、C1- 12H1-25O、C1-12H1-25O2、C1-12H3-26N、C1-12H1-26NO、C1-12H3-27N2、C1-12F3-25Substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted C3-C10 heteroaryl, and the like.
The term "alkyl" includes not only straight-chain or branched-chain saturated hydrocarbon groups such as methyl, ethyl, propyl (e.g., n-propyl, isopropyl), butyl (e.g., n-butyl, isobutyl, sec-butyl, tert-butyl), pentyl (e.g., n-pentyl, isopentyl, neopentyl) and the like, but also alkyl substituents bearing other substituents known in the art, such as hydroxyl, alkylsulfonyl, halogen atoms, cyano, nitro, amino, carboxyl and the like. Thus, "alkyl" includes ether groups, haloalkyl groups, nitroalkyl groups, carboxyalkyl groups, hydroxyalkyl groups, sulfoalkyl groups, and the like. In various embodiments, the C1-C20 alkyl groups, i.e., alkyl groups, can contain 1-20 carbon atoms.
The term "alkoxy" refers to-O-alkyl. Examples of alkoxy groups include, but are not limited to, methoxy, ethoxy, propoxy (e.g., n-propoxy, isopropoxy), butoxy (e.g., n-butoxy, isobutoxy, sec-butoxy, tert-butoxy), and the like.
The term "alkylthio" refers to-S-alkyl. Examples of alkylthio include, but are not limited to, methylthio, ethylthio, propylthio (e.g., n-propylthio, isopropylthio), butylthio (e.g., n-butylthio, isobutylthio, sec-butylthio, tert-butylthio), and the like.
The term "cycloalkyl" refers to a non-aromatic carbocyclic group, including cyclized alkyl, alkenyl, and alkynyl groups. Cycloalkyl groups can be monocyclic (e.g., cyclohexyl) or polycyclic (e.g., fused, bridged, and/or spiro rings). Examples of cycloalkyl groups include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclopentenyl, cyclohexenyl. In various embodiments, the 3-20 membered cycloalkyl group can contain 3-20 carbon atoms for forming a ring.
The term "heterocycloalkyl" refers to a cycloalkyl group in which one or more of the atoms in the ring is an element other than carbon (e.g., N, O, S, etc.), and optionally contains one or more double or triple bonds. "optionally comprising" means that it may or may not be comprised. In some embodiments, the nitrogen atom of a cycloheteroalkyl group may contain one substituent, such as a hydrogen atom, an alkyl group, or other substituents as described herein. Examples of cycloheteroalkyl groups include, but are not limited to, morpholinyl, thiomorpholinyl, pyranyl, imidazolidinyl, imidazolinyl, oxazolidinyl, pyrazolidinyl, pyrazolinyl, pyrrolidinyl, pyrrolinyl, tetrahydrofuranyl, tetrahydrothienyl, piperidinyl, piperazinyl, and similar heterocycloalkyl groups. In various embodiments, the 3-20 membered heterocycloalkyl group, i.e., heterocycloalkyl group, can contain 3-20 carbon atoms for forming a ring.
The term "aryl (ring)" refers to a closed aromatic ring or ring system. Examples of aryl (rings) include, but are not limited to, phenyl (rings), naphthyl (rings), fluorenyl (rings), indenyl (rings), anthracenyl (rings), phenanthrenyl (rings), pyrenyl (rings), spirobifluorenyl (rings), and the like. In various embodiments, the 6-to 40-membered aryl (ring), i.e., aryl (ring), can contain 6 to 40 carbon atoms for forming a ring.
The term "heteroaryl (ring)" means that one or more atoms in the ring of the aryl (ring) is an element other than carbon (e.g., N, O, S, etc.). In some embodiments, the 5-40 membered heteroaryl (ring) as a whole may contain 1-10 or 1-6 ring heteroatoms (e.g., N, O, S, etc.). Examples of heteroaryl (rings) include, but are not limited to, pyrrolyl (ring), furanyl (ring), thienyl (ring), pyridyl (ring), pyrimidinyl (ring), pyridazinyl (ring), pyrazinyl (ring), triazolyl (ring) (e.g., 1,2, 3-triazolyl (ring), 1,3, 4-triazolyl (ring), 1,2, 5-triazolyl (ring)), tetrazolyl (ring), triazinyl (ring) (e.g., 1,3, 5-triazinyl (ring)), tetrazinyl (ring), pyrazolyl (ring), imidazolyl (ring), isothiazolyl (ring), thiazolyl (ring), thiadiazolyl (ring), isoxazolyl (ring), oxazolyl (ring), oxadiazolyl (ring) (e.g., 1,3, 4-oxadiazolyl (ring), 1,2, 5-oxadiazolyl (ring)), indolyl (ring), Isoindolyl (ring), carbazolyl (ring), phenanthrolinyl (ring), benzofuranyl (ring), benzothienyl (ring), quinolinyl (ring), isoquinolinyl (ring), quinoxalinyl (ring), quinazolinyl (ring), acridinyl (ring), benzotriazolyl (ring), benzimidazolyl (ring), benzothiazolyl (ring), benzisothiazolyl (ring), benzisoxazolyl (ring), benzoxadiazolyl (ring), benzoxazolyl (ring), cinnolinyl (ring), 1H-indazolyl (ring), 2H-indazolyl (ring), indolizinyl (ring), isobenzofuranyl (ring), naphthyridinyl (ring) (e.g. 1, 8-naphthyridinyl (ring)), pterizinyl (ring), pteridinyl (ring), purinyl (ring), oxazolopyridyl (ring), thiazolopyridyl (ring), Imidazopyridinyl (ring), furopyridinyl (ring), thienopyridinyl (ring), pyridopyrimidinyl (ring), pyridopyrazinyl (ring), pyridopyridazinyl (ring), thienothiazolyl (ring), thienooxazolyl (ring), thienoimidazolyl (ring), and similar heteroaryl (ring). In various embodiments, the 5-to 40-membered aryl (ring), i.e., aryl (ring), can contain 5-40 atoms (including carbon and heteroatoms) for forming a ring.
The term "alkenyl" refers to a straight or branched chain alkyl group containing one or more C ═ C bonds. Examples of alkenyl groups include, but are not limited to, ethenyl, propenyl, butenyl (e.g., 1-butenyl, 2-butenyl, isobutenyl), butadienyl, pentenyl, hexenyl, and the like. In some embodiments, an alkenyl group can be substituted with an aryl or heteroaryl group as described herein.
The term "alkynyl" refers to a straight or branched chain alkyl group containing one or more carbon-carbon triple bonds. Examples of alkynyl groups include, but are not limited to, ethynyl, propynyl, butynyl (e.g., 1-butynyl, 2-butynyl), pentynyl, and the like. In some embodiments, an alkynyl group can be substituted with an aryl or heteroaryl group as described herein.
The term "halo" or "halogen" refers to fluorine, chlorine, bromine and iodine, such as fluorine.
The term "hydrogen" means1H (protium, H),2H (deuterium, D) or3H (tritium, T). In various embodiments, "hydrogen" may be1H (protium, H).
Throughout this specification, substituents of compounds are disclosed in groups or ranges. It is expressly intended that such description include each individual sub-combination of members of these groups and ranges. For example, the term "C1-C6 alkyl" is expressly contemplated to disclose C1, C2, C3, C4, C5, C6, C1-C6, C1-C5, C1-C4, C1-C3, C1-C2, C2-C6, C2-C5, C2-C4, C2-C3, C3-C6, C3-C5, C3-C4, C4-C6, C4-C5, and C5-C6 alkyl, individually. As other examples, integers ranging from 5 to 40 are expressly contemplated to disclose individually 5, 6, 7, 8, 9,10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, and 40; integers in the range of 1 to 20 are expressly contemplated to disclose 1,2,3, 4,5, 6, 7, 8, 9,10, 11, 12, 13, 14, 15, 16, 17, 18, 19 and 20 individually. Accordingly, other groups or ranges are expressly contemplated.
Herein, the expression that a single bond crosses a single ring or multiple ring system means that a single bond may be attached at any accessible position of the single ring or multiple ring system.
In an embodiment of the first aspect, the present invention provides a compound having the structure shown in formula 1,
Figure BDA0002561772300000061
wherein the content of the first and second substances,
ab represents an optionally substituted benzene ring, an optionally substituted naphthalene ring, an optionally substituted phenanthrene ring, an optionally substituted azabenzene ring, an optionally substituted azanaphthalene ring, or an optionally substituted azaphenanthrene ring,
ab is fused to Aa to form a fusion protein,
y is a number of 0 or 1,
when y is 0, Ab shares a1 and a 3C with Aa,
when y is 1, Ab shares a1 and a2 position C, a2 and a3 position C, or a1, a2 and a3 position C with Aa,
ac represents an optionally substituted 6-to 40-membered aromatic ring or an optionally substituted 5-to 40-membered aromatic heterocycle,
y represents C (Z)1)2、N(Z1)、O、S、Si(Z1)2Or PO (Z)1) Wherein Z is1Independently represent an optionally substituted C1-C20 alkyl group, an optionally substituted C1-C20 alkoxy group, an optionally substituted C1-C20 alkylthio group, an optionally substituted 3-to 20-membered cycloalkyl group, an optionally substituted 6-to 40-membered aryl group, or an optionally substituted 5-to 40-membered heteroaryl group,
r represents an optionally substituted 3-to 20-membered heterocycloalkyl group, an optionally substituted 6-to 40-membered aryl groupOptionally substituted 5-to 30-membered heteroaryl, -PO (Z)2)2、–PS(Z2)2、–Z2S(＝O)2(Z3)、–Z4–(Z5)nor-Z6–Z7–(Z8)n，
Z2And Z3Each independently represents an optionally substituted 6-to 40-membered aryl group or an optionally substituted 5-to 40-membered heteroaryl group,
Z4、Z6and Z7Independently represent a C2-C10 alkenyl group, a C2-C10 alkynyl group, a 6-to 30-membered aryl group or a 5-to 30-membered heteroaryl group,
Z5and Z8Each independently represents an optionally substituted 3-to 20-membered heterocycloalkyl group, an optionally substituted 6-to 40-membered aryl group, an optionally substituted 5-to 30-membered heteroaryl group, -PO (Z)2)2、–PS(Z2)2or-Z2S(＝O)2(Z3)，
n is 1,2 or 3.
In some embodiments, y is 0 and Ab represents an optionally substituted phenyl ring. For example, the compound has a structure represented by formula 1-1.
In some embodiments, y is 0 and Ab represents an optionally substituted azabenzene ring. Alternatively, the compound has a structure represented by formula 1-2, formula 1-3, formula 1-4, formula 1-5, formula 1-6, formula 1-7, or formula 1-8, but is not limited thereto. For example, the compound has a structure represented by formula 1-2, formula 1-3, formula 1-4, formula 1-5, or formula 1-6. For another example, the compound has a structure represented by formula 1-2, formula 1-3, or formula 1-4.
In some embodiments, y is 0 and Ab represents an optionally substituted naphthalene ring. For example, the compounds have the structure shown in formulas 1-9 or formulas 1-10.
In some embodiments, y is 0 and Ab represents an optionally substituted phenanthrene ring. For example, the compounds have the structures shown in formulas 1-12.
In some embodiments, y is 0 and Ab represents an optionally substituted azanaphthalene ring. For example, in the formulae 1 to 9 or the formulae 1 to 10, C-R1、C-R2、C-R3、C-R4、C-R5And C-R6One or several of which are replaced by N. Alternatively, the "several" here may be one, two or three. For example, C-R in the formulae 1 to 91And/or C-R6The compound obtained by substituting N. As another example, C-R in the formulae 1 to 104And/or C-R5The compound obtained by substituting N.
In some embodiments, y is 0 and Ab represents an optionally substituted azaphenanthrene ring. For example, in the formulae 1 to 12, C-R1、C-R2、C-R3、C-R4、C-R5、C-R6、C-R7And C-R8One or several of which are replaced by N. Alternatively, the "several" here may be one, two or three. For example, C-R in the formulae 1 to 124And/or C-R5The compound obtained by substituting N.
In some embodiments, y is 1 and Ab represents an optionally substituted naphthalene ring. For example, the compounds have the structures shown in formulas 1-11.
In some embodiments, y is 1 and Ab represents an optionally substituted azanaphthalene ring. For example, in the formulae 1 to 11, C-R1、C-R2、C-R3、C-R4、C-R5And C-R6One or several of which are replaced by N. Alternatively, the "several" herein may be one or two. For example, C-R in the formulae 1 to 113And/or C-R4The compound obtained by substituting N.
In some embodiments, y is 1 and Ab represents an optionally substituted phenanthrene ring. For example, the compounds have the structures shown in formulas 1-13.
In some embodiments, y is 1 and Ab represents an optionally substituted azaphenanthrene ring. For example, in the formulae 1 to 13, C-R1、C-R2、C-R3、C-R4、C-R5、C-R6、C-R7And C-R8One or several of which are replaced by N. Alternatively, the "several" herein may be one or two. For example, C-R in the formulae 1 to 135And C-R6The compound obtained by substituting N.
Figure BDA0002561772300000081
Figure BDA0002561772300000091
In any embodiment, R1～R8Each independently represents hydrogen, optionally substituted 3-to 20-membered heterocycloalkyl, optionally substituted 6-to 40-membered aryl, or optionally substituted 5-to 30-membered heteroaryl. As an example, R1～R8Each occurrence independently represents hydrogen, pyrrolidinyl, phenyl, furyl, thienyl, pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl, or the like. In various embodiments, R1～R8And when present may all represent hydrogen.
In any of the embodiments described herein, the first and second electrodes are,
Figure BDA0002561772300000092
(hereinafter referred to as YAc, wherein d1, d2, d3 and d4 are used to represent the number of the C position of the benzene ring) may be attached at any substitutable position on the benzene ring. By way of example, YAc is attached to the C at position C1. As another example, YAc is attached to the C at position C2.
In any embodiment, Y may represent S.
In any embodiment, Y may represent O.
In any embodiment, Y may represent C (Z)1)2Wherein Z is1As defined herein. For example, Z1Independently represent methyl, ethyl, methoxy, ethoxy, methylthio, ethylthio, cyclopropyl, cyclohexyl, phenyl or pyridyl group, etc. As an example, Z1Represents a methyl group.
In any embodiment, Ac may represent a benzene ring. For example, YAc may be, but is not limited to, SAc, OAc, or CAc.
Figure BDA0002561772300000101
In any embodiment, Ac may represent a naphthalene ring. YAc can be, but is not limited to, YAc-1, YAc-2, or YAc-3.
Figure BDA0002561772300000102
In some alternative embodiments, the compounds may have the structure shown in formulas 1-14, wherein R, R1～R4Each as defined herein. Alternatively, the compounds may have the structure shown in formulas 1-15, wherein R, R1～R4Each as defined herein. Alternatively, the compounds may have the structure shown in formulas 1-16, wherein R, R1～R4Each as defined herein.
Figure BDA0002561772300000103
In any embodiment, YAc can access the parent nucleus through any attachable position of the phenyl ring (i.e., the d1, d2, d3, or d4 position C). For example, YAc accesses the parent core through d2 bit C. As another example, YAc accesses the parent core through d3 bit C. As another example, YAc accesses the parent core through d1 bit C.
In some embodiments, the compound can have a structure as shown in formulas 14 a-14 d, 15 a-15 d, or 16 a-16 d. Wherein, R, R1～R4Each as defined herein. For example R1～R4All represent hydrogen.
Figure BDA0002561772300000111
In some embodiments, the compounds may include compounds in which Ab in formula 1-14, formula 14 a-14 d, formula 1-15, formula 15 a-15 d, formula 1-16, formula 16 a-16 d is converted to an azabenzene ring, e.g., a compound obtained by converting Ab according to formula 1-2, formula 1-3, formula 1-4, formula 1-5, or formula 1-6 to the corresponding azabenzene ring.
In any embodiment, R may be attached at any substitutable position on the phenyl ring. As an example, R is attached to C at position b 1. As another example, R is attached to C at position b 2.
In any embodiment, R may represent an optionally substituted 6-to 40-membered aryl group. For example, R may represent phenyl, naphthyl, anthryl, phenanthryl, perylene, or the like.
In any embodiment, R may represent an optionally substituted 5-30 membered heteroaryl. For example, R may represent a triazolyl group (e.g. 1,2, 3-triazolyl, 1,3, 4-triazolyl, 1,2, 5-triazolyl), a triazinyl group (e.g. 1,3, 5-triazinyl), an oxadiazolyl group (e.g. 1,3, 4-oxadiazolyl, 1,2, 5-oxadiazolyl) or a 9-to 14-membered hetero-fused ring aryl group (as described herein).
In any embodiment, R may represent-PO (Z)2)2Wherein Z is2As defined herein. For example, Z2Represents a phenyl group.
In any embodiment, R may represent-PS (Z)2)2Wherein Z is2As defined herein. For example, Z2Represents a phenyl group.
In any embodiment, R may represent-Z2S(＝O)2(Z3) Wherein Z is2And Z3Each as defined herein. For example, Z2And Z3Both represent phenyl.
In any embodiment, R may represent-Z4–(Z5)nWherein Z is4、Z5And n are each as defined herein. In various embodiments, Z4May represent a 6-to 30-membered aryl group or a 5-to 30-membered heteroaryl group. For example, Z4May be selected from any one of W-1 to W-47. Alternatively, Z4Represents naphthyl, anthryl or phenanthryl, such as anthryl. Or, Z4Can be selected from any one of W-24 to W-37 and W-42 to W-45. Further, Z4May be selected from any one of W-24 to W-37. Further, Z4Can be selected from any one of W-24 to W-29; or Z4Any one selected from W-30 to W-35; or Z4Selected from W-36 or W-37.
Figure BDA0002561772300000121
# and # each independently represent the ligation site. In W-38 and W-39, Y isAs otherwise defined herein. In any embodiment, in W-38 and W-39, Y may independently represent O; alternatively, Y may independently represent S; or, Y may independently represent C (CH)3)2。
Although only one Z is shown in the above-mentioned W-1 to W-475It will be appreciated that there may also be a second or second and third Z connection sites5Attached to these groups give the corresponding R. Second and third Z5Can be attached to any substitutable position of the group.
In any embodiment, Z5May independently represent an optionally substituted 6-to 40-membered aryl group. For example phenyl, biphenyl, P1(M represents C (Z)1)2E.g. C (CH)3)2) P7 to P11, naphthyl, P46 to P48 (with the access position on the benzene ring), P49 to P51, P76 to P78 (with the access position on the benzene ring), and P87.
In any embodiment, Z5May independently represent an optionally substituted 5-30 membered heteroaryl group. For example, P1(M represents O or S), P2 to P6, P12 to P14, P15 to P21, P22 to P24, P25 to P45, P46 to P48 (at the pyridine ring), P52 to P63, P67 to P75, P76 to P78 (at the pyridine ring), and P79 to P86.
In any embodiment, Z5Can independently represent-PO (Z)2)2Wherein Z is2As defined herein. For example, Z5Representing P64.
In any embodiment, Z5Independently represent-PS (Z)2)2Wherein Z is2As defined herein. For example, Z5Representing P65.
In any embodiment, Z5Can independently represent-Z2S(＝O)2(Z3) Wherein Z is2As defined herein. For example, Z5Representing P66.
Figure BDA0002561772300000131
Figure BDA0002561772300000141
Figure BDA0002561772300000151
M independently represents C (Z)1)2S or O, Z1As defined herein. For example, Z1Represents a methyl group. # denotes the ligation site.
P1 may be selected from P1a, P1b, P1c at each occurrence. P6 may be selected from P6a, P6b, P6c at each occurrence. P43 may be selected from P43a, P43b at each occurrence. P44 may be selected from P44a, P44b at each occurrence. P45 may be selected from P45a, P45b, P45c at each occurrence. P46 may be selected from P46a, P46b, P46c, P46d, P46e at each occurrence. P47 may be selected from P47a, P47b, P47c, P47d, P47e at each occurrence. P48 may be selected from P48a, P48b, P48c, P48d, P48e at each occurrence. P49 may be selected from P49a, P49b, P49c at each occurrence. P52 may be selected from P52a, P52b, P52c at each occurrence. P53 may be selected from P53a, P53b at each occurrence. P54 may be selected from P54a, P54b, P54c at each occurrence. P55 may be selected from P55a, P55b, P55c at each occurrence. P58 may be selected from P58a, P58b, P58c at each occurrence. P66, P70-P78 may be selected at each occurrence from P66a, P70 a-P78 a, respectively. P86 may be selected separately at each occurrence from P86 a.
Figure BDA0002561772300000152
Figure BDA0002561772300000161
In which R represents-Z4–(Z5)nExamples of R include, but are not limited to, R1-R35, R54.
Figure BDA0002561772300000162
Figure BDA0002561772300000171
Specific examples of R24, R32, R33, R34, R35 may include, but are not limited to, R24a, R32a, R33a, R34a, R35a, respectively.
Figure BDA0002561772300000172
In any embodiment, R may represent-Z6–Z7–(Z8)nWherein Z is6、Z7、Z8And n are each as defined herein.
In any embodiment, Z6And Z7Each independently represents a 6-to 30-membered aryl group or a 5-to 30-membered heteroaryl group. For example, Z6And Z7Each independently represents any one of W-1 to W-47.
In any embodiment, Z6And Z7One of them represents any one of W-20 to W-46, and the other represents any one of W-1 to W-19 and W-47. Further, Z6Represents any one of W-20 to W-46, Z7Represents any one of W-1 to W-19 and W-47. Further, Z6Represents any one of W-24 to W-37 and W-42 to W-45, or any one of W-24 to W-37, or any one of W-30 to W-35. Further, Z7Represents any one of W-1 to W-3, or any one of W-4 to W-9. As an example, Z6Represents any one of W-24 to W-37, or any one of W-30 to W-35, and Z7Represents any one of W-1 to W-3, or any one of W-4 to W-9.
Although when Z is7When any one of W-1 to W-47 is represented, only one Z is shown in the above W-1 to W-478It will be appreciated that there may also be a second or second and third Z connection sites8Attached to these groups give the corresponding R. Second and third Z5Can be attached to any substitutable position of the group.
In any embodiment, Z8May independently represent an optionally substituted 6-to 40-membered aryl group. For example phenyl, biphenyl, P1(M represents C (Z)1)2) P7 to P11, naphthyl, P46 to P48 (with the access position on the benzene ring), P49 to P51, P76 to P78 (with the access position on the benzene ring), and P87.
In any embodiment, Z8May independently represent an optionally substituted 5-30 membered heteroaryl group. For example, P1(M represents O or S), P2 to P6, P12 to P14, P15 to P21, P22 to P24, P25 to P45, P46 to P48 (with the access position being in the pyridine ring), P52 to P54, P55, P56, P57 to P63, P67 to P75, P76 to P78 (with the access position being in the pyridine ring), and P79 to P86.
In any embodiment, Z8Can independently represent-PO (Z)2)2Wherein Z is2As defined herein. For example, Z5Representing P64.
In any embodiment, Z8Independently represent-PS (Z)2)2Wherein Z is2As defined herein. For example, Z5Representing P65.
In any embodiment, Z8Can independently represent-Z2S(＝O)2(Z3) Wherein Z is2As defined herein. For example, Z5Representing P66.
In which R represents-Z6–Z7–(Z8)nExamples of R include, but are not limited to, R5-R31, R32-R34, or R35-R54.
Figure BDA0002561772300000181
Specific examples of R36-R53 may include, but are not limited to, R36 a-R53 a.
Figure BDA0002561772300000191
In some embodiments, the compound has a structure as shown in any one of H1-H50, K1-K50, E1-E53, G1-G53, T1-T50, L1-L50, J1-J53, Q1-Q53.
Figure BDA0002561772300000192
Figure BDA0002561772300000201
Figure BDA0002561772300000211
Figure BDA0002561772300000221
Figure BDA0002561772300000231
Figure BDA0002561772300000241
Figure BDA0002561772300000251
Figure BDA0002561772300000261
Figure BDA0002561772300000271
Figure BDA0002561772300000281
Figure BDA0002561772300000291
Figure BDA0002561772300000301
Figure BDA0002561772300000311
Figure BDA0002561772300000321
Figure BDA0002561772300000331
Figure BDA0002561772300000341
Figure BDA0002561772300000351
Figure BDA0002561772300000361
Figure BDA0002561772300000371
Figure BDA0002561772300000381
Figure BDA0002561772300000391
It should be noted that those skilled in the art can also obtain other compounds according to the description herein, such as compounds obtained by converting R, YAc connection positions, Ab selection types, etc. for H1-H50, K1-K50, E1-E53, G1-G53, T1-T50, L1-L50, J1-J53, and Q1-Q53, and these compounds are all within the scope of the present invention. For example, compounds obtained by converting Ab in the above compounds to an azabenzene ring, such as compounds obtained by converting Ab to the corresponding azabenzene ring according to formula 1-2, formula 1-3, formula 1-4, formula 1-5 or formula 1-6. For example, but not limited to, any of compounds X1-X60.
Figure BDA0002561772300000401
Figure BDA0002561772300000411
Figure BDA0002561772300000421
Figure BDA0002561772300000431
The compounds of the present invention may be prepared according to the following exemplary scheme I. The specific methods for carrying out each synthetic step are readily available to those skilled in the art from the relevant scientific literature or standard textbooks in the art, according to this exemplary scheme I. Unless otherwise indicated, commercially available or literature-known compounds are used as starting materials for the synthesis.
It is to be understood that, unless otherwise indicated, when typical or preferred process conditions (i.e., reaction temperatures, times, molar ratios of reactants, solvents, pressures, etc.) are given, other process conditions may also be used. The optimum reaction conditions may vary with the particular reactants or solvents used, but these conditions can be determined by one skilled in the art by routine optimization procedures. One skilled in the art of organic synthesis will recognize that the nature and order of the synthetic steps presented may be varied for the purpose of optimizing the production of the compounds described herein.
Scheme I
Figure BDA0002561772300000441
Wherein Z is1And Z2Each independently represents a halogen. For example，Z1And Z2Each independently represents F, Cl, Br or I, for example Br. Other code numbers are as defined herein.
The processes described herein may be monitored according to any suitable method known in the art. For example, product formation can be by spectroscopic means such as nuclear magnetic resonance spectroscopy (NMR, e.g. of1H or13C) Infrared spectroscopy (IR), spectrophotometry (e.g. UV visible), Mass Spectrometry (MS) or by chromatography such as High Performance Liquid Chromatography (HPLC), Gas Chromatography (GC), Gel Permeation Chromatography (GPC) or Thin Layer Chromatography (TLC).
The compound of the present invention is useful for display panels and display devices. In some embodiments, the compounds of the present invention may have higher solubility in conventional solvents (such as dichloromethane, chloroform, toluene, DMF, THF, ethanol, etc.), facilitate the preparation of organic thin film layers, and achieve better film formation uniformity, and reduce or avoid the occurrence of voids.
In an embodiment of another aspect, the present invention provides a display panel including an organic light emitting device including an anode, a cathode, and a multi-layered organic thin film layer between the anode and the cathode, the multi-layered organic thin film layer including at least an emission layer (EML) and an Electron Transport Layer (ETL); wherein the electron transport layer contains any one or more of the compounds of the present invention.
In some embodiments, the electron transport layer may also optionally include other electron transport materials known in the art, such as one or more of the following:
Figure BDA0002561772300000451
Figure BDA0002561772300000452
and the like.
In some embodiments, the light emitting layer may include a light emitting material as is known in the art. Further, the light emitting material may include a host material and a guest material. Wherein the host material can be selected from host luminescent materials known in the art and/or any one or more of the compounds described herein. The guest material may be selected from guest light emitting materials known in the art. The host (guest) light emitting material known in the art may be a fluorescent light emitting material, a phosphorescent light emitting material, or the like, and may be a blue light emitting material, a green light emitting material, a red light emitting material, or the like.
In some embodiments, the anode material may include a metal (e.g., copper, gold, silver, iron, chromium, nickel, manganese, palladium, platinum, etc., and alloys thereof), a metal oxide (e.g., indium oxide, zinc oxide, Indium Tin Oxide (ITO), Indium Zinc Oxide (IZO), etc.), a conductive polymer (e.g., polyaniline, polypyrrole, poly (3-methylthiophene), etc.). In addition to the above materials and combinations thereof that facilitate hole injection, other known materials suitable for use as anodes may be included.
In some embodiments, the cathode can include a metal layer (e.g., aluminum, magnesium, silver, indium, tin, titanium, and the like, and alloys thereof), a multi-layer cathode formed by compounding a metal layer and a layer comprising one or more of a metal oxide and a metal halide (e.g., LiF/Al, LiO)2/Al、BaF2Al, etc.). In addition to the above materials and combinations thereof that facilitate electron injection, other known materials suitable for use as cathodes are also included.
In the display panel of the present invention, the organic thin film layers may further include other functional layers. As an example, other functional layers may include a Hole Blocking Layer (HBL). In some embodiments, the Hole Blocking Material (HBM) of the Hole Blocking Layer (HBL) may be selected from HBM known in the art (e.g., BCP, TPBi, TmPyPB, DPEPO, PO-T2T, TAZ, etc.) and/or any one or more of the compounds described herein.
Figure BDA0002561772300000461
In some embodiments, the other functional layers may further include a Hole Injection Layer (HIL), a Hole Transport Layer (HTL), an Electron Blocking Layer (EBL), an Electron Injection Layer (EIL). The materials of the layers (e.g. hole injection material HIM, hole transport material HTM, electron blocking material EBM, electron injection material EIM) may each be selected from the corresponding materials known in the art.
Fig. 1 shows an organic light emitting device as an example, which includes a substrate 1, an anode 2, a hole injection layer 3, a hole transport layer 4, a light emitting layer 5, a hole blocking layer 6, an electron transport layer 7, an electron injection layer 8, a cathode 9, and a cap layer 10, which are sequentially stacked. The hole transport layer 4 in the drawing is a composite layer structure including a first hole transport layer 41 and a second hole transport layer 42. The arrows in the figure indicate the light direction.
The display panel may be fabricated using methods known in the art. An exemplary method of fabrication includes: an anode is formed on a transparent or opaque smooth substrate, a plurality of organic thin film layers are formed on the anode, and a cathode is formed on the organic thin film layers. The organic thin film layer can be formed by a known film formation method such as evaporation, sputtering, spin coating, dipping, ion plating, or the like.
In another embodiment, the present invention provides a display device including the display panel according to the present invention. Examples of the display device include, but are not limited to, a mobile phone (e.g., the mobile phone 100 shown in fig. 2), a computer, a television, a smart watch, a smart car, a VR or AR helmet, and the like, which are not particularly limited in this respect.
Examples
The present disclosure is more particularly described in the following examples that are intended as illustrations only, since various modifications and changes within the scope of the present disclosure will be apparent to those skilled in the art. Unless otherwise stated, all parts, percentages, and ratios reported in the following examples are on a weight basis, and all reagents used in the examples are commercially available or synthesized according to conventional methods and can be used directly without further treatment, and the equipment used in the examples is commercially available.
Example 1: preparation of Compound J53
(A)
Figure BDA0002561772300000471
Under nitrogen atmosphere at 80mL of acetic acid was added with o-phenylenediamine (8.8mmol) and 4,4' -dibromodibenzoyl (8mmol), and the mixture was stirred at elevated temperature and reacted at 100 ℃ for 24 hours. After the reaction is finished, cooling to room temperature, pouring the mixture into ice water under stirring, carrying out suction filtration, collecting a filter cake, dissolving the filter cake into dichloromethane, adding water for extraction, collecting an organic phase, and using anhydrous Na2SO4Drying, collecting filtrate by suction filtration, removing the solvent by rotation, and purifying by column chromatography to obtain an intermediate Me-1 (yield 85%).
LC-MS: calculated m/z: C20H12Br2N2:440.13, found: 439.89.
(II)
Figure BDA0002561772300000472
Under nitrogen, 100mL of toluene: ethanol: water (10:1:1) mixed solvent, adding K in sequence2CO3(2.5mmol), intermediate Me-1(1mmol), dibenzofuran-4-boronic acid (1mmol), and Pd (PPh)3)4(0.05mmol), the temperature was raised to 90 ℃ and the reaction was carried out overnight. After the reaction is finished, cooling to room temperature, adding dichloromethane/H2Extracting with O, and collecting organic phase with anhydrous Na2SO4Drying, collecting the filtrate by suction filtration, removing the solvent by rotation, and purifying by column chromatography to obtain an intermediate Me-2 (yield 71%).
LC-MS: calculated m/z: C32H19BrN2O:527.41, found: 527.19.
(III)
Figure BDA0002561772300000473
Under nitrogen, 100mL of toluene: ethanol: water (10:1:1) mixed solvent, adding K in sequence2CO3(2.5mmol), anthracene-9, 10-diboronic acid (1mmol), Re-1(1mmol), and Pd (PPh)3)4(0.05mmol), the temperature was raised to 90 ℃ and the reaction was carried out overnight. After the reaction is finished, cooling to room temperature, adding dichloromethane/H2Extracting with O, and collecting organic phase with anhydrous Na2SO4Drying, suction filtering to collect filtrate, removing solvent by rotation and carrying outPurification by column chromatography gave the intermediate Me-3 (yield 69%).
LC-MS: calculated m/z: C30H21BN2O2:452.31, found: 452.09.
(IV)
Figure BDA0002561772300000481
Under the nitrogen atmosphere, 100mL of dioxane solvent is added into a 250mL reaction bottle, and K is sequentially added2CO3(2.5mmol) aqueous solution, intermediate Me-2(1mmol), intermediate Me-3(1mmol), and Pd (PPh)3)4(0.05mmol), the temperature was raised to 100 ℃ and the reaction was carried out overnight. After the reaction is finished, cooling to room temperature, adding dichloromethane/H2Extracting with O, and collecting organic phase with anhydrous Na2SO4Drying, collecting the filtrate by suction filtration, removing the solvent by rotation, and purifying by column chromatography to obtain compound J53 (yield 83%).
LC-MS: calculated m/z: C62H38N4O:854.99, found: 854.78.
compound elemental analysis results: calculated values: C62H38N4O (%): C87.10, H4.48, N6.55; test values are: c87.11, H4.47, N6.56.
Example 2: preparation of Compound J34
(A)
Figure BDA0002561772300000482
Intermediate Me-4 was prepared analogously to Me-3, except that Re-1 in step (III) of example 1 was replaced with an equimolar amount of Re-2, giving intermediate Me-4 (yield 65%).
LC-MS: calculated m/z: C29H20BN3O2:453.30, found: 453.09.
(II)
Figure BDA0002561772300000483
Compound J34 was prepared analogously to J53, with the exception that Me-3 in step (four) of example 1 was replaced with an equimolar amount of Me-4 to give compound J34 (yield 80%).
LC-MS: calculated m/z: C61H37N5O:855.98, found 855.67.
Compound elemental analysis results: calculated values: C61H37N5O (%): C85.59, H4.36, N8.18; test values are: c85.60, H4.35, N8.20.
Example 3: preparation of Compound J12
(A)
Figure BDA0002561772300000491
Intermediate Me-5 was prepared analogously to Me-3, except that Re-1 in step (III) of example 1 was replaced by an equimolar amount of Re-3, giving intermediate Me-5 (yield 62%).
LC-MS: calculated m/z: C29H20BN3O2:453.30, found: 453.12.
(II)
Figure BDA0002561772300000492
Compound J33 was prepared analogously to J53, with the exception that Me-3 in step (four) of example 1 was replaced with an equimolar amount of Me-5 to give compound J12 (yield 77%).
LC-MS: calculated m/z: C61H37N5O:855.98, found: 855.63.
compound elemental analysis results: calculated values: C61H37N5O (%): C85.59, H4.36, N8.18; test values are: c85.58, H4.35, N8.21.
Example 4: preparation of Compound E12
(A)
Figure BDA0002561772300000493
Intermediate Me-6 was prepared analogously to Me-2, with the difference that dibenzofuran-4-boronic acid from step (two) of example 1 was replaced with an equimolar amount of dibenzothiophene-4-boronic acid, yielding intermediate Me-6 (yield 70%).
LC-MS: calculated m/z: C32H19BrN2S:543.48, found: 543.13.
(II)
Figure BDA0002561772300000501
Compound E12 was prepared analogously to J12, with the difference that Me-2 in step (two) of example 3 was replaced by an equimolar amount of Me-6 to give compound E12 (yield 75%).
LC-MS: calculated m/z: C61H37N5S:872.04, found: 871.87.
compound elemental analysis results: calculated values: C61H37N5S (%): C84.02, H4.28, N8.03; test values are: c84.01, H4.27, N8.05.
Example 5: preparation of Compound T12
(A)
Figure BDA0002561772300000502
Intermediate Me-7 was prepared analogously to Me-2, with the difference that dibenzofuran-4-boronic acid from step (two) of example 1 was replaced with an equimolar amount of dibenzofuran-3-boronic acid, yielding intermediate Me-7 (yield 75%).
LC-MS: calculated m/z: C32H19BrN2O:527.41, found: 527.13.
(II)
Figure BDA0002561772300000503
Compound E12 was prepared analogously to J12, with the difference that Me-2 in step (two) of example 3 was replaced by an equimolar amount of Me-7 to give compound T12 (yield 80%).
LC-MS: calculated m/z: C61H37N5O:855.98, found: 855.73.
compound elemental analysis results: calculated values: C61H37N5O (%): C85.59, H4.36, N8.18; test values are: c85.60, H4.35, N8.19.
Example 6: preparation of Compound Q34
(A)
Figure BDA0002561772300000511
O-phenylenediamine (8.8mmol) and 1, 2-bis (3-bromophenyl) ethane-1, 2-dione (8mmol) were added to 80mL of acetic acid under a nitrogen atmosphere, and the mixture was stirred, warmed and reacted at 100 ℃ for 24 hours. After the reaction is finished, cooling to room temperature, pouring the mixture into ice water under stirring, carrying out suction filtration, collecting a filter cake, dissolving the filter cake into dichloromethane, adding water for extraction, collecting an organic phase, and using anhydrous Na2SO4Drying, collecting the filtrate by suction filtration, removing the solvent by rotation, and purifying by column chromatography to obtain an intermediate Me-8 (yield 81%).
LC-MS: calculated m/z: C20H12Br2N2:440.13, found: 439.81.
(II)
Figure BDA0002561772300000512
Under nitrogen, 100mL of toluene: ethanol: water (10:1:1) mixed solvent, adding K in sequence2CO3(2.5mmol), Me-8(1mmol), dibenzofuran-4-boronic acid (1mmol), and Pd (PPh)3)4(0.05mmol), the temperature was raised to 90 ℃ and the reaction was carried out overnight. After the reaction is finished, cooling to room temperature, adding dichloromethane/H2Extracting with O, and collecting organic phase with anhydrous Na2SO4Drying, collecting the filtrate by suction filtration, removing the solvent by rotation, and purifying by column chromatography to obtain an intermediate Me-9 (yield 70%).
LC-MS: calculated m/z: C32H19BrN2O:527.41, found: 527.16.
(III)
Figure BDA0002561772300000513
Under the nitrogen atmosphere, 100mL of dioxane solvent is added into a 250mL reaction bottle, and K is sequentially added2CO3(2.5mmol) aqueous solution, Me-9(1mmol), Me-4(1mmol), and Pd (PPh)3)4(0.05mmol), the temperature was raised to 100 ℃ and the reaction was carried out overnight. After the reaction is finished, cooling to room temperature, adding dichloromethane/H2Extracting with O, and collecting organic phase with anhydrous Na2SO4Drying and pumpingThe filtrate was collected by filtration, the solvent was removed by rotation, and column chromatography purification was performed to obtain compound Q34 (yield 87%).
LC-MS: calculated m/z: C61H37N5O:855.98, found: 855.79.
compound elemental analysis results: calculated values: C61H37N5O (%): C85.59, H4.36, N8.18; test values are: c85.58, H4.35, N8.20.
Example 7: preparation of Compound Q12
Figure BDA0002561772300000521
Compound Q12 was prepared analogously to Q34, with the difference that Me-4 in step (iii) of example 6 was replaced by an equimolar amount of Me-5 to give compound Q12 (yield 76%).
LC-MS: calculated m/z: C61H37N5O:855.98, found: 855.57.
compound elemental analysis results: calculated values: C61H37N5O (%): C85.59, H4.36, N8.18; test values are: c85.58, H4.35, N8.20.
Example 8: preparation of Compound X34
(A)
Figure BDA0002561772300000522
Under a nitrogen atmosphere, 2, 3-diaminopyridine (5.5mmol) and 1, 2-bis (3-bromophenyl) ethane-1, 2-dione (5mmol) were added to 80mL of acetic acid, and the mixture was stirred, warmed and reacted at 100 ℃ for 24 hours. After the reaction is finished, cooling to room temperature, pouring the mixture into ice water under stirring, carrying out suction filtration, collecting a filter cake, dissolving the filter cake into dichloromethane, adding water for extraction, collecting an organic phase, and using anhydrous Na2SO4Drying, collecting the filtrate by suction filtration, removing the solvent by rotation, and purifying by column chromatography to obtain the intermediate Me-10 (yield 79%).
LC-MS: calculated m/z: C19H11Br2N3:441.12, found: 440.93.
(II)
Figure BDA0002561772300000531
Under nitrogen, 100mL of toluene: ethanol: water (10:1:1) mixed solvent, adding K in sequence2CO3(2.5mmol), Me-10(1mmol), dibenzofuran-4-boronic acid (1mmol), and Pd (PPh)3)4(0.05mmol), the temperature was raised to 90 ℃ and the reaction was carried out overnight. After the reaction is finished, cooling to room temperature, adding dichloromethane/H2Extracting with O, and collecting organic phase with anhydrous Na2SO4Drying, collecting the filtrate by suction filtration, removing the solvent by rotation, and purifying by column chromatography to obtain intermediate Me-11 (yield 68%).
LC-MS: calculated m/z: C31H18BrN3O:528.40, found: 528.19.
(III)
Figure BDA0002561772300000532
Under the nitrogen atmosphere, 100mL of dioxane solvent is added into a 250mL reaction bottle, and K is sequentially added2CO3(2.5mmol) aqueous solution, Me-11(1mmol), Me-5(1mmol), and Pd (PPh)3)4(0.05mmol), the temperature was raised to 100 ℃ and the reaction was carried out overnight. After the reaction is finished, cooling to room temperature, adding dichloromethane/H2Extracting with O, and collecting organic phase with anhydrous Na2SO4Drying, collecting the filtrate by suction filtration, removing the solvent by rotation, and purifying by column chromatography to obtain compound X34 (yield 80%).
LC-MS: calculated m/z: C60H36N6O:856.97, found: 856.76.
compound elemental analysis results: calculated values: C60H36N6O (%): C84.09, H4.23, N9.81; test values are: c84.08, H4.22, N9.83.
Example 9: preparation of Compound X22
(A)
Figure BDA0002561772300000533
Under a nitrogen atmosphere, 80mL of acetic acid was added with 3, 4-diaminopyridine (5.5mmol) and 1, 2-bis (3-bromophenyl) ethane-1, 2-dione (5 m)mol), stirring and raising the temperature, and reacting for 24 hours at 100 ℃. After the reaction is finished, cooling to room temperature, pouring the mixture into ice water under stirring, carrying out suction filtration, collecting a filter cake, dissolving the filter cake into dichloromethane, adding water for extraction, collecting an organic phase, and using anhydrous Na2SO4Drying, collecting the filtrate by suction filtration, removing the solvent by rotation, and purifying by column chromatography to obtain intermediate Me-12 (yield 77%).
LC-MS: calculated m/z: C19H11Br2N3:441.12, found: 440.89.
(II)
Figure BDA0002561772300000541
Under nitrogen, 100mL of toluene: ethanol: water (10:1:1) mixed solvent, adding K in sequence2CO3(2.5mmol), Me-12(1mmol), dibenzofuran-4-boronic acid (1mmol), and Pd (PPh)3)4(0.05mmol), the temperature was raised to 90 ℃ and the reaction was carried out overnight. After the reaction is finished, cooling to room temperature, adding dichloromethane/H2Extracting with O, and collecting organic phase with anhydrous Na2SO4Drying, collecting the filtrate by suction filtration, removing the solvent by rotation, and purifying by column chromatography to obtain intermediate Me-13 (yield 67%).
LC-MS: calculated m/z: C31H18BrN3O:528.40, found: 528.21.
(III)
Figure BDA0002561772300000542
Under the nitrogen atmosphere, 100mL of dioxane solvent is added into a 250mL reaction bottle, and K is sequentially added2CO3(2.5mmol) aqueous solution, Me-13(1mmol), Me-5(1mmol), and Pd (PPh)3)4(0.05mmol), the temperature was raised to 100 ℃ and the reaction was carried out overnight. After the reaction is finished, cooling to room temperature, adding dichloromethane/H2Extracting with O, and collecting organic phase with anhydrous Na2SO4Drying, collecting the filtrate by suction filtration, removing the solvent by rotation, and purifying by column chromatography to obtain compound X22 (yield 78%).
LC-MS: calculated m/z: C60H36N6O:856.97, found: 856.81.
compound elemental analysis results: calculated values: C60H36N6O (%): C84.09, H4.23, N9.81; test values are: c84.07, H4.22, N9.82.
Example 10: preparation of Compound X47
(A)
Figure BDA0002561772300000551
Under a nitrogen atmosphere, 4, 5-diaminopyrimidine (4.4mmol) and 1, 2-bis (3-bromophenyl) ethane-1, 2-dione (4mmol) were added to 80mL of acetic acid, and the mixture was stirred, warmed and reacted at 100 ℃ for 24 hours. After the reaction is finished, cooling to room temperature, pouring the mixture into ice water under stirring, carrying out suction filtration, collecting a filter cake, dissolving the filter cake into dichloromethane, adding water for extraction, collecting an organic phase, and using anhydrous Na2SO4Drying, collecting the filtrate by suction filtration, removing the solvent by rotation, and purifying by column chromatography to obtain the intermediate Me-14 (yield 75%).
LC-MS: calculated m/z: C18H10Br2N4:442.11, found: 441.89.
(II)
Figure BDA0002561772300000552
Under nitrogen, 100mL of toluene: ethanol: water (10:1:1) mixed solvent, adding K in sequence2CO3(2.5mmol), Me-14(1mmol), dibenzofuran-4-boronic acid (1mmol), and Pd (PPh)3)4(0.05mmol), the temperature was raised to 90 ℃ and the reaction was carried out overnight. After the reaction is finished, cooling to room temperature, adding dichloromethane/H2Extracting with O, and collecting organic phase with anhydrous Na2SO4Drying, collecting the filtrate by suction filtration, removing the solvent by rotation, and purifying by column chromatography to obtain intermediate Me-15 (yield 67%).
LC-MS: calculated m/z: C30H17BrN4O:529.39, found: 529.08.
(III)
Figure BDA0002561772300000553
Under the nitrogen atmosphere, 100mL of dioxane solvent is added into a 250mL reaction bottle, and K is sequentially added2CO3(2.5mmol) aqueous solution, Me-15(1mmol), Me-4(1mmol), and Pd (PPh)3)4(0.05mmol), the temperature was raised to 100 ℃ and the reaction was carried out overnight. After the reaction is finished, cooling to room temperature, adding dichloromethane/H2Extracting with O, and collecting organic phase with anhydrous Na2SO4Drying, collecting the filtrate by suction filtration, removing the solvent by rotation, and purifying by column chromatography to obtain compound X47 (yield 76%).
LC-MS: calculated m/z: C59H35N7O:857.96, found: 857.74.
compound elemental analysis results: calculated values: C59H35N7O (%): C82.60, H4.11, N11.43; test values are: c82.59, H4.10, N11.45.
Example 11: preparation of Compound X59
(A)
Figure BDA0002561772300000561
Under a nitrogen atmosphere, 2, 3-diaminopiperazine (4.4mmol) and 1, 2-bis (3-bromophenyl) ethane-1, 2-dione (4mmol) were added to 80mL of acetic acid, and the mixture was stirred, warmed and reacted at 100 ℃ for 24 hours. After the reaction is finished, cooling to room temperature, pouring the mixture into ice water under stirring, carrying out suction filtration, collecting a filter cake, dissolving the filter cake into dichloromethane, adding water for extraction, collecting an organic phase, and using anhydrous Na2SO4Drying, collecting the filtrate by suction filtration, removing the solvent by rotation, and purifying by column chromatography to obtain intermediate Me-16 (yield 73%).
LC-MS: calculated m/z: C18H10Br2N4:442.11, found: 441.84.
(II)
Figure BDA0002561772300000562
Under nitrogen, 100mL of toluene: ethanol: water (10:1:1) mixed solvent, adding K in sequence2CO3(2.5mmol)，Me-16(1mmol)，Dibenzofuran-4-boronic acid (1mmol), and Pd (PPh)3)4(0.05mmol), the temperature was raised to 90 ℃ and the reaction was carried out overnight. After the reaction is finished, cooling to room temperature, adding dichloromethane/H2Extracting with O, and collecting organic phase with anhydrous Na2SO4Drying, collecting the filtrate by suction filtration, removing the solvent by rotation, and purifying by column chromatography to obtain an intermediate Me-17 (yield 65%).
LC-MS: calculated m/z: C30H17BrN4O:529.39, found: 529.04.
(III)
Figure BDA0002561772300000563
Under the nitrogen atmosphere, 100mL of dioxane solvent is added into a 250mL reaction bottle, and K is sequentially added2CO3(2.5mmol) aqueous solution, Me-17(1mmol), Me-4(1mmol), and Pd (PPh)3)4(0.05mmol), the temperature was raised to 100 ℃ and the reaction was carried out overnight. After the reaction is finished, cooling to room temperature, adding dichloromethane/H2Extracting with O, and collecting organic phase with anhydrous Na2SO4Drying, collecting the filtrate by suction filtration, removing the solvent by rotation, and purifying by column chromatography to obtain compound X59 (yield 73%).
LC-MS: calculated m/z: C59H35N7O:857.96, found: 857.73.
compound elemental analysis results: calculated values: C59H35N7O (%): C82.60, H4.11, N11.43; test values are: c82.58, H4.10, N11.45.
Comparative example 1: comparative Compound 1
Figure BDA0002561772300000571
Simulated calculation of compound energy levels: the energy levels of the compounds of the examples and comparative examples were calculated by simulation using the Density Functional Theory (DFT). The distribution of the molecular front line orbitals HOMO and LUMO was optimized and calculated at the B3LYP/6-31G (d) calculation level by the Guassian 09 package (Guassian Inc.). The results are shown in Table 1.
TABLE 1
Serial number Compound (I) HOMO(eV) LUMO(eV) Eg(eV)
Example 1 J53 -5.30 -2.00 3.30
Example 2 J34 -5.39 -2.03 3.36
Example 3 J12 -5.22 -1.96 3.26
Example 4 E12 -5.21 -1.96 3.25
Example 5 T12 -5.20 -1.97 3.23
Example 6 Q34 -5.37 -2.01 3.36
Example 7 Q12 -5.22 -1.95 3.27
Example 8 X34 -5.38 -2.09 3.29
Example 9 X22 -5.39 -2.10 3.29
Example 10 X47 -5.41 -2.13 3.28
Example 11 X59 -5.40 -2.15 3.25
Comparative example 1 Comparative Compound 1 -5.08 -1.78 3.30
As can be seen from table 1, through the special design of the molecular structure, the HOMO level of the compound in the embodiment of the present invention is relatively deep (for example, less than or equal to-5.20 eV), so that holes can be effectively blocked, and the holes are limited in the light emitting region, which is beneficial to widening the light emitting region and improving the light emitting efficiency of the device; and the LUMO energy level of the compound is deeper (for example, less than or equal to-1.95 eV), so that the injection of electrons is facilitated, the injection barrier can be reduced, and the voltage of a device is reduced. Meanwhile, the organic compound provided by the invention has good thermal stability and film stability, is beneficial to the stability of the device, and prolongs the service life of the device.
Compound application example 1
The present embodiment provides an OLED device (organic light emitting device) including a substrate 1, an anode 2, a hole injection layer 3, a hole transport layer 4 (including a first hole transport layer 41 and a second hole transport layer 42), a light emitting layer 5, a hole blocking layer 6, an electron transport layer 7, an electron injection layer 8, a cathode 9, and a Capping layer 10, which are sequentially stacked as shown in fig. 1. The arrows in the figure indicate the light direction.
The specific preparation steps of the OLED device are as follows:
1) cutting a glass substrate (with the thickness of 10nm) with an Indium Tin Oxide (ITO) anode into sizes of 50mm multiplied by 0.7mm, respectively carrying out ultrasonic treatment in isopropanol and deionized water for 30 minutes, then exposing the glass substrate to ozone for about 10min for cleaning, and mounting the cleaned glass substrate on a vacuum deposition device;
2) evaporating a hole injection layer material compound a on the ITO anode layer in a vacuum evaporation mode, wherein the thickness of the hole injection layer material compound a is 10nm and the hole injection layer material compound a is used as a hole injection layer;
3) vacuum evaporating a hole transport material compound b on the hole injection layer, wherein the thickness of the hole transport material compound b is 100nm, and the hole transport material compound b is used as a first hole transport layer;
4) vacuum evaporating a compound c on the first hole transport layer to form a second hole transport layer, wherein the thickness of the compound c is 10 nm;
5) a luminescent main body material compound d and a doping material compound e are evaporated on the second hole transport layer in a vacuum way, the doping proportion is 3 percent (mass ratio), the thickness is 20nm, and the luminescent main body material compound d and the doping material compound e are used as a luminescent layer;
6) a compound f is evaporated on the luminescent layer in vacuum with the thickness of 5nm and is used as a hole blocking layer;
7) co-evaporating the compound J53 and Liq of example 1 in a mass ratio of 1:1 and having a thickness of 30nm as an electron transport layer on the hole blocking layer in vacuum;
8) evaporating compound LiF on the electron transport layer in vacuum with the thickness of 5nm to be used as an electron injection layer;
9) and (3) performing vacuum evaporation on the electron injection layer to form a magnesium-silver electrode, wherein the mass ratio of Mg to Ag is 1:9, the thickness is 10nm, and the magnesium-silver electrode is used as a cathode.
10) Compound g was vacuum deposited onto the cathode to a thickness of 70nm as a cap layer.
The compounds used in the preparation of the above-described OLED devices are as follows:
Figure BDA0002561772300000591
the compound application examples 2 to 11 and the comparative example 1 were similar to the compound application example 1 except that the compound J53 for the electron transport layer in the step 7) was replaced with the compounds of examples 2 to 11 and the comparative compound 1, respectively.
Performance evaluation of OLED devices: testing the current of the OLED device under different voltages by using a Keithley 2365A digital nano-volt meter, and then dividing the current by the light-emitting area to obtain an OLED, current densities of the device under different voltages; testing the brightness and radiant energy flux density of the OLED device under different voltages by using a Konicaminolta CS-2000 spectroradiometer; testing each device at the same current density (10 mA/cm) according to the current density and brightness of the OLED device at different voltages2) Lower luminous efficiency CE/CIEy (cd/A), VWork byIs 10mA/cm2A lower operating voltage; the lifetime LT95 (at 50 mA/cm) was obtained by measuring the time when the luminance of the OLED device reached 95% of the initial luminance2Under test conditions); the test data are shown in table 2.
TABLE 2
OLED device Compound (I) VWork by(V) CE/CIEy(cd/A) Life LT95(h)
Application example 1 J53 3.79 150 60
Application example 2 J34 3.70 154 64
Application example3 J12 3.74 158 70
Application example 4 E12 3.76 157 68
Application example 5 T12 3.73 160 67
Application example 6 Q34 3.71 152 63
Application example 7 Q12 3.77 156 66
Application example 8 X34 3.72 157 67
Application example 9 X22 3.71 156 68
Application example 10 X47 3.71 158 69
Application example 11 X59 3.70 159 68
Comparative example 1 Comparative Compound 1 3.85 145 55
As can be seen from Table 2, the OLED device prepared by using the organic compound provided by the invention as an electron transport layer material has lower working voltage, higher luminous efficiency and longer service life. For example, the operating voltage may be 3.79V or less, the luminous efficiency CE/CIEy may be 150cd/A or more, and the lifetime LT95 may be 60h or more. Compared with the comparative example 1, the performances of the OLED device provided by the application examples 1-11 are obviously improved, and the organic compound provided by the invention has a deeper HOMO value as an electron transport material, can effectively block holes, limits the holes in a light emitting region to be compounded with electrons, is beneficial to widening the light emitting compound region and improving the light emitting efficiency of the device; the LUMO energy level is deeper, so that the electron injection is smoother, and the working voltage of the device is reduced; meanwhile, the organic compound provided by the invention has good thermal stability and film-forming property, is beneficial to the stability of devices, and prolongs the service life of the devices.
While the invention has been described with reference to specific embodiments, the invention is not limited thereto, and various equivalent modifications and substitutions can be easily made by those skilled in the art within the technical scope of the invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.

Claims (20)

1. A compound having a structure represented by formula 1,
Figure FDA0002561772290000011
wherein the content of the first and second substances,
ab represents an optionally substituted benzene ring, an optionally substituted naphthalene ring, an optionally substituted phenanthrene ring, an optionally substituted azabenzene ring, an optionally substituted azanaphthalene ring, or an optionally substituted azaphenanthrene ring,
ab is fused to Aa to form a fusion protein,
y is a number of 0 or 1,
when y is 0, Ab shares a1 and a 3C with Aa,
when y is 1, Ab and Aa share a1 and a2 position C, a2 and a3 position C, or a1, a2 and a3 position C, Ac represents an optionally substituted 6-40 membered aromatic ring or an optionally substituted 5-40 membered aromatic heterocyclic ring,
y represents C (Z)1)2、N(Z1)、O、S、Si(Z1)2Or PO (Z)1) Wherein Z is1Independently represent an optionally substituted C1-C20 alkyl group, an optionally substituted C1-C20 alkoxy group, an optionally substituted C1-C20 alkylthio group, an optionally substituted 3-to 20-membered cycloalkyl group, an optionally substituted 6-to 40-membered aryl group, or an optionally substituted 5-to 40-membered heteroaryl group,
r represents an optionally substituted 3-to 20-membered heterocycloalkyl group, an optionally substituted 6-to 40-membered aryl group, an optionally substituted 5-to 30-membered heteroaryl group, -PO (Z)2)2、–PS(Z2)2、–Z2S(＝O)2(Z3)、–Z4–(Z5)nor-Z6–Z7–(Z8)n，
Z2And Z3Each independently represents an optionally substituted 6-to 40-membered aryl group or an optionally substituted 5-to 40-membered heteroaryl group,
Z4、Z6and Z7Independently represent a C2-C10 alkenyl group, a C2-C10 alkynyl group, a 6-to 30-membered aryl group or a 5-to 30-membered heteroaryl group,
Z5and Z8Each independently represents an optionally substituted 3-to 20-membered heterocycloalkyl group, an optionally substituted 6-to 40-membered aryl group, an optionally substituted 5-to 30-membered heteroaryl group, -PO (Z)2)2、–PS(Z2)2or-Z2S(＝O)2(Z3)，
n is 1,2 or 3.
2. The compound of claim 1, wherein y is 0.
3. A compound according to claim 1, wherein Ab represents an optionally substituted benzene ring, an optionally substituted naphthalene ring, an optionally substituted phenanthrene ring or an optionally substituted azabenzene ring.
4. The compound of claim 1, wherein the compound has a structure represented by any one of formula 1-1 to formula 1-13,
Figure FDA0002561772290000021
Figure FDA0002561772290000031
wherein R is1～R8Each independently represents hydrogen, an optionally substituted 3-to 20-membered heterocycloalkyl group, an optionally substituted 6-to 40-membered aryl group, or an optionally substituted 5-to 30-membered heteroaryl group,
r is attached to the C at position b1 or b2,
Figure FDA0002561772290000032
independently through the C at position d1, d2, d3 or d4 to the C at position C1 or C2,
r, Y and Ac are each as defined in claim 1.
5. A compound according to claim 1, wherein Y represents S.
6. A compound according to claim 1, wherein Y represents O.
7. A compound according to claim 1, wherein Y represents C (Z)1)2Wherein Z is1As defined in claim 1.
8. A compound according to claim 1, characterized in that Ac represents a benzene ring or a naphthalene ring.
9. The compound of claim 1, wherein the compound has a structure represented by formula 1-14, formula 1-15, or formula 1-16,
Figure FDA0002561772290000033
wherein R is1～R4Each independently represents hydrogen, an optionally substituted 3-to 20-membered heterocycloalkyl group, an optionally substituted 6-to 40-membered aryl group, or an optionally substituted 5-to 30-membered heteroaryl group,
r is attached to the C at position b1 or b2, R is as defined in claim 1,
Figure FDA0002561772290000041
independently linked to the C at position C1 or C2 via C at position d1, d2, d3 or d4, respectively.
10. A compound according to claim 1, wherein R represents-Z4–(Z5)nor-Z6–Z7–(Z8)n。
11. The compound of claim 10, wherein Z is4、Z6And Z7Each independently represents a 6-to 30-membered aryl group or a 5-to 30-membered heteroaryl group.
12. The compound of claim 10, wherein Z is4、Z6And Z7Each independently selected from any one of the groups represented by W-1 to W-47,
Figure FDA0002561772290000042
Figure FDA0002561772290000051
wherein Y is as defined in claim 1, # and # each independently represent a linking site.
13. The compound of claim 12, wherein Z is4Represents a naphthalene ring, an anthracene ring or a phenanthrene ring, or Z4Represents any one of W-24 to W-37;
Z6and Z7One of them represents any one of W-24 to W-37, and the other represents any one of W-1 to W-16.
14. The compound of claim 10, wherein Z is5And Z8Independently represents phenyl, biphenyl or any one of P1-P87,
Figure FDA0002561772290000052
Figure FDA0002561772290000061
wherein M independently represents C (Z)1)2S or O, Z1As defined in claim 1, # denotes the attachment position.
15. A compound according to claim 1, wherein R represents any one of the groups represented by R1 to R54,
Figure FDA0002561772290000071
Figure FDA0002561772290000081
16. the compound of claim 1, wherein the compound has a structure represented by any one of the following,
Figure FDA0002561772290000082
Figure FDA0002561772290000091
Figure FDA0002561772290000101
Figure FDA0002561772290000111
Figure FDA0002561772290000121
Figure FDA0002561772290000131
Figure FDA0002561772290000141
Figure FDA0002561772290000151
Figure FDA0002561772290000161
Figure FDA0002561772290000171
Figure FDA0002561772290000181
Figure FDA0002561772290000191
Figure FDA0002561772290000201
Figure FDA0002561772290000211
Figure FDA0002561772290000221
Figure FDA0002561772290000231
Figure FDA0002561772290000241
Figure FDA0002561772290000251
Figure FDA0002561772290000261
Figure FDA0002561772290000271
Figure FDA0002561772290000281
Figure FDA0002561772290000291
Figure FDA0002561772290000301
Figure FDA0002561772290000311
Figure FDA0002561772290000321
17. a display panel includes an organic light emitting device including an anode, a cathode, and an organic thin film layer between the anode and the cathode, the organic thin film layer including a light emitting layer and an electron transport layer; the electron transport layer comprises at least one compound according to any of claims 1 to 16.
18. The display panel according to claim 17, wherein the organic thin film layer comprises a hole blocking layer comprising the compound according to any one of claims 1 to 16.
19. The display panel according to claim 17, wherein the light-emitting material of the light-emitting layer comprises a host material and a guest material, and the host material comprises the compound according to any one of claims 1 to 16.
20. A display device comprising the display panel of any one of claims 17-19.
CN202010610141.0A 2020-06-30 2020-06-30 Compound, display panel and display device Pending CN111718338A (en)

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