Phosphaheptacyclo compounds and uses thereof

Abstract

The application discloses a phosphinane heptacyclic compound and application thereof. The structure of the phosphinane heptacyclic compound is shown in formula (IA) or formula (IB). The phosphinane heptacyclic compound can be applied to an organic functional layer of an OLED device, in particular, an electron transport layer and / or a charge generation layer. The unique seven-membered ring structure of the phosphinane heptacyclic compound of formula (I) can be mixed with a metal to generate a stronger interaction, and the core seven-membered ring and the specific three aromatic systems form a more stable molecular conjugated system, which can significantly reduce the working voltage of the device, improve the current efficiency, and improve the service life of the device.

Description

Technical Field

[0001] This invention relates to the field of electroluminescent materials, and more particularly to a phosphonoheptanyl compound and its applications. Background Technology

[0002] Electroluminescence (EL) refers to the phenomenon that luminescent materials emit light when excited by electric current and electric field under the influence of an electric field. It is a light-emitting process that directly converts electrical energy into light energy.

[0003] Organic light-emitting diodes (OLEDs) have attracted much attention due to their thin profile, high brightness emission at low driving voltages, and ability to emit multiple colors by selecting appropriate luminescent materials. Since CWTang et al. from Kodak revealed that organic thin-film devices could emit light with high brightness, numerous researchers in the OLED industry have conducted extensive research and advancements on their applications.

[0004] Typically, OLED devices consist of three main parts: an anode, a cathode, and an organic layer between the anode and the cathode.

[0005] Functionalized organic materials commonly used in OLED devices include: hole injection materials, hole transport materials, hole blocking materials, electron injection materials, electron transport materials, electron blocking materials, as well as light-emitting host materials and light-emitting guest materials (dyes).

[0006] For example, a typical organic electroluminescent device structure includes: an anode / hole injection layer (HIL) / hole transport layer (HTL) / emitting layer (EML, emitting host material: emitting guest material) / electron transport layer (ETL) / cathode. These are stacked sequentially on a substrate, and the HIL, HTL, EML, and ETL are thin films formed from organic compounds. The basic working principle of an OLED device is as follows: when a voltage is applied to the anode and cathode, holes injected from the anode move to the EML via the HTL, while electrons injected from the cathode move to the EML via the ETL. The holes and electrons recombine in the EML to generate excitons. When the excitons transition from the excited state to the ground state, they emit light. Embedding a hole transport layer between the anode and the emitting layer, and an electron transport layer between the cathode and the emitting layer, not only lowers the carrier injection barrier and balances the carrier transport rate, but also confines the excitons within the emitting layer, improving the device's luminous efficiency.

[0007] Currently, those skilled in the art are continuously developing and improving the above-mentioned functionalized organic materials with the aim of improving the brightness / illuminance of OLED devices while minimizing the operating voltage, and ensuring that the injection and flow of holes and electrons are balanced, so that OLEDs with the above structure have excellent efficiency and / or long lifetime.

[0008] In existing devices, nitrogen-containing heterocyclic materials such as pyridine, pyrimidine, oxadiazole, triazole, and imidazole, which contain electron-withdrawing groups in their structure, are usually used as electron transport materials. However, these materials have low electron mobility and high hole mobility, which causes an electron-hole imbalance inside the light-emitting device, resulting in problems such as reduced device efficiency, poor stability, and short lifespan.

[0009] Therefore, those skilled in the art desire to improve the performance of organic semiconductor layers, organic semiconductor materials, and their organic electroluminescent devices, particularly by improving the properties of the organic compounds contained therein to achieve higher efficiency and / or longer lifetime, especially by reducing operating voltage and / or improving efficiency and lifetime. Summary of the Invention

[0010] To address the aforementioned technical problems, the first aspect of the present invention provides a phosphateheptane compound as shown in Formula IA or Formula IB:

[0011]

[0012] in,

[0013] X1 is selected from O, S, NR 4 R 4 Selected from substituted or unsubstituted C1-C 20 Straight-chain or branched alkyl or C3-C 12 Cycloalkyl, substituted or unsubstituted cyclocarbon atoms with C6-C 30 The aryl group, "a 5-30 membered heteroaryl group containing 1-10 heteroatoms independently selected from O, N, and S", substituted or unsubstituted "a 5-30 membered heteroaryl group containing 1-10 heteroatoms independently selected from O, N, and S", or R 4 It forms a ring with adjacent atomic bonds;

[0014] Ar1 is selected from substituted or unsubstituted C6 to C1. 30 aryl or substituted or unsubstituted C3-C 30 heteroaryl groups;

[0015] Ar2 and Ar3 are independently substituted or unsubstituted C6-C6. 30 aryl or substituted or unsubstituted C3-C 30 heteroaryl groups;

[0016] R 1 R 2 and R 3 Independently hydrogen, deuterium, substituted or unsubstituted C1-C 20 The straight-chain or branched alkyl or cycloalkyl group, with substituted or unsubstituted cyclic carbon atoms, has a carbon number of C6-C. 30 The aryl, substituted, or unsubstituted cyclic carbon atoms have a C3-C2 number. 30 heteroaryl, or any two R 1 R 2 or R 3 Independently forms C3-C with the atoms it is attached to. 10 Cyclic alkenes or C3-C olefins substituted with one or more substituents 10 Cycloolefins;

[0017] n1 is any integer from 0 to 4;

[0018] n2 and n3 are independent integers from 0 to 8;

[0019] The substituents in the substitution are selected from hydrogen, deuterium, substituted or unsubstituted C1-C10 straight-chain or branched alkyl groups, C3-C4... 10 cycloalkyl, C1-C 10 alkoxy groups, C6-C 20 aryl, substituted or unsubstituted C3-C 20 heteroaryl groups;

[0020] In this embodiment, any hydrogen position in formula (IA) or formula (IB) may optionally be replaced by deuterium.

[0021] The present invention also provides an organic electroluminescent device comprising:

[0022] First electrode;

[0023] Second electrode;

[0024] At least one organic functional layer is located between the first electrode and the second electrode, and at least includes a light-emitting layer;

[0025] At least one of the organic functional layers comprises a phosphateheptane compound as shown in formula (IA) or formula (IB) as previously described.

[0026] A second aspect of the present invention provides an electronic device comprising the organic electroluminescent device as described above.

[0027] In one embodiment, the organic electroluminescent device is a stacked device comprising two or more light-emitting layers, wherein the charge-generating layer contains a phosphateheptane compound as shown in formula (IA) or formula (IB).

[0028] The organic electroluminescent device provided by this invention comprises at least one organic functional layer containing a phosphateheptane compound as shown in formula (IA) or formula (IB) as previously described. On the one hand, compared with conventional five-membered heterocyclic compounds and non-cyclic compounds, the phosphateheptane compound of formula (I) has a unique seven-membered ring stereostructure, which can interact more strongly with metals when used together. On the other hand, the phosphateheptane compound of formula (I) has a core seven-membered ring that forms a more stable molecular conjugated system with three specific aromatic systems (Ar1 and two naphthyl groups), which can significantly reduce the operating voltage of the device, improve current efficiency, and improve device lifespan. Attached Figure Description

[0029] The following accompanying drawings describe in detail the exemplary embodiments disclosed in this application. The same reference numerals denote similar structures in several views of the drawings. Those skilled in the art will understand that these embodiments are non-limiting and exemplary, and the drawings are for illustrative purposes only and are not intended to limit the scope of this application. Other embodiments may similarly fulfill the inventive intent of this application. It should be understood that the drawings are not drawn to scale. Wherein:

[0030] Figure 1 This is a schematic cross-sectional view of an organic light-emitting device (OLED) 100 according to an exemplary embodiment of the present invention. The OLED 100 includes a substrate 101, an anode 102, a hole injection layer 103, a first hole transport layer 104, a second hole transport layer 105, an organic light-emitting layer 106, a hole blocking layer 107, an electron transport layer 108, and a cathode 109.

[0031] Figure 2 This is a schematic cross-sectional view of a stacked organic light-emitting device (OLED) according to an exemplary embodiment of the present invention, the stacked OLED including a charge-generating layer. Reference Figure 2 The OLED 200 includes an anode 210, a first light-emitting unit 220a, a charge-generating layer 230, a second light-emitting unit 220b, and a cathode 240.

[0032] The first light-emitting unit 220a includes: a hole injection layer 221a, a first hole transport layer 222a, a second hole transport layer 223a, and a first organic light-emitting layer 224a.

[0033] The charge generation layer 230 includes: an n-type charge generation layer 231 and a p-type charge generation layer 232;

[0034] The second light-emitting unit 220b includes: a first hole transport layer 222b, a second hole transport layer 223b, a second organic light-emitting layer 224b, a hole blocking layer 225b, an electron transport layer 226b, and an electron injection layer 227b. Detailed Implementation

[0035] Unless otherwise stated, the following words, phrases and symbols used in this specification generally have the meanings described below.

[0036] Generally, the nomenclature used herein (e.g., IUPAC nomenclature) and the laboratory procedures described below (including those for organic chemistry, analytical chemistry, etc.) are those well-known and commonly used in the art. Unless otherwise defined, all scientific and technical terms used herein in conjunction with the disclosure described herein have the same meaning as commonly understood by one of ordinary skill in the art. Additionally, in the claims and / or description, the term “a” or “an” used in conjunction with the term “comprising” or a noun may mean “one,” but also is consistent with the meaning of “one or more,” “at least one,” and “one or more.” Similarly, the term “another” or “other” may mean at least a second or more.

[0037] It should be understood that whenever this document uses the terms “comprising” or “including” to describe a particular aspect, other similar aspects described by “consisting of” and / or “substantially consisting of” are also provided.

[0038] In this paper, the term "phosphonoheptane compound" refers to an organic compound with a seven-membered ring structure containing phosphorus atoms.

[0039] In this document, the term "chiral compound" refers to a compound with structural asymmetry; chiral compounds cannot be superimposed on their mirror image, thus exhibiting unique optical activity; generally, chiral compounds are optically active and deflect plane-polarized light. In the "phosphonohexane compound" of this application, the P atom is the chiral center.

[0040] In this document, the term "substituted or unsubstituted" means that a hydrogen atom in a functional group is replaced by another atom or functional group (i.e., a substituent), for example, by one or more of the following substituents: deuterium, halogen group, nitrile group, nitro group, hydroxyl group, carbonyl group, ester group, imide group, amino group, phosphine oxide group, alkoxy group, alkyl thio group, aryloxy group, aryl thio group, alkyl sulfonyl group, aryl sulfonyl group, silyl group, boron group, straight-chain or branched alkyl group, cycloalkyl group, alkenyl group, aryl group, aralkyl group, aryl-alkenyl group, alkylaryl group, alkylamine group, aralkylamine group, heteroarylamine group, arylamine group, arylphosphine group, heterocyclic group; or by two or more combinations of substituents from the examples above, for example, biphenyl, terphenyl.

[0041] In this document, the term "straight-chain or branched alkyl group" preferably refers to "a straight-chain or branched alkyl group having 1 to 10 carbon atoms," wherein the number of carbon atoms is preferably 1 to 8, more preferably 1 to 6, and even more preferably 1 to 4. In some embodiments, the alkyl group may include, but is not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, sec-butyl, etc.

[0042] In this document, "cycloalkyl" preferably refers to "cycloalkyl with 3 to 10 carbon atoms," more preferably, a mono- or polycyclic hydrocarbon having 3 to 10 cyclic skeletal carbon atoms, wherein the number of carbon atoms is preferably 3 to 9, more preferably 3 to 8, and even more preferably 3 to 7. In some embodiments, cycloalkyl may include, but is not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopentylmethyl, cyclohexylmethyl, etc.

[0043] In this document, the term "alkoxy" refers to -O (alkyl). Optionally, the alkyl portion of an alkoxy group may contain 1-10 carbon atoms, 1-6 carbon atoms, or 1-4 carbon atoms, etc. In some embodiments, an alkoxy group may include, but is not limited to, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, sec-butoxy, etc.

[0044] In this document, the term "aryl" preferably refers to a substituted or unsubstituted (aryl) group having 6 to 30 carbon atoms, meaning a monocyclic or fused-ring group derived from an aromatic hydrocarbon having 6 to 30 carbon atoms in its ring skeleton, wherein the number of carbon atoms in the ring skeleton is preferably 6 to 25, 6 to 20, 6 to 15, 6 to 12, more preferably 6 to 10. In some embodiments, the monocyclic (aryl) group includes, but is not limited to, phenyl, biphenyl, terphenyl, tetraphenyl, pentaphenyl, etc. In some embodiments, the fused-ring (aryl) group includes, but is not limited to, naphthyl, anthracene, phenanthryl, pyrene, perylene, fluorene, etc. In some embodiments, the fused-ring (aryl) group may be substituted, such as a substituted fluorene group, optionally methylfluorenel, dimethylfluorenel (optionally, 9,9-dimethylfluorenel), phenylfluorenel, diphenylfluorenel (optionally, 9,9-diphenylfluorenel), benzo[a]fluorenel. In other embodiments, the fused-ring (ane)aryl group may also include a spirostructure; for example, 9,9'-spirodifluorene.

[0045] The above description of aryl groups can be applied to aryl groups in the following categories: aryloxy, aryloxysulfonyl, aryloxysulfonyl, arylphosphinyl, aralkyl, arylalkylamine, arylenyl, alkylaryl, and arylamine.

[0046] In this document, the term "heteroaryl" preferably refers to a substituted or unsubstituted (hybrid)aryl group having 5 to 30 carbon atoms, which is an aryl group having a ring skeleton atom comprising at least one heteroatom selected from N, O, and S, wherein the number of ring skeleton carbon atoms is preferably 5 to 30, 5 to 25, 5 to 20, 5 to 15, 5 to 12, or 5 to 10. The number of heteroatoms in the heteroaryl group is preferably 1 to 4. The aforementioned heteroaryl group can be a monocyclic ring or a fused ring condensed with at least one benzene ring. Furthermore, in this document, the aforementioned heteroaryl group can be a heteroaryl group formed by linking at least one heteroaryl group or aryl group to a heteroaryl group via one or more single bonds. In some embodiments, monocyclic heteroaryl groups include, but are not limited to, furanyl, thiophene, pyrrole, imidazolyl, pyrazolyl, thiazolyl, oxazolyl, azinoyl, azole, pyridinyl, pyrazinyl, pyrimidinyl, pyridazinyl, etc. In other embodiments, the fused-ring heteroaryl groups include, but are not limited to, benzofuranyl, benzothiophenyl, dibenzofuranyl, dibenzothiophenyl, dinaphthofuranyl, naphthobenzofuranyl, dinaphthothiophenyl, naphthobenzothiophenyl, naphridinyl, acridineyl, xanthonyl, phenanthridineyl, diazanaphthyl, triazaindyl, indoleyl, terazinyl, benzocarbazoyl, benzothiazoyl, benzooxazolyl, benzoimidazoyl, benzocarbazoyl, benzopyrazinyl, pyrimidindoleyl, pyrazinindoleyl, imidazopyridyl, spirofluorenoxanthyl, spirofluorenoxanthyl, etc.

[0047] The above description of heteroaryl groups applies to heteroaryl amines and heteroaryl heteroaryl amines.

[0048] In this specification, the phrase "forming a ring with adjacent atomic bonds" refers to the situation where adjacent genes can bond with each other to form a ring.

[0049] This application provides an organic electroluminescent device, comprising:

[0050] First electrode;

[0051] Second electrode;

[0052] At least one organic functional layer is located between the first electrode and the second electrode, and at least includes a light-emitting layer;

[0053] At least one of the organic functional layers comprises a phosphonoheptane compound as described above.

[0054] A second aspect of the present invention provides an electronic device comprising the organic electroluminescent device as described above.

[0055] The phosphaheptanyl compounds of this application are chiral compounds with structural asymmetry, for example, with the p atom as the chiral center. The phosphaheptanyl compounds of this application can have the structure of formula (I'), the structure of formula (I"), or a combination of formulas (I') and (I"), but the chiral structure of the phosphaheptanyl compounds of this application is not limited to these; for example, they can have other chiral centers besides the p atom or contain multiple chiral centers. The phosphaheptanyl compounds of this application include mixtures of different diastereomers or corresponding racemates and single isolated diastereomers or enantiomers. Using the phosphaheptanyl compounds of this application in the preparation of organic light-emitting diodes (OLEDs), the unique spatial arrangement of the chiral compounds can effectively improve the light efficiency of OLEDs, thus laying the foundation for subsequent OLED research and applications.

[0056] In one or more embodiments, the organic electroluminescent device is a stacked device comprising two or more light-emitting layers, wherein the charge-generating layer contains the phosphateheptane compound.

[0057] In some embodiments, X1 is O, S, or NR. 4 R 4 For C1-C 20 R is preferred 4 It is C1-C4, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, or tert-butyl.

[0058] In some embodiments, Ar1 is phenyl, naphthyl, phenanthryl, biphenyl, pyrene, triphenylene, dibenzofuranyl, or dibenzothiophene.

[0059] In some embodiments, Ar2 and Ar3 are independently phenyl, naphthyl, phenanthryl, benzofuranyl, benzothiophenyl, dibenzofuranyl, dibenzothiophenyl, quinolinyl, isoquinolinyl, indolyl, thiophenyl, furanyl, pyrroleyl, pyridyl, or carbazoleyl.

[0060] In some embodiments, C3~C 30 The heteroaryl group is a 5-30 member heteroaryl group containing 1-10 heteroatoms, each heteroatom being independently selected from O, N, and S.

[0061] In some embodiments, R 1 R 2 and R 3 Independent of deuterium, C1-C 20 Alkyl, deuterated methyl, substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted biphenyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothiopheneyl; or any two R 1 R 2 or R3 Independently forms a C3-C bond with the attached atom, which is substituted with one or more C1-C10 alkyl groups. 10 Cyclic olefins.

[0062] In some embodiments, R 1 R 2 and R 3 Independently for C1-C 20 Alkyl, deuterated methyl, phenyl, naphthyl, substituted or unsubstituted biphenyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothiophene, or a ring formed by bonds with adjacent atoms.

[0063] In some embodiments, Ar1 is selected from substituted or unsubstituted aryl groups having 6 to 30 carbon atoms, and substituted or unsubstituted heteroaryl groups having 3 to 30 carbon atoms. Optionally, the substituted or unsubstituted aryl groups having 6 to 30 carbon atoms may have 6 to 28, 8 to 25, 10 to 22, 12 to 20, or 14 to 18 carbon atoms. Optionally, the substituted or unsubstituted heteroaryl groups having 3 to 30 carbon atoms may have 3 to 28, 5 to 25, 6 to 22, 8 to 20, 12 to 18, or 14 to 16 carbon atoms.

[0064] Preferably, the Ar1 is selected from one or a combination of several of the following: substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted phenanthryl, substituted or unsubstituted anthraquinyl, substituted or unsubstituted biphenyl, substituted or unsubstituted triphenylene, substituted or unsubstituted pyrene, substituted or unsubstituted dibenzofuranyl, and substituted or unsubstituted dibenzothiophene.

[0065] In some embodiments, R 1 The quantity n1 is 0, 1, 2, 3, 4, 5 or 6; preferably, n1 is 0, 1 or 2.

[0066] In some embodiments, R 2 The quantity n2 is 0, 1, 2, 3, 4, 5 or 6; preferably, n2 is 0, 1 or 2.

[0067] In some embodiments, R 1 and R 2 It is independently selected from deuterium, methyl, deuterated methyl, substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted biphenyl, substituted or unsubstituted furanyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted thiophene, substituted or unsubstituted dibenzothiophene, substituted or unsubstituted pyridyl, substituted or unsubstituted pyrroleyl, substituted or unsubstituted indolyl, substituted or unsubstituted pyrimidinyl, substituted or unsubstituted quinolinyl, substituted or unsubstituted isoquinolinyl; or any two adjacent R1 or any two adjacent R2 are bonded to each other to form a ring.

[0068] In some embodiments, the substituent in the term "substitution" is selected from deuterium, substituted or unsubstituted C1-C1 groups. 10 Straight-chain or branched alkyl groups, substituted or unsubstituted C3-C4 10 cycloalkyl, substituted or unsubstituted C1-C 10 alkoxy, substituted or unsubstituted C6-C 20 aryl, substituted or unsubstituted C3-C 20 Mixed aromatic compounds.

[0069] Preferably, the substituents in the "substitution" are selected from deuterium, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, sec-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopentylmethyl, cyclohexylmethyl, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, sec-butoxy, phenyl, methylphenyl, tert-butylphenyl, naphthyl, biphenyl, pyridine, etc.

[0070] In some embodiments, in the phosphaheptanyl compounds represented as of formula (IA) or formula (IB), C6~C 30 aryl or substituted or unsubstituted C3-C 30 The heteroaryl group is preferably phenyl, naphthyl, phenanthryl, benzofuranyl, benzothiophene, dibenzofuranyl, dibenzothiophene, quinolinyl, isoquinolinyl, indolyl, thiophene, furanyl, pyrroleyl, pyridyl or carbazoleyl.

[0071] In some embodiments, the phosphaheptanyl compound represented by formula (IA) or formula (IB) as described above is characterized in that the phosphaheptanyl compound represented by formula (IA) or formula (IB) has any of the following structural formulas:

[0072]

[0073]

[0074]

[0075]

[0076]

[0077]

[0078] In the formulas (E1) to (E240), R 1 and R 5Each of the following is independently selected from deuterium, methyl, deuterated methyl, phenyl, naphthyl, biphenyl, dibenzofuranyl or dibenzothiophene;

[0079] n1 is any integer from 0 to 4;

[0080] n5 is any integer from 0 to 8 independently;

[0081] Alternatively, any number of hydrogen atoms at any position in equations (E1) to (E240) can be replaced by deuterium.

[0082] In some embodiments, the phosphateheptane compound represented by formula (IA) or formula (IB) as described above is any of the following compounds:

[0083]

[0084]

[0085] In some embodiments, the organic layer further comprises at least one n-type dopant;

[0086] Preferably, the n-type dopant is selected from metals or metal compounds; the metal is selected from alkali metals, alkaline earth metals, and rare earth metals; the metal compound is selected from alkali metal compounds, alkaline earth metal compounds, or rare earth metal compounds.

[0087] More preferably, the n-type dopant is selected from any one or a combination of the following metals: Li, Na, K, Be, Mg, Ca, Sr, Ba, Sc, Y, La, Sm, Eu, Tb, Yb, Lu, Ti, V, Mn.

[0088] In some preferred embodiments, the organic functional layer includes an electron transport layer, an electron injection layer, or a charge generation layer; the electron transport layer may be a single-layer electron transport layer or a multi-layer electron transport layer.

[0089] More preferably, the organic electroluminescent device is a single-layer device, wherein the electron transport layer contains the phosphonium-heptanium compound; or, the organic electroluminescent device is a multilayer device, wherein the multilayer device comprises two or more light-emitting layers, wherein the electron transport layer and / or charge-generating layer contains the phosphonium-heptanium compound.

[0090] More preferably, the organic electroluminescent device is a stacked device, the stacked device comprising two or more light-emitting layers, wherein the charge-generating layer contains the phosphine-heptanyl compound.

[0091] In some embodiments, the organic electroluminescent device includes a first electrode and a second electrode disposed opposite to each other, and an organic layer located between the first electrode and the second electrode, wherein the organic layer includes a light-emitting layer. As an example, the first electrode is an anode, and the second electrode is a cathode. The cathode may be one or more layers. The organic layer may be a single-layer structure or a multilayer tandem structure with two or more organic layers laminated together. The organic layer may include at least one of a hole injection layer, a hole transport layer, an electron blocking layer, a light-emitting layer, a hole blocking layer, an electron transport layer, and an electron injection layer.

[0092] In some specific embodiments, the structure of the organic electroluminescent device may be selected from one of the following:

[0093] (1) An organic electroluminescent device includes an anode, a hole injection layer, a first hole transport layer, a light-emitting layer, a first electron transport layer, and a cathode stacked in sequence, that is, anode / hole injection layer / first hole transport layer / light-emitting layer / first electron transport layer / cathode. The device structure will be expressed in this simplified way below.

[0094] (2) Anode / hole injection layer / first hole transport layer / second hole transport layer / light-emitting layer / first electron transport layer / cathode.

[0095] (3) Anode / hole injection layer / first hole transport layer / second hole transport layer / light-emitting layer / first electron transport layer / second electron transport layer / cathode.

[0096] (4) Anode / hole injection layer / first hole transport layer / second hole transport layer / light-emitting layer / first electron transport layer / second electron transport layer / electron injection layer / cathode.

[0097] (5) Anode / hole injection layer / first hole transport layer / second hole transport layer / light-emitting layer / first electron transport layer / second electron transport layer / multilayer cathode.

[0098] (6) Anode / hole injection layer / first hole transport layer / first light-emitting layer / charge generation layer / first hole transport layer / second light-emitting layer / first electron transport layer / cathode.

[0099] (7) Anode / hole injection layer / first hole transport layer / first light-emitting layer / charge generation layer / first hole transport layer / second light-emitting layer / first electron transport layer / second electron transport layer / cathode.

[0100] (8) Anode / hole injection layer / first hole transport layer / second hole transport layer / first light-emitting layer / charge generation layer / first hole transport layer / second light-emitting layer / first electron transport layer / cathode.

[0101] (9) Anode / hole injection layer / first hole transport layer / second hole transport layer / first light-emitting layer / charge generation layer / first hole transport layer / second light-emitting layer / first electron transport layer / second electron transport layer / cathode.

[0102] (10) Anode / hole injection layer / hole transport layer / electron blocking layer / light emission layer / electron transport layer / electron injection layer / cathode.

[0103] (11) Anode / hole injection layer / first hole transport layer / second hole transport layer / light-emitting layer / hole blocking layer / electron transport layer / cathode.

[0104] (12) Anode / hole injection layer / first hole transport layer / second hole transport layer / light-emitting layer / hole blocking layer / electron transport layer / electron injection layer / cathode.

[0105] (13) Anode / hole injection layer / hole transport layer / electron blocking layer / light emission layer / electron transport layer / cathode.

[0106] (14) Anode / hole injection layer / hole transport layer / electron blocking layer / light emitting layer / hole blocking layer / electron transport layer / cathode.

[0107] (15) Anode / hole injection layer / first hole transport layer / second hole transport layer / first light-emitting layer / hole blocking layer / electron transport layer / charge generation layer / first hole transport layer / second hole transport layer / second light-emitting layer / hole blocking layer / electron transport layer / cathode.

[0108] (16) Anode / hole injection layer / first hole transport layer / second hole transport layer / first light-emitting layer / hole blocking layer / electron transport layer / charge generation layer / first hole transport layer / second hole transport layer / second light-emitting layer / hole blocking layer / electron transport layer / electron injection layer / cathode.

[0109] The organic electroluminescent device can emit light from either the anode side or the cathode side. When emitting light from the cathode side, the difference from the above structure is that an additional cover layer needs to be added to the cathode side.

[0110] The specific construction is as follows:

[0111] 1) Anode / hole injection layer / first hole transport layer / light emission layer / first electron transport layer / cathode / capping layer.

[0112] 2) Anode / hole injection layer / first hole transport layer / second hole transport layer / light-emitting layer / first electron transport layer / cathode / capping layer.

[0113] 3) Anode / hole injection layer / first hole transport layer / second hole transport layer / light-emitting layer / first electron transport layer / second electron transport layer / cathode / capping layer.

[0114] 4) Anode / hole injection layer / first hole transport layer / second hole transport layer / light-emitting layer / first electron transport layer / second electron transport layer / electron injection layer / cathode / capping layer.

[0115] 5) Anode / hole injection layer / first hole transport layer / second hole transport layer / light-emitting layer / first electron transport layer / second electron transport layer / multilayer cathode / capping layer.

[0116] 6) Anode / hole injection layer / first hole transport layer / first light-emitting layer / charge generation layer / first hole transport layer / second light-emitting layer / first electron transport layer / cathode / capping layer.

[0117] 7) Anode / hole injection layer / first hole transport layer / first light-emitting layer / charge generation layer / first hole transport layer / second light-emitting layer / first electron transport layer / second electron transport layer / cathode / capping layer.

[0118] 8) Anode / Hole Injection Layer / First Hole Transport Layer / Second Hole Transport Layer / First Light Emitting Layer / Charge Generation Layer / First Hole Transport Layer / Second Light Emitting Layer / First Electron Transport Layer / Cathode / Covering Layer.

[0119] 9) Anode / Hole Injection Layer / First Hole Transport Layer / Second Hole Transport Layer / First Light Emitting Layer / Charge Generation Layer / First Hole Transport Layer / Second Light Emitting Layer / First Electron Transport Layer / Second Electron Transport Layer / Cathode / Covering Layer.

[0120] 10) Anode / hole injection layer / hole transport layer / electron blocking layer / light emission layer / electron transport layer / electron injection layer / cathode / capping layer.

[0121] 11) Anode / Hole injection layer / First hole transport layer / Second hole transport layer / Light emission layer / Hole blocking layer / Electron transport layer / Cathode / Covering layer.

[0122] 12) Anode / hole injection layer / hole transport layer / electron blocking layer / light emission layer / electron transport layer / cathode / capping layer.

[0123] 13) Anode / hole injection layer / hole transport layer / electron blocking layer / light emitting layer / hole blocking layer / electron transport layer / cathode / capping layer.

[0124] The following describes some specific functional layers in the organic electroluminescent device.

[0125] Substrate:

[0126] The substrate is generally located below the anode. The substrate can be made of plastic or glass, and can be rigid or flexible. The substrate has a driving unit that can drive the corresponding pixel to emit light.

[0127] anode:

[0128] Organic EL (Organic Electro-Luminescence) devices typically require the anode to have good conductivity, a smooth surface, and be resistant to cracking. They also have certain requirements for work function, mainly to match the hole injection layer and achieve the hole injection effect.

[0129] When using a top-emitting method (cathode-side light emission), the anode is a metal compound with a work function of 4.2 eV or higher, such as indium tin oxide, tin oxide, indium zinc oxide, gold, silver, platinum, copper, carbon nanotubes, carbon nanowires, graphene, etc. The thickness is 10 nm to 200 nm, preferably 10 nm to 50 nm. A reflective electrode is placed below the anode (near the substrate end). The reflective electrode is generally made of metal or metal alloy, such as silver, copper, aluminum, gold, or alloys of these metals with other metals. The reflective electrode has high reflectivity, requiring a reflectivity of over 90%, and its thickness is typically between 100 nm and 500 nm, preferably in the range of 80 nm to 150 nm.

[0130] When bottom-emitting (light emission from the cathode side) is used, the anode is a metal compound with a work function of 4.2 eV or higher, such as indium tin oxide alloy, tin oxide, indium zinc oxide, gold, silver, platinum, copper, carbon nanotubes, carbon nanowires, graphene, etc. The thickness is 10 nm to 1 μm, preferably 50 nm to 200 nm.

[0131] The anode can be made by forming a thin film from the electrode material using methods such as vapor deposition, sputtering, or coating.

[0132] Hole injection layer :

[0133] To make light-emitting devices more efficient, the hole injection layer needs to have good hole injection capability. The hole injection layer is made of a hybrid material of hole dopant and hole transport host material.

[0134] The thickness of the hole injection layer can be

[0135] The mass ratio of hole dopant to hole transport host is 1% to 5%.

[0136] The hole dopant can be selected from organic compounds or metal oxides, such as arbutins. for example:

[0137]

[0138] In the above formula (a), R1 to R... 15 In the above formula (b), R1 to R2 are each independently selected from fluorine, trifluoromethyl, cyano, and nitro.

[0139] Specifically, the following compounds can be selected:

[0140]

[0141] The host material for hole transport can be selected from monoamine and diamine compounds, specifically from the following:

[0142]

[0143] In the above equations (c) to (f),

[0144] L1 to L3 are each independently selected from single bonds or phenylene;

[0145] Ar1 to A4 are each independently selected from aryl and heteroaryl groups with 6 to 30 carbon atoms, whether substituted or unsubstituted, and the substituent is an alkyl group with 1 to 10 carbon atoms; preferably selected from phenyl, biphenyl, dimethylfluorenyl, dibenzofuranyl, dibenzothiophenyl, N-phenylcarbazoyl, benzo[B]naphtho[2,3-D]furan, benzo[B]naphtho[1,2-D]furan, and benzo[B]naphtho[2,1-D]furan.

[0146] In some preferred embodiments, the hole transport body material is selected from the group consisting of:

[0147]

[0148] Hole transport layer:

[0149] The hole transport layer may include one or more hole transport materials, which may be a single-layer structure or a multi-layer structure.

[0150] First hole transport layer:

[0151] The thickness of the first hole transport layer can be 3nm to 500nm. When there is no second hole transport layer, the thickness of the first hole transport layer is generally 40nm to 150nm; when there is a second hole transport layer, the thickness of the first hole transport layer is generally 3nm to 500nm. The material selection of the first hole transport layer can refer to the hole transport host material.

[0152] Second hole transport layer:

[0153] The thickness of the second hole transport layer is typically 5 nm to 150 nm. Aromatic amine compounds are commonly used; either monoaryl amines or polyaryl amines can be employed. Hole transport materials are required to have high hole mobility, reduce driving voltage, and have a glass transition temperature exceeding 100°C to avoid crystallization at high temperatures.

[0154] Electron blocking layer:

[0155] The electron blocking layer can simultaneously possess both hole transport and electron blocking functions. Furthermore, the higher triplet excitation energy level of the electron blocking layer can confine excitons generated in the emissive layer within it, thereby improving the device's luminous efficiency.

[0156] Emissive layer:

[0157] The material of the light-emitting layer generally includes a host material and a guest dopant material, wherein the content of the host material is greater than that of the guest dopant material. Optionally, the mass percentage of the guest dopant material in the light-emitting layer is 1% to 20%.

[0158] Guest dopants used as luminescent materials can include phosphorescent or fluorescent materials or thermally activated delayed fluorescence materials. Red, green, and blue light can be selected from these three types of guest dopants. For example, the guest dopant material for the luminescent layer corresponding to a red luminescent unit and the luminescent layer corresponding to a green luminescent unit is a phosphorescent material, while the guest dopant material for the luminescent layer corresponding to a blue luminescent unit is a fluorescent material.

[0159] For example, the guest doping material of the light-emitting layer corresponding to the light-emitting unit with a red emission color and the light-emitting layer corresponding to the light-emitting unit with a green emission color is a phosphorescent material, and the guest doping material of the light-emitting layer corresponding to the light-emitting unit with a blue emission color is a phosphorescent material.

[0160] For example, the guest doping material of the light-emitting layer corresponding to the light-emitting unit with a red emission color and the light-emitting layer corresponding to the light-emitting unit with a green emission color is a thermally activated delayed fluorescence material, and the guest doping material of the light-emitting layer corresponding to the light-emitting unit with a blue emission color is a fluorescent material.

[0161] For example, the guest doping material of the light-emitting layer corresponding to the light-emitting unit with a red emission color and the light-emitting layer corresponding to the light-emitting unit with a green emission color is a thermally activated delayed fluorescence material, and the guest doping material of the light-emitting layer corresponding to the light-emitting unit with a blue emission color is a phosphorescent material.

[0162] To reduce the power consumption of organic light-emitting display panels in organic electroluminescent devices, guest doping materials with superior luminescent properties can be selected. Taking a top-emitting device as an example, optionally, the light-emitting unit with a red emission color has a luminous intensity of 1000 cd / m². 2 A green light-emitting unit with a current efficiency greater than 30 cd / A and a luminous intensity of 6000 cd / m² is used. 2 A light-emitting unit with a current efficiency greater than 100 cd / A and a fluorescent blue emission color has a luminous intensity of 1000 cd / m². 2 With a current efficiency greater than 5 cd / A as the standard, and by selecting suitable guest doping materials, a phosphorescent blue emitting unit is achieved with a luminous intensity of 1000 cd / m². 2 The standard is a current efficiency greater than 10 cd / A. Higher current efficiency can reduce power consumption.

[0163] As the main light-emitting material, one or two main light-emitting materials can be selected.

[0164] Cavity blocking layer:

[0165] To enhance the balance between hole and electron concentrations, a hole blocking layer is inserted to balance carrier concentration and prevent exciton quenching. Typically, the hole blocking layer is located between the emitting layer and the electron transport layer, and the hole blocking layer material must meet conditions such as high stability, good film-forming properties, and a sufficiently high highest molecular occupied orbital.

[0166] Electron transport layer:

[0167] Electron transport materials can include mixtures of organic electron transport materials and metal compounds, or mixtures of organic electron transport materials and metals.

[0168] When organic electron transport materials are mixed with metal compound materials, such as alkali metal compounds, alkaline earth metal compounds, and rare earth metal compounds, more specifically, they can be mixed with lithium metal compounds, calcium metal compounds, Mg metal compounds, samarium metal compounds, ytterbium metal compounds, etc., and even more specifically, they can be mixed with lithium 8-hydroxyquinoline, lithium fluoride, magnesium fluoride, ytterbium fluoride, calcium fluoride, etc. When used in combination with metal compounds, the mass percentage of the organic electron transport material can be 20%–80%, 20%–40%, 40%–60%, or 60%–80%, etc.

[0169] When organic electron transport materials are used in combination with metals, such as alkali metals, alkaline earth metals, and rare earth metals, or more specifically, with lithium metal, magnesium metal, calcium metal, ytterbium metal, and samarium metal, the mass ratio of the organic electron transport material can be 80%–99%, 80%–89%, 89%–99%, 80%–85%, 85%–90%, 90%–95%, or 95%–99%, etc.

[0170] Electron injection layer:

[0171] The electron injection layer material can be selected from alkali metals, alkaline earth metals, rare earth metals, or their inorganic or coordination compounds.

[0172] Charge generation layer:

[0173] When a single-layer light-emitting device is used, holes and electrons are injected from the anode and cathode respectively, eliminating the need for a charge generation layer. When using double or multiple light-emitting layers, a charge generation layer is required between the light-emitting layers to achieve charge generation, injection, and transport. This charge generation layer is located between the two light-emitting layers and is typically composed of two P / N type materials. The P-type material is a hole injection material, while the N-type material is an organic electron transport material mixed with a metal. The organic electron transport layer material is selected from the second electron transport layer mentioned earlier, and the metal is selected from alkali metals, alkaline earth metals, and rare earth metals. More specifically, examples include lithium, magnesium, calcium, ytterbium, and samarium. When organic electron transport materials are mixed with metals, the mass percentage of the organic electron transport material can be 80%–99%, 80%–89%, 89%–99%, 80%–85%, 85%–90%, 90%–95%, or 95%–99%, etc.

[0174] cathode:

[0175] The cathode requires materials with good electrical conductivity and a smooth surface. To improve electron injection capability, materials with a low work function are typically chosen. Cathode materials can be single-layer, double-layer, or multi-layer cathodes, generally made of metals or metal alloys. For single-layer cathodes, silver, copper, aluminum, gold, or alloys of these metals with other metals, such as rare earth metals, alkali metals, and alkaline earth metals, can be used. Examples include magnesium-indium alloys, magnesium-aluminum alloys, aluminum-potassium alloys, aluminum-scandium-potassium alloys, magnesium-silver alloys, silver-ytterbium alloys, and silver-samarium alloys. If a double-layer metal cathode is used, the cathode layer closer to the light-emitting layer can be made of alkali metals, alkaline earth metals, or rare earth metals, such as lithium, calcium, magnesium, and ytterbium, to increase electron injection capability. The cathode layer farther from the light-emitting side is mainly used to improve conductivity, and generally uses silver, copper, aluminum, gold, or alloys of these metals with other metals, such as alloys with rare earth metals, alkali metals, or alkaline earth metals. Examples include magnesium-indium alloys, magnesium-aluminum alloys, aluminum-potassium alloys, aluminum-scandium-potassium alloys, magnesium-silver alloys, silver-ytterbium alloys, and silver-samarium alloys. The cathode can also be formed into a thin film using methods such as vapor deposition or sputtering.

[0176] When light exits from the anode side, the cathode must be opaque, and a cathode with a thickness of not less than 100 nm can be deposited. When light exits from the cathode side, the cathode must be transparent, with a transmittance greater than 40% and a thickness of 10 nm to 20 nm.

[0177] Overlay:

[0178] When light emerges from the cathode side, photons resonate with electrons in the cathode metal, reducing the light emission efficiency. Adding a capping layer to the side of the cathode away from the light-emitting layer can reduce this effect and effectively improve the light efficiency.

[0179] When adding a capping layer, a capping layer material with a high refractive index and a low absorption coefficient should be used directly. For example,

[0180] For example, materials with a refractive index greater than 1.9 and an absorptivity less than 0.01% at a wavelength of 460 nm are preferred; materials with a refractive index greater than 2.0 and an absorptivity less than 0.01% at a wavelength of 460 nm are even more preferred; materials with a refractive index greater than 2.1 and an absorptivity less than 0.01% at a wavelength of 460 nm are even more preferred; and materials with a refractive index greater than 2.2 and an absorptivity less than 0.01% at a wavelength of 460 nm are preferred.

[0181] The coating layer lists some of the compounds as follows:

[0182]

[0183] This application also provides an electronic device that includes the above-described organic electroluminescent device, preferably a display device or a lighting device.

[0184] The technical solution of this application will be clearly and completely described below with reference to the embodiments of this application. Unless otherwise specified, the reagents and raw materials used can be purchased commercially. Experimental methods in the following embodiments that do not specify specific conditions are generally determined according to national standards. If there is no corresponding national standard, then general international standards, conventional methods and conditions, or conditions recommended by the manufacturer, or the product instructions shall be followed. Unless otherwise stated, all parts are parts by weight, and all percentages are weight percentages.

[0185] Measurement instruments and methods

[0186] Mass spectrometry and nuclear magnetic resonance

[0187] In this application, mass spectrometry was performed using a Waters Corporation single quadrupole mass spectrometer, and nuclear magnetic resonance was performed using a 400MHz nuclear magnetic resonance spectrometer (manufactured by Bruker GmbH, Germany).

[0188] Lifespan Measurement

[0189] The device lifetime testing involved in this application was obtained using a Fostar lifetime measurement system equipped with a power supply and a photodiode as detection units.

[0190] [Raw Materials and Reagents]

[0191] The initial raw materials and solvents used in this application were purchased from Shanghai Titan Technology Co., Ltd., and some commonly used OLED intermediates were purchased from domestic OLED intermediate manufacturers; various palladium catalysts and ligands were purchased from Shaanxi Ruike New Materials Co., Ltd. 1 HNMR data were determined using a 400MHz nuclear magnetic resonance spectrometer (manufactured by Bruker GmbH, Germany); HPLC data were determined using a Waters Corporation UPLC ultra-high performance liquid chromatograph. LC-MS (liquid chromatography-mass spectrometry) was performed on a Waters Corporation UPLC+SQD2 instrument.

[0192] Synthesis Examples

[0193] Synthetic common operations:

[0194]

[0195] or

[0196]

[0197] Step 1 reaction: Synthesis of A3 (A3'):

[0198] 1 molar equivalent of A1 (A') and 1.1 molar equivalent of A2 were added, along with 1% molar equivalent of catalyst Pd2 (dba)3, 2% molar equivalent of S-phos (abbreviation of 2-bicyclohexylphosphine-2',6'-dimethoxy-1,1'-diphenyl), 2 molar equivalents of K2CO3, 7–20 times the weight of A1 in toluene, 1–3 times the weight of ethanol, and 1–3 times the weight of water. The system was purged with nitrogen three times, and the reaction was heated to reflux and stirred for 4–8 hours. The reaction solution was cooled to room temperature, separated, and concentrated. Rapid silica gel column chromatography (hot toluene) was performed, and the concentrate was refluxed. Hexane was added dropwise during the cooling process. After complete cooling, the mixture was stirred for 2–4 hours, filtered to remove the solid, and dried.

[0199] Second step reaction: Synthesis of A5 (A5'):

[0200] Add 1 molar equivalent of compound A3 (A3') to a three-necked flask, purge thoroughly with N2 three times, then add 15–30 times the weight of anhydrous tetrahydrofuran of A3 (A3'). Stir the solution at -78°C, then slowly add 2.2 molar equivalents of 2.5 M n-butyllithium dissolved in n-hexane. After the addition is complete, stir at -78°C for 2 hours, then add 0.8 molar equivalents of compound A4, and continue stirring at -78°C for another 2 hours.

[0201] The reaction solution was filtered through silica gel, then washed with a 1:1 mixture of dichloromethane and n-hexane. The filtrate was concentrated, recrystallized from toluene and n-hexane, and filtered to obtain the solid.

[0202] Third step reaction: Synthesis of A (A')

[0203] Dissolve solid A5 (A5') in 20–50 times its weight of dichloromethane, add 1–10 times its weight of hydrogen peroxide (H2O2), and react at room temperature for 4 hours. Separate the liquid, dry the organic phase, concentrate, slurry with n-hexane, and filter to obtain a white solid.

[0204] The following are several exemplary methods for preparing compounds:

[0205] Chiral compounds can be obtained by synthesizing chiral starting materials or by chiral physical resolution of the obtained racemic compounds.

[0206] The product of the above synthetic route, "compound A (A')," is any one of the structural formulas (I) of this application.

[0207] The following are several exemplary methods for preparing compounds:

[0208]

[0209] Step 1 reaction: Synthesis of 1-3:

[0210] Components 1-1 (24 g, 60 mmol) and 1-2 (16.5 g, 66 mmol) were added to a catalyst, Pd₂(dba)₃ (0.55 g, 0.6 mmol), and molar equivalents of S-phos (0.5 g, 1.2 mmol), along with K₂CO₃ (16.5 g, 120 mmol), 200 mL of toluene, 40 mL of ethanol, and 40 mL of water. The system was purged with nitrogen three times. The reaction mixture was heated to reflux and stirred for 6 h. The reaction solution was cooled to room temperature, separated, and concentrated. Rapid silica gel column chromatography (hot toluene) was performed. The concentrate was refluxed, and n-hexane was added dropwise during cooling. After complete cooling, the mixture was stirred for 2 h. The solid was filtered, dried, and yielded 14 g (49% yield).

[0211] Second step reaction: Synthesis of 1-5:

[0212] Compounds 1-3 (14 g, 29 mmol) were added to a three-necked flask, and the mixture was completely purged with N2 three times. Then, 250 mL of anhydrous tetrahydrofuran was added, and the solution was stirred at -78 °C. Next, 25.5 mL of 2.5 M n-butyllithium (63.8 mmol) dissolved in n-hexane was slowly added dropwise. After the addition was complete, the mixture was stirred at -78 °C for 2 h. Then, compound 1-4 (4.2 g, 23.2 mmol) was added, and the mixture was stirred at -78 °C for another 2 h.

[0213] The reaction solution was filtered through silica gel, then washed with a 1:1 mixture of dichloromethane and n-hexane. The filtrate was concentrated and recrystallized from 300 mL of toluene / n-hexane. The solid was then filtered to obtain 5.4 g, with a yield of 44%.

[0214] Third step reaction: Synthesis of compound 1

[0215] Intermediate 1-5 (5.4 g, 12.6 mmol) was dissolved in 200 mL of dichloromethane, and 20 mL of hydrogen peroxide was added. The reaction was carried out at room temperature for 4 hours. The mixture was separated, the organic phase was dried, concentrated, slurried in n-hexane, and filtered to give 4 g of white solid, with a yield of 72% and an overall yield of 15.5% for the three steps.

[0216] 1 H NMR(Chloroform-d)δ8.16(d,1H),7.97(d,1H),7.86(m,2H),7.74(m,2H),7.73(t,3H),7.62–7.54(m,2H),7.50(d,3H),7.38(m,5H).

[0217] Synthesis Example 2

[0218] Synthesis of Compound 5

[0219]

[0220] The synthesis of compound 5 was performed using the same method as compound 1, except that the starting material in the first step was replaced with 5-1 instead of 1-1, and the starting material in the second step was replaced with 5-4 instead of 1-4. The overall yield of compound 5 was 16.3%.

[0221] 1 H NMR(Chloroform-d)δ8.13(d,1H),8.03(d,2H),7.93(m,2H),7.75(m,2H),7.73(d, 1H),7.66(d,1H),7.66–7.58(m,2H),7.62–7.55(m,2H),7.55(d,2H),7.33(m,6H).

[0222] Synthesis Example 3

[0223] Synthesis of Compound 6

[0224]

[0225] First step reaction: Synthesis of 6-3:

[0226] Compounds 6-1 (30 g, 88.5 mmol) and 6-2 (36.7 g, 97.4 mmol) were added to the catalysts Pd₂(dba)₃ (0.81 g, 0.89 mmol) and S-phos (0.72 g, 1.77 mmol), along with K₂CO₃ (24.4 g, 177 mmol), 250 mL of toluene, 50 mL of ethanol, and 50 mL of water. The system was purged with nitrogen three times. The reaction mixture was heated to reflux and stirred for 6 h. The reaction solution was cooled to room temperature, separated, and concentrated. Rapid silica gel column chromatography (hot toluene) was performed. The concentrate was refluxed, and n-hexane was added dropwise during cooling. After complete cooling, the mixture was stirred for 3 h. The solid was filtered and dried to give 25.3 g of compound 6-3, with a yield of 52.5%.

[0227] Second step reaction: Synthesis of 6-5:

[0228] Compound 6-3 (25.3 g, 46.5 mmol) was added to a three-necked flask, and the mixture was completely purged with N2 three times. Then, 400 mL of anhydrous tetrahydrofuran was added, and the solution was stirred at -78 °C. Next, 41 mL of 2.5 M n-butyllithium (102.3 mmol) dissolved in n-hexane was slowly added dropwise. After the addition was complete, the mixture was stirred at -78 °C for 2 h. Then, compound 6-4 (10.6 g, 37.2 mmol) was added, and the mixture was stirred at -78 °C for another 2 h.

[0229] The reaction solution was filtered through silica gel, then washed with a 1:1 mixture of dichloromethane and n-hexane. The filtrate was concentrated and recrystallized from 300 mL of toluene / n-hexane. The solid was then filtered to obtain 12.5 g of solid, with a yield of 45%.

[0230] Third step reaction: Synthesis of compound 6

[0231] Intermediate 6-5 (12.5 g, 20.9 mmol) was dissolved in 250 mL of dichloromethane, and 25 mL of hydrogen peroxide was added. The reaction was carried out at room temperature for 4 hours. The mixture was separated, the organic phase was dried, concentrated, slurried in n-hexane, and filtered to give 9.1 g of white solid, with a yield of 71% and an overall yield of 16.8% for the three steps.

[0232] 1 H NMR(Chloroform-d)δ8.34(d,1H),8.25(s,1H),8.19(d,1H),8.13(d,1H),8.07(d,1H),7.83(m,6H),7.78(d 2H),7.72–7.63(m,2H),7.63(m,2H),7.53(m,4H),7.33(t,2H).

[0233] Synthesis Example 4

[0234] Synthesis of Compound 7

[0235]

[0236] The synthesis of compound 7 was performed in the same manner as in Example 1, except that the starting material 1-1 in the first step reaction was replaced with 7-1, and the starting material 1-4 in the second step reaction was replaced with 7-4. The overall yield of the three steps was 18.4%.

[0237] 1 H NMR(Chloroform-d)δ8.21(s,1H),8.15(d,1H),8.02(d,1H),7.91(m,5H),7.86(m,2H),7.65(t,1H),7.59(m,1H),7.40(m,8H),7.28(m,2H).

[0238] Synthesis Example 5

[0239] Synthesis of Compound 11

[0240]

[0241] The synthesis of compound 11 was performed in the same manner as in Example 1, except that the starting material 1-1 in the first step was replaced with 11-1, 1-2 was replaced with 11-2, and the starting material 1-4 in the second step was replaced with 11-4. The overall yield of the three steps was 14.6%.

[0242] 1 H NMR(Chloroform-d)δ8.30(d,1H),8.19(d,1H),8.11(m,1H),7.91(m,2H),7.79(m, 2H),7.77(d1H),7.63(s,1H),7.41(m,6H),1.88(m,2H),1.71(m,2H),1.31(d,12H).

[0243] Synthesis Example 6

[0244] Synthesis of Compound 8

[0245]

[0246] The synthesis of compound 8 was performed in the same manner as in Example 1, except that the starting material 1-1 in the first step was replaced with 8-1, 1-2 was replaced with 8-2, and the starting material 1-4 in the second step was replaced with 8-4. The overall yield of the three steps was 13.4%.

[0247] 1 H NMR(Chloroform-d)δ8.19(d,1H),8.11–8.00(m,4H),7.70–7.31(m,12H),7.25(d,1H),2.46(s,3H).

[0248] Synthesis Example 7

[0249] Synthesis of Compound 13

[0250]

[0251] The synthesis of compound 13 was performed in the same manner as in Example 1, except that the starting material 1-1 in the first step was replaced with 13-1 and 1-2 was replaced with 13-2. The overall yield of the three steps was 15.8%.

[0252] 1 H NMR(Chloroform-d)δ8.83(d,1H),8.60(d,1H),8.19(m,2H),8.16(t,1H),7.82(m,5H),7.64(m,4H),7.45(m,6H),7.37(m,2H),7.29(t,1H).

[0253] Synthesis Example 8

[0254] Synthesis of Compound 15

[0255]

[0256] The synthesis of compound 15 was performed in the same manner as in Example 1, except that the starting material 1-1 in the first step was replaced with 15-1, 1-2 with 15-2, and the starting material 1-4 in the second step was replaced with 15-4. The overall yield of the three steps was 17.1%.

[0257] 1 H NMR(Chloroform-d)δ8.38(t,2H),8.20(d,1H),7.97(d,1H),7.95–7.89(m,2H),7.86( t,1H),7.68(m,3H),7.58(m,3H),7.52(t,1H),7.29(m,9H),4.24(q,2H),1.39(t,3H).

[0258] Other compounds were obtained using similar synthetic methods.

[0259] Compounds 2, 3, 7-19, and 21-25 were prepared using the corresponding reactants X-1 and X-2 listed in Table 1 below, following the synthetic method described above. The corresponding yields and LC MS:M / Z results are shown in Table 1 below.

[0260] Table 1

[0261]

[0262]

[0263]

[0264]

[0265] Device Examples

[0266] Example 1 of a single-layer device (a device comprising a phosphonohepyl compound as an electron transport layer)

[0267] refer to Figure 1 The method for preparing the organic electroluminescent device in this embodiment includes:

[0268] (1) A transparent anode ITO film (150 nm thick) is formed on a glass substrate 101 by magnetron sputtering to obtain the first electrode as the anode 102.

[0269] (2) A mixture of compounds M1 and M2 is deposited on the surface of the anode 102 by vacuum evaporation as a hole injection layer 103, with a mixing ratio of 97:3 (mass ratio) and a thickness of [missing information].

[0270] (3) Subsequently, compound M1 (thickness) was deposited on the surface of hole injection layer 103 by vapor deposition. ), thus obtaining the first hole transport layer 104;

[0271] (4) Deposit compound M3 (thickness) onto the first hole transport layer 104 by vapor deposition. This forms the second hole transport layer 105;

[0272] (5) On the surface of the second hole transport layer 105, compounds M4 and M5 are co-deposited at a mass ratio of 98:2 to form an organic light-emitting layer 106 (thickness). );

[0273] (6) A hole blocking layer 107 (thickness) is formed by vapor deposition of compound M6 on the organic light-emitting layer 106. );

[0274] (7) An electron transport layer 108 (thickness) is formed by vapor deposition of a mixture of compound 1 of the present invention and metallic Yb in a mass ratio of 97:3 on the hole blocking layer 107. );

[0275] (8) Magnesium (Mg) and silver (Ag) are mixed and deposited on the electron injection layer 108 at a vapor deposition rate of 1:10, forming a layer with a thickness of [missing information]. The second electrode serves as the cathode 109, thus completing the fabrication of the organic electroluminescent device.

[0276] The compounds involved in the above device fabrication examples are shown below:

[0277]

[0278]

[0279] Single-layer device examples 2-8

[0280] Device Example 2 was fabricated using the same method as in Single-Layer Device Example 1, except that, when forming the electron transport layer, the electron transport layer materials listed in Table 1 were used instead of the electron transport layer materials in Example 1.

[0281] Single-layer device comparative example 1-2

[0282] Except that the materials in Example 1 are replaced with those in Table 1 when forming the electron transport layer, the organic electroluminescent device is fabricated using the same method as in Example 1 of the blue light device.

[0283] The operating voltage and efficiency of the organic electroluminescent device prepared above were calculated using a computer-controlled Keithley 2400 testing system (test current 10 mA / cm²). 2Device lifetime under dark conditions was obtained using a Fostar lifetime measurement system equipped with a power supply and photodiode as detection units (room temperature lifetime test conditions: ambient temperature 25℃, constant current 50mA / cm). 2 LT95 refers to the time required for the brightness to decrease from the initial brightness to 95%, with the time in Device Example 1 taken as 100%, and the lifetime of other examples being relative values ​​for comparison.

[0284] The test results are shown in Table 3.

[0285] Table 3

[0286] Device Examples Electron transport materials relative drive voltage relative current efficiency LT95 (hours) Single-layer device comparative example 1 Compound C1 100％ 100％ 100％ Single-layer device comparative example 2 Compound C2 88％ 143％ 125％ Single-layer device example 1 Compound 1 75％ 150％ 165％ Single-layer device example 2 Compound 5 77％ 149％ 152％ Single-layer device embodiment 3 Compound 6 78％ 150％ 153％ Single-layer device Example 4 Compound 7 75％ 153％ 152％ Single-layer device Example 5 Compound 11 74％ 151％ 155％ Single-layer device Example 6 Compound 8 76％ 148％ 150％ Single-layer device Example 7 Compound 13 75％ 150％ 167％ Single-layer device Example 8 Compound 15 73％ 151％ 168％

[0287] Example 1 of a multilayer device (a device comprising a phosphine-heptane compound as an n-type charge generation layer)

[0288] refer to Figure 2 Methods for fabricating stacked organic electroluminescent devices include:

[0289] (1) A transparent anode ITO film (150 nm thick) is formed on a glass substrate by magnetron sputtering to obtain the first electrode as the anode;

[0290] (2) A mixture of compounds M1 and M2 is deposited on the surface of the anode 210 by vacuum evaporation as a hole injection layer 221a, with a mixing ratio of 97:3 (mass ratio) and a thickness of [missing information].

[0291] (3) Subsequently, compound M1 (thickness) was deposited on the surface of hole injection layer 221a. ), thus obtaining the first hole transport layer 222a;

[0292] (4) Deposit compound M3 (thickness) on the first hole transport layer 222a by vapor deposition. This forms the second hole transport layer 223a;

[0293] (5) On the surface of the second hole transport layer 223a, compounds M4, M5 and M6 are co-deposited in a mass ratio of 45:45:10 to form the first organic light-emitting layer 224a (thickness). );

[0294] (6) A hole blocking layer 225a (thickness) is formed by vapor deposition of compound M7 on the first organic light-emitting layer 224a. );

[0295] (7) An electron transport layer (ETL1) 226a (thickness) is formed by evaporating compounds C3 and LiQ in a mass ratio of 5:5 on the hole blocking layer 225a. );

[0296] (8) Subsequently, a mixture of compound 1 and metallic Yb with a mass ratio of 97:3 is vapor-deposited onto electron transport layer 226a to form an n-type charge generation layer 231 (n-CGL, Next, a mixture of compounds M1 and M2 is vapor-deposited as the p-type charge generation layer 232 (p-CGL), with a mixing ratio of 98:2 (mass ratio) and a thickness of [missing information].

[0297] (9) Subsequently, the vapor-deposited compound M1 serves as the first hole transport layer 222b (thickness) );

[0298] (10) A second hole transport layer 223b (thickness) is formed by vapor deposition of compound M3 on the first hole transport layer 222b. );

[0299] (11) On the surface of the second hole transport layer 223b, compounds M4, M5 and M6 are co-deposited in a mass ratio of 45:45:10 to form the second organic light-emitting layer 224b (thickness). );

[0300] (12) A hole blocking layer 225b (thickness) is formed by vapor deposition of compound M7 on the second organic light-emitting layer 224b. );

[0301] (13) Subsequently, a mixture of compound C1 and LiQ in a mass ratio of 5:5 (thickness) was deposited on the hole blocking layer 225b. An electron transport layer (ETL2) 226b is formed, followed by the deposition of metal Yb (thickness). An electron injection layer 227b is formed;

[0302] (14) Magnesium (Mg) and silver (Ag) were mixed and deposited on the electron-injected layer 227b at a vapor deposition rate of 1:10 to form The second electrode serves as the cathode 240, completing the fabrication of the organic electroluminescent device.

[0303] The compounds involved in the above device fabrication examples are shown in Table 4 below:

[0304] Table 4

[0305]

[0306] Example 2 of stacked device

[0307] Device Example 8 was fabricated using the same method as Device Example 7, except that, when forming the n-type charge generation layer (n-CGL), the materials used in Example 7 were replaced with the materials listed in Table 5.

[0308] Comparative Examples of Multilayer Devices 1-2

[0309] Except that when forming the n-type charge generation layer (n-CGL), the organic electroluminescent device was fabricated using the same method as in device example 7, except that compounds C1 and C2 were used to replace the materials in device example 7.

[0310] The test results are shown in Table 5.

[0311] Table 5

[0312] Device Examples n-CGL relative drive voltage relative current efficiency LT95 (hours) Comparative Example 1 of Multilayer Devices Compound C1 100％ 100％ 100％ Comparative Example 2 of Multilayer Devices Compound C2 83％ 115％ 106％ Example 1 of stacked device Compound 1 68％ 123％ 123％ Example 2 of stacked device Compound 5 67％ 125％ 120％ Example 3 of stacked device Compound 6 67％ 126％ 123％ Example 4 of stacked device Compound 7 65％ 128％ 122％ Example 5 of stacked device Compound 11 68％ 124％ 121％ Stacked device embodiment 6 Compound 8 67％ 125％ 123％ Example 7 of stacked device Compound 13 65％ 124％ 126％ Example 8 of stacked device Compound 15 67％ 126％ 127％

Claims

1. A phosphateheptane compound as shown in formula (IA) or formula (IB): in, X1 is selected from O, S, NR 4 R 4 Selected from substituted or unsubstituted C1-C 20 Straight-chain or branched alkyl or C3-C 12 Cycloalkyl, substituted or unsubstituted cyclocarbon atoms with C6-C 30 The aryl group, "containing 1-10 heteroatoms, the heteroatoms being independently selected from O, N, and S, 5-30 membered heteroaryl groups", substituted or unsubstituted, "containing 1-10 heteroatoms, the heteroatoms being independently selected from O, N, and S, 5-30 membered heteroaryl groups", or R 4 It forms a ring with adjacent atomic bonds; Ar1 is selected from substituted or unsubstituted C6 to C1. 30 aryl or substituted or unsubstituted C3-C 30 heteroaryl groups; Ar2 and Ar3 are independently substituted or unsubstituted C6-C6. 30 aryl or substituted or unsubstituted C3-C 30 heteroaryl groups; R 1 R 2 and R 3 Independently hydrogen, deuterium, substituted or unsubstituted C1-C 20 The straight-chain or branched alkyl or cycloalkyl group, with substituted or unsubstituted cyclic carbon atoms, has a carbon number of C6-C. 30 The aryl, substituted, or unsubstituted cyclic carbon atoms have a C3-C2 number. 30 heteroaryl, or any two R 1 R 2 Or R 3 Independently forms C3-C with the atoms it is attached to. 10 Cyclic alkenes or C3-C olefins substituted with one or more substituents 10 Cycloolefins; n1 is any integer from 0 to 4; n2 and n3 are independent integers from 0 to 8; The substituents in the substitution are selected from hydrogen, deuterium, substituted or unsubstituted C1-C10 straight-chain or branched alkyl groups, C3-C4... 10 cycloalkyl, C1-C 10 alkoxy groups, C6-C 20 aryl, substituted or unsubstituted C3-C 20 heteroaryl groups; In this embodiment, any hydrogen position in formula (IA) or formula (IB) may optionally be replaced by deuterium.

2. The phosphaheptanyl compound as shown in formula (IA) or (IB) according to claim 1, characterized in that, Ar1 is phenyl, naphthyl, phenanthryl, biphenyl, pyrene, triphenylene, dibenzofuranyl, or dibenzothiophene.

3. The phosphaheptanyl compound as shown in formula (IA) or formula (IB) according to claim 1, characterized in that, Ar2 and Ar3 are independently substituted or unsubstituted with the following groups: phenyl, naphthyl, phenanthryl, benzofuranyl, benzothiophene, dibenzofuranyl, dibenzothiophene, quinolinyl, isoquinolinyl, indolyl, thiophene, furanyl, pyrroleyl, pyridyl, or carbazoyl.

4. The phosphaheptanyl compound as described in formula (IA) or (IB) according to claim 1, characterized in that, R 1 R 2 and R 3 Independently, it is hydrogen, deuterium, methyl, deuterated methyl, substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted biphenyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothiopheneyl, or R 1 R 2 and R 3 It can independently form rings with adjacent atomic bonds.

5. The phosphaheptanyl compound as shown in formula (IA) or formula (IB) according to any one of claims 1-4, characterized in that, In the phosphaheptanyl compounds represented by formula (IA) or formula (IB), C6~C 30 aryl or substituted or unsubstituted C3-C 30 The heteroaryl group is preferably phenyl, naphthyl, phenanthryl, benzofuranyl, benzothiophene, dibenzofuranyl, dibenzothiophene, quinolinyl, isoquinolinyl, indolyl, thiophene, furanyl, pyrroleyl, pyridyl or carbazoleyl.

6. The phosphaheptanyl compound as shown in formula (IA) or formula (IB) according to any one of claims 1-5, characterized in that, The phosphateheptane compounds represented by formula (IA) or (IB) have any of the following structural formulas: In the formulas (E1) to (E240), R 1 and R 5 Each of the following is independently selected from deuterium, methyl, deuterated methyl, phenyl, naphthyl, biphenyl, dibenzofuranyl or dibenzothiophene; n1 is any integer from 0 to 4; n5 is any integer from 0 to 8 independently; Alternatively, any number of hydrogen atoms at any position in equations (E1) to (E240) can be replaced by deuterium.

7. The phosphaheptanyl compound as shown in formula (IA) or formula (IB) according to any one of claims 1-6, characterized in that, The phosphateheptane compound represented by formula (IA) or formula (IB) is any of the following compounds:

8. An organic electroluminescent device, comprising: First electrode; Second electrode; At least one organic functional layer is located between the first electrode and the second electrode, and at least includes a light-emitting layer; At least one of the said organic functional layers comprises a phosphateheptane compound as shown in formula (IA) or formula (IB) as described in any one of claims 1-5.

9. The organic electroluminescent device as described in claim 8, characterized in that: The organic electroluminescent device is a stacked device, which includes two or more light-emitting layers, wherein the charge-generating layer contains a phosphateheptane compound as shown in formula (IA) or formula (IB) as described in any one of claims 1-5.

10. The organic electroluminescent device as described in claim 8 or 9, characterized in that: The organic functional layer further comprises at least one n-type dopant; Preferably, the n-type dopant is selected from metals or metal compounds; the metal is selected from alkali metals, alkaline earth metals, and rare earth metals; the metal compound is selected from alkali metal compounds, alkaline earth metal compounds, or rare earth metal compounds. More preferably, the n-type dopant is selected from any one or a combination of the following metals: Li, Na, K, Be, Mg, Ca, Sr, Ba, Sc, Y, La, Sm, Eu, Tb, Yb, Lu, Ti, V, Mn; Preferably, the content of n-type dopant in the organic functional layer is in the range of 0.5% to 25% by weight, more preferably in the range of 1% to 20% by weight, more preferably in the range of 1% to 15% by weight, and most preferably in the range of 1% to 10% by weight.

11. The organic electroluminescent device as described in claim 8 or 9, characterized in that: The organic functional layer includes an electron transport layer, an electron injection layer, or a charge generation layer; the electron transport layer may be a single-layer electron transport layer or a multi-layer electron transport layer. Preferably, the organic electroluminescent device is a single-layer device, wherein the electron transport layer contains the phosphine-heptanyl compound.

12. An electronic device, characterized in that, The electronic device includes the organic electroluminescent device as described in claim 11; preferably, the electronic device is a display or lighting device.

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