CN115583887A - Organic electroluminescent compound and preparation method and application thereof - Google Patents
Organic electroluminescent compound and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides an organic electroluminescent compound and a preparation method and application thereof, wherein the organic electroluminescent compound has a structure shown in a formula I. Through the design and compounding of the parent nucleus structure and the groups, the organic electroluminescent compound has excellent hole transmission efficiency and electron blocking capacity, and the molecules are not easy to crystallize and aggregate through the steric effect of the spiro ring in the parent nucleus structure, so that an amorphous disordered film is formed. Meanwhile, the design of the mother-nucleus structure in the invention ensures that the molecular weight is increased, effectively shortens the conjugation interval of the whole molecule, improves the triplet state energy level, ensures the hole transmission capability and increases the limiting effect on the outward expansion of the luminescent exciton. The organic electroluminescent compound is used as a hole transport material for an organic electroluminescent device, so that the luminous efficiency of the device is improved, the service life of the device is prolonged, the driving voltage is reduced, and the organic electroluminescent compound has more excellent comprehensive performance.
Description
Technical Field
The invention belongs to the technical field of luminescent materials, and particularly relates to an organic electroluminescent compound, and a preparation method and application thereof.
Background
Organic electroluminescent diodes (hereinafter referred to as OLEDs) are important electroluminescent devices, and attract the attention of many researchers due to the advantages of no need of backlight source for active light emission, high luminous efficiency, large visual angle, high response speed, large temperature adaptation range, low energy consumption, lightness, thinness, flexible display and the like, and huge application prospects.
Currently, 4,4'-N, N' -dicarbazole-biphenyl (CBP) is the most widely known phosphorescent host material. Recently, pioneer (japan) et al developed a high-performance organic EL device using Bathocuproine (BCP) and aluminum (III) bis (2-methyl-8-quinolinic acid) (4-phenylphenol) (BAlq) or the like as host materials, which are called hole blocking materials.
Although the foregoing materials can provide good luminescent characteristics, they have the following disadvantages: (1) Due to its lower glass transition temperature and poor thermal stability, it may degrade in vacuum during high temperature deposition processes and the lifetime of the device is reduced. (2) The power efficiency of an organic EL device is given by "(pi/voltage) × current efficiency", and the power efficiency is inversely proportional to the voltage. Although organic EL devices containing phosphorescent host materials provide higher current efficiencies (in cd/a) than organic EL devices containing fluorescent materials, significantly high drive voltages are necessary; therefore, there is no advantage in terms of power efficiency (in lm/W) of the foregoing materials. (3) The organic EL device has a short life span and still needs to improve the luminous efficiency, and the foregoing materials cannot satisfy the multifaceted performance requirements of life span, efficiency, driving voltage.
Therefore, development of a material capable of effectively improving durability and light emitting performance of an organic EL device is an urgent problem to be solved in the art.
Disclosure of Invention
In view of the defects of the prior art, the present invention aims to provide an organic electroluminescent compound, a preparation method and applications thereof, wherein the organic electroluminescent compound has excellent photoelectric properties, is used as a hole transport material for an organic electroluminescent device, and can enable the device to have excellent luminous efficiency, lower driving voltage and long service life.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides an organic electroluminescent compound having a structure represented by formula I:
in the formula I, L 1 、L 2 Each independently selected from a single bond, a substituted or unsubstituted C6-C30 arylene group, a substituted or unsubstituted C3-C20 any one of heteroarylenes; when said L is 1 、L 2 And when the structure is a single bond, the structure represents that the N atom is directly connected with the parent nucleus structure through the single bond.
In the formula I, ar 1 、Ar 2 、Ar 3 、Ar 4 Each independently selected from any one of substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C3-C20 heterocycloalkyl, substituted or unsubstituted C6-C30 aryl, and substituted or unsubstituted C3-C30 heteroaryl.
In the formula I, X is selected from CR 1 R 2 O or NR 3 Any one of them.
In the formula I, Y is selected from CR 4 R 5 O or S.
R 1 、R 2 、R 4 、R 5 Each independently selected from any one of hydrogen, deuterium, halogen, cyano, and substituted or unsubstituted C1-C6 straight or branched alkyl.
R 3 Any one selected from substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C3-C20 heterocycloalkyl, substituted or unsubstituted C6-C30 aryl, and substituted or unsubstituted C3-C30 heteroaryl.
L 1 、L 2 、Ar 1 、Ar 2 、Ar 3 、Ar 4 、R 1 、R 2 、R 3 、R 4 、R 5 The substituted substituent as described in (1), R 11 、R 12 Each independently selected from at least one of deuterium, cyano, halogen, nitro, hydroxyl, phosphate, boryl, silyl, C1-C10 linear or branched alkyl, C2-C10 alkenyl, C2-C10 alkynyl, C6-C20 aryl, C3-C20 heteroaryl, C1-C10 alkoxy, C3-C60 heteroarylamino, C6-C60 arylamino.
In the formula I, m and n respectively represent arylamine groups
The number of (a) is independently 0 or 1.
When m and n are both 0, X is NR 3 Said R is 3 Is a C3-C30 cycloalkyl substituted by RAny one of R ' substituted C3-C20 heterocycloalkyl, R ' substituted C6-C30 aryl, and R ' substituted C3-C30 heteroaryl; r' is at least one selected from C3-C60 heteroaryl amino and C6-C60 aryl amino.
In the formula I, s 1 、s 2 Each represents a substituent R 11 、R 12 The number of (b) s is independently selected from integers of 0 to 4, and may be, for example, 0, 1, 2, 3 or 4. When s is 1 、s 2 When not less than 2, a plurality of (at least 2) radicals R 11 、R 12 Are identical or different radicals.
The organic electroluminescent compound provided by the invention has a structure shown as a formula I, has a spiro-condensed parent nucleus structure, and is connected with at least one arylamine group (I)
R 3 ) The arylamine group has lower ionization potential, better electron donating property and higher hole mobility. According to the invention, by designing a specific parent nucleus structure and adjusting the position or the activity of a group, the symmetry of molecules can be reduced, the conformational isomer of the molecules can be increased, the organic electroluminescent compound has excellent hole transmission efficiency and electron blocking capability, and the intermolecular distance is increased by the steric effect of the spiro structure in the parent nucleus, so that the molecules are not easy to crystallize and aggregate, and thus, the amorphous disordered film can be formed, and the photo-thermal stability is excellent. Meanwhile, the parent nucleus structure in the organic electroluminescent compound is a heteroanthracene spiro ring, and due to the existence of SP3 hybridized C and X which does not participate in conjugation in the spiro ring structure, the molecular weight is increased, the conjugation interval of the whole molecule is effectively shortened, the triplet state energy level is improved, and the electron transmission capacity is ensured, and the limiting effect on the external expansion of luminescent excitons is increased. The organic electroluminescent compound is used as a hole transport material for an organic electroluminescent device, so that the luminous efficiency of the device can be effectively improved, the service life is prolonged, the driving voltage is reduced, and the device has more excellent comprehensive performance.
Herein, the C6-C30 may each be C6, C8, C9, C10, C12, C13, C14, C15, C16, C18, C20, C22, C24, C26, or C28, etc.
The C3-C20 can be C3, C4, C5, C6, C8, C9, C10, C12, C13, C14, C15, C16 or C18, etc.
The C3-C30 can be C3, C4, C5, C6, C8, C9, C10, C12, C13, C14, C15, C16, C18, C20, C22, C24, C26 or C28, etc.
The C1-C6 can be C1, C2, C3, C4, C5 or C6.
The C1-C10 can be C1, C2, C3, C4, C5, C6, C8, C9 or C10.
The C2-C10 can be C2, C3, C4, C5, C6, C8, C9 or C10.
The C6-C20 can be C6, C8, C9, C10, C12, C13, C14, C15, C16 or C18, etc.
The C3-C60 can be C3, C4, C5, C6, C9, C10, C12, C14, C16, C18, C20, C22, C24, C26, C28, C30, C32, C35, C38, C40, C42, C45, C48, C50, C52, C55, C58, etc.
The C6-C60 can be C6, C9, C10, C12, C14, C16, C18, C20, C22, C24, C26, C28, C30, C32, C35, C38, C40, C42, C45, C48, C50, C52, C55, C58 and the like.
Herein, the heteroatoms in the "heteroarylene", "heteroaryl", "heterocycloalkyl", "heteroarylamino" are each independently at least one of O, S or N.
Herein, the halogen includes fluorine, chlorine, bromine or iodine; the same description is hereinafter referred to with the same meaning.
Herein, the C1-C10 linear or branched alkyl group, preferably the C1-C6 linear or branched alkyl group, illustratively includes, but is not limited to: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, n-octyl, n-heptyl, n-nonyl or n-decyl, and the like.
Herein, said C3-C20 cycloalkyl, preferably C3-C10 cycloalkyl, illustratively includes but is not limited to: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl and the like.
Herein, the C6-C30 aryl group, preferably C6-C20 aryl group, and further preferably C6-C18 aryl group, including monocyclic aryl group or condensed ring aryl group, illustratively include, but are not limited to: phenyl, biphenyl, terphenyl, phenylnaphthyl, naphthylphenyl, naphthylbiphenyl, naphthyl, anthryl, phenanthryl, indenyl, fluorenyl and derivatives thereof (9,9-dimethylfluorenyl, 9,9-diphenylfluorenyl, 9,9-dinaphthylfluorenyl, spirobifluorenyl, benzofluorenyl, etc.), triphenylene, pyrenyl, perylenyl, indenyl, azulenyl, benzophenanthryl, etc.; the foregoing list of groups includes all possible attachment means thereof.
Herein, the C3-C30 heteroaryl, preferably C3-C20 heteroaryl, further preferably C3-C18 heteroaryl, heteroatom is O, S or N, exemplary including but not limited to: furyl, thienyl, pyrrolyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, triazinyl, oxazolyl, isoxazolyl, imidazolyl, thiazolyl, isothiazolyl, thiadiazolyl, oxadiazolyl, pyrazolyl, triazolyl, indolyl, quinolyl, isoquinolyl, acridinyl, purinyl, pteridinyl, benzofuranyl, benzothienyl, benzimidazolyl, benzothiazolyl, benzotriazolyl, benzooxadiazolyl, benzoxazolyl, cinnoline, quinoxalinyl, dibenzofuranyl, dibenzothienyl, carbazolyl and derivatives thereof (N-phenylcarbazolyl, N-naphthylcarbazolyl, benzocarbazolyl, dibenzocarbazolyl, indolocarbazolyl, azacarbazolyl, etc.), phenanthrolinyl, indolizinyl, naphthyridinyl, phthalazinyl, etc.; the foregoing list of groups includes all possible attachment means thereof.
Specific examples of the C6-C30 arylene group include divalent groups obtained by removing one hydrogen atom from the above-mentioned examples of the aryl group; specific examples of the C3-C20 heteroarylene group include divalent groups obtained by removing one hydrogen atom from the above-mentioned examples of the heteroaryl group.
In the present invention, the C6-C60 arylamino group, preferably the C6-C30 arylamino group, is-NH 2 A monovalent group formed by substitution of at least one H on the above with an aryl group as exemplified above; said C3-C60 heteroarylAmino, preferably C3-C30 arylamino, i.e. -NH 2 And (c) a monovalent radical formed by substitution of at least one of the hydrogens with a heteroaryl group as listed above.
Preferably, said s 1 And s 2 Are all 0.
Preferably, the organic electroluminescent compound has a structure represented by any one of formula I-1, formula I-2, formula I-3 or formula I-4:
wherein L is 1 、L 2 、Ar 1 、Ar 2 、Ar 3 、Ar 4 X, Y has the same limitations as formula I;
in the formula I-3, R 3 Is any one of R 'substituted C3-C30 cycloalkyl, R' substituted C3-C20 heterocycloalkyl, R 'substituted C6-C30 aryl and R' substituted C3-C30 heteroaryl.
R' is at least one selected from C3-C60 heteroaryl amino and C6-C60 aryl amino.
Preferably, said L 1 、L 2 Each independently selected from any one of a single bond, a substituted or unsubstituted C6-C18 (e.g., C6, C8, C9, C10, C12, C13, C14, C15, C16, C18, etc.) arylene group, a substituted or unsubstituted C3-C18 (e.g., C3, C4, C5, C6, C8, C9, C10, C12, C13, C14, C15, C16, C18, etc.) heteroarylene group; l is 1 、L 2 Wherein each of said substituted substituents is independently selected from at least one of C1-C10 (e.g., C2, C3, C4, C5, C6, C7, C8, C9, etc.) straight or branched chain alkyl, C6-C20 (e.g., C6, C9, C10, C12, C14, C16, C18, etc.) aryl, C3-C20 (e.g., C3, C4, C5, C6, C9, C10, C12, C14, C16, C18, etc.) heteroaryl.
Preferably, said L 1 、L 2 Each independently selected from a single bond, a substituted or unsubstituted C6-C18 arylene; the substitution beingThe substituent is at least one selected from C1-C6 straight chain or branched chain alkyl and C6-C12 aryl.
Preferably, said L 1 、L 2 Each independently selected from a single bond,
(phenylene) to a polymer,
(methylene-phenyl),
(biphenylene),
(biphenylene),
(naphthylene group),
(naphthyl-substituted phenylene),
Any one of (naphthyl-substituted phenylene); the dotted line represents the attachment site of the group.
Preferably, ar is 1 、Ar 2 、Ar 3 、Ar 4 Each independently selected from any one of the following substituted or unsubstituted groups:
wherein the dotted line represents the attachment site of the group.
Ar 11 Selected from C6-C18 (e.g., C6, C9, C10, C12, C14, C16, or C18, etc.) aryl, C3-C18 (e.g., C3, C4, C5, C6, C9, C10, C12, C14, C16, or C18, etc.) heteroaryl.
Z 1 Selected from O, S, NR 21 Or CR 22 R 23 Any one of them.
R 21 、R 22 、R 23 Each independently selected from any one of C1-C10 (e.g., C2, C3, C4, C5, C6, C7, C8, C9, etc.) straight or branched chain alkyl, C6-C20 (e.g., C6, C9, C10, C12, C14, C16, C18, etc.) aryl, or C3-C20 (e.g., C3, C4, C5, C6, C9, C10, C12, C14, C16, C18, etc.) heteroaryl.
The substituted substituent is selected from at least one of C1-C6 (such as C2, C3, C4 or C5) straight-chain or branched alkyl;
preferably, ar is 11 Selected from phenyl
Naphthyl radical
Phenanthryl radical
Anthracenyl radicals
Dibenzofuranyl radical
Dibenzothienyl radical
Dimethyl fluorenyl radical
Carbazolyl group
N-phenylcarbazolyl
Any one of them.
Preferably, said R is 21 Is a C6-C18 (e.g., C6, C9, C10, C12, C14, C16, or C18, etc.) aryl group, and a phenyl group is more preferable.
Preferably, said R is 22 、R 23 Each independently selected from C1-C6 (e.g., C2, C3, C4, or C5, etc.) straight or branched chain alkyl groups, with methyl being further preferred.
Preferably, ar is 1 、Ar 2 、Ar 3 、Ar 4 Each independently selected from any one of the following groups:
R 21 Any one selected from a C6-C20 (e.g., C6, C9, C10, C12, C14, C16, C18, etc.) aryl group or a C3-C20 (e.g., C3, C4, C5, C6, C9, C10, C12, C14, C16, C18, etc.) heteroaryl group, preferably a C6-C18 aryl group, and further preferably a phenyl group.
Preferably, said R is 1 、R 2 、R 4 、R 5 Each independently selected from any one of C1-C6 (e.g., C2, C3, C4, or C5, etc.) straight or branched chain alkyl groups, with methyl being further preferred.
Preferably, said R is 3 And R' is at least one selected from C6-C60 arylamino.
Preferably, said R is 3 Is composed of
The dotted line represents the attachment site of the group.
Ar is 21 、Ar 22 Each independently selected from C6-C20 (e.g., C6, C9, C10, C12, C14, C16, or C18, etc.) aryl, preferably phenyl
Naphthyl radical
Biphenyl radical
Terphenyl radical
Naphthyl phenyl
Or phenylnaphthyl
Any one of them.
Preferably, the organic electroluminescent compound is selected from any one of the following structures 1 to 256:
in a second aspect, the present invention provides a method for producing an organic electroluminescent compound according to the first aspect, comprising the steps of:
(1) Reacting the compound A with the compound B to obtain a compound C; carrying out a ring closure reaction on the compound C to obtain an intermediate D;
the reaction formula is as follows:
(2) Carrying out coupling reaction on the intermediate D obtained in the step (1) and an arylamine compound to obtain the organic electroluminescent compound; the arylamine compound is a compound E and/or a compound F;
the compound E has the structure
The compound F has the structure
When the L is 1 Not being a single bond and/or L 2 When not a single bond, the coupling reaction in step (2) further comprises a step (1'): reacting the intermediate D with a bridging compound to obtain an intermediate D'; carrying out coupling reaction on the intermediate D' and an arylamine compound to obtain the organic electroluminescent compound;
the bridging compound is
And/or
The intermediate D' is
Wherein L is 1 、L 2 、Ar 1 、Ar 2 、Ar 3 、Ar 4 、X、Y、R 11 、R 12 、m、n、s 1 、s 2 Having the same limitations as formula I;
Hal 1 、Hal 2 、Hal 3 、Hal 4 、Hal 5 each independently selected from halogen, preferably Cl, br or I.
Preferably, the reaction of step (1) is carried out in the presence of a catalyst, which is an organolithium reagent, further preferably n-butyllithium (n-BuLi).
Preferably, the ring closure reaction of step (1) is carried out in the presence of trifluoromethanesulfonic acid (TfOH).
Preferably, the coupling reaction of step (2) is carried out in the presence of a transition metal catalyst, preferably a palladium catalyst, exemplary including but not limited to: tetratriphenylphosphine palladium, tris (dibenzylideneacetone) dipalladium Pd 2 (dba) 3 。
Preferably, both m and n are 0,X NR 3 The preparation method does not include the step (2).
In a third aspect, the present invention provides a use of an organic electroluminescent compound as described in the first aspect in an electronic device.
Preferably, the electronic device includes an organic electroluminescent device (OLED), an Organic Solar Cell (OSC), an electronic paper (e-paper), an Organic Photoreceptor (OPC), or an Organic Thin Film Transistor (OTFT).
Preferably, the organic electroluminescent compounds are used as hole transport materials for electronic devices.
In a fourth aspect, the present invention provides an organic electroluminescent device comprising a first electrode, a second electrode, and at least one organic layer disposed between the first and second electrodes; the organic layer comprises at least one organic electroluminescent compound according to the first aspect.
In the present invention, the organic layer may have a single-layer structure, but may have a multilayer structure including at least two (for example, 2, 3,4, 5, 6, 7, 8, etc.) organic layers. For example, the organic layers of the organic electroluminescent device include a hole injection layer, a hole transport layer, a hole injection and transport layer, an electron blocking layer, a light emitting layer, an electron transport layer, an electron injection layer, a hole blocking layer, an electron injection and transport layer, and the like. Of course, the structure of the organic electroluminescent device is not limited thereto, and a smaller number of organic layers or a larger number of organic layers may be included.
Preferably, the organic layer comprises a hole transport layer comprising at least one organic electroluminescent compound according to the first aspect.
Preferably, the organic layer comprises a hole injection layer comprising a combination of at least one organic electroluminescent compound according to the first aspect and a P-type dopant (P-dopant).
In the present invention, one of the first electrode and the second electrode is an anode, and the other is a cathode. For example, the first electrode is an anode and the second electrode is a cathode, or the first electrode is a cathode and the second electrode is an anode.
Preferably, the organic electroluminescent device includes an anode, a Hole Injection Layer (HIL), a Hole Transport Layer (HTL), an Electron Blocking Layer (EBL), an emission layer (EML), a Hole Blocking Layer (HBL), an Electron Transport Layer (ETL), an Electron Injection Layer (EIL), and a cathode, which are sequentially disposed.
Preferably, the cathode is further provided with a light extraction layer on the side away from the EIL.
As an anode material of the anode, a material having a large work function is generally preferred so that holes are smoothly injected into the organic layer. Specific examples of the anode material that can be used herein include: metals such as vanadium, chromium, copper, zinc and gold, or alloys thereof; metal oxides such as zinc oxide, indium Tin Oxide (ITO), or Indium Zinc Oxide (IZO); combinations of metals and oxides, e.g. ZnO: al or SnO 2 Sb; conductive polymers such as poly (3-methylthiophene), poly (3,4-ethylenedioxythiophene) (PEDOT), polypyrrole and polyaniline, but are not limited thereto.
The hole injecting material is a material that advantageously receives holes from the anode at low voltages, and the Highest Occupied Molecular Orbital (HOMO) of the hole injecting material is preferably between the work function of the anode material and the HOMO of the surrounding organic layer. Specific examples of the hole injection material include metalloporphyrin, oligothiophene, arylamine-based organic material, hexanenitrile-based hexaazatriphenylene-based organic material, quinacridone-based organic material, perylene-based organic material, anthraquinone, polyaniline-based or polythiophene-based conductive polymer, and the like, but are not limited thereto, and may further include another compound capable of p-doping.
The hole transport material is a material capable of receiving holes from the anode or the hole injection layer and transporting the holes to the light emitting layer, and a material having high hole mobility is suitable. Preferably, the hole transport material comprises the organic electroluminescent compound provided by the invention and having the structure shown in formula I.
The light emitting layer may emit red, green or blue light, and may be formed of a phosphorescent material or a fluorescent material. The light emitting material is a material capable of emitting light in the visible light region by receiving holes and electrons from the hole transport layer and the electron transport layer, respectively, and combining the holes and the electrons, and is preferably a material having favorable quantum efficiency for fluorescence or phosphorescence. Specific examples thereof include: 8-Hydroxyquinoline aluminum (Alq) 3 ) (ii) a A carbazole-based compound; a di-polystyrene based compound; BAlq; 10-hydroxybenzoquinoline-metal compounds; a benzocarbazole-based compound; a benzothiazole-based compound; a benzimidazole-based compound; poly (p-phenylene vinylene) based polymers (PPV); a spiro compound; a polyfluorene; rubrene, and the like, but is not limited thereto.
The host material of the light-emitting layer includes a condensed aromatic ring derivative, a heterocyclic ring-containing compound, and the like. Specifically, the fused aromatic ring derivative includes an anthracene derivative, a pyrene derivative, a naphthalene derivative, a pentacene derivative, a phenanthrene compound, a fluoranthene compound, and the like, and the heterocycle-containing compound includes a carbazole derivative, a dibenzofuran derivative, a ladder-type furan compound, a pyrimidine derivative, and the like, but the material is not limited thereto.
The electron transport layer may function to facilitate electron transport. The electron transport material is a material that favorably receives electrons from the cathode and transports the electrons to the light emitting layer, and a material having high electron mobility is suitable. Specific examples thereof include: al complexes of 8-hydroxyquinoline; comprising Alq 3 The complex of (1); an organic radical compound; hydroxyflavone-metal complexes, and the like, but are not limited thereto. The thickness of the electron transport layer may be 1 to 50nm. The electron transport layer has an advantage of preventing a decrease in electron transport characteristics and an advantage of preventing an increase in driving voltage for enhancing electron transfer caused by an electron transport layer being too thick.
The electron injection layer may function to promote electron injection. The properties of the electron injection material include: has an ability to transport electrons, has an electron injection effect from a cathode, has an excellent electron injection effect on a light emitting layer or a light emitting material, prevents excitons generated in the light emitting layer from migrating to a hole injection layer, and, in addition, has an excellent thin film forming ability. Specific examples thereof include fluorenone, anthraquinone dimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylene tetracarboxylic acid, fluorenylidene methane, anthrone, and the like and derivatives thereof, metal complexes, nitrogen-containing five-membered ring derivatives, and the like, but are not limited thereto.
As the cathode material, a material having a small work function is generally preferred so that electrons are smoothly injected into the organic material layer. Specific examples of the cathode material include: metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, and lead, or alloys thereof; materials of multilayer structure, e.g. LiF/Al, liO 2 Al, etc., but are not limited thereto.
Compared with the prior art, the invention has the following beneficial effects:
the organic electroluminescent compound provided by the invention has a structure shown in a formula I, contains a spiro-fused mother nucleus structure, has a lower ionization potential, better electron donating property and higher hole mobility by designing the mother nucleus structure and adjusting the position of a substituent or the activity of the substituent and connecting an arylamine group to a characteristic site of the mother nucleus structure. Through the design and the compounding effect of a mother nucleus structure and a group, the organic electroluminescent compound has excellent hole transmission efficiency and electron blocking capability. Meanwhile, the distance between molecules is increased through the steric effect of the spiro ring in the parent nucleus structure, so that the molecules are not easy to crystallize and aggregate, and the amorphous disordered thin film is favorably formed. Meanwhile, compared with the prior art, the invention designs a specific mother nucleus structure containing the heteroanthracene type spiro ring, and due to the existence of the SP3 hybridized C and the X which does not participate in conjugation on the spiro ring, the molecular weight is increased, the conjugation interval of the whole molecule is effectively shortened, the triplet state energy level is improved, and the organic electroluminescent compound has excellent transmission capability and simultaneously has a limiting effect on the external expansion of luminescent excitons. The organic electroluminescent compound is used as a hole transport material for an organic electroluminescent device, so that the luminous efficiency of the device is improved, the service life of the device is prolonged, the driving voltage is reduced, and the organic electroluminescent compound has more excellent comprehensive performance.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitation of the present invention.
In one embodiment, the organic electroluminescent compound has a structure as shown in any one of formula I-1, formula I-2 or formula I-3; the compound is prepared by adopting the following synthetic route:
(1) X is NR 3 The synthetic route is as follows:
feed 1-A (1.0 eq) was charged to the reaction flask and solvent dichloromethane DCM was added. And triethylamine (2.0 eq) is added, under the protection of nitrogen, the raw material 1-B (1.2 eq) is added dropwise at 0 ℃, and after the dropwise addition is finished, the temperature is raised to room temperature and stirring reaction is carried out for 3 hours. The mixture solution was purified by column chromatography using dichloromethane to petroleum ether (DCM: PE) =1:4 to obtain intermediate 1-1.
The intermediate 1-1 (1.0 eq) and the starting material 1-C (1.0 eq) were dissolved in toluene and then the mixture was purified by filtration in N 2 Adding Pd under atmosphere 2 (dba) 3 (0.01 eq), tris (tert-butyl) phosphine P (t-Bu) 3 (0.05 eq) and sodium t-BuONa (2.0 eq), heating to 100-120 ℃ and stirring to react for 10-12h, after the reaction is finished, suction-filtering with diatomaceous earth while hot, removing salts and catalyst, cooling the filtrate to room temperature, adding distilled water to the filtrate for washing, after liquid separation, retaining the organic phase, extracting the aqueous phase with ethyl acetate, then drying the combined organic layers with magnesium sulfate, removing the solvent with a rotary evaporator, and finally purifying the remaining material with column chromatography using a mixture of DCM and PE as eluent (DCM: PE = 1.
Adding the intermediate 2-1 (1.0 eq) and active manganese dioxide (10.0 eq) into a reaction bottle, adding DCM solvent, and heating to 50 ℃ for reaction overnight. Subsequent filtration and removal of the solvent using a rotary evaporator gave intermediate 3-1.
(2) Y is C (CH) 3 ) 2 I.e. R 4 And R 5 All are methyl, and the synthetic route is as follows:
raw material 2-a (1.0 eq) and potassium carbonate (1.5 eq) were added to a reaction flask, solvent N, N-Dimethylformamide (DMF) was added, and stirred. At room temperature, iodomethane (1.0 eq) is added dropwise, after the temperature is raised to 100 ℃, iodomethane (2.0 eq) is added dropwise after reaction for 1 hour, and after reaction for 2 hours, iodomethane (2.0 eq) is added dropwise and the reaction is carried out overnight. After cooling to room temperature, the reaction was poured into cold water, then extracted with ethyl acetate, washed twice with water, then dried over anhydrous magnesium sulfate for 10min, and finally the remaining material was purified by column chromatography using a mixture of DCM and PE as eluent (DCM: PE =1 16) to give intermediate 1-2.
Adding the intermediate 1-2 (1.0 eq) into a three-neck flask, adding tetrahydrofuran THF solution, cooling to-78 deg.C under nitrogen protection, and stirring for 30min. Then, n-BuLi (1.2 eq) was added and the reaction was carried out for 2 hours. Triisopropyl borate (1.2 eq) was added and the reaction was carried out for 1h with gradual warming overnight. Then adding hydrochloric acid for acidification, adjusting pH value to 3-4, and stirring for 30min. Then, the solution was separated, the organic phase was retained, dried using anhydrous magnesium sulfate, and the solvent was removed using a rotary evaporator; adding the organic matter into petroleum ether, heating to 50 ℃, stirring for 1h, then cooling to room temperature, carrying out suction filtration and drying to obtain an intermediate 2-2.
Under the protection of nitrogen, dissolving the intermediate 2-2 (1.0 eq) and the raw material 2-b (1.0 eq) in toluene, ethanol and water solution, adding potassium carbonate (2.0 eq) and tetratriphenylphosphine palladium (0.05 eq), stirring uniformly, heating to 90 ℃, and carrying out reflux reaction for 6 hours; after the reaction is finished, cooling the filtrate to room temperature, separating liquid, retaining an organic phase, and extracting an aqueous phase by using ethyl acetate; after combining the organic phases, drying was performed using anhydrous magnesium sulfate, and the solvent was removed using a rotary evaporator; the remaining material was purified by column chromatography using a mixed solution of DCM and PE (V: V = 2:1) to afford intermediate 3-2.
When Y is O or S, the synthesis is similar to the above described synthesis except that no first step of reaction with methyl iodide is required, i.e. the route is:
(3) Synthesis of intermediate D
Adding the compound B (1.0 eq) into a three-neck flask under the protection of nitrogen, adding anhydrous THF, then cooling the reaction system to-78 ℃, adding n-BuLi (1.2 eq) dropwise, and stirring for 2h. The compound A (1.2 eq) was dissolved in THF solution, then added dropwise to the reaction system, after the addition was complete, the temperature was raised to room temperature, and stirred for 10h. Then, a saturated ammonium chloride solution was added to quench the reaction, the reaction solution was extracted 3 times with ethyl acetate, and the organic phases were combined and successively washed with water and saturated brine, followed by drying over anhydrous magnesium sulfate. Adding the dried solid into an ethanol solution, heating to 80 ℃, stirring for 5 hours, carrying out suction filtration on the solution while the solution is hot to obtain a solid, leaching with petroleum ether, and drying to prepare a compound C;
adding the compound C (1.0 eq) into a three-necked bottle, adding a DCM solution, stirring uniformly, then cooling to 0 ℃, and then adding TfOH (4.0 eq) into the solution dropwise for reacting for 4 hours. After warming to room temperature, the organic phase was collected, dried over anhydrous magnesium sulfate, the solvent was removed by rotary evaporator and the remaining material was purified by column chromatography using a mixture of DCM and PE as eluent (DCM: PE =1 16) to give compound D.
(4) The organic electroluminescent compound has a structure shown as a formula I-1, namely n =1 and m =0, and the synthetic route is as follows:
under the protection of nitrogen, dissolving the intermediate D-1 (1.0 eq) and the raw material 4-1 (1.0 eq) in a mixed solution of toluene, ethanol and water, adding potassium carbonate (2.0 eq) and tetratriphenylphosphine palladium (0.05 eq), uniformly stirring, and heating to 90 ℃ for reflux reaction for 6 hours; after the reaction is finished, cooling the filtrate to room temperature, separating liquid, retaining an organic phase, and extracting a water phase by using ethyl acetate; after combining the organic phases, drying over anhydrous magnesium sulfate and removing the solvent using a rotary evaporator; the remaining material was purified by column chromatography using a mixed solution of DCM and PE (V: V = 2:1) to give intermediate D' -1.
Under the protection of nitrogen, dissolving the intermediate D' -1 (1.0 eq) and the raw material 4-2 (1.0 eq) in a toluene solution, and adding Pd 2 (dba) 3 (0.01eq)，P(t-Bu) 3 (0.05 eq) and t-BuONa (2.0 eq), stirring uniformly, heating to 90 ℃, and refluxing for reaction for 5 hours; after the reaction is finished, slightly cooling to 75 ℃, filtering by using diatomite to remove salt and a catalyst, cooling the filtrate to room temperature, washing by using water for three times to keep an organic phase, and extracting an aqueous phase by using ethyl acetate; after the organic phases were combined, dried using anhydrous magnesium sulfate, and the solvent was removed using a rotary evaporator; the remaining material was purified by column chromatography using a mixture of DCM and PE (DCM: PE = 10) as eluent to obtain the target product of the structure shown in formula I-1.
When L is 2 When the intermediate is a single bond, the intermediate D-1 and the raw material 4-2 react to obtain a target product without reacting with the raw material 4-1.
The organic electroluminescent compound has a structure shown as a formula I-2, namely n =0 and m =1, and the synthetic route is as follows; the specific synthetic process is the same as formula I-1 and is not repeated.
In the above synthetic route, L 1 、L 2 、Ar 1 、Ar 2 、Ar 3 、Ar 4 X, Y, m, n, having the formulaI is the same as defined; hal 11 、Hal 21 、Hal 22 、Hal 23 、Hal 24 、Hal 1 、Hal 2 、Hal 3 、Hal 4 、Hal 5 Each independently selected from Cl, br or I.
The organic electroluminescent compound provided by the invention can be prepared by selecting different raw materials on the basis of the synthetic route. The preparation method of the organic electroluminescent compound includes, but is not limited to, the above synthetic method, and can also be prepared by other synthetic methods known in the art.
The following examples of the present invention illustratively provide specific synthetic methods representative of the compounds, and the solvents and reagents used in the examples are commercially available from the chemical product market.
In the following embodiments of the present invention, the purity of the target product is measured by High Performance Liquid Chromatography (HPLC), and the Mass Spectrometry (MS) data and the elemental analysis data are measured by ultra high liquid mass spectrometry (Waters XEVO TQD) and organic element analyzer (vacuum ELcube).
Example 1
Organic electroluminescent compound (compound-3)
) The preparation method comprises the following steps:
raw material a-3 (30.00 mmol) and potassium carbonate (45.00 mmol) were added to a reaction flask, 60.00mL of DMF solvent was added, and stirred. At room temperature, iodomethane (30.00 mmol) was added dropwise, and after the temperature was raised to 100 ℃, iodomethane (60.00 mmol) was added dropwise after 1 hour of reaction, and after 2 hours of reaction, iodomethane (60.00 mmol) was added dropwise and the reaction was allowed to proceed overnight. After cooling to room temperature, the reaction solution was poured into cold water, followed by extraction with ethyl acetate, washing twice with water, followed by drying over anhydrous magnesium sulfate for 10min, and finally the remaining material was purified by column chromatography using a mixture of DCM: PE =1 16 dichloromethane and petroleum ether as an eluent to give intermediate 1-2 (4.81 g, yield: 71.8%).
Adding the intermediate 1-2 (20.17 mmol) into a three-neck flask, adding 50.00mL of THF solution, cooling to-78 deg.C under nitrogen protection, and stirring for 30min. Then n-BuLi (24.20 mmol) was added and the reaction was continued for 2h. Triisopropyl borate (24.20 mmol) was added, and the reaction was carried out for 1 hour with gradually increasing temperature overnight. Then adding hydrochloric acid for acidification, adjusting the pH value to 4, and stirring for 30min. Then, the solution was separated, the organic phase was retained, dried using anhydrous magnesium sulfate, and the solvent was removed using a rotary evaporator; the organic was added to petroleum ether and heated to 50 ℃ and stirred for 1h, then cooled to room temperature, filtered with suction and dried to give intermediate 2-2 (3.24 g, yield: 85.3%).
Under the protection of nitrogen, dissolving the intermediate 2-2 (15.95 mmol) and the raw material b-3 (15.95 mmol) in 80.00mL of toluene, ethanol and aqueous solution, adding potassium carbonate (31.90 mmol) and tetrakistriphenylphosphine palladium (0.80 mmol), uniformly stirring, heating to 90 ℃, and carrying out reflux reaction for 6h; after the reaction is finished, cooling the filtrate to room temperature, separating liquid, retaining an organic phase, and extracting an aqueous phase by using ethyl acetate; after the organic phases were combined, dried using anhydrous magnesium sulfate, and the solvent was removed using a rotary evaporator; the remaining material was purified by column chromatography using a mixed solution of DCM and PE (V: V = 2:1) to obtain intermediate 3-2 (4.41 g, yield: 92.4%).
Under the protection of nitrogen, intermediate 3-1 (11.14 mmol) was added into a three-necked flask, 40.00mL of anhydrous THF was added, and then the reaction system was cooled to-78 deg.C, n-BuLi (13.37 mmol) was added dropwise and stirred for 2h. Intermediate 3-2 (13.37 mmol) was dissolved in 40.00mL of THF solution, added dropwise to the above reaction system, and after completion of the addition, warmed to room temperature and stirred for 10h. Then, a saturated ammonium chloride solution was added to quench the reaction, the reaction solution was extracted 3 times with ethyl acetate, and the organic phases were combined and successively washed with water and saturated brine, followed by drying over anhydrous magnesium sulfate. The dried solid was then added to an ethanol solution and warmed to 80 ℃ and stirred for 5h, and the solution was then suction filtered while hot to give a solid which was then rinsed with petroleum ether and dried to afford intermediate 4 (4.86 g, yield: 83.7%).
Intermediate 4 (8.63 mmol) was added to a three-necked flask, 45.00mL of DCM solution was added, stirring was uniform, then cooling to 0 ℃ and TfOH (34.52 mmol) was added dropwise to the above solution, and reaction was carried out for 4h. After warming to room temperature, the organic phase was collected, dried over anhydrous magnesium sulfate, and the solvent was removed by rotary evaporator, and finally the remaining material was purified by column chromatography using a mixture of DCM: PE = 1.
Under the protection of nitrogen, intermediate 5 (6.95 mmol) and raw material 2-3 (6.95 mmol) are dissolved in 80.00mL of toluene solution, and Pd is added 2 (dba) 3 (0.07mmol)、P(t-Bu) 3 (0.35 mmol) and t-BuONa (13.90 mmol), stirring uniformly, heating to 90 ℃, and refluxing for 5h; after the reaction is finished, slightly cooling to 75 ℃, filtering by using diatomite to remove salt and a catalyst, cooling the filtrate to room temperature, washing by using water for three times to keep an organic phase, and extracting an aqueous phase by using ethyl acetate; after the organic phases were combined, dried using anhydrous magnesium sulfate, and the solvent was removed using a rotary evaporator; the remaining material was purified by column chromatography using a mixed solution of DCM: PE = 10.
The compound-3 thus obtained was subjected to detection analysis, and the results were as follows:
HPLC purity: is more than 99 percent.
MS(ESI，m/z)：[M+H] + 743.85。
Elemental analysis: the calculated values are: c92.02, H6.10, N1.88;
the test values are: c91.78, H6.36, N2.16.
Nuclear magnetic hydrogen spectrum test: 1 H-NMR(500MHz，CDCl 3 )：δ7.58(dd,J＝8.3,1.4Hz,4H),7.51(d,J＝7.7Hz,4H),7.44(t,J＝7.8Hz,4H),7.41–7.34(m,6H),7.30(t,J＝7.3Hz,6H),7.16(d,J＝6.3Hz,2H),7.10–7.04(m,3H),7.02(d,J＝6.9Hz,1H),6.98(d,J＝2.2Hz,1H),6.73(dd,J＝5.1,3.0Hz,2H),1.61(s,3H),1.57(s,3H),1.44(s,3H),1.40(s,3H)。
example 2
An organic electroluminescent compoundCompound-160
) The preparation method comprises the following steps:
under the protection of nitrogen, intermediate 3-1 (11.14 mmol) was added into a three-necked flask, 40.00mL of anhydrous THF was added, and then the reaction system was cooled to-78 deg.C, n-BuLi (13.37 mmol) was added dropwise and stirred for 2h. Intermediate 3-2 (13.37 mmol, prepared in the same manner as in example 1) was dissolved in 40.00mL of THF solution, added dropwise to the above reaction system, and after completion of the addition, warmed to room temperature and stirred for 10h. Then, a saturated ammonium chloride solution was added to quench the reaction, the reaction solution was extracted 3 times with ethyl acetate, and the organic phases were combined and successively washed with water and saturated brine, followed by drying over anhydrous magnesium sulfate. The dried solid was then added to an ethanol solution and heated to 80 ℃ and stirred for 5 hours, and the solution was then suction filtered while hot to give a solid which was then rinsed with petroleum ether and dried to afford intermediate 4 (4.65 g, yield: 84.2%).
Intermediate 4 (9.08 mmol) was added to a three-necked flask, 45.00mL of DCM solution was added, stirring was uniform, then cooling to 0 ℃ and TfOH (36.32 mmol) was added dropwise to the above solution, and reaction was carried out for 4h. After warming to room temperature, the organic phase was collected, dried over anhydrous magnesium sulfate was added, the solvent was removed by rotary evaporator, and finally the remaining material was purified by column chromatography using a mixture of DCM: PE = 1.
Under the protection of nitrogen, dissolving intermediate 5 (7.33 mmol) and raw material 2-160 (7.33 mmol) in 80.00mL of toluene solution, and adding Pd 2 (dba) 3 (0.07mmol)、P(t-Bu) 3 (0.37 mmol) and t-BuONa (14.66 mmol), stirring uniformly, heating to 90 ℃, and refluxing for 5h; after the reaction is finished, slightly cooling to 75 ℃, filtering by using diatomite to remove salt and catalyst, cooling the filtrate to room temperature, washing with water for three times, and retaining an organic phaseThe aqueous phase was then extracted with ethyl acetate; after the organic phases were combined, dried using anhydrous magnesium sulfate, and the solvent was removed using a rotary evaporator; the remaining material was purified by column chromatography using a mixed solution of DCM: PE = 10.
The detection analysis was performed on the obtained compound-160, and the results were as follows:
HPLC purity: is more than 99 percent.
MS(ESI，m/z)：[M+H] + 794.23。
Elemental analysis: the calculated values are: c90.76, H5.46, N,1.76, O2.01;
the test values are: c90.49, H5.71, N1.92 and O2.23.
Example 3
Organic electroluminescent compound (compound-175)
) The preparation method comprises the following steps:
under the protection of nitrogen, dissolving the raw material c-175 (30.00 mmol) and the raw material b-175 (30.00 mmol) in 120.00mL of toluene, ethanol and aqueous solution, adding potassium carbonate (60.00 mmol) and tetrakistriphenylphosphine palladium (1.50 mmol), uniformly stirring, heating to 90 ℃, and carrying out reflux reaction for 6h; after the reaction is finished, cooling the filtrate to room temperature, separating liquid, retaining an organic phase, and extracting an aqueous phase by using ethyl acetate; after combining the organic phases, drying was performed using anhydrous magnesium sulfate, and the solvent was removed using a rotary evaporator; the remaining material was purified by column chromatography using a mixed solution of DCM and PE (V: V = 2:1) to obtain intermediate 3-2 (8.12 g, yield: 90.4%).
Under the protection of nitrogen, adding the intermediate 3-1 (19.50 mmol) into a three-neck flask, adding 60.00mL of anhydrous THF, then cooling the reaction system to-78 ℃, adding n-BuLi (23.39 mmol) dropwise, and stirring for 2h. Intermediate 3-2 (23.39 mmol) was dissolved in 70.00mL of THF solution and added dropwise to the above reaction system, after the addition was complete, the temperature was raised to room temperature and stirring was continued for 10h. Then, a saturated ammonium chloride solution was added to quench the reaction, the reaction solution was extracted 3 times with ethyl acetate, and the organic phases were combined and successively washed with water and saturated brine, followed by drying over anhydrous magnesium sulfate. The dried solid was then added to an ethanol solution and warmed to 80 ℃ and stirred for 5h, and the solution was then suction filtered while hot to give a solid which was then rinsed with petroleum ether and dried to afford intermediate 4 (8.08 g, yield: 83.6%).
Intermediate 4 (14.91 mmol) was added to a three-necked flask, 70.00mL of DCM solution was added, stirred well, then cooled to 0 deg.C, and TfOH (59.64 mmol) was added dropwise to the above solution and reacted for 4h. After warming to room temperature, the organic phase was collected, dried over anhydrous magnesium sulfate, and the solvent was removed by rotary evaporator, and finally the remaining material was purified by column chromatography using a mixture of DCM: PE = 1.
Under the protection of nitrogen, dissolving intermediate 5 (11.08 mmol) and raw material 2-175 (11.08 mmol) in 100.00mL of toluene solution, and adding Pd 2 (dba) 3 (0.11mmol)、P(t-Bu) 3 (0.55 mmol) and t-BuONa (22.16 mmol), stirring uniformly, heating to 90 ℃, and refluxing for 5h; after the reaction is finished, slightly cooling to 75 ℃, filtering by using diatomite to remove salt and a catalyst, cooling the filtrate to room temperature, washing for three times by using water to keep an organic phase, and extracting a water phase by using ethyl acetate; after combining the organic phases, drying was performed using anhydrous magnesium sulfate, and the solvent was removed using a rotary evaporator; the remaining material was purified by column chromatography using a mixed solution of DCM: PE = 10.
The detection analysis of the obtained compound-175 showed the following results:
HPLC purity: is more than 99 percent.
MS(ESI，m/z)：[M+H] + 768.04。
Elemental analysis: the calculated values are: c89.15, H,4.86, N1.82, O4.17;
the test values are: c88.89, H5.06, N2.09, O4.31.
The synthesis methods of other compounds are the same as the above examples, which are not repeated herein, and the compound numbers, chemical formulas and Mass Spectrometry (MS) test results of the other synthesis examples are shown in table 1 below:
TABLE 1
The following are some device examples in which the organic electroluminescent compounds are used as hole transport materials in organic electroluminescent devices:
device example 1
An organic electroluminescent device comprising, arranged in sequence: an ITO anode, a Hole Injection Layer (HIL), a Hole Transport Layer (HTL), an Electron Blocking Layer (EBL), an emission layer (EML), a Hole Blocking Layer (HBL), an Electron Transport Layer (ETL), an Electron Injection Layer (EIL), a cathode, and a light extraction layer.
The preparation method of the organic electroluminescent device comprises the following steps:
a. an ITO anode: coating with a thickness of
The ITO-Ag-ITO glass substrate is cleaned in distilled water for 2 times, ultrasonically cleaned for 30min, repeatedly cleaned with distilled water for 2 times, ultrasonically cleaned for 10min, ultrasonically cleaned with methanol, acetone and isopropanol sequentially (each time for 5 min), dried, then transferred to a plasma cleaning machine for cleaning for 5min, and then transferred to an evaporation machine, and other functional layers are sequentially evaporated on the substrate serving as an anode.
b. HIL: to be provided with
The compound 1 and P-dopant provided in the above example were vacuum evaporated on an ITO anode as a hole injection layer material; the evaporation rate ratio of the compound 1 to the P-dopant is 97, and the thickness is 10nm;
c. HTL: to be provided with
The compound 1 provided in the above example, as a hole transport layer, was vacuum evaporated on HIL at 130 nm;
d. EBL: to be provided with
Vacuum evaporating 10nm compound EB-1 on HTL as EBL (also called luminescence auxiliary layer);
e. EML: on the EBL, in
The evaporation rate of (1), wherein a Host material (Host-1) and a Dopant material (Dopant-1) with a thickness of 20nm are vacuum evaporated to form a luminescent layer, and the ratio of the evaporation rates of Host-1 and Dopant-1 is 98;
f. HBL: to be provided with
The evaporation rate of (1) is that a hole blocking material HB with the thickness of 5.0nm is evaporated on an EML in vacuum;
g. ETL: to be provided with
The evaporation rate of (1), wherein ET-1 and Liq with the thickness of 35nm are vacuum evaporated on the HBL to be used as electron transport layers, and the evaporation rate ratio of ET-1 to Liq is 50;
h. EIL: to be provided with
The evaporation rate of (2) and 1.0nm of a Yb film layer is evaporated on the ETL to form an electron injection layer;
i. cathode: to be provided with
The evaporation rate of (3) is that magnesium and silver with the thickness of 18nm are evaporated on the EIL, and the ratio of the evaporation rate to the evaporation rate of 1:9 is obtained to obtain a cathode;
j. light extraction layer: to be provided with
The evaporation rate of (3), CPL with a thickness of 70nm was vacuum evaporated on the cathode as a light extraction layer;
k. then packaging the evaporated substrate; firstly, coating the cleaned cover plate by using UV glue through gluing equipment, then moving the coated cover plate to a pressing working section, placing the evaporated substrate on the upper end of the cover plate, finally, attaching the substrate and the cover plate under the action of attaching equipment, and simultaneously, finishing illumination curing of the UV glue to obtain the organic electroluminescent device.
The structure of the compound referred to in device example 1 is as follows:
device examples 2 to 45
An organic electroluminescent device which differs from device example 1 only in that the materials in the HIL and HTL (compound 1, steps b, c) were replaced by compounds 2, 3,4, 8, 13, 14, 21, 26, 28, 29, 30, 31, 42, 43, 45, 47, 49, 54, 55, 80, 84, 87, 90, 103, 106, 107, 114, 115, 123, 132, 134, 135, 145, 147, 160, 166, 175, 210, 211, 233, 234, 134, 245, 252; the ratio of the evaporation rate of the foregoing compound to that of P-dopant in HIL was the same as in example 1; the other levels, thicknesses, materials and fabrication methods were the same as in device example 1.
Comparative device examples 1 to 6
An organic electroluminescent device which differs from device example 1 only in that the materials in the HIL and HTL (compound 1, steps b, c) were replaced by comparative compounds a, b, c, d, e, f as shown below; the other levels, thicknesses, materials, and fabrication methods were the same as in device example 1.
Testing the performance of the device:
the driving voltage (V) and the luminous efficiency (current efficiency, cd/A) of the organic electroluminescent devices provided in device examples 1-45 and device comparative examples 1-6 were measured at 1000 (nits) luminance by using IVL test equipment, and the lifetime of the devices was measured by using lifetime measuring equipment (model: D3000-96);
since the current efficiency is greatly influenced by chromaticity in a blue top emission device, the invention considers the influence factor of chromaticity on the efficiency, and defines the ratio of the current efficiency to the CIEy as a BI value, namely BI = luminous efficiency (cd/a)/CIEy;
the results of the measurements and calculations are shown in table 2 below:
TABLE 2
As can be seen from the performance test data in table 2, the device performance is changed by changing the substituents in the compound and the positions of the substituents; compared with the organic electroluminescent device provided by the comparative compound, the organic electroluminescent device prepared by using the organic electroluminescent compound provided by the invention as a hole transport material has the advantages that the luminous efficiency, the BI value and the service life are improved, and the driving voltage is reduced.
According to the invention, through the design and the cooperation of the structure of the mother core, the type of the group connected with the mother core, the type of the aromatic amine group and the bonding position, the organic electroluminescent compound is used as a material of an organic electroluminescent device, so that the hole transmission efficiency and the electron blocking capability are improved to a great extent, the charge balance of holes and electrons in a light-emitting layer is increased, and light emission is well formed in the light-emitting layer. Meanwhile, compared with the prior art (such as device comparative examples 1-6), the organic electroluminescent compound provided by the invention has the advantages that a specific spiro-type mother-nucleus structure is designed to be bonded with an aromatic amine group, and a heteroanthracene-type spiro ring is adopted as the spiro ring structure, so that the molecular weight is increased, the conjugation interval of the whole molecule is effectively shortened, and the triplet state energy level is improved due to the existence of SP3 hybridized C and X (such as ether bond when X is O) which does not participate in conjugation. The limiting effect on the outward expansion of the luminescent exciton is increased while the hole transmission capability is ensured, so that the luminous efficiency of the device is improved, the service life is prolonged, and the driving voltage is reduced.
The applicant states that the present invention is illustrated by the above examples to the organic electroluminescent compounds of the present invention and the preparation method and application thereof, but the present invention is not limited to the above examples, i.e. it is not meant that the present invention must be implemented by the above examples. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (10)
1. An organic electroluminescent compound, wherein the organic electroluminescent compound has a structure represented by formula I:
wherein L is 1 、L 2 Each independently selected from any one of a single bond, a substituted or unsubstituted C6-C30 arylene group, and a substituted or unsubstituted C3-C20 heteroarylene group;
Ar 1 、Ar 2 、Ar 3 、Ar 4 each independently selected from any one of substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C3-C20 heterocycloalkyl, substituted or unsubstituted C6-C30 aryl, and substituted or unsubstituted C3-C30 heteroaryl;
x is selected from CR 1 R 2 O or NR 3 Any one of the above;
y is selected from CR 4 R 5 Any one of O or S;
R 1 、R 2 、R 4 、R 5 each independently selected from any one of hydrogen, deuterium, halogen, cyano, and substituted or unsubstituted C1-C6 straight or branched alkyl;
R 3 any one selected from substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C3-C20 heterocycloalkyl, substituted or unsubstituted C6-C30 aryl, and substituted or unsubstituted C3-C30 heteroaryl;
L 1 、L 2 、Ar 1 、Ar 2 、Ar 3 、Ar 4 、R 1 、R 2 、R 3 、R 4 、R 5 the substituted substituent as described in (1), R 11 、R 12 Each independently selected from at least one of deuterium, cyano, halogen, nitro, hydroxyl, phosphate, boryl, silyl, C1-C10 linear or branched alkyl, C2-C10 alkenyl, C2-C10 alkynyl, C6-C20 aryl, C3-C20 heteroaryl, C1-C10 alkoxy, C3-C60 heteroarylamino, C6-C60 arylamino;
m and n are each independently 0 or 1;
when m and n are both 0, X is NR 3 Said R is 3 Is any one of R 'substituted C3-C30 cycloalkyl, R' substituted C3-C20 heterocycloalkyl, R 'substituted C6-C30 aryl and R' substituted C3-C30 heteroaryl; r' is selected from at least one of C3-C60 heteroaryl amino and C6-C60 aryl amino;
s 1 、s 2 each independently selected from integers from 0 to 4.
2. The organic electroluminescence according to claim 1A luminescent compound, characterized in that s is 1 And s 2 Are all 0;
preferably, the organic electroluminescent compound has a structure represented by any one of formula I-1, formula I-2, formula I-3 or formula I-4:
wherein L is 1 、L 2 、Ar 1 、Ar 2 、Ar 3 、Ar 4 X, Y has the same limitations as formula I;
R 3 is any one of R 'substituted C3-C30 cycloalkyl, R' substituted C3-C20 heterocycloalkyl, R 'substituted C6-C30 aryl, R' substituted C3-C30 heteroaryl;
r' is at least one selected from C3-C60 heteroaryl amino and C6-C60 aryl amino.
3. The organic electroluminescent compound according to claim 1 or 2, wherein L is 1 、L 2 Each independently selected from any one of a single bond, a substituted or unsubstituted C6-C18 arylene group, and a substituted or unsubstituted C3-C18 heteroarylene group; l is 1 、L 2 Wherein each of the substituted substituents is independently at least one selected from the group consisting of C1-C10 linear or branched alkyl, C6-C20 aryl, and C3-C20 heteroaryl;
preferably, said L 1 、L 2 Each independently selected from the group consisting of a single bond,
Any one of the above; the dotted line represents the attachment site of the group.
4. The organic electroluminescent compound according to any one of claims 1 to 3, wherein Ar is Ar 1 、Ar 2 、Ar 3 、Ar 4 Each independently selected from any one of the following substituted or unsubstituted groups:
wherein the dotted line represents the attachment site of the group;
Ar 11 any one selected from C6-C18 aryl and C3-C18 heteroaryl;
Z 1 selected from O, S, NR 21 Or CR 22 R 23 Any one of the above;
R 21 、R 22 、R 23 each independently selected from any one of C1-C10 straight chain or branched chain alkyl, C6-C20 aryl or C3-C20 heteroaryl;
the substituted substituent is selected from at least one of C1-C6 straight-chain or branched alkyl;
preferably, ar is 11 Any one selected from phenyl, naphthyl, phenanthryl, anthracyl, dibenzofuranyl, dibenzothienyl, dimethylfluorenyl, carbazolyl, and N-phenylcarbazolyl;
preferably, said R is 21 Is C6-C18 aryl, further preferably phenyl;
preferably, said R is 22 、R 23 Each independently selected from C1-C6 linear or branched alkyl groups, further preferably methyl groups.
5. The organic electroluminescent compound according to any one of claims 1 to 4, wherein Ar is Ar 1 、Ar 2 、Ar 3 、Ar 4 Each independentlyAny one selected from the following groups:
wherein the dotted line represents the attachment site of the group;
R 21 is selected from any one of C6-C20 aryl or C3-C20 heteroaryl, preferably C6-C18 aryl, and more preferably phenyl.
6. The organic electroluminescent compound according to any one of claims 1 to 5, wherein R is 1 、R 2 、R 4 、R 5 Each independently selected from any one of C1-C6 straight chain or branched chain alkyl, preferably methyl;
preferably, said R is 3 Any one selected from unsubstituted or R 'substituted C6-C30 aryl, wherein R' is at least one selected from C6-C60 arylamino;
preferably, said R is 3 Is composed of
Ar is 21 、Ar 22 Each independently selected from C6-C20 aryl, preferably any one of phenyl, naphthyl, biphenyl, terphenyl, naphthylphenyl or phenylnaphthyl.
7. The organic electroluminescent compound according to any one of claims 1 to 6, wherein the organic electroluminescent compound is selected from any one of the following structures 1 to 256:
8. a method for producing an organic electroluminescent compound according to any one of claims 1 to 7, comprising the steps of:
(1) Reacting the compound A with the compound B to obtain a compound C; carrying out a ring closure reaction on the compound C to obtain an intermediate D;
the reaction formula is as follows:
(2) Carrying out coupling reaction on the intermediate D obtained in the step (1) and an arylamine compound to obtain the organic electroluminescent compound; the arylamine compound is a compound E and/or a compound F;
the compound E has the structure
The compound F has the structure
When the L is 1 Not being a single bond and/or L 2 When not a single bond, the coupling reaction in step (2) further comprises a step (1'): reacting the intermediate D with a bridging compound to obtain an intermediate D'; carrying out coupling reaction on the intermediate D' and an arylamine compound to obtain the organic electroluminescent compound;
the bridging compound is
And/or
Said intermediate D' is
Wherein L is 1 、L 2 、Ar 1 、Ar 2 、Ar 3 、Ar 4 、X、Y、R 11 、R 12 、m、n、s 1 、s 2 Having the same limitations as formula I;
Hal 1 、Hal 2 、Hal 3 、Hal 4 、Hal 5 each independently selected from halogen.
9. Use of an organic electroluminescent compound as claimed in any of claims 1 to 7 in an electronic device;
preferably, the electronic device includes an organic electroluminescent device, an organic solar cell, electronic paper, an organic photoreceptor, or an organic thin film transistor;
preferably, the organic electroluminescent compounds are used as hole transport materials for electronic devices.
10. An organic electroluminescent device, characterized in that it comprises a first electrode, a second electrode and at least one organic layer arranged between said first and second electrodes; the organic layer comprises at least one organic electroluminescent compound as claimed in any one of claims 1 to 7;
preferably, the organic layer comprises a hole transport layer comprising at least one organic electroluminescent compound as claimed in any one of claims 1 to 7.
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| CN116041268A (en) * | 2023-02-10 | 2023-05-02 | 吉林奥来德光电材料股份有限公司 | Organic compound and application thereof |
| CN116987054A (en) * | 2023-09-26 | 2023-11-03 | 吉林奥来德光电材料股份有限公司 | Light-emitting auxiliary material, preparation method thereof, organic electroluminescent device and organic electroluminescent device |
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| WO2021227655A1 (en) * | 2020-05-11 | 2021-11-18 | 北京鼎材科技有限公司 | Compound, organic electroluminescent device, and display device |
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| CN116987054A (en) * | 2023-09-26 | 2023-11-03 | 吉林奥来德光电材料股份有限公司 | Light-emitting auxiliary material, preparation method thereof, organic electroluminescent device and organic electroluminescent device |
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