WO2017099516A1 - Organic electroluminescent compound and organic electroluminescent device comprising the same - Google Patents

Organic electroluminescent compound and organic electroluminescent device comprising the same Download PDF

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Publication number
WO2017099516A1
WO2017099516A1 PCT/KR2016/014435 KR2016014435W WO2017099516A1 WO 2017099516 A1 WO2017099516 A1 WO 2017099516A1 KR 2016014435 W KR2016014435 W KR 2016014435W WO 2017099516 A1 WO2017099516 A1 WO 2017099516A1
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Prior art keywords
substituted
unsubstituted
alkyl
organic electroluminescent
aryl
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PCT/KR2016/014435
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French (fr)
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Hyun Kim
Ga-Won Lee
Sung-Woo Jang
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Rohm And Haas Electronic Materials Korea Ltd.
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Priority claimed from KR1020160165699A external-priority patent/KR20170069151A/en
Application filed by Rohm And Haas Electronic Materials Korea Ltd. filed Critical Rohm And Haas Electronic Materials Korea Ltd.
Priority to US15/779,607 priority Critical patent/US10276808B2/en
Priority to CN201680069116.8A priority patent/CN108290914B/en
Publication of WO2017099516A1 publication Critical patent/WO2017099516A1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D221/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00
    • C07D221/02—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00 condensed with carbocyclic rings or ring systems
    • C07D221/04—Ortho- or peri-condensed ring systems
    • C07D221/18—Ring systems of four or more rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D491/00—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00
    • C07D491/02—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00 in which the condensed system contains two hetero rings
    • C07D491/04—Ortho-condensed systems
    • C07D491/044—Ortho-condensed systems with only one oxygen atom as ring hetero atom in the oxygen-containing ring
    • C07D491/048—Ortho-condensed systems with only one oxygen atom as ring hetero atom in the oxygen-containing ring the oxygen-containing ring being five-membered
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
    • C07D495/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
    • C07D495/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System
    • C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System compounds of the platinum group
    • C07F15/0033—Iridium compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/62—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing gallium, indium or thallium
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/30—Coordination compounds
    • H10K85/341—Transition metal complexes, e.g. Ru(II)polypyridine complexes
    • H10K85/342—Transition metal complexes, e.g. Ru(II)polypyridine complexes comprising iridium
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2101/00—Properties of the organic materials covered by group H10K85/00
    • H10K2101/10—Triplet emission
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers

Definitions

  • the present disclosure relates to organic electroluminescent compounds and an organic electroluminescent device comprising the same.
  • an electroluminescent device is a self-light-emitting device which has advantages in that it provides a wider viewing angle, a greater contrast ratio, and a faster response time.
  • the first organic EL device was developed by Eastman Kodak, by using small aromatic diamine molecules and aluminum complexes as materials for forming a light-emitting layer [Appl. Phys. Lett. 51, 913, 1987].
  • An organic electroluminescent device has a structure comprising an anode, a cathode, and an organic layer between the anode and the cathode, wherein the organic layer may comprise a hole injection layer, a hole transport layer, an electron blocking layer, a light-emitting layer, a hole blocking layer, an electron transport layer, an electron injection layer, etc.
  • OLED organic electroluminescent device
  • when a voltage is applied holes and electrons are injected from the anode and the cathode, respectively, to the light-emitting layer, in which excitons having high energies are formed by a recombination of the holes and the electrons.
  • the excition s energy puts the organic luminescent compound in an excited state, and light is emitted by energy released while returning from the excited state to a ground state. Accordingly, the most important factor determining luminous efficiency in an organic electroluminescent device is a light-emitting material.
  • the EL material can be categorized into a host material and a dopant material according to their functions.
  • a device having the most excellent EL characteristic has a structure comprising a light-emitting layer formed by doping a dopant to a host.
  • a host/dopant system is for increasing light-emitting efficiency by energy transfer from a host to a dopant.
  • the host and dopant materials greatly influence the efficiency and lifespan of the EL device when using a dopant/host material system.
  • iridium(III) complexes have been widely known as a dopant of phosphorescent materials, and bis(2-(2’-benzothienyl)-pyridinato-N,C3’)iridium(acetylacetonate) ((acac)Ir(btp) 2 ), tris(2-phenylpyridine)iridium (Ir(ppy) 3 ) and bis(4,6-difluorophenylpyridinato-N,C2)picolinate iridium (Firpic) as red, green, and blue light-emitting material, respectively.
  • saturated color In particular, in order to realize full color display, to which an organic EL device is applied, a pixel configured to emit a particular color called “saturated” color is required. In particular, saturated red, green, and blue pixels are required. These saturated colors can be measured by using a CIE coordinate publicly known in the art.
  • a color purity of each of red, green, and blue should be high.
  • red color the closer to the red color coordinate near 0.680 (CIE X-coordinate standard), the higher the color purity is. Accordingly, a requirement for a suitable dopant compound is increased.
  • U.S. patent No. 7,951,472 discloses iridium complexes having 2-phenylquinoline-based ligand as a dopant compound of OLED, but iridium complexes having fused azabenzofluorene is not disclosed.
  • the object of the present disclosure is first, to provide compounds capable of producing an organic electroluminescent device with excellent color purity and efficiency, and second, to provide an organic electroluminescent device comprising the compounds.
  • X represents CR 11 R 12 , O or S
  • R 1 to R 3 each independently, represent hydrogen, deuterium, a substituted or unsubstituted (C1-C10)alkyl, or a substituted or unsubstituted (C6-C30)aryl;
  • R 4 represents hydrogen, or a substituted or unsubstituted (C1-C10)alkyl
  • R 11 and R 12 each independently, represent a substituted or unsubstituted (C1-C10)alkyl, or a substituted or unsubstituted (C6-C30)aryl;
  • n and n each independently, represent an integer of 0 to 4.
  • o represents an integer of 0 to 2;
  • each of R 1 , each of R 2 , or each of R 3 may be the same or different;
  • L represents or ;
  • R 5 to R 7 each independently, represent hydrogen, deuterium, a substituted or unsubstituted (C1-C10)alkyl, or a substituted or unsubstituted (C6-C30)aryl;
  • R 8 to R 10 each independently, represent hydrogen, deuterium, a substituted or unsubstituted (C1-C10)alkyl, or a substituted or unsubstituted (C6-C30)aryl; or may be linked to an adjacent substituent to form a substituted or unsubstituted 9- to 20-membered heteroaryl including the pyridine ring linked to R 8 to R 10 ; and
  • the heteroaryl may comprise one or more hetero atoms selected from a nitrogen, an oxygen, and a sulfur, in addition to the nitrogen atom of the pyridine ring.
  • an organic electroluminescent device showing significant improvement in color purity and efficiency can be prepared.
  • the present disclosure relates to a compound represented by formula 1 above, an organic electroluminescent material comprising said compound, and an organic electroluminescent device comprising said compound.
  • (C1-C10)alkyl indicates a linear or branched alkyl having 1 to 10 carbon atoms, in which the number of carbon atoms is preferably 1 to 5, and more preferably 1 to 4, and includes, as a specific example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 2,2-dimethylpropyl, and 1-ethylpropyl.
  • (C6-C30)aryl indicates a monocyclic or fused ring radical derived from an aromatic hydrocarbon having 6 to 30 ring backbone carbon atoms, in which the number of ring backbone carbon atoms is preferably 6 to 20, more preferably 6 to 15, and includes, as a specific example, phenyl, biphenyl, terphenyl, naphthyl, binaphthyl, phenylnaphthyl, naphthylphenyl, phenylterphenyl, fluorenyl, phenylfluorenyl, benzofluorenyl, dibenzofluorenyl, phenanthrenyl, phenylphenanthrenyl, anthracenyl, indenyl, triphenylenyl, pyrenyl, tetracenyl, perylenyl, chrysenyl, naphthacenyl, fluoranthenyl, etc.
  • 3- to 30-membered heteroaryl indicates an aryl group having 3 to 30 ring backbone atoms, including at least one hetero atom selected from the group consisting of B, N, O, S, Si, and P, in which, the number of ring backbone atoms is preferably 9 to 20, and more preferably 9 to 16, and the number of hetero atoms is preferably 1 to 4.
  • heteroaryl may be a monocyclic ring, or a fused ring condensed with at least one benzene ring; may be partially saturated; and the heteroaryl may be one formed by linking at least one heteroaryl or aryl group to a heteroaryl group via a single bond(s); and includes a monocyclic ring-type heteroaryl such as furyl, thiophenyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, thiadiazolyl, isothiazolyl, isoxazolyl, oxazolyl, oxadiazolyl, triazinyl, tetrazinyl, triazolyl, tetrazolyl, furazanyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, etc., and a fused ring-type heteroaryl such as benzofuranyl, benzothioph
  • substituted in the expression “substituted or unsubstituted” means that hydrogen atom in a certain functional group is replaced with another atom or another functional group, i.e. a substituent.
  • the substituents of the substituted alkyl, the substituted aryl, or the substituted heteroaryl each independently, are at least one selected from the group consisting of deuterium; a halogen; a cyano; a carboxyl; a nitro; a hydroxyl; a (C1-C30)alkyl; a halo(C1-C30)alkyl; a (C2-C30)alkenyl; a (C2-C30)alkynyl; a (C1-C30)alkoxy; a (C1-C30)alkylthio; a (C3-C30)cycloalkyl; a (C3-C30)cycl
  • X represents CR 11 R 12 , O or S.
  • R 1 to R 3 are each independently hydrogen, deuterium, a substituted or unsubstituted (C1-C10)alkyl, or a substituted or unsubstituted (C6-C30)aryl; preferably, hydrogen, a substituted or unsubstituted (C1-C5)alkyl, or a substituted or unsubstituted (C6-C20)aryl; more preferably, hydrogen, an unsubstituted (C1-C4)alkyl, or a (C6-C15)aryl unsubstituted or substituted with a (C1-C4)alkyl.
  • R 1 to R 3 may be each independently hydrogen, methyl, isobutyl, tert-butyl, or phenyl unsubstituted or substituted with methyl, isobutyl, or tert-butyl.
  • R 4 represents hydrogen, or a substituted or unsubstituted (C1-C10)alkyl; and preferably, hydrogen.
  • L represents or .
  • R 5 to R 7 are each independently hydrogen, deuterium, a substituted or unsubstituted (C1-C10)alkyl, or a substituted or unsubstituted (C6-C30)aryl; preferably, hydrogen, a substituted or unsubstituted (C1-C5)alkyl, or a substituted or unsubstituted (C6-C15)aryl; more preferably, hydrogen, an unsubstituted (C1-C15)alkyl, or an unsubstituted (C6-C15)aryl.
  • L may be hydrogen, methyl, isobutyl, tert-butyl, pentyl, or phenyl.
  • R 8 to R 10 may be each independently hydrogen, deuterium, a substituted or unsubstituted (C1-C10)alkyl, or a substituted or unsubstituted (C6-C30)aryl or at least two of R 8 to R 10 may be linked to each other as an adjacent substituent to form a substituted or unsubstituted 9- to 20-membered heteroaryl including the pyridine ring linked to R 8 to R 10 , and the heteroaryl may comprise one or more hetero atoms selected from a nitrogen, an oxygen, and a sulfur in addition to the nitrogen atom of the pyridine ring; preferably, hydrogen, a substituted or unsubstituted (C1-C5)alkyl, or a substituted or unsubstituted (C6-C20)aryl or at least two of R 8 to R 10 may be linked to an adjacent substituent to form a 9- to 16-membered heteroaryl which includes the pyridine
  • R 11 and R 12 are each independently, a substituted or unsubstituted (C1-C10)alkyl, or a substituted or unsubstituted (C6-C30)aryl.
  • R 11 and R 12 each independently may be preferably a substituted or unsubstituted (C1-C5)alkyl, or a substituted or unsubstituted (C6-C20)aryl; more preferably, a (C1-C4)alkyl unsubstituted or substituted with deuterium, or an unsubstituted (C6-C15)aryl; and for example, methyl unsubstituted or substituted with deuterium, ethyl unsubstituted or substituted with deuterium, or phenyl.
  • n and n each independently, represent an integer of 0 to 4; o represents an integer of 0 to 2; and where m, n or o is an integer of 2 or more, each of R 1 , each of R 2 , or each of R 3 may be the same or different.
  • X may represent CR 11 R 12 , O or S;
  • R 1 to R 3 may be each independently hydrogen, a substituted or unsubstituted (C1-C5)alkyl, or a substituted or unsubstituted (C6-C20)aryl;
  • R 4 may represent hydrogen;
  • L may represent ;
  • R 5 to R 7 may be each independently hydrogen, a substituted or unsubstituted (C1-C5)alkyl, or a substituted or unsubstituted (C6-C15)aryl;
  • R 11 and R 12 may be each independently, a substituted or unsubstituted (C1-C5)alkyl, or a substituted or unsubstituted (C6-C20)aryl;
  • m and n each independently, represent an integer of 0 to 4;
  • o represents an integer of 0 to 2; and where m, n or o is an integer of 2 or more, each of R 1 , each
  • X may represent CR 11 R 12 , O or S;
  • R 1 to R 3 may be each independently hydrogen, a substituted or unsubstituted (C1-C5)alkyl, or a substituted or unsubstituted (C6-C20)aryl;
  • R 4 may represent hydrogen;
  • L may represent ;
  • R 8 to R 10 may be each independently hydrogen, a substituted or unsubstituted (C1-C5)alkyl, or a substituted or unsubstituted (C6-C20)aryl, or at least two of R 8 to R 10 may be linked to each other as an adjacent substituent to form a 9- to 16-membered heteroaryl which includes the pyridine ring linked to R 8 to R 10 and is unsubstitued or substituted with a (C1-C15)alkyl, and the heteroaryl may comprise one or more hetero atoms selected from a nitrogen, an oxygen, and a sulfur in addition to a
  • X may represent CR 11 R 12 , O or S;
  • R 1 to R 3 may be each independently hydrogen, an unsubstituted (C1-C4)alkyl, or a (C6-C15)aryl unsubstituted or substituted with a (C1-C4)alkyl;
  • R 4 may represent hydrogen;
  • L may represent ;
  • R 5 to R 7 may be each independently hydrogen, an unsubstituted (C1-C15)alkyl, or an unsubstituted (C6-C15)aryl;
  • R 11 and R 12 may be each independently a (C1-C4)alkyl unsubstituted or substituted with deuterium, or an unsubstituted (C6-C15)aryl;
  • m and n each independently, may represent an integer of 0 to 4;
  • o may represent an integer of 0 to 2; and where m, n or o is an integer of 2 or more, each of R 1
  • X may represent CR 11 R 12 , O or S;
  • R 1 to R 3 may be each independently hydrogen, an unsubstituted (C1-C4)alkyl, or a (C6-C15)aryl unsubstituted or substituted with a (C1-C4)alkyl;
  • R 4 may represent hydrogen;
  • L may represent ;
  • R 8 to R 10 may be each independently hydrogen, methyl, or phenyl substituted with methyl, or at least two of R 8 to R 10 may be linked to each other as an adjacent substituent to form a quinoline which includes the pyridine ring linked to R 8 to R 10 and is unsubstituted or substituted with a (C1-C6)alkyl;
  • R 11 and R 12 may be each independently, a (C1-C4)alkyl unsubstituted or substituted with deuterium, or an unsubstituted (C6-C15)aryl;
  • m and n each independently, may
  • X may represent CR 11 R 12 , O or S;
  • R 1 to R 3 may be each independently hydrogen, methyl, isobutyl, tert-butyl, or phenyl unsubstituted or substituted with methyl, isobutyl, or tert-butyl;
  • R 4 may represent hydrogen;
  • L may represent ;
  • R 5 to R 7 may be each independently hydrogen, methyl, isobutyl, tert-butyl, pentyl, or phenyl;
  • R 11 and R 12 may be each independently methyl unsubstituted or substituted with deuterium, ethyl unsubstituted or substituted with deuterium, or phenyl;
  • m and n each independently, may represent an integer of 0 to 4;
  • o may represent an integer of 0 to 2; and where m, n or o is an integer of 2 or more, each of R 1 , each of R 2 , or each of R
  • X may represent CR 11 R 12 , O or S;
  • R 1 to R 3 may be each independently hydrogen, methyl, isobutyl, tert-butyl, or phenyl unsubstituted or substituted with methyl, isobutyl, or tert-butyl;
  • R 4 may represent hydrogen;
  • L may represent ;
  • R 8 to R 10 may be each independently hydrogen, methyl, or phenyl substituted with methyl; or at least two of R 8 to R 10 may be linked to each other as an adjacent substituent to form a quinoline which includes the pyridine ring linked to R 8 to R 10 and is unsubstituted or substituted with a (C1-C6)alkyl;
  • R 11 and R 12 may be each independently methyl unsubstituted or substituted with deuterium, ethyl unsubstituted or substituted with deuterium, or phenyl;
  • m and n each independently, may represent an integer of
  • the compound represented by formula 1 includes the following compounds, but is not limited thereto:
  • the compound according to the present disclosure may be produced by a synthetic method known to a person skilled in the art. For example, it may be produced by the following reaction scheme 1:
  • R 1 to R 7 , X, m, n, and o are as defined in formula 1.
  • the present disclosure also discloses an organic electroluminescent material comprising the compound of formula 1, and an organic electroluminescent device comprising the material.
  • the organic electroluminescent material may consist of the organic electroluminescent compound of the present disclosure as a sole compound, or may further comprise conventional materials generally used in organic electroluminescent materials.
  • the organic electroluminescent device of the present disclosure may comprise a first electrode, a second electrode, and at least one organic layer between the first and second electrodes.
  • the organic layer may comprise at least one organic electroluminescent compound of formula 1.
  • the organic layer may comprise a light-emitting layer, and may further comprise at least one layer selected from a hole injection layer, a hole transport layer, a hole auxiliary layer, a light-emitting auxiliary layer, an electron transport layer, an electron injection layer, an interlayer, a hole blocking layer, an electron buffer layer, and an electron blocking layer.
  • the light-emitting auxiliary layer may be placed between the anode and the light-emitting layer, or the cathode and the light-emitting layer, which may be used for facilitating the injection and/or transport of the hole or for blocking the overflow of the electron when placed between the anode and the light-emitting layer, or which may be used for facilitating the injection and/or transport of the electron or for blocking the overflow of the hole when placed between the cathode and the light-emitting layer.
  • the hole auxiliary layer is placed between the hole transport layer (or the hole injection layer) and the light-emitting layer, which may exhibit facilitating a transport rate (or injection rate) of a hole or blocking a hole, thereby controlling a charge balance.
  • the electron blocking layer is placed between the hole transport layer (or the hole injection layer) and the light-emitting layer, which prevents light leakage by blocking the overflow of the electron from the light-emitting layer and confining excitons in the light-emitting layer.
  • the additional hole transport layer(s) which is (are) included in addition to the hole transport layer, may be used as the hole auxiliary layer or electron blocking layer.
  • the hole auxiliary layer or the electron blocking layer provides excellent efficiencies and improved lifespan of an organic electroluminescent device.
  • the compound represented by formula 1 of the present disclosure is a dopant material, which may be included in the light-emitting layer.
  • the light-emitting layer may further include one or more host materials.
  • the host compounds which are capable of being used with the compound of the present disclosure may be the following compounds represented by formula 2.
  • Ma represents a substituted or unsubstituted, nitrogen-containing 5- to 11-membered heteroaryl
  • La represents a single bond, or a substituted or unsubstituted (C6-C30)arylene
  • Xa to Xh each independently, represent hydrogen, deuterium, a halogen, a cyano, a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C2-C30)alkenyl, a substituted or unsubstituted (C2-C30)alkynyl, a substituted or unsubstituted (C3-C30)cycloalkyl, a substituted or unsubstituted (C6-C60)aryl, a substituted or unsubstituted 3- to 30-membered heteroaryl, a substituted or unsubstituted tri(C1-C30)alkylsilyl, a substituted or unsubstituted tri(C6-C30)arylsilyl, a substituted or unsubstituted di(C1-C30)alkyl(C6-C30)arylsilyl, a substituted or un
  • the heteroaryl contains at least one hetero atom selected from B, N, O, S, Si, and P.
  • the substituents of a substituted alkyl, a substituted alkenyl, a substituted alkynyl, a substituted cycloalkyl, a substituted aryl, a substituted heteroaryl, a substituted trialkylsilyl, a substituted triarylsilyl, a substituted dialkylarylsilyl, a substituted alkyldiarylsilyl, a substituted alkylarylamino, a substituted monoarylamino, a substituted diarylamino, or a substituted mono- or polycyclic, alicyclic or aromatic ring may be each independently, at least one selected from the group consisting of deuterium; a halogen; a cyano; a carboxyl; a nitro; a hydroxyl; a (C1-C30)alkyl; a halo(C1-C30)alkyl; a (C2-C30)alkenyl; a (C2-
  • La may represent preferably, a single bond, or a substituted or unsubstituted (C6-C12)arylene; and more preferably, a single bond, or a (C6-C12)arylene unsubstituted or substituted with a tri(C6-C10)arylsilyl.
  • La may represent a single bond, a substituted or unsubstituted phenylene, a substituted or unsubstituted naphthylene, or a substituted or unsubstituted biphenylene.
  • Ma may represent preferably, a substituted or unsubstituted, nitrogen-containing 5- to 11-membered heteroaryl; and more preferably, a nitrogen-containing 6- to 11-membered heteroaryl unsubstitued or substituted with a cyano, a (C1-C6)alkyl, a tri(C6-C12)arylsilyl, a (C6-C18)aryl, or a 5- to 15-membered heteroaryl.
  • Ma may represent a substituted or unsubstituted pyrrolyl, a substituted or unsubstituted imidazolyl, a substituted or unsubstituted pyrazolyl, a substituted or unsubstituted triazinyl, a substituted or unsubstituted tetrazinyl, a substituted or unsubstituted triazolyl, a substituted or unsubstituted tetrazolyl, a substituted or unsubstituted pyridyl, a substituted or unsubstituted pyrazinyl, a substituted or unsubstituted pyrimidinyl, a substituted or unsubstituted pyridazinyl, a substituted or unsubstituted benzimidazolyl, a substituted or unsubstituted isoindolyl, a substituted or unsubstituted indolyl,
  • Ma may represent a substituted or unsubstituted triazinyl, a substituted or unsubstituted pyrimidinyl, a substituted or unsubstituted pyridyl, a substituted or unsubstituted quinolyl, a substituted or unsubstituted isoquinolyl, a substituted or unsubstituted quinazolinyl, a substituted or unsubstituted naphthyridinyl, or a substituted or unsubstituted quinoxalinyl.
  • Xa to Xh each independently, may represent hydrogen, a cyano, a substituted or unsubstituted (C6-C15)aryl, a substituted or unsubstituted 6- to 20-membered heteroaryl, or a substituted or unsubstituted tri(C6-C15)arylsilyl; or may be linked to an adjacent substituent(s) to form a substituted or unsubstituted 6- to 20-membered, mono- or polycyclic aromatic ring, whose carbon atom(s) may be replaced with at least one hetero atom selected from the group consisting of nitrogen, oxygen, and sulfur.
  • Xa to Xh each independently, may represent hydrogen, a cyano, a (C6-C15)aryl unsubstituted or substituted with a tri(C6-C12)arylsilyl, or a 10- to 20-membered heteroaryl unsubstituted or substituted with a (C6-C12)aryl; or may be linked to an adjacent substituent(s) to form a substituted or unsubstituted benzene, a substituted or unsubstituted indole, a substituted or unsubstituted benzoindole, a substituted or unsubstituted indene, a substituted or unsubstituted benzofuran, or a substituted or unsubstituted benzothiophene.
  • At least one of Xa to Xh may represent a substituted or unsubstituted dibenzothiophene, a substituted or unsubstituted dibenzofuran, a substituted or unsubstituted carbazole, or a substituted or unsubstituted benzocarbazole; or may be linked to an adjacent substituent(s) to form a substituted or unsubstituted benzene, a substituted or unsubstituted indole, a substituted or unsubstituted benzindole, a substituted or unsubstituted indene, a substituted or unsubstituted benzofuran, or a substituted or unsubstituted benzothiophene.
  • the compound of formula 2 includes the following, but is not limited thereto.
  • a combination of the compound represented by formula 1 and the compound represented by formula 2, and an organic electroluminescent device comprising the combination are provided.
  • a mixture or a composition for preparing an organic electroluminescent device comprises the compound represented by formula 1.
  • the mixture or composition may be for preparing a light-emitting layer of an organic electroluminescent device.
  • the mixture or composition may comprise a host compound represented by formula 2, besides the compound of the present disclosure.
  • the mixture or composition may comprise the compound represented by formula 1, which is combined with a host compound represented by formula 2.
  • the mixture or composition may further comprise a conventional material which is included for preparing an organic electroluminescent device.
  • the organic electroluminescent device of the present disclosure comprises the compound represented by formula 1, at the same time, the organic electroluminescent device comprises at least one compound selected from the group consisting of arylamine-based compounds and styrylarylamine-based compounds.
  • the organic layer may further comprise at least one metal selected from the group consisting of metals of Group 1, metals of Group 2, transition metals of the 4 th period, transition metals of the 5 th period, lanthanides and organic metals of the d-transition elements of the Periodic Table, or at least one complex compound, besides the compound represented by formula 1.
  • the organic electroluminescent device of the present disclosure may emit white light by further comprising at least one light-emitting layer, which comprises a blue electroluminescent compound, a red electroluminescent compound or a green electroluminescent compound known in the art, besides the light-emitting layer of the present disclosure. If necessary, it may further comprise a yellow light-emitting layer or an orange light-emitting layer.
  • at least one light-emitting layer which comprises a blue electroluminescent compound, a red electroluminescent compound or a green electroluminescent compound known in the art, besides the light-emitting layer of the present disclosure. If necessary, it may further comprise a yellow light-emitting layer or an orange light-emitting layer.
  • a surface layer may be placed on an inner surface(s) of one or both electrode(s), selected from a chalcogenide layer, a metal halide layer, and a metal oxide layer.
  • a chalcogenide (includes oxides) layer of silicon or aluminum is preferably placed on an anode surface of an electroluminescent medium layer
  • a metal halide layer or a metal oxide layer is preferably placed on a cathode surface of an electroluminescent medium layer.
  • the chalcogenide includes SiO X (1 ⁇ X ⁇ 2), AlO X (1 ⁇ X ⁇ 1.5), SiON, SiAlON, etc.;
  • the metal halide includes LiF, MgF 2 , CaF 2 , a rare earth metal fluoride, etc.; and the metal oxide includes Cs 2 O, Li 2 O, MgO, SrO, BaO, CaO, etc.
  • a mixed region of an electron transport compound and a reductive dopant, or a mixed region of a hole transport compound and an oxidative dopant may be placed on at least one surface of a pair of electrodes.
  • the electron transport compound is reduced to an anion, and thus it becomes easier to inject and transport electrons from the mixed region to an electroluminescent medium.
  • the hole transport compound is oxidized to a cation, and thus it becomes easier to inject and transport holes from the mixed region to the electroluminescent medium.
  • the oxidative dopant includes various Lewis acids and acceptor compounds
  • the reductive dopant includes alkali metals, alkali metal compounds, alkaline earth metals, rare-earth metals, and mixtures thereof.
  • a reductive dopant layer may be employed as a charge generating layer to prepare an electroluminescent device having two or more light-emitting layers and emitting white light.
  • dry film-forming methods such as vacuum evaporation, sputtering, plasma and ion plating methods, or wet film-forming methods such as ink jet printing, nozzle printing, slot coating, spin coating, dip coating, and flow coating methods can be used.
  • a thin film can be formed by dissolving or diffusing materials forming each layer into any suitable solvent such as ethanol, chloroform, tetrahydrofuran, dioxane, etc.
  • the solvent can be any solvent where the materials forming each layer can be dissolved or diffused, and where there are no problems in film-formation capability.
  • OLED comprising the organic electroluminescent compound of the present disclosure was produced.
  • a transparent electrode indium tin oxide (ITO) thin film (10 ⁇ /sq) on a glass substrate for an organic light-emitting diode (OLED) (Geomatec) was subjected to an ultrasonic washing with acetone, ethanol, and distilled water, sequentially, and then was stored in isopropanol.
  • the ITO substrate was then mounted on a substrate holder of a vacuum vapor depositing apparatus.
  • HI-1 was introduced into a cell of the vacuum vapor depositing apparatus, and then the pressure in the chamber of said apparatus was controlled to 10 -6 torr.
  • HI-2 was introduced into another cell of the vacuum vapor depositing apparatus, and was evaporated by applying an electric current to the cell, thereby forming a second hole injection layer having a thickness of 5 nm on the first hole injection layer.
  • HT-1 was introduced into a cell of the vaccum vapor depositing apparatus, and was evaporated by applying an electric current to the cell, thereby forming a first hole transport layer having a thickness of 10 nm on the second hole injection layer.
  • HT-2 was introduced into another cell of the vacuum vapor depositing apparatus, and was evaporated by applying an electric current to the cell, thereby forming a second hole transport layer having a thickness of 60 nm on the first hole transport layer. Then, the light-emitting layer on the hole injection layers and the hole transport layers was formed as follows. Compound H2-16 was introduced into one cell of the vacuum vapor depositing apparatus as a host, and a dopant material shown in Table 1 below was introduced into another cell.
  • the host material was evaporated, and simultaneously, the dopant material was evaporated at different rates from the host material, so that the dopant was deposited in a doping amount of 3 wt% based on the total amount of the host and dopant to form a light-emitting layer having a thickness of 40 nm on the second hole transport layer.
  • ET-1 and EI-1 were introduced into two cells of the vacuum vapor depositing apparatus, respectively, and evaporated at a 1:1 rate to form an electron transport layer having a thickness of 30 nm on the light-emitting layer.
  • an Al cathode having a thickness of 80 nm was then deposited by another vacuum vapor deposition apparatus on the electron injection layer to produce OLED.
  • OLED was produced in the same manner as in Device Example 1-1, except that compound RD-1 below was used as a dopant for a light-emitting layer.
  • an organic electroluminescent compound of the present disclosure it is possible to provide an organic electroluminescent device with excellent efficiency and color purity compared to the conventional electroluminescent compound.
  • an azabenzo[b]fluorene ligand of the Device Example attributes the organic electroluminescent device to have better efficiency compared to the quinoline ligand of the Comparative Example.
  • the substituent alkyl substituent in the Device Example above
  • the substituent applies a steric hindrance to the octahedral structure of the iridium complex, thereby reducing Triplet-Triplet Annihilation to maximize the characteristic which improves efficiency.
  • the bond distance between the azabenzo[b]fluorene ligand and the iridium metal is shorter than the one between the azabenzo[a]fluorene ligand and the iridium metal. It can be predicted that the shorter the bond distance, the stronger the spin orbital coupling by an iridium atom is applied to have better efficiency.

Abstract

The present disclosure relates to an organic electroluminescent compound and an organic electroluminescent device comprising the same. The organic electroluminescent compound according to the present disclosure is capable of producing an organic electroluminescent device with reasonably improved color purity and efficiency.

Description

ORGANIC ELECTROLUMINESCENT COMPOUND AND ORGANIC ELECTROLUMINESCENT DEVICE COMPRISING THE SAME
The present disclosure relates to organic electroluminescent compounds and an organic electroluminescent device comprising the same.
Among display devices, an electroluminescent device (EL device) is a self-light-emitting device which has advantages in that it provides a wider viewing angle, a greater contrast ratio, and a faster response time. The first organic EL device was developed by Eastman Kodak, by using small aromatic diamine molecules and aluminum complexes as materials for forming a light-emitting layer [Appl. Phys. Lett. 51, 913, 1987].
An organic electroluminescent device (OLED) has a structure comprising an anode, a cathode, and an organic layer between the anode and the cathode, wherein the organic layer may comprise a hole injection layer, a hole transport layer, an electron blocking layer, a light-emitting layer, a hole blocking layer, an electron transport layer, an electron injection layer, etc. In the organic electroluminescent device, when a voltage is applied, holes and electrons are injected from the anode and the cathode, respectively, to the light-emitting layer, in which excitons having high energies are formed by a recombination of the holes and the electrons. The excition’s energy puts the organic luminescent compound in an excited state, and light is emitted by energy released while returning from the excited state to a ground state. Accordingly, the most important factor determining luminous efficiency in an organic electroluminescent device is a light-emitting material.
The EL material can be categorized into a host material and a dopant material according to their functions. Generally, a device having the most excellent EL characteristic has a structure comprising a light-emitting layer formed by doping a dopant to a host. A host/dopant system is for increasing light-emitting efficiency by energy transfer from a host to a dopant. The host and dopant materials greatly influence the efficiency and lifespan of the EL device when using a dopant/host material system.
Until now, iridium(III) complexes have been widely known as a dopant of phosphorescent materials, and bis(2-(2’-benzothienyl)-pyridinato-N,C3’)iridium(acetylacetonate) ((acac)Ir(btp)2), tris(2-phenylpyridine)iridium (Ir(ppy)3) and bis(4,6-difluorophenylpyridinato-N,C2)picolinate iridium (Firpic) as red, green, and blue light-emitting material, respectively.
However, considering EL characteristic requirements for a middle or large-sized panel of OLED, a development of a dopant compound of iridium complexes providing more excellent EL performance, such as long lifespan, high efficiency and high color purity, is still needed.
In particular, in order to realize full color display, to which an organic EL device is applied, a pixel configured to emit a particular color called “saturated” color is required. In particular, saturated red, green, and blue pixels are required. These saturated colors can be measured by using a CIE coordinate publicly known in the art.
In order to express more various colors, a color purity of each of red, green, and blue should be high. In case of red color, the closer to the red color coordinate near 0.680 (CIE X-coordinate standard), the higher the color purity is. Accordingly, a requirement for a suitable dopant compound is increased.
U.S. patent No. 7,951,472 discloses iridium complexes having 2-phenylquinoline-based ligand as a dopant compound of OLED, but iridium complexes having fused azabenzofluorene is not disclosed.
The object of the present disclosure is first, to provide compounds capable of producing an organic electroluminescent device with excellent color purity and efficiency, and second, to provide an organic electroluminescent device comprising the compounds.
As a result of intensive studies to achieve the technical objects above, the present inventors found that the object can be achieved by an organic electroluminescent compound represented by the following formula 1:
Figure PCTKR2016014435-appb-I000001
wherein
X represents CR11R12, O or S;
R1 to R3, each independently, represent hydrogen, deuterium, a substituted or unsubstituted (C1-C10)alkyl, or a substituted or unsubstituted (C6-C30)aryl;
R4 represents hydrogen, or a substituted or unsubstituted (C1-C10)alkyl;
R11 and R12, each independently, represent a substituted or unsubstituted (C1-C10)alkyl, or a substituted or unsubstituted (C6-C30)aryl;
m and n, each independently, represent an integer of 0 to 4;
o represents an integer of 0 to 2;
where m, n or o is an integer of 2 or more, each of R1, each of R2, or each of R3 may be the same or different;
L represents
Figure PCTKR2016014435-appb-I000002
or
Figure PCTKR2016014435-appb-I000003
;
where L is
Figure PCTKR2016014435-appb-I000004
,
R5 to R7, each independently, represent hydrogen, deuterium, a substituted or unsubstituted (C1-C10)alkyl, or a substituted or unsubstituted (C6-C30)aryl;
where L is
Figure PCTKR2016014435-appb-I000005
,
R8 to R10, each independently, represent hydrogen, deuterium, a substituted or unsubstituted (C1-C10)alkyl, or a substituted or unsubstituted (C6-C30)aryl; or may be linked to an adjacent substituent to form a substituted or unsubstituted 9- to 20-membered heteroaryl including the pyridine ring linked to R8 to R10; and
the heteroaryl may comprise one or more hetero atoms selected from a nitrogen, an oxygen, and a sulfur, in addition to the nitrogen atom of the pyridine ring.
By using a compound according to the present disclosure, an organic electroluminescent device showing significant improvement in color purity and efficiency can be prepared.
Hereinafter, the present disclosure will be described in detail. However, the following description is intended to explain the invention, and is not meant in any way to restrict the scope of the invention.
The present disclosure relates to a compound represented by formula 1 above, an organic electroluminescent material comprising said compound, and an organic electroluminescent device comprising said compound.
Hereinafter, the compound represented by formula 1 of the present disclosure will be specifically described in detail.
Herein, "(C1-C10)alkyl" indicates a linear or branched alkyl having 1 to 10 carbon atoms, in which the number of carbon atoms is preferably 1 to 5, and more preferably 1 to 4, and includes, as a specific example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 2,2-dimethylpropyl, and 1-ethylpropyl. Herein, “(C6-C30)aryl” indicates a monocyclic or fused ring radical derived from an aromatic hydrocarbon having 6 to 30 ring backbone carbon atoms, in which the number of ring backbone carbon atoms is preferably 6 to 20, more preferably 6 to 15, and includes, as a specific example, phenyl, biphenyl, terphenyl, naphthyl, binaphthyl, phenylnaphthyl, naphthylphenyl, phenylterphenyl, fluorenyl, phenylfluorenyl, benzofluorenyl, dibenzofluorenyl, phenanthrenyl, phenylphenanthrenyl, anthracenyl, indenyl, triphenylenyl, pyrenyl, tetracenyl, perylenyl, chrysenyl, naphthacenyl, fluoranthenyl, etc.
Herein, “3- to 30-membered heteroaryl” indicates an aryl group having 3 to 30 ring backbone atoms, including at least one hetero atom selected from the group consisting of B, N, O, S, Si, and P, in which, the number of ring backbone atoms is preferably 9 to 20, and more preferably 9 to 16, and the number of hetero atoms is preferably 1 to 4. Herein, heteroaryl may be a monocyclic ring, or a fused ring condensed with at least one benzene ring; may be partially saturated; and the heteroaryl may be one formed by linking at least one heteroaryl or aryl group to a heteroaryl group via a single bond(s); and includes a monocyclic ring-type heteroaryl such as furyl, thiophenyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, thiadiazolyl, isothiazolyl, isoxazolyl, oxazolyl, oxadiazolyl, triazinyl, tetrazinyl, triazolyl, tetrazolyl, furazanyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, etc., and a fused ring-type heteroaryl such as benzofuranyl, benzothiophenyl, isobenzofuranyl, dibenzofuranyl, dibenzothiophenyl, benzoimidazolyl, benzothiazolyl, benzoisothiazolyl, benzoisoxazolyl, benzoxazolyl, isoindolyl, indolyl, indazolyl, benzothiadiazolyl, quinolyl, isoquinolyl, cinnolinyl, quinazolinyl, quinoxalinyl, carbazolyl, phenoxazinyl, phenanthridinyl, benzodioxolyl, etc.
Herein, “substituted” in the expression “substituted or unsubstituted” means that hydrogen atom in a certain functional group is replaced with another atom or another functional group, i.e. a substituent. In R1 to R12 of formula 1 of the present disclosure, the substituents of the substituted alkyl, the substituted aryl, or the substituted heteroaryl each independently, are at least one selected from the group consisting of deuterium; a halogen; a cyano; a carboxyl; a nitro; a hydroxyl; a (C1-C30)alkyl; a halo(C1-C30)alkyl; a (C2-C30)alkenyl; a (C2-C30)alkynyl; a (C1-C30)alkoxy; a (C1-C30)alkylthio; a (C3-C30)cycloalkyl; a (C3-C30)cycloalkenyl; a 3- to 7-membered heterocycloalkyl; a (C6-C30)aryloxy; a (C6-C30)arylthio; a 3- to 30-membered heteroaryl unsubstituted or substituted with a (C6-C30)aryl; a (C6-C30)aryl unsubstituted or substituted with a (C1-C30)alkyl, a cyano, a 3- to 30-membered heteroaryl or a tri(C6-C30)arylsilyl; a tri(C1-C30)alkylsilyl; a tri(C6-C30)arylsilyl; a di(C1-C30)alkyl(C6-C30)arylsilyl; a (C1-C30)alkyldi(C6-C30)arylsilyl; an amino; a mono- or di- (C1-C30)alkylamino; a mono- or di- (C6-C30)arylamino; a (C1-C30)alkyl(C6-C30)arylamino; a (C1-C30)alkylcarbonyl; a (C1-C30)alkoxycarbonyl; a (C6-C30)arylcarbonyl; a di(C6-C30)arylboronyl; a di(C1-C30)alkylboronyl; a (C1-C30)alkyl(C6-C30)arylboronyl; a (C6-C30)aryl(C1-C30)alkyl; and a (C1-C30)alkyl(C6-C30)aryl; preferably, are each independently, deuterium or a (C1-C6)alkyl.
In formula 1, X represents CR11R12, O or S.
In formula 1, R1 to R3 are each independently hydrogen, deuterium, a substituted or unsubstituted (C1-C10)alkyl, or a substituted or unsubstituted (C6-C30)aryl; preferably, hydrogen, a substituted or unsubstituted (C1-C5)alkyl, or a substituted or unsubstituted (C6-C20)aryl; more preferably, hydrogen, an unsubstituted (C1-C4)alkyl, or a (C6-C15)aryl unsubstituted or substituted with a (C1-C4)alkyl. For example, R1 to R3 may be each independently hydrogen, methyl, isobutyl, tert-butyl, or phenyl unsubstituted or substituted with methyl, isobutyl, or tert-butyl.
In formula 1, R4 represents hydrogen, or a substituted or unsubstituted (C1-C10)alkyl; and preferably, hydrogen.
In formula 1, L represents
Figure PCTKR2016014435-appb-I000006
or
Figure PCTKR2016014435-appb-I000007
.
In formula 1, if L is
Figure PCTKR2016014435-appb-I000008
, R5 to R7 are each independently hydrogen, deuterium, a substituted or unsubstituted (C1-C10)alkyl, or a substituted or unsubstituted (C6-C30)aryl; preferably, hydrogen, a substituted or unsubstituted (C1-C5)alkyl, or a substituted or unsubstituted (C6-C15)aryl; more preferably, hydrogen, an unsubstituted (C1-C15)alkyl, or an unsubstituted (C6-C15)aryl. For example, L may be hydrogen, methyl, isobutyl, tert-butyl, pentyl, or phenyl.
In formula 1, if L is
Figure PCTKR2016014435-appb-I000009
, R8 to R10 may be each independently hydrogen, deuterium, a substituted or unsubstituted (C1-C10)alkyl, or a substituted or unsubstituted (C6-C30)aryl or at least two of R8 to R10 may be linked to each other as an adjacent substituent to form a substituted or unsubstituted 9- to 20-membered heteroaryl including the pyridine ring linked to R8 to R10, and the heteroaryl may comprise one or more hetero atoms selected from a nitrogen, an oxygen, and a sulfur in addition to the nitrogen atom of the pyridine ring; preferably, hydrogen, a substituted or unsubstituted (C1-C5)alkyl, or a substituted or unsubstituted (C6-C20)aryl or at least two of R8 to R10 may be linked to an adjacent substituent to form a 9- to 16-membered heteroaryl which includes the pyridine ring linked to R8 to R10 and is unsubstitued or substituted with a (C1-C15)alkyl, and the heteroaryl may comprise one or more hetero atoms selected from a nitrogen, an oxygen, and a sulfur in addition to the nitrogen atom of the pyridine ring; and for example, hydrogen, methyl, or phenyl substituted with methyl or at least two of R8 to R10 may be linked to each other as an adjacent substituent to form a quinoline which includes the pyridine ring linked to R8 to R10 and is unsubstituted or substituted with a (C1-C6)alkyl.
In formula 1, R11 and R12 are each independently, a substituted or unsubstituted (C1-C10)alkyl, or a substituted or unsubstituted (C6-C30)aryl. R11 and R12 each independently may be preferably a substituted or unsubstituted (C1-C5)alkyl, or a substituted or unsubstituted (C6-C20)aryl; more preferably, a (C1-C4)alkyl unsubstituted or substituted with deuterium, or an unsubstituted (C6-C15)aryl; and for example, methyl unsubstituted or substituted with deuterium, ethyl unsubstituted or substituted with deuterium, or phenyl.
In formula 1, m and n, each independently, represent an integer of 0 to 4; o represents an integer of 0 to 2; and where m, n or o is an integer of 2 or more, each of R1, each of R2, or each of R3 may be the same or different.
According to one embodiment of the present disclosure, in formula 1, X may represent CR11R12, O or S; R1 to R3 may be each independently hydrogen, a substituted or unsubstituted (C1-C5)alkyl, or a substituted or unsubstituted (C6-C20)aryl; R4 may represent hydrogen; L may represent
Figure PCTKR2016014435-appb-I000010
; R5 to R7 may be each independently hydrogen, a substituted or unsubstituted (C1-C5)alkyl, or a substituted or unsubstituted (C6-C15)aryl; R11 and R12 may be each independently, a substituted or unsubstituted (C1-C5)alkyl, or a substituted or unsubstituted (C6-C20)aryl; m and n, each independently, represent an integer of 0 to 4; o represents an integer of 0 to 2; and where m, n or o is an integer of 2 or more, each of R1, each of R2, or each of R3 may be the same or different.
According to another embodiment of the present disclosure, in formula 1, X may represent CR11R12, O or S; R1 to R3 may be each independently hydrogen, a substituted or unsubstituted (C1-C5)alkyl, or a substituted or unsubstituted (C6-C20)aryl; R4 may represent hydrogen; L may represent
Figure PCTKR2016014435-appb-I000011
; R8 to R10 may be each independently hydrogen, a substituted or unsubstituted (C1-C5)alkyl, or a substituted or unsubstituted (C6-C20)aryl, or at least two of R8 to R10 may be linked to each other as an adjacent substituent to form a 9- to 16-membered heteroaryl which includes the pyridine ring linked to R8 to R10 and is unsubstitued or substituted with a (C1-C15)alkyl, and the heteroaryl may comprise one or more hetero atoms selected from a nitrogen, an oxygen, and a sulfur in addition to a nitrogen atom of the pyridine ring; R11 and R12 may be each independently, a substituted or unsubstituted (C1-C5)alkyl, or a substituted or unsubstituted (C6-C20)aryl; m and n, each independently, may represent an integer of 0 to 4; o may represent an integer of 0 to 2; and where m, n or o is an integer of 2 or more, each of R1, each of R2, or each of R3 may be the same or different.
According to another embodiment of the present disclosure, in formula 1, X may represent CR11R12, O or S; R1 to R3 may be each independently hydrogen, an unsubstituted (C1-C4)alkyl, or a (C6-C15)aryl unsubstituted or substituted with a (C1-C4)alkyl; R4 may represent hydrogen; L may represent
Figure PCTKR2016014435-appb-I000012
; R5 to R7 may be each independently hydrogen, an unsubstituted (C1-C15)alkyl, or an unsubstituted (C6-C15)aryl; R11 and R12 may be each independently a (C1-C4)alkyl unsubstituted or substituted with deuterium, or an unsubstituted (C6-C15)aryl; m and n, each independently, may represent an integer of 0 to 4; o may represent an integer of 0 to 2; and where m, n or o is an integer of 2 or more, each of R1, each of R2, or each of R3 may be the same or different.
According to another embodiment of the present disclosure, in formula 1, X may represent CR11R12, O or S; R1 to R3 may be each independently hydrogen, an unsubstituted (C1-C4)alkyl, or a (C6-C15)aryl unsubstituted or substituted with a (C1-C4)alkyl; R4 may represent hydrogen; L may represent
Figure PCTKR2016014435-appb-I000013
; R8 to R10 may be each independently hydrogen, methyl, or phenyl substituted with methyl, or at least two of R8 to R10 may be linked to each other as an adjacent substituent to form a quinoline which includes the pyridine ring linked to R8 to R10 and is unsubstituted or substituted with a (C1-C6)alkyl; R11 and R12 may be each independently, a (C1-C4)alkyl unsubstituted or substituted with deuterium, or an unsubstituted (C6-C15)aryl; m and n, each independently, may represent an integer of 0 to 4; o may represent an integer of 0 to 2; and where m, n or o is an integer of 2 or more, each of R1, each of R2, or each of R3 may be the same or different.
According to another embodiment of the present disclosure, in formula 1, X may represent CR11R12, O or S; R1 to R3 may be each independently hydrogen, methyl, isobutyl, tert-butyl, or phenyl unsubstituted or substituted with methyl, isobutyl, or tert-butyl; R4 may represent hydrogen; L may represent
Figure PCTKR2016014435-appb-I000014
; R5 to R7 may be each independently hydrogen, methyl, isobutyl, tert-butyl, pentyl, or phenyl; R11 and R12 may be each independently methyl unsubstituted or substituted with deuterium, ethyl unsubstituted or substituted with deuterium, or phenyl; m and n, each independently, may represent an integer of 0 to 4; o may represent an integer of 0 to 2; and where m, n or o is an integer of 2 or more, each of R1, each of R2, or each of R3 may be the same or different.
According to another embodiment of the present disclosure, in formula 1, X may represent CR11R12, O or S; R1 to R3 may be each independently hydrogen, methyl, isobutyl, tert-butyl, or phenyl unsubstituted or substituted with methyl, isobutyl, or tert-butyl; R4 may represent hydrogen; L may represent
Figure PCTKR2016014435-appb-I000015
; R8 to R10 may be each independently hydrogen, methyl, or phenyl substituted with methyl; or at least two of R8 to R10 may be linked to each other as an adjacent substituent to form a quinoline which includes the pyridine ring linked to R8 to R10 and is unsubstituted or substituted with a (C1-C6)alkyl; R11 and R12 may be each independently methyl unsubstituted or substituted with deuterium, ethyl unsubstituted or substituted with deuterium, or phenyl; m and n, each independently, may represent an integer of 0 to 4; o may represent an integer of 0 to 2; and where m, n or o is an integer of 2 or more, each of R1, each of R2, or each of R3 may be the same or different.
The compound represented by formula 1 includes the following compounds, but is not limited thereto:
Figure PCTKR2016014435-appb-I000016
Figure PCTKR2016014435-appb-I000017
Figure PCTKR2016014435-appb-I000018
Figure PCTKR2016014435-appb-I000019
Figure PCTKR2016014435-appb-I000020
Figure PCTKR2016014435-appb-I000021
Figure PCTKR2016014435-appb-I000022
Figure PCTKR2016014435-appb-I000023
Figure PCTKR2016014435-appb-I000024
Figure PCTKR2016014435-appb-I000025
Figure PCTKR2016014435-appb-I000026
Figure PCTKR2016014435-appb-I000027
Figure PCTKR2016014435-appb-I000028
Figure PCTKR2016014435-appb-I000029
Figure PCTKR2016014435-appb-I000030
Figure PCTKR2016014435-appb-I000031
Figure PCTKR2016014435-appb-I000032
Figure PCTKR2016014435-appb-I000033
The compound according to the present disclosure may be produced by a synthetic method known to a person skilled in the art. For example, it may be produced by the following reaction scheme 1:
[Reaction Scheme 1]
Figure PCTKR2016014435-appb-I000034
Figure PCTKR2016014435-appb-I000035
wherein, R1 to R7, X, m, n, and o are as defined in formula 1.
The present disclosure also discloses an organic electroluminescent material comprising the compound of formula 1, and an organic electroluminescent device comprising the material.
The organic electroluminescent material may consist of the organic electroluminescent compound of the present disclosure as a sole compound, or may further comprise conventional materials generally used in organic electroluminescent materials.
The organic electroluminescent device of the present disclosure may comprise a first electrode, a second electrode, and at least one organic layer between the first and second electrodes. The organic layer may comprise at least one organic electroluminescent compound of formula 1.
One of the first and second electrodes may be an anode, and the other may be a cathode. The organic layer may comprise a light-emitting layer, and may further comprise at least one layer selected from a hole injection layer, a hole transport layer, a hole auxiliary layer, a light-emitting auxiliary layer, an electron transport layer, an electron injection layer, an interlayer, a hole blocking layer, an electron buffer layer, and an electron blocking layer.
Herein, the light-emitting auxiliary layer may be placed between the anode and the light-emitting layer, or the cathode and the light-emitting layer, which may be used for facilitating the injection and/or transport of the hole or for blocking the overflow of the electron when placed between the anode and the light-emitting layer, or which may be used for facilitating the injection and/or transport of the electron or for blocking the overflow of the hole when placed between the cathode and the light-emitting layer. In addition, the hole auxiliary layer is placed between the hole transport layer (or the hole injection layer) and the light-emitting layer, which may exhibit facilitating a transport rate (or injection rate) of a hole or blocking a hole, thereby controlling a charge balance. In addition, the electron blocking layer is placed between the hole transport layer (or the hole injection layer) and the light-emitting layer, which prevents light leakage by blocking the overflow of the electron from the light-emitting layer and confining excitons in the light-emitting layer. If two or more hole transport layers are included, the additional hole transport layer(s), which is (are) included in addition to the hole transport layer, may be used as the hole auxiliary layer or electron blocking layer. The hole auxiliary layer or the electron blocking layer provides excellent efficiencies and improved lifespan of an organic electroluminescent device.
The compound represented by formula 1 of the present disclosure is a dopant material, which may be included in the light-emitting layer. In addition, the light-emitting layer may further include one or more host materials.
The host compounds which are capable of being used with the compound of the present disclosure may be the following compounds represented by formula 2.
Figure PCTKR2016014435-appb-I000036
wherein
Ma represents a substituted or unsubstituted, nitrogen-containing 5- to 11-membered heteroaryl;
La represents a single bond, or a substituted or unsubstituted (C6-C30)arylene;
Xa to Xh, each independently, represent hydrogen, deuterium, a halogen, a cyano, a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C2-C30)alkenyl, a substituted or unsubstituted (C2-C30)alkynyl, a substituted or unsubstituted (C3-C30)cycloalkyl, a substituted or unsubstituted (C6-C60)aryl, a substituted or unsubstituted 3- to 30-membered heteroaryl, a substituted or unsubstituted tri(C1-C30)alkylsilyl, a substituted or unsubstituted tri(C6-C30)arylsilyl, a substituted or unsubstituted di(C1-C30)alkyl(C6-C30)arylsilyl, a substituted or unsubstituted (C1-C30)alkyldi(C6-C30)arylsilyl, a substituted or unsubstituted (C1-C30)alkyl(C6-C30)arylamino, or a substituted or unsubstituted mono- or di-(C6-C30)arylamino; or may be linked to an adjacent substituent(s) to form a substituted or unsubstituted (C3-C30) mono- or polycyclic, alicyclic or aromatic ring, whose carbon atom(s) may be replaced with at least one hetero atom selected from the group consisting of nitrogen, oxygen, and sulfur; and
the heteroaryl contains at least one hetero atom selected from B, N, O, S, Si, and P.
In formula 2, the substituents of a substituted alkyl, a substituted alkenyl, a substituted alkynyl, a substituted cycloalkyl, a substituted aryl, a substituted heteroaryl, a substituted trialkylsilyl, a substituted triarylsilyl, a substituted dialkylarylsilyl, a substituted alkyldiarylsilyl, a substituted alkylarylamino, a substituted monoarylamino, a substituted diarylamino, or a substituted mono- or polycyclic, alicyclic or aromatic ring may be each independently, at least one selected from the group consisting of deuterium; a halogen; a cyano; a carboxyl; a nitro; a hydroxyl; a (C1-C30)alkyl; a halo(C1-C30)alkyl; a (C2-C30)alkenyl; a (C2-C30)alkynyl; a (C1-C30)alkoxy; a (C1-C30)alkylthio; a (C3-C30)cycloalkyl; a (C3-C30)cycloalkenyl; a 3- to 7-membered heterocycloalkyl; a (C6-C30)aryloxy; a (C6-C30)arylthio; a 3- to 30-membered heteroaryl unsubstituted or substituted with a tri(C6-C30)arylsilyl, a (C6-C30)aryl, a (C1-C30)alkyl(C6-C30)aryl, or a tri(C6-C30)arylsilyl(C6-C30)aryl; a (C6-C30)aryl unsubstituted or substituted with a (C1-C30)alkyl, a halogen, a (C6-C30)aryl or a 3- to 30-membered heteroaryl; a tri(C1-C30)alkylsilyl; a tri(C6-C30)arylsilyl; a di(C1-C30)alkyl(C6-C30)arylsilyl; a (C1-C30)alkyldi(C6-C30)arylsilyl; an amino; a mono- or di- (C1-C30)alkylamino; a mono- or di- (C6-C30)arylamino; a (C1-C30)alkyl(C6-C30)arylamino; a (C1-C30)alkylcarbonyl; a (C1-C30)alkoxycarbonyl; a (C6-C30)arylcarbonyl; a di(C6-C30)arylboronyl; a di(C1-C30)alkylboronyl; a (C1-C30)alkyl(C6-C30)arylboronyl; a (C6-C30)aryl(C1-C30)alkyl; and a (C1-C30)alkyl(C6-C30)aryl.
In formula 2, La may represent preferably, a single bond, or a substituted or unsubstituted (C6-C12)arylene; and more preferably, a single bond, or a (C6-C12)arylene unsubstituted or substituted with a tri(C6-C10)arylsilyl. Specifically, La may represent a single bond, a substituted or unsubstituted phenylene, a substituted or unsubstituted naphthylene, or a substituted or unsubstituted biphenylene.
In formula 2, Ma may represent preferably, a substituted or unsubstituted, nitrogen-containing 5- to 11-membered heteroaryl; and more preferably, a nitrogen-containing 6- to 11-membered heteroaryl unsubstitued or substituted with a cyano, a (C1-C6)alkyl, a tri(C6-C12)arylsilyl, a (C6-C18)aryl, or a 5- to 15-membered heteroaryl.
Specifically, Ma may represent a substituted or unsubstituted pyrrolyl, a substituted or unsubstituted imidazolyl, a substituted or unsubstituted pyrazolyl, a substituted or unsubstituted triazinyl, a substituted or unsubstituted tetrazinyl, a substituted or unsubstituted triazolyl, a substituted or unsubstituted tetrazolyl, a substituted or unsubstituted pyridyl, a substituted or unsubstituted pyrazinyl, a substituted or unsubstituted pyrimidinyl, a substituted or unsubstituted pyridazinyl, a substituted or unsubstituted benzimidazolyl, a substituted or unsubstituted isoindolyl, a substituted or unsubstituted indolyl, a substituted or unsubstituted indazolyl, a substituted or unsubstituted benzothiadiazolyl, a substituted or unsubstituted quinolyl, a substituted or unsubstituted isoquinolyl, a substituted or unsubstituted cinnolinyl, a substituted or unsubstituted quinazolinyl, a substituted or unsubstituted naphthyridinyl, or a substituted or unsubstituted quinoxalinyl. More specifically, Ma may represent a substituted or unsubstituted triazinyl, a substituted or unsubstituted pyrimidinyl, a substituted or unsubstituted pyridyl, a substituted or unsubstituted quinolyl, a substituted or unsubstituted isoquinolyl, a substituted or unsubstituted quinazolinyl, a substituted or unsubstituted naphthyridinyl, or a substituted or unsubstituted quinoxalinyl.
Preferably, Xa to Xh, each independently, may represent hydrogen, a cyano, a substituted or unsubstituted (C6-C15)aryl, a substituted or unsubstituted 6- to 20-membered heteroaryl, or a substituted or unsubstituted tri(C6-C15)arylsilyl; or may be linked to an adjacent substituent(s) to form a substituted or unsubstituted 6- to 20-membered, mono- or polycyclic aromatic ring, whose carbon atom(s) may be replaced with at least one hetero atom selected from the group consisting of nitrogen, oxygen, and sulfur. More preferably, Xa to Xh, each independently, may represent hydrogen, a cyano, a (C6-C15)aryl unsubstituted or substituted with a tri(C6-C12)arylsilyl, or a 10- to 20-membered heteroaryl unsubstituted or substituted with a (C6-C12)aryl; or may be linked to an adjacent substituent(s) to form a substituted or unsubstituted benzene, a substituted or unsubstituted indole, a substituted or unsubstituted benzoindole, a substituted or unsubstituted indene, a substituted or unsubstituted benzofuran, or a substituted or unsubstituted benzothiophene. Specifically, at least one of Xa to Xh, for example, Xb, Xc, Xf, or Xg, each independently, may represent a substituted or unsubstituted dibenzothiophene, a substituted or unsubstituted dibenzofuran, a substituted or unsubstituted carbazole, or a substituted or unsubstituted benzocarbazole; or may be linked to an adjacent substituent(s) to form a substituted or unsubstituted benzene, a substituted or unsubstituted indole, a substituted or unsubstituted benzindole, a substituted or unsubstituted indene, a substituted or unsubstituted benzofuran, or a substituted or unsubstituted benzothiophene.
More specifically, the compound of formula 2 includes the following, but is not limited thereto.
Figure PCTKR2016014435-appb-I000037
Figure PCTKR2016014435-appb-I000038
Figure PCTKR2016014435-appb-I000039
Figure PCTKR2016014435-appb-I000040
Figure PCTKR2016014435-appb-I000041
Figure PCTKR2016014435-appb-I000042
Figure PCTKR2016014435-appb-I000043
Figure PCTKR2016014435-appb-I000044
Figure PCTKR2016014435-appb-I000045
Figure PCTKR2016014435-appb-I000046
Figure PCTKR2016014435-appb-I000047
Figure PCTKR2016014435-appb-I000048
Figure PCTKR2016014435-appb-I000049
Figure PCTKR2016014435-appb-I000050
Figure PCTKR2016014435-appb-I000051
Figure PCTKR2016014435-appb-I000052
Figure PCTKR2016014435-appb-I000053
Figure PCTKR2016014435-appb-I000054
Figure PCTKR2016014435-appb-I000055
Figure PCTKR2016014435-appb-I000056
Figure PCTKR2016014435-appb-I000057
Figure PCTKR2016014435-appb-I000058
Figure PCTKR2016014435-appb-I000059
Figure PCTKR2016014435-appb-I000060
Figure PCTKR2016014435-appb-I000061
Figure PCTKR2016014435-appb-I000062
Figure PCTKR2016014435-appb-I000063
Figure PCTKR2016014435-appb-I000064
Figure PCTKR2016014435-appb-I000065
Figure PCTKR2016014435-appb-I000066
Figure PCTKR2016014435-appb-I000067
Figure PCTKR2016014435-appb-I000068
Figure PCTKR2016014435-appb-I000069
Figure PCTKR2016014435-appb-I000071
Figure PCTKR2016014435-appb-I000072
Figure PCTKR2016014435-appb-I000073
Figure PCTKR2016014435-appb-I000074
Figure PCTKR2016014435-appb-I000075
Figure PCTKR2016014435-appb-I000076
Figure PCTKR2016014435-appb-I000077
Figure PCTKR2016014435-appb-I000078
Figure PCTKR2016014435-appb-I000079
Figure PCTKR2016014435-appb-I000080
Figure PCTKR2016014435-appb-I000081
Figure PCTKR2016014435-appb-I000082
Figure PCTKR2016014435-appb-I000083
Figure PCTKR2016014435-appb-I000084
Figure PCTKR2016014435-appb-I000085
Figure PCTKR2016014435-appb-I000086
Figure PCTKR2016014435-appb-I000087
Figure PCTKR2016014435-appb-I000088
Figure PCTKR2016014435-appb-I000089
Figure PCTKR2016014435-appb-I000090
Figure PCTKR2016014435-appb-I000091
Figure PCTKR2016014435-appb-I000092
Figure PCTKR2016014435-appb-I000093
Figure PCTKR2016014435-appb-I000094
Figure PCTKR2016014435-appb-I000095
Figure PCTKR2016014435-appb-I000096
Figure PCTKR2016014435-appb-I000097
Figure PCTKR2016014435-appb-I000098
Figure PCTKR2016014435-appb-I000099
Figure PCTKR2016014435-appb-I000100
Figure PCTKR2016014435-appb-I000101
Figure PCTKR2016014435-appb-I000102
Figure PCTKR2016014435-appb-I000103
Figure PCTKR2016014435-appb-I000104
Figure PCTKR2016014435-appb-I000105
Figure PCTKR2016014435-appb-I000106
Figure PCTKR2016014435-appb-I000107
Figure PCTKR2016014435-appb-I000108
Figure PCTKR2016014435-appb-I000109
Figure PCTKR2016014435-appb-I000110
Figure PCTKR2016014435-appb-I000111
Figure PCTKR2016014435-appb-I000112
Figure PCTKR2016014435-appb-I000113
Figure PCTKR2016014435-appb-I000114
Figure PCTKR2016014435-appb-I000115
Figure PCTKR2016014435-appb-I000116
Figure PCTKR2016014435-appb-I000117
Figure PCTKR2016014435-appb-I000118
According to another embodiment of the present disclosure, a combination of the compound represented by formula 1 and the compound represented by formula 2, and an organic electroluminescent device comprising the combination are provided.
According to another embodiment of the present disclosure, a mixture or a composition for preparing an organic electroluminescent device is provided. The mixture or composition comprises the compound represented by formula 1. The mixture or composition may be for preparing a light-emitting layer of an organic electroluminescent device. The mixture or composition may comprise a host compound represented by formula 2, besides the compound of the present disclosure. In addition, the mixture or composition may comprise the compound represented by formula 1, which is combined with a host compound represented by formula 2. In addition, the mixture or composition may further comprise a conventional material which is included for preparing an organic electroluminescent device.
The organic electroluminescent device of the present disclosure comprises the compound represented by formula 1, at the same time, the organic electroluminescent device comprises at least one compound selected from the group consisting of arylamine-based compounds and styrylarylamine-based compounds.
In the organic electroluminescent device of the present disclosure, the organic layer may further comprise at least one metal selected from the group consisting of metals of Group 1, metals of Group 2, transition metals of the 4th period, transition metals of the 5th period, lanthanides and organic metals of the d-transition elements of the Periodic Table, or at least one complex compound, besides the compound represented by formula 1.
In addition, the organic electroluminescent device of the present disclosure may emit white light by further comprising at least one light-emitting layer, which comprises a blue electroluminescent compound, a red electroluminescent compound or a green electroluminescent compound known in the art, besides the light-emitting layer of the present disclosure. If necessary, it may further comprise a yellow light-emitting layer or an orange light-emitting layer.
In the organic electroluminescent device of the present disclosure, preferably, at least one layer (hereinafter, "a surface layer”) may be placed on an inner surface(s) of one or both electrode(s), selected from a chalcogenide layer, a metal halide layer, and a metal oxide layer. Specifically, a chalcogenide (includes oxides) layer of silicon or aluminum is preferably placed on an anode surface of an electroluminescent medium layer, and a metal halide layer or a metal oxide layer is preferably placed on a cathode surface of an electroluminescent medium layer. Such a surface layer provides operation stability for the organic electroluminescent device. Preferably, the chalcogenide includes SiOX(1≤X≤2), AlOX(1≤X≤1.5), SiON, SiAlON, etc.; the metal halide includes LiF, MgF2, CaF2, a rare earth metal fluoride, etc.; and the metal oxide includes Cs2O, Li2O, MgO, SrO, BaO, CaO, etc.
In the organic electroluminescent device of the present disclosure, a mixed region of an electron transport compound and a reductive dopant, or a mixed region of a hole transport compound and an oxidative dopant may be placed on at least one surface of a pair of electrodes. In this case, the electron transport compound is reduced to an anion, and thus it becomes easier to inject and transport electrons from the mixed region to an electroluminescent medium. Furthermore, the hole transport compound is oxidized to a cation, and thus it becomes easier to inject and transport holes from the mixed region to the electroluminescent medium. Preferably, the oxidative dopant includes various Lewis acids and acceptor compounds, and the reductive dopant includes alkali metals, alkali metal compounds, alkaline earth metals, rare-earth metals, and mixtures thereof. A reductive dopant layer may be employed as a charge generating layer to prepare an electroluminescent device having two or more light-emitting layers and emitting white light.
In order to form each layer of the organic electroluminescent device of the present disclosure, dry film-forming methods such as vacuum evaporation, sputtering, plasma and ion plating methods, or wet film-forming methods such as ink jet printing, nozzle printing, slot coating, spin coating, dip coating, and flow coating methods can be used.
When using a wet film-forming method, a thin film can be formed by dissolving or diffusing materials forming each layer into any suitable solvent such as ethanol, chloroform, tetrahydrofuran, dioxane, etc. The solvent can be any solvent where the materials forming each layer can be dissolved or diffused, and where there are no problems in film-formation capability.
Hereinafter, the compound according to the present disclosure, the preparation method thereof, and the luminescent properties of the device will be explained in detail with reference to the following representative compounds.
Example 1: Praparation of compound D-1
Figure PCTKR2016014435-appb-I000119
Figure PCTKR2016014435-appb-I000120
Figure PCTKR2016014435-appb-I000121
Figure PCTKR2016014435-appb-I000122
1) Preparation of compound 1-1
After introducing malonic acid (38 g, 358 mmol) and POCl3 (356 mL, 3822 mmol) into a reaction vessel, the mixture was stirred for 10 minutes at room temperature. After slowly adding 9,9-dimethyl-9H-fluorene-2-amine (50 g, 239 mmol) dropwise thereto, the mixture was stirred at 150℃. After slowly adding H2O dropwise to the mixture, an extractioin with methylene chloride (MC) was conducted. After removing the solvent, the resultant was purified by column chromatography to obtain compound 1-1 (33.5 g, 45 %).
2) Preparation of compound 1-2
After introducing compound 1-1 (16.5 g, 53 mmol), 3,5-dimethylphenylboronic acid (9.45 g, 63 mmol), Pd(PPh3)4 (1.82 g, 1.58 mmol), Na2CO3 (16.70 g, 157.53 mmol), toluene (214 mL), and H2O (79 mL) into a reaction vessel, the mixture was under reflux at 120℃. The resultant was cooled to room temperature, extracted with ethyl acetate and H2O, and then purified by column chromatography to obtain compound 1-2 (15.3 g, 76 %).
3) Preparation of compound 1-3
After introducing compound 1-2 (15.3 g, 39.85 mmol), isobutyl boronic acid (8.198 g, 79.71 mmol), 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl(S-Phos) (1.30 g, 2.81 mmol), K3PO4 (41.43 g, 172.28 mmol), tris(dibenzylideneacetone)dipalladium(0)(Pd2(dba)3) (1.46 g, 1.41 mmol), and toluene (266 mL) into the reaction vessel, the mixture was stirred for 12 hours. The resultant was cooled to room temperature, extracted with ethyl acetate and H2O, and then purified by column chromatography to obtain compound 1-3 (15.1 g, 93 %).
4) Preparation of compound 1-4
After introducing compound 1-3 (15.1 g, 37.23 mmol), IrCl3ㆍxH2O (5.05 g, 16.92 mmol), 2-ethoxy ethanol (130 mL), and H2O (43.4 mL) into the reaction vessel, the mixture was under reflux for 24 hours at 130℃, and then the resultant was cooled to room temperature. After introducing H2O, the mixture was stirred for 30 minutes, and then filtered to obtain compound 1-4 (7.9 g, 45 %) as solid.
5) Preparation of compound D-1
After introducing compound 1-4 (3.5 g, 1.69 mmol), 2,8-dimethylnonane-4,6-dione (3.11 g, 16.88 mmol), K2CO3 (2.34 g, 16.88 mmol), and 2-ethoxyethanol (21 mL) into the reaction vessel, the mixture was reacted overnight at room temperature and filtered. The obtained solid was purified by column chromatography to obtain compound D-1 (0.7 g, 18 %).
Figure PCTKR2016014435-appb-I000123
Example 2: Praparation of compound D-12
Figure PCTKR2016014435-appb-I000124
Figure PCTKR2016014435-appb-I000125
After introducing compound 1-4 (7.9 g, 3.81 mmol), acetylacetone (3.8 g, 38.10 mmol), Na2CO3 (4.04 g, 38.10 mmol), and 2-ethoxyethanol (48 mL), the mixture was reacted overnight and then filtered. The obtained solid was purified by column chromatography to obtain compound D-12 (3 g, 36 %).
Figure PCTKR2016014435-appb-I000126
Example 3: Praparation of compound D-61
Figure PCTKR2016014435-appb-I000127
Figure PCTKR2016014435-appb-I000128
1) Preparation of compound 3-1
After introducing compound 1-2 (67.2 g, 181.68 mmol), m-tolyl boronic acid (49.40 g, 363.35 mmol), tris(dibenzylideneacetone)dipalladium(0)(Pd2(dba)3) (6.65 g, 7.27 mmol), K3PO4 (188.97 g, 890.23 mmol), 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl(s-phos) (6.00 g, 14.53 mmol), and toluene (1200 mL) into a 2L round-bottom flask, the mixture was stirred under reflux for 24 hours. After completion of the reaction, the reaction product was cooled to room temperature, then extracted with ethyl acetate and treated with MgSO4. The reaction mixture was purified by column chromatography to obtain compound 3-1 (46 g, 58%).
2) Preparation of compound 3-2
After introducing compound 3-1(46 g, 104.64 mmol), IrCl3·xH2O(14.22 g, 47.56 mmol), 2-ethoxyethanol (365 mL, 0.13 M), and H2O(122 mL) into a 1L round-bottom flask under nitrogen atmosphere, the mixture was stirred under reflux for 24 hours. The reaction mixture was cooled to room temperature. The solvent was removed therefrom as much as possible, and then after adding water (500 mL), the mixture was stirred for 30 minutes. The reaction mixture was rinsed with methanol and hexane and dried to obtain compound 3-2 (50.7 g, 97%).
3) Preparation of compound D-61
After introducing compound 3-2 (10 g, 4.53 mmol), picolinic acid (1.11 g, 9.05 mmol), NaOH(0.36 g, 9.05 mmol), 2-ethoxyethanol (105 mL, 0.043 M) and H2O(10 mL) into a 250 mL round-bottom flask under nitrogen atmosphere, the mixture was stirred at room temperature for 24 hours. After completion of the reaction, water (330 mL) was added. Thereafter, the mixture was stirred for 30 minutes and then filtered. The obtained resultant was purified by column chromatography to obtain compound D-61(0.8 g, 30%).
[Device Examples 1-1 and 1-2] Preparation of OLED comprising a dopant
of the present disclosure
OLED comprising the organic electroluminescent compound of the present disclosure was produced. A transparent electrode indium tin oxide (ITO) thin film (10 Ω/sq) on a glass substrate for an organic light-emitting diode (OLED) (Geomatec) was subjected to an ultrasonic washing with acetone, ethanol, and distilled water, sequentially, and then was stored in isopropanol. The ITO substrate was then mounted on a substrate holder of a vacuum vapor depositing apparatus. HI-1 was introduced into a cell of the vacuum vapor depositing apparatus, and then the pressure in the chamber of said apparatus was controlled to 10-6 torr. Thereafter, an electric current was applied to the cell to evaporate the above introduced material, thereby forming a first hole injection layer having a thickness of 80 nm on the ITO substrate. HI-2 was introduced into another cell of the vacuum vapor depositing apparatus, and was evaporated by applying an electric current to the cell, thereby forming a second hole injection layer having a thickness of 5 nm on the first hole injection layer. HT-1 was introduced into a cell of the vaccum vapor depositing apparatus, and was evaporated by applying an electric current to the cell, thereby forming a first hole transport layer having a thickness of 10 nm on the second hole injection layer. HT-2 was introduced into another cell of the vacuum vapor depositing apparatus, and was evaporated by applying an electric current to the cell, thereby forming a second hole transport layer having a thickness of 60 nm on the first hole transport layer. Then, the light-emitting layer on the hole injection layers and the hole transport layers was formed as follows. Compound H2-16 was introduced into one cell of the vacuum vapor depositing apparatus as a host, and a dopant material shown in Table 1 below was introduced into another cell. Thereafter, the host material was evaporated, and simultaneously, the dopant material was evaporated at different rates from the host material, so that the dopant was deposited in a doping amount of 3 wt% based on the total amount of the host and dopant to form a light-emitting layer having a thickness of 40 nm on the second hole transport layer. ET-1 and EI-1 were introduced into two cells of the vacuum vapor depositing apparatus, respectively, and evaporated at a 1:1 rate to form an electron transport layer having a thickness of 30 nm on the light-emitting layer. After depositing EI-1 as an electron injection layer having a thickness of 2 nm, an Al cathode having a thickness of 80 nm was then deposited by another vacuum vapor deposition apparatus on the electron injection layer to produce OLED.
Figure PCTKR2016014435-appb-I000129
[Comparative Example 1-1] Preparation of OLED comprising a conventional
dopant
OLED was produced in the same manner as in Device Example 1-1, except that compound RD-1 below was used as a dopant for a light-emitting layer.
Figure PCTKR2016014435-appb-I000130
The evaluation result of the OLED prepared in Device Examples 1-1 and 1-2, and Comparative Example 1-1 above is shown in Table 1 below.
Figure PCTKR2016014435-appb-I000131
By using an organic electroluminescent compound of the present disclosure, it is possible to provide an organic electroluminescent device with excellent efficiency and color purity compared to the conventional electroluminescent compound.
This can be understood that an azabenzo[b]fluorene ligand of the Device Example attributes the organic electroluminescent device to have better efficiency compared to the quinoline ligand of the Comparative Example. Besides, the substituent (alkyl substituent in the Device Example above) is introduced on the outside of azabenzo[b]fluorene ligand according to the present disclosure, and it can be understood that the substituent applies a steric hindrance to the octahedral structure of the iridium complex, thereby reducing Triplet-Triplet Annihilation to maximize the characteristic which improves efficiency.
Upon comparing the azabenzo[b]fluorene ligand of the present disclosure with an azabenzo[a]fluorene ligand, according to the quantum mechanics simulation results, the bond distance between the azabenzo[b]fluorene ligand and the iridium metal is shorter than the one between the azabenzo[a]fluorene ligand and the iridium metal. It can be predicted that the shorter the bond distance, the stronger the spin orbital coupling by an iridium atom is applied to have better efficiency.

Claims (8)

  1. An organic electroluminescent compound represented by the following formula 1:
    Figure PCTKR2016014435-appb-I000132
    wherein
    X represents CR11R12, O or S;
    R1 to R3, each independently, represent hydrogen, deuterium, a substituted or unsubstituted (C1-C10)alkyl, or a substituted or unsubstituted (C6-C30)aryl;
    R4 represents hydrogen, or a substituted or unsubstituted (C1-C10)alkyl;
    R11 and R12, each independently, represent a substituted or unsubstituted (C1-C10)alkyl, or a substituted or unsubstituted (C6-C30)aryl;
    m and n, each independently, represent an integer of 0 to 4;
    o represents an integer of 0 to 2;
    where m, n or o is an integer of 2 or more, each of R1, each of R2, or each of R3 may be the same or different;
    L represents
    Figure PCTKR2016014435-appb-I000133
    or
    Figure PCTKR2016014435-appb-I000134
    ;
    where L is
    Figure PCTKR2016014435-appb-I000135
    ,
    R5 to R7, each independently, represent hydrogen, deuterium, a substituted or unsubstituted (C1-C10)alkyl, or a substituted or unsubstituted (C6-C30)aryl; where L is
    Figure PCTKR2016014435-appb-I000136
    ,
    R8 to R10, each independently, represent hydrogen, deuterium, a substituted or unsubstituted (C1-C10)alkyl, or a substituted or unsubstituted (C6-C30)aryl; or may be linked to an adjacent substituent to form a substituted or unsubstituted 9- to 20-membered heteroaryl including the pyridine ring linked to R8 to R10; and the heteroaryl may comprise one or more hetero atoms selected from a nitrogen, an oxygen, and a sulfur in addition to the nitrogen atom of the pyridine ring.
  2. The organic electroluminescent compound according to claim 1, wherein
    R11 and R12 are each independently, a substituted or unsubstituted (C1-C5)alkyl, or a substituted or unsubstituted (C6-C20)aryl.
  3. The organic electroluminescent compound according to claim 1, wherein
    R1 to R3 are each independently hydrogen, a substituted or unsubstituted (C1-C5)alkyl, or a substituted or unsubstituted (C6-C20)aryl.
  4. The organic electroluminescent compound according to claim 1, wherein
    R11 and R12 are each independently, a (C1-C4)alkyl unsubstituted or substituted deuterium, or an unsubstituted (C6-C15)aryl;
    R1 to R3 are each independently hydrogen, an unsubstituted (C1-C4)alkyl, or a (C6-C15)aryl unsubstituted or substituted with a (C1-C4)alkyl; and
    R4 is hydrogen.
  5. The organic electroluminescent compound according to claim 1, wherein
    R5 to R7 are each independently hydrogen, a substituted or unsubstituted (C1-C5)alkyl, or a substituted or unsubstituted (C6-C15)aryl.
  6. The organic electroluminescent compound according to claim 1, wherein
    R8 to R10 are each independently hydrogen, a substituted or unsubstituted (C1-C5)alkyl, or a substituted or unsubstituted (C6-C20)aryl; or at least two of R8 to R10 may be linked to each other as an adjacent substituent to form a 9- to 16-membered heteroaryl which includes the pyridine ring linked to R8 to R10 and is unsubstitued or substituted with a (C1-C15)alkyl, and the heteroaryl may comprise one or more hetero atoms selected from a nitrogen, an oxygen, and a sulfur in addition to a nitrogen atom of the pyridine ring.
  7. The organic electroluminescent compound according to claim 1, wherein the compound represented by formula 1 is selected from the group consisting of:
    Figure PCTKR2016014435-appb-I000137
    Figure PCTKR2016014435-appb-I000138
    Figure PCTKR2016014435-appb-I000139
    Figure PCTKR2016014435-appb-I000140
    Figure PCTKR2016014435-appb-I000141
    Figure PCTKR2016014435-appb-I000142
    Figure PCTKR2016014435-appb-I000143
    Figure PCTKR2016014435-appb-I000144
    Figure PCTKR2016014435-appb-I000145
    Figure PCTKR2016014435-appb-I000146
    Figure PCTKR2016014435-appb-I000147
    Figure PCTKR2016014435-appb-I000148
    Figure PCTKR2016014435-appb-I000149
    Figure PCTKR2016014435-appb-I000150
    Figure PCTKR2016014435-appb-I000151
    Figure PCTKR2016014435-appb-I000152
    Figure PCTKR2016014435-appb-I000153
    Figure PCTKR2016014435-appb-I000154
  8. The organic electroluminescent device comprising the organic electroluminescent compound according to claim 1.
PCT/KR2016/014435 2015-12-10 2016-12-09 Organic electroluminescent compound and organic electroluminescent device comprising the same WO2017099516A1 (en)

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CN110914379A (en) * 2017-07-21 2020-03-24 罗门哈斯电子材料韩国有限公司 Organic electroluminescent compounds and organic electroluminescent device comprising the same
CN110914379B (en) * 2017-07-21 2024-01-02 罗门哈斯电子材料韩国有限公司 Organic electroluminescent compound and organic electroluminescent device comprising the same
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WO2021131697A1 (en) * 2019-12-27 2021-07-01 住友化学株式会社 Metal complex, composition containing same, and luminescent element

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