WO2017095156A1 - Organic electroluminescent compounds and organic electroluminescent device comprising the same - Google Patents

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

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Publication number
WO2017095156A1
WO2017095156A1 PCT/KR2016/014013 KR2016014013W WO2017095156A1 WO 2017095156 A1 WO2017095156 A1 WO 2017095156A1 KR 2016014013 W KR2016014013 W KR 2016014013W WO 2017095156 A1 WO2017095156 A1 WO 2017095156A1
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substituted
unsubstituted
alkyl
organic electroluminescent
aryl
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PCT/KR2016/014013
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French (fr)
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Doo-Hyeon Moon
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Rohm And Haas Electronic Materials Korea Ltd.
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Priority claimed from KR1020160158003A external-priority patent/KR20170066241A/en
Application filed by Rohm And Haas Electronic Materials Korea Ltd. filed Critical Rohm And Haas Electronic Materials Korea Ltd.
Priority to US15/777,747 priority Critical patent/US10547010B2/en
Priority to CN201680067317.4A priority patent/CN108391433B/en
Publication of WO2017095156A1 publication Critical patent/WO2017095156A1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
    • C07D487/12—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains three hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
    • C07D487/22—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains four or more hetero 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
    • C07D491/22—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 four or more hetero rings
    • 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
    • C07D495/22—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 four or more hetero rings
    • 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
    • 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
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
    • 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
    • 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
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
    • H10K85/636—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine comprising heteroaromatic hydrocarbons as substituents on the nitrogen atom
    • 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
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6574—Polycyclic condensed heteroaromatic hydrocarbons comprising only oxygen in the heteroaromatic polycondensed ring system, e.g. cumarine dyes
    • 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
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6576—Polycyclic condensed heteroaromatic hydrocarbons comprising only sulfur in the heteroaromatic polycondensed ring system, e.g. benzothiophene

Definitions

  • the present disclosure relates to an organic electroluminescent compound and an organic electroluminescent device comprising the same.
  • An electroluminescent (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.
  • An organic EL device was first developed by Eastman Kodak, by using small aromatic diamine molecules and aluminum complexes as materials to form a light-emitting layer [Appl. Phys. Lett. 51, 913, 1987].
  • the most important factor determining luminous efficiency in the organic EL device is light-emitting materials.
  • fluorescent materials have been widely used as light-emitting material.
  • phosphorescent materials theoretically enhance luminous efficiency by four (4) times compared to fluorescent materials, phosphorescent light-emitting materials have been widely researched.
  • Iridium(III) complexes have been widely known as phosphorescent materials, including bis(2-(2’-benzothienyl)-pyridinato-N,C-3’)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-emitting materials, respectively.
  • CBP 4,4’-N,N’-dicarbazol-biphenyl
  • BCP bathocuproine
  • BAlq aluminum(III) bis(2-methyl-8-quinolinate)(4-phenylphenolate)
  • Japanese Patent Application Laying-Open No. 2014-160813 discloses an organic electroluminescent device comprising a nitrogen-containing heteroaryl compound formed by condensing a pyrrole ring, an aromatic aryl ring, and a 7-membered aryl ring, as host/dopant materials. However, it does not specifically disclose a compound in which a carbazole and an indole are fused with a 7-membered ring.
  • Korean Patent Application Laying-Open No. 10-2015-077220 discloses a compound in which an amine radical is fused with dibenzo residue including a carbazole, fluorene, or 5-membered hetero ring to form a ring. However, it does not specifically disclose a compound wherein a parent nucleus formed by a fusion of a carbazole, an indole, and a 7-membered ring, is connected, directly or via a linker of arylene or heteroarylene, to a 10-membered nitrogen-containing heteroaryl.
  • the objective of the present disclosure is to provide an organic electroluminescent compound, which is effective in preparing an organic electroluminescent device having a remarkably improved lifespan, and an organic electroluminescent device comprising the organic electroluminescent compound.
  • X and Y each independently, represent CR 4 or N;
  • L 1 represents a single bond, a substituted or unsubstituted (C6-C30)arylene, or a substituted or unsubstituted (3- to 30-membered) heteroarylene;
  • A represents hydrogen, a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted (3- to 30-membered) heteroaryl;
  • R 1 to R 3 each independently, represent hydrogen, deuterium, a halogen, a cyano, a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C6-C30)aryl, a substituted or unsubstituted (3- to 30-membered) heteroaryl, a substituted or unsubstituted (C3-C30)cycloalkyl, a substituted or unsubstituted (C1-C30)alkoxy, a substituted or unsubstituted tri(C1-C30)alkylsilyl, 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 tri(C6-C
  • R 4 represents hydrogen, deuterium, a halogen, a cyano, a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C6-C30)aryl, a substituted or unsubstituted (3- to 30-membered) heteroaryl, a substituted or unsubstituted (C3-C30)cycloalkyl, a substituted or unsubstituted (C1-C30)alkoxy, a substituted or unsubstituted tri(C1-C30)alkylsilyl, 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 tri(C6-C30)arylsilyl
  • heteroaryl(ene) contains one or more heteroatoms selected from the group consisting of B, N, O, S, Si, and P;
  • a, b, and c each independently, represent an integer of 1 to 3,
  • each of R 1 , R 2 or R 3 may be the same or different.
  • the present disclosure provides an organic electroluminescent device that has a remarkably improved lifespan.
  • the compound of formula 1 is more specifically described below.
  • an organic electroluminescent compound indicates a compound that may be used for an organic electroluminescent device.
  • the compound may be comprised in any layer of the organic electroluminescent device, as necessary.
  • X and Y each independently, may represent CR 4 or N.
  • any one of X and Y is CR 4 , and the other one is N.
  • L 1 may represent a single bond or a substituted or unsubstituted (C6-C30)arylene, or a substituted or unsubstituted (3- to 30-membered) heteroarylene, preferably a single bond, a substituted or unsubstituted (C6-C25)arylene, or a substituted or unsubstituted (5- to 25-membered)heteroarylene, and more preferably a single bond, a substituted or unsubstituted (C6-C18)arylene, or an unsubstituted (5- to 18-membered)heteroarylene, such as a single bond, an unsubstituted phenyl, an unsubstituted naphthyl, fluorenyl substituted with dimethyl, or an unsubstituted pyridyl.
  • A may respresent hydrogen, a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted (3- to 30-membered) heteroaryl, preferably hydrogen, or a substituted or unsubstituted (C6-C25)aryl, and more preferably hydrogen, or an unsubstituted (C6-C18)aryl, such as hydrogen, an unsubstituted phenyl, an unsubstituted naphthyl, or an unsubstituted phenanthrenyl.
  • R 1 to R 3 each independently, may represent hydrogen, deuterium, a halogen, a cyano, a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C6-C30)aryl, a substituted or unsubstituted (3- to 30-membered) heteroaryl, a substituted or unsubstituted (C3-C30)cycloalkyl, a substituted or unsubstituted (C1-C30)alkoxy, a substituted or unsubstituted tri(C1-C30)alkylsilyl, 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 tri(
  • R 4 may represent hydrogen, deuterium, a halogen, a cyano, a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C6-C30)aryl, a substituted or unsubstituted (3- to 30-membered) heteroaryl, a substituted or unsubstituted (C3-C30)cycloalkyl, a substituted or unsubstituted (C1-C30)alkoxy, a substituted or unsubstituted tri(C1-C30)alkylsilyl, 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 tri(C6-C30)aryl
  • heteroaryl(ene) contains one or more heteroatoms selected from the group consisting of B, N, O, S, Si, and P; and preferably, one or more heteroatoms selected from the group consisting of N, O, and S.
  • a, b or c each independently, may represent an integer of 1 to 3; preferably an integer of 1 or 2; and when a, b or c represents an integer of 2 or more, each of R 1 , R 2 or R 3 may be the same or different.
  • the compound of formula 1 of the present disclosure may be represented by any one of the following formulae 2 to 9:
  • L 1 , R 1 to R 4 , and, a, b, and c are as defined in formula 1 above.
  • organic electroluminescent compound of formula 1 may be represented by the following formula 10:
  • Z represents O, S, CR 5 R 6 , or NR 7 , wherein R 5 to R 7 , each independently, are the same as the definition of R 4 in formula 1.
  • R 5 to R 7 each independently, may represent hydrogen, deuterium, a halogen, a cyano, a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C6-C30)aryl, a substituted or unsubstituted (3- to 30-membered) heteroaryl, a substituted or unsubstituted (C3-C30)cycloalkyl, a substituted or unsubstituted (C1-C30)alkoxy, a substituted or unsubstituted tri(C1-C30)alkylsilyl, a substituted or unsubstituted di(C1-C30)alkyl(C6-C30)arylsilyl, a substituted or unsubsti
  • d and e each independently, represent 0 or 1.
  • (C1-C30)alkyl indicates a linear or branched alkyl having 1 to 30, preferably 1 to 20, and more preferably 1 to 10 carbon atoms, and includes methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, etc.
  • “(C2-C30) alkenyl” indicates a linear or branched alkenyl having 2 to 30, preferably 2 to 20, and more preferably 2 to 10 carbon atoms and includes vinyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 2-methylbut-2-enyl, etc.
  • (C2-C30)alkynyl indicates a linear or branched alkynyl having 2 to 30, preferably 2 to 20, and more preferably 2 to 10 carbon atoms and includes ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-methylpent-2-ynyl, etc.
  • (C3-C30)cycloalkyl indicates a mono- or polycyclic hydrocarbon having 3 to 30, preferabley 3 to 20, more preferably 3 to 7 ring backbone carbon atoms.
  • the cycloalkyl includes cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc.
  • “(3 to 7-membered)heterocycloalkyl” indicates a cycloalkyl having 3 to 7, preferably 5 to 7 ring backbone atoms including at least one hetero atom selected from B, N, O, S, Si, and P, preferably O, S, and N, and includes tetrahydrofuran, pyrrolidine, thiolan, tetrahydropyran, etc.
  • (C6-C30)aryl(ene) indicates a monocyclic ring-type or fused ring-type radical derived from aromatic hydrocarbon having 6 to 30, preferabley 6 to 20, more preferably 6 to 15 ring backbone carbon atoms.
  • the aryl may have a spiro structure.
  • the aryl includes phenyl, biphenyl, terphenyl, naphthyl, binaphthyl, phenylnaphthyl, naphthylphenyl, fluorenyl, phenylfluorenyl, benzofluorenyl, dibenzofluorenyl, phenanthrenyl, phenylphenanthrenyl, anthracenyl, indenyl, triphenylenyl, pyrenyl, tetracenyl, perylenyl, chrysenyl, naphthacenyl, fluoranthenyl, spirobifluorenyl, etc.
  • (3 to 30-membered) heteroaryl(ene) indicates an aryl group having 3 to 30 ring backbone atoms including at least one, preferably 1 to 4, heteroatoms selected from the group consisting of B, N, O, S, Si, and P; may be a monocyclic ring, or a fused ring condensed with at least one benzene ring; may be partially saturated; may be one formed by linking at least one heteroaryl or aryl group to a heteroaryl group via a single bond(s); and may have a spiro structure.
  • the heteroaryl 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
  • substituted in the expression, “substituted or unsubstituted,” means that a hydrogen atom in a certain functional group is replaced with another atom or group, i.e. a substituent.
  • the substituent each independently, is at least one selected from the group consisting of a (C1-C20)alkyl, an unsubstituted (C6-C25)aryl, and an unsubstituted (5- to 25-membered)heteroaryl. More preferably, the substituent, each independently, is at least one selected from the group consisting of a (C1-C10)alkyl, an unsubstituted (C6-C18)aryl, and an unsubstituted (5- to 18-membered)heteroaryl.
  • the substituent, each independently may be at least one selected from the group consisting of methyl, an unsubstituted phenyl, and an unsubstituted benzofuranyl.
  • the organic electroluminescent compound of formula 1 includes the following, but is not limited thereto:
  • the organic electroluminescent compound of the present disclosure can be prepared by a synthetic method known to one skilled in the art. For example, it can be prepared according to the following reaction scheme 1.
  • the compounds C-40 and C-66 of the present disclosure can be prepared according to the following reaction schemes 2 and 3.
  • the present disclosure provides an organic electroluminescent material comprising the organic electroluminescent compound of formula 1, and an organic electroluminescent device comprising the material.
  • the material may consist of the organic electroluminescent compound of the present disclosure. Otherwise, the material may further comprise a conventional compound(s) which has been comprised for an organic electroluminescent material, in addition to the compound of the present disclosure.
  • the organic electroluminescent device may comprise a first electrode, a second electrode, and at least one organic layer disposed between the first and second electrodes.
  • the organic layer may comprise at least one 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, an auxiliary light-emitting layer, an electron transport layer, an electron injection layer, an interlayer, a hole blocking layer, an electron blocking layer, and an electron buffering layer, wherein the auxiliary light-emitting layer is disposed between the anode and the light-emitting layer or between the cathode and the light-emitting layer; the auxiliary light-emitting layer may be used to facilitate injection and/or transport of holes or to block overflow of electrons when it is disposed between the anode and the light-emitting layer, or the auxiliary light-emitting layer may be used to facilitate injection and/or transport of electrons or to block overflow of holes when it is disposed between the cathode and the light-emitting layer.
  • the hole auxiliary layer is disposed between the hole transport layer (or the hole injection layer) and the light-emitting layer and shows the effect to increase the hole transport speed (or the hole injection speed) or to block holes, and thereby, may control charge balance.
  • an electron blocking layer is disposed between the hole transport layer (or the hole injection layer) and the light-emitting layer and blocks electron overflow from the light-emitting layer to trap excitons within the light-emitting layer, and thereby, to prevent light leakage.
  • the additional hole transport layer may be used as the hole auxiliary layer or the electron blocking layer.
  • the hole auxiliary layer and the electron blocking layer have the effects to provide improvement in efficiency and lifespan of the organic electroluminescent device.
  • the organic electroluminescent compound of formula 1 of the present disclosure may be comprised in the light-emitting layer.
  • the organic electroluminescent compound of formula 1 of the present disclosure may be comprised as a host material.
  • the light-emitting layer may further comprise at least one dopant. If needed, it may comprise a compound other than the organic electroluminescent compound of formula 1 of the present disclosure as a second host material.
  • the weight ratio between the first host material and the second host material is in the range of 1:99 to 99:1.
  • the second host material may be from any of the known phosphorescent host materials. Specifically, the compound selected from the group consisting of the compounds of formulae 11 to 16 below is preferable as the second host material in view of luminous efficiency:
  • E represents -O- or -S-;
  • R 21 to R 24 each independently, represent hydrogen, deuterium, a halogen, a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C6-C30)aryl, a substituted or unsubstituted (5 to 30-membered) heteroaryl or -SiR 25 R 26 R 27 ;
  • R 25 to R 27 each independently, represent a substituted or unsubstituted (C1-C30)alkyl, or a substituted or unsubstituted (C6-C30)aryl;
  • L 4 represents a single bond, a substituted or unsubstituted (C6-C30)arylene, or a substituted or unsubstituted (5 to 30-membered) heteroarylene;
  • M represents a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted (5 to 30-membered) heteroaryl
  • Y 3 to Y 5 each independently, represent CR 34 or N;
  • R 34 each independently, represent hydrogen, a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted (5 to 30-membered)heteroaryl;
  • B 1 and B 2 each independently, represent hydrogen, a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted (5 to 30-membered)heteroaryl;
  • B 3 represents a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted (5 to 30-membered)heteroaryl;
  • L 5 represents a single bond or a substituted or unsubstituted (C6-C30)arylene, or a substituted or unsubstituted (5 to 30-membered)heteroarylene.
  • the second host material includes the following:
  • the dopant to be comprised in the organic electroluminescent device of the present disclosure is preferably at least one phosphorescent dopant.
  • the phosphorescent dopant material for the organic electroluminescent device of the present disclosure is not limited, but may be preferably selected from metallated complex compounds of iridium (Ir), osmium (Os), copper (Cu) or platinum (Pt), more preferably selected from ortho-metallated complex compounds of iridium (Ir), osmium (Os), copper (Cu) or platinum (Pt), and even more preferably ortho-metallated iridium complex compounds.
  • the compounds represented by the following formulae 101 to 103 may be used as the dopant to be comprised in the organic electroluminescent device of the present disclosure:
  • L is selected from the following structures:
  • R 100 represents hydrogen, a substituted or unsubstituted (C1-C30)alkyl, or a substituted or unsubstituted (C3-C30)cycloalkyl;
  • R 101 to R 109 and R 111 to R 123 each independently, represent hydrogen, deuterium, a halogen, a (C1-C30)alkyl substituted or unsubstituted with a halogen, a substituted or unsubstituted (C3-C30)cycloalkyl, a substituted or unsubstituted (C6-C30)aryl, a cyano, or a substituted or unsubstituted (C1-C30)alkoxy;
  • R 106 to R 109 each independently, may be linked to an adjacent substituent(s) to form a substituted or unsubstituted fused ring, for example, a fluorene substituted or unsubstituted with an alkyl, a dibenzothiophene substituted or unsubstituted with an alkyl, or a dibenzofuran substituted or unsubstituted with an alkyl;
  • R 120 to R 123 each independently
  • R 124 to R 127 each independently, represent hydrogen, deuterium, a halogen, a substituted or unsubstituted (C1-C30)alkyl, or a substituted or unsubstituted (C6-C30)aryl;
  • R 124 to R 127 each independently, may be linked to an adjacent substituent(s) to form a substituted or unsubstituted fused ring, for example, a fluorene substituted or unsubstituted with an alkyl, a dibenzothiophene substituted or unsubstituted with an alkyl, or a dibenzofuran substituted or unsubstituted with an alkyl;
  • R 201 to R 211 each independently, represent hydrogen, deuterium, a halogen, a (C1-C30)alkyl substituted or unsubstituted with a halogen, a substituted or unsubstituted (C3-C30)cycloalkyl, or a substituted or unsubstituted (C6-C30)aryl;
  • R 208 to R 211 each independently, may be linked to an adjacent substituent(s) to form a substituted or unsubstituted fused ring, for example, a fluorene substituted or unsubstituted with an alkyl, a dibenzothiophene substituted or unsubstituted with an alkyl, or a dibenzofuran substituted or unsubstituted with an alkyl;
  • f and g each independently, represent an integer of 1 to 3; when f or g is an integer of 2 or more, each of R 100 may be the same or different; and
  • n an integer of 1 to 3.
  • the phosphorescent dopant includes the following:
  • compositions for preparing an organic electroluminescent device may comprise the compound of the present disclosure, as a host material or a hole transport material.
  • the organic electroluminescent device of the present disclosure may comprise a first electrode, a second electrode, and at least one organic layer disposed between the first and second electrodes.
  • the organic layer may comprise a light-emitting layer, which may comprise the composition for the organic electroluminescent device of the present disclosure.
  • the organic electroluminescent device of the present disclosure comprises an organic electroluminescent compound of formula 1, and may further comprise at least one compound selected from the group consisting of arylamine-based compounds and styrylarylamine-based compounds.
  • the organic layer may further comprise, in addition to the compound of formula 1, 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 comprising the metal.
  • the organic layer may further comprise an auxiliary light-emitting layer, a hole auxiliary layer, and a charge generating layer, besides the light-emitting layer.
  • 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 field, besides the compound of the present disclosure. If necessary, it may further comprise an orange light-emitting layer or a yellow 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 field, besides the compound of the present disclosure. If necessary, it may further comprise an orange light-emitting layer or a yellow 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 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.
  • An OLED was produced using the organic electroluminescent compound of the present disclosure as follows.
  • a transparent electrode indium tin oxide (ITO) thin film (10 ⁇ /sq) on a glass substrate for an organic electroluminescent device (OLED) (Geomatec) was subjected to an ultrasonic washing with acetone and isopropanol sequentially and was then stored in isopropanol.
  • the ITO substrate was then mounted on a substrate holder of a vacuum vapor depositing apparatus.
  • Compound HIL-1 was introduced into a cell of the vacuum vapor depositing apparatus and then the pressure in the chamber of the apparatus was controlled to 10 -6 torr.
  • an electric current was applied to the cell to evaporate compound HIL-1 , thereby forming a first hole injection layer having a thickness of 80nm on the ITO substrate.
  • Compound HIL-2 was then introduced into another cell of the vacuum vapor depositing apparatus and evaporated by applying electric current to the cell, thereby forming a second hole injection layer having a thickness of 5nm on the first hole injection layer.
  • Compound HTL-1 was introduced into one cell of the vacuum vapor depositing apparatus and evaporated by applying electric current to the cell, thereby forming a first hole transport layer having a thickness of 10nm on the second hole injection layer.
  • Compound HTL-2 was then introduced into another cell of the vacuum vapor depositing apparatus and evaporated by applying electric current to the cell, thereby forming a second hole transport layer having a thickness of 60nm on the first hole transport layer.
  • a light-emitting layer was deposited thereon as follows.
  • Compound C-1 was introduced, as a host material, into a cell of the vacuum vapor depositing apparatus and compound D-71 was introduced into another cell. The two compounds were then evaporated at different rates, 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 40nm on the hole transport layer.
  • the time taken to be 98% of the luminance was 80 hours or more.
  • An OLED was produced in the same manner as in Device Example 1, except for using the following compound B-1 as a host for a light-emitting layer.
  • Comparative Device Example 1 when an initial luminance at 5000 nit and a constant current is set at 100% as in Device Example 1, the time taken to be 98% of the luminance was 40 hours or more.
  • the OLED employing the organic electroluminescent compound of the present disclosure has better properties including more improved lifespan than the conventional OLED employing the conventional organic electroluminescent compound.
  • Compound B-1 used in Comparative Device Example 1 or triazine derivatives suggested in the above-mentioned Korean Patent Application Laying-Open No. 10-2015-077220 has a planar structure, and thereby, has good driving voltage. However, they have insufficient thermal stability, since they have high Ts (Sublimation Temperature) due to strong molecular interactions by said planar structure.
  • the triazine has relatively short conjugation length, and such short conjugation results in instability of material itself, since the function of the conjugation is to stabilize electrons (radicals).
  • the organic electroluminescent compound of the present disclosure has a naphthalene-based substituent in the substituent position corresponding to the triazine, such as a quinazoline or a quinoxaline.
  • the naphthalene-based substituent has a non-planar structure relative to the triazine, and thereby, it may give higher driving voltage relative to the triazine.
  • the naphthalene-based substituent in contrast to the triazine, has low Ts and longer conjugation length relative to the triazine, and thereby, it may give superior heat stability and electron stabilization properties to the triazine.
  • the effects of the present disclosure confirmed by the Device Example and the Comparative Device Example may be considered in that the intermediate properties, between the naphthalene-based substituent and the triazine, of the organic electroluminescent compound of the present disclosure having the naphthalene-based substituent in the substituent position corresponding to the triazine, comprehensively affect lifespan of the OLED of the present disclosure, and thereby, the OLED of the present disclosure may have superior lifespan to the conventional OLED, due to the presence of the naphthalene-based substituent in the organic electroluminescent compound of the present disclosure.

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Abstract

The present disclosure relates to an organic electroluminescent compound and an organic electroluminescent device comprising the same. The organic electroluminescent compound of the present disclosure provides an organic electroluminescent device having a remarkably improved lifespan.

Description

ORGANIC ELECTROLUMINESCENT COMPOUNDS AND ORGANIC ELECTROLUMINESCENT DEVICE COMPRISING THE SAME
The present disclosure relates to an organic electroluminescent compound and an organic electroluminescent device comprising the same.
An electroluminescent (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. An organic EL device was first developed by Eastman Kodak, by using small aromatic diamine molecules and aluminum complexes as materials to form a light-emitting layer [Appl. Phys. Lett. 51, 913, 1987].
The most important factor determining luminous efficiency in the organic EL device is light-emitting materials. Until now, fluorescent materials have been widely used as light-emitting material. However, in view of electroluminescent mechanisms, since phosphorescent materials theoretically enhance luminous efficiency by four (4) times compared to fluorescent materials, phosphorescent light-emitting materials have been widely researched. Iridium(III) complexes have been widely known as phosphorescent materials, including bis(2-(2’-benzothienyl)-pyridinato-N,C-3’)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-emitting materials, respectively.
At present, 4,4’-N,N’-dicarbazol-biphenyl (CBP) is the most widely known host material for phosphorescent materials. Recently, Pioneer (Japan) et al., developed a high performance organic EL device using bathocuproine (BCP) and aluminum(III) bis(2-methyl-8-quinolinate)(4-phenylphenolate) (BAlq) etc., as host materials, which were known as hole blocking materials.
Although these materials provide good light-emitting characteristics, they have the following disadvantages: (1) Due to their low glass transition temperature and poor thermal stability, their degradation may occur during a high-temperature deposition process in a vacuum, which results in poor lifespan. (2) The power efficiency of the organic EL device is given by [(π/voltage) × current efficiency], and the power efficiency is inversely proportional to the voltage. Although the organic EL device comprising phosphorescent host materials provides higher current efficiency (cd/A) than one comprising fluorescent materials, a significantly high driving voltage is necessary. Thus, there is no merit in terms of power efficiency (lm/W). (3) Furthermore, the operational lifespan of the organic EL device is short, and luminous efficiency is still required to be improved. Accordingly, in order to embody the advantageous properties of the organic EL device, it is important to suitably select the materials that are comprised in the organic layer of the organic EL device, especially the host or dopant materials that are comprised in the light-emitting materials.
Japanese Patent Application Laying-Open No. 2014-160813 discloses an organic electroluminescent device comprising a nitrogen-containing heteroaryl compound formed by condensing a pyrrole ring, an aromatic aryl ring, and a 7-membered aryl ring, as host/dopant materials. However, it does not specifically disclose a compound in which a carbazole and an indole are fused with a 7-membered ring.
Korean Patent Application Laying-Open No. 10-2015-077220 discloses a compound in which an amine radical is fused with dibenzo residue including a carbazole, fluorene, or 5-membered hetero ring to form a ring. However, it does not specifically disclose a compound wherein a parent nucleus formed by a fusion of a carbazole, an indole, and a 7-membered ring, is connected, directly or via a linker of arylene or heteroarylene, to a 10-membered nitrogen-containing heteroaryl.
The objective of the present disclosure is to provide an organic electroluminescent compound, which is effective in preparing an organic electroluminescent device having a remarkably improved lifespan, and an organic electroluminescent device comprising the organic electroluminescent compound.
As a result of an earnest study for solving the above-described problems, the present inventor found that the above objective can be achieved by an organic electroluminescent compound represented by the following formula 1 and has come to complete the present disclosure:
Figure PCTKR2016014013-appb-I000001
wherein
X and Y, each independently, represent CR4 or N;
L1 represents a single bond, a substituted or unsubstituted (C6-C30)arylene, or a substituted or unsubstituted (3- to 30-membered) heteroarylene;
A represents hydrogen, a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted (3- to 30-membered) heteroaryl;
R1 to R3, each independently, represent hydrogen, deuterium, a halogen, a cyano, a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C6-C30)aryl, a substituted or unsubstituted (3- to 30-membered) heteroaryl, a substituted or unsubstituted (C3-C30)cycloalkyl, a substituted or unsubstituted (C1-C30)alkoxy, a substituted or unsubstituted tri(C1-C30)alkylsilyl, 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 tri(C6-C30)arylsilyl, a substituted or unsubstituted mono- or di-(C1-C30)alkylamino, a substituted or unsubstituted mono- or di-(C6-C30)arylamino, or a substituted or unsubstituted (C1-C30)alkyl(C6-C30)arylamino; or may be linked to an adjacent substituent(s) to form a substituted or unsubstituted (3 to 30-membered), mono- or polycyclic, alicyclic or aromatic ring, or a fused ring of the alicyclic ring and the aromatic ring, whose carbon atom(s) may be replaced with at least one heteroatom selected from the group consisting of nitrogen, oxygen, and sulfur;
R4 represents hydrogen, deuterium, a halogen, a cyano, a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C6-C30)aryl, a substituted or unsubstituted (3- to 30-membered) heteroaryl, a substituted or unsubstituted (C3-C30)cycloalkyl, a substituted or unsubstituted (C1-C30)alkoxy, a substituted or unsubstituted tri(C1-C30)alkylsilyl, 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 tri(C6-C30)arylsilyl, a substituted or unsubstituted mono- or di-(C1-C30)alkylamino, a substituted or unsubstituted mono- or di-(C6-C30)arylamino, or a substituted or unsubstituted (C1-C30)alkyl(C6-C30)arylamino;
wherein the heteroaryl(ene) contains one or more heteroatoms selected from the group consisting of B, N, O, S, Si, and P;
a, b, and c, each independently, represent an integer of 1 to 3,
and when a, b, or c is an integer of 2 or more, each of R1, R2 or R3 may be the same or different.
The present disclosure provides an organic electroluminescent device that has a remarkably improved lifespan.
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 compound of formula 1 is more specifically described below.
Herein, “an organic electroluminescent compound” indicates a compound that may be used for an organic electroluminescent device. The compound may be comprised in any layer of the organic electroluminescent device, as necessary.
In formula 1, X and Y, each independently, may represent CR4 or N. Preferably, any one of X and Y is CR4, and the other one is N.
In formula 1, L1 may represent a single bond or a substituted or unsubstituted (C6-C30)arylene, or a substituted or unsubstituted (3- to 30-membered) heteroarylene, preferably a single bond, a substituted or unsubstituted (C6-C25)arylene, or a substituted or unsubstituted (5- to 25-membered)heteroarylene, and more preferably a single bond, a substituted or unsubstituted (C6-C18)arylene, or an unsubstituted (5- to 18-membered)heteroarylene, such as a single bond, an unsubstituted phenyl, an unsubstituted naphthyl, fluorenyl substituted with dimethyl, or an unsubstituted pyridyl.
In formula 1, A may respresent hydrogen, a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted (3- to 30-membered) heteroaryl, preferably hydrogen, or a substituted or unsubstituted (C6-C25)aryl, and more preferably hydrogen, or an unsubstituted (C6-C18)aryl, such as hydrogen, an unsubstituted phenyl, an unsubstituted naphthyl, or an unsubstituted phenanthrenyl.
In formula 1, R1 to R3, each independently, may represent hydrogen, deuterium, a halogen, a cyano, a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C6-C30)aryl, a substituted or unsubstituted (3- to 30-membered) heteroaryl, a substituted or unsubstituted (C3-C30)cycloalkyl, a substituted or unsubstituted (C1-C30)alkoxy, a substituted or unsubstituted tri(C1-C30)alkylsilyl, 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 tri(C6-C30)arylsilyl, a substituted or unsubstituted mono- or di-(C1-C30)alkylamino, a substituted or unsubstituted mono- or di-(C6-C30)arylamino, or a substituted or unsubstituted (C1-C30)alkyl(C6-C30)arylamino; may be linked to an adjacent substituent(s) to form a substituted or unsubstituted (3 to 30-membered), mono- or polycyclic, alicyclic or aromatic ring, or a fused ring of the alicyclic ring and the aromatic ring, whose carbon atom(s) may be replaced with at least one heteroatom selected from the group consisting of nitrogen, oxygen, and sulfur; preferably R1 to R3, each independently, may represent hydrogen, or R1 to R3, each independently, may be linked to an adjacent substituent(s) to form a substituted or unsubstituted (C3-C25) mono- or polycyclic aromatic ring, whose carbon atom(s) may be replaced with at least one heteroatom selected from the group consisting of nitrogen, oxygen, and sulfur; more preferably R1 to R3, each independently, may represent hydrogen, or R1 to R3, each independently, may be linked to an adjacent substituent(s) to form a substituted or unsubstituted (C5-C18) mono- or polycyclic aromatic ring, whose carbon atom(s) may be replaced with at least one heteroatom selected from the group consisting of nitrogen, oxygen, and sulfur; for example, R1 to R3, each independently, may represent hydrogen, or R1 to R3, each independently, may be linked to an adjacent substituent(s) to form a substituted or unsubstituted benzene ring, a substituted or unsubstituted naphthalene ring, a substituted or unsubstituted indole ring, a substituted or unsubstituted benzofuran ring, a substituted or unsubstituted benzothiophene ring, or a substituted or unsubstituted indene ring; and specifically, an unsubstituted benzene ring, an unsubstituted naphthalene ring, an indole ring substituted with phenyl, an unsubstituted benzofuran ring, an unsubstituted benzothiophene ring, or an indene ring substituted with dimethyl.
In formula 1, R4 may represent hydrogen, deuterium, a halogen, a cyano, a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C6-C30)aryl, a substituted or unsubstituted (3- to 30-membered) heteroaryl, a substituted or unsubstituted (C3-C30)cycloalkyl, a substituted or unsubstituted (C1-C30)alkoxy, a substituted or unsubstituted tri(C1-C30)alkylsilyl, 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 tri(C6-C30)arylsilyl, a substituted or unsubstituted mono- or di-(C1-C30)alkylamino, a substituted or unsubstituted mono- or di-(C6-C30)arylamino, or a substituted or unsubstituted (C1-C30)alkyl(C6-C30)arylamino; preferably a substituted or unsubstituted (C6-C25)aryl, or a substituted or unsubstituted (5- to 25-membered)heteroaryl; more preferably a substituted or unsubstituted (C6-C18)aryl, or a substituted or unsubstituted (5- to 18-membered)heteroaryl, such as phenyl substituted or unsubstituted with benzofuran, an unsubstituted biphenyl, fluorenyl substituted with dimethyl or diphenyl, benzofluorenyl substituted with dimethyl, an unsubstituted benzofuranyl, an unsubstituted benzothiophenyl, carbazolyl substituted with phenyl, pyridyl substituted with phenyl, pyrimidinyl substituted with phenyl, or triazinyl substituted with phenyl.
In formula 1, heteroaryl(ene) contains one or more heteroatoms selected from the group consisting of B, N, O, S, Si, and P; and preferably, one or more heteroatoms selected from the group consisting of N, O, and S.
In formula 1, a, b or c, each independently, may represent an integer of 1 to 3; preferably an integer of 1 or 2; and when a, b or c represents an integer of 2 or more, each of R1, R2 or R3 may be the same or different.
The compound of formula 1 of the present disclosure may be represented by any one of the following formulae 2 to 9:
Figure PCTKR2016014013-appb-I000002
Figure PCTKR2016014013-appb-I000003
Figure PCTKR2016014013-appb-I000004
Figure PCTKR2016014013-appb-I000005
In formulae 2 to 9,
L1, R1 to R4, and, a, b, and c are as defined in formula 1 above.
Furthermore, the organic electroluminescent compound of formula 1 may be represented by the following formula 10:
Figure PCTKR2016014013-appb-I000006
wherein, X, Y, L1, A, R3, and c are as defined in formula 1 above.
In formula 10, Z represents O, S, CR5R6, or NR7, wherein R5 to R7, each independently, are the same as the definition of R4 in formula 1. Specifically, R5 to R7, each independently, may represent hydrogen, deuterium, a halogen, a cyano, a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C6-C30)aryl, a substituted or unsubstituted (3- to 30-membered) heteroaryl, a substituted or unsubstituted (C3-C30)cycloalkyl, a substituted or unsubstituted (C1-C30)alkoxy, a substituted or unsubstituted tri(C1-C30)alkylsilyl, 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 tri(C6-C30)arylsilyl, a substituted or unsubstituted mono- or di-(C1-C30)alkylamino, a substituted or unsubstituted mono- or di-(C6-C30)arylamino, or a substituted or unsubstituted (C1-C30)alkyl(C6-C30)arylamino; preferably a substituted or unsubstituted (C1-C20)alkyl, or a substituted or unsubstituted (C6-C25)aryl; and more preferably an unsubstituted (C1-C10)alkyl, or an unsubstituted (C6-C18)aryl. For example, R5 and R6, each independently, may respresent an unsubstituted methyl, and R7 may respresent an unsubstituted phenyl.
In formula 10, d and e, each independently, represent 0 or 1.
Herein, “(C1-C30)alkyl” indicates a linear or branched alkyl having 1 to 30, preferably 1 to 20, and more preferably 1 to 10 carbon atoms, and includes methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, etc. “(C2-C30) alkenyl” indicates a linear or branched alkenyl having 2 to 30, preferably 2 to 20, and more preferably 2 to 10 carbon atoms and includes vinyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 2-methylbut-2-enyl, etc. “(C2-C30)alkynyl” indicates a linear or branched alkynyl having 2 to 30, preferably 2 to 20, and more preferably 2 to 10 carbon atoms and includes ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-methylpent-2-ynyl, etc. Herein, “(C3-C30)cycloalkyl” indicates a mono- or polycyclic hydrocarbon having 3 to 30, preferabley 3 to 20, more preferably 3 to 7 ring backbone carbon atoms. The cycloalkyl includes cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc. Herein, “(3 to 7-membered)heterocycloalkyl” indicates a cycloalkyl having 3 to 7, preferably 5 to 7 ring backbone atoms including at least one hetero atom selected from B, N, O, S, Si, and P, preferably O, S, and N, and includes tetrahydrofuran, pyrrolidine, thiolan, tetrahydropyran, etc. Herein, “(C6-C30)aryl(ene)” indicates a monocyclic ring-type or fused ring-type radical derived from aromatic hydrocarbon having 6 to 30, preferabley 6 to 20, more preferably 6 to 15 ring backbone carbon atoms. The aryl may have a spiro structure. The aryl includes phenyl, biphenyl, terphenyl, naphthyl, binaphthyl, phenylnaphthyl, naphthylphenyl, fluorenyl, phenylfluorenyl, benzofluorenyl, dibenzofluorenyl, phenanthrenyl, phenylphenanthrenyl, anthracenyl, indenyl, triphenylenyl, pyrenyl, tetracenyl, perylenyl, chrysenyl, naphthacenyl, fluoranthenyl, spirobifluorenyl, etc. Herein, “(3 to 30-membered) heteroaryl(ene)” indicates an aryl group having 3 to 30 ring backbone atoms including at least one, preferably 1 to 4, heteroatoms selected from the group consisting of B, N, O, S, Si, and P; may be a monocyclic ring, or a fused ring condensed with at least one benzene ring; may be partially saturated; may be one formed by linking at least one heteroaryl or aryl group to a heteroaryl group via a single bond(s); and may have a spiro structure. The heteroaryl 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, phenothiazinyl, phenanthridinyl, benzodioxolyl, dihydroacridinyl, etc. Further, “halogen” includes F, Cl, Br, and I.
Furthermore, herein, “substituted” in the expression, “substituted or unsubstituted,” means that a hydrogen atom in a certain functional group is replaced with another atom or group, i.e. a substituent. In L1, A, and R1 to R4, the substituent of the substituted aryl(ene), the substituted heteroaryl(ene), the substituted alkyl, the substituted cycloalkyl, the substituted alkoxy, the substituted trialkylsilyl, the substituted dialkylarylsilyl, the substituted alkyldiarylsilyl, the substituted triarylsilyl, the substituted mono- or di-alkylamino, the substituted mono- or di- arylamino, the substituted alkylarylamino, and the substituted mono- or polycyclic, alicyclic or aromatic ring, or a fused ring of the alicyclic ring and the aromatic ring, each independently, is at least one selected from the group consisting of deuterium; a halogen; a cyano; a carboxy; a nitro; a hydroxy; 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 substituted or unsubstituted with a (C1-C30)alkyl or a (C6-C30)aryl; a (C6-C30)aryl substituted or unsubstituted with 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. Preferably, the substituent, each independently, is at least one selected from the group consisting of a (C1-C20)alkyl, an unsubstituted (C6-C25)aryl, and an unsubstituted (5- to 25-membered)heteroaryl. More preferably, the substituent, each independently, is at least one selected from the group consisting of a (C1-C10)alkyl, an unsubstituted (C6-C18)aryl, and an unsubstituted (5- to 18-membered)heteroaryl. For example, the substituent, each independently, may be at least one selected from the group consisting of methyl, an unsubstituted phenyl, and an unsubstituted benzofuranyl.
The organic electroluminescent compound of formula 1 includes the following, but is not limited thereto:
Figure PCTKR2016014013-appb-I000007
Figure PCTKR2016014013-appb-I000008
Figure PCTKR2016014013-appb-I000009
Figure PCTKR2016014013-appb-I000010
Figure PCTKR2016014013-appb-I000011
Figure PCTKR2016014013-appb-I000012
Figure PCTKR2016014013-appb-I000013
Figure PCTKR2016014013-appb-I000014
Figure PCTKR2016014013-appb-I000015
Figure PCTKR2016014013-appb-I000016
Figure PCTKR2016014013-appb-I000017
The organic electroluminescent compound of the present disclosure can be prepared by a synthetic method known to one skilled in the art. For example, it can be prepared according to the following reaction scheme 1.
[Reaction Scheme 1]
Figure PCTKR2016014013-appb-I000018
Figure PCTKR2016014013-appb-I000019
As a specific example of the synthetic method according to the above reaction scheme 1, the compounds C-40 and C-66 of the present disclosure can be prepared according to the following reaction schemes 2 and 3.
[Reaction Scheme 2]
Figure PCTKR2016014013-appb-I000020
Figure PCTKR2016014013-appb-I000021
[Reaction Scheme 3]
Figure PCTKR2016014013-appb-I000022
Figure PCTKR2016014013-appb-I000023
In the above reaction scheme 1, X, Y, L1, A, R1 to R3, and a, b, and c are as defined in formula 1 above.
Furthermore, the present disclosure provides an organic electroluminescent material comprising the organic electroluminescent compound of formula 1, and an organic electroluminescent device comprising the material.
The material may consist of the organic electroluminescent compound of the present disclosure. Otherwise, the material may further comprise a conventional compound(s) which has been comprised for an organic electroluminescent material, in addition to the compound of the present disclosure.
The organic electroluminescent device may comprise a first electrode, a second electrode, and at least one organic layer disposed between the first and second electrodes. The organic layer may comprise at least one 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, an auxiliary light-emitting layer, an electron transport layer, an electron injection layer, an interlayer, a hole blocking layer, an electron blocking layer, and an electron buffering layer, wherein the auxiliary light-emitting layer is disposed between the anode and the light-emitting layer or between the cathode and the light-emitting layer; the auxiliary light-emitting layer may be used to facilitate injection and/or transport of holes or to block overflow of electrons when it is disposed between the anode and the light-emitting layer, or the auxiliary light-emitting layer may be used to facilitate injection and/or transport of electrons or to block overflow of holes when it is disposed between the cathode and the light-emitting layer. In addition, the hole auxiliary layer is disposed between the hole transport layer (or the hole injection layer) and the light-emitting layer and shows the effect to increase the hole transport speed (or the hole injection speed) or to block holes, and thereby, may control charge balance. Furthermore, an electron blocking layer is disposed between the hole transport layer (or the hole injection layer) and the light-emitting layer and blocks electron overflow from the light-emitting layer to trap excitons within the light-emitting layer, and thereby, to prevent light leakage. When two or more hole transport layers are included, the additional hole transport layer may be used as the hole auxiliary layer or the electron blocking layer. The hole auxiliary layer and the electron blocking layer have the effects to provide improvement in efficiency and lifespan of the organic electroluminescent device.
The organic electroluminescent compound of formula 1 of the present disclosure may be comprised in the light-emitting layer. When used in the light-emitting layer, the organic electroluminescent compound of formula 1 of the present disclosure may be comprised as a host material. Preferably, the light-emitting layer may further comprise at least one dopant. If needed, it may comprise a compound other than the organic electroluminescent compound of formula 1 of the present disclosure as a second host material. The weight ratio between the first host material and the second host material is in the range of 1:99 to 99:1.
The second host material may be from any of the known phosphorescent host materials. Specifically, the compound selected from the group consisting of the compounds of formulae 11 to 16 below is preferable as the second host material in view of luminous efficiency:
Figure PCTKR2016014013-appb-I000024
Figure PCTKR2016014013-appb-I000025
Figure PCTKR2016014013-appb-I000026
Figure PCTKR2016014013-appb-I000027
Figure PCTKR2016014013-appb-I000028
Wherein, Cz represents the following structure:
Figure PCTKR2016014013-appb-I000029
E represents -O- or -S-;
R21 to R24 each independently, represent hydrogen, deuterium, a halogen, a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C6-C30)aryl, a substituted or unsubstituted (5 to 30-membered) heteroaryl or -SiR25R26R27; R25 to R27, each independently, represent a substituted or unsubstituted (C1-C30)alkyl, or a substituted or unsubstituted (C6-C30)aryl; L4 represents a single bond, a substituted or unsubstituted (C6-C30)arylene, or a substituted or unsubstituted (5 to 30-membered) heteroarylene; M represents a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted (5 to 30-membered) heteroaryl; Y1 and Y2 each independently, represent -O-, -S-, -N(R31)- or -C(R32)(R33)-, and Y1 and Y2 do not occur concurrently; R31 to R33, each independently, represent a substituted or unsubstituted (C1-C30)alky, a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted (5 to 30-membered) heteroaryl, R32 and R33 may be the same or different; h and i, each independently, represent an integer of 1 to 3; g represents an integer of 0 to 3; j, k, l, and m, each independently, represent an integer of 0 to 4; when g, h, i, j, k, l, or m is an integer of 2 or more, each of (Cz-L4), each of (Cz), each of R21, each of R22, each of R23 or each of R24 may be the same or different;
Figure PCTKR2016014013-appb-I000030
wherein
Y3 to Y5, each independently, represent CR34 or N;
R34, each independently, represent hydrogen, a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted (5 to 30-membered)heteroaryl;
B1 and B2, each independently, represent hydrogen, a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted (5 to 30-membered)heteroaryl;
B3 represents a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted (5 to 30-membered)heteroaryl; and
L5 represents a single bond or a substituted or unsubstituted (C6-C30)arylene, or a substituted or unsubstituted (5 to 30-membered)heteroarylene.
Specifically, the second host material includes the following:
Figure PCTKR2016014013-appb-I000031
Figure PCTKR2016014013-appb-I000032
Figure PCTKR2016014013-appb-I000033
Figure PCTKR2016014013-appb-I000034
Figure PCTKR2016014013-appb-I000035
Figure PCTKR2016014013-appb-I000036
Figure PCTKR2016014013-appb-I000037
Figure PCTKR2016014013-appb-I000038
Figure PCTKR2016014013-appb-I000039
Figure PCTKR2016014013-appb-I000040
Figure PCTKR2016014013-appb-I000041
Figure PCTKR2016014013-appb-I000042
Figure PCTKR2016014013-appb-I000043
Figure PCTKR2016014013-appb-I000044
Figure PCTKR2016014013-appb-I000045
Figure PCTKR2016014013-appb-I000046
Figure PCTKR2016014013-appb-I000047
Figure PCTKR2016014013-appb-I000048
Figure PCTKR2016014013-appb-I000049
Figure PCTKR2016014013-appb-I000050
Figure PCTKR2016014013-appb-I000051
Figure PCTKR2016014013-appb-I000052
Figure PCTKR2016014013-appb-I000053
Figure PCTKR2016014013-appb-I000054
Figure PCTKR2016014013-appb-I000055
Figure PCTKR2016014013-appb-I000056
Figure PCTKR2016014013-appb-I000057
Figure PCTKR2016014013-appb-I000058
[wherein TPS represents triphenylsilyl.]
The dopant to be comprised in the organic electroluminescent device of the present disclosure is preferably at least one phosphorescent dopant. The phosphorescent dopant material for the organic electroluminescent device of the present disclosure is not limited, but may be preferably selected from metallated complex compounds of iridium (Ir), osmium (Os), copper (Cu) or platinum (Pt), more preferably selected from ortho-metallated complex compounds of iridium (Ir), osmium (Os), copper (Cu) or platinum (Pt), and even more preferably ortho-metallated iridium complex compounds.
The compounds represented by the following formulae 101 to 103 may be used as the dopant to be comprised in the organic electroluminescent device of the present disclosure:
Figure PCTKR2016014013-appb-I000060
Figure PCTKR2016014013-appb-I000061
Figure PCTKR2016014013-appb-I000062
wherein L is selected from the following structures:
Figure PCTKR2016014013-appb-I000063
R100 represents hydrogen, a substituted or unsubstituted (C1-C30)alkyl, or a substituted or unsubstituted (C3-C30)cycloalkyl;
R101 to R109 and R111 to R123, each independently, represent hydrogen, deuterium, a halogen, a (C1-C30)alkyl substituted or unsubstituted with a halogen, a substituted or unsubstituted (C3-C30)cycloalkyl, a substituted or unsubstituted (C6-C30)aryl, a cyano, or a substituted or unsubstituted (C1-C30)alkoxy; R106 to R109, each independently, may be linked to an adjacent substituent(s) to form a substituted or unsubstituted fused ring, for example, a fluorene substituted or unsubstituted with an alkyl, a dibenzothiophene substituted or unsubstituted with an alkyl, or a dibenzofuran substituted or unsubstituted with an alkyl; R120 to R123, each independently, may be linked to an adjacent substituent(s) to form a substituted or unsubstituted fused ring, for example, a quinoline substituted or unsubstituted with an alkyl or aryl;
R124 to R127, each independently, represent hydrogen, deuterium, a halogen, a substituted or unsubstituted (C1-C30)alkyl, or a substituted or unsubstituted (C6-C30)aryl; R124 to R127, each independently, may be linked to an adjacent substituent(s) to form a substituted or unsubstituted fused ring, for example, a fluorene substituted or unsubstituted with an alkyl, a dibenzothiophene substituted or unsubstituted with an alkyl, or a dibenzofuran substituted or unsubstituted with an alkyl;
R201 to R211, each independently, represent hydrogen, deuterium, a halogen, a (C1-C30)alkyl substituted or unsubstituted with a halogen, a substituted or unsubstituted (C3-C30)cycloalkyl, or a substituted or unsubstituted (C6-C30)aryl; R208 to R211, each independently, may be linked to an adjacent substituent(s) to form a substituted or unsubstituted fused ring, for example, a fluorene substituted or unsubstituted with an alkyl, a dibenzothiophene substituted or unsubstituted with an alkyl, or a dibenzofuran substituted or unsubstituted with an alkyl;
f and g, each independently, represent an integer of 1 to 3; when f or g is an integer of 2 or more, each of R100 may be the same or different; and
n represents an integer of 1 to 3.
Specifically, the phosphorescent dopant includes the following:
Figure PCTKR2016014013-appb-I000064
Figure PCTKR2016014013-appb-I000065
Figure PCTKR2016014013-appb-I000066
Figure PCTKR2016014013-appb-I000067
Figure PCTKR2016014013-appb-I000068
Figure PCTKR2016014013-appb-I000069
Figure PCTKR2016014013-appb-I000070
Figure PCTKR2016014013-appb-I000071
Figure PCTKR2016014013-appb-I000072
Figure PCTKR2016014013-appb-I000073
Figure PCTKR2016014013-appb-I000074
Figure PCTKR2016014013-appb-I000075
Figure PCTKR2016014013-appb-I000076
Figure PCTKR2016014013-appb-I000077
Figure PCTKR2016014013-appb-I000078
Figure PCTKR2016014013-appb-I000079
Figure PCTKR2016014013-appb-I000080
Figure PCTKR2016014013-appb-I000081
Figure PCTKR2016014013-appb-I000082
Figure PCTKR2016014013-appb-I000083
Figure PCTKR2016014013-appb-I000084
Figure PCTKR2016014013-appb-I000085
Figure PCTKR2016014013-appb-I000086
Figure PCTKR2016014013-appb-I000087
Figure PCTKR2016014013-appb-I000088
According to an additional aspect of the present disclosure, a composition for preparing an organic electroluminescent device is provided. The composition may comprise the compound of the present disclosure, as a host material or a hole transport material.
The organic electroluminescent device of the present disclosure may comprise a first electrode, a second electrode, and at least one organic layer disposed between the first and second electrodes. The organic layer may comprise a light-emitting layer, which may comprise the composition for the organic electroluminescent device of the present disclosure.
The organic electroluminescent device of the present disclosure comprises an organic electroluminescent compound of formula 1, and may further comprise 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, in addition to the compound of formula 1, 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 comprising the metal. The organic layer may further comprise an auxiliary light-emitting layer, a hole auxiliary layer, and a charge generating layer, besides the light-emitting layer.
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 field, besides the compound of the present disclosure. If necessary, it may further comprise an orange light-emitting layer or a yellow 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.
Furthermore, 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 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 of the present disclosure, the preparation method of the compound, and the luminescent properties of the device will be explained in detail with reference to the following examples.
[Example 1] Preparation of compound C-1
Figure PCTKR2016014013-appb-I000089
Figure PCTKR2016014013-appb-I000090
1) Preparation of compound 1-1
After introducing compound A (36.0g, 152.3mmol), 2-(4,4,5,5-tetramethyl-1,3,2-dioxaboran-2-yl)aniline (40g, 182.7mmol), tetrakis(triphenylphosphine)palladium (5.28g, 4.6mmol), cesium carbonate (124.0g, 380.6mmol), toluene (760mL), EtOH (190mL), and distilled water (190mL) into a reaction vessel, the mixture was stirred at 120°C for 5 hours. After completion of the reaction, the mixture was washed with distilled water and extracted with ethyl acetate. The obtained organic layer was dried with magnesium sulfate and the solvent was removed therefrom by a rotary evaporator. The products were purified by column chromatography to obtain compound 1-1 (19.3g, yield: 50.4%).
2) Preparation of compound 1-2
After introducing compound 1-1 (19.2g, 77.2mmol) and acetonitrile (768mL) into a reaction vessel, para-toluenesulfonic acid monohydrate (44.06g, 231.6mmol) was added at 0℃. After 10 minutes, sodium nitrite (10.66g, 154.4mmol) and potassium iodide (32.0g, 193.0mmol) were dissolved in distilled water (576mL), and then slowly added dropwise to the mixture. After completion of the dropwise addition, the mixture was warmed slowly to room temperature and then additionally stirred for 5 hours. After completion of the reaction, an aqueous solution of sodium thiosulfate was added thereto to stop the reaction. The mixture was then extracted with ethyl acetate. The obtained organic layer was dried with magnesium sulfate and the solvent was removed therefrom by a rotary evaporator. The products were purified by column chromatography to obtain compound 1-2 (18.6g, yield: 67.0%).
3) Preparation of compound 1-3
After introducing compound 1-2 (18.6g, 51.7mmol), 1-(4,4,5,5-tetramethyl-1,3,2-dioxaboran-2-yl)-9H-carbazole (15.3g, 62.1mmol), tetrakis(triphenylphosphine)palladium (3.0g, 2.6mmol), cesium carbonate (13.7g, 129.3mmol), toluene (260mL), EtOH (65mL), and distilled water (65mL) into a reaction vessel, the mixture was stirred at 120°C for 4 hours. After completion of the reaction, the mixture was washed with distilled water and extracted with ethyl acetate. The obtained organic layer was dried with magnesium sulfate and the solvent was removed therefrom by a rotary evaporator. The products were purified by column chromatography to obtain compound 1-3 (11.4g, yield: 55.3%).
4) Preparation of compound 1-4
After introducing compound 1-3 (11.0g, 27.6mmol), palladium(II)acetate (3.1g, 13.8mmol), tri-tert-butylphosphine (11.16g, 27.6mmol), cesium carbonate (35.94g, 110.4mmol), and o-xylene (184 mL) into a reaction vessel, the mixture was stirred under reflux for 3 hours. After completion of the reaction, the mixture was washed with distilled water and extracted with ethyl acetate. The obtained organic layer was dried with magnesium sulfate and the solvent was removed therefrom by a rotary evaporator. The products were purified by column chromatography to obtain compound 1-4 (5.4g, yield: 54.0%).
5) Preparation of compound 1-5
After introducing compound 1-4 (5.4g, 14.9mmol), triphenylphosphine (11.7g, 44.7mmol), and 1,2-dichlorobenzene (75 mL) into a reaction vessel, the mixture was stirred at 200°C for 8 hours. After completion of the reaction, the mixture was distilled under reduced pressure to remove the solvent. The mixture was then washed with distilled water and extracted with ethyl acetate. The obtained organic layer was dried with magnesium sulfate and the solvent was removed therefrom by a rotary evaporator. The products were purified by column chromatography to obtain compound 1-5 (4.5g, yield: 91.3%).
6) Preparation of compound C-1
After dissolving compound 1-5 (3.5g, 10.6mmol), 2-chloro-4-phenylquinazoline (3.06g, 12.7mmol), dimethylaminopyridine(DMAP) (0.65g, 5.3mmol), potassium carbonate (K2CO3) (1.47g, 10.6mmol), and dimethyl formamide (53mL) into a reaction vessel, the mixture was stirred at 155°C for 4 hours. After completion of the reaction, the mixture was cooled to between 5°C and 10°C. Then, MeOH (50mL) and distilled water (60mL) were added thereto, the mixture was stirred for 30 minutes, and then filtered to obtain compound C-1 (5.4g, yield: 95.3%).
Figure PCTKR2016014013-appb-I000091
[Device Example 1] OLED comprising the compound of the present
disclosure as a host
An OLED was produced using the organic electroluminescent compound of the present disclosure as follows. A transparent electrode indium tin oxide (ITO) thin film (10 Ω/sq) on a glass substrate for an organic electroluminescent device (OLED) (Geomatec) was subjected to an ultrasonic washing with acetone and isopropanol sequentially and was then stored in isopropanol. The ITO substrate was then mounted on a substrate holder of a vacuum vapor depositing apparatus. Compound HIL-1 was introduced into a cell of the vacuum vapor depositing apparatus and then the pressure in the chamber of the apparatus was controlled to 10-6 torr. Thereafter, an electric current was applied to the cell to evaporate compound HIL-1, thereby forming a first hole injection layer having a thickness of 80nm on the ITO substrate. Compound HIL-2 was then introduced into another cell of the vacuum vapor depositing apparatus and evaporated by applying electric current to the cell, thereby forming a second hole injection layer having a thickness of 5nm on the first hole injection layer. Compound HTL-1 was introduced into one cell of the vacuum vapor depositing apparatus and evaporated by applying electric current to the cell, thereby forming a first hole transport layer having a thickness of 10nm on the second hole injection layer. Compound HTL-2 was then introduced into another cell of the vacuum vapor depositing apparatus and evaporated by applying electric current to the cell, thereby forming a second hole transport layer having a thickness of 60nm on the first hole transport layer. After forming the hole injection layer and the hole transport layer, a light-emitting layer was deposited thereon as follows. Compound C-1 was introduced, as a host material, into a cell of the vacuum vapor depositing apparatus and compound D-71 was introduced into another cell. The two compounds were then evaporated at different rates, 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 40nm on the hole transport layer. Compounds ETL-1 and Liq were then introduced into another two cells of the vacuum vapor depositing apparatus, respectively, and evaporated at the same rate of 1:1, thereby forming an electron transport layer having a thickness of 30nm on the light-emitting layer. After depositing compound Liq as an electron injection layer having a thickness of 2nm on the electron transport layer, an Al cathode having a thickness of 80nm was then deposited by another vacuum vapor deposition apparatus on the electron injection layer to produce the OLED.
Figure PCTKR2016014013-appb-I000092
Figure PCTKR2016014013-appb-I000093
When an initial luminance at 5000 nit and a constant current is set at 100%, the time taken to be 98% of the luminance was 80 hours or more.
[Comparative Device Example 1] OLED comprising a conventional organic
electroluminescent compound
An OLED was produced in the same manner as in Device Example 1, except for using the following compound B-1 as a host for a light-emitting layer.
Figure PCTKR2016014013-appb-I000094
In Comparative Device Example 1, when an initial luminance at 5000 nit and a constant current is set at 100% as in Device Example 1, the time taken to be 98% of the luminance was 40 hours or more.
As confirmed by the Device Example and the Comparative Device Example, the OLED employing the organic electroluminescent compound of the present disclosure has better properties including more improved lifespan than the conventional OLED employing the conventional organic electroluminescent compound. Compound B-1 used in Comparative Device Example 1 or triazine derivatives suggested in the above-mentioned Korean Patent Application Laying-Open No. 10-2015-077220 has a planar structure, and thereby, has good driving voltage. However, they have insufficient thermal stability, since they have high Ts (Sublimation Temperature) due to strong molecular interactions by said planar structure. Furthermore, the triazine has relatively short conjugation length, and such short conjugation results in instability of material itself, since the function of the conjugation is to stabilize electrons (radicals).
On the other hand, the organic electroluminescent compound of the present disclosure has a naphthalene-based substituent in the substituent position corresponding to the triazine, such as a quinazoline or a quinoxaline. The naphthalene-based substituent has a non-planar structure relative to the triazine, and thereby, it may give higher driving voltage relative to the triazine. In addition, the naphthalene-based substituent, in contrast to the triazine, has low Ts and longer conjugation length relative to the triazine, and thereby, it may give superior heat stability and electron stabilization properties to the triazine.
The effects of the present disclosure confirmed by the Device Example and the Comparative Device Example may be considered in that the intermediate properties, between the naphthalene-based substituent and the triazine, of the organic electroluminescent compound of the present disclosure having the naphthalene-based substituent in the substituent position corresponding to the triazine, comprehensively affect lifespan of the OLED of the present disclosure, and thereby, the OLED of the present disclosure may have superior lifespan to the conventional OLED, due to the presence of the naphthalene-based substituent in the organic electroluminescent compound of the present disclosure.

Claims (6)

  1. An organic electroluminescent compound represented by the following formula 1:
    Figure PCTKR2016014013-appb-I000095
    wherein
    X and Y, each independently, represent CR4 or N;
    L1 represents a single bond, a substituted or unsubstituted (C6-C30)arylene, or a substituted or unsubstituted (3- to 30-membered) heteroarylene;
    A represents hydrogen, a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted (3- to 30-membered) heteroaryl;
    R1 to R3, each independently, represent hydrogen, deuterium, a halogen, a cyano, a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C6-C30)aryl, a substituted or unsubstituted (3- to 30-membered) heteroaryl, a substituted or unsubstituted (C3-C30)cycloalkyl, a substituted or unsubstituted (C1-C30)alkoxy, a substituted or unsubstituted tri(C1-C30)alkylsilyl, 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 tri(C6-C30)arylsilyl, a substituted or unsubstituted mono- or di-(C1-C30)alkylamino, a substituted or unsubstituted mono- or di-(C6-C30)arylamino, or a substituted or unsubstituted (C1-C30)alkyl(C6-C30)arylamino; or may be linked to an adjacent substituent(s) to form a substituted or unsubstituted (3 to 30-membered), mono- or polycyclic, alicyclic or aromatic ring, or a fused ring of the alicyclic ring and the aromatic ring, whose carbon atom(s) may be replaced with at least one heteroatom selected from the group consisting of nitrogen, oxygen, and sulfur;
    R4 represents hydrogen, deuterium, a halogen, a cyano, a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C6-C30)aryl, a substituted or unsubstituted (3- to 30-membered) heteroaryl, a substituted or unsubstituted (C3-C30)cycloalkyl, a substituted or unsubstituted (C1-C30)alkoxy, a substituted or unsubstituted tri(C1-C30)alkylsilyl, 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 tri(C6-C30)arylsilyl, a substituted or unsubstituted mono- or di-(C1-C30)alkylamino, a substituted or unsubstituted mono- or di-(C6-C30)arylamino, or a substituted or unsubstituted (C1-C30)alkyl(C6-C30)arylamino;
    wherein the heteroaryl(ene) contains one or more heteroatoms selected from the group consisting of B, N, O, S, Si, and P;
    a, b, and c, each independently, represent an integer of 1 to 3,
    and when a, b, or c is an integer of 2 or more, each of R1, R2 or R3 may be the same or different.
  2. The organic electroluminescent compound according to claim 1, wherein the organic electroluminescent compound of formula 1 is represented by any of the following formulae 2 to 9:
    Figure PCTKR2016014013-appb-I000096
    Figure PCTKR2016014013-appb-I000097
    Figure PCTKR2016014013-appb-I000098
    Figure PCTKR2016014013-appb-I000099
    In formulae 2 to 9,
    L1, R1 to R4, and, a, b, and c are as defined in claim 1.
  3. The organic electroluminescent compound according to claim 1, wherein the organic electroluminescent compound of formula 1 is represented by the following formula 10:
    Figure PCTKR2016014013-appb-I000100
    wherein
    X, Y, L1, A, R3, and c are as defined in claim 1,
    Z represents O, S, CR5R6, or NR7,
    R5 to R7, each independently, are the same as R4 defined in claim 1, and
    d and e , each independently, represent an integer of 0 or 1.
  4. The organic electroluminescent compound according to claim 1, wherein in the L1, A, and R1 to R4, the substituent of the substituted aryl(ene), the substituted heteroaryl(ene), the substituted alkyl, the substituted cycloalkyl, the substituted alkoxy, the substituted trialkylsilyl, the substituted dialkylarylsilyl, the substituted alkyldiarylsilyl, the substituted triarylsilyl, the substituted mono- or di- alkylamino, the substituted mono- or di- arylamino, the substituted alkylarylamino, and the substituted mono- or polycyclic, alicyclic or aromatic ring, or a fused ring of the alicyclic ring and the aromatic ring, each independently, is at least one selected from the group consisting of deuterium; a halogen; a cyano; a carboxy; a nitro; a hydroxy; 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 substituted or unsubstituted with a (C1-C30)alkyl or a (C6-C30)aryl; a (C6-C30)aryl substituted or unsubstituted with 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.
  5. The organic electroluminescent compound according to claim 1, wherein the compound represented by formula 1 is selected from the group consisting of:
    Figure PCTKR2016014013-appb-I000101
    Figure PCTKR2016014013-appb-I000102
    Figure PCTKR2016014013-appb-I000103
    Figure PCTKR2016014013-appb-I000104
    Figure PCTKR2016014013-appb-I000105
    Figure PCTKR2016014013-appb-I000106
    Figure PCTKR2016014013-appb-I000107
    Figure PCTKR2016014013-appb-I000108
    Figure PCTKR2016014013-appb-I000109
    Figure PCTKR2016014013-appb-I000110
    Figure PCTKR2016014013-appb-I000111
  6. An organic electroluminescent device comprising the organic electroluminescent compound according to claim 1.
PCT/KR2016/014013 2015-12-04 2016-12-01 Organic electroluminescent compounds and organic electroluminescent device comprising the same WO2017095156A1 (en)

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CN112400010A (en) * 2018-07-25 2021-02-23 罗门哈斯电子材料韩国有限公司 Organic electroluminescent compounds and organic electroluminescent device comprising the same
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JP2021193080A (en) * 2020-06-05 2021-12-23 北京夏禾科技有限公司 Electroluminescent material and element
KR102670402B1 (en) 2020-06-05 2024-05-29 베이징 썸머 스프라우트 테크놀로지 컴퍼니 리미티드 Electroluminescent material and device

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