WO2017105040A1 - 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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WO2017105040A1
WO2017105040A1 PCT/KR2016/014458 KR2016014458W WO2017105040A1 WO 2017105040 A1 WO2017105040 A1 WO 2017105040A1 KR 2016014458 W KR2016014458 W KR 2016014458W WO 2017105040 A1 WO2017105040 A1 WO 2017105040A1
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substituted
unsubstituted
alkyl
organic electroluminescent
aryl
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Hong-Se OH
Su-Hyun Lee
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DuPont Specialty Materials Korea Ltd
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Rohm and Haas Electronic Materials Korea Ltd
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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
    • C07D487/22—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
    • C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
    • C07D471/22—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed systems 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
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D498/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D498/22—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms in which the condensed system contains four or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D513/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for in groups C07D463/00, C07D477/00 or C07D499/00 - C07D507/00
    • C07D513/22—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for in groups C07D463/00, C07D477/00 or C07D499/00 - C07D507/00 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 materials, e.g. electroluminescent or chemiluminescent
    • C09K11/06—Luminescent materials, e.g. electroluminescent or chemiluminescent containing organic luminescent materials
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/12—Light sources with substantially two-dimensional [2D] radiating surfaces
    • H05B33/14—Light sources with substantially two-dimensional [2D] radiating surfaces characterised by the chemical or physical composition or the arrangement of the electroluminescent material, or by the simultaneous addition of the electroluminescent material in or onto the light source
    • 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
    • H10K85/653—Aromatic compounds comprising a hetero atom comprising only oxygen as heteroatom
    • 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
    • H10K85/654—Aromatic compounds comprising a hetero atom comprising only nitrogen as heteroatom
    • 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
    • H10K85/655—Aromatic compounds comprising a hetero atom comprising only sulfur as heteroatom
    • 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
    • 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

Definitions

  • the present disclosure relates to an organic electroluminescent compound and an organic electroluminescent device comprising the same.
  • an electroluminescent device is a self-light-emitting display 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 in 1987, by using small aromatic diamine molecules and aluminum complexes as materials for forming a light-emitting layer [Appl. Phys. Lett. 51, 913, 1987].
  • CBP 4,4'-N,N'-dicarbazol-biphenyl
  • BCP bathocuproine
  • BAlq aluminum(III) bis(2-methyl-8-quinolinate)(4-phenylphenolate)
  • Korean Patent No. 10-1511115 discloses a compound having the structure fused with two carbazoles and an organic electroluminescent device comprising the compound.
  • the above reference does not specifically disclose a compound having a structure wherein nitrogen atoms comprised in the two carbazoles are linked to each other via an aryl or a heteroaryl as a linker to form a 7- to 10-membered ring, and wherein the aryls comprised in each carbazole are linked to each other via a heteroatom as a linker.
  • the object of the present disclosure is firstly, to provide an organic electroluminescent compound effective to produce an organic electroluminescent device having low driving voltage, and/or excellent power and/or luminous efficiencies, and secondly, to provide an organic electroluminescent device comprising the organic electroluminescent compound.
  • X represents O, S or NR 5 ;
  • R 1 to R 4 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
  • R 5 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)aryls
  • the heteroaryl contains at least one heteroatom selected from B, N, O, S, Si, and P;
  • a and b each independently, represent an integer of 1 to 4
  • c and d each independently, represent an integer of 1 or 2; where if a to d, each independently, represent an integer of 2 or more, each of R 1 to R 4 may be the same or different.
  • the organic electroluminescent compound of the present disclosure can produce an organic electroluminescent device having low driving voltage and/or excellent power and/or luminous efficiencies.
  • an organic electroluminescent compound in the present disclosure means a compound that may be used in an organic electroluminescent device, and may be comprised in any layers constituting an organic electroluminescent device, if necessary.
  • an organic electroluminescent material in the present disclosure means a material that may be used in an organic electroluminescent device, and may comprise at least one compound. If necessary, the organic electroluminescent material may be comprised in any layers constituting an organic electroluminescent device.
  • the organic electroluminescent material may be a hole injection material, a hole transport material, a hole auxiliary material, a light-emitting auxiliary material, an electron blocking material, a light-emitting material, an electron buffer material, a hole blocking material, an electron transport material, an electron injection material, etc.
  • X represents O, S or NR 5 .
  • ring Y represents a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted (3- to 30-membered)heteroaryl; preferably, a substituted or unsubstituted (C6-C25)aryl, or a substituted or unsubstituted (5- to 25-membered)heteroaryl; and more preferably, a substituted or unsubstituted (C6-C18)aryl, or a substituted or unsubstituted (5- to 18-membered)heteroaryl.
  • ring Y represents a substituted or unsubstituted benzene, a substituted or unsubstituted pyridine, a substituted or unsubstituted pyrimidine, a substituted or unsubstituted pyrazine, a substituted or unsubstituted thiophene, or a substituted or unsubstituted furan, and the benzene, the pyridine, the pyrimidine, the pyrazine, the thiophene, or the furan may be an unsubstituted ring.
  • R 1 to R 4 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
  • R 5 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)ary
  • R 5 may represent a substituted or unsubstituted phenyl, an unsubstituted naphthylphenyl, an unsubstituted biphenyl, an unsubstituted terphenyl, a triazinyl substituted with one or two phenyl(s), a quinazolinyl substituted with a phenyl, a quinoxalinyl substituted with a phenyl, a pyrimidinyl substituted with one or two phenyl(s), or a substituted pyridyl, wherein the substituent of the substituted phenyl may be a triazinyl substituted with one or two phenyl(s), a triazinyl substituted with a phenyl and/or a biphenyl, a quinoxalinyl substituted with a phenyl, or an unsubstituted pyridyl, and wherein the substituent of
  • the heteroaryl contains at least one heteroatom selected from B, N, O, S, Si, and P; preferably, contains at least one heteroatom selected from N, O and S; and more preferably, represents a nitrogen-containing heteroaryl comprising at least one nitrogen.
  • a and b each independently, represent an integer of 1 to 4
  • c and d each independently, represent an integer of 1 or 2; where if a to d, each independently, represent an integer of 2 or more, each of R 1 to R 4 may be the same or different.
  • a to d each independently, represent an integer of 1.
  • ring Y represents a substituted or unsubstituted (C6-C25)aryl, or a substituted or unsubstituted (5- to 25-membered)heteroaryl
  • X represents O, S or NR 5
  • R 1 to R 4 each independently, represent hydrogen, a substituted or unsubstituted (C6-C25)aryl, or a substituted or unsubstituted (5- to 25-membered)heteroaryl
  • R 5 represents a substituted or unsubstituted (C6-C25)aryl, or a substituted or unsubstituted (5- to 25-membered)heteroaryl
  • a to d each independently, represent an integer of 1.
  • ring Y represents a substituted or unsubstituted (C6-C18)aryl, or a substituted or unsubstituted (5- to 18-membered)heteroaryl
  • X represents O, S or NR 5
  • R 1 to R 4 each independently, represent hydrogen, or a substituted or unsubstituted (5- to 18-membered)heteroaryl
  • R 5 represents a substituted or unsubstituted (C6-C18)aryl, or a substituted or unsubstituted (5- to 18-membered)heteroaryl
  • a to d each independently, represent an integer of 1.
  • ring Y represents a substituted or unsubstituted benzene, a substituted or unsubstituted pyridine, a substituted or unsubstituted pyrimidine, a substituted or unsubstituted pyrazine, a substituted or unsubstituted thiophene, or a substituted or unsubstituted furan;
  • X represents O, S or NR 5 ;
  • R 1 to R 4 each independently, represent hydrogen, a triazinyl substituted with a diphenyl, or an unsubstituted pyridyl;
  • R 5 represents a substituted or unsubstituted phenyl, an unsubstituted naphthylphenyl, an unsubstituted biphenyl, an unsubstituted terphenyl, a triazinyl substituted with a diphenyl, a quinazoliny
  • (C1-C30)alkyl is meant to be a linear or branched alkyl having 1 to 30 carbon atoms constituting the chain, in which the number of carbon atoms is preferably 1 to 20, more preferably 1 to 10, and includes methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, etc.
  • (C2-C30)alkenyl is meant to be a linear or branched alkenyl having 2 to 30 carbon atoms constituting the chain, in which the number of carbon atoms is preferably 2 to 20, more preferably 2 to 10, and includes vinyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 2-methylbut-2-enyl, etc.
  • (C2-C30)alkynyl is meant to be a linear or branched alkynyl having 2 to 30 carbon atoms constituting the chain, in which the number of carbon atoms is preferably 2 to 20, more preferably 2 to 10, and includes ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-methylpent-2-ynyl, etc.
  • (C3-C30)cycloalkyl is a mono- or polycyclic hydrocarbon having 3 to 30 ring backbone carbon atoms, in which the number of carbon atoms is preferably 3 to 20, more preferably 3 to 7, and includes cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc.
  • (3- to 7- membered) heterocycloalkyl is a cycloalkyl having 3 to 7, preferably 5 to 7, ring backbone atoms, including at least one heteroatom selected from B, N, O, S, Si, and P, preferably O, S, and N, and includes tetrahydrofuran, pyrrolidine, thiolan, tetrahydropyran, etc.
  • (C6-C30)aryl is a monocyclic or fused ring radical derived from an aromatic hydrocarbon having 6 to 30 ring backbone carbon atoms, in which the number of the ring backbone carbon atoms is preferably 6 to 20, more preferably 6 to 15, may be partially saturated, and may comprise a spiro structure.
  • the above aryl may include 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 is an aryl 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.
  • the above heteroaryl 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); may comprise a spiro structure; 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, and pyridazinyl, and a fused ring-type heteroaryl such as benzofuranyl, be
  • substituted in the expression “substituted or unsubstituted” means that a hydrogen atom in a certain functional group is replaced with another atom or another functional group, i.e. a substituent.
  • the organic electroluminescent compound represented by formula 1 includes the following compounds, but is not limited thereto:
  • the organic electroluminescent compound of the present disclosure may be produced by a synthetic method known to a person skilled in the art referring to the following reaction scheme 1, but is not limited thereto.
  • ring Y, R 1 to R 4 , and a to d are as defined in formula 1.
  • the present disclosure also discloses an organic electroluminescent material comprising the organic electroluminescent 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 blocking layer, and an electron buffer layer.
  • the light-emitting auxiliary layer may be placed between the anode and the light-emitting layer, or between the cathode and the light-emitting layer.
  • the light-emitting auxiliary layer When the light-emitting auxiliary layer is placed between the anode and the light-emitting layer, it can be used for promoting the hole injection and/or the hole transport, or for preventing the overflow of electrons.
  • the light-emitting auxiliary layer is placed between the cathode and the light-emitting layer, it can be used for promoting the electron injection and/or the electron transport, or for preventing the overflow of holes.
  • the hole auxiliary layer may be placed between the hole transport layer (or hole injection layer) and the light-emitting layer, and may be effective to promote or block the hole transport rate (or the hole injection rate), thereby enabling the charge balance to be controlled.
  • the electron blocking layer may be placed between the hole transport layer (or hole injection layer) and the light-emitting layer, and can confine the excitons in the light-emitting layer by blocking the overflow of electrons from the light-emitting layer to prevent a light-emitting leakage.
  • the hole transport layer which is further included, may be used as a hole auxiliary layer or an electron blocking layer.
  • the light-emitting auxiliary layer, the hole auxiliary layer or the electron blocking layer may have an effect of improving the efficiency and/or the lifespan of the organic electroluminescent device.
  • the organic electroluminescent compound represented by formula 1 may be comprised in the light-emitting layer.
  • the organic electroluminescent compound of formula 1 may be comprised as a host material.
  • the light-emitting layer may further comprise at least one dopant.
  • another compound besides the organic electroluminescent compound of formula 1 may be further comprised as a second host material.
  • the weight ratio of the first host material to the second host material is in the range of 1:99 to 99:1.
  • the second host material can use any of the known phosphorescent hosts.
  • the second host material may comprise the compound selected from the group consisting of the compounds represented by the following formulas 11 to 16:
  • A 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 ; in which 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-member
  • Y 3 to Y 5 each independently, represent CR 34 or N, in which R 34 represents 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, a substituted or unsubstituted (C6-C30)arylene, or a substituted or unsubstituted (5- to 30-membered)heteroarylene.
  • the preferred examples of the second host material are as follows:
  • TPS represents a triphenylsilyl group.
  • the dopant comprised in the organic electroluminescent device of the present disclosure is preferably at least one phosphorescent dopant.
  • the phosphorescent dopant material applied to the organic electroluminescent device of the present disclosure is not particulary limited, but may be preferably selected from the metallated complex compounds of iridium (Ir), osmium (Os), copper (Cu), and platinum (Pt), more preferably selected from ortho-metallated complex compounds of iridium (Ir), osmium (Os), copper (Cu), and platinum (Pt), and even more preferably ortho-metallated iridium complex compounds.
  • the dopant comprised in the organic electroluminescent device of the present disclosure may comprise the compound selected from the group consisting of the compounds represented by the following formulas 101 to 103:
  • L is selected from the following structures:
  • R 100 represents hydrogen, deuterium, 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 unsubstituted or substituted 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 may be linked to adjacent R 106 to R 109 , respectively, to form a substituted or unsubstituted fused ring, e.g., a fluorene unsubstituted or substituted with an alkyl, a dibenzothiophene unsubstituted or substituted with an alkyl, or a dibenzofuran unsubstituted or substituted with an alkyl; and R 120 to R
  • 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; and R 124 to R 127 may be linked to adjacent R 124 to R 127 , respectively, to form a substituted or unsubstituted fused ring, e.g., a fluorene unsubstituted or substituted with an alkyl, a dibenzothiophene unsubstituted or substituted with an alkyl, or a dibenzofuran unsubstituted or substituted with an alkyl;
  • R 201 to R 211 each independently, represent hydrogen, deuterium, a halogen, a (C1-C30)alkyl unsubstituted or substituted with a halogen, a substituted or unsubstituted (C3-C30)cycloalkyl, or a substituted or unsubstituted (C6-C30)aryl; and R 208 to R 211 may be linked to adjacent R 208 to R 211 , respectively, to form a substituted or unsubstituted fused ring, e.g., a fluorene unsubstituted or substituted with an alkyl, a dibenzothiophene unsubstituted or substituted with an alkyl, or a dibenzofuran unsubstituted or substituted with an alkyl;
  • f and g each independently, represent an integer of 1 to 3; where if f or g is an integer of 2 or more, each R 100 may be the same or different; and
  • n an integer of 1 to 3.
  • compositions for producing an organic electroluminescent device may be 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 between the first and second electrodes.
  • the organic layer may comprise a light-emitting layer, and the light-emitting layer may comprise a composition for the organic electroluminescent device of the present disclosure.
  • the organic electroluminescent device of the present disclosure may comprise the organic electroluminescent compound of formula 1, and further comprise at least one compound selected from the group consisting of arylamine-based compounds and styrylarylamine-based compounds, simultaneously.
  • 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 one or more additional light-emitting layers and a charge generating 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, a red, or a green electroluminescent compound known in the field, besides the compound of the present disclosure. If necessary, it may further comprise a yellow or an orange light-emitting layer.
  • a surface layer may be placed on an inner surface(s) of one or both electrode(s).
  • 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 organic electroluminescent device having two or more light-emitting layers and emitting white light.
  • dry film-forming methods such as vacuum evaporation, sputtering, plasma, ion plating methods, etc.
  • wet film-forming methods such as ink jet printing, nozzle printing, slot coating, spin coating, dip coating, flow coating methods, etc.
  • 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.
  • the luminescent properties of the organic light-emitting diode (OLED) device comprising the compound of the present disclosure will be explained in detail.
  • the present disclosure is not limited by the following examples.
  • An OLED device was produced by using the organic electroluminescent compound according to the present disclosure.
  • a transparent electrode indium tin oxide (ITO) thin film (10 ⁇ /sq) on a glass substrate for an OLED device (GEOMATEC CO., LTD., Japan) 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 deposition apparatus.
  • Compound HI-1 was introduced into a cell of the vacuum vapor deposition apparatus, and then the pressure in the chamber of the apparatus was controlled to 10 -6 torr.
  • compound HI-2 was introduced into another cell of the vacuum vapor deposition 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.
  • Compound HT-1 was then introduced into another cell of the vacuum vapor deposition 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.
  • Compound HT-2 was then introduced into another cell of the vacuum vapor deposition apparatus, and was evaporated by applying an electric current to the cell, thereby forming a second hole transport layer having a thickness of 30 nm on the first hole transport layer.
  • a light-emitting layer was formed thereon as follows: Compound C-1 was introduced into one cell of the vacuum vapor depositing apparatus as a host, and compound D-74 was introduced into another cell as a dopant.
  • the two materials were evaporated at a different rate, and the dopant was deposited in a doping amount of 10 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.
  • Compound ET-1 and compound EI-1 were then introduced into another two cells, and respectively evaporated at a rate of 4:6 to form an electron transport layer having a thickness of 35 nm on the light-emitting layer.
  • an Al cathode having a thickness of 80 nm was deposited on the electron injection layer by another vacuum vapor deposition apparatus.
  • an OLED device was produced.
  • Each of the materials used for producing the OLED device was purified by vacuum sublimation at 10 -6 torr.
  • An OLED device was produced in the same manner as in Device Example 1-1, except for using the following compound CBP as a host.
  • the driving voltage, the luminous efficiency, the power efficiency, and the CIE color coordinate based on 10 mA/cm 2 of the OLED devices produced as set forth above are provided in Table 1 below.
  • An OLED device was produced in the same manner as in Device Example 1-1, except for using compound D-1 as a dopant.
  • Comparative Example 2-1 Producing an OLED device using a conventional
  • An OLED device was produced in the same manner as in Device Example 1-1, except for the following: A light-emitting layer having a thickness of 40 nm was deposited on the second hole transport layer by using compound CBP as a host and compound D-1 as a dopant; compound Balq was deposited as a hole blocking layer having a thickness of 10 nm; and thereafter, compound ET-1 and compound EI-1 were introduced into another two cells, and evaporated at a rate of 4:6 to form an electron transport layer having a thickness of 25 nm on the light-emitting layer.
  • the driving voltage, the luminous efficiency, the power efficiency, and the CIE color coordinate based on a luminance of 1,000 nits of the OLED devices produced as set forth above are provided in Table 2 below.

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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 can provide an organic electroluminescent device having low driving voltage, and/or excellent power and/or luminous efficiencies.

Description

ORGANIC ELECTROLUMINESCENT COMPOUND AND ORGANIC ELECTROLUMINESCENT DEVICE COMPRISING THE SAME
The present disclosure relates to an organic electroluminescent compound and an organic electroluminescent device comprising the same.
Among display devices, an electroluminescent device (EL device) is a self-light-emitting display 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 in 1987, by using small aromatic diamine molecules and aluminum complexes as materials for forming a light-emitting layer [Appl. Phys. Lett. 51, 913, 1987].
The most important factor determining luminous efficiency in an organic electroluminescent device is light-emitting materials. Until now, fluorescent materials have been widely used as the light-emitting material. However, in view of electroluminescent mechanisms, since phosphorescent light-emitting materials theoretically enhance luminous efficiency by four (4) times compared to fluorescent light-emitting materials, phosphorescent light-emitting materials have been widely researched. Iridium(III) complexes have been widely known as phosphorescent light-emitting 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)picolinato iridium (Firpic) as red-, green- and blue-emitting materials, respectively.
In conventional technology, 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 electroluminescent 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 luminous 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, and the lifespan of the device may be shortened. (2) The power efficiency of the organic electroluminescent device is given by [(π/voltage) × current efficiency], and the power efficiency is inversely proportional to the voltage. Although the organic electroluminescent 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) Also, the operational lifespan of the organic electroluminescent device is short, and luminous efficiency is still necessary to improve. Accordingly, the materials constituting the organic layer in the device, in particular a host or a dopant constituting the light-emitting material, must be selected appropriately in order to realize the excellent characteristics of the organic EL device.
Korean Patent No. 10-1511115 discloses a compound having the structure fused with two carbazoles and an organic electroluminescent device comprising the compound. However, the above reference does not specifically disclose a compound having a structure wherein nitrogen atoms comprised in the two carbazoles are linked to each other via an aryl or a heteroaryl as a linker to form a 7- to 10-membered ring, and wherein the aryls comprised in each carbazole are linked to each other via a heteroatom as a linker.
The object of the present disclosure is firstly, to provide an organic electroluminescent compound effective to produce an organic electroluminescent device having low driving voltage, and/or excellent power and/or luminous efficiencies, and secondly, to provide an organic electroluminescent device comprising the organic electroluminescent compound.
As a result of intensive studies to solve the technical problem above, the present inventors found that an organic electroluminescent compound having the specific structure described herein can remarkably improve the power and/or luminous efficiencies of an organic electroluminescent device. Specifically, the present inventors found that the above objective can be achieved by an organic electroluminescent compound represented by the following formula 1:
Figure PCTKR2016014458-appb-I000001
wherein
ring Y represents a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted (3- to 30-membered)heteroaryl;
X represents O, S or NR5;
R1 to R4, 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 are linked to adjacent R1 to R4 to form a substituted or unsubstituted, mono- or polycyclic, (C3-C30) alicyclic or aromatic ring, or the combination thereof, whose carbon atom(s) may be replaced with at least one heteroatom selected from nitrogen, oxygen, and sulfur;
R5 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;
the heteroaryl contains at least one heteroatom selected from B, N, O, S, Si, and P; and
a and b, each independently, represent an integer of 1 to 4, and c and d, each independently, represent an integer of 1 or 2; where if a to d, each independently, represent an integer of 2 or more, each of R1 to R4 may be the same or different.
The organic electroluminescent compound of the present disclosure can produce an organic electroluminescent device having low driving voltage and/or excellent power and/or luminous efficiencies.
Hereinafter, the present disclosure will be described in detail. However, the following description is intended to explain the disclosure, and is not meant in any way to restrict the scope of the disclosure.
The term “an organic electroluminescent compound” in the present disclosure means a compound that may be used in an organic electroluminescent device, and may be comprised in any layers constituting an organic electroluminescent device, if necessary.
The term “an organic electroluminescent material” in the present disclosure means a material that may be used in an organic electroluminescent device, and may comprise at least one compound. If necessary, the organic electroluminescent material may be comprised in any layers constituting an organic electroluminescent device. For example, the organic electroluminescent material may be a hole injection material, a hole transport material, a hole auxiliary material, a light-emitting auxiliary material, an electron blocking material, a light-emitting material, an electron buffer material, a hole blocking material, an electron transport material, an electron injection material, etc.
The compound represented by formula 1 will be described in detail as follows.
In formula 1, X represents O, S or NR5.
In formula 1, ring Y represents a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted (3- to 30-membered)heteroaryl; preferably, a substituted or unsubstituted (C6-C25)aryl, or a substituted or unsubstituted (5- to 25-membered)heteroaryl; and more preferably, a substituted or unsubstituted (C6-C18)aryl, or a substituted or unsubstituted (5- to 18-membered)heteroaryl. According to one embodiment of the present disclosure, ring Y represents a substituted or unsubstituted benzene, a substituted or unsubstituted pyridine, a substituted or unsubstituted pyrimidine, a substituted or unsubstituted pyrazine, a substituted or unsubstituted thiophene, or a substituted or unsubstituted furan, and the benzene, the pyridine, the pyrimidine, the pyrazine, the thiophene, or the furan may be an unsubstituted ring.
In formula 1, R1 to R4, 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 are linked to adjacent R1 to R4 to form a substituted or unsubstituted, mono- or polycyclic, (C3-C30) alicyclic or aromatic ring, or the combination thereof, whose carbon atom(s) may be replaced with at least one heteroatom selected from nitrogen, oxygen, and sulfur; preferably, hydrogen, a substituted or unsubstituted (C6-C25)aryl, or a substituted or unsubstituted (5- to 25-membered)heteroaryl; more preferably, hydrogen, or a substituted or unsubstituted (5- to 18-membered)heteroaryl; and, for example, hydrogen, a triazinyl substituted with one or two phenyl(s), or an unsubstituted pyridyl.
In formula 1, R5 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; preferably, a substituted or unsubstituted (C6-C25)aryl, or a substituted or unsubstituted (5- to 25-membered)heteroaryl; and more preferably, a substituted or unsubstituted (C6-C18)aryl, or a substituted or unsubstituted (5- to 18-membered)heteroaryl. For example, R5 may represent a substituted or unsubstituted phenyl, an unsubstituted naphthylphenyl, an unsubstituted biphenyl, an unsubstituted terphenyl, a triazinyl substituted with one or two phenyl(s), a quinazolinyl substituted with a phenyl, a quinoxalinyl substituted with a phenyl, a pyrimidinyl substituted with one or two phenyl(s), or a substituted pyridyl, wherein the substituent of the substituted phenyl may be a triazinyl substituted with one or two phenyl(s), a triazinyl substituted with a phenyl and/or a biphenyl, a quinoxalinyl substituted with a phenyl, or an unsubstituted pyridyl, and wherein the substituent of the substituted pyridyl may be a triazinyl substituted with one or two phenyl(s).
In formula 1, the heteroaryl contains at least one heteroatom selected from B, N, O, S, Si, and P; preferably, contains at least one heteroatom selected from N, O and S; and more preferably, represents a nitrogen-containing heteroaryl comprising at least one nitrogen.
In formula 1, a and b, each independently, represent an integer of 1 to 4, and c and d, each independently, represent an integer of 1 or 2; where if a to d, each independently, represent an integer of 2 or more, each of R1 to R4 may be the same or different. Preferably, a to d, each independently, represent an integer of 1.
According to one embodiment of the present disclosure, in formula 1, ring Y represents a substituted or unsubstituted (C6-C25)aryl, or a substituted or unsubstituted (5- to 25-membered)heteroaryl; X represents O, S or NR5; R1 to R4, each independently, represent hydrogen, a substituted or unsubstituted (C6-C25)aryl, or a substituted or unsubstituted (5- to 25-membered)heteroaryl; R5 represents a substituted or unsubstituted (C6-C25)aryl, or a substituted or unsubstituted (5- to 25-membered)heteroaryl; and a to d, each independently, represent an integer of 1.
According to one embodiment of the present disclosure, in formula 1, ring Y represents a substituted or unsubstituted (C6-C18)aryl, or a substituted or unsubstituted (5- to 18-membered)heteroaryl; X represents O, S or NR5; R1 to R4, each independently, represent hydrogen, or a substituted or unsubstituted (5- to 18-membered)heteroaryl; R5 represents a substituted or unsubstituted (C6-C18)aryl, or a substituted or unsubstituted (5- to 18-membered)heteroaryl; and a to d, each independently, represent an integer of 1.
According to one embodiment of the present disclosure, in formula 1, ring Y represents a substituted or unsubstituted benzene, a substituted or unsubstituted pyridine, a substituted or unsubstituted pyrimidine, a substituted or unsubstituted pyrazine, a substituted or unsubstituted thiophene, or a substituted or unsubstituted furan; X represents O, S or NR5; R1 to R4, each independently, represent hydrogen, a triazinyl substituted with a diphenyl, or an unsubstituted pyridyl; R5 represents a substituted or unsubstituted phenyl, an unsubstituted naphthylphenyl, an unsubstituted biphenyl, an unsubstituted terphenyl, a triazinyl substituted with a diphenyl, a quinazolinyl substituted with a phenyl, a quinoxalinyl substituted with a phenyl, a pyrimidinyl substituted with a diphenyl, or a substituted pyridyl; and a to d, each independently, represent an integer of 1.
Herein, the term “(C1-C30)alkyl” is meant to be a linear or branched alkyl having 1 to 30 carbon atoms constituting the chain, in which the number of carbon atoms is preferably 1 to 20, more preferably 1 to 10, and includes methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, etc. The term “(C2-C30)alkenyl” is meant to be a linear or branched alkenyl having 2 to 30 carbon atoms constituting the chain, in which the number of carbon atoms is preferably 2 to 20, more preferably 2 to 10, and includes vinyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 2-methylbut-2-enyl, etc. The term “(C2-C30)alkynyl” is meant to be a linear or branched alkynyl having 2 to 30 carbon atoms constituting the chain, in which the number of carbon atoms is preferably 2 to 20, more preferably 2 to 10, and includes ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-methylpent-2-ynyl, etc. The term “(C3-C30)cycloalkyl” is a mono- or polycyclic hydrocarbon having 3 to 30 ring backbone carbon atoms, in which the number of carbon atoms is preferably 3 to 20, more preferably 3 to 7, and includes cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc. The term “(3- to 7- membered) heterocycloalkyl” is a cycloalkyl having 3 to 7, preferably 5 to 7, ring backbone atoms, including at least one heteroatom selected from B, N, O, S, Si, and P, preferably O, S, and N, and includes tetrahydrofuran, pyrrolidine, thiolan, tetrahydropyran, etc. The term “(C6-C30)aryl” is a monocyclic or fused ring radical derived from an aromatic hydrocarbon having 6 to 30 ring backbone carbon atoms, in which the number of the ring backbone carbon atoms is preferably 6 to 20, more preferably 6 to 15, may be partially saturated, and may comprise a spiro structure. The above aryl may include phenyl, biphenyl, terphenyl, naphthyl, binaphthyl, phenylnaphthyl, naphthylphenyl, fluorenyl, phenylfluorenyl, benzofluorenyl, dibenzofluorenyl, phenanthrenyl, phenylphenanthrenyl, anthracenyl, indenyl, triphenylenyl, pyrenyl, tetracenyl, perylenyl, chrysenyl, naphthacenyl, fluoranthenyl, spirobifluorenyl, etc. The term “(3- to 30-membered)heteroaryl” is an aryl 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. The above heteroaryl 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); may comprise a spiro structure; 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, and pyridazinyl, and a fused ring-type heteroaryl such as benzofuranyl, benzothiophenyl, isobenzofuranyl, dibenzofuranyl, dibenzothiophenyl, benzimidazolyl, benzothiazolyl, benzoisothiazolyl, benzoisoxazolyl, benzoxazolyl, isoindolyl, indolyl, indazolyl, benzothiadiazolyl, quinolyl, isoquinolyl, cinnolinyl, quinazolinyl, quinoxalinyl, carbazolyl, benzocarbazolyl, phenoxazinyl, phenothiazinyl, phenanthridinyl, benzodioxolyl, and dihydroacridinyl. Furthermore, “halogen” includes F, Cl, Br, and I.
Herein, “substituted” in the expression “substituted or unsubstituted” means that a 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, the substituted heteroaryl, 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 the combination thereof, in ring Y, and R1 to R5 of formula 1, 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 (C1-C30)alkyl and/or a (C6-C30)aryl; a (C6-C30)aryl unsubstituted or substituted 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, are at least one selected from the group consisting of a (C6-C25)aryl unsubstituted or substituted with a (5- to 18-membered)heteroaryl, and a (5- to 25-membered)heteroaryl unsubstituted or substituted with a (C6-C25)aryl; more preferably, are at least one selected from the group consisting of an unsubstituted (C6-C18)aryl, and a (5- to 18-membered)heteroaryl unsubstituted or substituted with a (C6-C18)aryl; and for example, may be at least one selected from the group consisting of an unsubstituted phenyl, an unsubstituted naphthyl, an unsubstituted biphenyl, an unsubstituted pyridyl, a triazinyl substituted with one or two phenyl(s), a triazinyl substituted with a phenyl and/or a biphenyl, and a quinoxalinyl substituted with a phenyl.
The organic electroluminescent compound represented by formula 1 includes the following compounds, but is not limited thereto:
Figure PCTKR2016014458-appb-I000002
Figure PCTKR2016014458-appb-I000003
Figure PCTKR2016014458-appb-I000004
Figure PCTKR2016014458-appb-I000005
Figure PCTKR2016014458-appb-I000006
Figure PCTKR2016014458-appb-I000007
Figure PCTKR2016014458-appb-I000008
Figure PCTKR2016014458-appb-I000009
Figure PCTKR2016014458-appb-I000010
Figure PCTKR2016014458-appb-I000011
Figure PCTKR2016014458-appb-I000012
Figure PCTKR2016014458-appb-I000013
Figure PCTKR2016014458-appb-I000014
The organic electroluminescent compound of the present disclosure may be produced by a synthetic method known to a person skilled in the art referring to the following reaction scheme 1, but is not limited thereto.
[Reaction Scheme 1]
Figure PCTKR2016014458-appb-I000015
Figure PCTKR2016014458-appb-I000016
Figure PCTKR2016014458-appb-I000017
Figure PCTKR2016014458-appb-I000018
wherein, ring Y, R1 to R4, and a to d are as defined in formula 1.
The present disclosure also discloses an organic electroluminescent material comprising the organic electroluminescent 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 blocking layer, and an electron buffer layer.
The light-emitting auxiliary layer may be placed between the anode and the light-emitting layer, or between the cathode and the light-emitting layer. When the light-emitting auxiliary layer is placed between the anode and the light-emitting layer, it can be used for promoting the hole injection and/or the hole transport, or for preventing the overflow of electrons. When the light-emitting auxiliary layer is placed between the cathode and the light-emitting layer, it can be used for promoting the electron injection and/or the electron transport, or for preventing the overflow of holes. Also, the hole auxiliary layer may be placed between the hole transport layer (or hole injection layer) and the light-emitting layer, and may be effective to promote or block the hole transport rate (or the hole injection rate), thereby enabling the charge balance to be controlled. Further, the electron blocking layer may be placed between the hole transport layer (or hole injection layer) and the light-emitting layer, and can confine the excitons in the light-emitting layer by blocking the overflow of electrons from the light-emitting layer to prevent a light-emitting leakage. When an organic electroluminescent device includes two or more hole transport layers, the hole transport layer, which is further included, may be used as a hole auxiliary layer or an electron blocking layer. The light-emitting auxiliary layer, the hole auxiliary layer or the electron blocking layer may have an effect of improving the efficiency and/or the lifespan of the organic electroluminescent device.
The organic electroluminescent compound represented by formula 1 may be comprised in the light-emitting layer. When used in the light-emitting layer, the organic electroluminescent compound of formula 1 may be comprised as a host material. Preferably, the light-emitting layer may further comprise at least one dopant. If necessary, another compound besides the organic electroluminescent compound of formula 1 may be further comprised as a second host material. Herein, the weight ratio of the first host material to the second host material is in the range of 1:99 to 99:1.
The second host material can use any of the known phosphorescent hosts. Preferably, the second host material may comprise the compound selected from the group consisting of the compounds represented by the following formulas 11 to 16:
Figure PCTKR2016014458-appb-I000019
Figure PCTKR2016014458-appb-I000020
Figure PCTKR2016014458-appb-I000021
Figure PCTKR2016014458-appb-I000022
Figure PCTKR2016014458-appb-I000023
wherein
Cz represents the following structure:
Figure PCTKR2016014458-appb-I000024
A represents -O- or -S-; and
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; in which 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-, -NR31- or -CR32R33-, with the proviso that Y1 and Y2 are not present simultaneously; R31 to R33, each independently, represent a substituted or unsubstituted (C1-C30)alkyl, 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; j, k, l and m, each independently, represent an integer of 0 to 4; q represents an integer of 0 to 3; where if h, i, j, k, l, m or q represents an integer of 2 or more, each (Cz-L4), each (Cz), each R21, each R22, each R23 or each R24 may be the same or different;
Figure PCTKR2016014458-appb-I000025
wherein
Y3 to Y5, each independently, represent CR34 or N, in which R34 represents 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, a substituted or unsubstituted (C6-C30)arylene, or a substituted or unsubstituted (5- to 30-membered)heteroarylene.
Specifically, the preferred examples of the second host material are as follows:
Figure PCTKR2016014458-appb-I000026
Figure PCTKR2016014458-appb-I000027
Figure PCTKR2016014458-appb-I000028
Figure PCTKR2016014458-appb-I000029
Figure PCTKR2016014458-appb-I000030
Figure PCTKR2016014458-appb-I000031
Figure PCTKR2016014458-appb-I000032
Figure PCTKR2016014458-appb-I000033
Figure PCTKR2016014458-appb-I000034
Figure PCTKR2016014458-appb-I000035
Figure PCTKR2016014458-appb-I000036
Figure PCTKR2016014458-appb-I000037
Figure PCTKR2016014458-appb-I000038
Figure PCTKR2016014458-appb-I000039
Figure PCTKR2016014458-appb-I000040
Figure PCTKR2016014458-appb-I000041
Figure PCTKR2016014458-appb-I000042
Figure PCTKR2016014458-appb-I000043
Figure PCTKR2016014458-appb-I000044
Figure PCTKR2016014458-appb-I000045
Figure PCTKR2016014458-appb-I000046
Figure PCTKR2016014458-appb-I000047
Figure PCTKR2016014458-appb-I000048
Figure PCTKR2016014458-appb-I000049
Figure PCTKR2016014458-appb-I000050
Figure PCTKR2016014458-appb-I000051
Figure PCTKR2016014458-appb-I000052
Figure PCTKR2016014458-appb-I000053
Figure PCTKR2016014458-appb-I000054
[Wherein, TPS represents a triphenylsilyl group.]
The dopant comprised in the organic electroluminescent device of the present disclosure is preferably at least one phosphorescent dopant. The phosphorescent dopant material applied to the organic electroluminescent device of the present disclosure is not particulary limited, but may be preferably selected from the metallated complex compounds of iridium (Ir), osmium (Os), copper (Cu), and platinum (Pt), more preferably selected from ortho-metallated complex compounds of iridium (Ir), osmium (Os), copper (Cu), and platinum (Pt), and even more preferably ortho-metallated iridium complex compounds.
The dopant comprised in the organic electroluminescent device of the present disclosure may comprise the compound selected from the group consisting of the compounds represented by the following formulas 101 to 103:
Figure PCTKR2016014458-appb-I000055
Figure PCTKR2016014458-appb-I000056
Figure PCTKR2016014458-appb-I000057
wherein, L is selected from the following structures:
Figure PCTKR2016014458-appb-I000058
R100 represents hydrogen, deuterium, 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 unsubstituted or substituted 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 may be linked to adjacent R106 to R109, respectively, to form a substituted or unsubstituted fused ring, e.g., a fluorene unsubstituted or substituted with an alkyl, a dibenzothiophene unsubstituted or substituted with an alkyl, or a dibenzofuran unsubstituted or substituted with an alkyl; and R120 to R123 may be linked to adjacent R120 to R123, respectively, to form a substituted or unsubstituted fused ring, e.g., a quinoline unsubstituted or substituted with an alkyl or an 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; and R124 to R127 may be linked to adjacent R124 to R127, respectively, to form a substituted or unsubstituted fused ring, e.g., a fluorene unsubstituted or substituted with an alkyl, a dibenzothiophene unsubstituted or substituted with an alkyl, or a dibenzofuran unsubstituted or substituted with an alkyl;
R201 to R211, each independently, represent hydrogen, deuterium, a halogen, a (C1-C30)alkyl unsubstituted or substituted with a halogen, a substituted or unsubstituted (C3-C30)cycloalkyl, or a substituted or unsubstituted (C6-C30)aryl; and R208 to R211 may be linked to adjacent R208 to R211, respectively, to form a substituted or unsubstituted fused ring, e.g., a fluorene unsubstituted or substituted with an alkyl, a dibenzothiophene unsubstituted or substituted with an alkyl, or a dibenzofuran unsubstituted or substituted with an alkyl;
f and g, each independently, represent an integer of 1 to 3; where if f or g is an integer of 2 or more, each R100 may be the same or different; and
n represents an integer of 1 to 3.
The specific examples of the compound used as a dopant are as follows:
Figure PCTKR2016014458-appb-I000059
Figure PCTKR2016014458-appb-I000060
Figure PCTKR2016014458-appb-I000061
Figure PCTKR2016014458-appb-I000062
Figure PCTKR2016014458-appb-I000063
Figure PCTKR2016014458-appb-I000064
Figure PCTKR2016014458-appb-I000065
Figure PCTKR2016014458-appb-I000066
Figure PCTKR2016014458-appb-I000067
Figure PCTKR2016014458-appb-I000068
Figure PCTKR2016014458-appb-I000069
Figure PCTKR2016014458-appb-I000070
Figure PCTKR2016014458-appb-I000071
Figure PCTKR2016014458-appb-I000072
Figure PCTKR2016014458-appb-I000073
Figure PCTKR2016014458-appb-I000074
Figure PCTKR2016014458-appb-I000075
Figure PCTKR2016014458-appb-I000076
Figure PCTKR2016014458-appb-I000077
Figure PCTKR2016014458-appb-I000078
Figure PCTKR2016014458-appb-I000079
Figure PCTKR2016014458-appb-I000080
Figure PCTKR2016014458-appb-I000081
Figure PCTKR2016014458-appb-I000082
Figure PCTKR2016014458-appb-I000083
According to a further embodiment of the present disclosure, a composition for producing an organic electroluminescent device may be provided. The composition may comprise the compound of the present disclosure as a host material or a hole transport material.
Also, 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 a light-emitting layer, and the light-emitting layer may comprise a composition for the organic electroluminescent device of the present disclosure.
The organic electroluminescent device of the present disclosure may comprise the organic electroluminescent compound of formula 1, and further comprise at least one compound selected from the group consisting of arylamine-based compounds and styrylarylamine-based compounds, simultaneously.
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 one or more additional light-emitting layers and a charge generating 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, a red, or a green electroluminescent compound known in the field, besides the compound of the present disclosure. If necessary, it may further comprise a yellow or an orange light-emitting layer.
In the organic electroluminescent device of the present disclosure, preferably, at least one layer selected from a chalcogenide layer, a metal halide layer, and a metal oxide layer (hereinafter, "a surface layer”) may be placed on an inner surface(s) of one or both electrode(s). 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 organic 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, ion plating methods, etc., or wet film-forming methods such as ink jet printing, nozzle printing, slot coating, spin coating, dip coating, flow coating methods, etc., 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 preparation method of the organic electroluminescent compounds of the present disclosure, and the properties of the device comprising the compounds will be explained in detail with reference to the representative compounds of the present disclosure. However, the present disclosure is not limited by the following examples.
Example 1: Preparation of compound C-1
Figure PCTKR2016014458-appb-I000084
Figure PCTKR2016014458-appb-I000085
Figure PCTKR2016014458-appb-I000086
Figure PCTKR2016014458-appb-I000087
1) Preparation of compound 1-1
After introducing 39 g of compound A (132 mmol), 24 g of 1-bromo-2-nitrobenzene (120 mmol), 7 g of tetrakis(triphenylphosphine)palladium (6.0 mmol), 41 g of calcium carbonate (300 mmol), 600 mL of toluene and 140 mL of ethanol into a reaction vessel, 140 mL of distilled water was added, and the mixture was stirred for 5 hours at 120°C. After completion of the reaction, toluene and ethanol were removed with a rotary evaporator, and an organic layer was extracted with methylene chloride and distilled water. The organic layer was dried with magnesium sulfate. After removing the solvent with a rotary evaporator, the resulting product was purified by column chromatography to obtain 34.4 g of compound 1-1 (yield: 91%).
2) Preparation of compound 1-2
After introducing 34.4 g of compound 1-1 (119 mmol) and 500 mL of tetrahydrofuran into a reaction vessel, the mixture was stirred at room temperature. After completely dissolving 23.3 g of N-bromosuccinimide (NBS) (131 mmol) in 300 mL of tetrahydrofuran, the solution was added dropwise to the reaction vessel. The mixture was stirred for 6 hours at room temperature. After completion of the reaction, an organic layer was extracted with methylene chloride and distilled water, and the organic layer was dried with magnesium sulfate. After removing the solvent with a rotary evaporator, the resulting product was purified by column chromatography to obtain 41 g of compound 1-2 (yield: 94%).
3) Preparation of compound 1-3
After introducing 40 g of compound 1-2 (109 mmol), 36 g of bis(pinacolato)diboron (142 mmol), 3.8 g of dichloro(triphenylphosphine)palladium (5.5 mmol), 27 g of potassium acetate (273 mmol), and 700 mL of 1,4-dioxane into a reaction vessel, and the mixture was stirred for 6 hours at 160°C. After completion of the reaction, the reaction product was cooled to room temperature, and then the solid was removed by a celite filter. After removing the solvent with a rotary evaporator, the resulting product was purified by column chromatography to obtain 36 g of compound 1-3 (yield: 80%).
4) Preparation of compound 1-4
After introducing 45 g of compound 1-3 (109 mmol), 26.4 g of 1-bromo-2-nitrobenzene (130.8 mmol), 5.5 g of tetrakis(triphenylphosphine)palladium (6.3 mmol), 18.3 g of sodium carbonate (218 mmol), and 1000 mL of tetrahydrofuran into a reaction vessel, 436 mL of distilled water was added, and the mixture was stirred for 4 hours at 100°C. After completion of the reaction, tetrahydrofuran was removed with a rotary evaporator, and an organic layer was extracted with methylene chloride and distilled water. The organic layer was dried with magnesium sulfate. After removing the solvent with a rotary evaporator, the resulting product was purified by column chromatography to obtain 34 g of compound 1-4 (yield: 76%).
5) Preparation of compound 1-5
After introducing 10 g of compound 1-4 (24.4 mmol), 7.84 g of chlorobiphenyl triazine (29.3 mmol), 10.1 g of potassium carbonate (73.2 mmol), 2.98 g of 4-dimethylaminopyridine (24.4 mmol), and 244 mL of dimethylformamide into a reaction vessel, the mixture was stirred for 5 hours at 100°C. After completion of the reaction, the mixture was cooled to room temperature, and then 200 mL of methanol and 400 mL of distilled water were introduced into the reaction solution to terminate the reaction. A solid compound was obtained through a filter. After drying the obtained solid compound, the resulting product was purified by column chromatography to obtain 11 g of compound 1-5 (yield: 69%).
6) Preparation of compound 1-6
After introducing 9.5 g of compound 1-5 (14.8 mmol), 70 mL of triethylphosphite, and 100 mL of 1,2-dichlorobenzene into a reaction vessel, the mixture was stirred for 5 hours at 200°C. After completion of the reaction, the solvent was removed by distillation under reduced pressure. The reaction product was washed with distilled water, and an organic layer was extracted with ethyl acetate. After drying the organic layer with magnesium sulfate, the solvent was removed with a rotary evaporator. The resulting product was recrystallized with ethyl acetate and methanol to obtain 5.2 g of compound 1-6 (yield: 61%).
7) Preparation of compound C-1
After introducing 14 g of compound 1-6 (24.3 mmol), 7 g of 1-bromo-2-iodobenzene (29.2 mmol), 1.54 g of copper (24.3 mmol), 13.4 g of potassium carbonate (97.2 mmol), and 300 mL of 1,2-dichlorobenzene into a reaction vessel, the mixture was stirred for 8 hours at 200°C. After completion of the reaction, the solvent was removed by distillation under reduced pressure, and then purified by column chromatography. Thereafter, the resulting product was recrystallized with toluene to obtain 4.3 g of compound C-1 (yield: 27%).
Figure PCTKR2016014458-appb-I000088
Hereinafter, the luminescent properties of the organic light-emitting diode (OLED) device comprising the compound of the present disclosure will be explained in detail. However, the present disclosure is not limited by the following examples.
Device Example 1-1: Producing an OLED device comprising the compound of
the present disclosure as a host
An OLED device was produced by using the organic electroluminescent compound according to the present disclosure. A transparent electrode indium tin oxide (ITO) thin film (10 Ω/sq) on a glass substrate for an OLED device (GEOMATEC CO., LTD., Japan) 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 deposition apparatus. Compound HI-1 was introduced into a cell of the vacuum vapor deposition 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 the above-introduced material, thereby forming a first hole injection layer having a thickness of 80 nm on the ITO substrate. Next, compound HI-2 was introduced into another cell of the vacuum vapor deposition 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. Compound HT-1 was then introduced into another cell of the vacuum vapor deposition 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. Compound HT-2 was then introduced into another cell of the vacuum vapor deposition apparatus, and was evaporated by applying an electric current to the cell, thereby forming a second hole transport layer having a thickness of 30 nm on the first hole transport layer. After forming the hole injection layer and the hole transport layer, a light-emitting layer was formed thereon as follows: Compound C-1 was introduced into one cell of the vacuum vapor depositing apparatus as a host, and compound D-74 was introduced into another cell as a dopant. The two materials were evaporated at a different rate, and the dopant was deposited in a doping amount of 10 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. Compound ET-1 and compound EI-1 were then introduced into another two cells, and respectively evaporated at a rate of 4:6 to form an electron transport layer having a thickness of 35 nm on the light-emitting layer. After depositing compound EI-1 as an electron injection layer having a thickness of 2 nm on the electron transport layer, an Al cathode having a thickness of 80 nm was deposited on the electron injection layer by another vacuum vapor deposition apparatus. Thus, an OLED device was produced. Each of the materials used for producing the OLED device was purified by vacuum sublimation at 10-6 torr.
Figure PCTKR2016014458-appb-I000089
Comparative Example 1-1: Producing an OLED device using a conventional
luminescent material as a host
An OLED device was produced in the same manner as in Device Example 1-1, except for using the following compound CBP as a host.
Figure PCTKR2016014458-appb-I000090
The driving voltage, the luminous efficiency, the power efficiency, and the CIE color coordinate based on 10 mA/cm2 of the OLED devices produced as set forth above are provided in Table 1 below.
Figure PCTKR2016014458-appb-I000091
Device Example 2-1: Producing an OLED device comprising the compound of
the present disclosure as a host
An OLED device was produced in the same manner as in Device Example 1-1, except for using compound D-1 as a dopant.
Comparative Example 2-1: Producing an OLED device using a conventional
luminescent material as a host
An OLED device was produced in the same manner as in Device Example 1-1, except for the following: A light-emitting layer having a thickness of 40 nm was deposited on the second hole transport layer by using compound CBP as a host and compound D-1 as a dopant; compound Balq was deposited as a hole blocking layer having a thickness of 10 nm; and thereafter, compound ET-1 and compound EI-1 were introduced into another two cells, and evaporated at a rate of 4:6 to form an electron transport layer having a thickness of 25 nm on the light-emitting layer.
Figure PCTKR2016014458-appb-I000092
Figure PCTKR2016014458-appb-I000093
The driving voltage, the luminous efficiency, the power efficiency, and the CIE color coordinate based on a luminance of 1,000 nits of the OLED devices produced as set forth above are provided in Table 2 below.
Figure PCTKR2016014458-appb-I000094
From the Device Examples and the Comparative Examples above, it can be seen that the OLED device comprising the organic electroluminescent compound of the present disclosure has low driving voltage, and excellent power and luminous efficiencies, compared to the OLED device using a conventional organic electroluminescent compound.

Claims (8)

  1. An organic electroluminescent compound represented by the following formula 1:
    Figure PCTKR2016014458-appb-I000095
    wherein
    ring Y represents a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted (3- to 30-membered)heteroaryl;
    X represents O, S or NR5;
    R1 to R4, 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 are linked to adjacent R1 to R4 to form a substituted or unsubstituted, mono- or polycyclic, (C3-C30) alicyclic or aromatic ring, or the combination thereof, whose carbon atom(s) may be replaced with at least one heteroatom selected from nitrogen, oxygen, and sulfur;
    R5 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;
    the heteroaryl contains at least one heteroatom selected from B, N, O, S, Si, and P; and
    a and b, each independently, represent an integer of 1 to 4, and c and d, each independently, represent an integer of 1 or 2; where if a to d, each independently, represent an integer of 2 or more, each of R1 to R4 may be the same or different.
  2. The organic electroluminescent compound according to claim 1, wherein the substituents of the substituted alkyl, the substituted aryl, the substituted heteroaryl, 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 the combination thereof, in ring Y, and R1 to R5, 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 (C1-C30)alkyl or a (C6-C30)aryl; a (C6-C30)aryl unsubstituted or substituted 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.
  3. The organic electroluminescent compound according to claim 1, wherein ring Y represents a substituted or unsubstituted benzene, a substituted or unsubstituted pyridine, a substituted or unsubstituted pyrimidine, a substituted or unsubstituted pyrazine, a substituted or unsubstituted thiophene, or a substituted or unsubstituted furan.
  4. The organic electroluminescent compound according to claim 1, wherein
    ring Y represents a substituted or unsubstituted (C6-C25)aryl, or a substituted or unsubstituted (5- to 25-membered)heteroaryl;
    R1 to R4, each independently, represent hydrogen, a substituted or unsubstituted (C6-C25)aryl, or a substituted or unsubstituted (5- to 25-membered)heteroaryl;
    R5 represents a substituted or unsubstituted (C6-C25)aryl, or a substituted or unsubstituted (5- to 25-membered)heteroaryl; and
    a to d, each independently, represent an integer of 1.
  5. The organic electroluminescent compound according to claim 1, wherein
    ring Y represents a substituted or unsubstituted (C6-C18)aryl, or a substituted or unsubstituted (5- to 18-membered)heteroaryl;
    R1 to R4, each independently, represent hydrogen, or a substituted or unsubstituted (5- to 18-membered)heteroaryl;
    R5 represents a substituted or unsubstituted (C6-C18)aryl, or a substituted or unsubstituted (5- to 18-membered)heteroaryl; and
    a to d, each independently, represent an integer of 1.
  6. The organic electroluminescent compound according to claim 1, wherein the compound represented by formula 1 is selected from the group consisting of:
    Figure PCTKR2016014458-appb-I000096
    Figure PCTKR2016014458-appb-I000097
    Figure PCTKR2016014458-appb-I000098
    Figure PCTKR2016014458-appb-I000099
    Figure PCTKR2016014458-appb-I000100
    Figure PCTKR2016014458-appb-I000101
    Figure PCTKR2016014458-appb-I000102
    Figure PCTKR2016014458-appb-I000103
    Figure PCTKR2016014458-appb-I000104
    Figure PCTKR2016014458-appb-I000105
    Figure PCTKR2016014458-appb-I000106
    Figure PCTKR2016014458-appb-I000107
    Figure PCTKR2016014458-appb-I000108
  7. A host material comprising the organic electroluminescent compound according to claim 1.
  8. An organic electroluminescent device comprising the organic electroluminescent compound according to claim 1.
PCT/KR2016/014458 2015-12-14 2016-12-09 Organic electroluminescent compound and organic electroluminescent device comprising the same Ceased WO2017105040A1 (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113943300A (en) * 2020-07-15 2022-01-18 沈阳药科大学 Preparation method and application of 2, 7-dimethoxycarbazole fused compound
WO2025073675A1 (en) 2023-10-04 2025-04-10 Merck Patent Gmbh Materials for organic electroluminescent devices

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Publication number Priority date Publication date Assignee Title
KR20120098561A (en) * 2012-07-23 2012-09-05 주식회사 두산 Novel compounds and organic electro luminescence device using the same
WO2014098455A1 (en) * 2012-12-17 2014-06-26 주식회사 두산 Novel organic compound and organic electroluminescent element comprising same
KR20150121337A (en) * 2014-04-18 2015-10-29 덕산네오룩스 주식회사 Compound for organic electronic element, organic electronic element using the same, and an electronic device thereof

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KR20120098561A (en) * 2012-07-23 2012-09-05 주식회사 두산 Novel compounds and organic electro luminescence device using the same
WO2014098455A1 (en) * 2012-12-17 2014-06-26 주식회사 두산 Novel organic compound and organic electroluminescent element comprising same
KR20150121337A (en) * 2014-04-18 2015-10-29 덕산네오룩스 주식회사 Compound for organic electronic element, organic electronic element using the same, and an electronic device thereof

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113943300A (en) * 2020-07-15 2022-01-18 沈阳药科大学 Preparation method and application of 2, 7-dimethoxycarbazole fused compound
CN113943300B (en) * 2020-07-15 2023-02-10 沈阳药科大学 Preparation method and application of 2, 7-dimethoxycarbazole fused compound
WO2025073675A1 (en) 2023-10-04 2025-04-10 Merck Patent Gmbh Materials for organic electroluminescent devices

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