WO2014129846A1 - Organic electroluminescent compounds and an organic electroluminescent device comprising the same - Google Patents

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

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WO2014129846A1
WO2014129846A1 PCT/KR2014/001437 KR2014001437W WO2014129846A1 WO 2014129846 A1 WO2014129846 A1 WO 2014129846A1 KR 2014001437 W KR2014001437 W KR 2014001437W WO 2014129846 A1 WO2014129846 A1 WO 2014129846A1
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unsubstituted
substituted
membered
independently
aryl
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PCT/KR2014/001437
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French (fr)
Inventor
Doo-Hyeon Moon
Hee-Choon Ahn
Soo-Jin Yang
Ji-Song JUN
Tae-Jin Lee
Kyung-Joo Lee
Hyuck-Joo Kwon
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Rohm And Haas Electronic Materials Korea Ltd.
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Priority claimed from KR1020130149496A external-priority patent/KR102182270B1/en
Application filed by Rohm And Haas Electronic Materials Korea Ltd. filed Critical Rohm And Haas Electronic Materials Korea Ltd.
Priority to JP2015559186A priority Critical patent/JP6499590B2/en
Priority to CN201480006886.9A priority patent/CN105358554B/en
Publication of WO2014129846A1 publication Critical patent/WO2014129846A1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C07C211/57—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings being part of condensed ring systems of the carbon skeleton
    • C07C211/61—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings being part of condensed ring systems of the carbon skeleton with at least one of the condensed ring systems formed by three or more rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B59/00—Introduction of isotopes of elements into organic compounds ; Labelled organic compounds per se
    • C07B59/002—Heterocyclic compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C07C211/54—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to two or three six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C07C211/57—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings being part of condensed ring systems of the carbon skeleton
    • C07C211/58—Naphthylamines; N-substituted derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/94—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom spiro-condensed with carbocyclic rings or ring systems, e.g. griseofulvins
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/14—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing three or more hetero rings
    • 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 radiating surfaces
    • H05B33/22—Light sources with substantially two-dimensional radiating surfaces characterised by the chemical or physical composition or the arrangement of auxiliary dielectric or reflective layers
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2603/00—Systems containing at least three condensed rings
    • C07C2603/93—Spiro compounds
    • C07C2603/94—Spiro compounds containing "free" spiro atoms
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2101/00—Properties of the organic materials covered by group H10K85/00
    • H10K2101/10—Triplet emission
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • 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]
    • H10K50/14—Carrier transporting layers
    • H10K50/15—Hole transporting layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H10K85/623—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing five rings, e.g. pentacene

Definitions

  • the present invention relates to organic electroluminescent compounds and an organic electroluminescent device comprising the same.
  • An electroluminescent device is a self-light-emitting device which has advantages in that it provides a wider viewing angle, a greater contrast ratio, and a faster response time.
  • An organic EL device was first developed by Eastman Kodak, by using small aromatic diamine molecules, and aluminum complexes as materials for forming a light-emitting layer [Appl. Phys. Lett. 51, 913, 1987].
  • the most important factor determining luminous efficiency in an organic EL device is the light-emitting material.
  • fluorescent materials have been widely used as a light-emitting material.
  • phosphorescent materials theoretically enhance luminous efficiency by four (4) times compared to fluorescent materials, development of phosphorescent light-emitting materials are widely being researched.
  • Iridium(III) complexes have been widely known as phosphorescent materials, including bis(2-(2’-benzothienyl)-pyridinato-N,C3’)iridium(acetylacetonate) ((acac)Ir(btp) 2 ), tris(2-phenylpyridine)iridium (Ir(ppy) 3 ) and bis(4,6-difluorophenylpyridinato-N,C2)picolinate iridium (Firpic) as red, green and blue materials, respectively.
  • CBP 4,4’-N,N’-dicarbazol-biphenyl
  • BCP bathocuproine
  • BAlq aluminum(III)bis(2-methyl-8-quinolinate)(4-phenylphenolate)
  • CuPc copper phthalocyanine
  • NPB 4,4'-bis[N-(1-naphthyl)-N-phenylamino]biphenyl
  • TPD N,N'-diphenyl-N,N'-bis(3-methylphenyl)-(1,1'-biphenyl)-4,4'-diamine
  • MTDATA 4,4',4"-tris(3-methylphenylphenylamino)triphenylamine
  • an organic EL device using these materials is problematic in quantum efficiency and operational lifespan. It is because, when an organic EL device is driven under high current, thermal stress occurs between an anode and the hole injection layer. Thermal stress significantly reduces the operational lifespan of the device. Further, since the organic material used in the hole injection layer has very high hole mobility, the hole-electron charge balance may be broken and quantum yield (cd/A) may decrease.
  • WO 2012/034627 A1 discloses a compound in which a diarylamine group or a heteroaryl group is bonded directly or via an aryl group to a benzene ring of a spiro[fluoren-9,9'-fluorene] backbone unsubstituted or substituted with a halogen, an alkyl, or an aryl as a compound for an organic EL device.
  • US Patent No. 7,714,145 B2 discloses a compound in which a substituent such as a diarylamine group is bonded via a linker such as an aryl group to a 2,2'-disubstituted 9,9'-spirobifluorene-based triaryldiamine as a compound for an organic EL device.
  • the objective of the present invention is to provide an organic electroluminescent compound having excellent current efficiency and luminous efficiency.
  • A, B, and C each independently, represent and each of A, B, and C are the same or different;
  • L 1 represents a single bond, a substituted or unsubstituted (C1-C30)alkylene, a substituted or unsubstituted (C6-C30)arylene, or a substituted or unsubstituted (5- to 30-membered)heteroarylene;
  • L 2 represents a tertiary residue derived from a substituted or unsubstituted (C1-C30) acyclic hydrocarbon, a substituted or unsubstituted (C6-C30) aromatic hydrocarbon ring, or a substituted or unsubstituted (5- to 30-membered) aromatic heterocyclic ring;
  • Ar 1 to Ar 6 each independently, represent a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted (5- to 30-membered)heteroaryl; or Ar 1 and Ar 2 , Ar 3 and Ar 4 , or Ar 5 and Ar 6 may be linked to each other to form a substituted or unsubstituted (3- to 30-membered) mono- or polycyclic, alicyclic or aromatic ring whose carbon atom(s) may be replaced with at least one hetero atom selected from nitrogen, oxygen and sulfur;
  • X represents -O-, -S-, -C(R 1 )(R 2 )- or -N(R 3 )-;
  • R 1 to R 3 each independently, represent hydrogen, deuterium, a halogen, a cyano, a carboxyl, a nitro, a hydroxyl, a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C3-C30)cycloalkyl, a substituted or unsubstituted (C3-C30)cycloalkenyl, a substituted or unsubstituted (3- to 7-membered)heterocycloalkyl, a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted (5- to 30-membered)heteroaryl; or R 1 and R 2 may be linked to each other to form a (3- to 30-membered) mono- or polycyclic, alicyclic or aromatic ring whose carbon atom(s) may be replaced with at least one hetero atom selected from nitrogen, oxygen
  • R 4 to R 8 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, a substituted or unsubstituted (C3-C30)cycloalkyl, a substituted or unsubstituted (3- to 7-membered)heterocycloalkyl, a substituted or unsubstituted (C6-C30)aryl(C1-C30)alkyl, -N(R 10 )(R 11 ), -Si(R 12 )(R 13 )(R 14 ), -S(R 15 ), -O(R 16 ), a cyano, a nitro, or a hydroxyl; or may be linked to an adjacent substituent(s) to form
  • R 10 to R 16 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, a substituted or unsubstituted (3- to 7-membered)heterocycloalkyl, or a substituted or unsubstituted (C3-C30)cycloalkyl; or may be linked to an adjacent substituent(s) to form a (3- to 30-membered) mono- or polycyclic, alicyclic or aromatic ring whose carbon atom(s) may be replaced with at least one hetero atom selected from nitrogen, oxygen and sulfur;
  • a, c, d, and e each independently, represent an integer of 1 to 4; where a, c, d, or e is an integer of 2 or more, each of the substituents are the same or different;
  • b 1 or 2;
  • l, m, and n each independently, represent an integer of 0 to 2;
  • l+m+n is 1 or more
  • heterocycloalkyl and the heteroaryl(ene), each independently, contain at least one hetero atom selected from B, N, O, S, P( O), Si and P.
  • organic electroluminescent compound according to the present invention By using the organic electroluminescent compound according to the present invention, it is possible to manufacture an organic electroluminescent device having excellent current efficiency and luminous efficiency.
  • the present invention relates to an organic electroluminescent compound of formula 1, an organic electroluminescent material comprising the compound, and an organic electroluminescent device comprising the material.
  • the organic electroluminescent compound represented by the above formula 1 will be described in detail.
  • (C1-C30)alkyl(ene) is meant to be a linear or branched alkyl(ene) having 1 to 30 carbon atoms, in which the number of carbon atoms is preferably 1 to 10, more preferably 1 to 6, 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, 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
  • the compound represented by formula 1 can be represented by one selected from formulae 2 to 5:
  • A, B, C, X, R 4 to R 8 , a, b, c, d, and e are as defined in formula 1.
  • substituted in the expression “substituted or unsubstituted” means that a hydrogen atom in a certain functional group is replaced with another atom or group, i.e., a substituent.
  • A, B, and C each independently, represent and each of A, B, and C are the same or different, and preferably are the same.
  • L 1 represents a single bond, a substituted or unsubstituted (C1-C30)alkylene, a substituted or unsubstituted (C6-C30)arylene, or a substituted or unsubstituted (5- to 30-membered)heteroarylene, preferably represents a single bond, a substituted or unsubstituted (C6-C20)arylene, or an unsubstituted (5- to 20-membered)heteroarylene, and more preferably represents a single bond, a (C6-C15)arylene unsubstituted or substituted with a (C1-C6)alkyl(s), or an unsubstituted (5- to 15-membered)heteroarylene.
  • L 2 represents a tertiary residue derived from a substituted or unsubstituted (C1-C30) acyclic hydrocarbon, a substituted or unsubstituted (C6-C30) aromatic hydrocarbon ring, or a substituted or unsubstituted (5- to 30-membered) aromatic heterocyclic ring, preferably represents a tertiary residue derived from an unsubstituted (C6-C20) aromatic hydrocarbon ring, and more preferably represents a tertiary residue derived from an unsubstituted (C6-C15) aromatic hydrocarbon ring.
  • Ar 1 to Ar 6 each independently, represent a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted (5- to 30-membered)heteroaryl; or Ar 1 and Ar 2 , Ar 3 and Ar 4 , or Ar 5 and Ar 6 may be linked to each other to form a substituted or unsubstituted (3- to 30-membered) mono- or polycyclic, alicyclic or aromatic ring whose carbon atom(s) may be replaced with at least one hetero atom selected from nitrogen, oxygen and sulfur; preferably, each independently, represent a substituted or unsubstituted (C6-C20)aryl, or a substituted or unsubstituted (5- to 20-membered)heteroaryl; or Ar 1 and Ar 2 , Ar 3 and Ar 4 , or Ar 5 and Ar 6 may be linked to each other to form a substituted or unsubstituted (3- to 20-membered) polycyclic aromatic
  • X represents -O-, -S-, -C(R 1 )(R 2 )- or -N(R 3 )-.
  • R 1 to R 3 each independently, represent hydrogen, deuterium, a halogen, a cyano, a carboxyl, a nitro, a hydroxyl, a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C3-C30)cycloalkyl, a substituted or unsubstituted (C3-C30)cycloalkenyl, a substituted or unsubstituted (3- to 7-membered)heterocycloalkyl, a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted (5- to 30-membered)heteroaryl; or R 1 and R 2 may be linked to each other to form a (3- to 30-membered) mono- or polycyclic, alicyclic or aromatic ring whose carbon atom(s) may be replaced with at least one hetero atom selected from nitrogen, oxygen
  • R 4 to R 8 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, a substituted or unsubstituted (C3-C30)cycloalkyl, a substituted or unsubstituted (3- to 7-membered)heterocycloalkyl, a substituted or unsubstituted (C6-C30)aryl(C1-C30)alkyl, -N(R 10 )(R 11 ), -Si(R 12 )(R 13 )(R 14 ), -S(R 15 ), -O(R 16 ), a cyano, a nitro, or a hydroxyl; or may be linked to an adjacent substituent(s) to form
  • a, c, d, and e each independently, represent an integer of 1 to 4; where a, c, d, or e is an integer of 2 or more, each of the substituents are the same or different.
  • a represents 1 or 4
  • c and d each independently, represent an integer of 2 to 4
  • e represents 3 or 4.
  • b represents 1 or 2, and preferably 2.
  • l, m, and n each independently, represent an integer of 0 to 2.
  • l+m+n is 1 or more, and preferably 1 or 2.
  • A, B, and C each independently, represent and each of A, B, and C are the same;
  • L 1 represents a single bond, a substituted or unsubstituted (C6-C20)arylene, or an unsubstituted (5- to 20-membered)heteroarylene;
  • L 2 represents a tertiary residue derived from an unsubstituted (C6-C20) aromatic hydrocarbon ring;
  • Ar 1 to Ar 6 each independently, represent a substituted or unsubstituted (C6-C20)aryl, or a substituted or unsubstituted (5- to 20-membered)heteroaryl; or
  • Ar 1 and Ar 2 , Ar 3 and Ar 4 , or Ar 5 and Ar 6 may be linked to each other to form a substituted or unsubstituted (3- to 20-membered) polycyclic aromatic ring whose carbon atom(s) may be replaced with nitrogen;
  • X represents
  • A, B, and C each independently, represent and each of A, B, and C are the same;
  • L 1 represents a single bond, a (C6-C15)arylene unsubstituted or substituted with a (C1-C6)alkyl(s), or an unsubstituted (5- to 15-membered)heteroarylene;
  • L 2 represents a tertiary residue derived from an unsubstituted (C6-C15) aromatic hydrocarbon ring;
  • Ar 1 to Ar 6 each independently, represent a (C6-C20)aryl unsubstituted or substituted with deuterium, a halogen(s), a (C1-C6)alkyl(s), a (C6-C15)aryl(s), a di(C6-C15)arylamino(s), or a (5- to 15-membered)heteroaryl(s); or a (5- to 15-
  • the specific compounds of the present invention include the following compounds, but are not limited thereto:
  • organic electroluminescent compounds of the present invention can be prepared by a synthetic method known to a person skilled in the art. For example, they can be prepared according to the following reaction scheme.
  • L 1 , Ar 1 , Ar 2 , R 4 to R 8 , and a to e are as defined in formula 1 above, and Hal represents a halogen.
  • the present invention provides an organic electroluminescent material comprising the organic electroluminescent compound of formula 1, and an organic electroluminescent device comprising the material.
  • the above material can be comprised of the organic electroluminescent compound according to the present invention alone, or can further include conventional materials generally used in organic electroluminescent materials.
  • the organic electroluminescent device comprises 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 comprises a light-emitting layer, and may further comprise at least one layer selected from the group consisting of a hole injection layer, a hole transport layer, an electron transport layer, an electron injection layer, an interlayer, a hole blocking layer, and an electron blocking layer.
  • the organic electroluminescent compound according to the present invention can be comprised in at least one of the light-emitting layer and the hole transport layer. Where used in the hole transport layer, the organic electroluminescent compound represented by formula 1 can be comprised as a hole transport material. Where used in the light-emitting layer, the organic electroluminescent compound represented by formula 1 can be comprised as a host material.
  • the organic electroluminescent device comprising the organic electroluminescent compound of the present invention can further comprise one or more compounds other than the organic electroluminescent compound according to the present invention as host materials, and can further comprise one or more dopants.
  • the organic electroluminescent compound according to the present invention is comprised as a host material (first host material)
  • the other compound may be comprised as a second host material.
  • the ratio of the first host material to the second host material is in the range of 1:99 to 99:1.
  • the host material other than the organic electroluminescent compound according to the present invention can be from any of the known fluorescent or phosphorescent hosts.
  • the phosphorescent host selected from the group consisting of the compounds of formulae 6 to 8 below is preferable in view of luminous efficiency.
  • R 21 to R 24 each independently represent hydrogen, deuterium, a halogen, a substituted or unsubstituted (C1-C30)alkyl, a substituted of unsubstituted (C6-C30)aryl, a substituted or unsubstituted (3- to 30-membered)heteroaryl, or -SiR 25 R 26 R 27 ;
  • R 25 to R 27 each independently represent a substituted or unsubstituted (C1-C30)alkyl, or a substituted or unsubstituted (C6-C30)aryl;
  • L 4 represents a single bond, a substituted or unsubstituted (C6-C30)arylene, or a substituted or unsubstituted (5- to 30-membered)heteroarylene;
  • M represents a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted (5- to 30-membered)heteroaryl;
  • Y 1 and Y 2 each independently represent -O-, -S-, -N(R 31 )- or -C(R 32 )(R 33 )-, provided that Y 1 and Y 2 do not simultaneously exist;
  • R 31 to R 33 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, and R 32 and R 33 may be the same or different;
  • h and i each independently represent an integer of 1 to 3;
  • j, k, o and p each independently represent an integer of 0 to 4.
  • each of (Cz-L 4 ), each of (Cz), each of R 21 , each of R 22 , each of R 23 or each of R 24 may be the same or different.
  • preferable examples of the host material are as follows:
  • the dopant comprised in the organic electroluminescent device according to the present invention can be a fluorescent or phosphorescent dopant, and preferably is at least one phosphorescent dopant.
  • the dopant materials applied to the organic electroluminescent device according to the present invention are not limited, but may be preferably selected from metallated complex compounds of iridium, osmium, copper and platinum, more preferably selected from ortho-metallated complex compounds of iridium, osmium, copper and platinum, and even more preferably ortho-metallated iridium complex compounds.
  • the phosphorescent dopants may be preferably selected from compounds represented by the following formulae 9 to 11.
  • L is selected from the following structures:
  • R 100 represents hydrogen, or a substituted or unsubstituted (C1-C30)alkyl
  • 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(s); a cyano; a substituted or unsubstituted (C1-C30)alkoxy; or a substituted or unsubstituted (C3-C30)cycloalkyl; and adjacent substituents of R 120 to R 123 may be linked to each other to form a fused ring, e.g. quinoline;
  • 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; where R 124 to R 127 are aryl groups, adjacent substituents may be linked to each other to form a fused ring, e.g. fluorene;
  • R 201 to R 211 each independently represent hydrogen, deuterium, a halogen, a (C1-C30)alkyl unsubstituted or substituted with a halogen(s), or a substituted or unsubstituted (C6-C30)aryl;
  • o and p each independently represent an integer of 1 to 3; where o or p is an integer of 2 or more, each of R 100 may be the same or different; and
  • q represents an integer of 1 to 3.
  • the phosphorescent dopant materials include the following:
  • composition for an organic electroluminescent device comprises the compound according to the present invention as a host material or a hole transport material.
  • the organic electroluminescent device comprises a first electrode; a second electrode; and at least one organic layer between the first and second electrodes.
  • the organic layer comprises a light-emitting layer, and the light-emitting layer may comprise the composition for the organic electroluminescent device according to the present invention.
  • the organic electroluminescent device according to the present invention may further comprise, in addition to the organic electroluminescent compound represented by formula 1, at least one compound selected from the group consisting of arylamine-based compounds and styrylarylamine-based compounds.
  • the organic layer may further comprise at least one metal selected from the group consisting of metals of Group 1, metals of Group 2, transition metals of the 4 th period, transition metals of the 5 th period, lanthanides and organic metals of d-transition elements of the Periodic Table, or at least one complex compound comprising said metal.
  • the organic layer may further comprise a light-emitting layer and a charge generating layer.
  • the organic electroluminescent device according to the present invention may emit white light by further comprising at least one light-emitting layer which comprises a blue electroluminescent compound, a red electroluminescent compound or a green electroluminescent compound known in the field, besides the compound according to the present invention. Also, if needed, a yellow or orange light-emitting layer can be comprised in the device.
  • a surface layer is preferably placed on an inner surface(s) of one or both electrode(s); selected from a chalcogenide layer, a metal halide layer and a metal oxide layer.
  • a chalcogenide(includes oxides) layer of silicon or aluminum is preferably placed on an anode surface of an electroluminescent medium layer
  • a metal halide layer or a metal oxide layer is preferably placed on a cathode surface of an electroluminescent medium layer.
  • said chalcogenide includes SiO X (1 ⁇ X ⁇ 2), AlO X (1 ⁇ X ⁇ 1.5), SiON, SiAlON, etc.; said metal halide includes LiF, MgF 2 , CaF 2 , a rare earth metal fluoride, etc.; and said metal oxide includes Cs 2 O, Li 2 O, MgO, SrO, BaO, CaO, etc.
  • a mixed region of an electron transport compound and an reductive dopant, or a mixed region of a hole transport compound and an oxidative dopant is preferably 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; and the reductive dopant includes alkali metals, alkali metal compounds, alkaline earth metals, rare-earth metals, and mixtures thereof.
  • a reductive dopant layer may be employed as a charge generating layer to prepare an electroluminescent device having two or more electroluminescent layers and emitting white light.
  • dry film-forming methods such as vacuum evaporation, sputtering, plasma and ion plating methods, or wet film-forming methods such as spin coating, dip coating, and flow coating methods can be used.
  • a thin film can be formed by dissolving or diffusing materials forming each layer into any suitable solvent such as ethanol, chloroform, tetrahydrofuran, dioxane, etc.
  • the solvent can be any solvent where the materials forming each layer can be dissolved or diffused, and where there are no problems in film-formation capability.
  • An OLED device was produced using the light emitting material according to the present invention.
  • a transparent electrode indium tin oxide (ITO) thin film (15 ⁇ /sq) on a glass substrate for an organic light-emitting diode (OLED) device (Geomatec, Japan) was subjected to an ultrasonic washing with acetone and isopropan alcohol, sequentially, and then was stored in isopropan alcohol. Then, the ITO substrate was mounted on a substrate holder of a vacuum vapor depositing apparatus.
  • N 1 ,N 1' -([1,1'-biphenyl]-4,4'-diyl)bis(N 1 -(naphthalen-1-yl)-N 4 ,N 4 -diphenylbenzen-1,4-diamine) was introduced into a cell of said vacuum vapor depositing apparatus, and then the pressure in the chamber of said apparatus was controlled to 10 -6 torr. Thereafter, an electric current was applied to the cell to evaporate the above introduced material, thereby forming a hole injection layer having a thickness of 60 nm on the ITO substrate.
  • compound C-2 according to the present invention was introduced into another cell of said vacuum vapor depositing apparatus, and was evaporated by applying an electric current to the cell, thereby forming a hole transport layer having a thickness of 20 nm on the hole injection layer. Thereafter, 9-(3-(4,6-diphenyl-1,3,5-triazin-2-yl)phenyl)-9'-phenyl-9H,9'H-3,3'-bicarbazole was introduced into one cell of the vacuum vapor depositing apparatus, as a host material, and compound D-1 was introduced into another cell as a dopant.
  • the two materials were evaporated at different rates and were deposited in a doping amount of 15 wt% based on the total amount of the host and dopant to form a light-emitting layer having a thickness of 30 nm on the hole transport layer. Then, 2-(4-(9,10-di(naphthalene-2-yl)anthracen-2-yl)phenyl)-1-phenyl-1H-benzo[d]imidazole was introduced into one cell and lithium quinolate was introduced into another cell. The two materials were evaporated at the same rate and were deposited in a doping amount of 50 wt% each to form an electron transport layer having a thickness of 30 nm on the light-emitting layer.
  • an Al cathode having a thickness of 150 nm was deposited by another vacuum vapor deposition apparatus on the electron injection layer.
  • All the materials used for producing the OLED device were purified by vacuum sublimation at 10 -6 torr prior to use.
  • the produced OLED device showed a green emission having a luminance of 1100 cd/m 2 and a current density of 2.4 mA/cm 2 .
  • An OLED device was produced in the same manner as in Device Example 1, except for evaporating compound C-4 to form a hole transport layer in a thickness of 20 nm.
  • the produced OLED device showed a green emission having a luminance of 2200 cd/m 2 and a current density of 4.9 mA/cm 2 .
  • An OLED device was produced in the same manner as in Device Example 1, except for evaporating compound C-27 to form a hole transport layer in a thickness of 20 nm.
  • the produced OLED device showed a green emission having a luminance of 1500 cd/m 2 and a current density of 3.3 mA/cm 2 .
  • An OLED device was produced in the same manner as in Device Example 1, except for forming a hole transport layer having a thickness of 20 nm by using compound C-44 ; introducing 9-phenyl-3-(4-(9-(4-phenylquinazolin-2-yl)-9H-carbazol-3-yl)phenyl)-9H-carbazole into one cell of the vacuum vapor depositing apparatus as a host, introducing compound D-37 into another cell as a dopant, and evaporating the two materials at different rates and depositing them in a doping amount of 3 wt% based on the total amount of the host and dopant to form a light-emitting layer having a thickness of 30 nm on the hole transport layer.
  • the produced OLED device showed a red emission having a luminance of 1800 cd/m 2 and a current density of 13.2 mA/cm 2 .
  • An OLED device was produced in the same manner as in Device Example 4, except for evaporating compound C-125 to form a hole transport layer in a thickness of 20 nm.
  • the produced OLED device showed a red emission having a luminance of 1100 cd/m 2 and a current density of 8.3 mA/cm 2 .
  • An OLED device was produced in the same manner as in Device Example 1, except for using compound C-3 for the hole transport layer; compound H-1 as below for the host; and compound H-2 as below for the dopant.
  • the produced OLED device showed a blue emission having a luminance of 1200 cd/m 2 and a current density of 28.6 mA/cm 2 .
  • An OLED device was produced in the same manner as in Device Example 6, except for evaporating compound C-5 to form a hole transport layer in a thickness of 20 nm.
  • the produced OLED device showed a blue emission having a luminance of 800 cd/m 2 and a current density of 17.8 mA/cm 2 .
  • An OLED device was produced in the same manner as in Device Example 6, except for evaporating compound C-123 to form a hole transport layer in a thickness of 20 nm.
  • the produced OLED device showed a blue emission having a luminance of 900 cd/m 2 and a current density of 20.5 mA/cm 2 .
  • An OLED device was produced in the same manner as in Device Example 1, except for evaporating compound C-145 to form a hole transport layer in a thickness of 20 nm.
  • the produced OLED device showed a green emission having a luminance of 1600 cd/m 2 and a current density of 3.2 mA/cm 2 .
  • Comparative Example 1 Production of an OLED device using a conventional
  • An OLED device was produced in the same manner as in Device Example 1, except for evaporating compound R-1 as below to form a hole transport layer in a thickness of 20 nm.
  • the produced OLED device showed a green emission having a luminance of 11400 cd/m 2 and a current density of 30.7 mA/cm 2 .
  • Comparative Example 2 Production of an OLED device using a conventional
  • An OLED device was produced in the same manner as in Device Example 1, except for evaporating compound R-1 to form a hole transport layer in a thickness of 20 nm; using compound H-1 for the host, and using compound H-3 as below for the dopant of the light-emitting material to form a light-emitting layer having a thickness of 30 nm on the hole transport layer.
  • the produced OLED device showed a blue emission having a luminance of 3500 cd/m 2 and a current density of 100 mA/cm 2 .
  • Comparative Example 3 Production of an OLED device using a conventional
  • An OLED device was produced in the same manner as in Device Example 4, except for evaporating compound R-1 to form a hole transport layer in a thickness of 20 nm.
  • the produced OLED device showed a red emission having a luminance of 4800 cd/m 2 and a current density of 57.8 mA/cm 2 .
  • an organic electroluminescent device using the organic electroluminescent compound according to the present invention has excellent luminous characteristics, especially luminescent efficiency and current efficiency.

Abstract

The present invention relates to organic electroluminescent compounds of formula 1 (see below) wherein X, A, B, C and R4, R5, R6, R7, a, b, c. d. e, l, m, and n are as defined in the description. The invention also relates to organic electroluminescent devices using compounds of formula 1. An organic electroluminescent compound according to the present invention and its use in an organic electroluminescent device can have high luminescent efficiency and high current efficiency.

Description

ORGANIC ELECTROLUMINESCENT COMPOUNDS AND AN ORGANIC ELECTROLUMINESCENT DEVICE COMPRISING THE SAME
The present invention relates to organic electroluminescent compounds and an organic electroluminescent device comprising the same.
An electroluminescent device (EL device) is a self-light-emitting device which has advantages in that it provides a wider viewing angle, a greater contrast ratio, and a faster response time. An organic EL device was first developed by Eastman Kodak, by using small aromatic diamine molecules, and aluminum complexes as materials for forming a light-emitting layer [Appl. Phys. Lett. 51, 913, 1987].
The most important factor determining luminous efficiency in an organic EL device is the light-emitting material. Until now, fluorescent materials have been widely used as a light-emitting material. However, in view of electroluminescent mechanisms, since phosphorescent materials theoretically enhance luminous efficiency by four (4) times compared to fluorescent materials, development of phosphorescent light-emitting materials are widely being researched. Iridium(III) complexes have been widely known as phosphorescent materials, including bis(2-(2’-benzothienyl)-pyridinato-N,C3’)iridium(acetylacetonate) ((acac)Ir(btp)2), tris(2-phenylpyridine)iridium (Ir(ppy)3) and bis(4,6-difluorophenylpyridinato-N,C2)picolinate iridium (Firpic) as red, green and blue materials, respectively.
At present, 4,4’-N,N’-dicarbazol-biphenyl (CBP) is the most widely known phosphorescent host materials. Recently, Pioneer (Japan) et al. developed a high performance organic EL device using bathocuproine (BCP) and aluminum(III)bis(2-methyl-8-quinolinate)(4-phenylphenolate) (BAlq) etc. as host materials, which were known as hole blocking layer materials.
Though these materials provide good light-emitting characteristics, they have the following disadvantages: (1) Due to their low glass transition temperature and poor thermal stability, their degradation may occur during a high-temperature deposition process in a vacuum. (2) The power efficiency of an organic EL device is given by [(π/voltage) × current efficiency], and the power efficiency is inversely proportional to the voltage. Although an organic EL device comprising phosphorescent host materials provides higher current efficiency (cd/A) than one comprising fluorescent materials, a significantly high driving voltage is necessary. Thus, there is no merit in terms of power efficiency (lm/W). (3) Further, the operational lifespan of an organic EL device is short and luminous efficiency is still required to be improved.
Meanwhile, copper phthalocyanine (CuPc), 4,4'-bis[N-(1-naphthyl)-N-phenylamino]biphenyl (NPB), N,N'-diphenyl-N,N'-bis(3-methylphenyl)-(1,1'-biphenyl)-4,4'-diamine (TPD), 4,4',4"-tris(3-methylphenylphenylamino)triphenylamine (MTDATA), etc. were used as a hole injection and transport material.
However, an organic EL device using these materials is problematic in quantum efficiency and operational lifespan. It is because, when an organic EL device is driven under high current, thermal stress occurs between an anode and the hole injection layer. Thermal stress significantly reduces the operational lifespan of the device. Further, since the organic material used in the hole injection layer has very high hole mobility, the hole-electron charge balance may be broken and quantum yield (cd/A) may decrease.
International Patent Publication No. WO 2012/034627 A1 discloses a compound in which a diarylamine group or a heteroaryl group is bonded directly or via an aryl group to a benzene ring of a spiro[fluoren-9,9'-fluorene] backbone unsubstituted or substituted with a halogen, an alkyl, or an aryl as a compound for an organic EL device.
US Patent No. 7,714,145 B2 discloses a compound in which a substituent such as a diarylamine group is bonded via a linker such as an aryl group to a 2,2'-disubstituted 9,9'-spirobifluorene-based triaryldiamine as a compound for an organic EL device.
However, the above references do not disclose a compound in which one or more diarylamine groups are bonded directly or via an aryl group to a benzene ring of a spiro[fluoren-9,9'-fluorene] backbone fused with an aryl group or a heteroaryl group, or the benzene ring is substituted with an indole group, nor an organic EL device using the compound for a hole transport layer.
The objective of the present invention is to provide an organic electroluminescent compound having excellent current efficiency and luminous efficiency.
The present inventors found that the above objective can be achieved by an organic electroluminescent compound represented by the following formula 1:
Figure PCTKR2014001437-appb-I000001
wherein
A, B, and C, each independently, represent
Figure PCTKR2014001437-appb-I000002
and each of A, B, and C are the same or different;
L1 represents a single bond, a substituted or unsubstituted (C1-C30)alkylene, a substituted or unsubstituted (C6-C30)arylene, or a substituted or unsubstituted (5- to 30-membered)heteroarylene;
L2 represents a tertiary residue derived from a substituted or unsubstituted (C1-C30) acyclic hydrocarbon, a substituted or unsubstituted (C6-C30) aromatic hydrocarbon ring, or a substituted or unsubstituted (5- to 30-membered) aromatic heterocyclic ring;
Ar1 to Ar6, each independently, represent a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted (5- to 30-membered)heteroaryl; or Ar1 and Ar2, Ar3 and Ar4, or Ar5 and Ar6 may be linked to each other to form a substituted or unsubstituted (3- to 30-membered) mono- or polycyclic, alicyclic or aromatic ring whose carbon atom(s) may be replaced with at least one hetero atom selected from nitrogen, oxygen and sulfur;
X represents -O-, -S-, -C(R1)(R2)- or -N(R3)-;
R1 to R3, each independently, represent hydrogen, deuterium, a halogen, a cyano, a carboxyl, a nitro, a hydroxyl, a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C3-C30)cycloalkyl, a substituted or unsubstituted (C3-C30)cycloalkenyl, a substituted or unsubstituted (3- to 7-membered)heterocycloalkyl, a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted (5- to 30-membered)heteroaryl; or R1 and R2 may be linked to each other to form a (3- to 30-membered) mono- or polycyclic, alicyclic or aromatic ring whose carbon atom(s) may be replaced with at least one hetero atom selected from nitrogen, oxygen and sulfur;
R4 to R8, 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, a substituted or unsubstituted (C3-C30)cycloalkyl, a substituted or unsubstituted (3- to 7-membered)heterocycloalkyl, a substituted or unsubstituted (C6-C30)aryl(C1-C30)alkyl, -N(R10)(R11), -Si(R12)(R13)(R14), -S(R15), -O(R16), a cyano, a nitro, or a hydroxyl; or may be linked to an adjacent substituent(s) to form a (3- to 30-membered) mono- or polycyclic, alicyclic or aromatic ring whose carbon atom(s) may be replaced with at least one hetero atom selected from nitrogen, oxygen and sulfur;
R10 to R16, 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, a substituted or unsubstituted (3- to 7-membered)heterocycloalkyl, or a substituted or unsubstituted (C3-C30)cycloalkyl; or may be linked to an adjacent substituent(s) to form a (3- to 30-membered) mono- or polycyclic, alicyclic or aromatic ring whose carbon atom(s) may be replaced with at least one hetero atom selected from nitrogen, oxygen and sulfur;
a, c, d, and e, each independently, represent an integer of 1 to 4; where a, c, d, or e is an integer of 2 or more, each of the substituents are the same or different;
b represents 1 or 2;
l, m, and n, each independently, represent an integer of 0 to 2;
l+m+n is 1 or more; and
the heterocycloalkyl and the heteroaryl(ene), each independently, contain at least one hetero atom selected from B, N, O, S, P(=O), Si and P.
By using the organic electroluminescent compound according to the present invention, it is possible to manufacture an organic electroluminescent device having excellent current efficiency and luminous efficiency.
Hereinafter, the present invention will be described in detail. However, the following description is intended to explain the invention, and is not meant in any way to restrict the scope of the invention.
The present invention relates to an organic electroluminescent compound of formula 1, an organic electroluminescent material comprising the compound, and an organic electroluminescent device comprising the material.
The organic electroluminescent compound represented by the above formula 1 will be described in detail.
Herein, “(C1-C30)alkyl(ene)” is meant to be a linear or branched alkyl(ene) having 1 to 30 carbon atoms, in which the number of carbon atoms is preferably 1 to 10, more preferably 1 to 6, 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, 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, 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 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 ring backbone atoms including at least one heteroatom selected from B, N, O, S, P(=O), Si and P, preferably O, S and N, and includes tetrahydrofuran, pyrrolidine, thiolan, tetrahydropyran, etc.; “(C6-C30)aryl(ene)” is a monocyclic or fused ring derived from an aromatic hydrocarbon having 6 to 30 carbon atoms, in which the number of carbon atoms is preferably 6 to 20, more preferably 6 to 15, and includes phenyl, biphenyl, terphenyl, naphthyl, binaphthyl, phenylnaphthyl, naphthylphenyl, fluorenyl, phenylfluorenyl, benzofluorenyl, dibenzofluorenyl, phenanthrenyl, phenylphenanthrenyl, anthracenyl, indenyl, triphenylenyl, pyrenyl, tetracenyl, perylenyl, chrysenyl, naphthacenyl, fluoranthenyl, etc.; “(5- to 30-membered)heteroaryl(ene)” is an aryl having 5 to 30 ring backbone atoms including at least one, preferably 1 to 4 heteroatom selected from the group consisting of B, N, O, S, P(=O), Si and P; is a monocyclic ring, or a fused ring condensed with at least one benzene ring; may be partially saturated; may be one formed by linking at least one heteroaryl or aryl group to a heteroaryl group via a single bond(s); and includes a monocyclic ring-type heteroaryl including furyl, thiophenyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, thiadiazolyl, isothiazolyl, isoxazolyl, oxazolyl, oxadiazolyl, triazinyl, tetrazinyl, triazolyl, tetrazolyl, furazanyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, etc., and a fused ring-type heteroaryl including benzofuranyl, benzothiophenyl, isobenzofuranyl, dibenzofuranyl, dibenzothiophenyl, benzoimidazolyl, benzothiazolyl, benzoisothiazolyl, benzoisoxazolyl, benzoxazolyl, isoindolyl, indolyl, indazolyl, benzothiadiazolyl, quinolyl, isoquinolyl, cinnolinyl, quinazolinyl, quinoxalinyl, carbazolyl, phenoxazinyl, phenanthridinyl, benzodioxolyl, etc. Further, “halogen” includes F, Cl, Br and I.
The compound represented by formula 1 can be represented by one selected from formulae 2 to 5:
Figure PCTKR2014001437-appb-I000003
Figure PCTKR2014001437-appb-I000004
Figure PCTKR2014001437-appb-I000005
Figure PCTKR2014001437-appb-I000006
wherein
A, B, C, X, R4 to R8, a, b, c, d, and e are as defined in formula 1.
Herein, “substituted” in the expression “substituted or unsubstituted” means that a hydrogen atom in a certain functional group is replaced with another atom or group, i.e., a substituent. The substituents of the substituted (C1-C30)alkyl(ene), the substituted (C3-C30)cycloalkyl, the substituted (C3-C30)cycloalkenyl, the substituted (3- to 7- membered)heterocycloalkyl, the substituted (C6-C30)aryl(ene), the substituted (5- to 30- membered)heteroaryl(ene), and the substituted (C6-C30)aryl(C1-C30)alkyl in R1 to R8, R10 to R16, L1, L2, and Ar1 to Ar6 in formulae 1 to 5 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 (5- to 30- membered)heteroaryl unsubstituted or substituted with a (C6-C30)aryl, a (C6-C30)aryl unsubstituted or substituted with a (5- 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, and preferably each independently are at least one selected from the group consisting of deuterium, a halogen, a (C1-C6)alkyl, a (C6-C15)aryl, a (5- to 15- membered)heteroaryl, and a di(C6-C15)arylamino.
In formula 1 above, A, B, and C, each independently, represent
Figure PCTKR2014001437-appb-I000007
and each of A, B, and C are the same or different, and preferably are the same.
L1 represents a single bond, a substituted or unsubstituted (C1-C30)alkylene, a substituted or unsubstituted (C6-C30)arylene, or a substituted or unsubstituted (5- to 30-membered)heteroarylene, preferably represents a single bond, a substituted or unsubstituted (C6-C20)arylene, or an unsubstituted (5- to 20-membered)heteroarylene, and more preferably represents a single bond, a (C6-C15)arylene unsubstituted or substituted with a (C1-C6)alkyl(s), or an unsubstituted (5- to 15-membered)heteroarylene.
L2 represents a tertiary residue derived from a substituted or unsubstituted (C1-C30) acyclic hydrocarbon, a substituted or unsubstituted (C6-C30) aromatic hydrocarbon ring, or a substituted or unsubstituted (5- to 30-membered) aromatic heterocyclic ring, preferably represents a tertiary residue derived from an unsubstituted (C6-C20) aromatic hydrocarbon ring, and more preferably represents a tertiary residue derived from an unsubstituted (C6-C15) aromatic hydrocarbon ring.
Ar1 to Ar6, each independently, represent a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted (5- to 30-membered)heteroaryl; or Ar1 and Ar2, Ar3 and Ar4, or Ar5 and Ar6 may be linked to each other to form a substituted or unsubstituted (3- to 30-membered) mono- or polycyclic, alicyclic or aromatic ring whose carbon atom(s) may be replaced with at least one hetero atom selected from nitrogen, oxygen and sulfur; preferably, each independently, represent a substituted or unsubstituted (C6-C20)aryl, or a substituted or unsubstituted (5- to 20-membered)heteroaryl; or Ar1 and Ar2, Ar3 and Ar4, or Ar5 and Ar6 may be linked to each other to form a substituted or unsubstituted (3- to 20-membered) polycyclic aromatic ring whose carbon atom(s) may be replaced with nitrogen; and more preferably, each independently, represent a (C6-C20)aryl unsubstituted or substituted with deuterium, a halogen(s), a (C1-C6)alkyl(s), a (C6-C15)aryl(s), a di(C6-C15)arylamino(s), or a (5- to 15-membered)heteroaryl(s); or a (5- to 15-membered)heteroaryl unsubstituted or substituted with a (C6-C15)aryl(s); or Ar1 and Ar2, Ar3 and Ar4, or Ar5 and Ar6 may be linked to each other to form an indole ring unsubstituted or substituted with a (C6-C15)aryl(s); or an indolocarbazole ring substituted with a (C6-C15)aryl(s) unsubstituted or substituted with a (C1-C4)alkyl(s), a phenyl(s) or a naphthyl(s), or a (5- to 15-membered)heteroaryl(s) unsubstituted or substituted with a phenyl(s).
X represents -O-, -S-, -C(R1)(R2)- or -N(R3)-.
R1 to R3, each independently, represent hydrogen, deuterium, a halogen, a cyano, a carboxyl, a nitro, a hydroxyl, a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C3-C30)cycloalkyl, a substituted or unsubstituted (C3-C30)cycloalkenyl, a substituted or unsubstituted (3- to 7-membered)heterocycloalkyl, a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted (5- to 30-membered)heteroaryl; or R1 and R2 may be linked to each other to form a (3- to 30-membered) mono- or polycyclic, alicyclic or aromatic ring whose carbon atom(s) may be replaced with at least one hetero atom selected from nitrogen, oxygen and sulfur; preferably, each independently, represent an unsubstituted (C1-C10)alkyl or an unsubstituted (C6-C20)aryl; or R1 and R2 may be linked to each other to form a (3- to 20-membered) monocyclic alicyclic ring; and more preferably, each independently, represent an unsubstituted (C1-C6)alkyl or an unsubstituted (C6-C15)aryl; or R1 and R2 may be linked to each other to form a cyclopentane ring or a cyclohexane ring.
R4 to R8, 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, a substituted or unsubstituted (C3-C30)cycloalkyl, a substituted or unsubstituted (3- to 7-membered)heterocycloalkyl, a substituted or unsubstituted (C6-C30)aryl(C1-C30)alkyl, -N(R10)(R11), -Si(R12)(R13)(R14), -S(R15), -O(R16), a cyano, a nitro, or a hydroxyl; or may be linked to an adjacent substituent(s) to form a (3- to 30-membered) mono- or polycyclic, alicyclic or aromatic ring whose carbon atom(s) may be replaced with at least one hetero atom selected from nitrogen, oxygen and sulfur; preferably, each independently, represent hydrogen or an unsubstituted (C6-C20)aryl; or may be linked to an adjacent substituent(s) to form a (6- to 20-membered) monocyclic aromatic ring; and more preferably, each independently, represent hydrogen or an unsubstituted (C6-C15)aryl; or may be linked to an adjacent substituent(s) to form a benzene ring.
a, c, d, and e, each independently, represent an integer of 1 to 4; where a, c, d, or e is an integer of 2 or more, each of the substituents are the same or different. Preferably, a represents 1 or 4, c and d each independently, represent an integer of 2 to 4, and e represents 3 or 4.
b represents 1 or 2, and preferably 2.
l, m, and n, each independently, represent an integer of 0 to 2. l+m+n is 1 or more, and preferably 1 or 2.
According to one embodiment of the present invention, in formula 1 above, A, B, and C, each independently, represent
Figure PCTKR2014001437-appb-I000008
and each of A, B, and C are the same; L1 represents a single bond, a substituted or unsubstituted (C6-C20)arylene, or an unsubstituted (5- to 20-membered)heteroarylene; L2 represents a tertiary residue derived from an unsubstituted (C6-C20) aromatic hydrocarbon ring; Ar1 to Ar6, each independently, represent a substituted or unsubstituted (C6-C20)aryl, or a substituted or unsubstituted (5- to 20-membered)heteroaryl; or Ar1 and Ar2, Ar3 and Ar4, or Ar5 and Ar6 may be linked to each other to form a substituted or unsubstituted (3- to 20-membered) polycyclic aromatic ring whose carbon atom(s) may be replaced with nitrogen; X represents -O-, -S-, -C(R1)(R2)- or -N(R3)-; R1 to R3, each independently, represent an unsubstituted (C1-C10)alkyl or an unsubstituted (C6-C20)aryl; or R1 and R2 may be linked to each other to form a (3- to 20-membered) monocyclic alicyclic ring; R4 to R8, each independently, represent hydrogen or an unsubstituted (C6-C20)aryl, or may be linked to an adjacent substituent(s) to form a (6- to 20-membered) monocyclic aromatic ring; a represents 1 or 4; c and d, each independently, represent an integer of 2 to 4; e represents 3 or 4; where a, c, d or e is an integer of 2 or more, each of the substituents are the same or different; b represents 2; l, m, and n, each independently, represent an integer of 0 to 2; and l+m+n is 1 or 2.
According to another embodiment of the present invention, in formula 1 above, A, B, and C, each independently, represent
Figure PCTKR2014001437-appb-I000009
and each of A, B, and C are the same; L1 represents a single bond, a (C6-C15)arylene unsubstituted or substituted with a (C1-C6)alkyl(s), or an unsubstituted (5- to 15-membered)heteroarylene; L2 represents a tertiary residue derived from an unsubstituted (C6-C15) aromatic hydrocarbon ring; Ar1 to Ar6, each independently, represent a (C6-C20)aryl unsubstituted or substituted with deuterium, a halogen(s), a (C1-C6)alkyl(s), a (C6-C15)aryl(s), a di(C6-C15)arylamino(s), or a (5- to 15-membered)heteroaryl(s); or a (5- to 15-membered)heteroaryl unsubstituted or substituted with a (C6-C15)aryl(s); or Ar1 and Ar2, Ar3 and Ar4, or Ar5 and Ar6 may be linked to each other to form an indole ring unsubstituted or substituted with a (C6-C15)aryl(s); or an indolocarbazole ring substituted with a (C6-C15)aryl(s) unsubstituted or substituted with a (C1-C4)alkyl(s), a phenyl(s) or a naphthyl(s), or a (5- to 15-membered)heteroaryl(s) unsubstituted or substituted with a phenyl(s); X represents -O-, -S-, -C(R1)(R2)- or -N(R3)-; R1 to R3, each independently, represent an unsubstituted (C1-C6)alkyl or an unsubstituted (C6-C15)aryl; or R1 and R2 may be linked to each other to form a cyclopentane ring or a cyclohexane ring; R4 to R8, each independently, represent hydrogen or an unsubstituted (C6-C15)aryl, or may be linked to an adjacent substituent(s) to form a benzene ring; a represents 1 or 4; c and d, each independently, represent an integer of 2 to 4; e represents 3 or 4; where a, c, d, or e is an integer of 2 or more, each of the substituents are the same or different; b represents 2; l, m, and n, each independently, represent an integer of 0 to 2; and l+m+n is 1 or 2.
The specific compounds of the present invention include the following compounds, but are not limited thereto:
Figure PCTKR2014001437-appb-I000010
Figure PCTKR2014001437-appb-I000011
Figure PCTKR2014001437-appb-I000012
Figure PCTKR2014001437-appb-I000013
Figure PCTKR2014001437-appb-I000014
Figure PCTKR2014001437-appb-I000015
Figure PCTKR2014001437-appb-I000016
Figure PCTKR2014001437-appb-I000017
Figure PCTKR2014001437-appb-I000018
Figure PCTKR2014001437-appb-I000019
Figure PCTKR2014001437-appb-I000020
Figure PCTKR2014001437-appb-I000021
Figure PCTKR2014001437-appb-I000022
Figure PCTKR2014001437-appb-I000023
Figure PCTKR2014001437-appb-I000024
Figure PCTKR2014001437-appb-I000025
Figure PCTKR2014001437-appb-I000026
Figure PCTKR2014001437-appb-I000027
Figure PCTKR2014001437-appb-I000028
Figure PCTKR2014001437-appb-I000029
Figure PCTKR2014001437-appb-I000030
Figure PCTKR2014001437-appb-I000031
Figure PCTKR2014001437-appb-I000032
Figure PCTKR2014001437-appb-I000033
Figure PCTKR2014001437-appb-I000034
Figure PCTKR2014001437-appb-I000035
Figure PCTKR2014001437-appb-I000036
The organic electroluminescent compounds of the present invention can be prepared by a synthetic method known to a person skilled in the art. For example, they can be prepared according to the following reaction scheme.
[Reaction Scheme 1]
Figure PCTKR2014001437-appb-I000037
wherein L1, Ar1, Ar2, R4 to R8, and a to e are as defined in formula 1 above, and Hal represents a halogen.
The present invention provides an organic electroluminescent material comprising the organic electroluminescent compound of formula 1, and an organic electroluminescent device comprising the material.
The above material can be comprised of the organic electroluminescent compound according to the present invention alone, or can further include conventional materials generally used in organic electroluminescent materials.
The organic electroluminescent device comprises 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 is an anode, and the other is a cathode. The organic layer comprises a light-emitting layer, and may further comprise at least one layer selected from the group consisting of a hole injection layer, a hole transport layer, an electron transport layer, an electron injection layer, an interlayer, a hole blocking layer, and an electron blocking layer.
The organic electroluminescent compound according to the present invention can be comprised in at least one of the light-emitting layer and the hole transport layer. Where used in the hole transport layer, the organic electroluminescent compound represented by formula 1 can be comprised as a hole transport material. Where used in the light-emitting layer, the organic electroluminescent compound represented by formula 1 can be comprised as a host material.
The organic electroluminescent device comprising the organic electroluminescent compound of the present invention can further comprise one or more compounds other than the organic electroluminescent compound according to the present invention as host materials, and can further comprise one or more dopants.
Where the organic electroluminescent compound according to the present invention is comprised as a host material (first host material), the other compound may be comprised as a second host material. Herein, the ratio of the first host material to the second host material is in the range of 1:99 to 99:1.
The host material other than the organic electroluminescent compound according to the present invention can be from any of the known fluorescent or phosphorescent hosts. Specifically, the phosphorescent host selected from the group consisting of the compounds of formulae 6 to 8 below is preferable in view of luminous efficiency.
Figure PCTKR2014001437-appb-I000038
Figure PCTKR2014001437-appb-I000039
Figure PCTKR2014001437-appb-I000040
wherein Cz represents the following structure;
Figure PCTKR2014001437-appb-I000041
R21 to R24 each independently represent hydrogen, deuterium, a halogen, a substituted or unsubstituted (C1-C30)alkyl, a substituted of unsubstituted (C6-C30)aryl, a substituted or unsubstituted (3- to 30-membered)heteroaryl, or -SiR25R26R27;
R25 to R27 each independently represent a substituted or unsubstituted (C1-C30)alkyl, or a substituted or unsubstituted (C6-C30)aryl;
L4 represents a single bond, a substituted or unsubstituted (C6-C30)arylene, or a substituted or unsubstituted (5- to 30-membered)heteroarylene;
M represents a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted (5- to 30-membered)heteroaryl;
Y1 and Y2 each independently represent -O-, -S-, -N(R31)- or -C(R32)(R33)-, provided that Y1 and Y2 do not simultaneously exist;
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, and R32 and R33 may be the same or different;
h and i each independently represent an integer of 1 to 3;
j, k, o and p each independently represent an integer of 0 to 4; and
where h, i, j, k, o or p is an integer of 2 or more, each of (Cz-L4), each of (Cz), each of R21, each of R22, each of R23 or each of R24 may be the same or different.
Specifically, preferable examples of the host material are as follows:
Figure PCTKR2014001437-appb-I000042
Figure PCTKR2014001437-appb-I000043
Figure PCTKR2014001437-appb-I000044
Figure PCTKR2014001437-appb-I000045
Figure PCTKR2014001437-appb-I000046
Figure PCTKR2014001437-appb-I000047
Figure PCTKR2014001437-appb-I000048
Figure PCTKR2014001437-appb-I000049
Figure PCTKR2014001437-appb-I000050
Figure PCTKR2014001437-appb-I000051
Figure PCTKR2014001437-appb-I000052
Figure PCTKR2014001437-appb-I000053
Figure PCTKR2014001437-appb-I000054
[wherein TPS represents triphenylsilyl]
The dopant comprised in the organic electroluminescent device according to the present invention can be a fluorescent or phosphorescent dopant, and preferably is at least one phosphorescent dopant. The dopant materials applied to the organic electroluminescent device according to the present invention are not limited, but may be preferably selected from metallated complex compounds of iridium, osmium, copper and platinum, more preferably selected from ortho-metallated complex compounds of iridium, osmium, copper and platinum, and even more preferably ortho-metallated iridium complex compounds.
The phosphorescent dopants may be preferably selected from compounds represented by the following formulae 9 to 11.
Figure PCTKR2014001437-appb-I000055
Figure PCTKR2014001437-appb-I000056
Figure PCTKR2014001437-appb-I000057
wherein L is selected from the following structures:
Figure PCTKR2014001437-appb-I000058
R100 represents hydrogen, or a substituted or unsubstituted (C1-C30)alkyl;
R101 to R109, and R111 to R123 each independently represent hydrogen; deuterium; a halogen; a (C1-C30)alkyl unsubstituted or substituted with a halogen(s); a cyano; a substituted or unsubstituted (C1-C30)alkoxy; or a substituted or unsubstituted (C3-C30)cycloalkyl; and adjacent substituents of R120 to R123 may be linked to each other to form a fused ring, e.g. quinoline;
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; where R124 to R127 are aryl groups, adjacent substituents may be linked to each other to form a fused ring, e.g. fluorene;
R201 to R211 each independently represent hydrogen, deuterium, a halogen, a (C1-C30)alkyl unsubstituted or substituted with a halogen(s), or a substituted or unsubstituted (C6-C30)aryl;
o and p each independently represent an integer of 1 to 3; where o or p is an integer of 2 or more, each of R100 may be the same or different; and
q represents an integer of 1 to 3.
Specifically, the phosphorescent dopant materials include the following:
Figure PCTKR2014001437-appb-I000059
Figure PCTKR2014001437-appb-I000060
Figure PCTKR2014001437-appb-I000061
Figure PCTKR2014001437-appb-I000062
Figure PCTKR2014001437-appb-I000063
Figure PCTKR2014001437-appb-I000064
Figure PCTKR2014001437-appb-I000065
Figure PCTKR2014001437-appb-I000066
Figure PCTKR2014001437-appb-I000067
Figure PCTKR2014001437-appb-I000068
Figure PCTKR2014001437-appb-I000069
Figure PCTKR2014001437-appb-I000070
Figure PCTKR2014001437-appb-I000071
Figure PCTKR2014001437-appb-I000072
Figure PCTKR2014001437-appb-I000073
Figure PCTKR2014001437-appb-I000074
Figure PCTKR2014001437-appb-I000075
Figure PCTKR2014001437-appb-I000076
Figure PCTKR2014001437-appb-I000077
Figure PCTKR2014001437-appb-I000078
Figure PCTKR2014001437-appb-I000079
Figure PCTKR2014001437-appb-I000080
Figure PCTKR2014001437-appb-I000081
Figure PCTKR2014001437-appb-I000082
Figure PCTKR2014001437-appb-I000083
Figure PCTKR2014001437-appb-I000084
Figure PCTKR2014001437-appb-I000085
Figure PCTKR2014001437-appb-I000086
Figure PCTKR2014001437-appb-I000087
Figure PCTKR2014001437-appb-I000088
In another embodiment of the present invention, a composition for an organic electroluminescent device is provided. The composition comprises the compound according to the present invention as a host material or a hole transport material.
In addition, the organic electroluminescent device according to the present invention comprises a first electrode; a second electrode; and at least one organic layer between the first and second electrodes. The organic layer comprises a light-emitting layer, and the light-emitting layer may comprise the composition for the organic electroluminescent device according to the present invention.
The organic electroluminescent device according to the present invention may further comprise, in addition to the organic electroluminescent compound represented by formula 1, at least one compound selected from the group consisting of arylamine-based compounds and styrylarylamine-based compounds.
In the organic electroluminescent device according to the present invention, the organic layer may further comprise at least one metal selected from the group consisting of metals of Group 1, metals of Group 2, transition metals of the 4th period, transition metals of the 5th period, lanthanides and organic metals of d-transition elements of the Periodic Table, or at least one complex compound comprising said metal. The organic layer may further comprise a light-emitting layer and a charge generating layer.
In addition, the organic electroluminescent device according to the present invention may emit white light by further comprising at least one light-emitting layer which comprises a blue electroluminescent compound, a red electroluminescent compound or a green electroluminescent compound known in the field, besides the compound according to the present invention. Also, if needed, a yellow or orange light-emitting layer can be comprised in the device.
According to the present invention, at least one layer (hereinafter, "a surface layer”) is preferably placed on an inner surface(s) of one or both electrode(s); selected from a chalcogenide layer, a metal halide layer and a metal oxide layer. Specifically, a chalcogenide(includes oxides) layer of silicon or aluminum is preferably placed on an anode surface of an electroluminescent medium layer, and a metal halide layer or a metal oxide layer is preferably placed on a cathode surface of an electroluminescent medium layer. Such a surface layer provides operation stability for the organic electroluminescent device. Preferably, said chalcogenide includes SiOX(1≤X≤2), AlOX(1≤X≤1.5), SiON, SiAlON, etc.; said metal halide includes LiF, MgF2, CaF2, a rare earth metal fluoride, etc.; and said metal oxide includes Cs2O, Li2O, MgO, SrO, BaO, CaO, etc.
In the organic electroluminescent device according to the present invention, a mixed region of an electron transport compound and an reductive dopant, or a mixed region of a hole transport compound and an oxidative dopant is preferably 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. Further, the hole transport compound is oxidized to a cation, and thus it becomes easier to inject and transport holes from the mixed region to the electroluminescent medium. Preferably, the oxidative dopant includes various Lewis acids and acceptor compounds; and the reductive dopant includes alkali metals, alkali metal compounds, alkaline earth metals, rare-earth metals, and mixtures thereof. A reductive dopant layer may be employed as a charge generating layer to prepare an electroluminescent device having two or more electroluminescent layers and emitting white light.
In order to form each layer of the organic electroluminescent device according to the present invention, dry film-forming methods such as vacuum evaporation, sputtering, plasma and ion plating methods, or wet film-forming methods such as spin coating, dip coating, and flow coating methods can be used.
When using a wet film-forming method, a thin film can be formed by dissolving or diffusing materials forming each layer into any suitable solvent such as ethanol, chloroform, tetrahydrofuran, dioxane, etc. The solvent can be any solvent where the materials forming each layer can be dissolved or diffused, and where there are no problems in film-formation capability.
Hereinafter, the organic electroluminescent compound, the preparation method of the compound, and the luminescent properties of the device will be explained in detail with reference to the following examples.
Example 1: Preparation of compound C-2
Figure PCTKR2014001437-appb-I000089
Preparation of compound 1-1
After mixing 2-bromoiodobenzene (60 g, 212 mmol), 4-dibenzofuranboronic acid (30 g, 142 mmol), tetrakis(triphenylphosphine)palladium (3 g, 2.8 mmol), sodium carbonate (37 g, 354 mmol), toluene 1000 mL, and ethanol 200 mL in a reaction container, distilled water 200 mL was added to the mixture, and the mixture was stirred at 120°C for 6 hours. After the reaction, the mixture was washed with distilled water, and an organic layer was extracted with ethyl acetate. The extracted organic layer was dried using magnesium sulfate, and the solvent was removed using a rotary evaporator. The remaining substance was then purified with column chromatography to obtain compound 1-1 (32 g, 68%).
Preparation of compound 1-3
After mixing compound 1-1 (30 g, 93 mmol) and tetrahydrofuran 300 mL in a reaction container, the container was cooled to -78°C under nitrogen atmosphere. N-butyl lithium 48 mL (2.5 M, 120 mmol) was then slowly added dropwise to the mixture. After stirring the mixture for 2 hours at -78°C, 2-bromofluorenone dissolved in tetrahydrofuran 400 mL was slowly added dropwise to the mixture. After adding, the reaction temperature was slowly heated to room temperature, and the mixture was additionally stirred for 30 minutes. Ammonium chloride aqueous solution was then added to the reaction solution to complete the reaction, and the mixture was extracted with ethylacetate. The obtained organic layer was then dried using magnesium sulfate, and the solvent was removed using a rotary evaporator. Acetic acid 900 mL and HCl 0.5 mL were added to the produced compound 1-2, and the mixture was stirred at 120°C overnight. The solvent was then removed using a rotary evaporator, and the remaining substance was purified with column chromatography to obtain compound 1-3 (28 g, 75%).
Preparation of compound C-2
After mixing compound 1-3 (10 g, 23.3 mmol), N-phenylbiphenyl-4-amine (6 g, 24.5 mmol), palladium (II) acetate (0.2 g, 0.98 mmol), tri-t-butyl phosphine 1 mL (50%, 2.45 mmol), sodium tert-butoxide (3.5 g, 37 mmol), and o-xylene 120 mL in a reaction container, the mixture was stirred for 8 hours under reflux. The reaction mixture was then cooled to room temperature, and the produced solid was filtered, and washed with methylene chloride (MC). The filtrate was then distilled under reduced pressure, and purified with column chromatography to obtain compound C-2 (13 g, 82%).
Example 2: Preparation of compound C-122
Figure PCTKR2014001437-appb-I000090
Preparation of compound 2-1
After mixing 1-bromo-4-chloro-2-nitrobenzene (38 g, 161.82 mmol), 4-dibenzofuranboronic acid (37.7 g, 178 mmol), tetrakis(triphenylphosphine)palladium (5.6 g, 4.85 mmol), sodium carbonate (43 g, 404.55 mmol), toluene 800 mL, and ethanol 200 mL in a reaction container, distilled water 200 mL was added to the mixture, and the mixture was stirred at 120°C for 2 hours. After the reaction, the mixture was washed with distilled water, and an organic layer was extracted with ethyl acetate. The extracted organic layer was dried using magnesium sulfate, and the solvent was removed using a rotary evaporator. The remaining substance was then purified with column chromatography to obtain compound 2-1 (51 g, 97%).
Preparation of compound 2-2
After mixing compound 2-1 (51 g, 157.54 mmol), tin chloride (107 g, 472.62 mmol), and ethylacetate 1.6 L in a reaction container, the mixture was stirred for 4 hours under reflux. After the reaction, the mixture was washed with distilled water, and an organic layer was extracted with ethyl acetate. The extracted organic layer was dried using magnesium sulfate, and the solvent was removed using a rotary evaporator. The remaining substance was then purified with column chromatography to obtain compound 2-2 (31 g, 70%).
Preparation of compound 2-3
After dissolving compound 2-2 (28 g, 95.2 mmol) and para toluene sulfonic acid (56 g, 285.88 mmol) in acetonitrile in a reaction container, sodium nitrite (14 g, 190.68 mmol) and potassium iodide (39.2 g, 238.00 mmol) dissolved in water of 0°C were added to the mixture. The mixture was then stirred for 6 hours, washed with distilled water, and an organic layer was extracted with ethyl acetate. The extracted organic layer was dried using magnesium sulfate, and the solvent was removed using a rotary evaporator. The remaining substance was then purified with column chromatography to obtain compound 2-3 (30.4 g, 79%).
Preparation of compound 2-5
After mixing compound 2-3 (30.4 g, 75.12 mmol) and tetrahydrofuran 260 mL in a reaction container, the container was cooled to -78°C under nitrogen atmosphere. N-butyl lithium 40 mL (2.5 M, 97.68 mmol) was then slowly added dropwise to the mixture. After stirring the mixture for 2 hours at -78°C, fluorenone dissolved in tetrahydrofuran 260 mL was slowly added dropwise to the mixture. After adding, the reaction temperature was slowly heated to room temperature, and the mixture was additionally stirred for 30 minutes. Ammonium chloride aqueous solution was then added to the reaction solution to complete the reaction, and the mixture was extracted with ethylacetate. The obtained organic layer was then dried using magnesium sulfate, and the solvent was removed using a rotary evaporator. Acetic acid 720 mL and HCl 72 mL were added to the produced compound 2-4, and the mixture was stirred at 120°C overnight. The solvent was then removed using a rotary evaporator, and the remaining substance was purified with column chromatography to obtain compound 2-5 (18 g, 54%).
Preparation of compound C-122
After mixing compound 2-5 (4.5 g, 10.21 mmol), 4-(naphthalen-2-yl)-N-phenylaniline (3.3 g, 11.23 mmol), palladium (II) acetate (0.12 g, 0.51 mmol), 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl (0.4 g, 1.02 mmol), sodium tert-butoxide (2.0 g, 20.42 mmol), and o-xylene 51 mL in a reaction container, the mixture was stirred for 8 hours under reflux. The reaction mixture was then cooled to room temperature, the produced solid was filtered, and washed with methylene chloride (MC). The filtrate was then distilled under reduced pressure, and purified with column chromatography to obtain compound C-122 (4.1 g, 58%).
Example 3: Preparation of compound C-145
Figure PCTKR2014001437-appb-I000091
Preparation of compound 3-1
After mixing 2-bromo-9-phenylcarbazole (43 g, 133 mmol), 2-chloroaniline (20.7 mL, 200 mmol), palladium acetate (1.2 g, 5.33 mmol), tri-t-butyl phosphine 5.2 mL (50%, 10.6 mmol), sodium tert-butoxide (32 g, 333 mmol), and toluene 380 mL in a reaction container, the mixture was stirred for 3 hours under reflux. After the reaction, the mixture was washed with distilled water, and an organic layer was extracted with methylene chloride. The extracted organic layer was dried using magnesium sulfate, and the solvent was removed using a rotary evaporator. The remaining substance was then purified with column chromatography to obtain compound 3-1 (47 g, 96%).
Preparation of compound 3-2
After mixing compound 3-1 (47 g, 127 mmol), palladium acetate (1.4 g, 6.38 mmol), tricyclohexylphosphonium tetrafluoroborate (4.7 g, 12.7 mmol), cesium carbonate (124 g, 383 mmol), and dimethylacetamide 600 mL in a reaction container, the mixture was stirred for 3 hours under reflux. After the reaction, the mixture was washed with distilled water, and an organic layer was extracted with methylene chloride. The extracted organic layer was dried using magnesium sulfate, and the solvent was removed using a rotary evaporator. The remaining substance was then purified with column chromatography to obtain compound 3-2 (25 g, 59%).
Preparation of compound C-145
After mixing compound 1-3 (7.3 g, 15.0 mmol), compound 3-2 (5 g, 15.0 mmol), copper iodide (1.4 g, 7.52 mmol), ethylenediamine (2 mL, 30.0 mmol), cesium carbonate (12.2 g, 37.6 mmol), and ortho-xylene 75 mL in a reaction container, the mixture was stirred for 3 hours under reflux. After the reaction, the mixture was washed with distilled water, and an organic layer was extracted with methylene chloride. The extracted organic layer was dried using magnesium sulfate, and the solvent was removed using a rotary evaporator. The remaining substance was then purified with column chromatography to obtain compound C-145 (8.1 g, 73%).
Compounds C-1 to C-171 were prepared by the same method as in Examples 1 to 3. The detailed data of the representative compounds are shown in Table 1 below.
[Table 1]
Figure PCTKR2014001437-appb-I000092
Device Example 1: Production of an OLED device using the organic
electroluminescent compound according to the present invention
An OLED device was produced using the light emitting material according to the present invention. A transparent electrode indium tin oxide (ITO) thin film (15 Ω/sq) on a glass substrate for an organic light-emitting diode (OLED) device (Geomatec, Japan) was subjected to an ultrasonic washing with acetone and isopropan alcohol, sequentially, and then was stored in isopropan alcohol. Then, the ITO substrate was mounted on a substrate holder of a vacuum vapor depositing apparatus. N1,N1'-([1,1'-biphenyl]-4,4'-diyl)bis(N1-(naphthalen-1-yl)-N4,N4-diphenylbenzen-1,4-diamine) was introduced into a cell of said vacuum vapor depositing apparatus, and then the pressure in the chamber of said apparatus was controlled to 10-6 torr. Thereafter, an electric current was applied to the cell to evaporate the above introduced material, thereby forming a hole injection layer having a thickness of 60 nm on the ITO substrate. Then, compound C-2 according to the present invention was introduced into another cell of said vacuum vapor depositing apparatus, and was evaporated by applying an electric current to the cell, thereby forming a hole transport layer having a thickness of 20 nm on the hole injection layer. Thereafter, 9-(3-(4,6-diphenyl-1,3,5-triazin-2-yl)phenyl)-9'-phenyl-9H,9'H-3,3'-bicarbazole was introduced into one cell of the vacuum vapor depositing apparatus, as a host material, and compound D-1 was introduced into another cell as a dopant. The two materials were evaporated at different rates and were deposited in a doping amount of 15 wt% based on the total amount of the host and dopant to form a light-emitting layer having a thickness of 30 nm on the hole transport layer. Then, 2-(4-(9,10-di(naphthalene-2-yl)anthracen-2-yl)phenyl)-1-phenyl-1H-benzo[d]imidazole was introduced into one cell and lithium quinolate was introduced into another cell. The two materials were evaporated at the same rate and were deposited in a doping amount of 50 wt% each to form an electron transport layer having a thickness of 30 nm on the light-emitting layer. Then, after depositing lithium quinolate as an electron injection layer having a thickness of 2 nm on the electron transport layer, an Al cathode having a thickness of 150 nm was deposited by another vacuum vapor deposition apparatus on the electron injection layer. Thus, an OLED device was produced. All the materials used for producing the OLED device were purified by vacuum sublimation at 10-6 torr prior to use.
The produced OLED device showed a green emission having a luminance of 1100 cd/m2 and a current density of 2.4 mA/cm2.
Device Example 2: Production of an OLED device using the organic
electroluminescent compound according to the present invention
An OLED device was produced in the same manner as in Device Example 1, except for evaporating compound C-4 to form a hole transport layer in a thickness of 20 nm.
The produced OLED device showed a green emission having a luminance of 2200 cd/m2 and a current density of 4.9 mA/cm2.
Device Example 3: Production of an OLED device using the organic
electroluminescent compound according to the present invention
An OLED device was produced in the same manner as in Device Example 1, except for evaporating compound C-27 to form a hole transport layer in a thickness of 20 nm.
The produced OLED device showed a green emission having a luminance of 1500 cd/m2 and a current density of 3.3 mA/cm2.
Device Example 4: Production of an OLED device using the organic
electroluminescent compound according to the present invention
An OLED device was produced in the same manner as in Device Example 1, except for forming a hole transport layer having a thickness of 20 nm by using compound C-44; introducing 9-phenyl-3-(4-(9-(4-phenylquinazolin-2-yl)-9H-carbazol-3-yl)phenyl)-9H-carbazole into one cell of the vacuum vapor depositing apparatus as a host, introducing compound D-37 into another cell as a dopant, and evaporating the two materials at different rates and depositing them in a doping amount of 3 wt% based on the total amount of the host and dopant to form a light-emitting layer having a thickness of 30 nm on the hole transport layer.
The produced OLED device showed a red emission having a luminance of 1800 cd/m2 and a current density of 13.2 mA/cm2.
Device Example 5: Production of an OLED device using the organic
electroluminescent compound according to the present invention
An OLED device was produced in the same manner as in Device Example 4, except for evaporating compound C-125 to form a hole transport layer in a thickness of 20 nm.
The produced OLED device showed a red emission having a luminance of 1100 cd/m2 and a current density of 8.3 mA/cm2.
Device Example 6: Production of an OLED device using the organic
electroluminescent compound according to the present invention
An OLED device was produced in the same manner as in Device Example 1, except for using compound C-3 for the hole transport layer; compound H-1 as below for the host; and compound H-2 as below for the dopant.
Figure PCTKR2014001437-appb-I000093
Figure PCTKR2014001437-appb-I000094
The produced OLED device showed a blue emission having a luminance of 1200 cd/m2 and a current density of 28.6 mA/cm2.
Device Example 7: Production of an OLED device using the organic
electroluminescent compound according to the present invention
An OLED device was produced in the same manner as in Device Example 6, except for evaporating compound C-5 to form a hole transport layer in a thickness of 20 nm.
The produced OLED device showed a blue emission having a luminance of 800 cd/m2 and a current density of 17.8 mA/cm2.
Device Example 8: Production of an OLED device using the organic
electroluminescent compound according to the present invention
An OLED device was produced in the same manner as in Device Example 6, except for evaporating compound C-123 to form a hole transport layer in a thickness of 20 nm.
The produced OLED device showed a blue emission having a luminance of 900 cd/m2 and a current density of 20.5 mA/cm2.
Device Example 9: Production of an OLED device using the organic
electroluminescent compound according to the present invention
An OLED device was produced in the same manner as in Device Example 1, except for evaporating compound C-145 to form a hole transport layer in a thickness of 20 nm.
The produced OLED device showed a green emission having a luminance of 1600 cd/m2 and a current density of 3.2 mA/cm2.
Comparative Example 1: Production of an OLED device using a conventional
organic electroluminescent compound
An OLED device was produced in the same manner as in Device Example 1, except for evaporating compound R-1 as below to form a hole transport layer in a thickness of 20 nm.
Figure PCTKR2014001437-appb-I000095
The produced OLED device showed a green emission having a luminance of 11400 cd/m2 and a current density of 30.7 mA/cm2.
Comparative Example 2: Production of an OLED device using a conventional
organic electroluminescent compound
An OLED device was produced in the same manner as in Device Example 1, except for evaporating compound R-1 to form a hole transport layer in a thickness of 20 nm; using compound H-1 for the host, and using compound H-3 as below for the dopant of the light-emitting material to form a light-emitting layer having a thickness of 30 nm on the hole transport layer.
Figure PCTKR2014001437-appb-I000096
The produced OLED device showed a blue emission having a luminance of 3500 cd/m2 and a current density of 100 mA/cm2.
Comparative Example 3: Production of an OLED device using a conventional
organic electroluminescent compound
An OLED device was produced in the same manner as in Device Example 4, except for evaporating compound R-1 to form a hole transport layer in a thickness of 20 nm.
The produced OLED device showed a red emission having a luminance of 4800 cd/m2 and a current density of 57.8 mA/cm2.
It is verified that the luminous characteristics of the organic electroluminescent compound according to the present invention is superior to the conventional compounds. In addition, an organic electroluminescent device using the organic electroluminescent compound according to the present invention has excellent luminous characteristics, especially luminescent efficiency and current efficiency.

Claims (10)

  1. An organic electroluminescent compound represented by the following formula 1:
    Figure PCTKR2014001437-appb-I000097
    wherein
    A, B, and C, each independently, represent
    Figure PCTKR2014001437-appb-I000098
    and each of A, B, and C are the same or different;
    L1 represents a single bond, a substituted or unsubstituted (C1-C30)alkylene, a substituted or unsubstituted (C6-C30)arylene, or a substituted or unsubstituted (5- to 30-membered)heteroarylene;
    L2 represents a tertiary residue derived from a substituted or unsubstituted (C1-C30) acyclic hydrocarbon, a substituted or unsubstituted (C6-C30) aromatic hydrocarbon ring, or a substituted or unsubstituted (5- to 30-membered) aromatic heterocyclic ring;
    Ar1 to Ar6, each independently, represent a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted (5- to 30-membered)heteroaryl; or Ar1 and Ar2, Ar3 and Ar4, or Ar5 and Ar6 may be linked to each other to form a substituted or unsubstituted (3- to 30-membered) mono- or polycyclic, alicyclic or aromatic ring whose carbon atom(s) may be replaced with at least one hetero atom selected from nitrogen, oxygen and sulfur;
    X represents -O-, -S-, -C(R1)(R2)- or -N(R3)-;
    R1 to R3, each independently, represent hydrogen, deuterium, a halogen, a cyano, a carboxyl, a nitro, a hydroxyl, a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C3-C30)cycloalkyl, a substituted or unsubstituted (C3-C30)cycloalkenyl, a substituted or unsubstituted (3- to 7-membered)heterocycloalkyl, a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted (5- to 30-membered)heteroaryl; or R1 and R2 may be linked to each other to form a (3- to 30-membered) mono- or polycyclic, alicyclic or aromatic ring whose carbon atom(s) may be replaced with at least one hetero atom selected from nitrogen, oxygen and sulfur;
    R4 to R8, 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, a substituted or unsubstituted (C3-C30)cycloalkyl, a substituted or unsubstituted (3- to 7-membered)heterocycloalkyl, a substituted or unsubstituted (C6-C30)aryl(C1-C30)alkyl, -N(R10)(R11), -Si(R12)(R13)(R14), -S(R15), -O(R16), a cyano, a nitro, or a hydroxyl; or may be linked to an adjacent substituent(s) to form a (3- to 30-membered) mono- or polycyclic, alicyclic or aromatic ring whose carbon atom(s) may be replaced with at least one hetero atom selected from nitrogen, oxygen and sulfur;
    R10 to R16, 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, a substituted or unsubstituted (3- to 7-membered)heterocycloalkyl, or a substituted or unsubstituted (C3-C30)cycloalkyl; or may be linked to an adjacent substituent(s) to form a (3- to 30-membered) mono- or polycyclic, alicyclic or aromatic ring whose carbon atom(s) may be replaced with at least one hetero atom selected from nitrogen, oxygen and sulfur;
    a, c, d, and e, each independently, represent an integer of 1 to 4; where a, c, d, or e is an integer of 2 or more, each of the substituents are the same or different;
    b represents 1 or 2;
    l, m, and n, each independently, represent an integer of 0 to 2;
    l+m+n is 1 or more; and
    the heterocycloalkyl and the heteroaryl(ene), each independently, contain at least one hetero atom selected from B, N, O, S, P(=O), Si and P.
  2. The organic electroluminescent compound according to claim 1, wherein the compound is represented by the following formula 2:
    Figure PCTKR2014001437-appb-I000099
    wherein
    A, X, R4 to R8, a, b, c, d, and e are as defined in claim 1; and l is 1 or 2.
  3. The organic electroluminescent compound according to claim 1, wherein the compound is represented by the following formula 3:
    Figure PCTKR2014001437-appb-I000100
    wherein
    B, X, R4 to R8, a, b, c, d, and e are as defined in claim 1; and m is 1 or 2.
  4. The organic electroluminescent compound according to claim 1, wherein the compound is represented by the following formula 4:
    Figure PCTKR2014001437-appb-I000101
    wherein
    A, C, X, R4 to R8, a, b, c, d, and e are as defined in claim 1; and l and n, each independently, are 1.
  5. The organic electroluminescent compound according to claim 1, wherein the compound is represented by the following formula 5:
    Figure PCTKR2014001437-appb-I000102
    wherein
    B, C, X, R4 to R8, a, b, c, d, and e are as defined in claim 1; and m and n, each independently, are 1.
  6. The organic electroluminescent compound according to claim 1, wherein the substituents of the substituted (C1-C30)alkyl(ene), the substituted (C3-C30)cycloalkyl, the substituted (C3-C30)cycloalkenyl, the substituted (3- to 7-membered)heterocycloalkyl, the substituted (C6-C30)aryl(ene), the substituted (5- to 30-membered)heteroaryl(ene), and the substituted (C6-C30)aryl(C1-C30)alkyl in R1 to R8, R10 to R16, L1, L2, and Ar1 to Ar6, 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 (5- to 30-membered)heteroaryl unsubstituted or substituted with a (C6-C30)aryl(s), a (C6-C30)aryl unsubstituted or substituted with a (5- to 30-membered)heteroaryl(s), 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.
  7. The organic electroluminescent compound according to claim 1, wherein
    A, B, and C, each independently, represent
    Figure PCTKR2014001437-appb-I000103
    and A, B, and C are the same;
    L1 represents a single bond, a substituted or unsubstituted (C6-C20)arylene, or an unsubstituted (5- to 20-membered)heteroarylene;
    L2 represents a tertiary residue derived from an unsubstituted (C6-C20) aromatic hydrocarbon ring;
    Ar1 to Ar6, each independently, represent a substituted or unsubstituted (C6-C20)aryl, or a substituted or unsubstituted (5- to 20-membered)heteroaryl; or Ar1 and Ar2, Ar3 and Ar4, or Ar5 and Ar6 may be linked to each other to form a substituted or unsubstituted (3- to 20-membered) polycyclic aromatic ring whose carbon atom(s) may be replaced with nitrogen;
    X represents -O-, -S-, -C(R1)(R2)- or -N(R3)-;
    R1 to R3, each independently, represent an unsubstituted (C1-C10)alkyl or an unsubstituted (C6-C20)aryl; or R1 and R2 may be linked to each other to form a (3- to 20-membered) monocyclic alicyclic ring;
    R4 to R8, each independently, represent hydrogen or an unsubstituted (C6-C20)aryl; or may be linked to an adjacent substituent(s) to form a (6- to 20-membered) monocyclic aromatic ring;
    a represents 1 or 4; c and d, each independently, represent an integer of 2 to 4; e represents 3 or 4; where a, c, d or e is an integer of 2 or more, each of the substituents are the same or different;
    b represents 2;
    l, m, and n, each independently, represent an integer of 0 to 2; and
    l+m+n is 1 or 2.
  8. The organic electroluminescent compound according to claim 1, wherein
    A, B, and C, each independently, represent
    Figure PCTKR2014001437-appb-I000104
    and
    A, B, and C are the same;
    L1 represents a single bond, a (C6-C15)arylene unsubstituted or substituted with a (C1-C6)alkyl(s), or an unsubstituted (5- to 15-membered)heteroarylene;
    L2 represents a tertiary residue derived from an unsubstituted (C6-C15) aromatic hydrocarbon ring;
    Ar1 to Ar6, each independently, represent a (C6-C20)aryl unsubstituted or substituted with deuterium, a halogen(s), a (C1-C6)alkyl(s), a (C6-C15)aryl(s), a di(C6-C15)arylamino(s), or a (5- to 15-membered)heteroaryl(s); or a (5- to 15-membered)heteroaryl unsubstituted or substituted with a (C6-C15)aryl(s); or Ar1 and Ar2, Ar3 and Ar4, or Ar5 and Ar6 may be linked to each other to form an indole ring unsubstituted or substituted with a (C6-C15)aryl(s); or an indolocarbazole ring substituted with a (C6-C15)aryl(s) unsubstituted or substituted with a (C1-C4)alkyl(s), a phenyl(s) or a naphthyl(s), or a (5- to 15-membered)heteroaryl(s) unsubstituted or substituted with a phenyl(s);
    X represents -O-, -S-, -C(R1)(R2)- or -N(R3)-;
    R1 to R3, each independently, represent an unsubstituted (C1-C6)alkyl or an unsubstituted (C6-C15)aryl; or R1 and R2 may be linked to each other to form a cyclopentane ring or a cyclohexane ring;
    R4 to R8, each independently, represent hydrogen or an unsubstituted (C6-C15)aryl; or may be linked to an adjacent substituent(s) to form a benzene ring;
    a represents 1 or 4; c and d, each independently, represent an integer of 2 to 4; e represents 3 or 4; where a, c, d, or e is an integer of 2 or more, each of the substituents are the same or different;
    b represents 2;
    l, m, and n, each independently, represent an integer of 0 to 2; and
    l+m+n is 1 or 2.
  9. The organic electroluminescent compound according to claim 1, wherein the compound represented by formula 1 is selected from the group consisting of:
    Figure PCTKR2014001437-appb-I000105
    Figure PCTKR2014001437-appb-I000106
    Figure PCTKR2014001437-appb-I000107
    Figure PCTKR2014001437-appb-I000108
    Figure PCTKR2014001437-appb-I000109
    Figure PCTKR2014001437-appb-I000110
    Figure PCTKR2014001437-appb-I000111
    Figure PCTKR2014001437-appb-I000112
    Figure PCTKR2014001437-appb-I000113
    Figure PCTKR2014001437-appb-I000114
    Figure PCTKR2014001437-appb-I000115
    Figure PCTKR2014001437-appb-I000116
    Figure PCTKR2014001437-appb-I000117
    Figure PCTKR2014001437-appb-I000118
    Figure PCTKR2014001437-appb-I000119
    Figure PCTKR2014001437-appb-I000120
    Figure PCTKR2014001437-appb-I000121
    Figure PCTKR2014001437-appb-I000122
    Figure PCTKR2014001437-appb-I000123
    Figure PCTKR2014001437-appb-I000124
    Figure PCTKR2014001437-appb-I000125
    Figure PCTKR2014001437-appb-I000126
    Figure PCTKR2014001437-appb-I000127
    Figure PCTKR2014001437-appb-I000128
    Figure PCTKR2014001437-appb-I000129
    Figure PCTKR2014001437-appb-I000130
    Figure PCTKR2014001437-appb-I000131
  10. An organic electroluminescent device comprising the compound according to claim 1.
PCT/KR2014/001437 2013-02-21 2014-02-21 Organic electroluminescent compounds and an organic electroluminescent device comprising the same WO2014129846A1 (en)

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