WO2014171779A1 - Organic electroluminescent compounds and organic electroluminescent device comprising the same - Google Patents

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

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WO2014171779A1
WO2014171779A1 PCT/KR2014/003389 KR2014003389W WO2014171779A1 WO 2014171779 A1 WO2014171779 A1 WO 2014171779A1 KR 2014003389 W KR2014003389 W KR 2014003389W WO 2014171779 A1 WO2014171779 A1 WO 2014171779A1
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substituted
unsubstituted
membered
independently
alkyl
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PCT/KR2014/003389
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French (fr)
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Kyung-Joo Lee
Chi-Sik Kim
Hee-Choon Ahn
Doo-Hyeon Moon
Young-Jun Cho
Tae-Jin Lee
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Rohm And Haas Electronic Materials Korea Ltd.
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Priority to CN201480020836.6A priority Critical patent/CN105189455A/en
Publication of WO2014171779A1 publication Critical patent/WO2014171779A1/en

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Definitions

  • the present invention relates to an organic electroluminescent compound and an organic electroluminescent device comprising the same.
  • An electroluminescent (EL) device is a self-light-emitting device which has advantages in that it provides a wider viewing angle, a greater contrast ratio, and a faster response time.
  • An organic EL device was first developed by Eastman Kodak, by using small aromatic diamine molecules and aluminum complexes as materials to form a light-emitting layer [Appl. Phys. Lett. 51, 913, 1987].
  • the most important factor determining luminous efficiency in the organic EL device is light-emitting materials.
  • fluorescent materials have been widely used as the light-emitting material.
  • phosphorescent materials theoretically enhance luminous efficiency by four (4) times compared to fluorescent materials, 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-emitting materials, respectively.
  • the light-emitting material can be used as a combination of a host material and a dopant to improve color purity, luminous efficiency, and stability.
  • the host materials greatly influence the efficiency and performance of the EL device when using a host material/dopant system as the light emitting material, and thus their selection is important.
  • 4,4’-N,N’-dicarbazol-biphenyl (CBP) is the most widely known host material for phosphorescent materials.
  • phosphorescent host 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 the organic EL device is given by [( ⁇ /voltage) ⁇ current efficiency], and the power efficiency is inversely proportional to the voltage. Although the organic EL device comprising phosphorescent host materials provides higher current efficiency (cd/A) than one comprising fluorescent materials, the driving voltage is also significantly high. Thus, there is no merit in terms of power efficiency (lm/W). (3) Furthermore, the operational lifespan of the organic EL device is short, and luminous efficiency is still required in order to be improved.
  • 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
  • MTDATA 4,4',4"-tris(3-methylphenylphenylamino)triphenylamine
  • the organic EL device using these materials is problematic in quantum efficiency and operational lifespan. It is because, when the organic EL device is driven under high current, thermal stress occurs between an anode and a hole injection layer. Thermal stress significantly reduces the operational lifespan of the device. Furthermore, 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/
  • WO 2012/034627 discloses spirobifluorene-based triarylamine compounds or compounds having spirobifluorene bonded to polycyclic aliphatic or aromatic ring, as compounds for an organic EL device.
  • U.S. Patent No. 7,714,145 discloses di-substituted spirobifluorene-based triaryldiamine compounds, as compounds for an organic EL device.
  • the compounds of the above references cannot provide an organic EL device having satisfactory power efficiency, luminous efficiency, quantum efficiency, and lifespan.
  • the objective of the present invention is to provide an organic electroluminescent compound which shows excellence in luminous efficiency and lifespan, and an organic electroluminescent device which comprises the organic electroluminescent compound of the present invention in a light-emitting layer or a hole transport layer and has higher luminous efficiency and a longer lifespan.
  • R 1 , R 5 , and R 6 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 (5- to 7-membered)heterocycloalkyl, a substituted or unsubstituted (C6-C30)aryl(C1-C30)alkyl, -NR 10 R 11 , -SiR 12 R 13 R 14 , -SR 15 , -OR 16 , a cyano, a nitro, or a hydroxy;
  • R 2 and R 3 each independently, represent hydrogen, deuterium, a halogen, a cyano, a carboxy, a nitro, a hydroxy, 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 may be fused with each other to form a substituted or unsubstituted (C3-C30) mono- or polycyclic, alicyclic or aromatic ring;
  • R 4 and R 7 each independently, represent hydrogen, deuterium, a halogen, a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C3-C30)cycloalkyl, a substituted or unsubstituted (5- to 7-membered)heterocycloalkyl, a substituted or unsubstituted (C6-C30)aryl(C1-C30)alkyl, an amino, a mono- or di-(C1-C30)alkylamino, -SiR 12 R 13 R 14 , -SR 15 , -OR 16 , a cyano, a nitro, or a hydroxy;
  • X represents a chemical bond, -O-, -S-, -C(R 17 R 18 )-, -Si(R 19 R 20 )- or -N(R 21 )-;
  • R 10 to R 21 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 (5- 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 and d each independently, represent an integer of 1 to 4; where a or d is an integer of 2 or more, each of R 4 or R 7 may be the same or different;
  • b and c each independently, represent an integer of 1 or 2; where b or c is 2, each of R 5 or R 6 may be the same or different;
  • a and B each independently, represent a substituted or unsubstituted (C6-C30)aryl, a substituted or unsubstituted (5- to 30-membered)heteroaryl,
  • 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
  • l and m each independently, represent an integer of 0 to 3; where l or m is an integer of 2 or more, each of A or B may be the same or different;
  • the organic electroluminescent compound of the present invention can provide an organic electroluminescent device having high luminous efficiency and a long operational lifespan.
  • the organic electroluminescent compound of the present invention can be comprised in a light-emitting layer or a hole transport layer, and can improve current characteristics of an organic electroluminescent device, thereby enhancing power efficiency.
  • the present invention provides the organic electroluminescent compound of formula 1 above, an organic electroluminescent material comprising the same, and an organic electroluminescent device comprising the material.
  • (C1-C30)alkyl(ene) indicates a linear or branched alkyl(ene) having 1 to 30, preferably 1 to 20, more preferably 1 to 10 carbon atoms, and includes methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, etc.
  • “(C2-C30) alkenyl” indicates a linear or branched alkenyl having 2 to 30, preferably 2 to 20, more preferably 2 to 10 carbon atoms, and includes vinyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 2-methylbut-2-enyl, etc.
  • (C2-C30)alkynyl indicates a linear or branched alkynyl having 2 to 30, preferably 2 to 20, more preferably 2 to 10 carbon atoms, and includes ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-methylpent-2-ynyl, etc.
  • “(C3-C30)cycloalkyl” indicates a mono- or polycyclic hydrocarbon having 3 to 30, preferably 3 to 20, more preferably 3 to 7 carbon atoms, and includes cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc.
  • (C6-C30)aryl(ene) indicates a monocyclic or fused ring radical derived from an aromatic hydrocarbon and having 6 to 30, preferably 6 to 20, more preferably 6 to 15 ring backbone carbon atoms, and includes phenyl, biphenyl, terphenyl, naphthyl, fluorenyl, phenanthrenyl, anthracenyl, indenyl, triphenylenyl, pyrenyl, tetracenyl, perylenyl, chrysenyl, naphthacenyl, fluoranthenyl, etc.
  • 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 compound of formula 1 can be selected from the group consisting of the following formulae 2 to 6:
  • A, B, X, R 1 , R 4 to R 7 , a to d, l and m are as defined in formula 1;
  • C and D each independently, represent a substituted or unsubstituted (C6-C30)aryl, a substituted or unsubstituted (5- to 30-membered)heteroaryl,
  • 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
  • Ar 1 and Ar 2 , Ar 3 and Ar 4 , or Ar 5 represents a substituted or unsubsti
  • R 8 and R 9 each independently, represent hydrogen, deuterium, a halogen, a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C3-C30)cycloalkyl, a substituted or unsubstituted (5- to 7-membered)heterocycloalkyl, a substituted or unsubstituted (C6-C30)aryl(C1-C30)alkyl, an amino, a mono- or di-(C1-C30)alkylamino, -SiR 12 R 13 R 14 , -SR 15 , -OR 16 , a cyano, a nitro, or a hydroxy; or may be linked to an adjacent substituent(s) to form a (C3-C30), mono- or polycyclic aromatic ring;
  • e and f each independently, represent an integer of 1 to 4; where e or f is an integer of 2 or more, each of R 8 or R 9 may be the same or different;
  • n and o each independently, represent an integer of 0 to 3; where n or o is an integer of 2 or more, each of C or D may be the same or different;
  • the heteroaryl includes pyrrolyl, imidazolyl, triazinyl, tetrazinyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, dibenzofuranyl, dibenzothiophenyl, benzoimidazolyl, benzothiazolyl, benzoisothiazolyl, benzoisoxazolyl, benzoxazolyl, isoindolyl, indolyl, indazolyl, benzothiadiazolyl, quinolyl, isoquinolyl, quinazolinyl, quinoxalinyl, carbazolyl, phenoxazinyl, and phenanthridinyl.
  • R 1 , R 5 , and R 6 each independently, may represent hydrogen, 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 (5- to 7-membered)heterocycloalkyl, or -NR 10 R 11 ; and more preferably, hydrogen, or a substituted or unsubstituted (C6-C18)aryl.
  • R 2 and R 3 may be fused with each other to form a substituted or unsubstituted (C3-C30), mono- or polycyclic, alicyclic or aromatic ring.
  • X may represent -O-, -S-, -C(R 17 R 18 )-, or -N(R 21 )-.
  • R 17 , R 18 , and R 21 each independently, may represent a (C1-C10)alkyl, or a (C6-C18)aryl.
  • A, B, C, and D each independently, may represent a substituted or unsubstituted (5- to 18-membered)heteroaryl,
  • the substituted or unsubstituted (5- to 30-membered)heteroaryl may be a substituted or unsubstituted pyridyl, a substituted or unsubstituted pyrimidinyl, a substituted or unsubstituted triazinyl, a substituted or unsubstituted indolyl, a substituted or unsubstituted quinazolinyl, or a substituted or unsubstituted quinoxalinyl.
  • the substituents of the substituted heteroaryl may be a (C6-C18)aryl.
  • L 1 may represent a single bond, or a substituted or unsubstituted (C6-C18)arylene.
  • L 2 may represent a substituted or unsubstituted (C6-C18) aromatic hydrocarbon ring.
  • Ar 1 to Ar 6 may represent a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted (5- to 30-membered)heteroaryl.
  • Ar 1 to Ar 6 each independently, may represent a substituted or unsubstituted phenyl, a substituted or unsubstituted biphenyl, a substituted or unsubstituted terphenyl, a substituted or unsubstituted naphthyl, a substituted or unsubstituted fluorenyl, a substituted or unsubstituted pyridyl, a substituted or unsubstituted pyrimidinyl, a substituted or unsubstituted triazinyl, a substituted or unsubstituted indolyl, a substituted or unsubstituted quinazolinyl, a substituted or
  • the substituents of the substituted aryl and the substituted heteroaryl may be at least one selected from deuterium, a halogen, a (C1-C10)alkyl, a (C6-C18)aryl, a (5- to 18-membered) heteroaryl, and a di(C6-C18)arylamino.
  • R 8 and R 9 may be hydrogen, or may be linked to an adjacent substituent(s) to form a (C3-C30), mono- or polycyclic aromatic ring.
  • R 8 and R 9 may be hydrogen, or may be linked to an adjacent substituent(s) to form a phenyl ring.
  • Organic electroluminescent compounds of the present invention include the following, but are not limited thereto:
  • the compounds of the present invention can be prepared by a synthetic method known to one skilled in the art. For example, they can be prepared according to the following reaction scheme 1.
  • 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 material may consist of the organic electroluminescent compound of the present invention. Otherwise, the material may further comprise a conventional compound(s) which has been comprised in an organic electroluminescent material, in addition to the compound of the present invention.
  • the organic electroluminescent device of the present invention may comprise a first electrode, a second electrode, and at least one organic layer disposed between the first and second electrodes.
  • the organic layer may comprise at least one organic electroluminescent compound of formula 1.
  • the organic layer may comprise a light-emitting layer, and may further comprise at least one layer selected from a hole injection layer, a hole transport layer, an electron transport layer, an electron injection layer, an interlayer, a hole blocking layer, and an electron blocking layer.
  • the organic electroluminescent compound of the present invention may be comprised in at least one of a light-emitting layer and a hole transport layer.
  • the organic electroluminescent compound of the present invention may be comprised therein as a hole transport material.
  • the organic electroluminescent compound of the present invention may be comprised therein as a host material.
  • the organic electroluminescent device comprising the organic electroluminescent compound of the present invention may further comprise at least one host compound other than the organic electroluminescent compound of the present invention. Furthermore, the organic electroluminescent device may further comprise at least one dopant.
  • organic electroluminescent compound of the present invention is comprised as a host material (a first host material) in a light-emitting layer
  • another compound may be comprised as a second host material.
  • the weight ratio between the first host material and the second host material is in the range of 1:99 to 99:1.
  • the second host material may be from any of the known phosphorescent host materials. Specifically, the material selected from the group consisting of the compounds of formulae 6 to 8 below is preferable as the second host material 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 or unsubstituted (C6-C30)aryl, a substituted or unsubstituted (3- to 30-membered) heteroaryl, or R 25 R 26 R 27 Si-;
  • 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) heteroary
  • the second host material includes the following:
  • the dopant for the organic electroluminescent device of the present invention is preferably at least one phosphorescent dopant.
  • the phosphorescent dopant for the organic electroluminescent device of the present invention is not limited, but may be preferably selected from metallated complex compounds of iridium (Ir), osmium (Os), copper (Cu) and platinum (Pt), more preferably selected from ortho-metallated complex compounds of iridium (Ir), osmium (Os), copper (Cu) and platinum (Pt), and even more preferably ortho-metallated iridium complex compounds.
  • the phosphorescent dopants may be preferably selected from compounds represented by the following formulae 9 to 11.
  • L is selected from the following:
  • 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, a cyano, a substituted or unsubstituted (C1-C30)alkoxy, or a substituted or unsubstituted (C3-C30)cycloalkyl; or R 120 to R 123 may be linked with an adjacent substituent(s) to form a fused ring, e.g.
  • 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, they may be linked with an adjacent substituent(s) to form a fused ring, e.g.
  • R 201 to R 211 each independently, represent hydrogen, deuterium, a halogen, or a (C1-C30)alkyl unsubstituted or substituted with a halogen;
  • 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 is an integer of 1 to 3.
  • the phosphorescent dopant materials include the following:
  • the present invention provides a composition for preparing an organic electroluminescent device.
  • the composition comprises the compound of the present invention as a host material or a hole transport material.
  • the organic electroluminescent device of the present invention may comprise a first electrode, a second electrode, and at least one organic layer disposed between the first and second electrodes.
  • the organic layer may comprise a light-emitting layer, which may comprise the composition for the organic electroluminescent device of the present invention.
  • the organic electroluminescent device of the present invention may further comprise, in addition to the organic electroluminescent compound of 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, in addition to the organic electroluminescent compound of formula 1, at least one metal selected from the group consisting of metals of Group 1, metals of Group 2, transition metals of the 4 th period, transition metals of the 5 th period, lanthanides and organic metals of the d-transition elements of the Periodic Table, or at least one complex compound comprising the metal.
  • the organic layer may further comprise a light-emitting layer and a charge generating layer.
  • the organic electroluminescent device of 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 of the present invention. If necessary, it may further comprise an orange light-emitting layer or a yellow light-emitting layer.
  • at least one light-emitting layer which comprises a blue electroluminescent compound, a red electroluminescent compound or a green electroluminescent compound known in the field, besides the compound of the present invention. If necessary, it may further comprise an orange light-emitting layer or a yellow light-emitting layer.
  • a surface layer may be placed on an inner surface(s) of one or both electrode(s), selected from a chalcogenide layer, a metal halide layer and a metal oxide layer.
  • a chalcogenide (includes oxides) layer of silicon or aluminum is preferably placed on an anode surface of an electroluminescent medium layer
  • a metal halide layer or a metal oxide layer is preferably placed on a cathode surface of an electroluminescent medium layer.
  • the chalcogenide includes SiO X (1 ⁇ X ⁇ 2), AlO X (1 ⁇ X ⁇ 1.5), SiON, SiAlON, etc.;
  • the metal halide includes LiF, MgF 2 , CaF 2 , a rare earth metal fluoride, etc.; and the metal oxide includes Cs 2 O, Li 2 O, MgO, SrO, BaO, CaO, etc.
  • a mixed region of an electron transport compound and a reductive dopant, or a mixed region of a hole transport compound and an oxidative dopant may be placed on at least one surface of a pair of electrodes.
  • the electron transport compound is reduced to an anion, and thus it becomes easier to inject and transport electrons from the mixed region to an electroluminescent medium.
  • the hole transport compound is oxidized to a cation, and thus it becomes easier to inject and transport holes from the mixed region to the electroluminescent medium.
  • the oxidative dopant includes various Lewis acids and acceptor compounds
  • the reductive dopant includes alkali metals, alkali metal compounds, alkaline earth metals, rare-earth metals, and mixtures thereof.
  • a reductive dopant layer may be employed as a charge generating layer to prepare an electroluminescent device having two or more light-emitting layers and emitting white light.
  • dry film-forming methods such as vacuum evaporation, sputtering, plasma and ion plating methods, or wet film-forming methods such as spin coating, dip coating, and flow coating methods can be used.
  • a thin film can be formed by dissolving or diffusing materials forming each layer into any suitable solvent such as ethanol, chloroform, tetrahydrofuran, dioxane, etc.
  • the solvent can be any solvent where the materials forming each layer can be dissolved or diffused, and where there are no problems in film-formation capability.
  • OLED device was produced using the compound of the present invention as follows.
  • a transparent electrode indium tin oxide (ITO) thin film (15 ⁇ /sq) on a glass substrate for an organic light-emitting diode (OLED) device (Samsung Corning) was subjected to an ultrasonic washing with trichloroethylene, acetone, ethanol and distilled water, sequentially, and then was stored in isopropanol.
  • the ITO substrate was then mounted on a substrate holder of a vacuum vapor depositing apparatus.
  • N 1 ,N 1’ -([1,1’-biphenyl]-4,4’-diyl)bis(N 1 -(naphthalen-1-yl)-N 4 ,N 4 -diphenylbenzene-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-98 was then introduced into another cell of said vacuum vapor depositing apparatus, and evaporated by applying electric current to the cell, thereby forming a hole transport layer having a thickness of 20 nm on the hole injection layer. Thereafter, 9-(4-([1,1':4',1''-terphenyl]-3-yl)pyridin-2-yl)-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, so that the dopant was 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.
  • 2-(4-(9,10-di(naphthalen-2-yl)anthracen-2-yl)phenyl)-1-phenyl-1H-benzo[ d ]imidazole was then introduced into one cell, and lithium quinolate was introduced into another cell.
  • the two materials were evaporated at the same rate, so that they were respectively deposited in a doping amount of 50 wt% 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 then deposited by another vacuum vapor deposition apparatus on the electron injection layer.
  • An OLED device was produced. All the materials used for producing the OLED device were those purified by vacuum sublimation at 10 -6 torr. The produced OLED device showed green emission having a luminance of 2,450 cd/m 2 and a current density of 5.3 mA/cm 2 .
  • An OLED device was produced in the same manner as in Device Example 1, except that N,N'-di(4-biphenyl)-N,N'-di(4-biphenyl)-4,4'-diaminodiphenyl was used to form a hole transport layer having a thickness of 20 nm; 4,4'-N,N'-dicarbazole-biphenyl as a host material and compound D-15 as a dopant were used to form a light-emitting layer having a thickness of 30 nm on the hole transport layer; and aluminum(III) bis(2-methyl-8-quinolinato)-4-phenylphenolate was used to form a hole blocking layer having a thickness of 10 nm.
  • the produced OLED device showed green emission having a luminance of 3,650 cd/m 2 and a current density of 11.2 mA/cm 2 .
  • the organic electroluminescent compound according to the present invention shows better luminescent properties than conventional compounds.
  • the organic electroluminescent device shows excellent luminous properties by using the organic electroluminescent compound of the present invention.

Abstract

The present invention relates to a novel organic electroluminescent compound and an organic electroluminescent device comprising the same. The organic electroluminescent compound of the present invention can be used for a light-emitting layer or a hole transport layer, and has excellent luminous characteristics to provide an organic electroluminescent device showing improved current characteristics.

Description

ORGANIC ELECTROLUMINESCENT COMPOUNDS AND ORGANIC ELECTROLUMINESCENT DEVICE COMPRISING THE SAME
The present invention relates to an organic electroluminescent compound and an organic electroluminescent device comprising the same.
An electroluminescent (EL) device is a self-light-emitting device which has advantages in that it provides a wider viewing angle, a greater contrast ratio, and a faster response time. An organic EL device was first developed by Eastman Kodak, by using small aromatic diamine molecules and aluminum complexes as materials to form a light-emitting layer [Appl. Phys. Lett. 51, 913, 1987].
The most important factor determining luminous efficiency in the organic EL device is light-emitting materials. Until now, fluorescent materials have been widely used as the light-emitting material. However, in view of electroluminescent mechanisms, since phosphorescent materials theoretically enhance luminous efficiency by four (4) times compared to fluorescent materials, phosphorescent light-emitting materials 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-emitting materials, respectively.
The light-emitting material can be used as a combination of a host material and a dopant to improve color purity, luminous efficiency, and stability. The host materials greatly influence the efficiency and performance of the EL device when using a host material/dopant system as the light emitting material, and thus their selection is important. At present, 4,4’-N,N’-dicarbazol-biphenyl (CBP) is the most widely known host material for phosphorescent materials. Recently, Pioneer (Japan) et al., developed a high performance organic EL device using bathocuproine (BCP) and aluminum(III)bis(2-methyl-8-quinolinate)(4-phenylphenolate) (BAlq) etc., as host materials, which were known as hole blocking materials.
Although these phosphorescent host 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 the organic EL device is given by [(π/voltage) × current efficiency], and the power efficiency is inversely proportional to the voltage. Although the organic EL device comprising phosphorescent host materials provides higher current efficiency (cd/A) than one comprising fluorescent materials, the driving voltage is also significantly high. Thus, there is no merit in terms of power efficiency (lm/W). (3) Furthermore, the operational lifespan of the organic EL device is short, and luminous efficiency is still required in order 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, the organic EL device using these materials is problematic in quantum efficiency and operational lifespan. It is because, when the organic EL device is driven under high current, thermal stress occurs between an anode and a hole injection layer. Thermal stress significantly reduces the operational lifespan of the device. Furthermore, 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 discloses spirobifluorene-based triarylamine compounds or compounds having spirobifluorene bonded to polycyclic aliphatic or aromatic ring, as compounds for an organic EL device. U.S. Patent No. 7,714,145 discloses di-substituted spirobifluorene-based triaryldiamine compounds, as compounds for an organic EL device. However, the compounds of the above references cannot provide an organic EL device having satisfactory power efficiency, luminous efficiency, quantum efficiency, and lifespan.
The objective of the present invention is to provide an organic electroluminescent compound which shows excellence in luminous efficiency and lifespan, and an organic electroluminescent device which comprises the organic electroluminescent compound of the present invention in a light-emitting layer or a hole transport layer and has higher luminous efficiency and a longer lifespan.
The present inventors found that the above objective can be achieved by a compound represented by the following formula 1:
Figure PCTKR2014003389-appb-I000001
wherein,
R1, R5, and R6, 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 (5- to 7-membered)heterocycloalkyl, a substituted or unsubstituted (C6-C30)aryl(C1-C30)alkyl, -NR10R11, -SiR12R13R14, -SR15, -OR16, a cyano, a nitro, or a hydroxy;
R2 and R3, each independently, represent hydrogen, deuterium, a halogen, a cyano, a carboxy, a nitro, a hydroxy, 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 may be fused with each other to form a substituted or unsubstituted (C3-C30) mono- or polycyclic, alicyclic or aromatic ring;
R4 and R7, each independently, represent hydrogen, deuterium, a halogen, a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C3-C30)cycloalkyl, a substituted or unsubstituted (5- to 7-membered)heterocycloalkyl, a substituted or unsubstituted (C6-C30)aryl(C1-C30)alkyl, an amino, a mono- or di-(C1-C30)alkylamino, -SiR12R13R14, -SR15, -OR16, a cyano, a nitro, or a hydroxy;
X represents a chemical bond, -O-, -S-, -C(R17R18)-, -Si(R19R20)- or -N(R21)-;
R10 to R21, 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 (5- 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 and d, each independently, represent an integer of 1 to 4; where a or d is an integer of 2 or more, each of R4 or R7 may be the same or different;
b and c, each independently, represent an integer of 1 or 2; where b or c is 2, each of R5 or R6 may be the same or different;
A and B, each independently, represent a substituted or unsubstituted (C6-C30)aryl, a substituted or unsubstituted (5- to 30-membered)heteroaryl,
Figure PCTKR2014003389-appb-I000002
or
Figure PCTKR2014003389-appb-I000003
, and may be 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;
l and m, each independently, represent an integer of 0 to 3; where l or m is an integer of 2 or more, each of A or B may be the same or different;
the heterocycloalkyl and heteroaryl(ene), each independently, contain at least one hetero atom selected from B, N, O, S, P(=O), Si and P.
The organic electroluminescent compound of the present invention can provide an organic electroluminescent device having high luminous efficiency and a long operational lifespan. The organic electroluminescent compound of the present invention can be comprised in a light-emitting layer or a hole transport layer, and can improve current characteristics of an organic electroluminescent device, thereby enhancing power 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 provides the organic electroluminescent compound of formula 1 above, an organic electroluminescent material comprising the same, and an organic electroluminescent device comprising the material.
Herein, “(C1-C30)alkyl(ene)” indicates a linear or branched alkyl(ene) having 1 to 30, preferably 1 to 20, more preferably 1 to 10 carbon atoms, and includes methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, etc. “(C2-C30) alkenyl” indicates a linear or branched alkenyl having 2 to 30, preferably 2 to 20, more preferably 2 to 10 carbon atoms, and includes vinyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 2-methylbut-2-enyl, etc. “(C2-C30)alkynyl” indicates a linear or branched alkynyl having 2 to 30, preferably 2 to 20, more preferably 2 to 10 carbon atoms, and includes ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-methylpent-2-ynyl, etc. “(C3-C30)cycloalkyl” indicates a mono- or polycyclic hydrocarbon having 3 to 30, preferably 3 to 20, more preferably 3 to 7 carbon atoms, and includes cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc. “(5- to 7-membered) heterocycloalkyl” indicates a cycloalkyl having 5 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. Furthermore, “(C6-C30)aryl(ene)” indicates a monocyclic or fused ring radical derived from an aromatic hydrocarbon and having 6 to 30, preferably 6 to 20, more preferably 6 to 15 ring backbone carbon atoms, and includes phenyl, biphenyl, terphenyl, naphthyl, fluorenyl, phenanthrenyl, anthracenyl, indenyl, triphenylenyl, pyrenyl, tetracenyl, perylenyl, chrysenyl, naphthacenyl, fluoranthenyl, etc. “(5- to 30-membered) heteroaryl(ene)” indicates an aryl group having 5 to 30, preferably 5 to 20, more preferably 5 to 15 ring backbone atoms including at least one, preferably 1 to 4 hetero atom selected from the group consisting of B, N, O, S, P(=O), Si and P; may be a monocyclic ring, or a fused ring condensed with at least one benzene ring; may be partially saturated; may be one formed by linking at least one heteroaryl or aryl group to a heteroaryl group via a single bond(s); and includes a monocyclic ring-type heteroaryl such as furyl, thiophenyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, thiadiazolyl, isothiazolyl, isoxazolyl, oxazolyl, oxadiazolyl, triazinyl, tetrazinyl, triazolyl, tetrazolyl, furazanyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, etc., and a fused ring-type heteroaryl such as benzofuranyl, benzothiophenyl, isobenzofuranyl, dibenzofuranyl, dibenzothiophenyl, benzoimidazolyl, benzothiazolyl, benzoisothiazolyl, benzoisoxazolyl, benzoxazolyl, isoindolyl, indolyl, indazolyl, benzothiadiazolyl, quinolyl, isoquinolyl, cinnolinyl, quinazolinyl, quinoxalinyl, carbazolyl, phenoxazinyl, phenanthridinyl, benzodioxolyl, etc. Furthermore, “halogen” includes F, Cl, Br and I.
Herein, “substituted” in the expression, “substituted or unsubstituted,” means that a hydrogen atom in a certain functional group is replaced with another atom or group, i.e. a substituent. In the formulae of the present invention, 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, of R1 to R21, L1, L2, and Ar1 to Ar6, each independently, are at least one selected from the group consisting of deuterium, a halogen, a cyano, a carboxy, a nitro, a hydroxy, a (C1-C30)alkyl, a halo(C1-C30)alkyl, a (C2-C30)alkenyl, a (C2-C30)alkynyl, a (C1-C30)alkoxy, a (C1-C30)alkylthio, a (C3-C30)cycloalkyl, a (C3-C30)cycloalkenyl, a (3- to 7-membered)heterocycloalkyl, a (C6-C30)aryloxy, a (C6-C30)arylthio, a (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.
Preferably, the compound of formula 1 can be selected from the group consisting of the following formulae 2 to 6:
Figure PCTKR2014003389-appb-I000004
Figure PCTKR2014003389-appb-I000005
Figure PCTKR2014003389-appb-I000006
Figure PCTKR2014003389-appb-I000007
Figure PCTKR2014003389-appb-I000008
wherein,
A, B, X, R1, R4 to R7, a to d, l and m are as defined in formula 1;
C and D, each independently, represent a substituted or unsubstituted (C6-C30)aryl, a substituted or unsubstituted (5- to 30-membered)heteroaryl,
Figure PCTKR2014003389-appb-I000009
or
Figure PCTKR2014003389-appb-I000010
, and may be 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; 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;
R8 and R9, each independently, represent hydrogen, deuterium, a halogen, a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C3-C30)cycloalkyl, a substituted or unsubstituted (5- to 7-membered)heterocycloalkyl, a substituted or unsubstituted (C6-C30)aryl(C1-C30)alkyl, an amino, a mono- or di-(C1-C30)alkylamino, -SiR12R13R14, -SR15, -OR16, a cyano, a nitro, or a hydroxy; or may be linked to an adjacent substituent(s) to form a (C3-C30), mono- or polycyclic aromatic ring;
e and f, each independently, represent an integer of 1 to 4; where e or f is an integer of 2 or more, each of R8 or R9 may be the same or different;
n and o, each independently, represent an integer of 0 to 3; where n or o is an integer of 2 or more, each of C or D may be the same or different;
the heterocycloalkyl and heteroaryl(ene), each independently, contain at least one hetero atom selected from B, N, O, S, P(=O), Si and P.
In the compound of formulae 1 to 6, the heteroaryl includes pyrrolyl, imidazolyl, triazinyl, tetrazinyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, dibenzofuranyl, dibenzothiophenyl, benzoimidazolyl, benzothiazolyl, benzoisothiazolyl, benzoisoxazolyl, benzoxazolyl, isoindolyl, indolyl, indazolyl, benzothiadiazolyl, quinolyl, isoquinolyl, quinazolinyl, quinoxalinyl, carbazolyl, phenoxazinyl, and phenanthridinyl.
Preferably, R1, R5, and R6, each independently, may represent hydrogen, 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 (5- to 7-membered)heterocycloalkyl, or -NR10R11; and more preferably, hydrogen, or a substituted or unsubstituted (C6-C18)aryl.
Preferably, R2 and R3 may be fused with each other to form a substituted or unsubstituted (C3-C30), mono- or polycyclic, alicyclic or aromatic ring.
Preferably, X may represent -O-, -S-, -C(R17R18)-, or -N(R21)-. Preferably, R17, R18, and R21, each independently, may represent a (C1-C10)alkyl, or a (C6-C18)aryl.
Preferably, A, B, C, and D, each independently, may represent a substituted or unsubstituted (5- to 18-membered)heteroaryl,
Figure PCTKR2014003389-appb-I000011
or
Figure PCTKR2014003389-appb-I000012
. Specifically, in the definitions of A to D, the substituted or unsubstituted (5- to 30-membered)heteroaryl may be a substituted or unsubstituted pyridyl, a substituted or unsubstituted pyrimidinyl, a substituted or unsubstituted triazinyl, a substituted or unsubstituted indolyl, a substituted or unsubstituted quinazolinyl, or a substituted or unsubstituted quinoxalinyl. Specifically, in the definitions of A to D, the substituents of the substituted heteroaryl may be a (C6-C18)aryl.
Preferably, L1 may represent a single bond, or a substituted or unsubstituted (C6-C18)arylene.
Preferably, L2 may represent a substituted or unsubstituted (C6-C18) aromatic hydrocarbon ring.
Preferably, Ar1 to Ar6, each independently, may represent a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted (5- to 30-membered)heteroaryl. Specifically, Ar1 to Ar6, each independently, may represent a substituted or unsubstituted phenyl, a substituted or unsubstituted biphenyl, a substituted or unsubstituted terphenyl, a substituted or unsubstituted naphthyl, a substituted or unsubstituted fluorenyl, a substituted or unsubstituted pyridyl, a substituted or unsubstituted pyrimidinyl, a substituted or unsubstituted triazinyl, a substituted or unsubstituted indolyl, a substituted or unsubstituted quinazolinyl, a substituted or unsubstituted quinoxalinyl, a substituted or unsubstituted carbazolyl, a substituted or unsubstituted dibenzothiophenyl, or a substituted or unsubstituted dibenzofuranyl. Specifically, in the definitions of Ar1 to Ar6, the substituents of the substituted aryl and the substituted heteroaryl, each independently, may be at least one selected from deuterium, a halogen, a (C1-C10)alkyl, a (C6-C18)aryl, a (5- to 18-membered) heteroaryl, and a di(C6-C18)arylamino.
Preferably, R8 and R9 may be hydrogen, or may be linked to an adjacent substituent(s) to form a (C3-C30), mono- or polycyclic aromatic ring. Specifically, R8 and R9 may be hydrogen, or may be linked to an adjacent substituent(s) to form a phenyl ring.
Organic electroluminescent compounds of the present invention include the following, but are not limited thereto:
Figure PCTKR2014003389-appb-I000013
Figure PCTKR2014003389-appb-I000014
Figure PCTKR2014003389-appb-I000015
Figure PCTKR2014003389-appb-I000016
Figure PCTKR2014003389-appb-I000017
Figure PCTKR2014003389-appb-I000018
Figure PCTKR2014003389-appb-I000019
Figure PCTKR2014003389-appb-I000020
Figure PCTKR2014003389-appb-I000021
Figure PCTKR2014003389-appb-I000022
Figure PCTKR2014003389-appb-I000023
Figure PCTKR2014003389-appb-I000024
Figure PCTKR2014003389-appb-I000025
Figure PCTKR2014003389-appb-I000026
Figure PCTKR2014003389-appb-I000027
Figure PCTKR2014003389-appb-I000028
The compounds of the present invention can be prepared by a synthetic method known to one skilled in the art. For example, they can be prepared according to the following reaction scheme 1.
[Reaction Scheme 1]
Figure PCTKR2014003389-appb-I000029
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 material may consist of the organic electroluminescent compound of the present invention. Otherwise, the material may further comprise a conventional compound(s) which has been comprised in an organic electroluminescent material, in addition to the compound of the present invention.
The organic electroluminescent device of the present invention may comprise a first electrode, a second electrode, and at least one organic layer disposed between the first and second electrodes. The organic layer may comprise at least one organic electroluminescent compound of formula 1.
One of the first and second electrodes may be an anode, and the other may be a cathode. The organic layer may comprise a light-emitting layer, and may further comprise at least one layer selected from a hole injection layer, a hole transport layer, an electron transport layer, an electron injection layer, an interlayer, a hole blocking layer, and an electron blocking layer.
The organic electroluminescent compound of the present invention may be comprised in at least one of a light-emitting layer and a hole transport layer. When used in the hole transport layer, the organic electroluminescent compound of the present invention may be comprised therein as a hole transport material. When used in the light-emitting layer, the organic electroluminescent compound of the present invention may be comprised therein as a host material.
The organic electroluminescent device comprising the organic electroluminescent compound of the present invention may further comprise at least one host compound other than the organic electroluminescent compound of the present invention. Furthermore, the organic electroluminescent device may further comprise at least one dopant.
Where the organic electroluminescent compound of the present invention is comprised as a host material (a first host material) in a light-emitting layer, another compound may be comprised as a second host material. The weight ratio between the first host material and the second host material is in the range of 1:99 to 99:1.
The second host material may be from any of the known phosphorescent host materials. Specifically, the material selected from the group consisting of the compounds of formulae 6 to 8 below is preferable as the second host material in view of luminous efficiency.
Figure PCTKR2014003389-appb-I000030
Figure PCTKR2014003389-appb-I000031
Figure PCTKR2014003389-appb-I000032
Wherein, Cz represents the following structure:
Figure PCTKR2014003389-appb-I000033
R21 to R24, each independently, represent hydrogen, deuterium, a halogen, a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C6-C30)aryl, a substituted or unsubstituted (3- to 30-membered) heteroaryl, or R25R26R27Si-; 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, the second host material includes the following:
Figure PCTKR2014003389-appb-I000034
Figure PCTKR2014003389-appb-I000035
Figure PCTKR2014003389-appb-I000036
Figure PCTKR2014003389-appb-I000037
Figure PCTKR2014003389-appb-I000038
Figure PCTKR2014003389-appb-I000039
Figure PCTKR2014003389-appb-I000040
Figure PCTKR2014003389-appb-I000041
Figure PCTKR2014003389-appb-I000042
Figure PCTKR2014003389-appb-I000043
Figure PCTKR2014003389-appb-I000044
Figure PCTKR2014003389-appb-I000045
Figure PCTKR2014003389-appb-I000046
The dopant for the organic electroluminescent device of the present invention is preferably at least one phosphorescent dopant. The phosphorescent dopant for the organic electroluminescent device of the present invention is not limited, but may be preferably selected from metallated complex compounds of iridium (Ir), osmium (Os), copper (Cu) and platinum (Pt), more preferably selected from ortho-metallated complex compounds of iridium (Ir), osmium (Os), copper (Cu) and platinum (Pt), and even more preferably ortho-metallated iridium complex compounds.
The phosphorescent dopants may be preferably selected from compounds represented by the following formulae 9 to 11.
Figure PCTKR2014003389-appb-I000047
Figure PCTKR2014003389-appb-I000048
Figure PCTKR2014003389-appb-I000049
wherein
L is selected from the following:
Figure PCTKR2014003389-appb-I000050
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, a cyano, a substituted or unsubstituted (C1-C30)alkoxy, or a substituted or unsubstituted (C3-C30)cycloalkyl; or R120 to R123 may be linked with an adjacent substituent(s) 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, they may be linked with an adjacent substituent(s) to form a fused ring, e.g. fluorene, dibenzothiophen, or dibenzofuran; R201 to R211, each independently, represent hydrogen, deuterium, a halogen, or a (C1-C30)alkyl unsubstituted or substituted with a halogen; 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 is an integer of 1 to 3.
Specifically, the phosphorescent dopant materials include the following:
Figure PCTKR2014003389-appb-I000051
Figure PCTKR2014003389-appb-I000052
Figure PCTKR2014003389-appb-I000053
Figure PCTKR2014003389-appb-I000054
Figure PCTKR2014003389-appb-I000055
Figure PCTKR2014003389-appb-I000056
Figure PCTKR2014003389-appb-I000057
Figure PCTKR2014003389-appb-I000058
Figure PCTKR2014003389-appb-I000059
Figure PCTKR2014003389-appb-I000060
Figure PCTKR2014003389-appb-I000061
Figure PCTKR2014003389-appb-I000062
Figure PCTKR2014003389-appb-I000063
The present invention, as another aspect, provides a composition for preparing an organic electroluminescent device. The composition comprises the compound of the present invention as a host material or a hole transport material.
The organic electroluminescent device of the present invention may comprise a first electrode, a second electrode, and at least one organic layer disposed between the first and second electrodes. The organic layer may comprise a light-emitting layer, which may comprise the composition for the organic electroluminescent device of the present invention.
The organic electroluminescent device of the present invention may further comprise, in addition to the organic electroluminescent compound of formula 1, at least one compound selected from the group consisting of arylamine-based compounds and styrylarylamine-based compounds.
In the organic electroluminescent device of the present invention, the organic layer may further comprise, in addition to the organic electroluminescent compound of formula 1, at least one metal selected from the group consisting of metals of Group 1, metals of Group 2, transition metals of the 4th period, transition metals of the 5th period, lanthanides and organic metals of the d-transition elements of the Periodic Table, or at least one complex compound comprising the metal. The organic layer may further comprise a light-emitting layer and a charge generating layer.
In addition, the organic electroluminescent device of 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 of the present invention. If necessary, it may further comprise an orange light-emitting layer or a yellow light-emitting layer.
In the organic electroluminescent device of the present invention, preferably, at least one layer (hereinafter, "a surface layer”) may be placed on an inner surface(s) of one or both electrode(s), selected from a chalcogenide layer, a metal halide layer and a metal oxide layer. Specifically, a chalcogenide (includes oxides) layer of silicon or aluminum is preferably placed on an anode surface of an electroluminescent medium layer, and a metal halide layer or a metal oxide layer is preferably placed on a cathode surface of an electroluminescent medium layer. Such a surface layer provides operation stability for the organic electroluminescent device. Preferably, the chalcogenide includes SiOX(1≤X≤2), AlOX(1≤X≤1.5), SiON, SiAlON, etc.; the metal halide includes LiF, MgF2, CaF2, a rare earth metal fluoride, etc.; and the metal oxide includes Cs2O, Li2O, MgO, SrO, BaO, CaO, etc.
In the organic electroluminescent device of the present invention, a mixed region of an electron transport compound and a reductive dopant, or a mixed region of a hole transport compound and an oxidative dopant may be placed on at least one surface of a pair of electrodes. In this case, the electron transport compound is reduced to an anion, and thus it becomes easier to inject and transport electrons from the mixed region to an electroluminescent medium. Furthermore, the hole transport compound is oxidized to a cation, and thus it becomes easier to inject and transport holes from the mixed region to the electroluminescent medium. Preferably, the oxidative dopant includes various Lewis acids and acceptor compounds, and the reductive dopant includes alkali metals, alkali metal compounds, alkaline earth metals, rare-earth metals, and mixtures thereof. A reductive dopant layer may be employed as a charge generating layer to prepare an electroluminescent device having two or more light-emitting layers and emitting white light.
In order to form each layer of the organic electroluminescent device of the present 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 compound of the present invention, 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-98
Preparation of compound C-98-3
Figure PCTKR2014003389-appb-I000064
After adding 4-dibenzofuranboronic acid (compound C-98-1) 127g (0.60mol), 2-bromo-nitrobenzene 100g (0.50mol), potassium carbonate 159g (1.50mol), and tetrakis (triphenylphosphine)palladium [Pd(PPh3)4] 29g (0.03mol) in toluene 3L, ethanol 750mL and purified water 750mL, the mixture was stirred under reflux for a day. The mixture was extracted with ethyl acetate 2L. The obtained organic layer was washed with distilled water 500 mL, dried with anhydrous magnesium sulfate, and the organic solvent was then removed under reduced pressure. The obtained solid was separated by silica gel column chromatography and recrystallization to obtain compound C-98-3 (126g, 87%).
Preparation of compound C-98-4
Figure PCTKR2014003389-appb-I000065
4-(2-nitrophenyl)dibenzo[b,d]furan (compound C-98-3) 126g(0.44mol) was dissolved in triethylphosphite [P(OTe)3] 1.1L, and the mixture was then stirred under reflux at 150°C. After 5 hours, the mixture was cooled to room temperature, and then distilled under reduced pressure. The resultant solid was separated by silica gel column chromatography and recrystallization to obtain compound C-98-4 (80g, 71%).
Preparation of compound C-98-6
Figure PCTKR2014003389-appb-I000066
5H-benzofuro[3,2-c]carbazole (compound C-98-4) 30g (116.60mmol), iodobenzene 20mL (174.90mmol), copper iodide 11g (58.30mmol), potassium phosphate 74.2g (349.80mmol) and ethylene diamine (EDA) 16mL (233.20mmol) were added to toluene 600mL, and the mixture was then stirred under reflux. After cooling to room temperature, the reaction mixture was extracted with ethyl acetate 300mL, and the obtained organic layer was then washed twice with distilled water 100mL. The organic layer was dried with anhydrous magnesium sulfate, and the organic solvent was then removed under reduced pressure. After separating by silica gel column chromatography and recrystallization, compound C-98-6 (31g, 80%) was obtained.
Preparation of compound C-98-7
Figure PCTKR2014003389-appb-I000067
After dissolving 5-phenyl-5H-benzofuro[3,2-c]carbazole (compound C-98-6) 31g (92.99mmol) in tetrahydrofuran (THF) 620mL, n-butyl lithium (2.5M in hexane) 75mL(185.97mmol) was added to the mixture at -78℃. The mixture was stirred at -78℃ for one hour, and trimethoxyborane [B(OMe)3] 31mL(278.96mmol) was then added thereto. The mixture was stirred for 2 hours. After completing the reaction with ammonium chloride 200 mL, the mixture was extracted with ethyl acetate 300 mL, and the obtained organic layer was then washed with distilled water 100 mL. The organic layer was dried with anhydrous magnesium sulfate, and the organic solvent was then removed under reduced pressure. The obtained solid was separated by recrystallizaton, thereby obtaining compound C-98-7 (32.8g, 93%).
Preparation of compound C-98-9
Figure PCTKR2014003389-appb-I000068
After adding (5-phenyl-5H-benzofuro[3,2-c]carbazol-11-yl)boronic acid (compound C-98-7) 20g (53.03mmol), 2-bromoiodobenzene 22.5g (79.55mmol), sodium carbonate 16.9g (159.09mmol), and tetrakis(triphenylphosphine)palladium [Pd(PPh3)4] 3.1g(2.65mmol) to toluene 260mL, ethanol 65mL and purified water 65mL, the mixture was stirred for 6 hours. After completing the reaction, the mixture was washed with distilled water, and extracted with ethyl acetate. After the organic layer was dried with anhydrous magnesium sulfate, the solvent was removed by rotary evaporator. By purifying with column chromatography, compound C-98-9 (13g, 51%) was obtained.
Preparation of compound C-98
Figure PCTKR2014003389-appb-I000069
11-(2-bromophenyl)-5-phenyl-5H-benzofuro[3,2-c]carbazole (compound C-98-9) 13g (26.62 mmol) and tetrahydrofuran 300mL were introduced to a reaction vessel, cooled to -78℃ under nitrogen atmosphere, and n-butyl lithium 14mL(2.5M, 34.60mmol) was then dropped slowly thereto. The mixture was stirred at -78℃ for 2 hours, and fluorenone 6.2g (34.60mmol) dissolved in 400 mL tetrahydrofuran was then dropped slowly thereto. After completing the dropping, the mixture was warmed slowly to room temperature, and then additionally stirred for 30 minutes. After adding ammonium chloride aqueous solution to the reaction mixture to complete the reaction, the mixture was extracted with ethyl acetate. The organic layer was dried with magnesium sulfate, and the solvent was then removed by rotary evaporator to obtain compound C-98-10. After adding acetic acid 266 mL and HCl 26 mL to the obtained compound C-98-10, the mixture was stirred at 120°C overnight, and the solvent was then removed by rotary evaporator. The resultant solid was separated by column chromatography and recrystallization to obtain compound C-98 (6g, 40%).
[Device Example 1] Production of an OLED device using the organic
electroluminescent compound of the present invention
OLED device was produced using the compound of the present invention as follows. A transparent electrode indium tin oxide (ITO) thin film (15 Ω/sq) on a glass substrate for an organic light-emitting diode (OLED) device (Samsung Corning) was subjected to an ultrasonic washing with trichloroethylene, acetone, ethanol and distilled water, sequentially, and then was stored in isopropanol. The ITO substrate was then mounted on a substrate holder of a vacuum vapor depositing apparatus. N1,N1’-([1,1’-biphenyl]-4,4’-diyl)bis(N1-(naphthalen-1-yl)-N4,N4-diphenylbenzene-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-98 was then introduced into another cell of said vacuum vapor depositing apparatus, and evaporated by applying electric current to the cell, thereby forming a hole transport layer having a thickness of 20 nm on the hole injection layer. Thereafter, 9-(4-([1,1':4',1''-terphenyl]-3-yl)pyridin-2-yl)-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, so that the dopant was 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. 2-(4-(9,10-di(naphthalen-2-yl)anthracen-2-yl)phenyl)-1-phenyl-1H-benzo[d]imidazole was then introduced into one cell, and lithium quinolate was introduced into another cell. The two materials were evaporated at the same rate, so that they were respectively deposited in a doping amount of 50 wt% to form an electron transport layer having a thickness of 30 nm on the light-emitting layer. 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 then 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 those purified by vacuum sublimation at 10-6 torr. The produced OLED device showed green emission having a luminance of 2,450 cd/m2 and a current density of 5.3 mA/cm2.
[Comparative Device Example 1] Production of an OLED device using
conventional compounds
An OLED device was produced in the same manner as in Device Example 1, except that N,N'-di(4-biphenyl)-N,N'-di(4-biphenyl)-4,4'-diaminodiphenyl was used to form a hole transport layer having a thickness of 20 nm; 4,4'-N,N'-dicarbazole-biphenyl as a host material and compound D-15 as a dopant were used to form a light-emitting layer having a thickness of 30 nm on the hole transport layer; and aluminum(III) bis(2-methyl-8-quinolinato)-4-phenylphenolate was used to form a hole blocking layer having a thickness of 10 nm. The produced OLED device showed green emission having a luminance of 3,650 cd/m2 and a current density of 11.2 mA/cm2.
As confirmed by the device example, the organic electroluminescent compound according to the present invention shows better luminescent properties than conventional compounds. The organic electroluminescent device shows excellent luminous properties by using the organic electroluminescent compound of the present invention.

Claims (7)

  1. An organic electroluminescent compound represented by the following formula 1:
    Figure PCTKR2014003389-appb-I000070
    wherein,
    R1, R5, and R6, 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 (5- to 7-membered)heterocycloalkyl, a substituted or unsubstituted (C6-C30)aryl(C1-C30)alkyl, -NR10R11, -SiR12R13R14, -SR15, -OR16, a cyano, a nitro, or a hydroxy;
    R2 and R3, each independently, represent hydrogen, deuterium, a halogen, a cyano, a carboxy, a nitro, a hydroxy, 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 may be fused with each other to form a substituted or unsubstituted (C3-C30) mono- or polycyclic, alicyclic or aromatic ring;
    R4 and R7, each independently, represent hydrogen, deuterium, a halogen, a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C3-C30)cycloalkyl, a substituted or unsubstituted (5- to 7-membered)heterocycloalkyl, a substituted or unsubstituted (C6-C30)aryl(C1-C30)alkyl, an amino, a mono- or di-(C1-C30)alkylamino, -SiR12R13R14, -SR15, -OR16, a cyano, a nitro, or a hydroxy;
    X represents a chemical bond, -O-, -S-, -C(R17R18)-, -Si(R19R20)- or -N(R21)-;
    R10 to R21, 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 (5- 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 and d, each independently, represent an integer of 1 to 4; where a or d is an integer of 2 or more, each of R4 or R7 may be the same or different;
    b and c, each independently, represent an integer of 1 or 2; where b or c is 2, each of R5 or R6 may be the same or different;
    A and B, each independently, represent a substituted or unsubstituted (C6-C30)aryl, a substituted or unsubstituted (5- to 30-membered)heteroaryl,
    Figure PCTKR2014003389-appb-I000071
    or
    Figure PCTKR2014003389-appb-I000072
    , and may be 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;
    l and m, each independently, represent an integer of 0 to 3; where l or m is an integer of 2 or more, each of A or B may be the same or different;
    the heterocycloalkyl and 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 of formula 1 is selected from the group consisting of the following formulae 2 to 6:
    Figure PCTKR2014003389-appb-I000073
    Figure PCTKR2014003389-appb-I000074
    Figure PCTKR2014003389-appb-I000075
    Figure PCTKR2014003389-appb-I000076
    Figure PCTKR2014003389-appb-I000077
    wherein,
    A, B, X, R1, R4 to R7, a to d, l and m are as defined in claim 1;
    C and D, each independently, represent a substituted or unsubstituted (C6-C30)aryl, a substituted or unsubstituted (5- to 30-membered)heteroaryl,
    Figure PCTKR2014003389-appb-I000078
    or
    Figure PCTKR2014003389-appb-I000079
    , and may be 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; 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;
    R8 and R9, each independently, represent hydrogen, deuterium, a halogen, a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C3-C30)cycloalkyl, a substituted or unsubstituted (5- to 7-membered)heterocycloalkyl, a substituted or unsubstituted (C6-C30)aryl(C1-C30)alkyl, an amino, a mono- or di-(C1-C30)alkylamino, -SiR12R13R14, -SR15, -OR16, a cyano, a nitro, or a hydroxy; or may be linked to an adjacent substituent(s) to form a (C3-C30), mono- or polycyclic aromatic ring;
    e and f, each independently, represent an integer of 1 to 4; where e or f is an integer of 2 or more, each of R8 or R9 may be the same or different;
    n and o, each independently, represent an integer of 0 to 3; where n or o is an integer of 2 or more, each of C or D may be the same or different;
    the heterocycloalkyl and heteroaryl(ene), each independently, contain at least one hetero atom selected from B, N, O, S, P(=O), Si and P.
  3. The organic electroluminescent compound according to claim 1, wherein the heteroaryl is selected from the group consisting of pyrrolyl, imidazolyl, triazinyl, tetrazinyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, dibenzofuranyl, dibenzothiophenyl, benzoimidazolyl, benzothiazolyl, benzoisothiazolyl, benzoisoxazolyl, benzoxazolyl, isoindolyl, indolyl, indazolyl, benzothiadiazolyl, quinolyl, isoquinolyl, quinazolinyl, quinoxalinyl, carbazolyl, phenoxazinyl, and phenanthridinyl.
  4. 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, of R1 to R21, L1, L2, and Ar1 to Ar6, each independently, are at least one selected from the group consisting of deuterium, a halogen, a cyano, a carboxy, a nitro, a hydroxy, a (C1-C30)alkyl, a halo(C1-C30)alkyl, a (C2-C30)alkenyl, a (C2-C30)alkynyl, a (C1-C30)alkoxy, a (C1-C30)alkylthio, a (C3-C30)cycloalkyl, a (C3-C30)cycloalkenyl, a (3- to 7-membered)heterocycloalkyl, a (C6-C30)aryloxy, a (C6-C30)arylthio, a (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.
  5. The organic electroluminescent compound according to claim 1, wherein R1, R5, and R6, each independently, represent hydrogen, 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 (5- to 7-membered)heterocycloalkyl, or -NR10R11; R2 and R3 are fused with each other to form a substituted or unsubstituted (C3-C30), mono- or polycyclic, alicyclic or aromatic ring; and X represents -O-, -S-, -C(R17R18)-, or -N(R21)-.
  6. The organic electroluminescent compound according to claim 1, wherein the compound represented by formula 1 is selected from the group consisting of:
    Figure PCTKR2014003389-appb-I000080
    Figure PCTKR2014003389-appb-I000081
    Figure PCTKR2014003389-appb-I000082
    Figure PCTKR2014003389-appb-I000083
    Figure PCTKR2014003389-appb-I000084
    Figure PCTKR2014003389-appb-I000085
    Figure PCTKR2014003389-appb-I000086
    Figure PCTKR2014003389-appb-I000087
    Figure PCTKR2014003389-appb-I000088
    Figure PCTKR2014003389-appb-I000089
    Figure PCTKR2014003389-appb-I000090
    Figure PCTKR2014003389-appb-I000091
    Figure PCTKR2014003389-appb-I000092
    Figure PCTKR2014003389-appb-I000093
    Figure PCTKR2014003389-appb-I000094
    Figure PCTKR2014003389-appb-I000095
  7. An organic electroluminescent device comprising the compound according to claim 1.
PCT/KR2014/003389 2013-04-19 2014-04-18 Organic electroluminescent compounds and organic electroluminescent device comprising the same WO2014171779A1 (en)

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