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Novel organic electroluminescent compounds and organic electroluminescent device using the same

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  • Patent Application
  • 20100019657
  • Publication Number
    20100019657
  • Date Filed
    December 31, 2008
    15 years ago
  • Date Published
    January 28, 2010
    14 years ago
Information
Abstract
The present invention relates to novel organic electroluminescent compounds, and organic electroluminescent devices employing the same as electroluminescent material. Specifically, the organic electroluminescent compounds according to the invention are characterized in that they are represented by Chemical Formula (1):
Description
FIELD OF THE INVENTION

The present invention relates to novel organic electroluminescent compounds, and organic electroluminescent devices employing the same as electroluminescent material.


BACKGROUND ART

Among display devices, electroluminescence devices (EL devices) are self-luminescent display devices showing the advantage of wide angle of view, excellent contrast and rapid response rate. Eastman Kodak developed in 1987 an organic EL device which employs a low molecular weight aromatic diamine and an aluminum complex, as a material for forming an EL layer, for the first time [Appl. Phys. Lett. 51, 913, 1987].


The most important factor to determine luminous efficiency, lifetime or the like in an organic EL device is electroluminescent material. Several properties required for such electroluminescent materials include that the material should have high fluorescent quantum yield in solid state and high mobility of electrons and holes, is not easily decomposed during vapor-deposition in vacuo, and forms uniform and stable thin film.


Organic electroluminescent materials can be generally classified into high-molecular materials and low-molecular materials. The low-molecular materials include metal complexes and purely organic electroluminescent materials which do not contain metal, from the aspect of molecular structure. Such electroluminescent materials include chelate complexes such as tris(8-quinolinolato)aluminum complexes, coumarin derivatives, tetraphenylbutadiene derivatives, bis(styrylarylene) derivatives, oxadiazole derivatives. From those materials, it is reported that light emission of visible region from blue to red can be obtained, so that the realization of full-colored display devices is expected.


In the meanwhile, for blue materials, a number of materials have been developed and commercialized since the development of DPVBi (Chemical Formula a) by Idemitsu-Kosan. In addition to the blue material system from Idemitsu-Kosan, dinaphthylanthracene (Chemical Formula b), tetra(t-butyl)perylene (Chemical Formula c) system or the like have been known. However, extensive research and development should be performed with respect to these materials. The distryl compound system of Idemitsu-Kosan, which is known to have highest efficiency up to now, has 6 lm/W of power efficiency and beneficial device lifetime of more than 30,000 hr. However, when it is applied to a full-colored display, the lifetime is merely several thousand hours, owing to the reduction of color purity over operation time. In case of blue electroluminescentce, it becomes advantageous from the aspect of the luminous efficiency, if the electroluminescent wavelength is shifted a little toward longer wavelength. However, it is not easy to apply the material to a display of high quality because of unsatisfactory color purity in blue. In addition, the research and development of such materials are urgent because of the problems in color purity, efficiency and thermal stability.







SUMMARY OF THE INVENTION

Thus, the inventors have intensively endeavored to overcome the problems described above and to develop a novel electroluminescent compound which can realize an organic electroluminescent device having excellent luminous efficiency and noticeably improved device life.


The object of the invention is to overcome the drawbacks of blue material as described above and to provide an organic electroluminescent compound having improved luminous efficiency and device life.


Another object of the invention is to provide an organic electroluminescent device having high efficiency and long life, which comprises the organic electroluminescent compounds described above as electroluminescent material. Another object of the present invention is to provide an organic electroluminescent device comprising an electroluminescent region which employs one or more compound(s) selected from anthracene derivatives and benz[a]anthracene derivatives as an electroluminescent host, in addition to one or more organic electroluminescent compound(s) as mentioned above.


Still another object of the present invention is to provide organic solar cells comprising said novel organic electroluminescent compounds.


Specifically, the present invention relates to novel organic electroluminescent compounds represented by Chemical Formula (1), and organic electroluminescent devices employing the same in the electroluminescent layer.







wherein,


Ar1 and Ar2 independently represent (C6-C60)arylene or (C5-C60)heteroarylene, and the arylene or heteroarylene of Ar1 and Ar2 may be further substituted by one or more substituent(s) selected from deuterium, linear or branched (C1-C60)alkyl and (C6-C60)aryl;


Ar3 through Ar6 independently represent linear or branched (C1-C60)alkyl, (C3-C60)cycloalkyl, 5- or 6-membered heterocycloalkyl containing one or more heteroatom(s) selected from N, O and S, (C6-C60)aryl or (C3-C60)heteroaryl, or Ar3 and Ar5, or Ar6 and Ar7 may be linked via (C3-C60)alkylene or (C3-C60)alkenylene with or without a fused ring to form an alicyclic ring, or a monocyclic or polycyclic aromatic ring; and


the aryl or heteroaryl of Ar3 through Ar6 may be further substituted by one or more substituent(s) selected from a group consisting of deuterium, (C6-C60)aryl with or without linear or branched (C1-C60)alkyl or (C6-C60)aryl substituent, linear or branched (C1-C60)alkyl with or without halogen substituent(s), (C1-C30)alkoxy, (C3-C60)cycloalkyl, halogen, cyano, tri(C1-C30)alkylsilyl, di(C1-C30)alkyl(C6-C30)arylsilyl and tri(C6-C30)arylsilyl.





BRIEF DESCRIPTION OF THE DRAWINGS


FIG. 1 is a cross-sectional view of an organic light emitting diode (OLED).





DETAILED DESCRIPTION OF THE INVENTION

Referring now to the Drawings, FIG. 1 illustrates AN OLED of the present invention comprising a Glass 1, a Transparent electrode 2, a Hole injection layer 3, a Hole transport layer 4, an Electroluminescent layer 5, an Electron transport layer 6, an Electron injection layer 7 and an Al cathode 8.


The term “alkyl”, “alkoxy” described herein and any substituents comprising “alkyl” moiety include both linear and branched species.


The term “aryl” described herein means an organic radical derived from aromatic hydrocarbon via elimination of one hydrogen atom. Each ring comprises a monocyclic or fused ring system containing from 4 to 7, preferably from 5 to 6 cyclic atoms. Specific examples include phenyl, naphthyl, biphenyl, anthryl, tetrahydronaphthyl, indenyl, fluorenyl, phenanthryl, triphenylenyl, pyrenyl, perylenyl, chrysenyl, naphthacenyl and fluoranthenyl, but they are not restricted thereto.


The term “heteroaryl” described herein means an aryl group containing from 1 to 4 heteroatom(s) selected from N, O and S as the aromatic cyclic backbone atom(s), and carbon atom(s) for remaining aromatic cyclic backbone atoms. The heteroaryl may be a 5- or 6-membered monocyclic heteroaryl or a polycyclic heteroaryl which is fused with one or more benzene ring(s), and may be partially saturated. The heteroaryl group may comprise a bivalent aryl group, of which the heteroatoms may be oxidized or quaternized to form N-oxide and quaternary salt. Specific examples include monocyclic heteroaryl groups such as furyl, thiophenyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, thiadiazolyl, isothiazolyl, isoxazolyl, oxazolyl, oxadiazolyl, triazinyl, tetrazinyl, triazolyl, tetrazolyl, furazanyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl; polycyclic heteroaryl groups such as benzofuranyl, benzothiophenyl, isobenzofuranyl, benzimidazolyl, benzothiazolyl, benzisothiazolyl, benzisoxazolyl, benzoxazolyl, isoindolyl, indolyl, indazolyl, benzothiadiazolyl, quinolyl, isoquinolyl, cinnolinyl, quinazolinyl, quinoxalinyl, carbazolyl, phenanthridinyl and benzodioxolyl; and corresponding N-oxides (for example, pyridyl N-oxide, quinolyl N-oxide) and quaternary salts thereof; but they are not restricted thereto.


The substituents comprising “(C1-C60)alkyl” moiety described herein may contain 1 to 60 carbon atoms, 1 to 20 carbon atoms, or 1 to 10 carbon atoms. The substituents comprising “(C6-C60)aryl” moiety may contain 6 to 60 carbon atoms, 6 to 20 carbon atoms, or 6 to 12 carbon atoms. The substituents comprising “(C3-C60)heteroaryl” moiety may contain 3 to 60 carbon atoms, 4 to 20 carbon atoms, or 4 to 12 carbon atoms. The substituents comprising “(C3-C60)cycloalkyl” moiety may contain 3 to 60 carbon atoms, 3 to 20 carbon atoms, or 3 to 7 carbon atoms. The substituents comprising “(C2-C60)alkenyl or alkynyl” moiety may contain 2 to 60 carbon atoms, 2 to 20 carbon atoms, or 2 to 10 carbon atoms.


In Chemical Formula (1), Ar1 and Ar2 are independently selected from the following structures, but they are not restricted thereto:






















wherein, R11 through R19 independently represent hydrogen, linear or branched (C1-C60)alkyl or (C6-C60)aryl, and the aryl may be further substituted by linear or branched (C1-C60)alkyl.


In Chemical Formula (1), Ar3 through Ar6 independently represent phenyl, naphthyl, fluorenyl, anthryl, phenanthryl, pyrenyl, perylenyl, fluoranthenyl, pyridyl, pyrrolyl, furanyl, thiophenyl, imidazolyl, benzimidazolyl, pyrazinyl, pyrimidinyl, pyridazinyl, quinolyl, triazinyl, benzofuranyl, benzothiophenyl, pyrazolyl, indolyl, carbazolyl, thiazolyl, oxazolyl, benzothiazolyl, benzoxazolyl, morpholino or thiomorpholino; and the phenyl, naphthyl, fluorenyl, anthryl, phenanthryl, pyrenyl, perylenyl, fluoranthenyl, pyridyl, pyrrolyl, furanyl, thiophenyl, imidazolyl, benzimidazolyl, pyrazinyl, pyrimidinyl, pyridazinyl, quinolyl, triazinyl, benzofuranyl, benzothiophenyl, pyrazolyl, indolyl, carbazolyl, thiazolyl, oxazolyl, benzothiazolyl, benzoxazolyl, morpholino or thiomorpholino may be further substituted by one or more substituent(s) selected from a group consisting of deuterium, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, n-pentyl, i-pentyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, decyl, dodecyl, hexadecyl, trifluoromethyl, perfluoroethyl, trifluoroethyl, perfluoropropyl, perfluorobutyl, methoxy, ethoxy, butoxy, hexyloxy, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, fluoro, cyano, trimethylsilyl, triethylsilyl, tripropylsilyl, tri(t-butyl)silyl, t-butyldimethylsilyl, dimethylphenylsilyl, triphenylsilyl, phenyl, biphenyl, 9,9-dimethylfluorenyl, 9,9-diphenylfluorenyl, naphthyl, phenanthryl and anthryl.


The naphthyl of Chemical Formula (1) may be 1-naphthyl or 2-naphthyl; the anthryl may be 1-anthryl, 2-anthryl or 9-anthryl; and the fluorenyl may be 1-fluorenyl, 2-fluorenyl, 3-fluorenyl, 4-fluorenyl or 9-fluorenyl.


The organic electroluminescent compounds according to the present invention can be specifically exemplified by the following compounds, but they are not restricted thereto:















































































wherein, Ar3 through Ar6 independently represent phenyl, naphthyl, fluorenyl, anthryl, phenanthryl, pyrenyl, perylenyl, fluoranthenyl, pyridyl, pyrrolyl, furanyl, thiophenyl, imidazolyl, benzimidazolyl, pyrazinyl, pyrimidinyl, pyridazinyl, quinolyl, triazinyl, benzofuranyl, benzothiophenyl, pyrazolyl, indolyl, carbazolyl, thiazolyl, oxazolyl, benzothiazolyl, benzoxazolyl, morpholino or thiomorpholino;


the phenyl, naphthyl, fluorenyl, anthryl, phenanthryl, pyrenyl, perylenyl, fluoranthenyl, pyridyl, pyrrolyl, furanyl, thiophenyl, imidazolyl, benzimidazolyl, pyrazinyl, pyrimidinyl, pyridazinyl, quinolyl, triazinyl, benzofuranyl, benzothiophenyl, pyrazolyl, indolyl, carbazolyl, thiazolyl, oxazolyl, benzothiazolyl, benzoxazolyl, morpholino or thiomorpholino of Ar3 through Ar6 may be further substituted by one or more substituent(s) selected from a group consisting of deuterium, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, n-pentyl, i-pentyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, decyl, dodecyl, hexadecyl, trifluoromethyl, perfluoroethyl, trifluoroethyl, perfluoropropyl, perfluorobutyl, methoxy, ethoxy, butoxy, hexyloxy, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, fluoro, cyano, trimethylsilyl, triethylsilyl, tripropylsilyl, tri(t-butyl)silyl, t-butyldimethylsilyl, dimethylphenylsilyl, triphenylsilyl, phenyl, biphenyl, 9,9-dimethylfluorenyl, 9,9-diphenylfluorenyl, naphthyl, phenanthryl and anthryl;


R11 through R16 independently represent hydrogen, deuterium, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, n-pentyl, i-pentyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, decyl, dodecyl, hexadecyl, phenyl, naphthyl, biphenyl, fluorenyl, phenanthryl, anthryl, fluoranthenyl, triphenylenyl, pyrenyl, chrysenyl, naphthacenyl or perylenyl; and


the phenyl, naphthyl, biphenyl, fluorenyl, phenanthryl, anthryl, fluoranthenyl, triphenylenyl, pyrenyl, chrysenyl, naphthacenyl or perylenyl of R11 through R16 may be further substituted by one or more substituent(s) selected from deuterium, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, n-pentyl, i-pentyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, decyl, dodecyl and hexadecyl.


More specifically, the organic electroluminescent compounds according to the present invention can be exemplified by the following compounds, but they are not restricted thereto.




























The organic electroluminescent compounds according to the present invention can be prepared according to the procedure illustrated by Reaction Scheme (1):







wherein, Ar1, Ar2, Ar3, Ar4, Ar5 and Ar6 are defined as in Chemical Formula (1).


In addition, the present invention provides organic solar cells, which comprise one or more organic electroluminescent compound(s) represented by Chemical Formula (1).


The present invention also provides an organic electroluminescent device which is comprised of a first electrode; a second electrode; and at least one organic layer(s) interposed between the first electrode and the second electrode; wherein the organic layer comprises one or more organic electroluminescent compound(s) represented by Chemical Formula (1).


The organic electroluminescent device according to the present invention is characterized in that the organic layer comprises an electroluminescent region, and the region comprises one or more compound(s) represented by Chemical Formula (1) as electroluminescent dopant, and one or more host(s).


The host applied to the electroluminescent device according to the invention is not particularly restricted, but preferably selected from the compounds represented Chemical Formula (2) or (3):





(Ar11)a-A-(Ar12)b  Chemical Formula 2





(Ar11)a-An-(Ar12)b  Chemical Formula 3


wherein,


Ar11 and Ar12 are independently selected from hydrogen, (C1-C60)alkyl, (C1-C60)alkoxy, halogen, (C4-C60)heteroaryl, (C5-C60)cycloalkyl and (C6-C60)aryl; and the cycloalkyl, aryl or heteroaryl of Ar11 and Ar12 may be further substituted by one or more substituent(s) selected from a group consisting of (C6-C60)aryl or (C4-C60)heteroaryl with or without one or more substituent(s) selected from a group consisting of deuterium, (C1-C60)alkyl with or without halogen substituent(s), (C1-C60)alkoxy, (C3-C60)cycloalkyl, halogen, cyano, tri(C1-C60)alkylsilyl, di(C1-C60)alkyl(C6-C60)arylsilyl and tri(C6-C60)arylsilyl; (C1-C60)alkyl with or without halogen substituent(s), (C1-C60)alkoxy, (C3-C60)cycloalkyl, halogen, cyano, tri(C1-C60)alkylsilyl, di(C1-C60)alkyl(C6-C60)arylsilyl and tri(C6-C60)arylsilyl;


A represents (C6-C60)arylene or (C4-C60)heteroarylene;


a and b independently represent an integer from 0 to 4; and


An comprises anthracene backbone with or without a substituent.


The hosts represented by Chemical Formula (2) or (3) can be exemplified by anthracene derivatives or benz[a]anthracene derivatives represented by one of Chemical Formulas (4) to (7).







In Chemical Formulas (4) to (6),


R41 and R42 independently represent (C6-C60)aryl, (C4-C60)heteroaryl, a 5- or 6-membered heterocycloalkyl containing one or more heteroatom(s) selected from N, O and S, or (C3-C60)cycloalkyl, and the aryl or heteroaryl of R41 and R42 may be further substituted by one or more substituent(s) selected from a group consisting of (C1-C60)alkyl, halo(C1-C60)alkyl, (C1-C60)alkoxy, (C3-C60)cycloalkyl, (C6-C60)aryl, (C4-C60)heteroaryl, halogen, cyano, tri(C1-C60)alkylsilyl, di(C1-C60)alkyl(C6-C60)arylsilyl and tri(C6-C60)arylsilyl;


R43 through R46 independently represent hydrogen, (C1-C60)alkyl, (C1-C60)alkoxy, halogen, (C4-C60)heteroaryl, (C5-C60)cycloalkyl or (C6-C60)aryl, and the heteroayl, cycloalkyl or aryl of R43 through R46 may be further substituted by one or more substituent(s) selected from a group consisting of (C1-C60)alkyl with or without halogen substituent(s), (C1-C60)alkoxy, (C3-C60)cycloalkyl, halogen, cyano, tri(C1-C60)alkylsilyl, di(C1-C60)alkyl(C6-C60)arylsilyl and tri(C6-C60)arylsilyl;


G1 and G2 independently represent a chemical bond, or (C6-C60)arylene with or without one or more substituent(s) selected from (C1-C60)alkyl, (C1-C60)alkoxy, (C6-C60)aryl, (C4-C60)heteroaryl and halogen;


Ar21 and Ar22 represent (C4-C60)heteroaryl or aryl selected from the following structures:







the aryl or heteroaryl of Ar21 and Ar22 may be substituted by one or more substituent(s) selected from (C1-C60)alkyl, (C1-C60)alkoxy, (C6-C60)aryl and (C4-C60)heteroaryl;


L11 represents (C6-C60)arylene, (C4-C60)heteroarylene or a compound represented by the following structural formula:







the arylene or heteroarylene of L11 may be substituted by one or more substituent(s) selected from (C1-C60)alkyl, (C1-C60)alkoxy, (C6-C60)aryl, (C4-C60)heteroaryl and halogen;


R51 through R54 independently represent hydrogen, (C1-C60)alkyl or (C6-C60)aryl, or each of them may be linked to an adjacent substituent via (C3-C60)alkylene or (C3-C60)alkenylene with or without a fused ring to form an alicyclic ring, or a monocyclic or polycyclic aromatic ring;


R61 through R64 independently represent hydrogen, (C1-C60)alkyl, (C1-C60)alkoxy, (C6-C60)aryl, (C4-C60)heteroaryl or halogen, or each of them may be linked to an adjacent substituent via (C3-C60)alkylene or (C3-C60)alkenylene with or without a fused ring to form an alicyclic ring, or a monocyclic or polycyclic aromatic ring.







In Chemical Formula 7,


L21 represents (C6-C60)arylene, (C3-C60)heteroarylene containing one or more heteroatom(s) selected from N, O and S, or a divalent group selected from the following structures:







L22 and L23 independently represent a chemical bond, (C1-C60)alkyleneoxy, (C1-C60)alkylenethio, (C6-C60)aryleneoxy, (C6-C60)arylenethio, (C6-C60)arylene, or (C3-C60)heteroarylene containing one or more heteroatom(s) selected from N, O and S;


Ar31 represents NR93R94, (C6-C60)aryl, (C3-C60)heteroaryl containing one or more heteroatom(s) selected from N, O and S, 5- or 6-membered heterocycloalkyl containing one or more heteroatom(s) selected from N, O and S, (C3-C60)cycloalkyl, adamantyl, (C7-C60)bicycloalkyl, or a substituent selected from the following structures:







wherein, R71 through R81 independently represent hydrogen, deuterium, halogen, (C1-C60)alkyl, (C6-C60)aryl, (C3-C60)heteroaryl containing one or more heteroatom(s) selected from N, O and S, morpholino, thiomorpholino, 5- or 6-membered heterocyloalkyl containing one or more heteroatom(s) selected from N, O and S, (C3-C60)cycloalkyl, tri(C1-C60)alkylsilyl, di(C1-C60)alkyl(C6-C60)arylsilyl, tri(C6-C60)arylsilyl, adamantyl, (C7-C60)bicycloalkyl, (C2-C60)alkenyl, (C2-C60)alkynyl, cyano, (C1-C60)alkylamino, (C6-C60)arylamino, (C6-C60)ar(C1-C60)alkyl, (C1-C60)alkyloxy, (C1-C60)alkylthio, (C6-C60)aryloxy, (C6-C60)arylthio, (C1-C60)alkoxycarbonyl, (C1-C60)alkylcarbonyl, (C6-C60)arylcarbonyl, carboxyl, nitro or hydroxyl, or each of R71 through R81 may be linked to an adjacent substituent via (C3-C60)alkylene or (C3-C60)alkenylene with or without a fused ring to form an alicyclic ring, or a monocyclic or polycyclic aromatic ring;


R82 through R92 independently represent hydrogen, deuterium, halogen, (C1-C60)alkyl, (C6-C60)aryl, (C3-C60)heteroaryl containing one or more heteroatom(s) selected from N, O and S, morpholino, thiomorpholino, 5- or 6-membered heterocyloalkyl containing one or more heteroatom(s) selected from N, O and S, (C3-C60)cycloalkyl, tri(C1-C60)alkylsilyl, di(C1-C60)alkyl(C6-C60)arylsilyl, tri(C6-C60)arylsilyl, adamantyl, (C7-C60)bicycloalkyl, (C2-C60)alkenyl, (C2-C60)alkynyl, cyano, (C1-C60)alkylamino, (C6-C60)arylamino, (C6-C60)ar(C1-C60)alkyl, (C1-C60)alkyloxy, (C1-C60)alkylthio, (C6-C60)aryloxy, (C6-C60)arylthio, (C1-C60)alkoxycarbonyl, (C1-C60)alkylcarbonyl, (C6-C60)arylcarbonyl, carboxyl, nitro or hydroxyl, or each of R82 through R92 may be linked to an adjacent substituent via (C3-C60)alkylene or (C3-C60)alkenylene with or without a fused ring to form an alicyclic ring, or a monocyclic or polycyclic aromatic ring;


R93 and R94 independently represent hydrogen, deuterium, halogen, (C1-C60)alkyl, (C6-C60)aryl, (C3-C60)heteroaryl containing one or more heteroatom(s) selected from N, O and S, morpholino, thiomorpholino, 5- or 6-membered heterocyloalkyl containing one or more heteroatom(s) selected from N, O and S, (C3-C60)cycloalkyl, tri(C1-C60)alkylsilyl, di(C1-C60)alkyl(C6-C60)arylsilyl, tri(C6-C60)arylsilyl, adamantyl, (C7-C60)bicycloalkyl, (C2-C60)alkenyl, (C2-C60)alkynyl, cyano, (C1-C60)alkylamino, (C6-C60)arylamino, (C6-C60)ar(C1-C60)alkyl, (C1-C60)alkyloxy, (C1-C60)alkylthio, (C6-C60)aryloxy, (C6-C60)arylthio, (C1-C60)alkoxycarbonyl, (C1-C60)alkylcarbonyl, (C6-C60)arylcarbonyl, carboxyl, nitro or hydroxyl, or R93 and R94 may be linked via (C3-C60)alkylene or (C3-C60)alkenylene with or without a fused ring to form an alicyclic ring, or a monocyclic or polycyclic aromatic ring;


R95 through R106 independently represent hydrogen, deuterium, halogen, (C1-C60)alkyl, (C6-C60)aryl, (C3-C60)heteroaryl containing one or more heteroatom(s) selected from N, O and S, morpholino, thiomorpholino, 5- or 6-membered heterocyloalkyl containing one or more heteroatom(s) selected from N, O and S, (C3-C60)cycloalkyl, tri(C1-C60)alkylsilyl, di(C1-C60)alkyl(C6-C60)arylsilyl, tri(C6-C60)arylsilyl, adamantyl, (C7-C60)bicycloalkyl, (C2-C60)alkenyl, (C2-C60)alkynyl, cyano, (C1-C60)alkylamino, (C6-C60)arylamino, (C6-C60)ar(C1-C60)alkyl, (C1-C60)alkyloxy, (C1-C60)alkylthio, (C6-C60)aryloxy, (C6-C60)arylthio, (C1-C60)alkoxycarbonyl, (C1-C60)alkylcarbonyl, (C6-C60)arylcarbonyl, carboxyl, nitro or hydroxyl, or each of R95 through R106 may be linked to an adjacent substituent via (C3-C60)alkylene or (C3-C60)alkenylene with or without a fused ring to form an alicyclic ring, or a monocyclic or polycyclic aromatic ring;


E and F independently represent a chemical bond, —(CR107R108)g—, —N(R109)—, —S—, —O—, —Si(R110)(R111)—, —P(R112)—, —C(═O)—, —B(R113)—, —In(R114)—, —Se—, —Ge(R115)(R116)—, —Sn(R117)(R118)—, —Ga(R119)— or —(R120)C═C(R121)—;


R107 through R121 independently represent hydrogen, deuterium, halogen, (C1-C60)alkyl, (C6-C60)aryl, (C3-C60)heteroaryl containing one or more heteroatom(s) selected from N, O and S, morpholino, thiomorpholino, 5- or 6-membered heterocyloalkyl containing one or more heteroatom(s) selected from N, O and S, (C3-C60)cycloalkyl, tri(C1-C60)alkylsilyl, di(C1-C60)alkyl(C6-C60)arylsilyl, tri(C6-C60)arylsilyl, adamantyl, (C7-C60)bicycloalkyl, (C2-C60)alkenyl, (C2-C60)alkynyl, cyano, (C1-C60)alkylamino, (C6-C60)arylamino, (C6-C60)ar(C1-C60)alkyl, (C1-C60)alkyloxy, (C1-C60)alkylthio, (C6-C60)aryloxy, (C6-C60)arylthio, (C1-C60)alkoxycarbonyl, (C1-C60)alkylcarbonyl, (C6-C60)arylcarbonyl, carboxyl, nitro or hydroxyl, or R107 and R108, R110 and R111, R115 and R116, R117 and R118, or R120 and R121 may be linked via (C3-C60)alkylene or (C3-C60)alkenylene with or without a fused ring to form an alicyclic ring, or a monocyclic or polycyclic aromatic ring;


the arylene or heteroarylene of L21 through L23, the aryl or heteroaryl of Ar31, or the alkyl, aryl, heteroaryl, heterocycloalkyl, cycloalkyl, trialkylsilyl, dialkylarylsilyl, triarylsilyl, alkenyl, alkynyl, alkylamino or arylamino of R71 through R121 may be further substituted independently by one or more substituent(s) selected from deuterium, halogen, (C1-C60)alkyl, halo(C1-C60)alkyl, (C6-C60)aryl, (C3-C60)heteroaryl containing one or more heteroatom(s) selected from N, O and S wherein the (C6-C60)aryl is with or without a substituent, morpholino, thiomorpholino, 5- or 6-membered heterocycloalkyl containing one or more heteroatom(s) selected from N, O and S, (C3-C60)cycloalkyl, tri(C1-C60)alkylsilyl, di(C1-C60)alkyl(C6-C60)arylsilyl, tri(C6-C60)arylsilyl, adamantyl, (C7-C60)bicycloalkyl, (C2-C60)alkenyl, (C2-C60)alkynyl, cyano, (C1-C60)alkylamino, (C6-C60)arylamino, (C6-C60)ar(C1-C60)alkyl, (C1-C60)alkyloxy, (C1-C60)alkylthio, (C6-C60)aryloxy, (C6-C60)arylthio, (C1-C60)alkoxycarbonyl, (C1-C60)alkylcarbonyl, (C6-C60)arylcarbonyl, carboxyl, nitro, hydroxyl,







g is an integer from 1 to 4; and


f is an integer from 1 to 4.


The electroluminescent layer means the layer where electroluminescence occurs, and it may be a single layer or a multi-layer consisting of two or more layers laminated. When a mixture of host-dopant is used according to the construction of the present invention, noticeable improvement in luminous efficiency due to the inventive electroluminescent host could be confirmed, as compared to the device simply employing the electroluminescent compound according to the present invention. This can be achieved by the doping concentration of 0.5 to 10% by weight. The host according to the present invention exhibits higher hole and electron conductivity, and excellent stability of the material as compared to other conventional host materials, and provides improved device life as well as luminous efficiency.


Thus, it can be described that use of the compound represented by one of Chemical Formulas (4) to (7) as an electroluminescent host significantly supplements electronic drawback of the organic electroluminescent compounds of Chemical Formula (1) according to the present invention.


The host compounds represented by one of Chemical Formulas (4) to (7) can be exemplified by the following compounds, but are not restricted thereto.













































































































The organic electroluminescent device according to the invention may further comprise one or more compound(s) selected from arylamine compounds and styrylarylamine compounds, as well as the organic electroluminescent compound represented by Chemical Formula (1). Examples of the arylamine or styrylarylamine compounds include the compounds represented by Chemical Formula (8), but they are not restricted thereto:







wherein, Ar41 and Ar42 independently represent (C1-C60)alkyl, (C6-C60)aryl, (C4-C60)heteroaryl, (C6-C60)arylamino, (C1-C60)alkylamino, a 5- or 6-membered heterocycloalkyl containing one or more heteroatom(s) selected from N, O and S, or (C3-C60)cycloalkyl, or Ar41 and Ar42 may be linked via (C3-C60)alkylene or (C3-C60)alkenylene with or without a fused ring to form an alicyclic ring, or a monocyclic or polycyclic aromatic ring;


when h is l, Ar43 represents (C6-C60)aryl, (C4-C60)heteroaryl, or a substituent represented by one of the following structural formulas:







when h is 2, Ar43 represents (C6-C60)arylene, (C4-C60)heteroarylene, or a substituent selected from the following structures:







wherein Ar44 and Ar45 independently represent (C6-C60)arylene or (C4-C60)heteroarylene;


R131 through R133 independently represent hydrogen, deuterium, (C1-C60)alkyl or (C6-C60)aryl;


i is an integer from 1 to 4, j is an integer of 0 or 1; and


the alkyl, aryl, heteroaryl, arylamino, alkylamino, cycloalkyl or heterocycloalkyl of Ar41 and Ar42, or the aryl, heteroaryl, arylene or heteroarylene of Ar43, or the arylene or heteroarylene of Ar44 and Ar45, or the alkyl or aryl of R131 through R133 may be further substituted by one or more substituent(s) selected from a group consisting of deuterium, halogen, (C1-C60)alkyl, (C6-C60)aryl, (C4-C60)heteroaryl, a 5- or 6-membered heterocycloalkyl containing one or more heteroatom(s) selected from N, O and S, (C3-C60)cycloalkyl, tri(C1-C60)alkylsilyl, di(C1-C60)alkyl(C6-C60)arylsilyl, tri(C6-C60)arylsilyl, adamantyl, (C7-C60)bicycloalkyl, (C2-C60)alkenyl, (C2-C60)alkynyl, cyano, (C1-C60)alkylamino, (C6-C60)arylamino, (C6-C60)ar(C1-C60)alkyl, (C6-C60)aryloxy, (C1-C60)alkyloxy, (C6-C60)arylthio, (C1-C60)alkylthio, (C1-C60)alkoxycarbonyl, (C1-C60)alkylcarbonyl, (C6-C60)arylcarbonyl, carboxyl, nitro and hydroxyl.


The arylamine compounds and styrylarylamine compounds may be more specifically exemplified by the following compounds, but are not restricted thereto.
















In an organic electroluminescent device according to the present invention, the organic layer may further comprise one or more metal(s) selected from a group consisting of organic metals of Group 1, Group 2, 4th period and 5th period transition metals, lanthanide metals and d-transition elements from the Periodic Table of Elements, as well as the organic electroluminescent compound represented by Chemical Formula (1). The organic layer may comprise an electroluminescent layer and a charge generating layer at the same time.


The present invention can realize an electroluminescent device having a pixel structure of independent light-emitting mode, which comprises an organic electroluminescent device containing the compound of Chemical Formula (1) as a sub-pixel, and one or more sub-pixel(s) comprising one or more metal compounds selected from a group consisting of Ir, Pt, Pd, Rh, Re, Os, Tl, Pb, Bi, In, Sn, Sb, Te, Au and Ag, patterned in parallel at the same time.


Further, the organic electroluminescent device is an organic display wherein the organic layer comprises, in addition to the organic electroluminescent compound represented by Chemical Formula (1), one or more compound(s) selected from compounds having the electroluminescent peak of wavelength of 500 to 560 nm, or those having the electroluminescent peak of wavelength of not less than 560 nm, at the same time. The compounds having electroluminescent peak of wavelength of 500 to 560 nm, or those having the electroluminescent peak of wavelength of not less than 560 nm may be exemplified by the compounds represented by one of Chemical Formulas (9) to (15), but they are not restricted thereto.





M1L101L102L103  Chemical Formula 9


In Chemical Formula (9), M1 is selected from Group 7, 8, 9, 10, 11, 13, 14, 15 and 16 metals in the Periodic Table of Elements, and ligands L101, L102 and L103 are independently selected from the following structures:















    • wherein, R201 through R203 independently represent hydrogen, deuterium, (C1-C60)alkyl with or without halogen substituent(s), (C6-C60)aryl with or without (C1-C60)alkyl substituent(s), or halogen;





R204 through R219 independently represent hydrogen, deuterium, (C1-C60)alkyl, (C1-C30)alkoxy, (C3-C60)cycloalkyl, (C2-C30)alkenyl, (C6-C60)aryl, mono or di(C1-C30)alkylamino, mono or di(C6-30)arylamino, SF5, tri(C1-C30)alkylsilyl, di(C1-C30)alkyl(C6-C30)arylsilyl, tri(C6-C30)arylsilyl, cyano or halogen, and the alkyl, cycloalkyl, alkenyl or aryl of R204 through R219 may be further substituted by one or more substituent(s) selected from deuterium, (C1-C60)alkyl, (C6-C60)aryl and halogen;


R220 through R223 independently represent hydrogen, deuterium, (C1-C60)alkyl with or without halogen substituent(s), (C6-C60)aryl with or without (C1-C60)alkyl substituent(s);


R224 and R225 independently represent hydrogen, deuterium, (C1-C60)alkyl, (C6-C60)aryl or halogen, or R224 and R225 may be linked via (C3-C12)alkylene or (C3-C12)alkenylene with or without a fused ring to form an alicyclic ring, or a monocyclic or polycyclic aromatic ring; and the alkyl or aryl of R224 and R225, or the alicyclic ring, or the monocyclic or polycyclic aromatic ring formed therefrom via (C3-C12)alkylene or (C3-C12)alkenylene with or without a fused ring may be further substituted by one or more substituent(s) selected from deuterium, (C1-C60)alkyl with or without halogen substituent(s), (C1-C30)alkoxy, halogen, tri(C1-C30)alkylsilyl, tri(C6-C30)arylsilyl and (C6-C60)aryl;


R226 represents (C1-C60)alkyl, (C6-C60)aryl, or (C5-C60)heteroaryl containing one or more heteroatom(s) selected from N, O and S, or halogen;


R227 through R229 independently represent hydrogen, deuterium, (C1-C60)alkyl, (C6-C60)aryl or halogen, and the alkyl or aryl of R226 through R229 may be further substituted by halogen or (C1-C60)alkyl;


Q represents







and R231 through R242 independently represent hydrogen, deuterium, (C1-C60)alkyl with or without halogen substituent(s), (C1-C30)alkoxy, halogen, (C6-C60)aryl, cyano or (C5-C60)cycloalkyl, or each of R231 through R242 may be linked to an adjacent substituent via alkylene or alkenylene to form a (C5-C7) spiro-ring or (C5-C9) fused ring, or each of them may be linked to R207 or R208 via alkylene or alkenylene to form a (C5-C7) fused ring.







In Chemical Formula (10), R301 through R304 independently represent (C1-C60)alkyl or (C6-C60)aryl, or each of them may be linked to an adjacent substituent via (C3-C60)alkylene or (C3-C60)alkenylene with or without a fused ring to form an alicyclic ring, or a monocyclic or polycyclic aromatic ring; and the alkyl or aryl of R301 through R304, or the alicyclic ring, or the monocyclic or polycyclic aromatic ring formed therefrom by linkage via (C3-C60)alkylene or (C3-C60)alkenylene with or without a fused ring may be further substituted by one or more substituent(s) selected from (C1-C60)alkyl with or without halogen substituent(s), (C1-C60)alkoxy, halogen, tri(C1-C60)alkylsilyl, tri(C6-C60)arylsilyl and (C6-C60)aryl.







In Chemical Formula (13), the ligands, L201 and L202 are independently selected from the following structures:







M2 is a bivalent or trivalent metal;


k is 0 when M2 is a bivalent metal, while k is 1 when M2 is a trivalent metal;


T represents (C6-C60)aryloxy or tri(C6-C60)arylsilyl, and the aryloxy and triarylsilyl of T may be further substituted by (C1-C60)alkyl or (C6-C60)aryl;


G represents O, S or Se;


ring C represents oxazole, thiazole, imidazole, oxadiazole, thiadiazole, benzoxazole, benzothiazole, benzimidazole, pyridine or quinoline;


ring D represents pyridine or quinoline, and ring D may be further substituted by (C1-C60)alkyl, or phenyl or naphthyl with or without (C1-C60)alkyl substituent(s);


R401 through R404 independently represent hydrogen, deuterium, (C1-C60)alkyl, halogen, tri(C1-C60)alkylsilyl, tri(C6-C60)arylsilyl or (C6-C60)aryl, or each of them may be linked to an adjacent substituent via (C3-C60)alkylene or (C3-C60)alkenylene to form a fused ring, and the pyridine or quinoline may form a chemical bond with R401 to form a fused ring;


ring C or the aryl group of R401 through R404 may be further substituted by (C1-C60)alkyl, halogen, (C1-C60)alkyl with halogen substituent(s), phenyl, naphthyl, tri(C1-C60)alkylsilyl, tri(C6-C60)arylsilyl or amino group.







In Chemical Formula (15), Ar51 represents (C6-C60)arylene with or without one or more substituent(s) selected from a group consisting of halogen, (C1-C60)alkyl, (C6-C60)aryl, (C4-C60)heteroaryl, 5- or 6-membered heterocycloalkyl containing one or more heteroatom(s) selected from N, O and S, (C3-C60)cycloalkyl, tri(C1-C60)alkylsilyl, di(C1-C60)alkyl(C6-C60)arylsilyl, tri(C6-C60)arylsilyl, adamantyl, (C7-C60)bicycloalkyl, (C2-C60)alkenyl, (C2-C60)alkynyl, (C1-C60)alkoxy, cyano, (C1-C60)alkylamino, (C6-C60)arylamino, (C6-C60)ar(C1-C60)alkyl, (C6-C60)aryloxy, (C6-C60)arylthio, (C1-C60)alkoxycarbonyl, carboxyl, nitro and hydroxyl; and the alkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, arylsilyl, alkylsilyl, alkylamino and arylamino substituent on the arylene may be further substituted by one or more substituent(s) selected from halogen, (C1-C60)alkyl, (C6-C60)aryl, (C4-C60)heteroaryl, 5- or 6-membered heterocycloalkyl containing one or more heteroatom(s) selected from N, O and S, (C3-C60)cycloalkyl, tri(C1-C60)alkylsilyl, di(C1-C60)alkyl(C6-C60)arylsilyl, tri(C6-C60)arylsilyl, adamantyl, (C7-C60)bicycloalkyl, (C2-C60)alkenyl, (C2-C60)alkynyl, (C1-C60)alkoxy, cyano, (C1-C60)alkylamino, (C6-C60)arylamino, (C6-C60)ar(C1-C60)alkyl, (C6-C60)aryloxy, (C6-C60)arylthio, (C1-C60)alkoxycarbonyl, carboxyl, nitro and hydroxyl;


R501 through R504 independently represent (C1-C60)alkyl, (C6-C60)aryl, (C4-C60)heteroaryl, (C6-C60)arylamino, (C1-C60)alkylamino, 5- or 6-membered heterocycloalkyl containing one or more heteroatom(s) selected from N, O and S, or (C3-C60)cycloalkyl, or R501 through R504 may be linked to an adjacent substituent via (C3-C60)alkylene or (C3-C60)alkenylene with or without a fused ring to form an alicyclic ring or a monocyclic or polycyclic ring; and


the alkyl, aryl, heteroaryl, arylamino, cycloalkyl and heterocycloalkyl of R501 through R504 may be further substituted by one or more substituent(s) selected from halogen, (C1-C60)alkyl, (C6-C60)aryl, (C4-C60)heteroaryl, 5- or 6-membered heterocycloalkyl containing one or more heteroatom(s) selected from N, O and S, (C3-C60)cycloalkyl, tri(C1-C60)alkylsilyl, di(C1-C60)alkyl(C6-C60)arylsilyl, tri(C6-C60)arylsilyl, adamantyl, (C7-C60)bicycloalkyl, (C2-C60)alkenyl, (C2-C60)alkynyl, (C1-C60)alkoxy, cyano, (C1-C60)alkylamino, (C6-C60)arylamino, (C6-C60)ar(C1-C60)alkyl, (C6-C60)aryloxy, (C6-C60)arylthio, (C1-C60)alkoxycarbonyl, carboxyl, nitro and hydroxyl.


The compounds having electroluminescent peak of wavelength of 500 to 560 nm, or those having electroluminescent peak of wavelength of not less than 560 nm, may be exemplified by the following compounds, but they are not restricted thereto.




















































































































































In an electroluminescent device according to the present invention, it is preferable to displace one or more layer(s) (here-in-below, referred to as the “surface layer”) selected from chalcogenide layers, metal halide layers and metal oxide layers, on the inner surface of at least one side of the pair of electrodes. Specifically, it is preferable to arrange a chalcogenide layer of silicon and aluminum metal (including oxides) on the anode surface of the EL medium layer, and a metal halide layer or a metal oxide layer on the cathode surface of the EL medium layer. As the result, stability in operation can be obtained.


Examples of chalcogenides preferably include SiOx (1≦X≦2), AlOx (1≦x≦1.5), SiON, SiAlON, or the like. Examples of metal halides preferably include LiF, MgF2, CaF2, fluorides of rare earth metal or the like. Examples of metal oxides preferably include Cs2O, Li2O, MgO, SrO, BaO, CaO, or the like.


In an electroluminescent device according to the present invention, it is also preferable to arrange, on at least one surface of the pair of electrodes thus manufactured, a mixed region of electron transport compound and a reductive dopant, or a mixed region of a hole transport compound with an oxidative dopant. Accordingly, the electron transport compound is reduced to an anion, so that injection and transportation of electrons from the mixed region to an EL medium are facilitated. In addition, since the hole transport compound is oxidized to form a cation, injection and transportation of holes from the mixed region to an EL medium are facilitated. Preferable oxidative dopants include various Lewis acids and acceptor compounds. Preferable reductive dopants include alkali metals, alkali metal compounds, alkaline earth metals, rare-earth metals, and mixtures thereof.


The organic electroluminescent compounds according to the present invention, having high blue luminous efficiency and excellent life property of material, is advantageous in that they can be employed to manufacture organic light emitting diodes (OLED's) having excellent operation life.


Best Mode

The present invention is further described by referring to representative compounds with regard to the organic electroluminescent compounds according to the invention, preparation thereof and luminous properties of the devices manufactured therefrom, but those examples are provided for better understanding of the invention and illustration of the embodiments only, not being intended to limit the scope of the invention by any means.


PREPARATION EXAMPLES
Preparation Example 1
Synthesis of Compound (1)






Preparation of Compound (A)


In tetrahydrofuran (350 mL), dissolved was 2,6-dibromofluorene (53.0 g, 0.15 mol), and n-BuLi (1.6 M in n-hexane) (63.2 mL, 158 mmol) was slowly added dropwise at −78° C. thereto. After stirring for 30 minutes, N,N-dimethylformamide (16.3 mL, 211 mmol) was added to the mixture. The temperature was slowly raised, and the reaction mixture was stirred for 2 hours. After adding aqueous NH4Cl solution (20 mL) and distilled water (20 mL) to quench the reaction, the organic layer was isolated and evaporated under reduced pressure. The residue was recrystallized from methanol: n-hexane (1/1, v/v) (100 mL) to obtain Compound (A) (20.9 g, 69.4 mmol).


Preparation of Compound (B)


The aldehyde compound (A) thus obtained (20.9 g, 69.4 mmol), diphenylamine (12.5 g, 104.1 mmol), cesium carbonate (24.1 g, 104.1 mmol) and palladium acetate (Pd(OAc)2) (332 mg, 2.1 mmol) were suspended in toluene (800 mL). After adding tri-t-butyl phosphine (P(t-Bu)3) (0.60 g, 4.2 mmol) thereto, the resultant mixture was stirred at 12° C. for 4 hours. Aqueous saturated ammonium chloride solution (30 mL) was added, and the mixture was extracted with ethyl acetate (50 mL) and filtered. Recrystallization from methanol: n-hexane (1/1, v/v) (50 mL) gave Compound (B) (15.2 g, 39.0 mmol).


Preparation of Compound (C)


Triphenyl phosphine (50 g, 190.6 mmol) was dissolved in dichloromethane (260 mL), and tetrabromomethane (CBr4) (31.6 g, 95.3 mmol) solution was slowly added thereto over 10 minutes. The mixture was stirred at room temperature until the solution became dark brown, and water (40 mL) was slowly added thereto to quench the reaction. The mixture was extracted, and the extract was dried under reduced pressure to obtain solid. The solid was added to methanol, and stirred under reflux. The insoluble solid was filtered off, and the filtrate was evaporated under reduced pressure. Recrystallization from ethyl acetate/methanol gave phosphine complex (45 g, 75%).


The phosphine complex thus obtained (19.8 g, 38.5 mmol) and potassium t-butoxide (KOC(CH3)3) (4.3 g, 38.5 mmol) were dissolved in tetrahydrofuran (250 mL), and Compound (B) (5 g, 12.8 mmol) was added thereto. After stirring at room temperature for 10 minutes, potassium t-butoxide (KOC(CH3)3) (11.5 g, 102.7 mmol) was added thereto, and the mixture was stirred at room temperature for 2 hours. When the reaction was completed, the reaction mixture was extracted by using water and ether, and dried under reduced pressure. Purification via column chromatography gave Compound (C) (1.9 g, 38%).


Preparation of Compound (1)


Compound (C) (10 g, 25.9 mmol), 7-bromo-9,9-dimethyl-N,N-diphenyl-9H-fluoren-2-amine (12.7 g, 28.8 mmol), Pd(dba)2 (0.2 g, 0.4 mmol), triphenylphosphine (0.8 g, 2.9 mmol) and copper (I) iodide (CuI) (0.5 g, 2.6 mmol) were dissolved in triethylamine (260 mL), and the solution was stirred under reflux for 24 hours. When the reaction was completed, the reaction mixture was cooled to room temperature, and extracted by using dichloromethane and water, and the extract was dried under reduced pressure. Purification via column chromatography gave Compound (1) (16 g, 72%).


Preparation Example 2
Preparation of Compound (1081)






Preparation of Compound (A)


In tetrahydrofuran (350 mL), dissolved was 2,6-dibromofluorene (53.0 g, 0.15 mmol), and n-BuLi (1.6 M in n-hexane) (63.2 mL, 158 mmol) was slowly added dropwise thereto at −78° C. After stirring for 30 minutes, N,N-dimethylformamide (16.3 mL, 211 mmol) was added thereto. The temperature was slowly raised, and stirring continued for 2 hours. Then, aqueous NH4Cl solution (20 mL) and distilled water (20 mL) were added thereto to quench the reaction. The organic layer isolated was evaporated under reduced pressure. Recrystallization from methanol: n-hexane (1/1, v/v) (100 mL) gave Compound (A) (20.9 g, 69.4 mmol).


Preparation of Compound (B)


The aldehyde compound (A) thus obtained (20.9 g, 69.4 mmol), diphenylamine (12.5 g, 104.1 mmol), cesium carbonate (24.1 g, 104.1 mmol) and palladium acetate (Pd(OAc)2) (332 mg, 2.1 mmol) were suspended in toluene (800 mL). Tri-t-butyl phosphine (P(t-Bu)3) (0.60 g, 4.2 mmol) was added thereto, and the resultant mixture was stirred at 120° C. for 4 hours. Aqueous saturated ammonium chloride solution (30 mL) was added thereto, and the mixture was extracted with ethyl acetate (50 mL), and filtered. Recrystallization from methanol: n-hexane (1/1, v/v) (50 mL) gave Compound (B) (15.2 g, 39.0 mmol).


Preparation of Compound (C)


Triphenyl phosphine (50 g, 190.6 mmol) was dissolved in dichloromethane (260 mL), and tetrabromomethane (CBr4) (31.6 g, 95.3 mmol) solution was slowly added thereto over 10 minutes. The mixture was stirred at room temperature until the solution became dark brown, and water (40 mL) was slowly added thereto to quench the reaction. The mixture was extracted, and the extract was dried under reduced pressure to obtain solid. The solid was added to methanol, and stirred under reflux. The insoluble solid was filtered off, and the filtrate was evaporated under reduced pressure. Recrystallization from ethyl acetate/methanol gave phosphine complex (45 g, 75%).


The phosphine complex thus obtained (19.8 g, 38.5 mmol) and potassium t-butoxide (KOC(CH3)3) (4.3 g, 38.5 mmol) were dissolved in tetrahydrofuran (250 mL), and Compound (B) (5 g, 12.8 mmol) was added thereto. After stirring at room temperature for 10 minutes, potassium t-butoxide (KOC(CH3)3) (11.5 g, 102.7 mmol) was added thereto, and the mixture was stirred at room temperature for 2 hours. When the reaction was completed, the reaction mixture was extracted by using water and ether, and dried under reduced pressure. Purification via column chromatography gave Compound (C) (1.9 g, 38%).


Preparation of Compound (1081)


In tetrahydrofuran (30 mL), dissolved were N-(4-bromophenyl)-N-phenylbenzenamine (0.9 g, 2.9 mmol), Pd2dba3 (12 mg, 0.013 mmol), tri-t-butyl phosphine (6.4 μL) (0.013 mmol, 50 wt % in toluene) and triethylamine (0.5 mL, 3.9 mmol). After stirring the solution for 5 minutes, Compound (C) (1 g, 2.6 mmol) was added thereto, and the resultant mixture was stirred under reflux for 12 hours. When the reaction was completed, the reaction mixture was cooled to room temperature, and extracted by using dichloromethane and water. The extract was dried under reduced pressure and purified by column chromatography to obtain Compound (1081) (0.96 g, 59%).


According to the same procedure as Preparation Examples 1 and 2, the organic electroluminescent compounds (Compounds 1 to 2771) listed in Table 1 were prepared, of which the 1H NMR and MS/FAB data are listed in Table 2.









TABLE 1

























No.
Ar1
Ar2
Ar3













1




















2




















3




















4




















5




















6




















7




















8




















9




















10




















11




















12




















13




















14




















15




















16




















17




















18




















19




















20




















21




















22




















23




















24




















25




















26




















27




















28




















29




















30




















31




















32




















33




















34




















35




















36




















37




















38




















39




















40




















41




















42




















43




















44




















45




















46




















47




















48




















49




















50




















51




















52




















53




















54




















55




















56




















57




















58




















59




















60




















61




















62




















63




















64




















65




















66




















67




















68




















69




















70




















71




















72




















73




















74




















75




















76




















77




















78




















79




















80




















81




















82




















83




















84




















85




















86




















87




















88




















89




















90




















91




















92




















93




















94




















95




















96




















97




















98




















99




















100




















101




















102




















103




















104




















105




















106




















107




















108




















109




















110




















111




















112




















113




















114




















115




















116




















117




















118




















119




















120




















121




















122




















123




















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1737






















1738






















1739






















1740






















1741






















1742






















1743






















1744






















1745






















1746






















1747






















1748






















1749






















1750






















1751






















1752






















1753






















1754






















1755






















1756






















1757






















1758






















1759






















1760






















1761






















1762






















1763






















1764






















1765






















1766






















1767






















1768






















1769






















1770






















1771






















1772






















1773






















1774






















1775






















1776






















1777






















1778






















1779






















1780






















1781






















1782






















1783






















1784






















1785






















1786






















1787






















1788






















1789






















1790






















1791






















1792






















1793






















1794






















1795






















1796






















1797






















1798






















1799






















1800






















1801






















1802






















1803






















1804






















1805






















1806






















1807






















1808






















1809






















1810






















1811






















1812






















1813






















1814






















1815






















1816






















1817






















1818






















1819






















1820






















1821






















1822






















1823






















1824






















1825






















1826






















1827






















1828






















1829






















1830






















1831






















1832






















1833






















1834






















1835






















1836






















1837






















1838






















1839






















1840






















1841






















1842






















1843






















1844






















1845






















1846






















1847






















1848






















1849






















1850






















1851






















1852






















1853






















1854






















1855






















1856






















1857






















1858






















1859






















1860






















1861






















1862






















1863






















1864






















1865






















1866






















1867






















1868






















1869






















1870






















1871






















1872






















1873






















1874






















1875






















1876






















1877






















1878






















1879






















1880






















1881






















1882






















1883






















1884






















1885






















1886






















1887






















1888






















1889






















1890






















1891






















1892






















1893






















1894






















1895






















1896






















1897






















1898






















1899






















1900






















1901






















1902






















1903






















1904






















1905






















1906






















1907






















1908






















1909






















1910






















1911






















1912






















1913






















1914






















1915






















1916






















1917






















1918






















1919






















1920






















1921






















1922






















1923






















1924






















1925






















1926






















1927






















1928






















1929






















1930






















1931






















1932






















1933






















1934






















1935






















1936






















1937






















1938






















1939






















1940






















1941






















1942






















1943






















1944






















1945






















1946






















1947






















1948






















1949






















1950






















1951






















1952






















1953






















1954






















1955






















1956






















1957






















1958






















1959






















1960






















1961






















1962






















1963






















1964






















1965






















1966






















1967






















1968






















1969






















1970






















1971






















1972






















1973






















1974






















1975






















1976






















1977






















1978






















1979






















1980






















1981






















1982






















1983






















1984






















1985






















1986






















1987






















1988






















1989






















1990






















1991






















1992






















1993






















1994






















1995






















1996






















1997






















1998






















1999






















2000






















2001






















2002






















2003






















2004






















2005






















2006






















2007






















2008






















2009






















2010






















2011






















2012






















2013






















2014






















2015






















2016






















2017






















2018






















2019






















2020






















2021






















2022






















2023






















2024






















2025






















2026






















2027






















2028






















2029






















2030






















2031






















2032






















2033






















2034






















2035






















2036






















2037






















2038






















2039






















2040






















2041






















2042






















2043






















2044






















2045






















2046






















2047






















2048






















2049






















2050






















2051






















2052






















2053






















2054






















2055






















2056






















2057






















2058






















2059






















2060






















2061






















2062






















2063






















2064






















2065






















2066






















2067






















2068






















2069






















2070






















2071






















2072






















2073






















2074






















2075






















2076






















2077






















2078






















2079






















2080






















2081






















2082






















2083






















2084






















2085






















2086






















2087






















2088






















2089






















2090






















2091






















2092






















2093






















2094






















2095






















2096






















2097






















2098






















2099






















2100






















2101






















2102






















2103






















2104






















2105






















2106






















2107






















2108






















2109






















2110






















2111






















2112






















2113






















2114






















2115






















2116






















2117






















2118






















2119






















2120






















2121






















2122






















2123






















2124






















2125






















2126






















2127






















2128






















2129






















2130






















2131






















2132






















2133






















2134






















2135






















2136






















2137






















2138






















2139






















2140






















2141






















2142






















2143






















2144






















2145






















2146






















2147






















2148






















2149






















2150






















2151






















2152






















2153






















2154






















2155






















2156






















2157






















2158






















2159






















2160






















2161






















2162






















2163






















2164






















2165






















2166






















2167






















2168






















2169






















2170






















2171






















2172






















2173






















2174






















2175






















2176






















2177






















2178






















2179






















2180






















2181






















2182






















2183






















2184






















2185






















2186






















2187






















2188






















2189






















2190






















2191






















2192






















2193






















2194






















2195






















2196






















2197






















2198






















2199






















2200






















2201






















2202






















2203






















2204






















2205






















2206






















2207






















2208






















2209






















2210






















2211






















2212






















2213






















2214






















2215






















2216






















2217






















2218






















2219






















2220






















2221






















2222






















2223






















2224






















2225






















2226






















2227






















2228






















2229






















2230






















2231






















2232






















2233






















2234






















2235






















2236






















2237






















2238






















2239






















2240






















2241






















2242






















2243






















2244






















2245






















2246






















2247






















2248






















2249






















2250






















2251






















2252






















2253






















2254






















2255






















2256






















2257






















2258






















2259






















2260






















2261






















2262






















2263






















2264






















2265






















2266






















2267






















2268






















2269






















2270






















2271






















2272






















2273






















2274






















2275






















2276






















2277






















2278






















2279






















2280






















2281






















2282






















2283






















2284






















2285






















2286






















2287






















2288






















2289






















2290






















2291






















2292






















2293






















2294






















2295






















2296






















2297






















2298






















2299






















2300






















2301






















2302






















2303






















2304






















2305






















2306






















2307






















2308






















2309






















2310






















2311






















2312






















2313






















2314






















2315






















2316






















2317






















2318






















2319






















2320






















2321






















2322






















2323






















2324






















2325






















2326






















2327






















2328






















2329






















2330






















2331






















2332






















2333






















2334






















2335






















2336






















2337






















2338






















2339






















2340






















2341






















2342






















2343






















2344






















2345






















2346






















2347






















2348






















2349






















2350






















2351






















2352






















2353






















2354






















2355






















2356






















2357






















2358






















2359






















2360






















2361






















2362






















2363






















2364






















2365






















2366






















2367






















2368






















2369






















2370






















2371






















2372






















2373






















2374






















2375






















2376






















2377






















2378






















2379






















2380






















2381






















2382






















2383






















2384






















2385






















2386






















2387






















2388






















2389






















2390






















2391






















2392






















2393






















2394






















2395






















2396






















2397






















2398






















2399






















2400






















2401






















2402






















2403






















2404






















2405






















2406






















2407






















2408






















2409






















2410






















2411






















2412






















2413






















2414






















2415






















2416






















2417






















2418






















2419






















2420






















2421






















2422






















2423






















2424






















2425






















2426






















2427






















2428






















2429






















2430






















2431






















2432






















2433






















2434






















2435






















2436






















2437






















2438






















2439






















2440






















2441






















2442






















2443






















2444






















2445






















2446






















2447






















2448






















2449






















2450






















2451






















2452






















2453






















2454






















2455






















2456






















2457






















2458






















2459






















2460






















2461






















2462






















2463






















2464






















2465






















2466






















2467






















2468






















2469






















2470






















2471






















2472






















2473






















2474






















2475






















2476






















2477






















2478






















2479






















2480






















2481






















2482






















2483






















2484






















2485






















2486






















2487






















2488






















2489






















2490






















2491






















2492






















2493






















2494






















2495






















2496






















2497






















2498






















2499






















2500






















2501






















2502






















2503






















2504






















2505






















2506






















2507






















2508






















2509






















2510






















2511






















2512






















2513






















2514






















2515






















2516






















2517






















2518






















2519






















2520






















2521






















2522






















2523






















2524






















2525






















2526






















2527






















2528






















2529






















2530






















2531






















2532






















2533






















2534






















2535






















2536






















2537






















2538






















2539






















2540






















2541






















2542






















2543






















2544






















2545






















2546






















2547






















2548






















2549






















2550






















2551






















2552






















2553






















2554






















2555






















2556






















2557






















2558






















2559






















2560






















2561






















2562






















2563






















2564






















2565






















2566






















2567






















2568






















2569






















2570






















2571






















2572






















2573






















2574






















2575






















2576






















2577






















2578






















2579






















2580






















2581






















2582






















2583






















2584






















2585






















2586






















2587






















2588






















2589






















2590






















2591






















2592






















2593






















2594






















2595






















2596






















2597






















2598






















2599






















2600






















2601






















2602






















2603






















2604






















2605






















2606






















2607






















2608






















2609






















2610






















2611






















2612






















2613






















2614






















2615






















2616






















2617






















2618






















2619






















2620






















2621






















2622






















2623






















2624






















2625






















2626






















2627






















2628






















2629






















2630






















2631






















2632






















2633






















2634






















2635






















2636






















2637






















2638






















2639






















2640






















2641






















2642






















2643






















2644






















2645






















2646






















2647






















2648






















2649






















2650






















2651






















2652






















2653






















2654






















2655






















2656






















2657






















2658






















2659






















2660






















2661






















2662






















2663






















2664






















2665






















2666






















2667






















2668






















2669






















2670






















2671






















2672






















2673






















2674






















2675






















2676






















2677






















2678






















2679






















2680






















2681






















2682






















2683






















2684






















2685






















2686






















2687






















2688






















2689






















2690






















2691






















2692






















2693






















2694






















2695






















2696






















2697






















2698






















2699






















2700






















2701






















2702






















2703






















2704






















2705






















2706






















2707






















2708






















2709






















2710






















2711






















2712






















2713






















2714






















2715






















2716






















2717






















2718






















2719






















2720






















2721






















2722






















2723






















2724






















2725






















2726






















2727






















2728






















2729






















2730






















2731






















2732






















2733






















2734






















2735






















2736






















2737






















2738






















2739






















2740






















2741






















2742






















2743






















2744






















2745






















2746






















2747






















2748






















2749






















2750






















2751






















2752






















2753






















2754






















2755






















2756






















2757






















2758






















2759






















2760






















2761






















2762






















2763






















2764






















2765






















2766






















2767






















2768






















2769






















2770






















2771


































TABLE 2









MS/FAB










Comp.

1H NMR (CDCl3, 200 MHz)
found
calculated













1
δ = 7.83 (d, 2H), 7.75 (d, 2H),
744.96
744.35



7.62-7.58 (m, 4H), 7.20 (m, 8H), 6.81-6.75 (m,



6H), 6.63-6.58 (m, 10H), 1.72 (s, 12H)


2
δ = 7.88-7.74 (m, 20H), 7.62-7.49 (m,
945.20
944.41



12H), 7.36 (m, 4H), 6.75 (s, 2H), 6.58 (m, 2H), 1.72 (s,



12H)


3
δ = 8.07-8.02 (m, 8H), 7.83 (m, 2H),
945.20
944.41



7.75 (s, 2H), 7.62-7.53 (m, 16H), 7.38 (m,



4H), 6.98 (m, 4H), 6.75 (s, 2H), 6.58 (m,



2H), 1.72 (s, 12H)


5
δ = 7.87-7.83 (m, 6H), 7.75 (s, 2H),
1209.60
1208.60



7.62-7.55 (m, 12H), 7.38 (m, 4H), 7.28 (m,



4H), 6.75 (s, 6H), 6.58 (m, 6H), 1.72 (s,



36H)


8
δ = 7.83 (d, 2H), 7.75 (d, 2H),
1049.35
1048.48



7.58-7.41 (m, 32H), 6.75 (s, 2H), 6.69 (m, 8H),



6.58 (m, 2H), 1.72 (s, 12H)


12
δ = 7.83 (d, 2H), 7.75 (d, 2H),
801.07
800.41



7.62-7.58 (m, 4H), 6.98 (m, 8H), 6.75 (s, 2H),



6.58-6.51 (m, 10H), 2.34 (s, 12H),



1.72 (s, 12H)


15
δ = 7.83 (d, 2H), 7.75 (d, 2H),
969.60
968.60



7.62-7.58 (m, 4H), 7.01 (m, 8H), 6.75 (m, 2H),



6.58-6.55 (m, 10H), 1.72 (s, 12H),



1.35 (s, 36H)


19
δ = 7.83 (d, 2H), 7.75 (d, 2H),
857.17
856.48



7.62-7.58 (m, 4H), 6.75-6.71 (m, 6H), 6.58 (m,



2H), 6.36 (m, 8H), 2.34 (s, 24H), 1.72 (s,



12H)


30
δ = 7.93-7.83 (m, 10H), 7.77-7.75 (m,
1513.99
1512.73



6H), 7.63-7.54 (m, 20H), 7.38 (m, 4H),



7.28 (m, 4H), 6.75 (s, 2H), 6.69 (m, 8H0,



6.58 (m, 2H), 1.72 (s, 36H)


47
δ = 7.88-7.74 (m, 12H), 7.62-7.49 (m, 8H),
845.08
844.38



7.36 (m, 2H), 7.20 (m, 4H), 6.81-6.75 (m,



4H), 6.63-6.58 (m, 6H), 1.72 (s, 12H)


49
δ = 8.93 (m, 4H), 8.12 (m, 4h),
945.20
944.41



7.88-7.75 (m, 12H), 7.62-7.58 (m, 4H), 7.20 (m,



4H), 6.91 (s, 2H), 6.81-6.75 (m, 4H),



6.63-6.58 (m, 6H), 1.72 (s, 12H)


52
δ = 7.83 (d, 2H), 7.75 (d, 2H), k
897.15
896.41



7.62-7.41 (m, 16H), 7.20 (m, 4H), 6.89-6.75 (m,



8H), 6.63-6.58 (m, 8H), 1.72 (s, 12H)


54
δ = 7.83 (d, 2H), 7.75 (d, 2H),
897.15
896.41



7.62-7.51 (m, 10H), 7.41 (m, 2h), 7.20-7.16 (m,



6H), 7.08 (m, 4H), 6.87-6.75 (m, 6H),



6.69-6.58 (m, 8H), 1.72 (s, 12H)


57
δ = 7.83 (d, 2H), 7.75 (d, 2H),
773.02
772.38



7.62-7.58 (m, 4H), 7.20 (m, 4H), 6.98 (m, 4H),



6.81 (m, 4H), 6.75 (s, 2H), 6.63-6.51 (m,



10H), 2.34 (s, 6H), 1.72 (s, 12H)


60
δ = 7.83 (d, 2H), 7.75 (d, 2H),
857.17
856.48



7.62-7.58 (m, 4H), 7.20 (m, 4H), 7.01 (m, 4H),



6.81-6.75 (m, 4H), 6.63-6.55 (m, 10H),



1.72 (s, 12H), 1.35 (s, 18H)


68
δ = 8.07 (m, 2H), 7.83 (d, 2H), 7.75 (d,
746.94
746.34



2H), 7.62-7.55 (m, 6H), 7.20 (m, 4H),



6.81-6.58 (m, 14H), 1.72 (s, 12H)


75
δ = 7.93-7.83 (m, 6H), 7.77-7.75 (m, 4H),
1129.47
1128.54



7.62-7.54 (m, 12H), 7.38 (m, 2H),



7.28 (m, 2H), 7.20 (m, 4H), 6.81-6.75 (m,



4H), 6.69-6.63 (m, 10H), 1.72 (s, 24H)


94
δ = 7.88-7.74 (m, 14H), 7.62-7.49 (m,
1077.40
1076.51



12H), 7.38-7.36 (m, 4H), 7.28 (m, 2H),



6.75 (m, 4H), 56.58 (m, 4H), 1.72 (s, 24H)


98
δ = 7.88-7.74 (m, 12H), 7.62-7.36 (m,
997.27
996.44



18H), 7.16-7.08 (m, 6H), 6.87 (m, 2H),



6.75 (m, 2H), 6.69 (m, 2H), 6.58 (m, 2H),



1.72 (s, 12H)


110
δ = 7.88-7.74 (m, 12H), 7.62-7.58 (m,
989.44
988.46



4H), 7.50-7.49 (m, 4H), 7.36 (m, 2H),



7.15 (m, 4H), 6.75 (m, 2H), 6.61-6.58 (m,



6H), 1.72 (s, 12H), 0.25 (s, 18H)


117
δ = 8.18 (m, 2H), 8.01 (m, 2H),
959.23
958.32



7.88-7.74 (m, 12H), 7.62-7.49 (m, 12H),



6.75 (m, 2H), 6.58 (m, 2H), 1.72 (s, 12H)


137
δ = 8.07-8.02 (m, 4H), 7.87-7.83 (m, 4H),
1077.40
1076.51



7.75 (m, 2H), 7.62-7.53 (m, 14H), 7.38 (m,



4H), 7.28 (m, 2H), 6.98 (m, 2H), 6.75 (m,



4H), 6.58 (m, 4H), 1.72 (s, 24H)


161
δ = 8.07-8.02 (m, 4H), 7.93 (m, 2H),
1229.59
1228.57



7.83 (m, 2H), 7.77-7.75 (m, 4H),



7.63-7.51 (m, 22H), 7.41-7.38 (m, 4H), 6.98 (m,



2H), 6.75 (m, 4H), 6.58 (m, 4H), 1.72 (s,



24H)


182
δ = 8.93 (m, 4H), 8.12 (m, 4H),
1097.39
1096.48



7.88-7.75 (m, 12H), 7.62-7.41 (m, 18H),



6.91 (m, 2H), 6.75-6.69 (m, 6H), 6.58 (m,



2H), 1.72 (s, 12H)


193
δ = 8.93 (m, 4H), 8.12 (m, 4H),
1001.30
1000.48



7.88-7.75 (m, 12H), 7.62-7.58 (m, 4H), 6.91 (m,



2H), 6.75-6.71 (m, 4H), 6.58 (m, 2H),



6.36 (m, 4H), 2.34 (s, 12H), 1.72 (s, 12H)


198
δ = 8.93 (m, 4H), 8.22 (m, 2H), 8.12 (m,
1047.29
1046.43



4H), 7.94-7.57 (m, 24H), 7.37 (m, 2H),



6.91 (m, 2H), 6.75 (m, 2H), 6.58 (m, 2H),



1.72 (s, 12H)


220
δ = 8.93 (m, 4H), 8.47 (m, 4H), 8.12 (m,
951.13
950.38



4H), 7.88-7.75 (m, 12H), 7.62-7.58 (m,



4H), 6.91 (m, 2H), 6.75 (m, 2H), 6.58 (m,



2H), 1.72 (s, 12H)


226
δ = 7.87-7.83 (m, 4H), 7.75 (m, 2H),
1281.67
1280.60



7.62-7.51 (m, 24H), 7.41-7.38 (m, 6H), 7.28 (m,



2H), 7.06 (m, 2H), 6.85 (m, 4h), 6.75 (m,



4h), 6.58 (m, 4H), 1.72 (s, 24H)


230
δ = 7.87-7.83 (m, 4H), 7.75 (m, 2H),
1089.49
1088.60



7.62-7.55 (m, 8H), 7.38 (m, 2H), 7.28 (m,



2H), 7.01 (m, 4H), 6.75 (m, 4H),



6.58-6.55 (m, 8H), 1.72 (s, 24H), 1.35 (s, 18H)


240
δ = 8.28 (m, 2H), 8.17 (m, 2H),
1079.38
1078.50



7.87-7.83 (m, 4H), 7.75 (m, 2h), 7.62-7.55 (m,



10H), 7.47-7.38 (m, 6H), 7.28 (m, 2H),



6.99 (m, 2H), 6.75 (m, 4H), 6.58 (m, 4H),



1.72 (s, 24H)


243
δ = 8.18 (m, 2H), 8.01 (m, 2H),
1091.43
1090.41



7.87-7.83 (m, 4H), 7.75 (m, 2H), 7.62-7.53 (m,



12H), 7.38 (m, 2H), 7.28 (m, 2H), 6.75 (m,



4H), 6.58 (m, 4H), 1.72 (s, 24H)


263
δ = 8.12 (m, 4H), 7.88-7.82 (m, 10H),
1145.43
1144.48



7.75-7.71 (m, 6H), 7.62-7.51 (m, 16H),



7.41 (m, 2H), 6.91 (m, 2H), 6.75-6.69 (m,



6H), 6.58 (m, 2H), 1.72 (s, 12H)


278
δ = 8.12-8.07 (m, 6H), 7.88-7.82 (m,
995.22
994.40



10H), 7.75-7.71 (m, 6H), 7.62-7.55 (m,



6H), 6.91 (m, 2h), 6.75-6.58 (m, 8H),



1.72 (s, 12H)


302
δ = 7.83 (m, 2H), 7.75 (m, 2H),
1049.35
1048.48



7.62-7.41 (m, 30H), 6.89-6.88 (m, 4H), 6.75 (m,



2H), 6.69 (m, 4H), 6.59-6.58 (m, 4H),



1.72 (s, 12H)


306
δ = 7.83 (m, 2H), 7.75 (m, 2H),
925.21
924.44



7.62-7.41 (m, 16H), 6.98 (m, 4H), 6.88 (m, 4H),



6.75 (m, 2H), 6.59-6.51 (m, 8H), 2.34 (s,



6H), 1.72 (s, 12H)


313
δ = 7.83 (m, 2H), 7.75 (m, 2H),
953.26
952.48



7.62-7.41 (m, 16H), 6.89-6.88 (m, 4H),



6.75-6.71 (m, 4H), 6.59-6.58 (m, 4H), 6.36 (m,



4H), 2.34 (s, 12H), 1.72 (s, 12H)


344
δ = 7.83 (m, 2H), 7.75 (m, 2H),
925.21
924.44



7.62-7.51 (m, 16H), 7.41 (m, 2H), 6.98 (m, 4H),



6.75-6.69 (m, 6H), 6.58-6.51 (m, 6H),



2.34 (s, 6H), 1.72 (s, 12H)


347
δ = 7.83 (m, 2H), 7.75 (m, 2H),
1009.37
1008.54



7.62-7.51 (m, 16H), 7.41 (m, 2H), 7.01 (m, 4H),



6.75 (m, 2H), 6.69 (m, 4H), 6.58-6.55 (m,



6H), 1.72 (s, 12H), 1.35 (s, 18H)


351
δ = 7.83 (m, 2h), 7.75 (m, 2H),
953.26
952.48



7.62-7.51 (m, 16H), 7.41 (m, 2H), 6.75-6.69 (m,



8H), 6.58 (m, 2H), 6.36 (m, 4H), 2.34 (s,



12H), 1.72 (s, 12H)


354
δ = 7.83-7.75 (m, 12H), 7.62-7.41 (m,
1201.54
1200.54



32H), 6.95 (m, 2H), 6.75-6.65 (m, 8H),



6.58 (m, 2H), 1.72 (s, 12H)


389
δ = 7.83 (m, 2H), 7.75 (m, 2H),
1033.15
1032.39



7.62-7.37 (m, 20H), 6.88 (m, 4H), 6.75 (m, 2h),



6.59-6.56 (m, 8H), 1.72 (s, 12H)


398
δ = 7.93 (m, 2H), 7.83 (m, 2H),
1281.67
1280.60



7.77-7.75 (m, 4h), 7.63-7.41 (m, 30H), 6.88 (m,



4H), 6.75 (m, 4H), 6.59-6.58 (m, 6H),



1.72 (s, 24H)


420
δ = 7.91 (m, 6H), 7.83 (m, 2H), 7.75 (m,
1205.57
1204.57



2H), 7.62-7.58 (m, 4H), 7.39-7.35 (m,



14H), 7.01 (m, 4H), 6.75 (m, 2H),



6.58-6.51 (m, 8H), 1.72 (s, 12H), 1.35 (s, 18H)


421
δ = 7.91 (m, 6H), 7.83 (m, 2H), 7.75 (m,
1153.41
1152.47



2H), 7.62-7.58 (m, 4H), 7.39-7.35 (m,



14H), 6.75-6.74 (m, 6H), 6.58-6.51 (m,



8H), 3.85 (s, 6H), 1.72 (s, 12H)


457
δ = 7.83 (m, 2H), 7.75 (m, 2H),
1133.51
1132.57



7.62-7.41 (m, 24H), 7.06 (m, 2H), 6.85 (m, 4H),



6.75 (m, 2H), 6.58 (m, 2H), 6.24 (m, 4H),



2.34 (s, 12H), 2.18 (s, 6H), 1.72 (s, 12H)


466
δ = 7.83-7.75 (m, 6H), 7.58-7.41 (m,
1067.36
1066.52



22H), 7.15 (m, 2H), 7.05 (m, 4H), 6.95 (m,



2H), 6.78 (m, 2H), 3.65 (m, 8H), 6.11 (m,



8H), 1.72 (s, 12H)


489
δ = 7.83 (m, 2H), 7.75 (m, 2H),
885.23
884.51



7.62-7.50 (m, 4H), 7.01-6.98 (m, 8H), 6.75 (m,



2H), 6.58-6.51 (m, 10H), 2.34 (s, 6H),



1.72 (s, 12H), 1.35 (s, 18H)


493
δ = 7.83 (m, 2H), 7.75 (m, 2H),
829.12
828.44



7.2-7.58 (m, 4H), 6.98 (m, 4H), 6.75-6.71 (m,



4H), 6.58 (m, 2H), 6.51 (m, 4H), 6.36 (m,



4H), 2.34 (s, 18H), 1.72 (s, 12H)


511
δ = 8.46 (m, 4H), 7.83 (m, 2H), 7.75 (m,
774.99
774.37



2H), 7.62-7.58 (m, 4H), 6.98 (m, 8H),



6.75 (m, 2H), 6.71-6.51 (m, 6H), 2.34 (s,



6H), 1.72 (s, 12H)


528
δ = 7.83 (m, 2H), 7.75 (m, 2H),
925.31
924.41



7.62-7.58 (m, 4H), 7.15 (m, 4H), 6.99 (m, 4h),



6.75 (m, 2H), 6.61 (m, 10H), 1.72 (s,



12H), 0.25 (s, 18H)


537
δ = 7.93-7.83 (m, 6H), 7.77-7.75 (m, 4H),
1165.45
1164.52



7.63-7.55 (m, 12H), 7.38 (m, 2H), 7.28 (m,



2h), 6.99 (m, 4H), 6.75 (m, 2H), 6.69 (m,



4H), 6.61-6.58 (m, 6H), 1.72 (s, 24H)


554
δ = 7.83 (m, 2H), 7.75 (m, 2H),
913.28
912.54



7.62-7.58 (m, 4H), 7.01 (m, 4H), 6.86 (m, 2H),



6.75 (m, 2H), 6.58-6.55 (m, 6H), 6.43 (m,



2H), 6.32 (m, 2H), 2.34 (s, 12H), 1.72 (s,



12), 1.35 (s, 18H)


558
δ = 7.83 (m, 2H), 7.759m, 2H),
857.17
856.48



7.62-7.58 (m, 4H), 6.86 (m, 2H), 6.75-6.71 (m,



4H), 6.58 (m, 2H), 6.43 (m, 2H),



6.36-6.32 (m, 6H), 2.34 (s, 24H), 1.72 (s, 12H)


568
δ = 7.93 (m, 2H), 7.83 (m, 2H),
1185.58
1184.60



7.77-7.75 (m, 4H), 7.63-7.51 (m, 16H),



7.41 (m, 2H), 6.86 (m, 2H), 6.75 (m, 4H),



6.58 (m, 4H), 6.43 (m, 2H), 6.32 (m, 2H),



2.34 (s, 12H), 1.72 (s, 24H)


571
δ = 8.55 (m, 2H), 8.42 (m, 2H),
1285.70
1284.63



8.08-8.04 (m, 4H), 7.93 (m, 2H), 7.83 (m, 2H),



7.77-7.75 (m, 4H), 7.63-7.55 (m, 14H),



6.86 (m, 2H), 6.75 (m, 4H), 6.58 (m, 4H),



6.43 (m, 2H), 6.32 (m, 2H), 2.34 (s, 12H),



1.72 (s, 24H)


617
δ = 7.83 (m, 2H), 7.75 (m, 2H),
889.17
888.47



7.62-7.58 (m, 4H), 6.75-6.74 (m, 6H),



6.52 (m, 6H), 6.24 (s, 4H), 3.83 (s, 6H),



2.34 (s, 12H), 2.18 (s, 6H), 1.72 (s, 12H)


681
δ = 8.22 (m, 2H), 7.94 (m, 2H),
959.27
958.50



7.83 (m, 2H), 7.75-7.57 (m, 12H),



7.37 (m, 2H), 6.75 (m, 2H), 6.58 (m, 2H),



6.22 (s, 2H), 2.34 (s, 12H), 2.12 (s,



12H), 1.72 (s, 12H)


711
δ = 8.42 (m, 4H), 8.10 (m, 4H),
1049.35
1048.35



7.83 (m, 2H), 7.75 (m, 2H), 7.67-7.49 (m,



10H), 7.34 (m, 2H), 6.91 (m, 2H),



6.75-6.71 (m, 4H), 6.58 (m, 2H), 6.36 (m, 4H),



2.34 (s, 12H), 1.72 (s, 12H)


741
δ = 8.55 (m, 2H), 8.42 (m, 2H),
1365.59
1364.54



8.08-8.04 (m, 4H), 7.93 (m, 2H),



7.77-7.75 (m, 4H), 7.63-7.55 (m, 14H), 7.37 (m,



4H), 6.75 (m, 4H), 6.58-6.56 (m, 8H),



1.72 (s, 24H)


757
δ = 8.07 (m, 2H), 7.83 (m, 2H),
891.30
890.42



7.75 (m, 2H), 7.62-7.55 (m, 6H),



7.15 (m, 4H), 6.75-6.70 (m, 4H),



6.62-6.58 (m, 8H), 1.72 (s, 12H), 0.25 (s, 18H)


764
δ = 7.93-7.83 (m, 6H), 7.77-7.75 (m, 4H),
1273.84
1272.62



7.63-7.54 (m, 12H), 7.38 (m, 2H), 7.28 (m,



2H), 7.15 (m, 4H), 6.75 (m, 2H), 6.69 (m,



4H), 6.61-6.58 (m, 6H), 1.72 (s, 24H),



0.25 (s, 18H)


805
δ = 8.22 (m, 2H), 8.07 (m, 2H), 7.94 (m,
849.03
849.36



2H), 7.83 (m, 2H), 7.75-7.55 (m, 14H),



7.37 (m, 2H), 6.70-6.58 (m, 8H), 1.72 (s,



12H)


832
δ = 8.22 (m, 2H), 7.94-7.93 (m, 4H),
1231.57
1230.56



7.83 (m, 2H), 7.75-7.51 (m, 26H),



7.41-7.37 (m, 4H), 6.75 (m, 4H), 6.58 (m, 4H),



1.72 (s, 24H)


881
δ = 8.46 (m, 4H), 7.83-7.75 (m, 6H),
764.96
764.38



7.58 (m, 2H), 6.99-6.93 (m, 6H),



6.78 (m, 2H), 3.65 (m, 8H), 3.11 (m, 8H),



1.72 (s, 12H)


910
δ = 8.18 (m, 2H), 8.01 (m, 2H),
1243.62
1242.47



7.93-7.83 (m, 6H), 7.77-7.75 (m, 4H),



7.63-7.53 (m, 16H), 7.38 (m, 2H), 7.28 (m, 2H),



6.75 (m, 2h), 6.69 (m, 4H), 6.58 (m, 2H),



1.72 (s, 24H)


928
δ = 7.93-7.83 (m, 8H), 7.77-7.75 (m, 6H),
1513.99
1512.73



7.63-7.51 (m, 24H), 7.41-7.38 (m, 4H),



7.28 (m, 2H), 6.75 (m, 4H), 6.69 (m, 4h),



6.58 (m, 4H), 1.72 (s, 36H)


1004
δ = 8.99-8.93 (m, 4H), 8.34 (m, 2H),
1582.02
1580.69



8.12-8.10 (m, 4H), 8.00-7.71 (m, 24H),



7.63-7.54 (m, 18H), 6.75-6.69 (m, 8H),



6.58 (m, 4H), 1.72 (s, 24H)


1047
δ = 8.90 (m, 2H), 8.50-8.45 (m, 8H),
752.87
752.31



7.83 (m, 2H), 7.75 (m, 2H), 7.62-7.58 (m,



4H), 6.93 (m, 2H), 6.58 (m, 2H), 1.72 (s,



12H)


1081
δ = 7.83 (m, 1H), 7.75 (m, 1H),
628.80
628.29



7.62-7.58 (m, 2H), 7.34 (m, 2H), 7.20 (m, 8H),



6.81-6.75 (m, 6H), 6.63-6.59 (m, 10H),



1.72 (s, 6H)


1082
δ = 7.88-7.74 (m, 18H), 7.62-7.49 (m,
829.04
828.35



10H), 7.36-7.34 (m, 6H), 6.75 (m, 1h),



6.58 (m, 3H), 1.72 (s, 6H)


1083
δ = 8.07-8.02 (m, 8H), 7.83 (m, 1H),
829.04
828.35



7.75 (m, 1H), 7.62-7.53 (m, 14H),



7.38-7.34 (m, 6H), 6.98 (m, 4H), 6.75 (m, 1H),



6.59 (m, 3H), 1.72 (s, 6H)


1085
δ = 7.87-7.83 (m, 5H), 7.75 (m, 1H),
1093.44
1092.54



7.62-7.55 (m, 10H), 7.38-7.28 (m, 10H),



6.75 (m, 5H), 6.58 (m, 7H), 1.72 (s, 30H)


1088
δ = 7.83 (m, 1H), 7.75 (m, 1H),
933.19
932.41



7.62-7.41 (m, 32H), 6.75 (m, 1H), 6.59 (m, 8H),



6.58 (m, 3H), 1.72 (s, 6H)


1092
δ = 7.83 (m, 1H), 7.75 (m, 1H),
684.91
684.35



7.62-7.58 (m, 2H), 7.34 (m, 2H), 6.98 (m, 8H),



6.75 (m, 1H), 6.58-6.51 (m, 11H), 2.34 (s,



12H), 1.72 (s, 6H)


1093
δ = 7.83 (m, 1H), 7.75 (m, 1H),
700.76
700.25



7.62-7.58 (m, 2H), 7.34 (m, 2H), 6.99 (m, 8H),



6.75 (m, 1H), 6.61-6.58 (m, 11H), 1.72 (s,



6H)


1095
δ = 7.83 (m, 1H), 7.75 (m, 1H),
853.23
852.54



7.62-7.58 (m, 2H), 7.34 (m, 2H), 7.01 (m, 8H),



6.75 (m, 1H), 6.58-6.55 (m, 11H), 1.72 (s,



6H), 1.35 (s, 36H)


1104
δ = 8.22 (m, 4H), 7.94 (m, 4H), 7.83 (m,
832.99
832.33



1H), 7.75-7.57 (m, 15H), 7.37-7.34 (m,



6H), 6.75 (m, 1H), 6.58 (m, 3H), 1.72 (s,



6H)


1127
δ = 7.88-7.74 (m, 10H), 7.62-7.49 (m, 6H),
728.92
728.32



7.36-7.34 (m, 4H), 7.20 (m, 4H),



6.81-6.75 (m, 3H), 6.63-6.58 (m, 7H), 1.72 (s,



6H)


1128
δ = 8.07-8.02 (m, 4H), 7.83 (m, 1H),
728.92
728.32



7.75 (m, 1H), 7.62-7.53 (m, 8H),



7.38-7.34 (m, 4H), 7.20 (m, 4H), 6.98 (m, 2H),



6.81-6.75 (m, 3H), 6.63-6.58 (m, 7H),



1.72 (s, 6H)


1136
δ = 7.83 (m, 1H), 7.75 (m, 1H),
933.19
932.41



7.62-7.34 (m, 24H), 7.20 (m, 4H), 7.06 (m, 2H),



6.85-6.81 (m, 7H), 6.63-6.58 (m, 7H),



1.72 (s, 6H)


1140
δ = 7.83 (m, 1H), 7.75 (m, 1H),
741.01
740.41



7.62-7.58 (m, 2H), 7.34 (m, 2H), 7.20 (m, 4H),



7.01 (m, 4H), 6.81-6.75 (m, 3H),



6.63-6.55 (m, 11H), 1.72 (s, 6H), 1.35 (s, 18H)


1142
δ = 7.83 (m, 1H), 7.75 (m, 1H),
712.96
712.38



7.62-7.58 (m, 2H), 7.34 (m, 2H), 7.20 (m, 4H),



6.81-6.75 (m, 3H), 6.63-6.58 (m, 7H),



6.24 (m, 4H), 2.34 (s, 12H), 2.18 (s, 6H),



1.72 (s, 6H)


1154
δ = 7.93 (m, 2H), 7.83 (m, 1H),
1013.31
1012.48



7.77-7.75 (m, 3H), 7.63-7.51 (m, 14H),



7.41-7.34 (m, 4H), 7.20 (m, 4H), 6.81-6.75 (m,



5H), 1.72 (s, 18H)


1159
δ = 8.00-7.92 (m, 8H), 7.83 (m, 1H),
1113.43
1112.51



7.77-7.73 (m, 5H), 7.63-7.58 (m, 12H),



7.34 (m, 2H), 7.20 (m, 4H), 6.81-6.75 (m,



5H), 6.63-6.58 (m, 9H), 1.72 (s, 18H)


1174
δ = 7.88-7.759m, 12H),
961.24
960.44



7.62-7.49 (m, 10H), 7.38-7.28 (m, 8H0, 6.75 (m,



3H), 6.58 (m, 5H), 1.72 (s, 18H)


1177
δ = 7.88-7.74 (m, 10H), 7.62-7.36 (m,
880.11
880.38



24H), 6.75 (m, 1H), 6.69 (m, 4H),



6.59-6.58 (m, 3H), 1.72 (s, 6H)


1180
δ = 7.88-7.74 (m, 10H), 7.62-7.34 (m,
1033.30
1032.44



30H), 7.06 (m, 2H), 6.85 (m, 4H),



6.75 (m, 1H), 6.59-6.58 (m, 3H), 1.72 (s,



6H)


1181
δ = 7.88-7.74 (m, 10H), 7.62-7.49 (m,
756.97
756.35



6H), 7.36-7.34 (m, 4H), 6.99 (m, 4h),



6.75 (m, 1h), 6.61-6.58 (m, 7H), 1.72 (s,



6H)


1182
δ = 7.88-7.74 (m, 10H), 7.62-7.49 (m, 6H),
764.90
764.30



7.36-7.34 (m, 4H), 6.99 (m, 4H),



6.75 (m, 1H), 6.61-6.58 (m, 7H), 1.72 (s,



6H)


1184
δ = 7.88-7.74 (m, 10H),
841.13
840.44



7.62-7.58 (m, 2H), 7.50-7.49 (m, 4H),



7.36-7.34 (m, 4H), 7.01 (m, 4H), 6.75 (m, 1h),



6.58-6.55 (m, 7H), 1.72 (s, 6H), 1.35 (s,



18H)


1185
δ = 7.88-7.74 (m, 10H), 7.62-7.49 (m,
788.97
788.34



6H), 7.36-7.34 (m, 4H), 6.75-6.74 (m,



5H), 6.59-6.52 (m, 7H), 3.83 (s, 6H),



1.72 (s, 6H)


1189
δ = 7.88-7.74 (m, 10H), 7.62-7.49 (m,
864.92
864.29



6H), 7.37-7.34 (m, 8H), 6.75 (m, 1H),



6.59-6.56 (m, 7H), 1.72 (s, 6H)


1190
δ = 7.88-7.74 (m, 10H), 7.62-7.58 (m,
873.28
872.40



2H), 7.50-7.49 (m, 4H), 7.36-7.34 (m,



4H), 7.15 (m, 4H), 6.75 (m, 1H),



6.61-6.59 (m, 7H), 1.72 (s, 6H), 0.25 (s, 18H)


1192
δ = 8.07 (m, 2H), 7.88-7.74 (m, 10H),
730.90
730.31



7.62-7.49 (m, 8H), 7.36-7.34 (m, 4H),



6.75-6.58 (m, 8H), 1.72 (s, 6H)


1197
δ = 8.18 (m, 2H), 8.01 (m, 2H),
843.07
842.25



7.88-7.74 (m, 10H), 7.58-7.49 (m, 10H),



7.36-7.34 (m, 4H), 6.75 (m, 1H), 6.59-6.58 (m,



3H), 1.72 (s, 6H)


1221
δ = 8.07-8.02 (m, 4H), 7.83 (m, 1H),
881.11
880.38



7.75 (m, 1H), 7.62-7.38 (m, 20H),



7.16-7.08 (m, 6H), 6.98 (m, 2H), 6.87 (m, 2H),



6.75-6.69 (m, 3H), 6.58 (m, 3H), 1.72 (s,



6H)


1227
δ = 8.07-7.02 (m, 4H), 7.83 (m, 1H),
841.13
840.44



7.75 (m, 1H), 7.62-7.53 (m, 8H),



7.38-7.34 (m, 4H), 7.01-6.98 (m, 6H), 6.75 (m,



1H), 6.59-6.55 (m, 7H), 1.72 (s, 6H),



1.35 (s, 18H)


1248
δ = 8.99-8.93 (m, 4H), 8.34 (m, 2H),
1181.46
1180.48



8.12-8.02 (m, 8H), 7.88-7.38 (m, 34H),



6.98 (m, 2H), 6.75 (m, 1H), 6.59-6.58 (m,



3H), 1.72 (s, 6H)


1259
δ = 8.93 (m, 4H), 8.12 (m, 4H),
1061.36
1060.48



7.88-7.75 (m, 12H), 7.62-7.55 (m, 6H),



7.38-7.28 (m, 6H), 6.91 (m, 2H), 6.75 (m, 3H),



6.58 (m, 5H), 1.72 (s, 18H)


1266
δ = 8.93 (m, 4H), 8.12 (m, 4H),
857.09
856.38



7.88-7.75 (m, 10H), 7.62-7.58 (m, 2H), 7.34 (m,



2H), 6.98-6.91 (m, 6H), 6.75 (m, 1H),



6.59-6.51 (m, 7H), 2.34 (s, 6H), 1.72 (s,



6H)


1272
δ = 8.93 (m, 4H), 8.12 (m, 4H),
941.25
940.48



7.88-7.75 (m, 10H), 7.62-7.58 (m, 2H), 7.34 (m,



2H), 6.91 (m, 2H), 6.75 (m, 1H), 6.59 (m,



3H), 6.22 (m, 2H), 2.34 (s, 12H), 2.12 (s,



12H), 1.72 (s, 6H)


1297
δ = 8.93 (m, 4H), 8.12 (m, 4H),
841.09
840.26



7.88-7.75 (m, 10H), 7.62-7.58 (m, 2H), 7.34 (m,



2H), 6.91-6.84 (m, 4H), 6.75-6.72 (m,



3H), 6.59-6.58 (m, 3H), 6.01 (m, 2H),



1.72 (s, 6H)


1314
δ = 7.87-7.83 (m, 3H), 7.75 (m, 1H),
917.23
916.48



7.62-7.55 (m, 6H), 7.38-7.28 (m, 6H),



6.75-6.71 (m, 5H), 6.58 (m, 5H), 6.36 (m,



4H), 2.34 (s, 12H), 1.72 (s, 18H)


1348
δ = 7.83 (m, 1H), 7.75 (m, 1H),
881.11
880.38



7.62-7.58 (m, 2H), 7.34 (m, 2H), 7.20 (m, 4H),



6.81-6.71 (m, 9H), 6.64-6.58 (m, 13H),



6.39-6.23 (m, 6H), 3.66 (m, 4H), 1.72 (s,



6H)


1382
δ = 7.83 (m, 1H), 7.75 (m, 1H),
933.19
932.41



7.62-7.41 (m, 30H), 6.89-6.88 (m, 4H), 6.75 (m,



1H), 6.69 (m, 4H), 6.59-6.58 (m, 5H),



1.72 (s, 6H)


1386
δ = 7.83 (m, 1H), 7.75 (m, 1H),
809.05
808.38



7.62-7.41 (m, 16H), 6.98 (m, 4H), 6.89-6.88 (m,



4H), 6.75 (m, 1H), 6.59-6.51 (m, 9H),



2.34 (s, 6H), 1.72 (s, 6H)


1390
δ = 7.83 (m, 1H), 7.75 (m, 1H),
841.05
840.37



7.62-7.41 (m, 16H), 6.88 (m, 4H), 6.75 (m, 5H),



6.59-6.52 (m, 9H), 3.83 (s, 6H), 1.72 (s,



6H)


1400
δ = 7.83-7.75 (m, 3H), 7.62-7.41 (m,
799.01
798.39



15H), 7.09 (m, 2H), 6.97-6.95 (m, 3H),



6.79 (m, 5H), 3.65 (m, 8H), 3.11 (m, 8H),



1.72 (s, 6H)


1405
δ = 8.49 (m, 2H), 8.07 (m, 2H),
1265.62
1264.57



7.93-7.75 (m, 10H), 7.62-7.41 (m, 28H),



7.04 (m, 2H), 6.88 (m, 4H), 6.75 (m, 1H),



6.59 (m, 5H), 1.72 (s, 18H)


1429
δ = 7.83 (m, 1H), 7.62-7.51 (m, 14H),
865.15
864.44



7.41-7.34 (m, 4H), 6.75 (m, 1H),



6.69 (m, 4H), 6.58 (m, 3H), 6.24 (m, 4H),



2.34 (s, 12H), 2.18 (s, 6H), 1.72 (s, 6H)


1462
δ = 7.83 (m, 1H), 7.75 (m, 1H),
816.97
816.33



7.62-7.51 (m, 8H), 7.41-7.34 (m, 4H),



7.16-6.99 (m, 10H), 6.87 (m, 2H), 6.69-6.58 (m,



10H), 1.72 (s, 6H)


1479
δ = 7.93-7.83 (m, 5H), 7.77-7.75 (m, 3H),
1165.51
1164.54



7.63-7.51 (m, 16H), 7.41-7.28 (m, 8H),



7.16 (m, 2H), 7.08 (m, 4H), 6.87 (m, 2H),



6.75 (m, 1H), 6.69 (m, 6H), 6.58 (m, 3H),



1.72 (s, 18H)


1500
δ = 8.42 (m, 4H), 8.10 (m, 4H),
989.29
988.48



7.83 (m, 1H), 7.75 (m, 1H), 7.62-7.49 (m,



8H), 7.34 (m, 4H), 7.01 (m, 4H),



6.91 (m, 2H), 6.75 (m, 1H), 6.59-6.55 (m,



7H), 1.72 (s, 6H), 1.35 (s, 18H)


1533
δ = 7.83 (m, 1H), 7.75 (m, 1H),
969.17
968.39



7.62-7.41 (m, 24H), 7.06-6.99 (m, 6H),



6.85 (m, 4H), 6.75 (m, 1H), 6.61-6.58 (m,



7H), 1.72 (s, 6H)


1569
δ = 7.83 (m, 1h), 7.75 (m, 1H),
769.07
768.44



7.62-7.58 (m, 2H), 7.34 (m, 2H), 7.01-6.98 (m,



8H), 6.75 (m, 1H), 6.58-6.51 (m, 11H),



2.34 (s, 6H), 1.72 (s, 6H), 1.35 (s, 18H)


1606
δ = 7.83 (m, 1h), 7.75 (m, 1h),
720.89
720.33



7.62-7.58 (m, 2H), 7.34 (m, 2H), 6.99 (m, 4H),



6.75-6.71 (m, 3H), 6.61-6.58 (m, 7H),



6.36 (m, 4H), 2.34 (s, 12H), 1.72 (s, 6H)


1739
δ = 7.93-7.83 (m, 5H), 7.77-7.75 (m, 3H),
1097.47
1096.57



7.63-7.54 (m, 10H), 7.38-7.28 (m, 6H),



6.75-6.69 (m, 5H), 6.58 (m, 3h), 6.24 (s,



4H), 2.34 (s, 12H), 2.18 (s, 6H), 1.72 (s,



18H)


1757
δ = 7.83 (m, 1H), 7.74 (m, 1H),
877.01
876.39



7.62-7.58 (m, 2H), 7.37-7.34 (m, 6H),



6.75 (m, 1H), 6.58-6.56 (m, 7H), 6.22 (s,



2H), 2.34 (s, 12H), 2.12 (s, 12H),



1.72 (s, 6H)


1793
δ = 7.93 (m, 2H), 7.83 (m, 1H),
1069.42
1068.54



7.77-7.75 (m, 3H), 7.62-7.51 (m, 14H),



7.41-7.34 (m, 4H)m 6.75-6.71 (m, 5H), 6.58 (m,



5H), 6.36 (m, 4H), 2.34 (s, 12H), 1.72 (s,



18H)


1844
δ = 7.93-7.83 (m, 5H), 7.77-7.75 (m, 3H),
1157.68
1156.55



7.62-7.54 (m, 10H), 7.38-7.28 (m, 6H),



7.38-7.28 (m, 6H), 7.15 (m, 4H),



6.75-6.69 (m, 5H), 6.61-6.58 (m, 7H), 1.72 (s,



18H), 0.25 (s, 18H)


1933
δ = 8.28 (m, 2H), 8.17 (m, 2H),
1115.41
1114.50



7.93 (m, 2H), 7.83 (m, 1H), 7.77-7.75 (m,



3H), 7.62-7.41 (m, 24H), 6.99 (m, 2H),



6.75 (m, 3H), 6.59-6.58 (m, 5H), 1.72 (s,



18H)


2008
δ = 7.93-7.83 (m, 7H), 7.77-7.75 (m, 5H),
1397.83
1396.66



7.63-7.51 (m, 22H), 7.41-7.28 (m, 8H),



6.75 (m, 3H), 6.69 (m, 4H), 6.58 (m, 5H),



14.72 (s, 30H)


2193
δ = 8.47-8.35 (m, 10H), 7.83 (m, 1H),
638.68
638.24



7.75 (m, 1H), 7.62-7.58 (m, 2H),



7.34 (m, 2H), 6.75 (m, 1H),



6.59-6.58 (m, 2H), 1.72 (s, 6H)


2161
δ = 8.02 (m, 2H), 7.54-7.53 (m, 2H),
562.70
562.24



7.35-7.34 (m, 3H), 7.20 (m, 8H),



6.94 (m, 1H), 6.81 (m, 4H), 6.63 (m, 10H)


2207
δ = 8.21 (m, 1H), 7.84 (m, 1H), 7.74 (m,
562.70
562.24



1H), 7.54-7.48 (m, 3H), 7.34 (m, 2H),



7.20 (m, 8H), 6.81 (m, 4H), 6.63 (m, 10H)


2300
δ = 8.89 (m, 1H), 8.68 (m, 1H),
612.76
612.26



8.32 (m, 1H), 8.08 (m, 1H), 7.71 (m, 2H),



7.34-7.32 (m, 3H), 7.20 (m, 8H), 7.08 (m,



1H), 6.81 (m, 4H), 6.63 (m, 10H)


2347
δ = 8.93-8.89 (m, 2H), 8.32 (m, 1H),
662.82
662.27



8.13-8.08 (m, 3H), 7.88-7.82 (m, 3H),



7.34 (m, 2H), 7.20 (m, 8H), 7.02 (m, 1H),



6.81 (m, 4H), 6.63 (m, 10H)


2391
δ = 7.83 (m, 1H), 7.75 (m, 3H),
750.93
750.30



7.62-7.58 (m, 2H), 7.35-7.34 (m, 4H),



7.20-7.16 (m, 12H), 6.81-6.75 (m, 5H),



6.63-6.58 (m, 11H)


2437
δ = 7.83 (m, 1H), 7.75 (m, 1H),
752.94
752.32



7.62-7.58 (m, 2H), 7.34-7.20 (m, 20H),



6.81-6.75 (m, 5H), 6.63-6.58 (m, 11H)


2483
δ = 7.69 (m, 2H), 7.33-7.20 (m, 14H),
638.80
628.27



6.87-6.77 (m, 6H), 6.63-6.61 (m, 7H),



6.31-6.23 (m, 3H), 4.59 (m, 1H),



3.66 (m, 1H)


2529
δ = 8.05 (m, 1H), 7.81-7.77 (m, 2H),
744.96
744.35



7.69-7.62 (m, 3H), 7.34 (m, 2H), 7.20 (m,



8H), 6.81-6.75 (m, 5H), 6.63-6.58 (m,



11H), 1.72 (s, 12H)


2575
δ = 7.91-7.87 (m, 3H), 7.74 (m, 1H),
686.84
686.27



7.59 (m, 1H), 7.39-7.34 (m, 6H), 7.20 (m,



8H), 6.81 (m, 4H), 6.63 (m, 11H)


2621
δ = 9.13 (m, 1H), 8.93 (m, 2H),
662.82
662.27



8.12 (m, 2H), 7.88-7.82 (m, 4H),



7.34 (m, 2H), 7.20 (m, 8H), 6.91 (m, 1H),



6.81 (m, 4H), 6.63 (m, 10H)









Example 1
Manufacture of OLED's by using the Compounds of the Invention

An OLED device was manufactured by using the electroluminescent compound according to the invention.


First, a transparent electrode ITO thin film (15Ω/□) prepared from glass for OLED was subjected to ultrasonic washing with trichloroethylene, acetone, ethanol and distilled water, sequentially, and stored in isopropanol before use.


Then, an ITO substrate was equipped in a substrate folder of a vacuum vapor-deposit device, and 4,4′,4″-tris(N,N-(2-naphthyl)-phenylamino)triphenylamine (2-TNATA) (of which the structure is shown below) was placed in a cell of the vacuum vapor-deposit device, which was then ventilated up to 10−6 torr of vacuum in the chamber. Electric current was applied to the cell to evaporate 2-TNATA, thereby providing vapor-deposit of a hole injection layer having 60 nm of thickness on the ITO substrate.







Then, to another cell of the vacuum vapor-deposit device, charged was N,N′-bis(α-naphthyl)-N,N′-diphenyl-4,4′-diamine (NPB) (of which the structure is shown below), and electric current was applied to the cell to evaporate NPB, thereby providing vapor-deposit of a hole transport layer of 20 nm of thickness on the hole injection layer.







After forming the hole injection layer and hole transport layer, an electroluminescent layer was vapor-deposited as follows. To one cell of a vacuum vapor-deposit device, charged was dinaphthylanthracene (DNA) (of which the structure is shown below) as electroluminescent material, and a compound according to the invention (e.g. Compound (2545)) was charged to another cell. An electroluminescent layer was vapor-deposited with a thickness of 30 nm on the hole transport layer at a vapor-deposition rate of 100:1.







Then, tris(8-hydroxyquinoline)aluminum (III) (Alq) (of which the structure is shown below) was vapor-deposited as an electron transport layer with a thickness of 20 nm, and lithium quinolate (Liq) (of which the structure shown below) was vapor-deposited as an electron injection layer with a thickness of 1 to 2 nm. Thereafter, an Al cathode was vapor-deposited with a thickness of 150 nm by using another vacuum vapor-deposit device to manufacture an OLED.







Each material employed for manufacturing an OLED was used as the electroluminescent material after purifying via vacuum sublimation under 10−6 torr.


Comparative Example 1
Manufacture of an OLED by using Conventional Electroluminescent Material

After forming a hole injection layer and hole transport layer according to the same procedure described in Example 1, dinaphthylanthracene (DNA) was charged to one cell of said vacuum vapor-deposit device as a blue electroluminescent material, and Compound (A) (of which the structure is shown below) was charged to another cell as another blue electroluminescent material. Then an electroluminescent layer having 30 nm of thickness was vapor-deposited on the hole transport layer at the vapor-deposition rate of 100:1.







Then, an electron transport layer and electron injection layer were vapor-deposited according to the same procedure of Example 1, and an Al cathode was vapor-deposited thereon with a thickness of 150 nm by using another vacuum vapor-deposit device to manufacture an OLED.


Example 2
Electroluminescent Properties of OLED's Manufactured

The luminous efficiencies of the OLED's comprising the organic EL compound according to the present invention (Examples 1) or conventional EL compound (Comparative Example 1) were measured at 1,000 cd/m2, and the results are shown in Table 3.














TABLE 3








Luminous





EL
EL
efficiency

Luminous


NO.
material 1
material 2
(cd/A)
Color
efficiency/Y




















1
DNA
Compound 2
6.2
Blue
47.7


2
DNA
Compound
5.9
Blue
45.4




12


3
DNA
Compound
5.1
Blue
42.5




34


4
DNA
Compound
6.2
Blue
47.7




347


5
DNA
Compound
6.7
Blue
51.5




713


6
DNA
Compound
7.2
Blue
51.4




817


7
DNA
Compound
5.7
Blue
43.8




1084


8
DNA
Compound
6.5
Blue
50.0




1115


9
DNA
Compound
6.6
Blue
50.7




1186


10
DNA
Compound
5.9
Blue
49.2




1427


11
DNA
Compound
7.1
Blue
50.7




1684


12
DNA
Compound
7.0
Blue
53.8




2189


13
DNA
Compound
6.8
Blue
52.3




2227


14
DNA
Compound
7.0
Blue
53.8




2301


15
DNA
Compound
5.8
Blue
44.6




2395


16
DNA
Compound
6.2
Blue
47.7




2450


17
DNA
Compound
7.7
Blue
54.2




2545


18
DNA
Compound
7.1
Blue
53.6




2585


19
DNA
Compound
6.7
Blue
47.8




2628


20
DNA
Compound
6.3
Blue
51.0




2677


21
DNA
Compound
6.2
Blue
47.3




2694


22
DNA
Compound
7.2
Blue
49.2




2713


Comp.
DNA
Compound A
7.3
Jade
35.8


Ex. 1



green









As can be seen from Table 3, it is found that the OLED's employing the organic EL compounds according to the present invention exhibited higher “luminous efficiency/Y” value (which shows similar tendency to quantum efficiency) as compared to an OLED comprising DNA: Compound (A) as conventional EL material (Comparative Example 1).


Accordingly, it is found that acetylene as backbone or the organic electroluminescent compounds according to the invention contributes to a material of high quantum efficiency, and the compounds enable realization higher efficiency and better color purity than conventional EL compounds. Particularly, Compound (2545) exhibited enhanced “luminous efficiency/Y” value by at least 60% as compared to the conventional EL material.


It is anticipated that the molecular structure comprising a triple bond, rather than the structure comprised of simple aromatic conjugation, provides the effect of enhancing overlap between orbitals of individual aromatic rings in the molecular structure to result in improved performance.


As shown above, the organic electroluminescent compounds according to the present invention can be employed as blue electroluminescent material of high efficiency, and provide advantages in terms of luminance, power consumption and device life, as being employed in OLED's, as compared to conventional full-colored OLED's.

Claims
  • 1. An organic electroluminescent compound represented by Chemical Formula (1):
  • 2. The organic electroluminescent compound according to claim 1, wherein Ar1 and Ar2 are independently selected from from the following structures:
  • 3. An organic electroluminescent device which is comprised of a first electrode; a second electrode; and at least one organic layer(s) interposed between the first electrode and the second electrode; wherein the organic layer comprises one or more organic electroluminescent compound(s) represented by the Chemical Formula (1):
  • 4. The organic electroluminescent device according to claim 3, wherein the organic layer comprises one or more compound(s) selected from a group consisting of arylamine compounds and styrylarylamine compounds.
  • 5. The organic electroluminescent device according to claim 3, wherein the organic layer comprises one or more metal(s) selected from a group consisting of organic metals of Group 1, Group 2, 4th period and 5th period transition metals, lanthanide metals and d-transition elements from the Periodic Table of Elements.
  • 6. The organic electroluminescent device according to claim 3, which is an organic display comprising a compound having the electroluminescent peak with wavelength of 500 to 560 nm.
  • 7. The organic electroluminescent device according to claim 3, wherein the organic layer comprises an electroluminescent layer and a charge generating layer.
  • 8. The organic electroluminescent device according to claim 3, wherein a mixed region of reductive dopant and organic substance, or a mixed region of oxidative dopant and organic substance is placed on the inner surface of one or both electrode(s) among the pair of electrodes.
  • 9. An organic solar cell which comprises an organic electroluminescent compound represented by Chemical Formula (1):
Priority Claims (1)
Number Date Country Kind
10-2007-0142000 Dec 2007 KR national