JP2016534980A - Organic electroluminescent compound and organic electroluminescent device comprising the same - Google Patents

Abstract

The present invention relates to a novel organic electroluminescent compound and an organic electroluminescent device including the same. The organic electroluminescent compounds according to the invention have an excellent thermal stability due to the high glass transition temperature. By using the organic electroluminescent compounds according to the present invention, it is possible to produce organic electroluminescent devices with outstanding current / power efficiency and long life. [Selection figure] None

Description

  The present invention relates to an organic electroluminescent compound and an organic electroluminescent device including the same.

  An electroluminescent device (EL device) is a self-emitting device that has advantages in that it provides a wider viewing angle, a better contrast ratio, and a faster response time. Organic EL devices were first developed by Eastman Kodak by using as a material a complex of an aromatic diamine small molecule and aluminum to form a light emitting layer [Appl. Phys. Lett. 51, 913, 1987].

The most important factor for determining the luminous efficiency in the organic EL device is the light emitting material. Until now, fluorescent materials have been widely used as luminescent materials. However, from the point of view of electroluminescence mechanism, phosphorescent materials theoretically improve luminous efficiency by a factor of four compared to fluorescent materials, and therefore, development of phosphorescent light emitting materials has been widely studied. Iridium (III) complexes are bis (2- (2′-benzothienyl) -pyridinato-N, C3 ′) iridium (acetylacetonate) ((acac) Ir (btp) ₂ ), tris (2-phenylpyridine) Phosphorescence comprising iridium (Ir (ppy) ₃ ) and bis (4,6-difluorophenylpyridinato-N, C2) picolinate iridium (Firpic) as red, green and blue materials, respectively Widely known as a material.

  At present, 4,4'-N, N'-dicarbazole-biphenyl (CBP) is the most widely known phosphorescent host material. Recently, Pioneer (Japan) et al. Reported bathocuproine (BCP) and aluminum (III) bis (2-methyl-8-quinolinate) (4-phenylphenolate) (BAlq), which were known as hole blocking layer materials. We developed a high-performance organic EL device to be used as a host material.

  Although these materials provide good luminescent characteristics, they have the following disadvantages. (1) Due to their low glass transition temperature and low thermal stability, their decomposition can occur during high temperature deposition processes even in vacuum, reducing the lifetime of the device. (2) The power efficiency of the organic EL device is obtained by [(π / voltage) × current efficiency], and this power efficiency is inversely proportional to the voltage. Organic EL devices that include phosphorescent host materials provide higher current efficiency (cd / A) than those that include fluorescent materials, but require very high drive voltages. Therefore, there is no advantage in terms of power efficiency (lm / W). (3) Furthermore, the operating life of organic EL devices is short, and the luminous efficiency still needs improvement.

  On the other hand, in order to improve the efficiency and stability, the organic EL device has a multilayer structure including a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer. Selection of the compound contained in the hole transport layer is known as a method for improving device characteristics such as the hole transport efficiency with respect to the light emitting layer, the light emission efficiency, the lifetime, and the like.

  As a result, copper phthalocyanine (CuPc), 4,4′-bis [N- (1-naphthyl) -N-phenylamino] biphenyl (NPB), N, N′-diphenyl-N, N′-bis (3 -Methylphenyl)-(1,1′-biphenyl) -4,4′-diamine (TPD), 4,4 ′, 4 ″ -tris (3-methylphenylphenylamino) triphenylamine (MTDATA), etc. Have been used as hole injection and transport materials. However, organic EL devices using these materials have problems in terms of quantum efficiency and operating lifetime. This is because thermal stress occurs between the anode and the hole injection layer when the organic EL device is driven under a high current. Thermal stress significantly reduces the operating life of the device. Furthermore, since the organic material used for the hole injection layer has very high hole mobility, the hole-electron charge balance may be lost, and the quantum efficiency (cd / A) may be reduced. .

  Accordingly, hole transport layers for improving the durability of organic EL devices still need to be developed.

  Japanese Patent No. 3065125 B discloses a compound in which the 2-position of fluorene is substituted with a diarylamine as a compound for an organic EL device. However, the above references do not disclose compounds in which the 9 position of fluorene is substituted with both diarylamine or heteroarylamine, and fluorene, dibenzothiophene, or dibenzofuran.

  An object of the present invention is to provide an organic electroluminescent compound having excellent power efficiency and long life.

  The inventors have found that the above objective can be achieved by an organic electroluminescent compound represented by Formula 1 below:

Where
Do Ar ₁ and Ar ₂ each independently represent substituted or unsubstituted (C1-C30) alkyl, substituted or unsubstituted (C6-C30) aryl, or substituted or unsubstituted (3 to 30 membered) heteroaryl? Or linked to adjacent substituent (s) to form a monocyclic or polycyclic (C3-C30) alicyclic or aromatic ring, the carbon atom (s) being nitrogen, May be replaced with at least one heteroatom selected from oxygen and sulfur;
X is, -O -, - S-, or _{-C (R 5) (R 6} ) - represents,
R _{1 to} R ₄ are each independently hydrogen, deuterium, halogen, cyano, carboxyl, nitro, hydroxyl, substituted or unsubstituted (C1-C30) alkyl, substituted or unsubstituted (C2-C30) alkenyl, substituted Or unsubstituted (C2-C30) alkynyl, substituted or unsubstituted (C1-C30) alkoxy, substituted or unsubstituted (C3-C30) cycloalkyl, substituted or unsubstituted (C3-C30) cycloalkenyl, substituted or unsubstituted ( 3-7 membered) heterocycloalkyl, substituted or unsubstituted (C6-C30) aryl, substituted or unsubstituted (3-30 membered) _{heteroaryl, -NR 7 R 8, -SiR 9} R 10 R 11, -SR 12 , _-OR 13, -COR ₁₄ or _-B (oR 15), or represents _{(oR 16),} Oh Or linked to adjacent substituent (s) to form a substituted or unsubstituted monocyclic or polycyclic (C3-C30) alicyclic or aromatic ring; May be substituted with at least one heteroatom selected from nitrogen, oxygen, and sulfur,
Each of R _{5 to} R ₁₆ independently represents substituted or unsubstituted (C1-C30) alkyl, substituted or unsubstituted (C6-C30) aryl, or substituted or unsubstituted (3 to 30 membered) heteroaryl; Or linked to adjacent substituent (s) to form a substituted or unsubstituted monocyclic or polycyclic (C3-C30) alicyclic or aromatic ring;
n is an integer from 0 to 2,
when n is 1 or 2, L ₁ represents a single bond, a substituted or unsubstituted (C6-C30) arylene, or a substituted or unsubstituted (3 to 30 membered) heteroarylene;
when n is 0, L ₁ represents substituted or unsubstituted (C1-C30) alkyl, substituted or unsubstituted (C6-C30) aryl, or substituted or unsubstituted (3-30 membered) heteroaryl;
a, b, and d each independently represent an integer of 1 to 4, and when a, b, or d is an integer of 2 or more, each of R ₁ , each of R ₂ , and R ₄ Each may be the same or different,
c represents an integer of 1 to 3, and when c is an integer of 2 or more, each of R ₃ may be the same or different,
Heterocycloalkyl and heteroaryl (ene) each independently contain at least one heteroatom selected from B, N, O, S, P (═O), Si, and P.

Advantageous Effects of the Invention By using the organic electroluminescent compounds according to the invention, it is possible to produce organic electroluminescent devices with outstanding current and power efficiency and long life.

  Hereinafter, the present invention will be described in detail. However, the following description is intended to illustrate the present invention and is not meant to limit the scope of the present invention in any way.

  The present invention relates to an organic electroluminescent compound of formula 1, an organic electroluminescent material comprising this compound, and an organic electroluminescent device comprising this material.

  The present invention was invented to provide a hole transport material used in an organic EL device that can solve the problems of the prior art. An ideal hole transport material requires high glass transition temperature, hole injection ability, and hole transport ability, as well as suitable triplet energy and LUMO energy. If the glass transition temperature is low, crystallization can occur due to thermal stress applied during or after the formation of the thin film, which can directly affect the lifetime of the device. Arylamine derivatives exhibit excellent hole transport capability and low driving voltage, but many arylamine derivatives have increased molecular weight by introducing large amounts of substituents to obtain a suitable glass transition temperature. There is a need. However, in this case, the pi conjugation is lengthened in order to shorten the triplet energy or LUMO energy, which in turn degrades the device performance. This contributes to the high triplet energy blocking the excitons transported from the host to the hole transport layer, and the high LUMO energy blocks the electrons transporting from the electron transport layer through the host to the hole transport layer. It is because it becomes a cause to do.

  Another problem with hole transport materials having high molecular weight by introducing large amounts of substituents is that good vapor deposition does not occur. As the molecular weight increases, so does the deposition temperature, and the molecules are likely to decompose into many shapes or break. Therefore, it is important to maintain a suitable glass transition temperature by introducing a suitable amount of substituents and to maintain a low deposition temperature for high molecular weight. Thus, the present invention proposes as a solution to introduce an arylamine and a selected heteroaryl or fluorene at position 9 of the fluorene.

  Introducing the arylamine and selected heteroaryl or fluorene at the 9-position of the fluorene increases the glass transition temperature, but does not significantly increase the deposition temperature compared to introducing a substituent at the 2-position. This is because the molecular linearity is relatively low. As the molecular linearity increases, the intermolecular force increases and the deposition temperature also increases.

  On the other hand, the reason for introducing the arylamine at the 9-position instead of the 2-position is to obtain a relatively high triplet energy by short conjugation. In order to obtain high triplet energy, it is best not to introduce any substituents. However, although the triplet energy is slightly lowered, it is possible to obtain excellent hole injection ability / transport ability, high power efficiency, long life and the like by introducing arylamine. In addition, by introducing heteroaryl or fluorene at the 9-position instead of the 2-position, proper glass transition without increasing the deposition temperature too high despite the high molecular weight due to the decrease in molecular linearity It is possible to obtain temperature.

  The organic electroluminescent compound represented by Formula 1 above is described in detail.

  In the present specification, “(C1-C30) alkyl” is linear or branched having 1 to 30 carbon atoms, preferably having 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms. And includes methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, etc., and “(C2-C30) alkenyl” preferably has the number of carbon atoms Means linear or branched alkenyl having 2 to 20 carbon atoms, more preferably 2 to 10, more preferably 2 to 10 and vinyl, 1-propenyl, 2-propenyl, 1- Including butenyl, 2-butenyl, 3-butenyl, 2-methylbut-2-enyl and the like, “(C2-C30) alkynyl” preferably has 2 to 20 carbon atoms, more preferably Or a linear or branched alkynyl having 2 to 30 carbon atoms, which is 2 to 10, and ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, Including 3-butynyl, 1-methylpent-2-ynyl and the like, “(C3-C30) cycloalkyl” preferably has 3 to 30 carbon atoms, more preferably 3 to 30 carbon atoms. Monocyclic or polycyclic hydrocarbons having 1 carbon atom and including cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc., “(3-7 membered) heterocycloalkyl” means B, N, O , S, P (= O), Si, and P, preferably cycloalkyl having 3-7 ring skeleton atoms containing at least one heteroatom selected from O, S, and N And “(C6-C30) aryl (ene)” preferably has 6 to 20 carbon atoms, more preferably 6 to 15 carbon atoms, including tetrahydrofuran, pyrrolidine, thiolane, tetrahydropyran and the like. Monocyclic or condensed rings derived from aromatic hydrocarbons having ˜30 carbon atoms, and phenyl, biphenyl, terphenyl, naphthy, binaphthyl, phenylnaphthyl, naphthylphenyl, fluorenyl, phenylfluorenyl, benzo Including fluorenyl, dibenzofluorenyl, phenanthrenyl, phenylphenanthrenyl, anthracenyl, indenyl, triphenylenyl, pyrenyl, tetracenyl, perylenyl, chrycenyl, naphthacenyl, fluoranthenyl, and the like ("(5-30 members) heteroaryl ( En) "is B, An aryl having 5-30 ring skeleton atoms containing at least one, preferably 1-4 heteroatoms selected from the group consisting of N, O, S, P (= O), Si, and P Which is a monocyclic ring or a condensed ring fused with at least one benzene ring, which may be partially saturated, wherein at least one heteroaryl or aryl group is bonded to a heteroaryl group by a single bond (s) And furyl, thiophenyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, thiadiazolyl, isothiazolyl, isoxazolyl, oxazolyl, oxadiazolyl, triazinyl, tetrazinyl, triazolyl, tetrazolyl, furazanyl, pyridyl, pyrazinyl, Pyrimidinyl, pyridazinyl, etc. Monocyclic ring heteroaryl, as well as benzofuranyl, benzothiophenyl, isobenzofuranyl, dibenzofuranyl, dibenzothiophenyl, benzimidazolyl, benzothiazolyl, benzoisothiazolyl, benzoisoxazolyl, benzoxazolyl, isoindolyl, Includes fused ring heteroaryls including indolyl, indazolyl, benzothiadiazolyl, quinolyl, isoquinolyl, cinolinyl, quinazolinyl, quinoxalinyl, carbazolyl, phenoxazinyl, phenanthridinyl, benzodioxolyl and the like. Further, “halogen” includes F, Cl, Br, and I.

In the present specification, the term “substituted” in the expression “substituted or unsubstituted” means that a hydrogen atom in a specific functional group is replaced with another atom or group, that is, a substituent. Ar ₁ , Ar ₂ , R _{1 to} R ₁₆ , and substituted (C1-C30) alkyl, substituted (C2-C30) alkenyl, substituted (C2-C30) alkynyl, substituted (C1-C30) alkoxy, substituted in L ₁ (C3-C30) cycloalkyl, substituted (C3-C30) cycloalkenyl, substituted (3-7 membered) heterocycloalkyl, substituted (C6-C30) aryl (ene), and substituted (3-30 membered) heteroaryl ( The substituents of ene) are each independently deuterium, halogen, cyano, carboxyl, nitro, hydroxyl, (C1-C30) alkyl, halo (C1-C30) alkyl, (C2-C30) alkenyl, (C2- C30) alkynyl, (C1-C30) alkoxy, (C1-C30) alkylthio, (C3-C30) cycloalkyl, (C -C30) cycloalkenyl, (3-7 membered) heterocycloalkyl, (C6-C30) aryloxy, (C6-C30) arylthio, unsubstituted or substituted with (C6-C30) aryl (3-30 membered) (C6-C30) aryl, tri (C1-C30) alkylsilyl, tri (C6-C30) arylsilyl, di (C1-C30) alkyl substituted with heteroaryl, unsubstituted or (3-30 membered) heteroaryl (C6-C30) arylsilyl, (C1-C30) alkyldi (C6-C30) arylsilyl, amino, mono- or di (C1-C30) alkylamino, mono- or di (C6-C30) arylamino, (C1-C30 ) Alkyl (C6-C30) arylamino, (C1-C30) alkylcarbonyl, (C -C30) alkoxycarbonyl, (C6-C30) arylcarbonyl, di (C6-C30) aryl boronyl, di (C1-C30) alkyl boronyl, (C1-C30) alkyl (C6-C30) aryl boronyl, ( C6-C30) aryl (C1-C30) alkyl and (C1-C30) alkyl (C6-C30) aryl. At least one selected from the group consisting of aryl (C1-C30) aryl, preferably each independently (C1-C6 ) At least one selected from the group consisting of alkyl and (C6-C15) aryl.

In Formula 1 above, Ar ₁ and Ar ₂ are each independently substituted or unsubstituted (C1-C30) alkyl, substituted or unsubstituted (C6-C30) aryl, or substituted or unsubstituted (3 to 30 members) ) Represents a heteroaryl or is linked to an adjacent substituent (s) to form a monocyclic or polycyclic (C3-C30) alicyclic or aromatic ring, the carbon atom ( (S) may be replaced with at least one heteroatom selected from nitrogen, oxygen, and sulfur, preferably each independently, substituted or unsubstituted (C6-C20) aryl, or substituted or unsubstituted Represents (5 to 20 membered) heteroaryl, more preferably each independently, unsubstituted or (C1-C6) alkyl or (C6-C12) aryl Substituted (C6-C20) aryl, or unsubstituted or (C6-C12) substituted with an aryl represents a (5-20 membered) heteroaryl.

R _{1 to} R ₄ are each independently hydrogen, deuterium, halogen, cyano, carboxyl, nitro, hydroxyl, substituted or unsubstituted (C1-C30) alkyl, substituted or unsubstituted (C2-C30) alkenyl, substituted Or unsubstituted (C2-C30) alkynyl, substituted or unsubstituted (C1-C30) alkoxy, substituted or unsubstituted (C3-C30) cycloalkyl, substituted or unsubstituted (C3-C30) cycloalkenyl, substituted or unsubstituted ( 3-7 membered) heterocycloalkyl, substituted or unsubstituted (C6-C30) aryl, substituted or unsubstituted (3-30 membered) _{heteroaryl, -NR 7 R 8, -SiR 9} R 10 R 11, -SR 12 , _-OR 13, -COR ₁₄ or _-B (oR 15), or represents _{(oR 16),} Oh Or linked to adjacent substituent (s) to form a substituted or unsubstituted monocyclic or polycyclic (C3-C30) alicyclic or aromatic ring; May be substituted with at least one heteroatom selected from nitrogen, oxygen, and sulfur, and preferably each independently represents hydrogen or —NR ₇ R ₈ or an adjacent substituent ( A substituted or unsubstituted monocyclic or polycyclic (C6-C20) alicyclic or aromatic ring, more preferably each independently hydrogen or- Represents NR ₇ R ₈ or is linked to adjacent substituent (s) to form an unsubstituted monocyclic (C 6 -C 20) aromatic ring.

Each of R _{5 to} R ₁₆ independently represents substituted or unsubstituted (C1-C30) alkyl, substituted or unsubstituted (C6-C30) aryl, or substituted or unsubstituted (3 to 30 membered) heteroaryl; Or linked to adjacent substituent (s) to form a substituted or unsubstituted monocyclic or polycyclic (C3-C30) alicyclic or aromatic ring, preferably each independently A substituted or unsubstituted (C1-C6) alkyl, or substituted or unsubstituted (C6-C20) aryl, or linked to adjacent substituent (s) to form a substituted or unsubstituted monocyclic ring A cyclic or polycyclic (C3-C30) alicyclic or aromatic ring, more preferably each independently an unsubstituted (C1-C6) alkyl, or unsubstituted ( 6-C20) or aryl, or in conjunction with an adjacent substituent (s), unsubstituted polycyclic (C3-C30) to form an aromatic ring.

When n is 1 or 2, L ₁ represents a single bond, substituted or unsubstituted (C6-C30) arylene, or substituted or unsubstituted (3 to 30 membered) heteroarylene, preferably a single bond or substituted Or an unsubstituted (C6-C20) arylene is represented, More preferably, an unsubstituted (C6-C20) arylene is represented.

When n is 0, L ₁ represents substituted or unsubstituted (C1-C30) alkyl, substituted or unsubstituted (C6-C30) aryl, or substituted or unsubstituted (3 to 30 membered) heteroaryl, preferably Represents substituted or unsubstituted (C6-C20) aryl, more preferably unsubstituted (C6-C20) aryl.

According to one embodiment of the present invention, in Formula 1 above, Ar ₁ and Ar ₂ are each independently substituted or unsubstituted (C 6 -C 20) aryl, or substituted or unsubstituted (5-20 membered) hetero. Represents aryl, X represents —O—, —S—, or —C (R ₅ ) (R ₆ ) —, and R _{1 to} R ₄ each independently represents hydrogen or —NR ₇ R ₈ . Or linked to adjacent substituent (s) to form a substituted or unsubstituted monocyclic or polycyclic (C6-C20) alicyclic or aromatic ring, R ₅ to Each R ₈ independently represents substituted or unsubstituted (C 1 -C 6) alkyl, or substituted or unsubstituted (C 6 -C 20) aryl, or linked to adjacent substituent (s) Or unsubstituted monocyclic or Cyclic (C3-C30) to form a ring alicyclic or aromatic, when n is 1 or 2, _{L 1} represents a single bond or a substituted or unsubstituted (C6-C20) arylene, n When is 0, L ₁ represents substituted or unsubstituted (C6-C20) aryl.

According to another embodiment of the present invention, in Formula 1 above, Ar ₁ and Ar ₂ are each independently unsubstituted or substituted with (C1-C6) alkyl or (C6-C12) aryl (C6 -C20) an aryl, or unsubstituted or (C6-C12) substituted with an aryl (5-20 membered) heteroaryl, X is, -O -, - S-, or -C _(R 5) (R ₆ )-and R _{1 to} R ₄ each independently represent hydrogen or —NR ₇ R ₈ or are linked to adjacent substituent (s) to form an unsubstituted monocyclic ( C6-C20) forms an aromatic ring, R _{5 to} R ₈ each independently represents an unsubstituted (C1-C6) alkyl or unsubstituted (C6-C20) aryl, or an adjacent substituent ( Multiple) Formula (C3-C30) to form an aromatic ring, when n is 1 or 2, _{L 1} is an unsubstituted (C6-C20) arylene, n is 0, _{L 1} is an unsubstituted (C6-C20) represents aryl.

  Specific compounds of the present invention include, but are not limited to, the following compounds:

  The organic electroluminescent compounds of the present invention can be prepared by synthetic methods known to those skilled in the art. For example, they can be prepared according to the following reaction scheme.

In the scheme, R _{1 to} R ₄ , X, Ar ₁ , Ar ₂ , L ₁ , n, and ad are as defined in Formula 1 above, and Hal represents halogen.

  The present invention provides an organic electroluminescent material comprising an organic electroluminescent compound of Formula 1 and an organic electroluminescent device comprising the material.

  The above material may consist of the organic electroluminescent compound alone according to the present invention or may further comprise conventional materials commonly used for organic electroluminescent materials.

  The organic electroluminescent device includes a first electrode, a second electrode, and at least one organic layer between the first electrode and the second electrode. The organic layer can include at least one organic electroluminescent compound of Formula 1.

  One of the first and second electrodes is an anode and the other is a cathode. The organic layer includes a light emitting layer, and at least one selected from the group consisting of a hole injection layer, a hole transport layer, an electron transport layer, an electron injection layer, an intermediate layer, a hole blocking layer, and an electron blocking layer. One layer may further be included.

  The organic electroluminescent compound according to the present invention may be included in at least one of the light emitting layer and the hole transport layer. When used in a hole transport layer, the organic electroluminescent compound represented by Formula 1 may be included as a hole transport material. When used in the light emitting layer, the organic electroluminescent compound represented by Formula 1 can be included as a host material.

  The organic electroluminescent device containing the organic electroluminescent compound of the present invention may further contain one or more compounds in addition to the organic electroluminescent compound according to the present invention as a host material, and may further contain one or more dopants.

  When the organic electroluminescent compound according to the present invention is included as a host material (first host material), other compounds may be included as a second host material. In this specification, the ratio between the first host material and the second host material is in the range of 1:99 to 99: 1.

  Host materials other than organic electroluminescent compounds according to the present invention can be derived from any of the known phosphorescent hosts. In particular, a phosphorescent host selected from the group consisting of the following compounds of formulas 11 to 13 is preferable from the viewpoint of luminous efficiency.

  In the formula, Cz represents the following structure:

R _{21 to} R ₂₄ are each independently hydrogen, deuterium, halogen, substituted or unsubstituted (C 1 -C 30) alkyl, unsubstituted (C 6 -C 30) aryl substituted, substituted or unsubstituted (3 to 30 members) ) Represents heteroaryl, or -SiR ₂₅ R ₂₆ R ₂₇
R _{25 to} R ₂₇ each independently represent a substituted or unsubstituted (C1-C30) alkyl, or a substituted or unsubstituted (C6-C30) aryl,
L ₄ represents a single bond, a substituted or unsubstituted (C6-C30) arylene, or a substituted or unsubstituted (5-30 membered) heteroarylene,
M represents substituted or unsubstituted (C6-C30) aryl, or substituted or unsubstituted (5-30 membered) heteroaryl,
Y ₁ and Y ₂ each independently represent —O—, —S—, —N (R ₃₁ ) —, or —C (R ₃₂ ) (R ₃₃ ) —, provided that Y ₁ and Y ₂ is not present at the same time,
R _{31 to} R ₃₃ each independently represents substituted or unsubstituted (C1-C30) alkyl, substituted or unsubstituted (C6-C30) aryl, or substituted or unsubstituted (5 to 30 membered) heteroaryl, R ₃₂ and R ₃₃ may be the same or different,
h and i each independently represent an integer of 1 to 3,
j, k, p, and q each independently represent an integer of 0 to 4;
When h, i, j, k, p, or q is an integer of 2 or more, each of (Cz−L ₄ ), each of (Cz), each of R ₂₁ , each of R ₂₂ , and each of R ₂₃ Or each of R ₂₄ may be the same or different.

  In particular, preferred examples of host materials are as follows:

  [Wherein TPS represents triphenylsilyl].

  The dopant contained in the organic electroluminescent device according to the invention is preferably at least one phosphorescent dopant. The dopant material applied to the organic electroluminescent device according to the present invention is, but not limited to, preferably selected from iridium, osmium, copper and platinum metallized complex compounds, more preferably iridium, It may be selected from ortho-metalated complex compounds of osmium, copper and platinum, even more preferably ortho-metalated iridium complex compounds.

  The phosphorescent dopant may preferably be selected from compounds represented by the following formulas 101-103.

  Where L is selected from the following structures:

R ₁₀₀ represents hydrogen or substituted or unsubstituted (C1-C30) alkyl;
R ₁₀₁ -R ₁₀₉ and R ₁₁₁ -R ₁₂₃ are each independently hydrogen, deuterium, halogen, unsubstituted or (C1-C30) alkyl, cyano, substituted or non-substituted with halogen (s). Represents substituted (C1-C30) alkoxy, or substituted or unsubstituted (C3-C30) cycloalkyl, R _{120 to} R ₁₂₃ are linked to adjacent substituent (s) to form a monocyclic or polycyclic ring A (3 to 30 membered) alicyclic or aromatic ring such as quinoline,
R _{124 to} R ₁₂₇ each independently represents hydrogen, deuterium, halogen, substituted or unsubstituted (C 1 -C 30) alkyl, or substituted or unsubstituted (C 6 -C 30) aryl, and R _{124 to} R ₁₂₇ are When they are aryl groups, they are linked to adjacent substituent (s) to form monocyclic or polycyclic (3 to 30 membered) alicyclic or aromatic rings such as fluorene. Get
R _{201 to} R ₂₁₁ each independently represents hydrogen, deuterium, halogen, or (C 1 -C 30) alkyl that is unsubstituted or substituted with halogen (s);
r and s each independently represent an integer of 1 to 3, and when r or s is an integer of 2 or more, each of R ₁₀₀ may be the same or different;
e represents an integer of 1 to 3.

  In particular, the phosphorescent dopant material includes:

  In another embodiment of the present invention, a compound for preparing an organic electroluminescent device is provided. The present compounds include compounds according to the present invention as host materials or hole transport materials.

  Moreover, the organic electroluminescent device according to the present invention comprises a first electrode, a second electrode, and at least one organic layer between the first electrode and the second electrode. The organic layer includes a light emitting layer, and the light emitting layer may include a compound for preparing an organic electroluminescent device according to the present invention.

  The organic electroluminescent device according to the present invention may further include at least one compound selected from the group consisting of an arylamine-based compound and a styrylarylamine-based compound in addition to the organic electroluminescent compound represented by Formula 1.

  In the organic electroluminescent device according to the present invention, the organic layer is composed of a Group 1 metal, a Group 2 metal, a 4th transition metal, a 5th transition metal, a lanthanide, and a d orbital transition element of the periodic table It may further comprise at least one metal selected from the group consisting of organic metals, or at least one complex compound containing the metal. The organic layer may further include a light emitting layer and a charge generation layer.

  Moreover, the organic electroluminescent device according to the present invention comprises at least one emissive layer containing, in addition to the compound according to the present invention, a blue electroluminescent compound, a red electroluminescent compound, or a green electroluminescent compound known in the art. Further inclusions can emit white light. Also, if required, a yellow or orange light emitting layer can be included in the device.

According to the present invention, at least one layer (hereinafter “surface layer”) is preferably an internal surface of one or both electrode (s), preferably selected from chalcogenide layers, metal halide layers, and metal oxide layers. Arranged on top (s). In particular, a chalcogenide (including oxide) layer of silicon or aluminum is preferably disposed on the anode surface of the electroluminescent medium layer, and the metal halide layer or metal oxide layer is preferably of the electroluminescent medium layer. Located on the cathode surface. Such a surface layer provides operational stability for the organic electroluminescent device. Preferably, the chalcogenide includes SiO _X (1 ≦ X ≦ 2), AlO _X (1 ≦ X ≦ 1.5), SiON, SiAlON, etc., and the metal halide layer includes LiF, MgF ₂ , CaF _2. And rare earth metal fluorides, and the metal oxides include Cs ₂ O, Li ₂ O, MgO, SrO, BaO, CaO, and the like.

  In the organic electroluminescent device according to the present invention, the mixed region of the electron transport compound and the reducing dopant or the mixed region of the hole transport compound and the oxidizing dopant is preferably on at least one surface of the pair of electrodes. Be placed. In this case, the electron transport compound is reduced to an anion, thus making it easier to inject and transport electrons from the mixed region to the electroluminescent medium. Further, the hole transport compound is oxidized to a cation, thus making it easier to inject and transport holes from the mixed region to the electroluminescent medium. Preferably, the oxidizing dopant includes various Lewis acids and acceptor compounds, and the reducing dopant includes alkali metals, alkali metal compounds, alkaline earth metals, rare earth metals, and mixtures thereof. The reducing dopant layer can be used as a charge generation layer to prepare an electroluminescent device that has two or more electroluminescent layers and emits white light.

  In order to form each layer of the organic electroluminescent device according to the present invention, dry film forming methods such as vacuum deposition, sputtering, plasma and ion plating methods, or wet film forming methods such as spin coating, dip coating, and flow coating methods are used. The method can be used.

  When using a wet film formation method, a thin film can be formed by dissolving or diffusing the material forming each layer in any suitable solvent such as ethanol, chloroform, tetrahydrofuran, dioxane, and the like. The solvent can be any solvent in which the material forming each layer can be dissolved or diffused and there is no problem with the film forming ability.

  Hereinafter, the organic electroluminescent compound, the preparation method of the present compound, and the light emission characteristics of the device will be described in detail with reference to the following examples.

  Example 1: Preparation of compound C-6

Preparation of Compound 1-1 Dibenzofuran (30 g, 178 mmol) and 500 mL of tetrahydrofuran were introduced into a reaction vessel, and then the vessel was cooled to −78 ° C. under a nitrogen atmosphere. Next, 71 mL (2.5 M, 178 mmol) of N-butyllithium was slowly added dropwise to the mixture. The mixture was stirred at -78 ° C for 30 minutes, then stirred at room temperature for 3 hours and cooled to -78 ° C. Thereafter, fluorenone (32 g, 178 mmol) dissolved in 500 mL of tetrahydrofuran was slowly added dropwise to the mixture. After the addition, the reaction temperature was slowly warmed to room temperature and the mixture was stirred for 16 hours. Then, an aqueous ammonium chloride solution was added to the reaction solution to complete the reaction, and the reaction solution was extracted with ethyl acetate. The extracted organic layer was then dried using magnesium sulfate and the solvent was removed using a rotary evaporator. The remaining material was then purified by column chromatography to give compound 1-1 (43 g, 70%).

Preparation of Compound 1-2 After introducing Compound 1-1 (10 g, 28.7 mmol), 4-bromodiphenylamine (7.4 g, 30.1 mmol), and 570 mL of methylene chloride (MC) into the reaction vessel, Introduced into a nitrogen atmosphere. Thereafter, boron trifluoride diethyl ether (3.8 mL, 30.1 mmol) dissolved in 120 mL of methylene chloride was slowly added dropwise to the mixture. After the mixture was stirred at room temperature for 2 hours, ethanol and distilled water were added thereto to complete the reaction, and the mixture was extracted with methylene chloride. The extracted organic layer was then dried using magnesium sulfate and the solvent was removed using a rotary evaporator. The remaining material was then purified by column chromatography to give compound 1-2 (15 g, 95%).

Preparation of Compound 1-3 Compound 1-2 (15 g, 26.9 mmol), phenylboronic acid (3.6 g, 29.6 mmol), tetrakis (triphenylphosphine) palladium (1.5 g, 1.34 mmol), potassium carbonate (8.9 g, 64.7 mmol), 160 mL of toluene, 40 mL of ethanol, and 40 mL of distilled water were introduced into the reaction vessel, and then the mixture was stirred at 120 ° C. for 1 hour. After the reaction, the mixture was washed with distilled water, and the organic layer was extracted with ethyl acetate. The extracted organic layer was dried using magnesium sulfate and the solvent was removed using a rotary evaporator. The remaining material was then purified by column chromatography to give compound 1-3 (12.3 g, 80%).

Preparation of Compound C-6 Compound 1-3 (8 g, 13.8 mmol), 4-bromobiphenyl (3.4 g, 14.5 mmol), palladium acetate (0.12 g, 0.55 mmol), S-phos (0. 57 g, 1.38 mmol), sodium tert-butoxide (3.3 g, 34.7 mmol), and 70 mL of toluene were introduced into the reaction vessel, and the mixture was stirred under reflux for 1 hour. After the reaction, the mixture was washed with distilled water, and the organic layer was extracted with methylene chloride (MC). The extracted organic layer was dried using magnesium sulfate and the solvent was removed using a rotary evaporator. The remaining material was then purified by column chromatography to give compound C-6 (8.2 g, 81%).

  UV: 360 nm (in toluene), PL: 396 nm (in toluene), MP: 270 ° C., MW: 727.89, Tg: 140 ° C.

  Example 2: Preparation of compound C-8

Preparation of Compound 2-2 After introducing Compound 2-1 (30 g, 86.1 mmol), 4-bromotriphenylamine (84 g, 259 mmol), and 600 mL of methylene chloride (MC) into the reaction vessel, the vessel was placed in a nitrogen atmosphere. Introduced. Thereafter, 3 mL of Eaton's reagent was slowly added dropwise to the mixture. After the mixture was stirred at room temperature for 2 hours, ethanol and distilled water were added thereto to complete the reaction, and the mixture was extracted with methylene chloride. The extracted organic layer was then dried using magnesium sulfate and the solvent was removed using a rotary evaporator. The remaining material was then purified by column chromatography to give compound 2-2 (42 g, 74%).

Preparation of Compound C-8 Compound 2-2 (10 g, 26.9 mmol), 2-naphthylboronic acid (3.2 g, 18.4 mmol), tetrakis (triphenylphosphine) palladium (0.7 g, 1.08 mmol), After potassium carbonate (5.3 g, 38.3 mmol), 60 mL of toluene, 20 mL of ethanol, and 20 mL of distilled water were introduced into the reaction vessel, the mixture was stirred at 120 ° C. for 3 hours. After the reaction, the mixture was washed with distilled water, and the organic layer was extracted with ethyl acetate. The extracted organic layer was dried using magnesium sulfate and the solvent was removed using a rotary evaporator. The residual material was then purified by column chromatography to give compound C-8 (7.7 g, 72%).

  UV: 324 nm (in toluene), PL: 407 nm (in toluene), MP: 145 ° C., MW: 701.27, Tg: 134 ° C.

  Example 3: Preparation of compound C-38

Preparation of Compound 3-1 After introducing 2-bromodibenzothiophene (27 g, 103 mmol) and 340 mL of tetrahydrofuran into the reaction vessel, the vessel was cooled to −78 ° C. under a nitrogen atmosphere. Next, 33 mL (2.5 M, 82 mmol) of N-butyllithium was slowly added dropwise to the mixture. After the mixture was stirred at −78 ° C. for 2 hours, 9H-fluoren-9-one (19 g, 103 mmol) dissolved in 340 mL of tetrahydrofuran was slowly added dropwise to the mixture. After the addition, the reaction temperature was slowly warmed to room temperature and the mixture was stirred for 30 minutes. Aqueous ammonium chloride was then added to the reaction solution to complete the reaction and the mixture was extracted with ethyl acetate. The extracted organic layer was then dried using magnesium sulfate and the solvent was removed using a rotary evaporator. The residual material was then purified by column chromatography to give compound 3-1 (23 g, 61%).

Preparation of Compound 3-2 Compound 3-1 (23 g, 63 mmol) and 4-bromotriphenylamine (41 g, 126 mmol) were dissolved in 315 mL of dichloromethane in a reaction vessel, and then 1.4 mL (0.9 M) of Eaton's reagent. 1.3 mmol) was slowly added dropwise to the mixture. After the mixture was stirred at room temperature for 30 minutes, the reaction was completed with sodium bicarbonate and the mixture was extracted with ethyl acetate. The extracted organic layer was then dried using magnesium sulfate and the solvent was removed using a rotary evaporator. The remaining material was then purified by column chromatography to give compound 3-2 (27 g, 65%).

Preparation of Compound C-38 Compound 3-2 (10 g, 14.91 mmol), 2-naphthylboronic acid (3.1 g, 17.89 mmol), tetrakis (triphenylphosphine) palladium (0.5 g, 0.45 mmol), Sodium carbonate (4 g, 37.28 mmol), 76 mL of toluene, 19 mL of ethanol, and 19 mL of distilled water were introduced into the reaction vessel, and then the mixture was stirred at 120 ° C. for 6 hours. After the reaction, the mixture was washed with distilled water and extracted with ethyl acetate. The extracted organic layer was dried using magnesium sulfate and the solvent was removed using a rotary evaporator. The remaining material was then purified by column chromatography to give compound C-38 (1.2 g, 11%).

  UV: 382 nm (in toluene), PL: 405 nm (in toluene), MP: 230 ° C., MW: 717.92, Tg: 140 ° C.

  Example 4: Preparation of compound C-9

Preparation of Compound 4-1 After introducing dibenzothiophene (30 g, 163 mmol) and 400 mL of tetrahydrofuran into the reaction vessel, the vessel was cooled to −78 ° C. under a nitrogen atmosphere. Next, 65 mL (2.5 M, 163 mmol) of N-butyllithium was slowly added dropwise to the mixture. After the mixture was stirred at −78 ° C. for 2 hours, 9H-fluoren-9-one (29 g, 163 mmol) dissolved in 400 mL of tetrahydrofuran was slowly added dropwise to the mixture. After the addition, the reaction temperature was slowly warmed to room temperature and the mixture was stirred for 30 minutes. Aqueous ammonium chloride was then added to the reaction solution to complete the reaction and the mixture was extracted with ethyl acetate. The extracted organic layer was then dried using magnesium sulfate and the solvent was removed using a rotary evaporator. The remaining material was then purified by column chromatography to give compound 4-1 (20 g, 34%).

Preparation of Compound 4-2 Compound 4-1 (7 g, 19 mmol) and 4-bromotriphenylamine (16 g, 48 mmol) were dissolved in 96 mL of dichloromethane in a reaction vessel, and then 0.5 mL (0.9 M) of Eaton's reagent was used. , 0.4 mmol) was slowly added dropwise to the mixture. After the mixture was stirred at room temperature for 30 minutes, the reaction was completed with sodium bicarbonate and the mixture was extracted with ethyl acetate. The extracted organic layer was then dried using magnesium sulfate and the solvent was removed using a rotary evaporator. The remaining material was then purified by column chromatography to give compound 4-2 (8 g, 62%).

Preparation of Compound C-9 Compound 4-2 (8 g, 11.93 mmol), 2-naphthylboronic acid (2.5 g, 14.31 mmol), tetrakis (triphenylphosphine) palladium (0.4 g, 0.36 mmol), After introducing sodium carbonate (3.2 g, 29.83 mmol), 60 mL of toluene, 15 mL of ethanol, and 15 mL of distilled water into the reaction vessel, the mixture was stirred at 120 ° C. for 6 hours. After the reaction, the mixture was washed with distilled water and extracted with ethyl acetate. The extracted organic layer was dried using magnesium sulfate and the solvent was removed using a rotary evaporator. The residual material was then purified by column chromatography to give compound C-9 (4.3 g, 50%).

  UV: 390 nm (in toluene), PL: 407 nm (in toluene), MP: 215 ° C., MW: 717.92, Tg: 151 ° C.

  Example 5: Preparation of compound C-78

Preparation of Compound C-78 Compound 1-3 (5.6 g, 9.72 mmol), 2-bromo-9,9-dimethylfluorene (2.9 g, 10.7 mmol), palladium acetate (0.08 g, 0.38 mmol) ), S-phos (0.39 g, 0.97 mmol), sodium tert-butoxide (2.3 g, 24.3 mmol), and 50 mL of toluene were introduced into the reaction vessel, and the mixture was stirred at reflux for 1 hour. . After the reaction, the mixture was washed with distilled water, and the organic layer was extracted with methylene chloride (MC). The extracted organic layer was dried using magnesium sulfate and the solvent was removed using a rotary evaporator. The residual material was then purified by column chromatography to give compound C-78 (6.2 g, 83%).

  UV: 322 nm (in toluene), PL: 398 nm (in toluene), MP: 242 ° C., MW: 767.95, Tg: 151 ° C.

  Example 6: Preparation of compound C-12

Preparation of Compound 5-2 Compound 1-1 (10 g, 28.7 mmol), diphenylamine (14 g, 86.1 mmol), and 570 mL of methylene chloride (MC) were introduced into the reaction vessel, and then the vessel was introduced into a nitrogen atmosphere. . Thereafter, boron trifluoride diethyl ether (3.8 mL, 30.1 mmol) dissolved in 120 mL of methylene chloride was slowly added dropwise to the mixture. After the mixture was stirred at room temperature for 2 hours, ethanol and distilled water were added thereto to complete the reaction, and the mixture was extracted with methylene chloride. The extracted organic layer was then dried using magnesium sulfate and the solvent was removed using a rotary evaporator. The remaining material was then purified by column chromatography to give compound 5-2 (11 g, 78%).

Preparation of Compound C-12 Compound 5-2 (11 g, 22.1 mmol), 2-bromo-9,9-dimethylfluorene (6.6 g, 24.4 mmol), palladium acetate (0.19 g, 0.88 mmol), After introducing S-phos (0.91 g, 2.21 mmol), sodium tert-butoxide (5.3 g, 55.4 mmol), and 110 mL of toluene into the reaction vessel, the mixture was stirred under reflux for 1 hour. After the reaction, the mixture was washed with distilled water, and the organic layer was extracted with methylene chloride (MC). The extracted organic layer was dried using magnesium sulfate and the solvent was removed using a rotary evaporator. The remaining material was then purified by column chromatography to give compound C-12 (12 g, 79%).

  UV: 344 nm (in toluene), PL: 387 nm (in toluene), MP: 225 ° C., MW: 691.86, Tg: 137 ° C.

  Example 7: Preparation of compound C-79

Preparation of Compound C-79 Compound 2-2 (6.7 g, 10.2 mmol), 4-biphenylboronic acid (2.4 g, 12.2 mmol), tetrakis (triphenylphosphine) palladium (0.47 g, 0.41 mmol) ), Potassium carbonate (3.5 g, 25.5 mmol), 45 mL of toluene, 15 mL of ethanol, and 15 mL of distilled water were introduced into the reaction vessel, and the mixture was stirred at 120 ° C. for 3 hours. After the reaction, the mixture was washed with distilled water, and the organic layer was extracted with ethyl acetate. The extracted organic layer was dried using magnesium sulfate and the solvent was removed using a rotary evaporator. The remaining material was then purified by column chromatography to give compound C-79 (5.0 g, 67%).

  UV: 344 nm (in toluene), PL: 397 nm (in toluene), MP: 255 ° C., MW: 727.29, Tg: 141 ° C.

  Example 8: Preparation of compound C-80

Preparation of Compound 6-1 After introducing 2-bromo-9,9′-dimethylfluorene (40 g, 146 mmol) and 500 mL of tetrahydrofuran into the reaction vessel, the vessel was cooled to −78 ° C. under a nitrogen atmosphere. Next, 60 mL (2.5 M, 146 mmol) of N-butyllithium was slowly added dropwise to the mixture. After the mixture was stirred at −78 ° C. for 90 minutes, fluorenone (26 g, 146 mmol) dissolved in 500 mL of tetrahydrofuran was slowly added dropwise to the mixture. After the addition, the reaction temperature was slowly warmed to room temperature and the mixture was stirred for 16 hours. Aqueous ammonium chloride was then added to the reaction solution to complete the reaction and the mixture was extracted with ethyl acetate. The extracted organic layer was then dried using magnesium sulfate and the solvent was removed using a rotary evaporator. The remaining material was then purified by column chromatography to give compound 6-1 (41 g, 72%).

Preparation of Compound C-80 Compound 6-1 (10 g, 26.7 mmol), Compound 6-2 (CAS number: 122215-84-3) (10.6 g, 26.7 mmol), and 134 mL of methylene chloride (MC) were added. After introduction into the reaction vessel, the vessel was introduced into a nitrogen atmosphere. Thereafter, 0.6 mL of Eaton's reagent was slowly added dropwise to the mixture. After the mixture was stirred at room temperature for 2 hours, ethanol and distilled water were added thereto to complete the reaction, and the mixture was extracted with methylene chloride. The extracted organic layer was then dried using magnesium sulfate and the solvent was removed using a rotary evaporator. The remaining material was then purified by column chromatography to give compound C-80 (17 g, 85%).

  UV: 378 nm (in toluene), PL: 395 nm (in toluene), MP: 178 ° C., MW: 753.34, Tg: 143 ° C.

  Example 9: Preparation of compound C-107

Preparation of Compound 7-1 2-bromo-9,9-diphenyl-9H-fluorene (15 g, 37.75 mmol) was dissolved in 125 mL of tetrahydrofuran in a reaction vessel, and then 15 mL of n-butyllithium (2.5 M 37.75 mmol) was slowly added dropwise to the mixture at −78 ° C. and the mixture was stirred for 2 hours. 9-Fluoren-one (6.2 g, 34.32 mmol) was then dissolved in 125 mL of tetrahydrofuran and slowly added dropwise to the mixture. The mixture was then stirred for 5 hours. After the reaction, the mixture was washed with distilled water and extracted with ethyl acetate. The extracted organic layer was then dried using magnesium sulfate and the solvent was removed using a rotary evaporator. The remaining material was then purified by column chromatography to give compound 7-1 (11.7 g, 62%).

Preparation of Compound C-107 Compound 7-1 (10 g, 20.06 mmol) and 9,9-dimethyl-N, N-diphenyl-9H-fluoren-2-amine (14.5 g, 40.12 mmol) in a reaction vessel Was dissolved in 100 mL of dichloromethane and Eaton's reagent (0.4 mL, 0.40 mmol) was slowly added dropwise thereto and stirred for 2 hours. After the reaction, the mixture was washed with distilled water and extracted with ethyl acetate. The extracted organic layer was then dried using magnesium sulfate and the solvent was removed using a rotary evaporator. The residual material was then purified by column chromatography to give compound C-107 (6.5 g, 38%).

  UV: 376 nm (in toluene), PL: 389 nm (in toluene), MP: 175 ° C., MW: 842.08, Tg: 150 ° C.

  Example 10: Preparation of compound C-81

Preparation of Compound 8-1 2-Bromofluorene (40 g, 146 mmol) and 500 mL of tetrahydrofuran were introduced into the reaction vessel, and then the vessel was cooled to −78 ° C. under a nitrogen atmosphere. N-butyllithium (60 mL, 146 mmol) was then slowly added dropwise to the mixture. After stirring the mixture for 2 hours, 9H-fluoren-9-one (26 g, 146 mmol) dissolved in 500 mL of tetrahydrofuran was slowly added dropwise to the mixture. After the addition, the reaction temperature was slowly warmed to room temperature and the mixture was stirred for 30 minutes. Aqueous ammonium chloride was then added to the reaction solution to complete the reaction and the mixture was extracted with ethyl acetate. The extracted organic layer was then dried using magnesium sulfate and the solvent was removed using a rotary evaporator. The remaining material was then purified by column chromatography to give compound 8-1 (41 g, 75%).

Preparation of Compound 8-2 Compound 8-1 (16 g, 43 mmol) and 4-bromotriphenylamine (28 g, 86 mmol) were dissolved in 213 mL of dichloromethane in a reaction vessel, and then Eaton's reagent (1 mL, 0.9 mmol). Was slowly added dropwise to the mixture. After the mixture was stirred at room temperature for 30 minutes, the reaction was completed with sodium bicarbonate and the mixture was extracted with ethyl acetate. The extracted organic layer was then dried using magnesium sulfate and the solvent was removed using a rotary evaporator. The remaining material was then purified by column chromatography to give compound 8-2 (20 g, 69%).

Preparation of Compound C-81 Compound 8-2 (10 g, 15 mmol), 2-naphthylboronic acid (3 g, 18 mmol), tetrakis (triphenylphosphine) palladium (0.5 g, 0.4 mmol), sodium carbonate (4 g, 37 mmol) ), 76 mL of toluene, and 19 mL of ethanol were introduced into the reaction vessel, 19 mL of distilled water was added thereto, and the mixture was stirred at 120 ° C. for 2 hours. After the reaction, the mixture was washed with distilled water and extracted with ethyl acetate. The extracted organic layer was dried using magnesium sulfate and the solvent was removed using a rotary evaporator. The remaining material was then purified by column chromatography to give compound C-81 (5.3 g, 50%).

  UV: 388 nm (in toluene), PL: 405 nm (in toluene), MP: 152 ° C., MW: 727.93, Tg: 136 ° C.

  Example 11: Preparation of compound C-108

Preparation of Compound 9-1 After introducing 2-bromofluorene (40 g, 146 mmol) and 500 mL of tetrahydrofuran into the reaction vessel, the vessel was cooled to −78 ° C. under a nitrogen atmosphere. N-butyllithium (60 mL, 146 mmol) was then slowly added dropwise to the mixture. After stirring the mixture for 2 hours, 9H-fluoren-9-one (26 g, 146 mmol) dissolved in 500 mL of tetrahydrofuran was slowly added dropwise to the mixture. After the addition, the reaction temperature was slowly warmed to room temperature and the mixture was stirred for 30 minutes. Aqueous ammonium chloride was then added to the reaction solution to complete the reaction and the mixture was extracted with ethyl acetate. The extracted organic layer was then dried using magnesium sulfate and the solvent was removed using a rotary evaporator. The remaining material was then purified by column chromatography to give compound 9-1 (41 g, 75%).

Preparation of Compound C-108 Compound 9-1 (10 g, 26.70 mmol) and N, N-diphenyl- [1,1′-biphenyl] -4-amine (17.2 g, 53.40 mmol) were added in a reaction vessel. After dissolving in 130 mL of dichloromethane, Eaton's reagent (0.6 mL, 0.53 mmol) was slowly added dropwise to the mixture. After the mixture was stirred at room temperature for 30 minutes, the reaction was completed with sodium bicarbonate and the mixture was extracted with ethyl acetate. The extracted organic layer was then dried using magnesium sulfate and the solvent was removed using a rotary evaporator. The residual material was then purified by column chromatography to give compound C-108 (6.7 g, 37%).

  UV: 370 nm (in toluene), PL: 391 nm (in toluene), MP: 153 ° C., MW: 677.87, Tg: 129 ° C.

Device Example 1: Preparation of an OLED device using an organic electroluminescent compound according to the present invention An OLED device was manufactured using a luminescent material according to the present invention. A transparent electrode indium tin oxide (ITO) thin film (15Ω / sq) on a glass substrate for an organic light emitting diode (OLED) device (Geomatec, Japan) was subjected to ultrasonic cleaning using acetone and isopropane alcohol sequentially. It was then stored in isopropane alcohol. Next, the ITO substrate was placed on the substrate holder of the vacuum deposition apparatus. ^{N 1, N 1 '- (} [1,1'- biphenyl] -4,4'-diyl) bis ^{(N 1} - ^{(naphthalen-1-yl)} -N ^{4, N} 4 - diphenyl-1,4 Diamine) was introduced into the cell of the vacuum deposition apparatus, and then the pressure in the chamber of the apparatus was controlled to 10 ⁻⁶ torr. Thereafter, current was applied to the cell to evaporate the introduced material, thereby forming a hole injection layer having a thickness of 60 nm on the ITO substrate. Compound C-6 is then introduced into another cell of the vacuum evaporation apparatus and evaporated by applying a current to the cell, thereby having a hole transport layer having a thickness of 20 nm on the hole injection layer Formed. 9- (3- (4,6-diphenyl-1,3,5-triazin-2-yl) phenyl) -9′-phenyl-9H, 9′H-3,3′-bicarbazole is then used as the host material. Was introduced into one cell of the vacuum deposition apparatus, and Compound D-1 was introduced into another cell as a dopant. The two materials were evaporated at different rates and deposited with a doping amount of 15% by weight based on the total amount of host and dopant to form a light emitting layer having a thickness of 30 nm on the hole transport layer. Then 2- (4- (9,10-di (naphthalen-2-yl) anthracen-2-yl) phenyl) -1-phenyl-1H-benzo [d] imidazole was introduced into one cell, Lithium quinolinate was introduced into another cell. The two materials were evaporated at the same rate and each was deposited with a doping amount of 50% by weight to form an electron transport layer having a thickness of 30 nm on the light emitting layer. Next, lithium quinolate was deposited on the electron transport layer as an electron injection layer having a thickness of 2 nm, and then an Al cathode having a thickness of 150 nm was deposited on the electron injection layer by another vacuum deposition apparatus. . Thus, an OLED device was manufactured. All materials used to fabricate OLED devices were purified by vacuum sublimation at ^10-6 torr before use.

The manufactured OLED device showed a green emission with a luminance of 900 cd / m ² and a current density of 1.9 mA / cm ² .

  The time for the luminance to decrease to 80% at 15,000 nits was 250 hours or more.

Device Example 2: Preparation of an OLED device using an organic electroluminescent compound according to the present invention An OLED device was manufactured in the same manner as Device Example 1, except that a thickness of 20 nm was obtained by using Compound C-9. A vacuum deposition apparatus using 7- (4-([1,1′-biphenyl] -4-yl) quinazolin-2-yl) -7H-benzo [c] carbazole as a host. Into one cell, compound D-87 is introduced as a dopant into another cell, the two materials are evaporated at different rates, and they are added at a doping amount of 3% by weight based on the total amount of host and dopant. Except that a light emitting layer having a thickness of 30 nm is formed on the hole transport layer.

The manufactured OLED device showed red emission with a luminance of 1000 cd / m ² and a current density of 6.7 mA / cm ² .

  The time for the luminance to decrease to 80% at 5,000 nits was 200 hours or more.

Device Example 3: Manufacture of an OLED device using an organic electroluminescent compound according to the present invention An OLED device was manufactured in the same manner as Device Example 1, except that compound C-8 was used as the host for the hole transport layer. In contrast, the following compound H-1 and the following compound FD-1 with respect to the dopant were used.

The manufactured OLED device showed blue emission with a luminance of 800 cd / m ² and a current density of 16.3 mA / cm ² .

  The time for the luminance to decrease to 50% at 2,000 nits was 170 hours or more.

Device Example 4: Production of an OLED device using an organic electroluminescent compound according to the invention An OLED device was produced in the same manner as in Device Example 2, except that the compound C-78 was evaporated to a thickness of 20 nm. Except for the formation of a hole transport layer.

The manufactured OLED device showed red emission with a luminance of 1700 cd / m ² and a current density of 11.7 mA / cm ² .

  The time for the luminance to decrease to 80% at 5,000 nits was 210 hours or more.

Device Example 5: Preparation of an OLED device using an organic electroluminescent compound according to the present invention An OLED device was manufactured in the same manner as Device Example 1, except that the compound C-79 was evaporated to a thickness of 20 nm. Except for the formation of a hole transport layer.

The manufactured OLED device showed a green emission with a luminance of 3000 cd / m ² and a current density of 4.2 mA / cm ² .

  The time for the luminance to decrease to 80% at 15,000 nits was 240 hours or more.

Device Example 6: Preparation of an OLED device using an organic electroluminescent compound according to the present invention An OLED device was manufactured in the same manner as in Device Example 1, except that the compound C-12 was evaporated to a thickness of 20 nm. Except for the formation of a hole transport layer.

The manufactured OLED device showed green emission with a luminance of 1500 cd / m ² and a current density of 3.2 mA / cm ² .

  The time for the luminance to decrease to 80% at 15,000 nits was 270 hours or more.

Device Example 7: Preparation of an OLED device using an organic electroluminescent compound according to the present invention An OLED device was manufactured in the same manner as Device Example 3, except that the compound C-81 was evaporated to a thickness of 20 nm. Except for the formation of a hole transport layer.

The manufactured OLED device showed blue emission with a luminance of 1200 cd / m ² and a current density of 22.6 mA / cm ² .

  The time for the luminance to decrease to 50% at 2,000 nits was 130 hours or more.

Device Example 8: Production of an OLED device using an organic electroluminescent compound according to the invention An OLED device was produced in the same manner as in device example 1, except that the compound C-80 was evaporated to a thickness of 20 nm. Except for the formation of a hole transport layer.

The manufactured OLED device showed green emission with a luminance of 1500 cd / m ² and a current density of 2.84 mA / cm ² .

  The time for the luminance to decrease to 80% at 15,000 nits was 230 hours or more.

Device Example 9: Production of an OLED device using an organic electroluminescent compound according to the invention An OLED device was produced in the same manner as in device example 2, except that the compound C-107 was evaporated to a thickness of 20 nm. Except for the formation of a hole transport layer.

The manufactured OLED device showed red emission with a luminance of 2000 cd / m ² and a current density of 12.64 mA / cm ² .

  The time for the luminance to decrease to 80% at 5,000 nits was 200 hours or more.

Device Example 10: Preparation of an OLED device using an organic electroluminescent compound according to the present invention An OLED device was manufactured in the same manner as Device Example 2, except that the compound C-108 was evaporated to a thickness of 20 nm. Except for the formation of a hole transport layer.

The manufactured OLED device showed a red emission with a luminance of 700 cd / m ² and a current density of 4.29 mA / cm ² .

  The time for the luminance to decrease to 80% at 5,000 nits was 180 hours or more.

Comparative Example 1 Production of OLED Device Using Conventional Organic Electroluminescent Compound An OLED device was produced in the same manner as Device Example 1 except that N, N′-di (4-biphenyl) -N, N Except that '-di (4-biphenyl) -4,4'-diaminobiphenyl was evaporated to form a 20 nm thick hole transport layer.

The manufactured OLED device showed a green emission with a luminance of 12000 cd / m ² and a current density of 32.6 mA / cm ² .

  The time for the luminance to decrease to 80% at 15,000 nits was 230 hours or more.

Comparative Example 2: Production of an OLED device using a conventional organic electroluminescent compound An OLED device was produced in the same manner as Device Example 3, except that N, N'-di (4-biphenyl) -N, N Except that '-di (4-biphenyl) -4,4'-diaminobiphenyl was evaporated to form a 20 nm thick hole transport layer.

OLED devices made showed a blue light emission having a current density of luminance and 138.1mA / cm ² of 5000 cd / ^{m 2.}

  The time for the luminance to decrease to 50% at 2,000 nits was 130 hours or more.

Comparative Example 3: Manufacture of OLED Device Using Conventional Organic Electroluminescent Compound An OLED device was manufactured in the same manner as Device Example 2, except that N, N'-di (4-biphenyl) -N, N Except that '-di (4-biphenyl) -4,4'-diaminobiphenyl was evaporated to form a 20 nm thick hole transport layer.

The manufactured OLED device showed red emission with a luminance of 10,000 cd / m ² and a current density of 131.6 mA / cm ² .

  The time for the luminance to decrease to 80% at 5,000 nits was 180 hours or more.

Comparative Example 4: Manufacture of OLED Device Using Conventional Organic Electroluminescent Compound An OLED device was manufactured in the same manner as Device Example 1, except that 9,9-dimethyl-N, N-diphenyl-9H-fluorene Except that -2-amine (Tg = 43 ° C.) was evaporated to form a 20 nm thick hole transport layer.

The manufactured OLED device showed green emission with a luminance of 9000 cd / m ² and a current density of 20.8 mA / cm ² .

  The time for the luminance to decrease to 80% at 15,000 nits was 25 hours or more.

  The organic electroluminescent compounds according to the present invention have a high glass transition temperature, demonstrating that the current efficiency is higher than conventional compounds. Moreover, organic electroluminescent devices using organic electroluminescent compounds according to the present invention have excellent luminescent properties, in particular current and power efficiency.

Claims (6)

An organic electroluminescent compound represented by the following formula I,

Where
Whether Ar ₁ and Ar ₂ each independently represent substituted or unsubstituted (C1-C30) alkyl, substituted or unsubstituted (C6-C30) aryl, or substituted or unsubstituted (3 to 30 membered) heteroaryl Or linked to adjacent substituent (s) to form a monocyclic or polycyclic (C3-C30) alicyclic or aromatic ring, the carbon atom (s) being nitrogen, May be replaced with at least one heteroatom selected from oxygen and sulfur;
X is, -O -, - S-, or _{-C (R 5) (R 6} ) - represents,
R _{1 to} R ₄ are each independently hydrogen, deuterium, halogen, cyano, carboxyl, nitro, hydroxyl, substituted or unsubstituted (C1-C30) alkyl, substituted or unsubstituted (C2-C30) alkenyl, substituted Or unsubstituted (C2-C30) alkynyl, substituted or unsubstituted (C1-C30) alkoxy, substituted or unsubstituted (C3-C30) cycloalkyl, substituted or unsubstituted (C3-C30) cycloalkenyl, substituted or unsubstituted ( 3-7 membered) heterocycloalkyl, substituted or unsubstituted (C6-C30) aryl, substituted or unsubstituted (3-30 membered) _{heteroaryl, -NR 7 R 8, -SiR 9} R 10 R 11, -SR 12 , _-OR 13, -COR ₁₄ or _-B (oR 15), or represents _{(oR 16),} Oh Or linked to adjacent substituent (s) to form a substituted or unsubstituted monocyclic or polycyclic (C3-C30) alicyclic or aromatic ring; May be substituted with at least one heteroatom selected from nitrogen, oxygen, and sulfur,
Whether R _{5 to} R ₁₆ each independently represents substituted or unsubstituted (C1-C30) alkyl, substituted or unsubstituted (C6-C30) aryl, or substituted or unsubstituted (3 to 30 membered) heteroaryl; Or linked to adjacent substituent (s) to form a substituted or unsubstituted monocyclic or polycyclic (C3-C30) alicyclic or aromatic ring;
n is an integer from 0 to 2,
when n is 1 or 2, L ₁ represents a single bond, a substituted or unsubstituted (C6-C30) arylene, or a substituted or unsubstituted (3 to 30 membered) heteroarylene;
when n is 0, L ₁ represents substituted or unsubstituted (C1-C30) alkyl, substituted or unsubstituted (C6-C30) aryl, or substituted or unsubstituted (3-30 membered) heteroaryl;
a, b, and d each independently represent an integer of 1 to 4, and when a, b, or d is an integer of 2 or more, each of R ₁ , each of R ₂ , and R ₄ Each may be the same or different,
when c represents an integer of 1 to 3 and c is an integer of 2 or more, each of R ₃ may be the same or different;
The heterocycloalkyl and the heteroaryl (ene) each independently contain at least one heteroatom selected from B, N, O, S, P (═O), Si, and P; Organic electroluminescent compound. Ar ₁ , Ar ₂ , R _{1 to} R ₁₆ , and the substituted (C1-C30) alkyl, the substituted (C2-C30) alkenyl, the substituted (C2-C30) alkynyl, the substituted (C1-C30) in L ₁ ) Alkoxy, said substituted (C3-C30) cycloalkyl, said substituted (C3-C30) cycloalkenyl, said substituted (3-7 membered) heterocycloalkyl, said substituted (C6-C30) aryl (ene), and said substituted The substituents of (3-30 membered) heteroaryl (ene) are each independently deuterium, halogen, cyano, carboxyl, nitro, hydroxyl, (C1-C30) alkyl, halo (C1-C30) alkyl, ( C2-C30) alkenyl, (C2-C30) alkynyl, (C1-C30) alkoxy, (C1-C30) alkylthio, C3-C30) cycloalkyl, (C3-C30) cycloalkenyl, (3-7 membered) heterocycloalkyl, (C6-C30) aryloxy, (C6-C30) arylthio, unsubstituted or (C6-C30) aryl Substituted (3-30 membered) heteroaryl, unsubstituted or (3-30 membered) heteroaryl-substituted (C6-C30) aryl, tri (C1-C30) alkylsilyl, tri (C6-C30) aryl Silyl, di (C1-C30) alkyl (C6-C30) arylsilyl, (C1-C30) alkyldi (C6-C30) arylsilyl, amino, mono or di (C1-C30) alkylamino, mono or di (C6- C30) arylamino, (C1-C30) alkyl (C6-C30) arylamino, (C -C30) alkylcarbonyl, (C1-C30) alkoxycarbonyl, (C6-C30) arylcarbonyl, di (C6-C30) arylboronyl, di (C1-C30) alkylboronyl, (C1-C30) alkyl (C6 The at least one selected from the group consisting of -C30) arylboronyl, (C6-C30) aryl (C1-C30) alkyl, and (C1-C30) alkyl (C6-C30) aryl. The said organic electroluminescent compound of description. Ar ₁ and Ar ₂ each independently represent substituted or unsubstituted (C 6 -C 20) aryl, or substituted or unsubstituted (5 to 20 membered) heteroaryl, and X represents —O—, —S—, Or —C (R ₅ ) (R ₆ ) —, wherein R _{1 to} R ₄ each independently represent hydrogen or —NR ₇ R ₈ , or are linked to adjacent substituent (s). A substituted or unsubstituted monocyclic or polycyclic (C6-C20) alicyclic or aromatic ring, and R _{5 to} R ₈ are each independently substituted or unsubstituted (C1 -C6) represents alkyl, or substituted or unsubstituted (C6-C20) aryl, or is linked to adjacent substituent (s) to form a substituted or unsubstituted monocyclic or polycyclic (C3- C30) Alicyclic or aromatic Is formed and when n is 1 or 2, _{L 1} represents a single bond or a substituted or unsubstituted (C6-C20) arylene, n is 0, _{L 1} is a substituted or unsubstituted (C6 The organic electroluminescent compound according to claim 1, which represents -C20) aryl. Ar ₁ and Ar ₂ are each independently unsubstituted or (C 6 -C 20) aryl substituted with (C 1 -C 6) alkyl or (C 6 -C 12) aryl, or unsubstituted or (C 6 -C 12) aryl Represents substituted (5-20 membered) heteroaryl, X represents —O—, —S—, or —C (R ₅ ) (R ₆ ) —, and R _{1 to} R ₄ are each independently Represents hydrogen or —NR ₇ R ₈ or is linked to adjacent substituent (s) to form an unsubstituted monocyclic (C 6 -C 20) aromatic ring, R _{5 to} R ₈ Each independently represents unsubstituted (C1-C6) alkyl or unsubstituted (C6-C20) aryl, or linked to adjacent substituent (s) to form an unsubstituted polycyclic (C3 -C30) forming an aromatic ring, n being 1 or If it is 2, _{L 1} is an unsubstituted (C6-C20) arylene, n is 0, _{L 1} represents an unsubstituted (C6-C20) aryl, wherein the organic according to claim 1 Electroluminescent compound. 2. The organic electroluminescent compound according to claim 1, wherein the compound represented by formula 1 is selected from the group consisting of:

  An organic electroluminescent device comprising the organic electroluminescent compound according to claim 1.