JP6478978B2 - Organic electroluminescent compound and organic electroluminescent device comprising the same - Google Patents

Description

  The present invention relates to organic electroluminescent compounds and organic electroluminescent devices comprising the same.

  Electroluminescent devices (EL devices) are self-luminous devices that have the advantage in that they provide a wider viewing angle, better contrast ratio, and faster response time. Organic EL devices were first developed by Eastman Kodak by using a complex of an aromatic diamine small molecule and aluminum as a material to form a light emitting layer [Appl. Phys. Lett. 51, 913, 1987].

The most important factor determining the luminous efficiency in the organic EL device is the luminous material. Heretofore, fluorescent materials have been widely used as light emitting materials. However, from the viewpoint of the electroluminescence mechanism, the development of phosphorescent materials has been widely studied, because phosphorescent materials theoretically improve the luminous efficiency by four times compared to fluorescent materials. The iridium (III) complex is bis (2- (2'-benzothienyl) -pyridinato-N, C3 ') iridium (acetylacetonate) ((acac) Ir (btp) ₂ ), tris (2-phenylpyridine) A phosphorescent composition comprising iridium (Ir (ppy) ₃ ) and bis (4,6-difluorophenylpyridinato-N, C2) picolinate iridium (Firpic) as red, green and blue materials, respectively It is 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 that it is known as a hole blocking layer material such as vasocuproin (BCP) and aluminum (III) bis (2-methyl-8-quinolinate) (4-phenylphenolate) (BAlq). We have developed a high-performance organic EL device that is used as a host material.

  Although these materials provide good light emission characteristics, they have the following disadvantages. (1) Due to their low glass transition temperature and low thermal stability, their decomposition can occur even during vacuum and high temperature deposition processes, 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 containing phosphorescent host materials provide higher current efficiencies (cd / A) than those containing 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 the organic EL device is short, and the light emission efficiency still needs improvement.

  On the other hand, in order to improve its 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. The choice of the compound contained in the hole transport layer is known as a method to improve the device properties such as the hole transport efficiency with respect to the light emitting layer, the luminous efficiency, the lifetime etc.

  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. That is because thermal stress occurs between the anode and the hole injection layer when the organic EL device is driven under high current. Thermal stress significantly reduces the operating life of the device. Furthermore, the organic material used for the hole injection layer has a very high hole mobility, so the balance of the hole-electron charge may be broken, and the quantum efficiency (cd / A) may be lowered. .

  Therefore, a hole transport layer to improve the durability of the organic EL device still needs 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 by both a diarylamine or heteroarylamine and fluorene, dibenzothiophene or dibenzofuran.

  An object of the present invention is to provide organic electroluminescent compounds having excellent power efficiency and long lifetime.

  We find that the above objective can be achieved by an organic electroluminescent compound represented by Formula 1 below:

During the ceremony
Does Ar ₁ and Ar ₂ each independently represent substituted or unsubstituted (C 1 -C 30) alkyl, substituted or unsubstituted (C 6 -C 30) aryl, or substituted or unsubstituted (3 to 30 member) 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, And 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 each independently represent 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 (C3-C30) 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, and the carbon atoms And (d) may be replaced with at least one hetero atom selected from nitrogen, oxygen and sulfur,
Does R _{5 to} R ₁₆ each independently represent substituted or unsubstituted (C 1 -C 30) alkyl, substituted or unsubstituted (C 6 -C 30) aryl, or substituted or unsubstituted (3 to 30 members) heteroaryl? Or linked with an adjacent substituent (s) to form a substituted or unsubstituted monocyclic or polycyclic (C3-C30) alicyclic or aromatic ring,
n is an integer of 0 to 2,
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 members) heteroarylene,
When n is 0, L ₁ represents substituted or unsubstituted (C 1 -C 30) alkyl, substituted or unsubstituted (C 6 -C 30) aryl, or substituted or unsubstituted (3 to 30 members) heteroaryl,
and each of a, b and d independently represents 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 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 compound according to the present invention, it is possible to produce an organic electroluminescent device having excellent current and power efficiency as well as a long lifetime.

  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 temperatures, hole injection and hole transport capabilities, as well as suitable triplet energy and LUMO energy. When the glass transition temperature is low, crystallization can occur due to thermal stress applied during or after formation of the thin film, which can directly affect the lifetime of the device. While arylamine derivatives exhibit excellent hole transport ability and low driving voltage, 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 lengthens to shorten the triplet energy or the LUMO energy, which in turn reduces the performance of the device. This is due to the high triplet energy contributing to blocking excitons transported from the host to the hole transport layer, and the high LUMO energy blocking electrons transported from the electron transporting layer through the host to the hole transporting layer To contribute to

  Another problem of hole transport materials with high molecular weight by introducing large amounts of substituents is that good deposition does not occur. As the molecular weight increases, the deposition temperature also increases, and the molecules are more likely to break down or break up into many shapes. 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 solution, to introduce arylamines and selected heteroaryls or fluorenes in position 9 of fluorene.

  Introducing the arylamine and the selected heteroaryl or fluorene at position 9 of the fluorene increases the glass transition temperature but does not increase the deposition temperature much compared to introducing a substituent at the 2 position. This is because the linearity of the molecule is relatively low. As the linearity of molecules 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 relatively high triplet energy by short conjugation. In order to obtain high triplet energy, it is best not to introduce any substituent. However, although the triplet energy is a little low, it is possible to obtain excellent hole injection ability / transport ability, high power efficiency, long life and the like by introducing an arylamine. Moreover, by introducing a heteroaryl or fluorene at the 9 position instead of the 2 position, despite the high molecular weight due to a decrease in molecular linearity, an appropriate glass transition without increasing the deposition temperature too high It is possible to obtain a temperature.

  The organic electroluminescent compounds represented by formula 1 above are described in detail.

  In the present specification, “(C 1 -C 30) alkyl” is a linear or branched having 1 to 30 carbon atoms in which the number of carbon atoms is preferably 1 to 10, more preferably 1 to 6 Alkyl, and includes methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl and the like, and “(C 2 -C 30) alkenyl” preferably has the number of carbon atoms Meant linear or branched alkenyl having 2 to 30 carbon atoms which is 2 to 20, more preferably 2 to 10, and vinyl, 1-propenyl, 2-propenyl, 1- Butenyl, 2-butenyl, 3-butenyl, 2-methylbut-2-enyl and the like, and “(C 2 -C 30) alkynyl” preferably has 2 to 20 carbon atoms, more preferably And means 2 to 10 linear or branched alkynyl having 2 to 30 carbon atoms, and ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3- (30) -butyl, 1-methylpent-2-ynyl and the like, and "(C3-C30) cycloalkyl" preferably has 3 to 20, more preferably 3 to 7 carbon atoms. Or a monocyclic or polycyclic hydrocarbon containing one or more carbon atoms, and includes cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and the like, and “(3 to 7-membered) heterocycloalkyl” is B, N, O S, P (7O), Si and P, preferably cycloalkyl having 3 to 7 ring skeleton atoms containing at least one hetero atom selected from O, S and N And “(C 6 -C 30) aryl (ene)” preferably has 6 to 20, more preferably 6 to 15 carbon atoms, and includes tetrahydrofuran, pyrrolidine, thiolane, tetrahydropyran and the like. A monocyclic or fused ring derived from an aromatic hydrocarbon having from 30 to 30 carbon atoms, and phenyl, biphenyl, terphenyl, naphth, binaphthyl, phenylnaphthyl, naphthylphenyl, fluorenyl, phenylfluorenyl, benzo “(5 to 30 members) heteroaryl (including fluorenyl, dibenzofluorenyl, phenanthrenyl, phenylphenanthrenyl, anthracenyl, indenyl, triphenylenyl, pyrenyl, tetracenyl, perylenyl, chrysenyl, naphthacenyl, fluoranthenyl etc.) En) ", B, Aryl having 5 to 30 ring skeleton atoms, containing at least one, preferably 1 to 4 heteroatoms selected from the group consisting of N, O, S, P (= O), Si and P Which is a fused ring fused to a monocyclic ring or at least one benzene ring, which may be partially saturated, a heteroaryl group through at least one heteroaryl or aryl 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 cyclic heteroaryl, as well as benzofuranyl, benzothiophenyl, isobenzofuranyl, dibenzofuranyl, dibenzothiophenyl, benzimidazolyl, benzothiazolyl, benzisothiazolyl, benzisoxazolyl, benzoxazolyl, isoindolyl, Included are 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, "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. Substituted (C1-C30) alkyl, substituted (C2-C30) alkenyl, substituted (C2-C30) alkynyl, substituted (C1-C30) alkoxy, substituted in Ar ₁ , Ar ₂ , R _{1 to} R ₁₆ and 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) 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) Heteroaryl, unsubstituted or (3 to 30 membered) heteroaryl substituted (C6-C30) aryl, tri (C1-C30) alkylsilyl, tri (C6-C30) arylsilyl, 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, (C1-C30) alkyl carbonyl, (C -C30) alkoxycarbonyl, (C6-C30) arylcarbonyl, di (C6-C30) arylboronyl, di (C1-C30) alkylboronyl, (C1-C30) alkyl (C6-C30) arylboronyl, At least one selected from the group consisting of C6-C30) aryl (C1-C30) alkyl and (C1-C30) alkyl (C6-C30) aryl, preferably each independently (C1-C6); And n) 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) And) represents a heteroaryl or links to an adjacent substituent (s) to form a monocyclic or polycyclic (C3-C30) alicyclic or aromatic ring, and the carbon atom And (b) 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 (5 to 20 members) represents a heteroaryl, more preferably independently each 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 each independently represent 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 (C3-C30) 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, and the carbon atoms And Y) may be replaced with at least one hetero atom selected from nitrogen, oxygen, and sulfur, preferably each independently representing hydrogen or -NR ₇ R ₈ , or an adjacent substituent ( And R 1 and R 2 are linked to form a substituted or unsubstituted monocyclic or polycyclic (C 6 -C 20) alicyclic or aromatic ring, and more preferably each independently hydrogen or It represents NR ₇ R ₈ or is linked with adjacent substituent (s) to form an unsubstituted monocyclic (C 6 -C 20) aromatic ring.

Does R _{5 to} R ₁₆ each independently represent substituted or unsubstituted (C 1 -C 30) alkyl, substituted or unsubstituted (C 6 -C 30) aryl, or substituted or unsubstituted (3 to 30 members) heteroaryl? Or linked with an adjacent substituent (s) to form a substituted or unsubstituted monocyclic or polycyclic (C3-C30) alicyclic or aromatic ring, preferably independently And represents a substituted or unsubstituted (C 1 -C 6) alkyl, or a substituted or unsubstituted (C 6 -C 20) aryl, or linked to an adjacent substituent (s) to form a substituted or unsubstituted single ring More preferably, each independently form unsubstituted (C 1 -C 6) alkyl, or unsubstituted (C 1 -C 6) 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 members) heteroarylene, preferably a single bond or substituted Or unsubstituted (C6-C20) arylene, more preferably unsubstituted (C6-C20) arylene.

When n is 0, L ₁ represents substituted or unsubstituted (C 1 -C 30) alkyl, substituted or unsubstituted (C 6 -C 30) aryl, or substituted or unsubstituted (3 to 30 members) heteroaryl, preferably Represents a substituted or unsubstituted (C6-C20) aryl, more preferably an 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 to 20 membered) hetero X represents an —O—, —S—, or —C (R ₅ ) (R ₆ ) —, and R _{1 to} R ₄ each independently represent hydrogen or —NR ₇ R ₈ R ₅ to R ₄ represents a substituted or unsubstituted monocyclic or polycyclic (C 6 -C 20) cycloaliphatic or aromatic ring, or represents an adjacent or adjacent substituent (s), Each R ₈ independently represents substituted or unsubstituted (C 1 -C 6) alkyl, or substituted or unsubstituted (C 6 -C 20) aryl, or is linked to an adjacent substituent (s) and substituted 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 (C 6 -C 20) aryl.

According to another embodiment of the present invention, in the above formula 1, Ar ₁ and Ar ₂ are each independently unsubstituted or substituted with (C 1 -C 6) alkyl or (C 6 -C 12) aryl (C 6 -C20) aryl or (5- to 20-membered) heteroaryl which is unsubstituted or substituted by (C6-C12) aryl; X is -O-, -S-, or -C (R ₅ ) (R ₆ )-, each of R _{1 to} R ₄ independently represents hydrogen or —NR ₇ R ₈ , or is linked to an adjacent substituent (s) to form an unsubstituted monocyclic ring ( C 6 -C 20) form an aromatic ring, and R _{5 to} R ₈ each independently represent unsubstituted (C 1 -C 6) alkyl or unsubstituted (C 6 -C 20) aryl, or an adjacent substituent ((C 6 -C 20)) Connected with 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) aryl is represented.

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

  The organic electroluminescent compounds of the 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 a to d are as defined in the above formula 1 and Hal represents a halogen.

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

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

  The organic electroluminescent device comprises a first electrode, a second electrode, and at least one organic layer between the first electrode and the second electrode. The organic layer may comprise at least one organic electroluminescent compound of Formula 1.

  One of the first and second electrodes is an anode and the other is a cathode. The organic layer 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. It may further comprise two layers.

  The organic electroluminescent compound according to the invention may be comprised 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 a light emitting layer, the organic electroluminescent compound represented by Formula 1 may be included as a host material.

  The organic electroluminescent device comprising the organic electroluminescent compound of the present invention may further comprise one or more compounds other than the organic electroluminescent compound according to the present invention as a host material and may further comprise 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. As used herein, the ratio of the first host material to 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 may be derived from any of the known phosphorescent hosts. In particular, phosphorescent hosts selected from the group consisting of compounds of the following formulas 11 to 13 are preferred in terms of luminous efficiency.

  Where Cz represents the following structure,

R _{21 to} R ₂₄ each independently represent a hydrogen, deuterium, a halogen, a substituted or unsubstituted (C1-C30) alkyl, or a substituted, substituted or unsubstituted (3 to 30 membered) unsubstituted (C6-C30) aryl A) heteroaryl or -SiR ₂₅ R ₂₆ R ₂₇ ;
R _{25 to} R ₂₇ each independently represent substituted or unsubstituted (C 1 -C 30) alkyl, or substituted or unsubstituted (C 6 -C 30) aryl,
L ₄ represents a single bond, substituted or unsubstituted (C 6 -C 30) arylene, or substituted or unsubstituted (5 to 30 members) heteroarylene,
M represents substituted or unsubstituted (C6-C30) aryl, or substituted or unsubstituted (5 to 30 members) heteroaryl;
Y ₁ and _{Y 2} are each independently, -O -, - S -, - N (R 31) -, or _{-C (R 32) (R 33} ) - represents a proviso, _{Y 1} and Y _Provided that ₂ do not exist simultaneously,
R _{31 to} R ₃₃ each independently represent substituted or unsubstituted (C 1 -C 30) alkyl, substituted or unsubstituted (C 6 -C 30) aryl, or substituted or unsubstituted (5 to 30 members) 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:

  [Wherein, TPS represents triphenylsilyl].

  The dopants comprised in the organic electroluminescent device according to the invention are preferably at least one phosphorescent dopant. The dopant material applied to the organic electroluminescent device according to the present invention may be selected from, but not limited to, metallized complex compounds of iridium, osmium, copper and platinum, 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 the compounds represented by the following formulas 101-103.

  Where L is selected from the following structures:

R ₁₀₀ represents hydrogen or substituted or unsubstituted (C 1 -C 30) alkyl,
R _{101 to} R ₁₀₉ and R _{111 to} R ₁₂₃ are each independently hydrogen, deuterium, halogen, (C1-C30) alkyl substituted with unsubstituted or halogen (s), cyano, substituted or non Represents substituted (C1-C30) alkoxy, or substituted or unsubstituted (C3-C30) cycloalkyl, and R _{120 to} R ₁₂₃ are monocyclic or polycyclic in combination with adjacent substituent (s) (3 to 30 members) of an alicyclic or aromatic ring, such as quinoline,
R _{124 to} R ₁₂₇ each independently represent hydrogen, deuterium, halogen, substituted or unsubstituted (C1-C30) alkyl, or substituted or unsubstituted (C6-C30) aryl, and R _{124 to} R ₁₂₇ represent When it is an aryl group, they are linked with adjacent substituent (s) to form a monocyclic or polycyclic (3 to 30 membered) alicyclic or aromatic ring, such as fluorene Get
R ₂₀₁ to R ₂₁₁ each independently represent hydrogen, deuterium, halogen, or unsubstituted or substituted by halogen (s) a (C1-C30) alkyl,
r and s each independently represent an integer of 1 to 3. 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 comprises:

  In another embodiment of the present invention, compounds are provided for preparing an organic electroluminescent device. The compounds comprise the compounds according to the invention as host material or hole transport material.

  Moreover, the organic electroluminescent device according to the 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 comprises a light emitting layer, which may comprise compounds for preparing an organic electroluminescent device according to the present invention.

  The organic electroluminescent device according to the present invention may further comprise, in addition to the organic electroluminescent compound represented by Formula 1, at least one compound selected from the group consisting of arylamine compounds and styrylarylamine compounds.

  In the organic electroluminescent device according to the present invention, the organic layer comprises a metal of group 1 of the periodic table, a metal of group 2, a transition metal of period 4, a transition metal of period 5, a lanthanide, and a d orbital transition element. It may further comprise at least one metal selected from the group consisting of organometallics, or at least one complex compound comprising said 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 light emitting layer comprising, in addition to the compounds according to the present invention, a blue electroluminescent compound, a red electroluminescent compound or a green electroluminescent compound known in the art. By further including, white light can be emitted. Also, if desired, a yellow or orange light emitting layer may be included in the device.

According to the invention, at least one layer (hereinafter "surface layer") is preferably the inner surface of one or both electrode (s) selected from chalcogenide layers, metal halide layers, and metal oxide layers. It is placed on (more than one). 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. It is disposed on the cathode surface. Such surface layers provide operational stability to the organic electroluminescent device. Preferably, the chalcogenide comprises SiO _x (1 ≦ x ≦ 2), AlO _x (1 ≦ x ≦ 1.5), SiON, SiAlON, etc., and the metal halide layer comprises LiF, MgF ₂ , CaF ₂ And rare earth metal fluorides and the like, 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 into the electroluminescent medium. In addition, the hole transport compound is oxidized to a cation, thus making it easier to inject and transport holes from the mixed region into the electroluminescent medium. Preferably, the oxidizing dopant comprises various Lewis acids and acceptor compounds, and the reducing dopant comprises alkali metals, alkali metal compounds, alkaline earth metals, rare earth metals, and mixtures thereof. The reducing dopant layer may be used as a charge generation layer to prepare an electroluminescent device having two or more electroluminescent layers and emitting white light.

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

  When using wet deposition methods, thin films can be formed by dissolving or diffusing the materials forming each layer into any suitable solvent such as ethanol, chloroform, tetrahydrofuran, dioxane, and the like. The solvent may be any solvent in which materials forming each layer can be dissolved or diffused, and has no problem in film forming ability.

  Hereinafter, the organic electroluminescent compound, the preparation method of the present compound, and the luminescent property 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 After introducing dibenzofuran (30 g, 178 mmol) and 500 mL of tetrahydrofuran into a reaction vessel, the vessel was cooled to −78 ° C. under a nitrogen atmosphere. Then 71 mL (2.5 M, 178 mmol) of N-butyllithium was slowly dropped into the mixture. The mixture was stirred at −78 ° C. for 30 minutes, then at room temperature for 3 hours and cooled to −78 ° C. Then, fluorenone (32 g, 178 mmol) dissolved in 500 mL of tetrahydrofuran was slowly dropped into the mixture. After addition, the reaction temperature was slowly warmed to room temperature and the mixture was stirred for 16 hours. Then, 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 a reaction vessel, the vessel is It was introduced into a nitrogen atmosphere. Then, boron trifluoride diethyl ether (3.8 mL, 30.1 mmol) dissolved in 120 mL of methylene chloride was slowly dropped into the mixture. The mixture was stirred at room temperature for 2 hours, then 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 After introducing (8.9 g, 64.7 mmol), 160 mL of toluene, 40 mL of ethanol, and 40 mL of distilled water into the reaction vessel, 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. 1). After introducing 57 g (1.38 mmol), sodium tert-butoxide (3.3 g, 34.7 mmol), and 70 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-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 a reaction vessel, the vessel was in a nitrogen atmosphere Introduced to Thereafter, 3 mL of Eaton's reagent was slowly dropped into the mixture. The mixture was stirred at room temperature for 2 hours, then 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 introducing potassium carbonate (5.3 g, 38.3 mmol), 60 mL of toluene, 20 mL of ethanol, and 20 mL of distilled water 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 remaining 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 a reaction vessel, the vessel was cooled to −78 ° C. under a nitrogen atmosphere. Then, 33 mL (2.5 M, 82 mmol) of N-butyllithium was slowly dropped into the mixture. The mixture was stirred at −78 ° C. for 2 hours, and then 9H-fluoren-9-one (19 g, 103 mmol) dissolved in 340 mL of tetrahydrofuran was slowly dropped into the mixture. After addition, the reaction temperature was slowly warmed to room temperature and the mixture was stirred for 30 minutes. Aqueous ammonium chloride solution 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 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 of Eaton's reagent (0.9 M) , 1.3 mmol) was slowly dropped into 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), After introducing sodium carbonate (4 g, 37.28 mmol), 76 mL of toluene, 19 mL of ethanol, and 19 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 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 a reaction vessel, the vessel was cooled to −78 ° C. under a nitrogen atmosphere. Then 65 mL (2.5 M, 163 mmol) of N-butyllithium was slowly dropped into the mixture. The mixture was stirred at -78 ° C for 2 hours, then 9H-fluoren-9-one (29 g, 163 mmol) dissolved in 400 mL of tetrahydrofuran was slowly dropped into the mixture. After addition, the reaction temperature was slowly warmed to room temperature and the mixture was stirred for 30 minutes. Aqueous ammonium chloride solution 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 In a reaction vessel, Compound 4-1 (7 g, 19 mmol) and 4-bromotriphenylamine (16 g, 48 mmol) were dissolved in 96 mL of dichloromethane, and then 0.5 mL of Eaton's reagent (0.9 M) , 0.4 mmol) was slowly dropped into 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 remaining 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) ) After introducing S-phos (0.39 g, 0.97 mmol), sodium tert-butoxide (2.3 g, 24.3 mmol), and 50 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-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 a reaction vessel, and then the vessel was introduced into a nitrogen atmosphere. . Then, boron trifluoride diethyl ether (3.8 mL, 30.1 mmol) dissolved in 120 mL of methylene chloride was slowly dropped into the mixture. The mixture was stirred at room temperature for 2 hours, then 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 then 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 a reaction vessel, the vessel was cooled to −78 ° C. under a nitrogen atmosphere. Then, 60 mL (2.5 M, 146 mmol) of N-butyllithium was slowly dropped into the mixture. The mixture was stirred at -78 [deg.] C for 90 minutes, then fluorenone (26 g, 146 mmol) dissolved in 500 mL of tetrahydrofuran was slowly dropped into the mixture. After addition, the reaction temperature was slowly warmed to room temperature and the mixture was stirred for 16 hours. Aqueous ammonium chloride solution 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) After being introduced into the reaction vessel, the vessel was introduced into a nitrogen atmosphere. Thereafter, 0.6 mL of Eaton's reagent was slowly dropped into the mixture. The mixture was stirred at room temperature for 2 hours, then 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 In a reaction vessel, 2-bromo-9,9-diphenyl-9H-fluorene (15 g, 37.75 mmol) was dissolved in 125 mL of tetrahydrofuran, and then 15 mL (2.5 M of n-butyllithium). , 37.75 mmol) was slowly added dropwise to the mixture at -78 ° C and the mixture was stirred for 2 hours. Then 9-fluoren-one (6.2 g, 34.32 mmol) was dissolved in 125 mL of tetrahydrofuran and slowly dropped into 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, 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 remaining 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 After introducing 2-bromofluorene (40 g, 146 mmol) and 500 mL of tetrahydrofuran into a reaction vessel, the vessel was cooled to −78 ° C. under a nitrogen atmosphere. Then N-butyllithium (60 mL, 146 mmol) was slowly dropped into the mixture. The mixture was stirred for 2 hours, then 9H-fluoren-9-one (26 g, 146 mmol) dissolved in 500 mL of tetrahydrofuran was slowly dropped into the mixture. After addition, the reaction temperature was slowly warmed to room temperature and the mixture was stirred for 30 minutes. Aqueous ammonium chloride solution 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 dropped into 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) ), Toluene (76 mL) and ethanol (19 mL) were introduced into the reaction vessel, then 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 a reaction vessel, the vessel was cooled to −78 ° C. under a nitrogen atmosphere. Then N-butyllithium (60 mL, 146 mmol) was slowly dropped into the mixture. The mixture was stirred for 2 hours, then 9H-fluoren-9-one (26 g, 146 mmol) dissolved in 500 mL of tetrahydrofuran was slowly dropped into the mixture. After addition, the reaction temperature was slowly warmed to room temperature and the mixture was stirred for 30 minutes. Aqueous ammonium chloride solution 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) in a reaction vessel After dissolving in 130 mL dichloromethane, Eaton's reagent (0.6 mL, 0.53 mmol) was slowly dropped into 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 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 Invention An OLED device was prepared using a luminescent material according to the invention. A transparent electrode indium tin oxide (ITO) thin film (15 Ω / sq) on a glass substrate for an organic light emitting diode (OLED) device (Geomatec, Japan) is subjected to ultrasonic cleaning using acetone and isopropane alcohol sequentially, It was then stored in isopropane alcohol. Then, 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 The 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, a current was applied to the cell to evaporate the above introduced material, thereby forming a hole injection layer having a thickness of 60 nm on the ITO substrate. Compound C-6 is then introduced into another cell of the vacuum deposition apparatus and evaporated by applying a current to the cell, whereby a hole transport layer having a thickness of 20 nm on the hole injection layer Formed. Thereafter, 9- (3- (4,6-diphenyl-1,3,5-triazin-2-yl) phenyl) -9'-phenyl-9H, 9'H-3,3'-bicarbazole as a host material The compound D-1 was introduced as a dopant into another cell of the vacuum evaporation apparatus as one. The two materials were evaporated at different rates and deposited at a doping 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 is introduced into one cell, Lithium quinolinate was introduced into another cell. The two materials were evaporated at the same rate, and each was deposited at a 50 wt% doping to form an electron transport layer with a thickness of 30 nm on the light emitting layer. Next, after lithium quinolinate was deposited as an electron injection layer having a thickness of 2 nm on the electron transport layer, an Al cathode having a thickness of 150 nm was deposited 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 prior to use.

The OLED device produced exhibited 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 brightness to decrease to 80% at 15,000 nits was over 250 hours.

Device Example 2: Preparation of an OLED Device Using an Organic Electroluminescent Compound According to the Invention An OLED device was prepared in the same manner as Device Example 1 except that Compound C-9 was used to a thickness of 20 nm. Forming a hole transport layer, 7- (4-([1,1'-biphenyl] -4-yl) quinazolin-2-yl) -7H-benzo [c] carbazole as a host in a vacuum evaporation apparatus Compound D-87 is introduced as a dopant into another cell, the two materials are evaporated at different rates, and they are doped at a 3 wt% doping amount based on the total amount of host and dopant. Except that the light emitting layer having a thickness of 30 nm was formed on the hole transport layer.

The OLED device produced 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 over 200 hours.

Device Example 3: Preparation of an OLED Device Using an Organic Electroluminescent Compound According to the Invention An OLED device was prepared in the same manner as in Device Example 1 except that for the hole transport layer compound C-8, the host With the exception of using compound H-1 as follows and compound FD-1 as below for the dopant.

The OLED device produced exhibited blue emission with a brightness 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 over 170 hours.

Device Example 4 Preparation of an OLED Device Using an Organic Electroluminescent Compound According to the Invention An OLED device was prepared in the same manner as device example 2 except that compound C-78 was evaporated to a thickness of 20 nm. Except that the hole transport layer was formed.

The OLED device produced 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 intensity to decrease to 80% at 5,000 nits was greater than 210 hours.

Device Example 5 Preparation of an OLED Device Using an Organic Electroluminescent Compound According to the Invention An OLED device was prepared in the same manner as device example 1 except that compound C-79 was evaporated to a thickness of 20 nm. Except that the hole transport layer was formed.

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

  The time to decrease the brightness to 80% at 15,000 nits was over 240 hours.

Device Example 6 Preparation of an OLED Device Using an Organic Electroluminescent Compound According to the Invention An OLED device was prepared in the same manner as device example 1 except that compound C-12 was evaporated to a thickness of 20 nm. Except that the hole transport layer was formed.

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

  The time for the brightness to decrease to 80% at 15,000 nits was over 270 hours.

Device Example 7: Preparation of an OLED Device Using an Organic Electroluminescent Compound According to the Invention An OLED device was prepared in the same manner as device example 3 except that compound C-81 was evaporated to a thickness of 20 nm. Except that the hole transport layer was formed.

The OLED device produced exhibited 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 over 130 hours.

Device Example 8 Preparation of an OLED Device Using an Organic Electroluminescent Compound According to the Invention An OLED device was prepared in the same manner as device example 1 except that compound C-80 was evaporated to a thickness of 20 nm. Except that the hole transport layer was formed.

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

  The time for the brightness to decrease to 80% at 15,000 nits was over 230 hours.

Device Example 9 Preparation of an OLED Device Using an Organic Electroluminescent Compound According to the Invention An OLED device was prepared in the same manner as device example 2 except that compound C-107 was evaporated to a thickness of 20 nm. Except that the hole transport layer was formed.

The OLED device produced exhibited 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 over 200 hours.

Device Example 10 Preparation of an OLED Device Using an Organic Electroluminescent Compound According to the Invention An OLED device was prepared in the same manner as device example 2 except that compound C-108 was evaporated to a thickness of 20 nm. Except that the hole transport layer was formed.

The OLED device produced showed 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 over 180 hours.

Comparative Example 1 Preparation of an OLED Device Using a Conventional Organic Electroluminescent Compound An OLED device was prepared in the same manner as Device Example 1, except that N, N'-di (4-biphenyl) -N, N. The 'di (4-biphenyl) -4,4'-diaminobiphenyl was evaporated, except that a 20 nm thick hole transport layer was formed.

The OLED device produced exhibited 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 brightness to decrease to 80% at 15,000 nits was over 230 hours.

Comparative Example 2 Preparation of an OLED Device Using a Conventional Organic Electroluminescent Compound An OLED device was prepared in the same manner as Device Example 3, except that N, N'-di (4-biphenyl) -N, N. The 'di (4-biphenyl) -4,4'-diaminobiphenyl was evaporated, except that a 20 nm thick hole transport layer was formed.

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 over 130 hours.

Comparative Example 3 Preparation of an OLED Device Using a Conventional Organic Electroluminescent Compound An OLED device was prepared in the same manner as Device Example 2, except that N, N'-di (4-biphenyl) -N, N. The 'di (4-biphenyl) -4,4'-diaminobiphenyl was evaporated, except that a 20 nm thick hole transport layer was formed.

The OLED device produced showed red emission with a brightness of 10000 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 over 180 hours.

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

The OLED device produced exhibited a green emission with a brightness of 9000 cd / m ² and a current density of 20.8 mA / cm ² .

  The time for the brightness to decrease to 80% at 15,000 nits was over 25 hours.

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

Claims (6)

Organic electroluminescent compounds represented by the following formula I,

During the ceremony
Does Ar ₁ and Ar ₂ each independently represent substituted or unsubstituted (C1-C30) alkyl, substituted or unsubstituted (C6-C30) aryl, or substituted or unsubstituted (3-30 member) 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, And at least one heteroatom selected from oxygen and sulfur,
X is, -O -, - S-, or _{-C (R 5) (R 6} ) - represents,
R ₁ and R ₂ are each independently hydrogen, deuterium, shea anode, 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 to 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 ₁₆ ) is represented or adjacent Forming a substituted or unsubstituted monocyclic or polycyclic (C3-C30) alicyclic or aromatic ring, and the carbon atom (s) thereof is And at least one heteroatom selected from nitrogen, oxygen and sulfur may be substituted,
R ₃ and 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 (C3-C30) 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 ₁₆ ), or Or linked to adjacent substituent (s) to form a substituted or unsubstituted monocyclic or polycyclic (C3-C30) alicyclic or aromatic ring, and the carbon atoms And (d) may be replaced with at least one hetero atom selected from nitrogen, oxygen and sulfur,
Do R _{5 to} R ₁₆ each independently represent substituted or unsubstituted (C 1 -C 30) alkyl, substituted or unsubstituted (C 6 -C 30) aryl, or substituted or unsubstituted (3 to 30 members) heteroaryl? Or linked with an adjacent substituent (s) to form a substituted or unsubstituted monocyclic or polycyclic (C3-C30) alicyclic or aromatic ring,
n is an integer of 1 to 2,
L ₁ represents a single bond, substituted or unsubstituted (C 6 -C 30) arylene, or substituted or unsubstituted (3 to 30 members) heteroarylene,
When a 1 , b and d each independently represent an integer of 1 to 4 and 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 containing at least one heteroatom selected from B, N, O, S, P (= O), Si, and P; Organic electroluminescent compounds. Said substituted (C1-C30) alkyl in Ar ₁ , Ar ₂ , R _{1 to} R ₁₆ and L ₁ , said substituted (C 2 -C 30) alkenyl, said substituted (C 2 -C 30) alkynyl, said substituted (C 1 -C 30) ) 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 to 30 members) 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- to 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) 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 compound according to claim 1, which is at least one selected from the group consisting of -C30) arylboronyl, (C6-C30) aryl (C1-C30) alkyl, and (C1-C30) alkyl (C6-C30) aryl. Yes electromechanical field emission compound according. And Ar ₁ and Ar ₂ each independently represent a substituted or unsubstituted (C 6 -C 20) aryl or a 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) Form a substituted or unsubstituted monocyclic or polycyclic (C6-C20) alicyclic or aromatic ring, and R _{5 to} R ₈ each independently represent a substituted or unsubstituted (C 1 -C6) Alkyl or substituted or unsubstituted (C6-C20) aryl, or linked to an adjacent substituent (s) to form a substituted or unsubstituted monocyclic or polycyclic (C3- C30) Alicyclic or aromatic Forming a, _{L 1} represents a single bond or a substituted or unsubstituted (C6-C20) to the table arylene, organic electromechanical field emission compound according to claim 1. Ar ₁ and Ar ₂ each independently represent (C 6 -C 20) aryl which is unsubstituted or substituted by (C 1 -C 6) alkyl or (C 6 -C 12) aryl, or unsubstituted or (C 6-C 12) aryl R represents a substituted (5 to 20 membered) heteroaryl, X represents -O-, -S-, or -C (R ₅ ) (R ₆ )-, and R _{1 to} R ₄ are each independently R ₅ represents a hydrogen or —NR ₇ R ₈ or is linked to an adjacent substituent (s) to form an unsubstituted monocyclic (C 6 -C 20) aromatic ring, R _{5 to} R ₈ And each independently represents unsubstituted (C 1 -C 6) alkyl or unsubstituted (C 6 -C 20) aryl, or is linked to an adjacent substituent (s) to form an unsubstituted polycyclic (C 3) -C30) form an aromatic ring, _{L 1} is, Substituted (C6-C20) to the table arylene, organic electromechanical field emission compound according to claim 1. It is selected from the group consisting of following, chromatic electromechanical field emission compounds.

In claim 1 including a perforated mechatronics field emission compounds described organic electroluminescent device.