WO2011081429A2 - Organic compound, and organic electroluminescent device using same - Google Patents

Abstract

The present invention relates to a novel organic compound, and an organic electroluminescent device using the same, and more specifically, to a compound having one or more fluoranthene derivative moieties and having a symmetric or asymmetric molecular structure, and an organic electroluminescent device with improved luminous efficiency, luminance, thermal stability, drive voltage, lifetime and the like by applying the compound, preferably to a hole injection layer material, a hole transport layer material, a host material of a fluorescent layer or a phosphorescent layer, and an electron transport and injection material.

Description

Organic Compounds and Organic Electroluminescent Devices Using the Same

The present invention relates to a novel organic compound and an organic electroluminescent device using the same, and more particularly, a compound having one or more fluoranthene derivative moieties and having a symmetric or asymmetric molecular structure, and the compound Applied to an organic electroluminescent device, preferably applied as a hole injection layer material, a hole transport layer material, a host material of a fluorescent or phosphorescent layer, an electron injection layer material and / or an electron transport layer material, luminous efficiency, brightness, thermal stability, drive voltage The present invention relates to an organic electroluminescent device having improved characteristics, such as lifespan.

In general, organic light emitting phenomenon refers to a phenomenon in which light appears when electric energy is applied to an organic material. That is, when the organic layer is positioned between the anode and the cathode and a voltage is applied between the two electrodes, holes are injected into the organic layer and electrons are injected into the cathode. When the injected holes and electrons meet, excitons are formed, and when the excitons fall back to the ground, they shine.

Organic electroluminescent (EL) devices (hereinafter, simply referred to as 'organic EL devices') are self-luminous display devices, and thus have excellent contrast ratio, wide viewing angle, and fast response time, which are suitable for high performance displays.

From the observation of organic thin-film emission by Bernanose in the 1950s, the study of organic EL devices that led to blue electroluminescence using anthracene single crystals in 1965 was carried out by Tang in 1987. EL devices have been proposed, and have been developed in the form of introducing each characteristic organic material layer in the device to make high efficiency, high life organic EL devices, leading to the development of specialized materials used therein.

As one method for making an organic EL device efficiently, research has been conducted to manufacture an organic layer in the device into a multilayer structure instead of a single layer.

In general, an organic EL device has a thin film multilayer structure in which an anode is formed on a substrate and a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and a cathode are sequentially formed on the anode. It is.

The reason why the organic EL device is manufactured in a multi-layer is that the movement speeds of the holes and the electrons are different. Therefore, if the appropriate hole injection layer, the transport layer, the electron transport layer, and the injection layer are made, the holes and the electrons can be effectively transferred. This is because the light emission efficiency can be improved by balancing the electrons.

Electrons injected from the electron injection layer and holes transferred from the hole injection layer recombine in the emission layer to form excitons, and fall from the singlet excited state to the ground state and are called fluorescence, and fall from the triplet excited state to the ground state. Luminescence is called phosphorescence. Theoretically, when the exciton is generated when the carrier is recombined in the emission layer, the ratio of singlet and triplet excitons is generated at a ratio of 1: 3, and when phosphorescence is used, the internal quantum efficiency may be 100%.

Initial reports on electron transport materials include oxadiazole derivatives (PBDs). It has since been reported that triazole derivatives (TAZ) and phenanthroline derivatives (BCP) exhibit electron transport properties. The electron transport layer is a good candidate for organometallic complexes having relatively high electron stability and electron transport rate, and Alq3 having high stability and electron affinity is the best candidate. It is used. In addition, conventionally known materials for electron transport include flavon derivatives published by Sanyo, germanium, and silicon cyclopentadiene derivatives of Chiso. (Japanese Laid-Open Patent Publication No. 1998-017860, Japanese Laid-Open Patent Publication No. 1999-087067).

As a conventional electron injection and transport material, many organic monomolecular materials having imidazole groups, oxazole groups, and thiazole groups have been reported. However, before these materials were reported as electron transport materials, application of metal complex compounds of these materials to Motorola blue or cyan light emitting layers has already been reported in Motorola EU 0700917 A2.

TPBI, published by Kodak in 1996 and described in US Pat. No. 5,645,948, is known as a representative electron transporting material with imidazole groups, whose structure is three N-phenyl benzimides at the 1,3,5 position of benzene. It is reported that not only the ability to transfer the electrons and functionally block the holes coming from the light emitting layer that contains the sol, but has a low thermal stability to be applied to the actual device.

Carbazole ring compounds such as CBP (4,4-dicarbazolybiphenyl) are used as the phosphorescent host material, and metal complex compounds containing heavy atoms such as Ir and Pt are widely used as phosphorescent guest materials.

However, CBP, which is currently used phosphorescent host material, has a low glass transition temperature (Tg) of about 110 ° C., and crystallization within the device is easy, resulting in a very short lifetime of about 150 hours.

Accordingly, an object of the present invention is to apply the organic EL device as a phosphorescent host material, a fluorescent host material, a hole injection material, a hole transport material, an electron injection material and / or an electron transport material to lower the driving voltage, and to reduce luminous efficiency, luminance and thermal properties. It is to provide a novel compound comprising a fluoranthene derivative structure that can improve the stability and device life.

Another object of the present invention is to provide an organic EL device using the compound.

The present invention to achieve the above object provides a compound represented by the following formula (1).

Formula 1

Where

X is selected from the group consisting of CR ₁₃ R ₁₄ , NR ₁₅ , O, S, S (= 0), S (= 0) ₂ and SiR ₁₆ R ₁₇ ,

이되,R ₁ to R ₁₇ are each independently

This,

n and m are each independently an integer of 0 to 10, except that at the same time 0;

At least one L is each independently selected from the group consisting of CA ¹ A ² , NA ³ , O, S and SiA ⁴ A ⁵ , and A ¹ to A ⁵ are each independently hydrogen, deuterium, substituted or unsubstituted C1-; C40 alkyl, substituted or unsubstituted C2-C40 alkenyl, substituted or unsubstituted C2-C40 alkynyl, substituted or unsubstituted C3-C40 cycloalkyl, substituted or unsubstituted heterocycloalkyl having 3 to 40 heteroatoms Alkyl, (substituted or unsubstituted C6-C60 aryl) C1-C40 alkyl, substituted or unsubstituted C1-C40 alkoxy, substituted or unsubstituted C6-C60 arylamine, substituted or unsubstituted C6-C60 diarylamine , Substituted or unsubstituted C6-C60 aryloxy, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted nuclear atom having 5 to 60 heteroaryl, substituted or unsubstituted nuclear atom having 5 to 50 condensation (fused) polycyclic aromatic hydrocarbons or substituted or unsubstituted 5 to 50 condensed atoms (fu sed) a polycyclic aromatic heterocycle, wherein A ¹ and A ² , A ⁴ and A ⁵ can combine with each other to form a cyclic ring;

At least one Q is independently hydrogen, deuterium, substituted or unsubstituted C1-C40 alkyl, substituted or unsubstituted C2-C40 alkenyl, substituted or unsubstituted C2-C40 alkynyl, substituted or unsubstituted C3- C40 cycloalkyl, substituted or unsubstituted heterocycloalkyl having 3 to 40 nuclear atoms, (substituted or unsubstituted C6-C60 aryl) C1-C40 alkyl, substituted or unsubstituted C1-C40 alkoxy, substituted or unsubstituted C6-C60 arylamine, substituted or unsubstituted C6-C60 diarylamine, substituted or unsubstituted C6-C60 aryloxy, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted nuclear atom 5 to 60 heteroaryl, substituted or unsubstituted C1-C30 alkylsilyl, substituted or unsubstituted C6-C60 arylsilyl, substituted or unsubstituted fused polycyclic aromatic hydrocarbon having 5 to 50 nuclear atoms, or Substituted or unsubstituted fused polycyclic 5 to 50 nuclear atoms Aromatic heterocycle;

R ₁ to R ₁₂ may combine with adjacent groups to form a fused aliphatic ring, a fused aromatic ring, a fused heteroaliphatic ring or a fused heteroaromatic ring;

R ₁₃ and R ₁₄ , R ₁₆ and R ₁₇ may combine with each other to form a cyclic ring.

In addition, the present invention, the anode; cathode; And at least one organic layer interposed between the anode and the cathode, wherein at least one of the organic layers includes the compound described above.

The compound of formula 1 according to the present invention may have both fluorescence and phosphorescence properties and has excellent thermal stability, so that when adopted as a blue, green or red fluorescent or phosphorescent host material, low power, high efficiency, high brightness and improved durability And life can be secured. In addition, by including both the electron and the hole substituents in the molecule, even as a hole injection layer, a hole transport layer, an electron injection layer and / or an electron transport layer material of an organic EL device comprising at least one organic layer between the anode and the cathode Can be applied. Therefore, the organic EL device including the compound of the present invention can be greatly improved in terms of light emitting performance and lifetime, and thus can be effectively applied to a full color display panel and the like.

1 is a schematic cross-sectional view of an organic EL device according to an embodiment of the present invention.

The compound represented by Formula 1 according to the present invention is a compound having one or more fluoranthene derivative moieties and having a symmetric or asymmetric molecular structure, and includes a phosphorescent host material, a fluorescent host material, a hole injection material, and a hole transporting material. It can be used in organic EL devices as materials, electron injection materials and / or electron transport materials.

In the compound of formula 1 of the present invention, X is selected from the group consisting of CR ₁₃ R ₁₄ , NR ₁₅ , O, S, S (= 0), S (= 0) ₂ and SiR ₁₆ R ₁₇ .

이되, n 및 m은 각각 독립적으로 0 내지 10의 정수이며, 동시에 0인 경우는 제외되고; 하나 이상의 L은 각각 독립적으로 CA¹A², NA³, O, S 및 SiA⁴A⁵로 이루어진 군에서 선택되며, A¹ 내지 A⁵는 각각 독립적으로 수소, 중수소, 치환 또는 비치환된 C1-C40 알킬, 치환 또는 비치환된 C2-C40 알케닐, 치환 또는 비치환된 C2-C40 알키닐, 치환 또는 비치환된 C3-C40 사이클로알킬, 치환 또는 비치환된 핵원자수 3 내지 40의 헤테로사이클로알킬, (치환 또는 비치환된 C6-C60 아릴로 치환된) C1-C40 알킬, 치환 또는 비치환된 C1-C40 알콕시, 치환 또는 비치환된 C6-C60 아릴아민, 치환 또는 비치환된 C6-C60 디아릴아민, 치환 또는 비치환된 C6-C60 아릴옥시, 치환 또는 비치환된 C6-C60 아릴, 치환 또는 비치환된 핵원자수 5 내지 60의 헤테로아릴, 치환 또는 비치환된 핵원자수 5 내지 50의 축합(fused) 폴리사이클릭 방향족 탄화수소, 또는 치환 또는 비치환된 핵원자수 5 내지 50의 축합(fused) 폴리사이클릭 방향족 헤테로환이고, A¹과 A², A⁴와 A⁵는 서로 결합하여 환상 고리를 형성할 수 있으며; 하나 이상의 Q는 각각 독립적으로 수소, 중수소, 치환 또는 비치환된 C1-C40 알킬, 치환 또는 비치환된 C2-C40 알케닐, 치환 또는 비치환된 C2-C40 알키닐, 치환 또는 비치환된 C3-C40 사이클로알킬, 치환 또는 비치환된 핵원자수 3 내지 40의 헤테로사이클로알킬, (치환 또는 비치환된 C6-C60 아릴로 치환된) C1-C40 알킬, 치환 또는 비치환된 C1-C40 알콕시, 치환 또는 비치환된 C6-C60 아릴아민, 치환 또는 비치환된 C6-C60 디아릴아민, 치환 또는 비치환된 C6-C60 아릴옥시, 치환 또는 비치환된 C6-C60 아릴, 치환 또는 비치환된 핵원자수 5 내지 60의 헤테로아릴, 치환 또는 비치환된 C1-C30 알킬실릴, 치환 또는 비치환된 C6-C60 아릴실릴, 치환 또는 비치환된 핵원자수 5 내지 50의 축합(fused) 폴리사이클릭 방향족 탄화수소, 또는 치환 또는 비치환된 핵원자수 5 내지 50의 축합(fused) 폴리사이클릭 방향족 헤테로환이다.R ₁ to R ₁₇ are each independently

Where n and m are each independently an integer from 0 to 10, except that at the same time 0; At least one L is each independently selected from the group consisting of CA ¹ A ² , NA ³ , O, S and SiA ⁴ A ⁵ , and A ¹ to A ⁵ are each independently hydrogen, deuterium, substituted or unsubstituted C1-; C40 alkyl, substituted or unsubstituted C2-C40 alkenyl, substituted or unsubstituted C2-C40 alkynyl, substituted or unsubstituted C3-C40 cycloalkyl, substituted or unsubstituted heterocycloalkyl having 3 to 40 heteroatoms Alkyl, C1-C40 alkyl (substituted or unsubstituted with C6-C60 aryl), substituted or unsubstituted C1-C40 alkoxy, substituted or unsubstituted C6-C60 arylamine, substituted or unsubstituted C6-C60 Diarylamine, substituted or unsubstituted C6-C60 aryloxy, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted nuclear atom 5 to 60 heteroaryl, substituted or unsubstituted nuclear atom 5 to 50 fused polycyclic aromatic hydrocarbons, or substituted or unsubstituted nuclear atoms 5 to 5 A fused polycyclic aromatic heterocycle of 0, and A ¹ and A ² , A ⁴ and A ⁵ may combine with each other to form a cyclic ring; At least one Q is independently hydrogen, deuterium, substituted or unsubstituted C1-C40 alkyl, substituted or unsubstituted C2-C40 alkenyl, substituted or unsubstituted C2-C40 alkynyl, substituted or unsubstituted C3- C40 cycloalkyl, substituted or unsubstituted heterocycloalkyl having 3 to 40 nuclear atoms, C1-C40 alkyl (substituted with substituted or unsubstituted C6-C60 aryl), substituted or unsubstituted C1-C40 alkoxy, substituted Or unsubstituted C6-C60 arylamine, substituted or unsubstituted C6-C60 diarylamine, substituted or unsubstituted C6-C60 aryloxy, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted nuclear atom Heteroaryl of 5 to 60 substituted or unsubstituted C1-C30 alkylsilyl, substituted or unsubstituted C6-C60 arylsilyl, substituted or unsubstituted fused polycyclic aromatic of 5 to 50 nuclear atoms Hydrocarbon or substituted or unsubstituted fused poly of 5 to 50 nuclear atoms Cyclic aromatic hetero ring.

Preferably, A ¹ to A ⁵ are each independently hydrogen, deuterium, substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C2-C20 alkenyl, substituted or unsubstituted C2-C20 alkynyl, substituted Or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted heterocycloalkyl having 3 to 20 nuclear atoms, C1-C20 alkyl (substituted with substituted or unsubstituted C6-C20 aryl), substituted or unsubstituted C1-C20 alkoxy, substituted or unsubstituted C6-C20 arylamine, substituted or unsubstituted C6-C20 diarylamine, substituted or unsubstituted C6-C30 aryloxy, substituted or unsubstituted C6-C30 aryl, substituted Or unsubstituted heteroaryl of 5 to 30 heteroaryl, substituted or unsubstituted nuclear atom of 5 to 20 fused polycyclic aromatic hydrocarbon, or substituted or unsubstituted nuclear atom of 5 to 20 condensation (fused) polycyclic aromatic heterocyclic ring, a ¹ and a ^2, a ⁴ and a ⁵ are standing Combine to form a cyclic ring having 5 to 8 nuclear atoms, and; At least one Q is independently hydrogen, deuterium, substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C2-C20 alkenyl, substituted or unsubstituted C2-C20 alkynyl, substituted or unsubstituted C3- C20 cycloalkyl, substituted or unsubstituted heterocycloalkyl having 3 to 20 nuclear atoms, (substituted or unsubstituted C6-C20 aryl) C1-C20 alkyl, substituted or unsubstituted C1-C20 alkoxy, substituted or unsubstituted C6-C20 arylamine, substituted or unsubstituted C6-C20 diarylamine, substituted or unsubstituted C6-C30 aryloxy, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted nuclear atom 5 to 30 heteroaryl, substituted or unsubstituted C1-C20 alkylsilyl, substituted or unsubstituted C6-C20 arylsilyl, substituted or unsubstituted fused polycyclic aromatic hydrocarbon having 5 to 20 nuclear atoms, or Substituted or unsubstituted fused polycyclic 5 to 20 nuclear atoms Aromatic heterocycle.

R ₁ to R ₁₂ may combine with adjacent groups to form, for example, a fused aliphatic ring, a fused aromatic ring, a fused heteroaliphatic ring or a fused heteroaromatic ring of 5 to 50 nuclear atoms, and R ₁₃ and R ₁₄ , R ₁₆ and R ₁₇ may be bonded to each other to form a cyclic ring, for example, a cyclic ring having 5 to 8 nuclear atoms.

일 수 있다.R ₁ to R ₁₇ are each independently n is 0 and m is an integer of 1 to 10, preferably 1 to 5

Can be.

Alkyl, alkenyl, alkynyl, cycloalkyl, heterocycloalkyl, arylalkyl, alkoxy, arylamine, diarylamine, aryloxy, aryl, heteroaryl, alkylsilyl, arylsilyl, condensed poly of R ₁ to R ₁₇ The cyclic aromatic hydrocarbons and the condensed polycyclic aromatic heterocycles are each independently deuterium, C1-C20 alkyl, C6-C20 aryl, C6-C20 arylamine, C6-C20 diarylamine, heteroaryl having 5 to 30 nuclear atoms It may be substituted with one or more substituents selected from the group consisting of a condensed polycyclic aromatic hydrocarbon having 5 to 30 nuclear atoms, and a condensed polycyclic aromatic heterocycle having 5 to 30 nuclear atoms. These substituents may be further substituted with C6-C20 aryl, heteroaryl having 5 to 30 nuclear atoms, and the like.

The following formulas are representative examples of the compound of formula 1 of the present invention, but the compounds of the present invention are not limited to those illustrated below.

As used herein, an "unsubstituted condensed polycyclic aromatic hydrocarbon" is an aromatic having 5 to 50, preferably 5 to 20, atoms formed by condensation of 5- to 8-membered aromatic rings with one another. Site, and non-limiting examples thereof include indene, fluorene, phenanthrene and the like.

"Unsubstituted condensed polycyclic aromatic heterocycle" refers to the condensation of 5- to 6-membered aromatic rings with each other to form an aromatic moiety of 5 to 50, preferably 5 to 20, atomic atoms. By at least one of the rings formed by condensation it is meant an aromatic moiety wherein at least one carbon, preferably 1 to 3 carbons, is substituted with a heteroatom such as N, O or S. Non-limiting examples thereof include carbazole and the like.

"Unsubstituted heterocycloalkyl" means a non-aromatic moiety having from 3 to 40, preferably from 3 to 20, nuclear atoms, wherein at least one carbon in the ring, preferably 1 to 3 carbons is N, O or Substituted with a hetero atom such as S. Non-limiting examples thereof include morpholine, piperazine and the like.

"Unsubstituted heteroaryl" means a monoheterocyclic or polyheterocyclic aromatic moiety of 5 to 60, preferably 5 to 30, nuclear atoms, wherein at least one carbon, preferably 1 to 3 carbon atoms in the ring Carbon is substituted with a heteroatom such as N, O or S. It is understood that two or more rings may be attached in a simple or fused form to each other and further include a condensed form with an aryl group. In the present invention, heteroaryl and aromatic heterocycle may be used in an overlapping sense.

Compounds of Formula 1 of the present invention can be synthesized according to general synthetic methods (see J. Org. Chem . 70 (13): 5014-5019 (2005); J. Org. Chem . 73: 7369 (2008), etc.). ). Detailed synthesis procedures for the compounds of the present invention will be described in detail in the synthesis examples described below.

An organic EL device according to the present invention comprises: an anode; Cathode; And at least one organic layer interposed between the anode and the cathode, wherein at least one of the at least one organic layer includes a compound represented by Chemical Formula 1.

The compound of Formula 1 may be included alone or in plurality.

The organic layer including the compound of Formula 1 of the present invention may be at least one of a hole injection layer, a hole transport layer, an electron injection layer, an electron transport layer, and a light emitting layer. In the present invention, the light emitting layer may include a phosphorescent dopant material or a fluorescent dopant material. Preferably, the compound of formula 1 of the present invention is included in the organic EL device as a blue, green, and / or red phosphorescent host, fluorescent host, hole transport material, hole injection material, electron injection material and / or electron transport material. Can be. In addition, the compound of formula 1 of the present invention may be a fluorescent guest material. More preferably, the compound of formula 1 of the present invention may be included in the organic EL device as a phosphorescent host or a fluorescent host, particularly preferably as a phosphorescent host.

Since the compound of the present invention has a high glass transition temperature of 150 ℃ or more, when the compound is used as an organic layer of the organic EL device, since the crystallization is minimized in the organic EL device, the driving voltage of the device can be lowered, luminous efficiency, luminance , Thermal stability, and lifetime characteristics can be improved.

As a non-limiting example of the organic EL device structure according to the present invention, a substrate, an anode, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer and a cathode may be sequentially stacked, wherein the light emitting layer, hole injection layer, At least one of the hole transport layer, the electron injection layer, and the electron transport layer may include a compound represented by Chemical Formula 1.

In addition, as described above, the organic EL device according to the present invention may not only have a structure in which an anode, at least one organic layer, and a cathode are sequentially stacked, but an insulating layer or an adhesive layer may be inserted at the interface between the electrode and the organic layer.

In the organic EL device of the present invention, the organic layer including the compound of Formula 1 may be formed by vacuum deposition or solution coating. Examples of the solution application include spin coating, dip coating, doctor blading, inkjet printing or thermal transfer method, but is not limited thereto.

The organic EL device of the present invention forms an organic layer and an electrode using materials and methods known in the art, except that at least one of the organic layers is formed to include the compound represented by the formula (1) of the present invention. can do.

For example, a silicon wafer, quartz, glass plate, metal plate, plastic film or sheet may be used as the substrate.

The anode material may be a metal such as vanadium, chromium, copper, zinc, gold or an alloy thereof; Metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), indium zinc oxide (IZO); Combinations of oxides with metals such as ZnO: Al or SnO ₂ : Sb; Conductive polymers such as polythiophene, poly (3-methylthiophene), poly [3,4- (ethylene-1,2-dioxy) thiophene] (PEDT), polypyrrole and polyaniline; Or carbon black, but is not limited thereto.

Cathode materials include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin or lead or alloys thereof; Multilayer structure materials such as LiF / Al or LiO ₂ / Al, and the like, but are not limited thereto.

The hole injection layer, the hole transport layer, the electron transport layer and the electron injection layer are not particularly limited, and conventional materials known in the art may be used.

A schematic structure of an organic EL device according to an embodiment of the present invention is shown in FIG. Referring to FIG. 1, the substrate 101, the anode 102, the hole injection layer 103, the hole transport layer 104, the light emitting layer 105, the electron transport layer 106, and the cathode 107 are sequentially stacked. .

Hereinafter, the present invention will be described in detail with reference to the following Examples. However, the following examples are merely to illustrate the present invention and the present invention is not limited by the following examples.

Synthesis Example 1 Synthesis of Compound Inv-3

<Step 1> Synthesis of 3- (2-nitrophenyl) fluoranthene

2- (fluoranthen-3-yl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane (8.4 g, 25.5934 mmol), 2-bromonitrobenzene (5.69 g, 28.1527 mmol) and Pd (PPh3) 4 (0.9 g, 0.7678 mmol) was added to the flask and dissolved in 200 mL of Toluene. A solution of Na ₂ CO ₃ (8.13 g) dissolved in 70 mL of distilled water was added to the flask, followed by stirring under reflux for 12 hours.

After the reaction was completed, the reaction solution was extracted and concentrated with methylene chloride and purified by silica gel column chromatography (Hexane: MC = 4: 1 (v / v)) to give the title compound (6.22 g, 75%). It was.

GC-Mass (Theoretical value: 323.24 g / mol, Measured value: 323 g / mol)

Step 2 Synthesis of 8H-fluoreno [9,1-bc] carbazole

The compound (6.22 g, 19.2367 mmol) synthesized in <Step 1> was dissolved in Triethylphosphite (20 ml, 115.4202 mmol) and stirred under reflux for 4 hours.

After the reaction was completed, the resulting solid was recrystallized from a filter and Hexane / Methylene Chloride to give the title compound (3.24 g, 58%).

GC-Mass (Theoretical value: 291.35 g / mol, Measured value: 291 g / mol)

<Step 3> Synthesis of Compound Inv-3

Compound (13.6 g, 46.6299 mmol), 1,3-dibromobenzene (5 g, 21.1954 mmol), Pd2 (dba) 3 (0.6 g, 0.6358 mmol), NaO (t-Bu) (synthesized in <Step 2> ( 6.1 g, 63.5862 mmol), and P (t-Bu) 3 (0.43 g, 2.1195 mmol) were dissolved in 100 mL of Toluene and stirred at reflux for 12 hours.

After the reaction was completed, the reaction solution was extracted with methylene chloride, the filtrate was concentrated using a silica gel filter, purified by silica gel column chromatography (Hexane: MC = 2: 1 (v / v)) to the desired The title compound Inv-3 (10 g, 77%) was obtained.

GC-Mass (Theoretical value: 656.77 g / mol, Measured value: 656 g / mol)

Synthesis Example 2 Synthesis of Compound Inv-6

Compound 8H-fluoreno [9,1-bc] carbazole (10 g, 34.33 mmol) and 5-bromo-m-terphenyl (12.74 g, 41.196 mmol) synthesized in <Step 2> of Synthesis Example 1 were dissolved in 150 ml of toluene. Except for dissolving, the same procedure as in <Step 3> of Synthesis Example 1 was performed to obtain the title compound Inv-6 (12 g, 67%).

GC-Mass (Theoretical value: 519.63 g / mol, Measured value: 519 g / mol)

Synthesis Example 3 Synthesis of Compound Inv-9

Compounds 8H-fluoreno [9,1-bc] carbazole (10 g, 34.33 mmol) and 2- (3-bromophenyl) -1-phenyl-1H-benzo [d] imidazole synthesized in <Step 2> of Synthesis Example 1 Except for dissolving (14.4 g, 41.2 mmol) in 150 ml of toluene, the same procedure as in <Step 3> of Synthesis Example 1 was performed to obtain the title compound Inv-9 (11 g, 58%).

GC-Mass (Theoretical value: 559.66 g / mol, Measured value: 559 g / mol)

Synthesis Example 4 Synthesis of Compound Inv-10

Compound 8H-fluoreno [9,1-bc] carbazole (10 g, 34.33 mmol) and 4-bromo-N, N-diphenylaniline (13.36 g, 41.2 mmol) synthesized in <Step 2> of Synthesis Example 1 were dissolved in Toluene 150. Except for dissolving in mL, the same procedure as in <Step 3> of Synthesis Example 1 was performed to obtain the title compound Inv-10 (14 g, 76%).

GC-Mass (Theoretical value: 534.65 g / mol, Measured value: 534 g / mol)

Synthesis Example 5 Synthesis of Compound Inv-22

Step 1 Synthesis of 8-phenyl-8H-fluoreno [9,1-bc] carbazole

Except for dissolving the compound 8H-fluoreno [9,1-bc] carbazole (10 g, 34.33 mmol) and Bromobenzene (6.47 g, 41.2 mmol) synthesized in <Step 2> of Synthesis Example 1 in 150 ml of Toluene The title compound (10.5 g, 83%) was obtained by the same procedure as <Step 3> of Synthesis Example 1.

GC-Mass (Theoretical value: 367.44 g / mol, Measured value: 367 g / mol)

Step 2 Synthesis of 5-bromo-8-phenyl-8H-fluoreno [9,1-bc] carbazole

Compound 8-phenyl-8H-fluoreno [9,1-bc] carbazole (5 g, 13.61 mmol) synthesized in <Step 1> was dissolved in 80 ml of N, N-dimethylformamide and then N-bromosuccinimide (2.42 g, 13.61 mmol) was added. The mixed solution was stirred at 80 ° C. for 12 hours and then 200 ml of distilled water was added.

The resulting solid was filtered and dissolved in methylene chloride and filtered through a silica gel filter. The filtrate was concentrated and recrystallized from Hexane / Methylene Chloride to give the title compound (5 g, 82%).

GC-Mass (Theoretical value: 446.34 g / mol, Measured value: 446 g / mol)

Step 3 Synthesis of Compound Inv-22

 Compounds 5-bromo-8-phenyl-8H-fluoreno [9,1-bc] carbazole (5 g, 11.2 mmol) and 3- (1-phenyl-1H-benzo [d] imidazol synthesized in the above <Step 2> -2-yl) phenylboronic acid (4.22 g, 13.44 mmol) was dissolved in 70 ml of Toluene, followed by the same procedure as <Step 1> of Synthesis Example 1 to obtain the title compound Inv-22 (5.2 g, 73%). Obtained.

GC-Mass (Theoretical value: 635.75 g / mol, Measured value: 635 g / mol)

Synthesis Example 6 Synthesis of Compound Inv-24

Compounds 5-bromo-8-phenyl-8H-fluoreno [9,1-bc] carbazole (5 g, 11.2 mmol) and 2- (4- (4,4,5) synthesized in <Step 2> of Synthesis Example 5 , 5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenyl) pyridine (3.78 g, 13.44 mmol) was dissolved in 70 ml of Toluene, and the same procedure as in <Step 1> of Synthesis Example 1 was performed. This gave the desired title compound Inv-24 (4.5 g, 77%).

GC-Mass (Theoretical value: 520.62 g / mol, Measured value: 520 g / mol)

Synthesis Example 7 Synthesis of Compound Inv-38

Step 1 Synthesis of 3-o-tolylfluoranthene

Except for dissolving Fluoranthen-3-ylboronic acid (5 g, 20.32 mmol) and 2-bromotoluene (4.17 g, 24.38 mmol) in 70 ml of Toluene, the same procedure as in <Step 1> of Synthesis Example 1 was performed. Compound (4.8 g, 81%) was obtained.

GC-Mass (Theoretical value: 292.37 g / mol, Measured value: 292 g / mol)

<Step 2> Synthesis of 2- (Fluoranthen-3-yl) benzoic acid

The compound 3-o-tolylfluoranthene (5 g, 17.1 mmol) synthesized in <Step 1> was dissolved in 90 ml of pyridine, and then a solution of potassium permanganate (13.5 g) dissolved in 15 ml of distilled water was added to reflux and stirred for 10 hours. It was.

After the reaction was completed, the precipitate was filtered off and the product remaining in the precipitate was washed with 500 ml of boiling distilled water. The filtrate was collected and hydrochloric acid was added little by little until it became acidic. The precipitate formed was filtered off and the filtered material was dried in an oven to give the title compound (3.1 g, 56%).

GC-Mass (Theoretical value: 322.36 g / mol, Measured value: 322 g / mol)

Step 3 Synthesis of 8H-indeno [2,1-b] fluoranthen-8-one

Compound 2- (fluoranthen-3-yl) benzoic acid (5 g, 15.51 mmol) synthesized in <Step 2> was added to PPA (10 g), followed by stirring at 130 ° C. for 3 hours.

After the reaction was completed, the obtained solution was put into 500 ml of distilled water, and the resulting solid was washed several times with distilled water and then with 200 ml of Methanol to obtain the title compound (3 g, 64%).

GC-Mass (Theoretical value: 304.34 g / mol, Measured value: 304 g / mol)

Step 4 Synthesis of 8H-indeno [2,1-b] fluoranthene

Potassium hydroxide (69.4 g, 1.24 mol) and diethylene glycol (600 ml) were added to a 1 L round bottom flask, followed by stirring, followed by compound 8H-indeno [2,1-b] fluoranthen-8- synthesized in <Step 3>. One (5 g, 16.44 mmol) and Hydrazine monohydrate (50.8 g, 1.02 mol) were added thereto, followed by stirring for 24 hours while heating to 185 ° C.

After the reaction was completed, the reaction solution was poured into a 2 L beaker containing ice and hydrochloric acid was slowly added while stirring. The precipitate formed was filtered, washed several times with distilled water and dried to give the title compound (3.5 g, 73%).

GC-Mass (Theoretical value: 290.36 g / mol, Measured value: 290 g / mol)

Step 5 Synthesis of 8,8-dimethyl-8H-indeno [2,1-b] fluoranthene

The compound 8H-indeno [2,1-b] fluoranthene (3 g, 10.32 mmol) synthesized in <Step 4> was added to a 250 ml round bottom flask, and dried in vacuo and charged with nitrogen gas. 100 ml THF was placed in the flask and cooled to -78 ° C. n-Butyllithium (1.6M in Hex.) (1.65 g, 25.8 mmol) was added slowly and stirred for 1 hour at the same temperature. Iodomethane (4.74 g, 25.8 mmol) was added and stirred for 3 hours.

After the reaction was completed, washed with 100 ml of distilled water, extracted with methylene chloride, water was removed with magnesium sulfate and the filtrate was concentrated.

The reaction solution was purified by column chromatography (Hexane: MC = 9: 1 (v / v)) to give the title compound (2.8 g, 85%).

GC-Mass (Theoretical value: 318.41 g / mol, Measured value: 318 g / mol)

Step 6 Synthesis of 6-bromo-8,8-dimethyl-8H-indeno [2,1-b] fluoranthene

Compound 8,8-dimethyl-8H-indeno [2,1-b] fluoranthene (5 g, 15.7 mmol) synthesized in step <5> was dissolved in 120 ml of N, N-dimethylformamide and then N-bromosuccinimide (2.79 g, 15.7 mmol) was added.

The mixed solution was stirred at 80 ° C. for 12 hours, and then 200 ml of distilled water was added, and the resulting solid was filtered and dissolved in 100 ml of MC, followed by Silicagel Filter. The filtrate was concentrated and then recrystallized from Methanol / Methylene Chloride to give the title compound (5.3 g, 85%).

GC-Mass (Theoretical value: 397.31 g / mol, Measured value: 397 g / mol)

Step 7 Synthesis of Compound Inv-38

Compounds 6-bromo-8,8-dimethyl-8H-indeno [2,1-b] fluoranthene (5 g, 12.58 mmol) and N1- (biphenyl-4-yl) -N4, synthesized in step <6>, Except for dissolving N4-diphenylbenzene-1,4-diamine (5.71 g, 13.84 mmol) in 100 ml of Toluene, the same procedure as in <Step 3> of Synthesis Example 1 was carried out to obtain the title compound Inv-38 (7.4 g , 81%) was obtained.

GC-Mass (Theoretical value: 728.92 g / mol, Measured value: 728 g / mol)

Synthesis Example 8 Synthesis of Compound Inv-42

Compounds 6-bromo-8,8-dimethyl-8H-indeno [2,1-b] fluoranthene (5 g, 12.58 mmol) and 3- (1-phenyl-1H) synthesized in <Step 6> of Synthesis Example 7 Except for dissolving -benzo [d] imidazol-2-yl) phenylboronic acid (4.35 g, 13.84 mmol) in 100 ml of Toluene, the same procedure as in <Step 1> of Synthesis Example 1 was performed. 42 (5.2 g, 70%) was obtained.

GC-Mass (Theoretical value: 586.72 g / mol, Measured value: 586 g / mol)

<Examples 1 to 6> Fabrication of Organic EL Devices (Application to Light-Emitting Layer)

 A glass substrate coated with ITO (Indium tin oxide) having a thickness of 1500 Å was washed with distilled water ultrasonically. After the washing of distilled water, ultrasonic cleaning with a solvent such as isopropyl alcohol, acetone, methanol, and the like was dried, transferred to a plasma cleaner, and then the substrate was cleaned for 5 minutes using an oxygen plasma, and then the substrate was transferred to a vacuum depositor.

NPB (40 nm) / each compound synthesized in Synthesis Examples 1-6 + 10% Ir (piq) 2 (acac) (20 nm) / BCP (10 nm) / Alq 3 (40 nm) / LiF ( An organic EL device was manufactured in the order of 1 nm) / Al (200 nm).

NPB

Ir (piq) 2 (acac)

BCP

Comparative Example 1 Fabrication of Organic EL Device

 An organic EL device was manufactured in the same manner as in Example 1, except that CBP was used as a light emitting host material, instead of the compound prepared in Synthesis Example, to form an emission layer.

CBP

<Evaluation Example 1>

For each organic EL device manufactured in Example 1-6 and Comparative Example 1, the driving voltage, current efficiency, and luminance were measured, and the results are shown in Table 1 below.

Table 1 device compound Voltage (V) Luminance (cd / m2) Efficiency (cd / A) color Example 1 Inv-3 (Synthesis Example 1) 3.4 72 7.2 Red Example 2 Inv-6 (Synthesis Example 2) 3.0 65 6.5 Red Example 3 Inv-9 (Synthesis Example 3) 2.8 78 7.8 Red Example 4 Inv-10 (Synthesis Example 4) 3.0 67 6.7 Red Example 5 Inv-22 (Synthesis Example 5) 2.8 74 7.4 Red Example 6 Inv-24 (Synthesis Example 6) 2.7 74 7.4 Red Comparative Example 1 CBP 5.4 64 6.4 Red

As shown in Table 1, the organic EL device (Example 1-6) using the compound according to the present invention exhibits superior performance in terms of voltage and efficiency than the organic EL device (Comparative Example 1) using the conventional CBP. Able to know.

<Examples 7 to 9, Comparative Example 2> Preparation of Organic EL Device (Application to Electron Injection and Transport Layer)

On the ITO transparent electrode prepared in Example 1, DS-HIL (Doosan Corporation, hereinafter referred to as DS-HIL) was thermally vacuum deposited to a thickness of 60 nm to form a hole injection layer. After depositing 15 nm thick N , N -di (naphthalene-1-yl) -N and N -diphenylbenzidine (NPB), the hole transporting material, ADN (9,10- A light emitting layer was deposited to a thickness of 30 nm using di (naphthalen-2-yl) anthracene (hereinafter referred to as ADN) and DS-405 (Doosan Corporation) serving as a dopant. Compounds Inv-9 (Example 7), Inv-22 (Example 8), and Inv-42 (Example 9) synthesized in Synthesis Examples 3, 5, and 8, respectively, as materials for injecting and transporting electrons on the light emitting layer. ) And a comparative material, aluminum tris (8-hydroxyquinoline) (Alq3) (Comparative Example 2), were deposited to a thickness of 25 nm, respectively. An organic EL device was fabricated by depositing LiF and Al having a thickness of 200 nm at a thickness of 1 nm sequentially on the electron injection and transport layer to form a cathode.

<Evaluation Example 2>

For each organic EL device manufactured in Example 7-9 and Comparative Example 2, the driving voltage, current efficiency and luminance were measured, and the results are shown in Table 2 below.

TABLE 2 device compound Voltage (V) Luminance (cd / m2) Efficiency (cd / A) color Example 7 Inv-9 (Synthesis Example 3) 4.7 681 6.8 blue Example 8 Inv-22 (Synthesis Example 5) 4.9 652 6.5 blue Example 9 Inv-42 (Synthesis Example 8) 4.8 650 6.5 blue Comparative Example 2 Alq3 5.7 600 6.0 blue

As shown in Table 2 above, the organic EL device (Example 7-9) using the compound according to the present invention showed superior performance in terms of voltage and efficiency than the organic EL device (Comparative Example 2) using the conventional Alq3. Able to know.

Example 10 Fabrication of Organic EL Device (Application to Hole Injection and Transport Layer)

On the ITO transparent electrode prepared in Example 1, the compound Inv-38 (40 nm) / CBP + 10% Ir (ppy) 2 (acac) (20 nm) / BCP (10 nm) / Alq 3 (40 nm) synthesized in Synthesis Example 7 ) / LiF (1 nm) / Al (200 nm) in order to produce an organic EL device.

Ir (ppy) 2 (acac)

Comparative Example 3 Fabrication of Organic EL Device

An organic EL device was manufactured in the same manner as in Example 10, except that NPB was used instead of the compound prepared in the synthesis example in forming the hole injection and transport layer.

<Evaluation Example 3>

For each organic EL device manufactured in Example 10 and Comparative Example 3, the driving voltage, current efficiency, and luminance were measured, and the results are shown in Table 3 below.

TABLE 3 device compound Voltage (V) Luminance (cd / m2) Efficiency (cd / A) color Example 10 Inv-38 (Synthesis Example 7) 5.7 224 22.4 green Comparative Example 3 NPB 7.94 174 17.4 green

As shown in Table 3, it can be seen that the organic EL device (Example 10) using the compound according to the present invention exhibits superior performance in terms of voltage and efficiency compared to NPB (Comparative Example 3).

Claims (7)

   Compound represented by the following formula (1): [Formula 1]

Where X is selected from the group consisting of CR ₁₃ R ₁₄ , NR ₁₅ , O, S, S (= 0), S (= 0) ₂ and SiR ₁₆ R ₁₇ , R ₁ to R ₁₇ are each independently

This, n and m are each independently an integer of 0 to 10, except that at the same time 0; At least one L is each independently selected from the group consisting of CA ¹ A ² , NA ³ , O, S and SiA ⁴ A ⁵ , and A ¹ to A ⁵ are each independently hydrogen, deuterium, substituted or unsubstituted C1-; C40 alkyl, substituted or unsubstituted C2-C40 alkenyl, substituted or unsubstituted C2-C40 alkynyl, substituted or unsubstituted C3-C40 cycloalkyl, substituted or unsubstituted heterocycloalkyl having 3 to 40 heteroatoms Alkyl, (substituted or unsubstituted C6-C60 aryl) C1-C40 alkyl, substituted or unsubstituted C1-C40 alkoxy, substituted or unsubstituted C6-C60 arylamine, substituted or unsubstituted C6-C60 diarylamine , Substituted or unsubstituted C6-C60 aryloxy, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted nuclear atom having 5 to 60 heteroaryl, substituted or unsubstituted nuclear atom having 5 to 50 condensation (fused) polycyclic aromatic hydrocarbons or substituted or unsubstituted 5 to 50 condensed atoms (fu sed) a polycyclic aromatic heterocycle, wherein A ¹ and A ² , A ⁴ and A ⁵ can combine with each other to form a cyclic ring; At least one Q is independently hydrogen, deuterium, substituted or unsubstituted C1-C40 alkyl, substituted or unsubstituted C2-C40 alkenyl, substituted or unsubstituted C2-C40 alkynyl, substituted or unsubstituted C3- C40 cycloalkyl, substituted or unsubstituted heterocycloalkyl having 3 to 40 nuclear atoms, (substituted or unsubstituted C6-C60 aryl) C1-C40 alkyl, substituted or unsubstituted C1-C40 alkoxy, substituted or unsubstituted C6-C60 arylamine, substituted or unsubstituted C6-C60 diarylamine, substituted or unsubstituted C6-C60 aryloxy, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted nuclear atom 5 to 60 heteroaryl, substituted or unsubstituted C1-C30 alkylsilyl, substituted or unsubstituted C6-C60 arylsilyl, substituted or unsubstituted fused polycyclic aromatic hydrocarbon having 5 to 50 nuclear atoms, or Substituted or unsubstituted fused polycyclic 5 to 50 nuclear atoms Aromatic heterocycle; R ₁ to R ₁₂ may combine with adjacent groups to form a fused aliphatic ring, a fused aromatic ring, a fused heteroaliphatic ring or a fused heteroaromatic ring; R ₁₃ and R ₁₄ , R ₁₆ and R ₁₇ may combine with each other to form a cyclic ring.  The method of claim 1, R ₁ to R ₁₇ are each independently n is 0 and m is an integer of 1 to 10

The compound characterized by the above-mentioned.  The method of claim 1, Alkyl, alkenyl, alkynyl, cycloalkyl, heterocycloalkyl, arylalkyl, alkoxy, arylamine, diarylamine, aryloxy, aryl, heteroaryl, alkylsilyl, arylsilyl, condensed poly of R ₁ to R ₁₇ Substituents of the cyclic aromatic hydrocarbons and the condensed polycyclic aromatic heterocycles are each independently deuterium, C 1 -C 20 alkyl, C 6 -C 20 aryl, C 6 -C 20 arylamine, C 6 -C 20 diarylamine, having 5 to 30 nuclear atoms. And at least one selected from the group consisting of heteroaryl, condensed polycyclic aromatic hydrocarbons having 5 to 30 nuclear atoms, and condensed polycyclic aromatic heterocycles having 5 to 30 nuclear atoms.  anode; cathode; And at least one organic layer interposed between the anode and the cathode. At least one of the organic layers comprises the compound according to any one of claims 1 to 3.   The method of claim 4, wherein And the organic layer is selected from the group consisting of a light emitting layer, an electron transport layer, an electron injection layer, a hole injection layer, and a hole transport layer.   The method of claim 4, wherein The compound is an organic electroluminescent device, characterized in that the phosphorescent host material or a fluorescent host material.   The method of claim 4, wherein The compound is an organic electroluminescent device, characterized in that the fluorescent guest material.

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