KR20170006658A - Phosphorescent iridium compound containing fixed carboranes, and organic light emitting diode using the same - Google Patents

Phosphorescent iridium compound containing fixed carboranes, and organic light emitting diode using the same Download PDF

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KR20170006658A
KR20170006658A KR1020150097618A KR20150097618A KR20170006658A KR 20170006658 A KR20170006658 A KR 20170006658A KR 1020150097618 A KR1020150097618 A KR 1020150097618A KR 20150097618 A KR20150097618 A KR 20150097618A KR 20170006658 A KR20170006658 A KR 20170006658A
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이민형
이영훈
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울산대학교 산학협력단
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Abstract

The present invention relates to a phosphorescent compound, and to an organic light emitting device using the same. According to the present invention, a phosphorescent compound has a structure introducing carborane acid to a prescribed position of a heteroleptic complex compound having iridium (Ir) as a central metal element, wherein the carborane acid is fixed by a linker. Thus, high color purity, high efficiency, and long lifespan characteristics of an organic light emitting device can be realized.

Description

[0001] The present invention relates to a phosphorescent compound containing fixed carboranes and an organic light emitting device using the same,

The present invention relates to a phosphorescent compound and an organic light emitting device using the phosphorescent compound. More particularly, the present invention relates to a phosphorescent compound in which carborane immobilized by a linker is introduced at a certain position of a heteroleptic complex having iridium (Ir) as a central metal element, And an organic light emitting device using the same.

OLED is a display capable of realizing characters and images of various colors by emitting a voltage by applying a voltage to a thin film made of an organic material so that organic materials emit light by itself. The OLED is a self-emitting type, ultra thin type (1/3 of LCD) (1000 times of LCD), low power consumption (1/2 of LCD), high definition and flexibility, it is attracting attention as a display for smart phones, tablets, notebooks, and wall-hanging TVs.

A typical patterning technique used in the manufacture of OLEDs is a vacuum deposition method using a fine metal mask. However, due to the high process cost and technical limitations, the vacuum deposition method has a limitation that it can not be applied to a large display. Accordingly, a variety of patterning techniques that can replace the vacuum deposition method have been developed. In particular, wet processing such as spin coating, inkjet printing, casting method, etc., does not require vacuum technology, It is easy to fabricate the device, and is attracting attention in the large display industry. However, when the organic thin film layer is formed by a wet process, there is a problem that the material of the lower film already formed is dissolved by the organic solvent. Because of this problem, it is difficult to stack the organic thin film layer in multiple layers. There is a problem that can not be implemented.

On the other hand, a heavy metal complex-based phosphorescent organic light emitting device (PhOLED) attracts attention because it can achieve theoretically 100% internal quantum efficiency by using both singlet and triplet excitons. Accordingly, various techniques for preparing an organic light emitting device in which a host material used in a light emitting layer and a phosphorescent iridium (III) complex are inserted into a single copolymer, for example, a covalently bonded conjugated copolymer of an iridium complex, or Studies on a copolymer in which an iridium complex and a host material are attached to a residue of a polymer backbone conjugated as a guest residue have been actively studied (Patent Documents 1 to 4). However, the above technologies use a wet process in the production of organic light emitting devices, and thus the light emitting devices manufactured in this way have a problem in that their performance is degraded as compared with devices manufactured using vacuum deposition.

Therefore, in order to improve the efficiency of the organic light emitting device, it is necessary to include a phosphorescent iridium complex as a low-molecular host and a guest residue, and thus to have high electrical properties such as high light-emitting properties of the iridium complex, There is an urgent need to develop a new phosphorescent compound which can be applied to organic EL devices having high efficiency.

Korea Patent Publication No. 2006-0098860 Korean Patent Publication No. 2008-0080765 Korean Patent No. 2012-0140034 Korea Patent Publication No. 2013-0070507

Lee, Y. H .; Park, J .; Jo, S.-J .; Kim, M .; Lee, J .; Lee, S. U .; Lee, M. H., Chem.Eur.J., 2015, 21, 2052-2061. Lamansky, S .; Djurovich, P .; Murphy, D .; Abdel-Razzaq, F .; Lee, H. E .; Adachi, C .; Burrows, P. E .; Forrest, S. R .; Thompson, M. E. J. Am. Chem. Soc. 2001, 123, 4304-4312. Baranoff, E .; Curchod, B. F. E .; Frey, J .; Scopelliti, R .; Kessler, F .; Tavernelli, I .; Rothlisberger, U .; Gratzel, M .; Nazeeruddin, M. K. Inorg. Chem. 2012, 51, 215-224.

Accordingly, an object of the present invention is to provide a phosphorescent compound which can be used in a wet process regardless of the polarity of a solvent and which can realize high color purity, high efficiency and long life, and an organic light emitting Device.

According to an aspect of the present invention,

A phosphorescent compound represented by the following formula (1)

[Chemical Formula 1]

Figure pat00001

In formula (1)

CB is a carboranyl group (C 2 B 10 H 10 )

Ln is an alkylene group having 1 to 15 carbon atoms or an arylalkylene group having 6 to 20 carbon atoms,

Figure pat00002
The
Figure pat00003
,
Figure pat00004
,
Figure pat00005
,
Figure pat00006
, or
Figure pat00007
ego,

Figure pat00008
The
Figure pat00009
,
Figure pat00010
,
Figure pat00011
,
Figure pat00012
,
Figure pat00013
,
Figure pat00014
,
Figure pat00015
, or
Figure pat00016
Lt;

Wherein R 1 to R 5 independently represent hydrogen, an aryl group of C 1 -12 alkyl or C 6 -20 of.

In addition, the present invention, in one embodiment,

An anode, a cathode, and an organic layer between both electrodes,

The organic layer includes the phosphorescent compound.

The phosphorescent compound according to the present invention has a structure in which carborane immobilized by a linker is introduced at a certain position of a heteroleptic complex having iridium (Ir) as a central metal element, whereby a high color purity, high efficiency and long life Properties can be implemented.

1 to 3 are sectional views showing the structure of an organic light emitting device according to the present invention.
4 is a graph showing UVvis absorption and photoluminescence (PL) spectra of a phosphorescent compound measured under toluene conditions according to one embodiment.
5 is a graph showing the photoluminescence (PL) spectrum of a phosphorescent compound measured under conditions of THF or PMMA thin film according to another embodiment.
6 is a graph showing the average CC variation (Δ (CC) T1 - S0 ) between the ground state (S 0 ) and the excited state (T 1 ) of the phosphorescent compounds derived from another embodiment, to be.

While the invention is susceptible to various modifications and alternative forms, specific embodiments thereof are shown by way of example in the drawings and will herein be described in detail.

It is to be understood, however, that the invention is not to be limited to the specific embodiments, but includes all modifications, equivalents, and alternatives falling within the spirit and scope of the invention.

In the present invention, the terms "comprising" or "having ", and the like, specify that the presence of a feature, a number, a step, an operation, an element, a component, But do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, or combinations thereof.

It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory and are intended to provide further explanation of the invention as claimed.

The term "HOMO" in the present invention means a molecular orbital energy possessed by a compound or a complex. As used herein, the term " HOMO " refers to a molecular orbital energy possessed by a compound or a complex. Lowest Unoccupied Molecular Orbital with the lowest energy level is called "LUMO".

The present invention relates to a phosphorescent compound and an organic light emitting device using the same.

OLED is a display capable of realizing characters and images of various colors by emitting a voltage by applying a voltage to a thin film made of an organic material so that organic materials emit light by itself. The OLED is a self-emitting type, ultra thin type (1/3 of LCD) (1000 times of LCD), low power consumption (1/2 of LCD), high definition and flexibility, it is attracting attention as a display for smart phones, tablets, notebooks, and wall-hanging TVs. In particular, phosphorescent organic light emitting devices based on heavy metal complexes are attracting interest because they can achieve theoretically 100% internal quantum efficiency by using both singlet and triplet excitons. Accordingly, various techniques for preparing an organic light emitting device in which a host material used in a light emitting layer and a phosphorescent iridium (III) complex are inserted into a single copolymer have been developed. However, a problem that the device performance is significantly reduced when applied to a wet process There is a problem that it can not be utilized in a large display industry or the like.

Accordingly, the present invention provides a phosphorescent compound in which carborane immobilized by a linker is introduced at a certain position of a heteroleptic complex having iridium (Ir) as a central metal element, and an organic light emitting device using the phosphorescent compound.

The phosphorescent compound according to the present invention has a structure in which carborane is introduced as a substituent at a certain position of a heteroleptic complex having iridium (Ir) as a central metal element, and the introduced carboranes are fixed with a linker, High color purity, high efficiency and long life characteristics of the device can be realized.

Hereinafter, the present invention will be described in more detail.

The present invention, in one embodiment,

A phosphorescent compound represented by the following formula (1)

Figure pat00017

In formula (1)

CB is a carboranyl group (C 2 B 10 H 10 )

Ln is an alkylene group having 1 to 15 carbon atoms or an arylalkylene group having 6 to 20 carbon atoms,

Figure pat00018
The
Figure pat00019
,
Figure pat00020
,
Figure pat00021
,
Figure pat00022
, or
Figure pat00023
ego,

Figure pat00024
The
Figure pat00025
,
Figure pat00026
,
Figure pat00027
,
Figure pat00028
,
Figure pat00029
,
Figure pat00030
,
Figure pat00031
, or
Figure pat00032
Lt;

Wherein R 1 to R 5 independently represent hydrogen, an aryl group of C 1 -12 alkyl or C 6 -20 of.

As one example, the CB can be an ortho-carboranyl, a meta-carboranyl or a para-carboranyl, -Carboranyl group (ortho-carboranyl).

The Ln may be a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group, or an octylene group,

Figure pat00033
The
Figure pat00034
,
Figure pat00035
, or
Figure pat00036
Lt;

The R 1 may be hydrogen, a methyl group, an ethyl group, a propyl group, a butyl group, or a phenyl group.

Specifically, Ln may be a propylene group, a butylene group, a pentylene group, a hexylene group or an octylene group,

Figure pat00037
The
Figure pat00038
,
Figure pat00039
or
Figure pat00040
Lt; / RTI >

Further, the compound represented by Formula 1 may be a compound represented by Formula 2:

Figure pat00041

In Formula 2,

Ln 1 is a propylene group, a butylene group, a pentylene group, a hexylene group or an octylene group,

Figure pat00042
The
Figure pat00043
,
Figure pat00044
,
Figure pat00045
,
Figure pat00046
,
Figure pat00047
or
Figure pat00048
to be.

Specifically, Ln 1 may be a butylene group or a hexylene group,

Figure pat00049
The
Figure pat00050
, or
Figure pat00051
Lt; / RTI >

In addition, the compound represented by Formula 1 may be a compound represented by Formula 3:

Figure pat00052

In Formula 3,

Ln 2 is a propylene group, a butylene group, a pentylene group, a hexylene group or an octylene group,

Figure pat00053
The
Figure pat00054
,
Figure pat00055
,
Figure pat00056
,
Figure pat00057
,
Figure pat00058
or
Figure pat00059
to be.

Specifically, Ln 2 may be a butylene group or a hexylene group,

Figure pat00060
The
Figure pat00061
, or
Figure pat00062
Lt; / RTI >

The phosphorescent compound represented by the general formula (1) according to the present invention contains iridium (Ir) as a central metal element, ligand

Figure pat00063
Wow
Figure pat00064
Is a cyclometalated complex coordinated to iridium.

The phosphorescent compound represented by Formula 1 is a ligand of the cyclic metal iridium complex (

Figure pat00065
) May have a structure in which carbene is substituted.

Since the iridium and the ligand have a metal-carbon bond, the metal-ligand charge transfer (MLCT) can easily occur in the cyclic metal iridium complex. As a result, the phosphorescence emission, which is a prohibited transition, is apt to occur and the triplet excitation life is shortened, so that the luminous efficiency of the cyclic metal iridium complex can be improved.

In addition, by partially modifying the cyclic metal iridium complex, the emission color over the entire visible light region can be controlled. Correction or adjustment of this phosphorescence color may be accomplished by using a ligand

Figure pat00066
) ≪ / RTI >

Specifically, ligands that affect the energy levels of HOMO (Highest Occupied Molecular Orbital) and LUMO (Lowest Unoccupied Molecular Orbital)

Figure pat00067
) Can be changed to change the excited state energy. For example,
Figure pat00068
, The HOMO of the cyclic metal iridium complex can be controlled by the π orbitals of the phenyl ring and the dπ orbitals of iridium and the LUMO can be controlled by the π * orbitals of the pyridine ring. As a result, the introduction of an electron withdrawing group such as a fluorine element into the phenyl ring of the ligand increases the HOMO-LUMO band gap by lowering the HOMO level, while the introduction of the ligand into the pyridine ring By lowering the LUMO level, the bandgap can be reduced. That is, the energy level of the triplet state formed from the HOMO-LUMO transition can be precisely controlled by changing the bandgap.

On the other hand, the carborane group is a substance having specific physical properties such as a highly polar σ-aromatic property, an electron deficiency characteristic, and excellent thermal and chemical stability, and is substituted at a specific position of the ligand, The luminescent efficiency of the iridium complex can be improved and the lifetime can be prolonged.

The carboranes not only directly contribute to the delocalization of the LUMO but also significantly lower the LUMO level due to the strong electron withdrawing effect. In addition, since the carbolane has a large molecular size, it can inhibit intermolecular interaction between the phosphorescent light emitting molecules, thereby preventing triplet-triplet extinction and concentration termination in a solid state. In particular, the cyclic metal iridium complex introduced or substituted at the carbon position 4 and / or 5 of the phenyl ring of the ligand with the ortho-carbene group has a red to blue The emission wavelength can be easily adjusted up to the shift.

In addition, the present invention, in one embodiment,

An anode, a cathode, and an organic layer between both electrodes,

Wherein the organic layer comprises a phosphorescent compound represented by Formula 1.

The organic light emitting device according to the present invention may be a display capable of realizing characters or images of various colors by emitting a self-luminous organic substance when a voltage is applied to a thin film made of an organic material. Among them, phosphorescent organic light emitting Phosphorescent organic light emitting diode (" PHOLED ").

In addition, the anode and the cathode may be transparent or opaque (reflective) electrodes as a material having excellent electrical conductivity. For example, in the case of a transparent electrode, the anode and the cathode may include indium tin oxide (ITO), tin oxide (SnO 2 ), or the like, and may be a single layer or ITO / silver Layer structure of two or more layers. In the case of an opaque (reflective) electrode, the positive electrode and the negative electrode may include a metal such as nickel, magnesium, calcium, silver, aluminum, indium, or an alloy containing two or more of these metals. In addition, the opaque electrode may have a single-layer structure or a multi-layer structure of two or more layers.

Further, the organic layer may include a phosphorescent compound represented by Formula 1 according to the present invention as a dopant material, and may have a single layer or a multi-layer structure of two or more layers. In addition, the organic layer can use a host material together with a phosphorescent dopant, and a low molecular weight or high molecular weight host can be used. Examples of the low molecular weight host include 9,9 '- (1,1'-biphenyl) -4,4'-diyl bis-9H-carbazole (CBP) and 9,9' (PNB-mCP), and poly- (N-vinylcarbazole) -bis-9H-carbazole (mCP). Examples of the high molecular weight host include polynorbornene-CBP (PVCz): PBD (or OXD-7).

Generally, a multilayered device in which a light emitting layer and a charge transport layer are combined, exhibits excellent device characteristics, rather than a single-layered device composed of only a single light emitting layer. This is because an appropriate combination of a light emitting material and a charge transporting material, The barrier is reduced, and the charge transport layer confines the holes or electrons injected from the electrodes to the light emitting layer region, so that the number density of injected holes and electrons is balanced. In particular, in the case of a phosphorescent organic light emitting device, since the emission duration of the phosphorescent compound is long, holes are confined in the light emitting layer to stay in the light emitting layer for a long time in order to increase the efficiency.

1 and 2, when the organic light emitting device 100 includes the anode 110, the first charge transport layer 120, the light emitting layer 130, the second charge transport layer 140, and the cathode 150 sequentially And the phosphorescent compound represented by Formula 1 may be included in the light emitting layer 130 as a dopant. In order to improve device characteristics such as luminous efficiency and lifetime, the first charge transport layer 120 may have a structure in which the first charge transport layer 120 has a stacked structure. And the second charge transport layer 140 may include a hole injection layer 121 and / or a hole transport layer 122 and an electron transport layer 141 and / or an electron injection layer 142, respectively.

The hole injection layer 121 may be inserted into a conventional hole injection layer including, for example, copper phthalocyanine (CuPc), and the electron injection layer 142 may include, for example, LiF And may be inserted into a conventional electron injecting layer.

The hole transport layer 122 may be formed using conventional hole transport materials such as 4,4-bis [N- (1-naphthyl) -N-phenylamine] biphenyl (N-NPD) Diphenyl-N, N-bis (3-methylphenyl) -1,1-biphenyl-4,4-diamine (TPD) and poly- (N-vinylcarbazole) (PVCz) And may have a multilayer structure in which two or more layers are stacked as required.

The electron transporting layer (electron transporting light emitting layer) 141 may be a conventional electron transporting material such as tris (8-quinolinolato) aluminum (Alq 3 ), 4,7-diphenyl-1,10-phenanthrol Bphen, rubrene, or the like, or a mixture of two or more thereof, and may have a multi-layer structure in which two or more layers are stacked as required.

3, the phosphorescent organic light emitting diode 100 includes an electron blocking layer 170 between the light emitting layer 130 and the first charge transporting layer, specifically, the hole transporting layer 122, ) And the second charge transporting layer, specifically, the electron transporting layer 141, may be further included.

As the electron blocking layer 170, a material having a large LUMO value is generally used, and iridium (III) tris (1-phenylpyrazole-N, C2 ') (Ir (ppz) 3 ) is suitable. Also, the hole blocking layer 160 has a lowest unoccupied molecular orbital (LUMO) value between 5.5 and 7.0, and has a hole transporting ability remarkably deteriorated, and a material having an excellent electron transporting ability, for example, 1,3,5-tris (BCP), 3- (4-biphenylyl) -4-phenyl-5- (4-t-butoxycarbonyl) -Butylphenyl) -1,2,4-triazole (TAZ), bis (8-hydroxy-2-methylquinolinato) -aluminum biphenoxide (BAlq) and the like.

The anode, the cathode, the light emitting layer, the transport layer, the injection layer, and the barrier layer may be formed by a conventional deposition method. Since the phosphorescent compound represented by Formula 1 is included as a dopant in the organic light emitting device and exhibits stable luminescence and exhibits excellent external quantum efficiency and power efficiency, As shown in FIG.

Hereinafter, the present invention will be described in more detail with reference to Examples and Experimental Examples.

However, the following Examples and Experimental Examples are merely illustrative of the present invention, and the present invention is not limited to the following Examples and Experimental Examples.

Example  One.

[Formula 1a]

Figure pat00069

Step 1: First Ligand  Produce

(0.32 g, 1.1 < RTI ID = 0.0 > mmol) < / RTI > was dissolved in dimethylformamide (5 mL) mmol) was slowly added dropwise to a solution of dimethylformamide (5 mL) at -20 ° C. Thereafter, the mixture was stirred at room temperature, cooled again to -20 占 폚, and 1,4-diiodobutane (0.16 g, 0.54 mmol) was added thereto, followed by stirring overnight at room temperature. NH 4 Cl aqueous solution was poured into the mixture to terminate the reaction and extracted three times with Et 2 O (30 mL). The extracted Et 2 O solution was washed three times with water (30 mL), water was removed with MgSO 4 , and the filtrate was concentrated under reduced pressure. The concentrated mixture was purified by column chromatography (silica gel, ethyl acetate / hexane = 1: 6 (v / v)) to obtain a white solid first ligand (Yield: 0.19 g, yield: 53%).

1 H NMR (CDCl 3): δ 8.72 (dq, J = 4.8, 0.9 Hz, 2H), 7.97 (d, J = 8.7 Hz, 4H), 7.83-7.73 (m, 4H), 7.63 (d, J = 8.7, 4H), 7.32-7.28 (m , 2H), 3.6-1.1 (br, 20H, B- H), 1.63 (t, J = 7.2 Hz, 4H, C 2 B 10 H 10 C H 2 -), 1.14 (quintet, J = 4.2 Hz , 4H, C 2 B 10 H 10 CHC H 2 -).

13 C NMR (CDCl 3 ): δ 156.5, 150.9, 142.5, 138.1, 132.5, 131.9, 128.3, 124.0, 121.8 (Ar- C ), 84.1, 82.6 (C 2 B 10 H 10 -C ), 35.5, 29.7 butylene- C ).

11 B NMR (CDCl 3): δ -3.7, -10.3.

mp = 179 [deg.] C.

HR EI-MS (C 30 H 44 B 20 N 2 ): m / z 652.5366 (theory); 652.5368 (measured).

Step 2: [1,4- ( CH 2 ) 4- (4- CBppy ) 2 ] Ir ( acac ) ≪ / RTI >

The first ligand (0.19 g, 0.29 mmol) prepared in Step 1 and IrCl 3 (0.09 g, 0.30 mmol) were dissolved in 2-ethoxyethanol (20 mL) and stirred at 110 ° C for 24 hours. The solid formed in the reaction was then filtered and washed with ethanol and Et 2 O to give a light yellow complex (0.12 g, 0.077 mmol) in the form of a dimer. The prepared complex was added to CH 3 CN (20 mL) with Na 2 CO 3 (0.1 g, 0.94 mmol) and 2,4-pentadione (0.1 g, 1.0 mmol) without further purification, At reflux for 24 hours. The reaction was then cooled to room temperature and filtered to give a yellow precipitate. The resulting precipitate was dissolved in CH 2 Cl 2 and concentrated under reduced pressure. The concentrated mixture was purified by column chromatography (silica gel, dichloromethane / hexane = 2: 1 (v / v)) to obtain the desired compound as a yellow solid (Yield: 0.05 g, yield: 35%).

1 H NMR (CDCl 3): 8.47 (d, J = 5.9, 2H), 8.00-7.85 (m, 4H), 7.50 (d, J = 8.4 Hz, 2H), 7.29-7.24 (m, 2H), 6.97 (dd, J = 8.1, 2.1 Hz, 2H), 6.22 (d, J = 2.1 Hz, 2H), 5.31 (s, 2H, acac-C H), 3.5-1.2 (br, 20H, B- H), 1.83 (s, 6H, acac- C H 3), 1.31-1.23 (m, 2H, C 2 B 10 H 10 C H 2 -), 1.19-1.10 (m, 2H, C 2 B 10 H 10 C H 2 -), 0.69-0.60 (m, 2H, -C H 2 CH 2 C 2 B 10 H 10 ), 0.43-0.38 (m, 2H, -C H 2 CH 2 C 2 B 10 H 10 ).

13 C NMR (CDCl 3): δ 185.1 (acac- C O), 166.6, 148.7, 147.2, 137.8, 135.6, 129.2, 124.5, 123.2, 122.9, 119.3 (Ar- C), 101.0 (acac- C H), 84.7, 81.9 ( 2 - C ), 32.2, 28.8, 27.1 (acac- C H 3 and butylene- C ).

11 B NMR (CDCl 3): δ -4.3, -11.1.

Dec. pt = 360 ° C.

Elemental analysis (C 35 H 49 B 20 IrN 2 O 2 ): C, 44.81; H, 5.26; N, 2.99 (theory). C, 44.36; H, 5.34; N, 2.74 (measured value).

Example  2.

[Chemical Formula 1b]

Figure pat00070

Step 1: First Ligand  Produce

(0.32 g, 1.1 mmol) and 1,4-diiodobutane (0.16 g, 0.54 mmol) in the step 1 of Example 1, (0.2 g, 0.63 mmol) and 1.6-dibromohexane (0.08 g, 0.32 mmol) instead of using 2- {m- (1,2- (Yield: 0.15 g, yield: 70%) was obtained in the same manner as in step 1 of Example 1,

1 H NMR (CDCl 3): δ 8.69 (d, J = 4.8 Hz, 0.9H), 8.24 (t, J = 1.8 Hz, 2H), 8.02 (dt, J = 7.8, 0.9 Hz, 2H), 7.77 ( td, J = 7.8, 1.8 Hz , 2H), 7.68 (dt, J = 8.1, 0.9 Hz, 2H), 7.59 (dq, J = 8.0, 0.9 Hz, 2H), 7.43 (t, J = 7.8 Hz, 2H ), 7.30-7.25 (m, 2H), 3.4-1.2 (br, 20H, B- H ), 1.69-1.62 (m, 4H, C 2 B 10 H 10 C H 2 CH 2 CH 2 - 1.22 (m, 4H, C 2 B 10 H 10 CH 2 C H 2 CH 2 -), 0.86-0.79 (m, 4H, C 2 B 10 H 10 CH 2 CH 2 C H 2 -).

13 C NMR (CDCl 3 ): δ 156.7, 150.9, 141.1, 138.1, 132.2, 132.1, 130.7, 130.3, 129.9, 123.9, 121.6 (Ar- C ), 84.4, 83.3 (C 2 B 10 H 10 -C ) 35.8, 30.1, 29.2 (hexylene- C ).

11 B NMR (CDCl 3): δ -3.4, -10.3.

mp = 132 [deg.] C.

HR EI-MS (C 32 H 48 B 20 N 2 ): m / z 680.5679 (theory); 680.5682 (measured).

Step 2: [l, 6- ( CH 2 ) 6 - (5- CBppy ) 2 ] Ir ( acac ) ≪ / RTI >

Instead of using the first ligand (0.07 g, 0.1 mmol) prepared in step 1 of Example 1 in step 2 of Example 1, the first ligand prepared in step 1 of Example 2 (0.07 g, 0.01 mmol ), The target compound (Formula 1b, Yield: 0.04 g, yield: 50%) was obtained in the same manner as in Step 2 of Example 1,

1 H NMR (CDCl 3): δ 8.48 (d, J = 5.4 Hz, 2H), 7.93 (d, J = 8.1 Hz, 2H), 7.83 (td, J = 7.2, 1.2 Hz, 2H), 7.68 (d , J = 2.1 Hz, 2H) , 7.27-7.22 (m, 2H), 6.80 (dd, J = 8.1, 1.8 Hz, 2H), 6.21 (d, J = 8.1 Hz, 2H), 5.27 (s, 1H, acac-C H), 3.8-1.2 ( br, 20H, B- H), 1.80 (s, 6H, acac-C H 3), 1.62-1.55 (m, 2H, hexylene-C H 2), 1.31-1.20 (m, 4H, hexylene-C H 2), 1.05-0.99 (m, 2H, hexylene-C H 2), 0.86-0.78 (m, 2H, hexylene-C H 2), 0.46-0.41 (m, 2H, hexylene-C H 2 ).

13 C NMR (CDCl 3): δ 186.0 (acac- C O), 168.0, 153.1, 149.4, 146.5, 138.5, 134.1, 132.1, 127.5, 123.9, 123.5, 120.1 (Ar- C), 101.8 (acac- C H ), 87.1, 83.6 (C 2 B 10 H 10 - C ), 35.3, 29.8, 29.7, 28.8 (acac - C H 3 and hexylene - C ).

11 B NMR (CDCl 3): δ -3.9, -10.7.

Dec. pt = 320 ° C.

Comparative Example  One.

[Chemical Formula 4]

Figure pat00071

The compound represented by the formula (4) was obtained by the method described in Non-Patent Document 1. [

Comparative Example  2.

[Chemical Formula 5]

Figure pat00072

Step 1: First Ligand  Produce

(1.48 g, 5.57 mmol), 2- (trimethylstannyl) -pyridine (1.48 g, 6.13 mmol) and tetra (4-chlorophenyl) tetrakis (triphenylphosphine) heating the solution obtained by dissolving palladium (Pd (PPh 3) 4, 0.13 g, 2.0 mol%) in toluene (70 mL) was stirred for 1 days to reflux. After cooling to room temperature, a saturated aqueous solution of NH 4 Cl was added to the reaction mixture. When the organic layer and the aqueous layer were separated, the aqueous layer was separated and further extracted with Et 2 O (30 mL). The combined organic layer was dried over MgSO 4 and concentrated under reduced pressure. The residue was purified by flash column chromatography using CH 2 Cl 2 / toluene (1/1, v / v) as the eluent. After drying in vacuo, 2- {p- (2-methyl-1,2-carbonyl-1-yl) phenyl} pyridine as white solid was obtained (Yield: 1.03 g, yield: 54%).

1 H NMR (CDCl 3): δ 8.70 (dq, 1H, J = 4.8, 0.9 Hz), 7.99 (dt, 2H, J = 8.7, 2.1 Hz), 7.70-7.80 (m, 4H), 7.27 (ddd, 1H, J = 6.9, 4.8, 1.5 Hz), 1.70 (s, 3H, B-CH 3), 1.50-3.70 (br, 10H, BH).

13 C NMR (CDCl 3): δ 155.7, 149.9, 141.5, 137.1, 131.5, 131.3, 127.3, 123.0, 120.8 (ppy-C), 81.8, 77.4 (C 2 B 10 H 10), 23.2 (B-CH 3 ).

11 B NMR (CDCl 3): -3.0, -4.4, -10.0.

HR EI-MS (C 14 H 21 B 10 N): m / z 313.2605 (theory); 313.2606 (measured).

Step 2: Preparation of first ring metal iridium complex

Phenyl) pyridine (1.03 g, 3.29 mmol) and IrCl 3 .3H 2 O (0.51 g, 1.43 mmol) were added to a solution of 2- {p- (2-methyl-1,2- Was dissolved in a mixed solvent of ethoxyethanol (40 mL) and distilled water (20 mL), and the mixture was heated to 110 DEG C and stirred for 1 day. After cooling to room temperature, 30 mL of distilled water was added to precipitate a solid material. The precipitate was filtered and washed twice with a small amount of ethanol (10 mL). The crude solid was extracted with CH 2 Cl 2 and the solution was dried with MgSO 4 . As a yellow solid state was filtered and vacuum drying [(4-CBppy) 2 Ir (μ-Cl)] 2 (CB: ortho-methyl-carborane, ppy: 2- phenylpyridinato Dina sat -C 2, N, Yield : 1.07 g, yield: 88%) was obtained

1 H NMR (CDCl 3): δ 9.31 (d, 4H, J = 5.7 Hz), 7.92 (m, 8H), 7.44 (d, 4H, J = 8.4 Hz), 7.01 (m, 8H), 6.01 (d , 4H, J = 1.8 Hz), 1.33 (s, 12H, B-CH3), 1.20-3.50 (br, 40H, BH).

13 C NMR (CDCl 3): δ 167.1, 151.7, 145.9, 144.1, 137.4, 132.7, 130.6, 124.4, 123.4, 123.2, 120.0, 82.0, 71.5 (C 2 B 10 H 10), 22.9 (B-CH 3) .

11 B NMR (CDCl 3): δ -4.3, -9.5.

Analysis (C 56 H 80 B 40 Cl 2 Ir 2 N 4 ): C, 39.63; H, 4.75; N, 3.30 (theory). C, 39.63; H, 4.81; N, 3.27 (measured).

Step 3: (4- CBppy ) 2 Ir ( acac ) ≪ / RTI >

[(4-CBppy) 2 Ir (μ-Cl)] 2 (CB: ortho-methyl-carborane, ppy: 2- phenylpyridinato Dina sat -C 2, N, 1.03 g, 0.63 mmol), 2,4- The flask was charged with pentanedione (0.19 g, 1.90 mmol), Na 2 CO 3 (0.67 g, 6.32 mmol) and acetonitrile (50 mL), and the mixture was heated to 80 ° C and stirred for 2 days. After cooling to room temperature, the orange precipitate formed was collected by filtration and washed with acetonitrile (10 mL). The undissolved solid was extracted with CH 2 Cl 2 to remove residual salts. The solution was dried with MgSO 4 and filtered. The solvent was evaporated and vacuum dried to obtain the target compound (Formula 5, yield: 0.95 g, yield: 83%) in the form of an orange solid.

1 H NMR (CDCl 3): δ 8.50 (d, 2H, J = 6.0 Hz), 7.87 (m, 4H), 7.42 (d, 2H, J = 8.4 Hz), 7.30 (td, 2H, J = 6.0, 2H, J = 2.1 Hz), 5.31 (s, 1H, acac-CH), 1.83 (s, 6H, acac-CH3 ), 1.14 (s, 6H, B-CH 3), 1.10-3.00 (br, 20H, BH).

13 C NMR (CD2Cl2): δ 185.7 (acac-CO), 167.2, 149.2, 147.9, 147.8, 138.5, 135.0, 130.4, 124.5, 123.8, 123.6, 120.0, 101.2 (acac-CH), 83.2, 77.9 (C2B10H10) , 28.8 (acac-CH 3) , 22.9 (B-CH 3).

11 B NMR (CDCl 3): δ -4.8 (br, 4B), -10.4 (br, 6B).

Analysis (C 33 H 47 B 20 IrN 2 O 2 ): C, 43.45; H, 5.19; N, 3.07 (calculated). C, 43.38; H, 5.19; N, 3.08 (measured).

Comparative Example  3.

[Chemical Formula 6]

Figure pat00073

Instead of using 1- (4-bromophenyl) -2-methyl-1,2-chloro- carbonylene (1.75 g, 5.57 mmol) in the step 1 of the above Comparative Example 2, Phenyl) -2-methyl-1,2-chloro- cyanolane (1.79 g, 5.72 mmol) was used in place of the target compound (Yield: 1.40 g, yield: 95%).

1 H NMR (CDCl 3): δ 8.48 (d, 2H, J = 5.4 Hz), 7.92 (d, 2H, J = 8.1 Hz), 7.83 (dt, 2H, J = 8.4, 1.5 Hz), 7.71 (d 2H, J = 2.1 Hz), 7.23 (m, 2H), 6.87 (dd, 2H, J = 8.1, 2.1 Hz), 6.22 CH), 1.79 (s, 6H , acac-CH3), 1.57 (s, 6H, B-CH 3), 1.10-3.10 (br, 20H, BH).

13 C NMR (CD 2 Cl 2 ): δ 185.4 (acac-CO), 167.0, 152.5, 148.7, 146.5, 138.1, 134.0, 131.2, 126.2, 123.7, 123.2, 119.4, 100.9 (acac-CH), 84.1, 78.1 (C 2 B 10 H 10 ), 28.5 (acac-CH 3 ), 23.3 (B-CH 3 ).

11 B NMR (CDCl 3): δ -4.5 (br, 4B), -10.1 (br, 6B).

Analysis (C 33 H 47 B 20 IrN 2 O 2 ): C, 43.45; H, 5.19; N, 3.07 (theory). C, 43.56; H, 5.21; N, 3.06 (measured).

Experimental Example  1. Phosphorous compound Optical physical  Character rating

Experiments were performed to evaluate the photophysical properties of the organic light emitting device including the phosphorescent compound according to the present invention in the light emitting layer. The results are shown in Table 1 and FIGS. 4 to 5.

Λ abs [nm]
(竜 X 10 -3 (M -1揃 cm -1 ) a Λ em [Nm] Φ PL τ
[탆] b toluene
(298K) b toluene
(77K) b THF
(298K) Toluene b, e THF c , e Example 1 415 (3.7), 472 (2.9) 526 517 531 0.24 <0.01 1.19 Example 2 405 (4.3), 455 (2.8) 502 490 504 0.96 0.37 1.32 Comparative Example 1 412 (4.2), 465 (3.2) 516 504 519 0.77 0.77 1.48 Comparative Example 2 416 (3.6), 473 (2.4) 529 521 534 0.47 <0.01 1.88 Comparative Example 3 407 (3.9), 456 (2.8) 503 492 506 0.83 0.011 1.22

Refund the markings listed in Table 1 above:

a - Measured in degassed dichloromethane (CH 2 Cl 2 )

b - the concentration of Example 1 and Comparative Example 2: 5.0 X 10 -6 M,

Concentration of Example 2 and Comparative Example 3: 2.0 X 10 &lt; -6 &gt; M.

c - the concentration of Example 1 and Comparative Example 2: 5.0 X 10 &lt; -5 &gt; M,

Concentration of Example 2 and Comparative Example 3: 1.0 X 10 &lt; -5 &gt;

d - fac - Ir (ppy) 3 was measured according to the following equation (1) with the quantum efficiency [PH PL = 0.97]

Figure pat00074

Η is the refractive index of the solvent, A is the absorbance at the excitation wavelength, I is the integral area under the luminescence spectrum, s, r is the specimen and the reference value. The η value of CH 2 Cl 2 is 1.424 and the η value of 0.5 MH 2 SO 4 is 1.346.

Referring to FIG. 4 (a), the phosphorescent compounds of Examples 1 and 2, in which carborane is fixed with an alkylene group as a linker, exhibit low energy bands due to spin to allow MLCT (metal to ligand charge transfer) Respectively. Specifically, the phosphorescent compound of Example 1 exhibited a strong absorption band in the region of 405 to 416 nm, and the phosphorescent compound of Example 2 exhibited a strong absorption band in the region of 455 to 473 nm. This aspect can be confirmed by the phosphorescent compounds of Comparative Examples 2 and 3 in which the carboranes are not fixed by the linker, but the degree is weak. The phosphorescent compounds of Example 1 and Comparative Example 2 in which carboranes were substituted at the 4-position of the phenyl ring were red-shifted compared to the phosphorescent compounds of Comparative Example 1 which did not contain carboranes as substituents, It was confirmed that the phosphorescent compounds of Example 2 and Comparative Example 3 substituted at the 5-position of the ring were blue-shifted. This means that the carbene substitution for the 4 position of the phenyl ring lowers the excited state energy while the substitution for the 5 position increases the excited state energy. This tendency can be confirmed also in the emission spectrum of the phosphorescent compound shown in Fig. 4 (b). Specifically, when toluene was used as the solvent, the phosphorescent compound of Example 1 showed a red shifted emission band at the center of 526 nm, while the phosphorescent compound of Example 2 showed a blue shifted band at 502 nm, The lifetimes were 1.19. And 1.32 각각 respectively.

5 (a), the phosphorescent compounds of Examples 1 and 2 and Comparative Examples 2 and 3 emitted green light at 298 K, and Example 1 in which carboranes were substituted at the 4-position of the phenyl ring and Comparative Example The phosphorescent compound of Example 2 and Comparative Example 3 in which carbene was substituted at the 5-position of the phenyl ring as compared with the phosphorescent compound of Comparative Example 2 showed higher quantum efficiency. In particular, the quantum efficiency (PH PL ) of the phosphorescent compound of Example 2 was about 0.96 ± 0.05, and the phosphorescent compound of Comparative Example 1 in which no carboranes were introduced was introduced into the 5-position of the phenyl ring, The quantum efficiency of the phosphorescent compound of Comparative Example 3 was found to be about 0.13 and 0.19 higher, respectively. On the other hand, the phosphorescent compound of Example 1 in which the carboranes fixed at the 4-position of the phenyl ring were substituted with the carboranes of Example 1 was found to be a phosphorescent compound of Comparative Example 2 in which carbene which was not fixed at the 4-position of the phenyl ring was substituted with an alkylene group The quantum efficiency was found to be about 0.33 lower compared to the compound. This indicates that inhibiting the rotation of carbene substituted with a phenyl ring can increase or decrease the quantum efficiency of the phosphorescent compound, and that quantum efficiency increase or decrease is determined according to the substitution position of the rotation-inhibited carbolane.

Further, referring to FIG. 5 (b), the phosphorescent compound of Example 2 was found to have a quantum efficiency of about 0.37 ± 0.02 in a polar solvent, tetrahydrofuran (THF), so that the comparison of the carboranes not fixed with the linker The phosphorescent compound (PH PL = 0.011 ± 0.001), it was confirmed that the quantum efficiency was about 30 times higher. This means that the phosphorescent compound having a structure in which carborane fixed at the 5-position of the phenyl ring is introduced has a high effect of reducing nonradiative decay.

Experimental Example  2. Evaluation of electrical properties of phosphorescent compounds

Experiments were conducted to evaluate the electrical characteristics of the organic light emitting device including the phosphorescent compound according to the present invention in the light emitting layer. The results are shown in Table 2 below.

E OX / V c [D E p / mV] a, b E red / V c [D E p / mV] a, c Example 1 0.58 -1.95 f Example 2 0.54 -2.10 f Comparative Example 1 e 0.41 -2.60 Comparative Example 2 d 0.51 -1.99 f Comparative Example 3 d 0.55 -2.09 f

Repeat the markings listed in Table 2 above for:

- a: Measured under dimethyl formamide (DMF) (1 mM, scan rate = 100-200 mV / s) based on Fc / Fc + redox couple

- b: measured in reversible oxidation condition (E 1/2)

- c: Measured under quasi-reversible reduction conditions

- d: Measured according to non-patent document 2

- e: Measured according to non-patent document 3

- f: measured at a reduction onset potential

Referring to Table 2, the phosphorescent compounds of Example 1 and Example 2 undergo reversible oxidation at 0.58V and 0.54V. This oxidation potential is shifted to the cathode in comparison with the phosphorescent compound of Comparative Example 1 because the HOMO of the phosphorescent compound according to Example 1 and Example 2 is effectively stabilized by the induction effect of carboranes in Comparative Example 1 Which means that the energy is lower than that of the phosphorescent compound. On the other hand, the phosphorescent compounds of Examples 1 and 2 exhibit chemically reversible but electrochemically quasi-reversible reduction processes. The carboranes substituted on the phenyl ring are generally subjected to a reduction process similar to that observed in Example 1 and Example 2, and such reduction characteristics may allow carbene to be involved in the reduction of pyridine. That is, carborane can affect the LUMO level, and the reduction behavior of these Example 1 and Example 2 phosphorescent compounds is associated with a strong induction electron withdrawing effect of carboranes and the participation of carboranes to LUMO non- .

Experimental Example  3. Evaluation of phosphorescent efficiency depending on the structure of the phosphorescent compound

In order to evaluate the phosphorescent efficiency according to the structure of the phosphorescent compound according to the present invention, the ground state (S 0 ) of the phosphorescent compounds according to Examples 1 and 2 and Comparative Examples 2 and 3 and the lowest triplet excitation state The lowest triplet excited state (T 1 ) was optimized by TD-DFT calculation. The average deviation of the carbene CC bond length between the ground state (S 0 ) and the excited state (T 1 ) (CC) T1 - S0 ). The results are shown in Fig.

6, the phosphorescent compounds of Examples 1 and 2 had a single morphology because the carbone was fixed by a linker and could not be rotated. In Comparative Examples 2 and 3, the carbone was rotatable, so that the methyl group Depending on the position, it has been confirmed that it has three types of structure of II, IO and OO, and each morphological structure has similar molecular orbital energy [I: methyl group is located inside the carboranes, O: methyl group is carboranes Located outside].

In addition, the phosphorescent compounds of Example 1 and Comparative Example 2 having a structure in which carbene was introduced at the 4-position of the phenyl ring had an average deviation of CC bond length of carboranes of about 0.30 + - 0.015 A Respectively. On the other hand, the phosphorescent compounds of Example 2 and Comparative Example 3 having a structure in which carborane was introduced at the 5-position of the phenyl ring had little influence on the LUMO level of carboranes in the lowest triplet excitation state (T 1 ) Regardless of the morphology, the CC bond length of carboranes was found to have an average deviation of less than or equal to about 0.01 ± 0.005 Å. This difference means that the phosphorescent compound of Example 2 and Comparative Example 3 in which carbene is introduced at the 5-position of the phenyl ring has high structural stability for emitting phosphorescence in the excited state (T 1 ). In addition, the phosphorescent compound of Comparative Example 3 was found to have a CC bond length average deviation of 0.00 to 0.03 A by rotation of the carbone. This variation in average deviation in the excited state (T 1 ) indicates that it can have low quantum efficiency in a polar solvent such as THF.

Claims (17)

A phosphorescent compound represented by the following formula (1):
[Chemical Formula 1]
Figure pat00075

In formula (1)
CB is a carboranyl group (C 2 B 10 H 10 )
Ln is an alkylene group having 1 to 15 carbon atoms or an arylalkylene group having 6 to 20 carbon atoms,
Figure pat00076
The
Figure pat00077
,
Figure pat00078
,
Figure pat00079
,
Figure pat00080
, or
Figure pat00081
ego,
Figure pat00082
The
Figure pat00083
,
Figure pat00084
,
Figure pat00085
,
Figure pat00086
,
Figure pat00087
,
Figure pat00088
,
Figure pat00089
, or
Figure pat00090
Lt;
Wherein R 1 to R 5 independently represent hydrogen, an aryl group of C 1 -12 alkyl or C 6 -20 of.
The method according to claim 1,
Wherein the CB is an ortho-carboranyl, meta-carboranyl or para-carboranyl group.
The method according to claim 1,
And CB is an ortho-carboranyl group.
The method according to claim 1,
Ln represents a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group or an octylene group,
Figure pat00091
The
Figure pat00092
,
Figure pat00093
, or
Figure pat00094
Lt;
Wherein R 1 is hydrogen, methyl, ethyl, propyl, butyl or phenyl.
The method according to claim 1,
Ln is a propylene group, a butylene group, a pentylene group, a hexylene group or an octylene group,
Figure pat00095
The
Figure pat00096
,
Figure pat00097
or
Figure pat00098
Phosphorus compound.
The method according to claim 1,
Wherein the compound represented by the formula (1) is a compound represented by the following formula (2):
(2)
Figure pat00099

In Formula 2,
Ln 1 is a propylene group, a butylene group, a pentylene group, a hexylene group or an octylene group,
Figure pat00100
The
Figure pat00101
,
Figure pat00102
,
Figure pat00103
,
Figure pat00104
,
Figure pat00105
or
Figure pat00106
to be.
The method according to claim 6,
Ln 1 is a butylene group or a hexylene group,
Figure pat00107
The
Figure pat00108
, or
Figure pat00109
Lt; / RTI &gt;
The method according to claim 1,
Wherein the compound represented by the formula (1) is a compound represented by the following formula (3):
(3)
Figure pat00110

In Formula 3,
Ln 2 is a propylene group, a butylene group, a pentylene group, a hexylene group or an octylene group,
Figure pat00111
The
Figure pat00112
,
Figure pat00113
,
Figure pat00114
,
Figure pat00115
,
Figure pat00116
or
Figure pat00117
to be.
9. The method of claim 8,
Ln 2 is a butylene group or a hexylene group,
Figure pat00118
The
Figure pat00119
, or
Figure pat00120
Lt; / RTI &gt;
An anode, a cathode, and an organic layer between both electrodes,
Wherein the organic layer comprises the phosphorescent compound according to claim 1.
11. The method of claim 10,
Wherein the organic layer is a light emitting layer.
11. The method of claim 10,
And a first charge transport layer on the anode and the organic layer.
13. The method of claim 12,
Wherein the first charge transporting layer comprises at least one selected from the group consisting of a hole injecting layer and a hole transporting layer.
11. The method of claim 10,
And a second charge transport layer between the cathode and the organic layer.
15. The method of claim 14,
And the second charge transporting layer comprises at least one selected from the group consisting of an electron transporting layer and an electron injecting layer.
13. The method of claim 12,
And an electron blocking layer between the organic layer and the first charge transporting layer.
15. The method of claim 14,
And a hole blocking layer between the organic layer and the second charge transporting layer.
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