KR102070939B1 - Novel compound and organic light emitting device comprising the same - Google Patents

Abstract

The present invention provides a novel compound including two heteroatomic-containing condensed ring structures in a molecule and an organic light emitting device comprising the same.

Description

Novel compound and organic light emitting device comprising the same

Cross Citation with Related Application (s)

This application claims the benefit of priority based on Korean Patent Application No. 10-2017-0067963 dated May 31, 2017, and all content disclosed in the literature of that Korean patent application is incorporated as part of this specification.

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

In general, organic light emitting phenomenon refers to a phenomenon of converting electrical energy into light energy using an organic material. The organic light emitting device using the organic light emitting phenomenon has a wide viewing angle, excellent contrast, fast response time, excellent brightness, driving voltage and response speed characteristics, many studies have been conducted.

The organic light emitting device generally has a structure including an anode and a cathode and an organic layer between the anode and the cathode. The organic layer is often formed of a multi-layered structure composed of different materials to increase the efficiency and stability of the organic light emitting device, for example, it may be made of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer. When the voltage is applied between the two electrodes in the structure of the organic light emitting device, holes are injected into the organic material layer at the anode, and electrons are injected into the organic material layer, and excitons are formed when the injected holes and the electrons meet each other. When it falls back to the ground, it glows.

There is a continuous demand for the development of new materials for organic materials used in such organic light emitting devices.

Korean Patent Publication No. 10-2000-0051826

The present invention relates to a novel compound comprising two heteroatomic-containing condensed ring structures in a molecule and an organic light emitting device comprising the same.

The present invention provides a compound of formula

[Formula 1]

In Chemical Formula 1,

L is a bond; Substituted or unsubstituted C _6-60 arylene; Or substituted or unsubstituted C _2-60 heteroarylene containing one or more heteroatoms of O, N, Si and S,

A and D are each independently any one of the functional groups of the formula 2-1 to 2-6, except that A and D are all one of the functional groups of the formula 2-1 to 2-6,

[Formula 2-1]

[Formula 2-2]

[Formula 2-3]

[Formula 2-4]

[Formula 2-5]

[Formula 2-6]

In Chemical Formulas 2-1 to 2-6,

X ₅ and X ₆ are each independently selected from the group consisting of O, S and CR ₁ R ₂ ,

R ₁ and R ₂ are each independently substituted or unsubstituted C _1-60 alkyl,

Z is-[(L ₁ ) _m -Y] _n , _wherein L ₁ is a bond; Substituted or unsubstituted C _6-60 arylene; Or substituted or unsubstituted C _2-60 heteroarylene containing one or more heteroatoms of O, N, Si and S,

Y is hydrogen; heavy hydrogen; halogen; Nitrile; Nitro; Amino; Substituted or unsubstituted C _1-60 alkyl; Substituted or unsubstituted C _3-60 cycloalkyl; Substituted or unsubstituted C _2-60 alkenyl; Substituted or unsubstituted C _6-60 aryl; Or O, N, Si and S, at least one heteroatom, a substituted or unsubstituted C _2-60 heterocyclic group,

m and n are each an integer of 0 or 1.

In addition, the present invention is a first electrode; A second electrode provided to face the first electrode; And at least one organic material layer provided between the first electrode and the second electrode, wherein at least one of the organic material layers includes the compound of Formula 1.

The compound of Chemical Formula 1 may be used as a material of the organic layer of the organic light emitting diode, and may improve efficiency, low driving voltage, and / or lifetime characteristics in the organic light emitting diode. In particular, the compound of Formula 1 may be used as a light emitting, electron transport, or electron injection material.

FIG. 1 shows an example of an organic light emitting element composed of a substrate 1, an anode 2, a light emitting layer 3, and a cathode 4.
2 shows an example of an organic light emitting element consisting of a substrate 1, an anode 2, a hole injection layer 5, a hole transport layer 6, a light emitting layer 7, an electron transport layer 8 and a cathode 4. It is.

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

는 다른 치환기에 연결되는 결합을 의미한다. In this specification,

Means a bond connected to another substituent.

As used herein, the term "substituted or unsubstituted" is deuterium; Halogen group; Nitrile group; Nitro group; Hydroxyl group; Carbonyl group; Ester group; Imide group; Amino group; Phosphine oxide groups; An alkoxy group; Aryloxy group; Alkyl thioxy group; Arylthioxy group; Alkyl sulfoxy groups; Aryl sulfoxy group; Silyl groups; Boron group; Alkyl groups; Cycloalkyl group; Alkenyl groups; Aryl group; Aralkyl group; Ar alkenyl group; Alkylaryl group; Alkylamine group; Aralkyl amine groups; Heteroarylamine group; Arylamine group; Aryl phosphine group; Or substituted or unsubstituted with one or more substituents selected from the group consisting of heterocyclic groups including one or more of N, O, and S atoms, or two or more substituents connected to the substituents exemplified above. . For example, "a substituent to which two or more substituents are linked" may be a biphenyl group. That is, the biphenyl group may be an aryl group, and can be interpreted as a substituent to which two phenyl groups are linked.

Although carbon number of a carbonyl group in this specification is not specifically limited, It is preferable that it is C1-C40. Specifically, it may be a compound having a structure as follows, but is not limited thereto.

In the present specification, the ester group may be substituted with oxygen of the ester group having 1 to 25 carbon atoms, a straight chain, branched chain or cyclic alkyl group or an aryl group having 6 to 25 carbon atoms. Specifically, it may be a compound of the following structural formula, but is not limited thereto.

In this specification, although carbon number of an imide group is not specifically limited, It is preferable that it is C1-C25. Specifically, it may be a compound having a structure as follows, but is not limited thereto.

In the present specification, the silyl group is specifically trimethylsilyl group, triethylsilyl group, t-butyldimethylsilyl group, vinyldimethylsilyl group, propyldimethylsilyl group, triphenylsilyl group, diphenylsilyl group, phenylsilyl And the like, but are not limited thereto.

In the present specification, the boron group specifically includes, but is not limited to, trimethylboron group, triethylboron group, t-butyldimethylboron group, triphenylboron group, phenylboron group, and the like.

In the present specification, examples of the halogen group include fluorine, chlorine, bromine or iodine.

In the present specification, the alkyl group may be linear or branched chain, carbon number is not particularly limited, but is preferably 1 to 40. According to an exemplary embodiment, the alkyl group has 1 to 20 carbon atoms. According to another exemplary embodiment, the alkyl group has 1 to 10 carbon atoms. According to another exemplary embodiment, the alkyl group has 1 to 6 carbon atoms. Specific examples of the alkyl group include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, n -Pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, Heptyl, n-heptyl, 1-methylhexyl, cyclopentylmethyl, cyclohexylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2, 2-dimethylheptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, 2-methylpentyl, 4-methylhexyl, 5-methylhexyl, and the like, but are not limited to these.

In the present specification, the alkenyl group may be linear or branched chain, carbon number is not particularly limited, but is preferably 2 to 40. According to an exemplary embodiment, the alkenyl group has 2 to 20 carbon atoms. According to another exemplary embodiment, the alkenyl group has 2 to 10 carbon atoms. According to another exemplary embodiment, the alkenyl group has 2 to 6 carbon atoms. Specific examples include vinyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 3-methyl-1- Butenyl, 1,3-butadienyl, allyl, 1-phenylvinyl-1-yl, 2-phenylvinyl-1-yl, 2,2-diphenylvinyl-1-yl, 2-phenyl-2- ( Naphthyl-1-yl) vinyl-1-yl, 2,2-bis (diphenyl-1-yl) vinyl-1-yl, stilbenyl group, styrenyl group and the like, but are not limited thereto.

In the present specification, the cycloalkyl group is not particularly limited, but preferably has 3 to 60 carbon atoms, and according to one embodiment, the cycloalkyl group has 3 to 30 carbon atoms. According to another exemplary embodiment, the cycloalkyl group has 3 to 20 carbon atoms. According to another exemplary embodiment, the cycloalkyl group has 3 to 6 carbon atoms. Specifically cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,3-dimethylcyclohexyl, 3,4,5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctyl, and the like, but is not limited thereto.

In the present specification, the aryl group is not particularly limited, but preferably has 6 to 60 carbon atoms, and may be a monocyclic aryl group or a polycyclic aryl group. According to an exemplary embodiment, the aryl group has 6 to 30 carbon atoms. According to an exemplary embodiment, the aryl group has 6 to 20 carbon atoms. The aryl group may be a phenyl group, a biphenyl group, a terphenyl group, etc. as the monocyclic aryl group, but is not limited thereto. The polycyclic aryl group may be a naphthyl group, anthracenyl group, phenanthryl group, pyrenyl group, perylenyl group, chrysenyl group, fluorenyl group, and the like, but is not limited thereto.

등이 될 수 있다. 다만, 이에 한정되는 것은 아니다.In the present specification, a fluorenyl group may be substituted, and two substituents may be bonded to each other to form a spiro structure. When the fluorenyl group is substituted,

And so on. However, the present invention is not limited thereto.

In the present specification, the heterocyclic group is a heterocyclic group such as heterocycloalkyl or heteroaryl including one or more heteroatoms of O, N, Si, and S as a dissimilar element, and the number of carbon atoms is not particularly limited, but the carbon number is 2 to It is preferable that it is 60. Examples of the heterocyclic group include thiophene group, furan group, pyrrole group, imidazole group, thiazole group, oxazole group, oxadiazole group, triazole group, pyridyl group, bipyridyl group, pyrimidyl group, triazine group, acridil group , Pyridazine group, pyrazinyl group, quinolinyl group, quinazoline group, quinoxalinyl group, phthalazinyl group, pyrido pyrimidinyl group, pyrido pyrazinyl group, pyrazino pyrazinyl group, isoquinoline group, indole group , Carbazole group, benzoxazole group, benzoimidazole group, benzothiazole group, benzocarbazole group, benzothiophene group, dibenzothiophene group, benzofuranyl group, phenanthroline group, isoxazolyl group, thiadia Although there are a sleepy group, a phenothiazinyl group, a dibenzofuranyl group, etc., it is not limited to these.

In the present specification, the aryl group in the aralkyl group, aralkenyl group, alkylaryl group, and arylamine group is the same as the example of the aryl group described above. In the present specification, the alkyl group among the aralkyl group, the alkylaryl group, and the alkylamine group is the same as the example of the alkyl group described above. In the present specification, the heteroaryl of the heteroarylamine may be applied to the description of the aforementioned heterocyclic group. In the present specification, the alkenyl group in the aralkenyl group is the same as the example of the alkenyl group described above. In the present specification, except that the arylene is a divalent group, the description of the aryl group described above may be applied. In the present specification, the description of the aforementioned heterocyclic group may be applied except that the heteroarylene is a divalent group. In the present specification, the hydrocarbon ring is not a monovalent group, and the description of the aforementioned aryl group or cycloalkyl group may be applied except that two substituents are formed by bonding. In the present specification, the heterocyclic group is not a monovalent group, and the description of the aforementioned heterocyclic group may be applied except that two substituents are formed by bonding.

On the other hand, the present invention provides a compound of Formula 1:

[Formula 1]

In Chemical Formula 1,

L is a bond; Substituted or unsubstituted C _6-60 arylene; Or substituted or unsubstituted C _2-60 heteroarylene containing one or more heteroatoms of O, N, Si and S,

A and D are each independently any one of the functional groups of Formulas 2-1 to 2-6, provided that both A and D are any of the functional groups of Formulas 2-1 to 2-6, ie A and D Except when is the same functional group of any one selected from the functional groups of Formula 2-1 to 2-6,

[Formula 2-1]

[Formula 2-2]

[Formula 2-3]

[Formula 2-4]

[Formula 2-5]

[Formula 2-6]

In Chemical Formulas 2-1 to 2-6,

X ₅ and X ₆ are each independently selected from the group consisting of O, S and CR ₁ R ₂ ,

R ₁ and R ₂ are each independently substituted or unsubstituted C _1-60 alkyl,

Z is-[(L ₁ ) _m -Y] _n , _wherein L ₁ is a bond; Substituted or unsubstituted C _6-60 arylene; Or substituted or unsubstituted C _2-60 heteroarylene containing one or more heteroatoms of O, N, Si and S,

Y is hydrogen; heavy hydrogen; halogen; Nitrile; Nitro; Amino; Substituted or unsubstituted C _1-60 alkyl; Substituted or unsubstituted C _3-60 cycloalkyl; Substituted or unsubstituted C _2-60 alkenyl; Substituted or unsubstituted C _6-60 aryl; Or O, N, Si and S, at least one heteroatom, a substituted or unsubstituted C _2-60 heterocyclic group,

m and n are each an integer of 0 or 1.

As described above, the compound of Formula 1 according to the present invention may form a large conjugated system in a molecule by including a large condensed ring structure in which five aromatic or heteroaromatic rings are condensed. As a result, carrier mobility of the layer including the compound of Formula 1 in the organic light emitting device may be increased, and as a result, lifespan characteristics of the device may be improved.

In addition, A and D contained in the compound of Formula 1 are each independently any one of the functional groups of Formulas 2-1 to 2-6, provided that both A and D are among the functional groups of Formulas 2-1 to 2-6 In any case, that is, when A and D are any one of the same functional groups selected from the functional groups of Chemical Formulas 2-1 to 2-6 (for example, when both A and D are functional groups of Chemical Formula 2-1, etc.) Exclude. As described above, since the condensed rings of A and D have different skeletal structures, they form an asymmetric structure around L. Accordingly, when the thin film is formed through deposition, the amorphousness of the film is further enhanced as compared with the case of the symmetrical structure, thereby reducing the barrier appearing at the interface with the peripheral layer, thereby lowering the driving voltage of the device.

Specifically, in Formula 1, L is a bond; Substituted or unsubstituted phenylene; Substituted or unsubstituted naphthalene-diyl; Substituted or unsubstituted carbazole-diyl; And it may be selected from the group consisting of substituted or unsubstituted dibenzofurandiyl. When L is substituted, C _1-20 alkyl; C _3-20 cycloalkyl; C _4-20 (cycloalkyl) alkyl; C _6-20 aryl; It may be substituted with one or more substituents selected from the group consisting of C _7-20 arylalkyl, and C _7-20 alkylaryl, more specifically the group consisting of methyl, ethyl, propyl, t-butyl and phenyl One to three may be substituted with one or more substituents selected from.

A and D are bonded to both sides of the L is a condensed ring group selected from the group consisting of Formulas 2-1 to 2-6, different from each other so that the compound of Formula 1 can form an asymmetric structure Have

In Chemical Formulas 2-1 to 2-6, X ₅ and X ₆ may each independently be a chalcogen atom selected from the group consisting of O and S, or CR ₁ R ₂ .

For example, in the functional groups of Formulas 2-1 to 2-6, when at least one of X ₅ and X ₆ is a chalcogen atom selected from the group consisting of O and S, at least one of A and D is a chalcogen It has a condensed ring structure containing an aromatic hetero ring containing an atom. In this case, the chalcogen atom contained in the condensed ring structure has a higher electronegativity than the carbon atom and at the same time has a non-covalent electron pair, which is advantageous in charge transport in the compound of Formula 1, and thus may exhibit an improvement in life characteristics.

When X ₅ or X ₆ is CR ₁ R ₂ , each of R ₁ and R ₂ is independently substituted or unsubstituted C _1-60 alkyl, and more specifically, substituted or unsubstituted C _{1- 20} alkyl, and more particularly substituted or unsubstituted methyl or ethyl. When R ₁ and R ₂ are substituted, C _1-20 alkyl; C _3-20 cycloalkyl; C _4-20 (cycloalkyl) alkyl; C _6-20 aryl; It may be substituted with one or more substituents selected from the group consisting of C _7-20 arylalkyl, and C _7-20 alkylaryl, more specifically the group consisting of methyl, ethyl, propyl, t-butyl and phenyl One to three may be substituted with one or more substituents selected from.

In addition, in Chemical Formulas 2-1 to 2-6, Z is-[(L ₁ ) _m -Y] _n , _wherein L ₁ , Y, m, and n are as defined above. More specifically, in Z, L ₁ is a bond; Substituted or unsubstituted C _6-60 arylene such as substituted or unsubstituted phenylene, substituted or unsubstituted naphthalene- _diyl ; Or substituted or unsubstituted C _2-60 hetero, including one or more heteroatoms of O, N, Si, and S, such as substituted or unsubstituted carbazole-diyl, substituted or unsubstituted dibenzofurandiyl Arylene. L ₁ is also a bond; Or substituted or unsubstituted C _6-20 arylene. When L ₁ is substituted, C _1-20 alkyl; C _3-20 cycloalkyl; C _4-20 (cycloalkyl) alkyl; C _6-20 aryl; It may be substituted with one or more substituents selected from the group consisting of C _7-20 arylalkyl, and C _7-20 alkylaryl, more specifically the group consisting of methyl, ethyl, propyl, t-butyl and phenyl One to three may be substituted with one or more substituents selected from.

In Z, Y is specifically hydrogen; Substituted or unsubstituted C _1-20 alkyl; Substituted or unsubstituted C _3-20 cycloalkyl; Substituted or unsubstituted C _6-20 aryl; Or it may be a substituted or unsubstituted C _2-20 heterocyclic group containing one or more heteroatoms of O, N, Si and S. Specific examples include, but are not limited to, the following functional groups:

More specifically, in Z, Y is hydrogen; Substituted or unsubstituted C _1-20 alkyl; Substituted or unsubstituted C _3-20 cycloalkyl; Or substituted or unsubstituted C _6-20 aryl, more specifically hydrogen; C _1-4 alkyl such as methyl and ethyl; C _3-6 cycloalkyl such as cyclohexyl; And it may be selected from the group consisting of phenyl.

And when said Y is substituted, C _1-20 alkyl; C _3-20 cycloalkyl; C _4-20 (cycloalkyl) alkyl; C _6-20 aryl; C _7-20 arylalkyl; And one or more substituents selected from the group consisting of C _7-20 alkylaryl, and more specifically, one or more substituents selected from the group consisting of methyl, ethyl, propyl, t-butyl and phenyl. 1 to 3 may be substituted.

The compound of Formula 1 may further improve the effect through the optimization of the functional group according to the structure.

Specifically, in the compound of Formula 1, when L is a bond in Formula 1, A and D are each independently any one of the functional groups of Formulas 2-1 to 2-6, provided that both A and D are Except in the case of any one of the functional groups of 2-1 to 2-6, and in the above formula 2-1 to 2-6, X ₅ and X ₆ are any one of O, S, and CR ₁ R ₂ Are the same, more specifically X ₅ and X ₆ are the same as O, Z is-[(L ₁ ) _m -Y] _n , m and n are each 0, may be a compound.

In addition, in the compound of Formula 1, when L is substituted or unsubstituted phenylene in Formula 1, A and D are each independently any one of the functional groups of Formulas 2-1 to 2-6, provided that And D is any one of the functional groups of the following formulas 2-1 to 2-6, and in the above formulas 2-1 to 2-6, Z is-[(L ₁ ) _m -Y] _n Wherein L ₁ is a bond; Or substituted or unsubstituted C _6-60 arylene, Y is hydrogen; Substituted or unsubstituted C _1-60 alkyl; Substituted or unsubstituted C _3-60 cycloalkyl; Or a substituted or unsubstituted C _6-60 aryl, m and n may each be an integer of 0 or 1, more specifically a compound wherein X ₅ and X ₆ are equally O or CR ₁ R ₂ ; Can be. At this time, R ₁ and R ₂ are as defined above.

In addition, the compound of Formula 1 is a naphthalene-diyl group in which L is substituted or unsubstituted in Formula 1, A and D are each independently any one of the functional groups of Formula 2-1 to 2-6, Except that A and D are both of the functional groups represented by the following Chemical Formulas 2-1 to 2-6, in the above Chemical Formulas 2-1 to 2-6, Z is-[(L ₁ ) _m -Y] _n Wherein L ₁ is a bond; Or substituted or unsubstituted C _6-60 arylene, Y is hydrogen; heavy hydrogen; Substituted or unsubstituted C _1-60 alkyl; Substituted or unsubstituted C _3-60 cycloalkyl; Or a substituted or unsubstituted C _6-60 aryl, m and n may each be an integer of 0 or 1, and more specifically, X ₅ and X ₆ may be the same O compound.

In the compound of Formula 1, in Formula 1, L is a substituted or unsubstituted carbazole group, more specifically, a phenyl substituted carbazole group, and A and D are each independently represented by Formula 2- Any one of the functional groups of 1 to 2-6, except that A and D are both any one of the functional groups of the formula 2-1 to 2-6, in the formula 2-1 to 2-6, Z Is-[(L ₁ ) _m -Y] _n , _wherein m and n may each be 0, and more specifically, X ₅ and X ₆ may be the same S.

In this case, the details of the respective functional groups in the above structures are as described above.

Representative examples of the compound of Formula 1 include, but are not limited to:

The compound of Formula 1 has two heteroatomic-containing condensed ring structures in the molecule, thereby enhancing the amorphousness of the film during thin film formation through deposition, thereby reducing the barrier at the interface with the surrounding layer. Can be. Therefore, the organic light emitting device using the same may have high efficiency, low driving voltage, high brightness, long life, and the like, compared to the organic light emitting device employing the compound having the same structure as the substituent of the amino group.

Meanwhile, Compound (I) of Formula 1 may be prepared by Suzuki reaction through coupling between functional group AL-containing halide (II) and functional group D-containing organoboron compound (III), as shown in Scheme 1 below. Can be. The manufacturing method may be more specific in the production examples to be described later.

Scheme 1

In Scheme 1, A, L and D are as defined above,

X is a halogen group or halogen-containing group such as I, Br, Cl, or -Otf (triflates),

B is a boron (B) containing organic group, such as a boronic acid group, a boronic acid ester group, or a boronic acid pinacol ester group.

In addition, although the halide (II) includes the functional group of AL- and the organoboron compound (III) includes the functional group of D in Scheme 1, the organoboron compound (III) contains the functional group of AL- The halide (II) may also contain a functional group of D.

Specifically, Compound (I) of Formula 1 may be prepared by Suzuki coupling reaction of the organoboron compound (III) with the halide (II) in the presence of a base and a palladium catalyst.

As the base, sodium carbonate, potassium carbonate, sodium hydroxide or potassium hydroxide may be used, and as the palladium catalyst, tetrakis- (triphenylphosphine) palladium (Pd (PPH ₃ ) ₄ ), palladium acetate, etc. may be used. Can be. In addition, the reaction may be carried out in one or more organic solvents such as tetrahydrofuran (THF), N, N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO) or toluene.

In addition, the Suzuki coupling reaction of Scheme 1 may be performed in the range of 80 ° C to 120 ° C.

On the other hand, the organoboron compound (III) may be prepared directly, or may be obtained commercially. For example, it may be prepared by the same method as in the method of Scheme 2 below. Scheme 2 below is only one example for describing the present invention, and the present invention is not limited thereto.

Scheme 2

In Scheme 2, NBS is n-bromosuccinimide, DMF is dimethyl formamide, NMP is N-methylpyrrolidone, THF is tetrahydrofuran, AN is acetonitrile, and KOAc is potassium acetate.

The compound of Formula 1 may be prepared by appropriately replacing the starting material in accordance with the structure of the compound to be prepared with reference to Schemes 1 and 2.

On the other hand, the present invention provides an organic light emitting device comprising the compound of Formula 1. In one embodiment, the present invention is a first electrode; A second electrode provided to face the first electrode; And at least one organic material layer provided between the first electrode and the second electrode, wherein at least one of the organic material layers includes the compound of Formula 1.

The organic material layer of the organic light emitting device of the present invention may be formed of a single layer structure, but may be formed of a multilayer structure in which two or more organic material layers are stacked. For example, the organic light emitting device of the present invention may have a structure including a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer or an electron injection layer as an organic material layer, and between the hole transport layer and the light emitting layer, and the light emitting layer and the electron transport layer Each may further include an electron blocking layer and a hole blocking layer. However, the structure of the organic light emitting device is not limited thereto and may include a smaller number of organic layers.

The organic layer may include a hole injection layer, a hole transport layer, or a layer for simultaneously injecting and transporting holes, and the hole injection layer, a hole transport layer, or a layer for simultaneously injecting and transporting a hole may be represented by Formula 1 above. Compound.

In addition, the organic material layer may include a light emitting layer, and the light emitting layer includes the compound of Formula 1.

In addition, the organic material layer may include an electron transport layer, or an electron injection layer, the electron transport layer, or the electron injection layer comprises a compound of the formula (1).

In addition, the electron transport layer, the electron injection layer, or a layer for simultaneously injecting and transporting electrons includes the compound of Formula 1. In particular, the compound of formula 1 according to the present invention has excellent thermal stability, has a deep HOMO level of 6.0 eV or higher, high triplet energy (ET), and hole stability. In addition, when the compound of Formula 1 is used in an organic material layer capable of simultaneously injecting and transporting electrons, an n-type dopant used in the art may be mixed.

In addition, the organic material layer may include a light emitting layer and an electron transport layer, and the electron transport layer may include the compound of Formula 1.

In addition, the organic light emitting device according to the present invention may be an organic light emitting device having a structure in which an anode, one or more organic material layers, and a cathode are sequentially stacked on a substrate. In addition, the organic light emitting diode according to the present invention may be an organic light emitting diode having an inverted type structure in which a cathode, one or more organic material layers, and an anode are sequentially stacked on a substrate. For example, the structure of an organic light emitting device according to an embodiment of the present invention is illustrated in FIGS. 1 and 2.

FIG. 1 shows an example of an organic light emitting element composed of a substrate 1, an anode 2, a light emitting layer 3, and a cathode 4. In such a structure, the compound of Formula 1 may be included in the light emitting layer.

2 shows an example of an organic light emitting element consisting of a substrate 1, an anode 2, a hole injection layer 5, a hole transport layer 6, a light emitting layer 7, an electron transport layer 8 and a cathode 4. It is. In such a structure, the compound of Formula 1 may be included in one or more layers of the hole injection layer, the hole transport layer, the light emitting layer and the electron transport layer, more specifically may be included in the light emitting layer.

In addition, the organic light emitting device according to an embodiment of the present invention, the substrate, an anode, a hole transport layer, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron transport layer, an electron injection layer and a cathode, in the above structure Compound of Formula 1 may be included in the light emitting layer.

The organic light emitting device according to the present invention may be manufactured by materials and methods known in the art, except that at least one layer of the organic material layer includes the compound of Formula 1. In addition, when the organic light emitting device includes a plurality of organic material layers, the organic material layers may be formed of the same material or different materials.

For example, the organic light emitting device according to the present invention may be manufactured by sequentially stacking a first electrode, an organic material layer, and a second electrode on a substrate. At this time, by using a physical vapor deposition (PVD) method such as sputtering or e-beam evaporation, a metal or conductive metal oxide or an alloy thereof is deposited on the substrate to form an anode. In addition, an organic material layer including at least one of a hole injection layer, a hole transport layer, a light emitting layer, and an electron transport layer may be formed thereon, and then, a material that may be used as a cathode may be deposited thereon. In addition, when the organic layer further includes an electron blocking layer and a hole blocking layer between the hole transport layer and the light emitting layer, and between the light emitting layer and the electron transport layer, the method may further include forming these layers. In addition to the above method, an organic light emitting device may be manufactured by sequentially depositing a cathode material, an organic material layer, and an anode material on a substrate.

In addition, the compound of Chemical Formula 1 may be formed as an organic layer by a solution coating method as well as a vacuum deposition method in the manufacture of the organic light emitting device. Here, the solution coating method means spin coating, dip coating, doctor blading, inkjet printing, screen printing, spray method, roll coating, etc., but is not limited thereto.

In addition to the above method, an organic light emitting device may be manufactured by sequentially depositing an organic material layer and an anode material on a substrate from a cathode material (WO 2003/012890). However, the manufacturing method is not limited thereto.

In one example, the first electrode is an anode, the second electrode is a cathode, or the first electrode is a cathode, the second electrode is an anode.

As the anode material, a material having a large work function is generally preferred to facilitate hole injection into the organic material layer. Specific examples of the positive electrode material include metals such as vanadium, chromium, copper, zinc and gold or alloys 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 poly (3-methylthiophene), poly [3,4- (ethylene-1,2-dioxy) thiophene] (PEDOT), polypyrrole and polyaniline, and the like, but are not limited thereto.

It is preferable that the cathode material is a material having a small work function to facilitate electron injection into the organic material layer. Specific examples of the negative electrode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, and 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 material is a layer for injecting holes from an electrode, and the hole injection material has a capability of transporting holes, and thus has a hole injection effect at an anode, an excellent hole injection effect for a light emitting layer or a light emitting material, and is generated in a light emitting layer The compound which prevents the movement of the excited excitons to the electron injection layer or the electron injection material, and is excellent in thin film formation ability is preferable. Preferably, the highest occupied molecular orbital (HOMO) of the hole injection material is between the work function of the positive electrode material and the HOMO of the surrounding organic layer. Specific examples of the hole injection material include metal porphyrin, oligothiophene, arylamine-based organic material, hexanitrile hexaazatriphenylene-based organic material, quinacridone-based organic material, and perylene-based Organic materials, anthraquinone and polyaniline and polythiophene-based conductive polymers, but are not limited thereto.

The hole transport layer is a layer for receiving holes from the hole injection layer and transporting holes to the light emitting layer. A hole transporting material is a material capable of transporting holes from an anode or a hole injection layer and transferring them to the light emitting layer. This is suitable. Specific examples thereof include an arylamine-based organic material, a conductive polymer, and a block copolymer having a conjugated portion and a non-conjugated portion together, but are not limited thereto.

The light emitting material is a material capable of emitting light in the visible region by transporting and combining holes and electrons from the hole transport layer and the electron transport layer, respectively, and a material having good quantum efficiency with respect to fluorescence or phosphorescence is preferable. Specific examples thereof include 8-hydroxyquinoline aluminum complex (Alq ₃ ); Carbazole series compounds; Dimerized styryl compounds; BAlq; 10-hydroxybenzo quinoline-metal compound; Benzoxazole, benzthiazole and benzimidazole series compounds; Poly (p-phenylenevinylene) (PPV) -based polymers; Spiro compounds; Polyfluorene, rubrene and the like, but are not limited thereto.

The light emitting layer may include a host material and a dopant material. The host material may be a condensed aromatic ring derivative or a hetero ring-containing compound. Specifically, the condensed aromatic ring derivatives include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, and fluoranthene compounds, and heterocyclic containing compounds include carbazole derivatives, dibenzofuran derivatives, and ladder types. Furan compounds, pyrimidine derivatives, and the like, but are not limited thereto.

Dopant materials include aromatic amine derivatives, styrylamine compounds, boron complexes, fluoranthene compounds, metal complexes, and the like. Specifically, the aromatic amine derivatives include condensed aromatic ring derivatives having a substituted or unsubstituted arylamino group, and include pyrene, anthracene, chrysene and periplanthene having an arylamino group, and a styrylamine compound may be substituted or unsubstituted. At least one arylvinyl group is substituted with the above-described arylamine, and one or two or more substituents selected from the group consisting of aryl group, silyl group, alkyl group, cycloalkyl group and arylamino group are substituted or unsubstituted. Specifically, styrylamine, styryldiamine, styryltriamine, styryltetraamine and the like, but is not limited thereto. In addition, the metal complex includes, but is not limited to, an iridium complex, a platinum complex, and the like. The dopant content may be from 1% to 99% relative to the host amount of the light emitting layer.

The electron transporting material is a layer that receives electrons from the electron injection layer and transports electrons to the light emitting layer. The electron transporting material is a material that can inject electrons well from the cathode and transfer them to the light emitting layer. This is suitable. Specific examples include Al complexes of 8-hydroxyquinoline; Complexes including Alq ₃ ; Organic radical compounds; Hydroxyflavone-metal complexes and the like, but are not limited thereto. The electron transport layer can be used with any desired cathode material as used according to the prior art. In particular, examples of suitable cathode materials are conventional materials having a low work function followed by an aluminum or silver layer. Specifically cesium, barium, calcium, ytterbium and samarium, followed by aluminum layers or silver layers in each case.

The electron injection layer is a layer for injecting electrons from an electrode, has a capability of transporting electrons, has an electron injection effect from the cathode, excellent electron injection effect to the light emitting layer or the light emitting material, and hole injection of excitons generated in the light emitting layer The compound which prevents the movement to a layer and is excellent in thin film formation ability is preferable. Specifically, fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, preorenylidene methane, anthrone and the derivatives thereof, metal Complex compounds, nitrogen-containing five-membered ring derivatives, and the like, but are not limited thereto.

Examples of the metal complex compound include 8-hydroxyquinolinato lithium, bis (8-hydroxyquinolinato) zinc, bis (8-hydroxyquinolinato) copper, bis (8-hydroxyquinolinato) manganese, Tris (8-hydroxyquinolinato) aluminum, tris (2-methyl-8-hydroxyquinolinato) aluminum, tris (8-hydroxyquinolinato) gallium, bis (10-hydroxybenzo [h] Quinolinato) beryllium, bis (10-hydroxybenzo [h] quinolinato) zinc, bis (2-methyl-8-quinolinato) chlorogallium, bis (2-methyl-8-quinolinato) ( o-cresolato) gallium, bis (2-methyl-8-quinolinato) (1-naphtholato) aluminum, bis (2-methyl-8-quinolinato) (2-naphtolato) gallium, etc. It is not limited to this.

When the organic light-emitting device further comprises at least one of an electron blocking layer and a hole blocking layer between the hole transport layer and the light emitting layer, and between the light emitting layer and the electron transport layer, the electron blocking layer prevents the electrons from reaching the anode. As a layer, it may be formed under the same conditions as the electron injection layer. The electron blocking layer is made of a material having a function of transporting holes and having a small ability to transport electrons, and can improve the probability of recombination of electrons and holes by blocking electrons while transporting holes.

In addition, the hole blocking layer is a layer that can prevent the injected holes to enter the electron transport layer through the light emitting layer to improve the life and efficiency of the device, nitrogen-containing heterocyclic derivatives such as oxadiazole derivatives and triazole derivatives , Phenanthroline derivatives, BCP or aluminum complex, but are not limited thereto. Specifically, the hole blocking layer may include a nitrogen-containing heterocyclic derivative as known in Korean Patent Registration No. 10-1052973 and Korean Patent Registration No. 10-1317495.

The organic light emitting device according to the present invention may be a top emission type, a bottom emission type or a double-sided emission type depending on the material used.

In addition, the compound of Formula 1 may be included in an organic solar cell or an organic transistor in addition to the organic light emitting device.

Preparation of the compound of Formula 1 and an organic light emitting device including the same will be described in detail in the following Examples. However, the following examples are only for illustrating the present invention, and the scope of the present invention is not limited thereto.

In the following Synthesis Examples and Examples, room temperature means 23 ± 5 ° C.

Synthesis Example 1 Synthesis of Compound A

Step 1) Synthesis of Compound A-1

In a three-necked flask, 1,2-difluoro-3,6-diiodobenzene (70.0 g, 191.3 mmol), 2-methoxyphenylboronic acid (69.8 g, 459.2 mmol), 2M aqueous solution of Na ₂ CO ₃ ( 383 ml, 765.3 mmol), 1,2-dimethoxyethane (DME) (383 ml), toluene (383 ml) and Pd (PPh ₃ ) ₄ (22.1 g, 19.1 mmol) were added and stirred under reflux conditions under an argon atmosphere for 8 hours. It was. After the reaction was completed, after cooling to room temperature, the resulting reaction solution was transferred to a separatory funnel, water (500 ml) was added and extracted with CH ₂ Cl ₂ . The extract was dried over MgSO ₄ , filtered and concentrated, and the resulting sample was purified by silica gel column chromatography to give 40.6 g of a white solid (yield 65%, MS [M + H] ⁺ = 326).

Step 2) Synthesis of Compound A-2

Compound A-1 (40.0 g, 122.6 mmol), NBS (21.8 g, 122.6 mmol), and dimethylformamide (DMF) (1200 ml) were added to a two-necked flask, and the mixture was reacted with stirring at room temperature for 8 hours under argon atmosphere. After the completion of the reaction, the resultant reaction solution was transferred to a separatory funnel, water (1000 ml) was added, and extracted with ethyl acetate (AcOEt). The resulting sample was purified by silica gel column chromatography to give 40.7 g of a white solid (yield: 82%, MS [M + H] ⁺ = 405).

Step 3) Synthesis of Compound A-3

Compound A-2 (40.0 g, 98.7 mmol), 1 M BBr ₃ CH ₂ Cl ₂ solution (237 ml, 236.9 mmol) and CH ₂ Cl ₂ (592 mmol) were added to a two-necked flask, and the mixture was adjusted to 0 ° C. under argon atmosphere for 8 hours. Was stirred. After stirring at room temperature for 4 more hours, the solution was neutralized with saturated aqueous NaHCO ₃ solution. The resulting reaction solution was transferred to a separatory funnel, extracted with CH ₂ Cl ₂ , and the extract was purified by silica gel column chromatography to give 31.6 g of a white solid (yield: 85%, MS [M + H] ⁺ = 377). )

Step 4) Synthesis of Compound A-4

Compound A-3 (30.0 g, 79.5 mmol), K ₂ CO ₃ (24.2 g, 175.0 mmol), and N-methyl pyrrolidone (NMP) (330 ml) were added to a two-necked flask at 150 ° C. for 8 hours. The reaction was stirred. After completion of the reaction, after cooling to room temperature, the resulting reaction solution was transferred to a separating funnel, water (500 ml) was added, and extracted with AcOEt. The resulting extract was purified by silica gel column chromatography to give 23.9 g of a white solid (yield: 89%, MS [M + H] ⁺ = 337).

Step 5) Synthesis of Compound A

Compound A-4 (20.0 g, 59.3 mmol) and THF (593 ml) were added to a three neck flask and cooled to -78 ° C. n-BuLi (1.6 M n-hexane solution, 41 ml, 65.2 mmol) was added dropwise, and stirred at -78 ° C for 20 minutes. Boric acid triisopropyl (33.47 g, 178.0 mmol) was added thereto, followed by stirring at −78 ° C. for 1 hour, followed by further stirring at room temperature for 4 hours. After adding 1N HCl (200ml) and stirred at room temperature for 1 hour, the resulting reaction solution was concentrated and transferred to a separating funnel, water (200ml) was added, and extracted with CH ₂ Cl ₂ . The extract was dried over MgSO ₄ , filtered, concentrated and recrystallized with toluene-hexane to give 10.8 g of compound A (yield: 60%, MS [M + H] ⁺ = 302).

Synthesis Example  2: synthesis of compound B

Synthesis Example 1 except that 1,2-difluoro-3,6-diiodobenzene was changed to 1,3-dibromo-4,6-difluorobenzene in Synthesis Example 1, and Compound B was synthesized using the same method.

Synthesis Example  3: Synthesis of Compound C

Synthesis Example 1 except that 1,2-difluoro-3,6-diiodobenzene was changed to 1,4-dibromo-2,5-difluorobenzene in Synthesis Example 1 and used. Compound C was synthesized using the same method.

Synthesis Example  4: Synthesis of Compound D

Synthesis Example 1 except that 1,2-difluoro-3,6-diiodobenzene was changed to 1,2-dibromo-3,6-difluorobenzene in Synthesis Example 1 and used. Compound D was synthesized using the same method.

Synthesis Example 5 Synthesis of Compound E

Step 1) Synthesis of Compound E-1

Compound A-1 (35.0 g, 107.3 mmol), NBS (38.2 g, 214.5 mmol) and DMF (1000 ml) were added to a two-necked flask, and the mixture was reacted with stirring at room temperature for 8 hours under argon atmosphere. After the reaction was completed, the reaction solution was transferred to a separatory funnel, water (1000 ml) was added, and extracted with AcOEt. The resulting sample was purified by silica gel column chromatography to give 40.5 g of a white solid (yield: 78%, MS [M + H] ⁺ = 484).

Step 2) Synthesis of Compound E-2

Compound E-1 (40.0g, 82.6mmol), 1M BBr ₃ CH ₂ Cl ₂ solution (198ml, 198.3mmol), CH ₂ Cl ₂ (496mmol) was added to a two-necked flask, and the mixture was adjusted to 0 ° C. under argon atmosphere for 8 hours Was stirred. After stirring at room temperature for 4 more hours, the solution was neutralized with saturated aqueous NaHCO ₃ solution. The resulting reaction solution was transferred to a separatory funnel, extracted with CH ₂ Cl ₂ , and the extract was purified by silica gel column chromatography to give 30.1 g of a white solid (yield: 80%, MS [M + H] ⁺ = 456). )

Step 3) Synthesis of Compound E-3

Compound E-2 (30.0 g, 65.8 mmol), K ₂ CO ₃ (20.0 g, 144.7 mmol), and NMP (270 ml) were added to a two-necked flask, and the mixture was reacted with stirring at 150 ° C. for 8 hours under argon atmosphere. After the reaction was completed and cooled to room temperature, the resulting reaction solution was transferred to a separatory funnel, water (400 ml) was added, and extracted with AcOEt. The resulting extract was purified by silica gel column chromatography to give 21.1 g of a white solid (yield: 77%, MS [M + H] ⁺ = 416).

Step 4) Synthesis of Compound E-4

Compound E-3 (20.0 g, 48.1 mmol), phenylboronic acid (5.9 g, 48.1 mmol), 2M Na ₂ CO ₃ aqueous solution (72 ml, 144.2 mmol), DME (95 ml), toluene (95 ml), Pd (PPh ₃ ) ₄ (5.6 g, 4.8 mmol) was added thereto, and the mixture was reacted with stirring under reflux conditions for 8 hours under an argon atmosphere. After the reaction was completed, the reaction mixture was cooled to room temperature, and the resulting reaction solution was transferred to a separating funnel, water (200 ml) was added thereto, and extracted with CH ₂ Cl ₂ . The extract was dried over MgSO ₄ , filtered and concentrated, and the resulting sample was purified by silica gel column chromatography to give 15.1 g of a white solid (yield: 76%, ms [M + H] + = 413).

Step 5) Synthesis of Compound E

Compound E-4 (15.0 g, 36.3 mmol) and THF (363 ml) were added to a three neck flask and cooled to -78 ° C. n-BuLi (1.6M n-hexane solution, 25.0 ml, 39.9 mmol) was added dropwise, and stirred at -78 ° C for 20 minutes. Boric acid triisopropyl (20.5 g, 108.9 mmol) was added thereto, followed by stirring at −78 ° C. for 1 hour, followed by further stirring at room temperature for 4 hours. After adding 1N HCl (120ml) and stirred at room temperature for 1 hour, the resulting reaction solution was concentrated and transferred to a separatory funnel, water (120ml) was added and extracted with CH ₂ Cl ₂ . The extract was dried over MgSO ₄ , filtered, concentrated and recrystallized with toluene-hexane to give 9.6 g of compound E (yield: 70%, MS [M + H] ⁺ = 378).

Synthesis Example  6: Synthesis of Compound F

Compound F was synthesized in the same manner as in Synthesis Example 5, except that Compound B-1 was used instead of Compound A-1 in Synthesis Example 5.

Synthesis Example  7: Synthesis of Compound G

Compound G was synthesized in the same manner as in Synthesis Example 5, except that Compound C-1 was used instead of Compound A-1 in Synthesis Example 5.

Synthesis Example  8: Synthesis of Compound H

Compound H was synthesized in the same manner as in Synthesis Example 5, except that Compound D-1 was used instead of Compound A-1 in Synthesis Example 5.

Preparation Example 1 Synthesis of Compound 1

Step 1) Synthesis of Compound 1-1

Compound G (8.0g, 21.2mmol), 3-bromoiodobenzene (6.0g, 21.2mmol), 2M Na ₂ CO ₃ aqueous solution (32ml, 63.5mmol) prepared in Synthesis Example 7 in a three neck flask, DME ( 42 ml), toluene (42 ml) and Pd (PPh ₃ ) ₄ (2.1 g, 2.1 mmol) were added thereto, and the mixture was stirred and reacted under reflux conditions under an argon atmosphere for 8 hours. After the reaction was completed, after cooling to room temperature, the resulting reaction solution was transferred to a separatory funnel, water (42 ml) was added and extracted with CH ₂ Cl ₂ . The extract was dried over MgSO ₄ , filtered and concentrated, and the resulting sample was purified by silica gel column chromatography to give 15.1 g of a white solid (yield: 70%, MS [M + H] ⁺ = 489). ).

Step 2) Synthesis of Compound 1

Compound 1-1 (7.0 g, 14.3 mmol) prepared in Step 1, Compound H (6.0 g, 15.7 mmol) prepared in Synthesis Example 8, 2M aqueous solution of Na ₂ CO ₃ (21 ml, 42.9 mmol) in a three-necked flask ), DME (30 ml), toluene (30 ml), and Pd (PPh ₃ ) ₄ (1.7 g, 1.4 mmol) were added thereto, and the mixture was reacted under reflux under an argon atmosphere for 8 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, the resulting reaction solution was transferred to a separatory funnel, water (60 ml) was added thereto, and extracted with CH ₂ Cl ₂ . The resulting extract was dried over MgSO ₄ , filtered and concentrated, and the resulting sample was purified by silica gel column chromatography, and then 5.3 g of Compound 1 was obtained through sublimation purification (yield: 50%, MS). [M + H] ⁺ = 743).

Preparation Example 2 Synthesis of Compound 2

Step 1) Synthesis of Compound 2-1

Compound B (6.5 g, 21.5 mmol), 4-bromoiodobenzene (6.1 g, 21.5 mmol), 2M Na ₂ CO ₃ aqueous solution (32 ml, 64.6 mmol), DME (prepared in Synthesis Example 2) in a three neck flask 45 ml), toluene (45 ml) and Pd (PPh ₃ ) ₄ (2.5 g, 2.2 mmol) were added, and the mixture was stirred and reacted under reflux conditions under an argon atmosphere for 8 hours. After the reaction was completed, after cooling to room temperature, the reaction solution was transferred to a separatory funnel, water (90ml) was added and extracted with CH ₂ Cl ₂ . The extract was dried over MgSO ₄ , filtered and concentrated, and the resulting sample was purified by silica gel column chromatography to give 6.0 g of a white solid (yield: 68%, MS [M + H] ⁺ = 489). ).

Step 2) Synthesis of Compound 2

Compound 2-1 (6.0 g, 14.5 mmol) prepared in Step 1, Compound E (6.0 g, 16.0 mmol) prepared in Synthesis Example 5, 2M Na ₂ CO ₃ aqueous solution (22 ml, 43.6 mmol) in a three-necked flask , DME (30 ml), toluene (30 ml) and Pd (PPh ₃ ) ₄ (1.7 g, 1.4 mmol) were added thereto, and the mixture was reacted under reflux under an argon atmosphere for 8 hours under reflux conditions. After the reaction was completed, the reaction mixture was cooled to room temperature, the resulting reaction solution was transferred to a separatory funnel, water (60 ml) was added thereto, and extracted with CH ₂ Cl ₂ . The resulting extract was dried over MgSO ₄ , filtered and concentrated, and the resulting sample was purified by silica gel column chromatography to give 4.6 g of compound 2 (yield: 48%, MS) through sublimation purification. [M + H] ⁺ = 667).

Preparation Example 3 Synthesis of Compound 3

Step 1) Synthesis of Compound 3-1

Compound D (7.0 g, 23.2 mmol), 2,7-dibromonaphthalene (6.6 g, 23.2 mmol), 2M Na ₂ CO ₃ aqueous solution (35 ml, 69.5 mmol) and DME prepared in Synthesis Example 4 in a three neck flask (45ml), toluene (45ml) and Pd (PPh ₃ ) ₄ (2.7g, 2.3mmol) were added thereto, and the mixture was reacted by stirring under reflux condition under an argon atmosphere for 8 hours. After the reaction was completed, after cooling to room temperature, the resulting reaction solution was transferred to a separatory funnel, water (90 ml) was added and extracted with CH ₂ Cl ₂ . The extract was dried over MgSO ₄ , filtered and concentrated, and the resulting sample was purified by silica gel column chromatography to yield 7.5 g of a white solid (yield: 70%, MS [M + H] ⁺ = 463). ).

Step 2) Synthesis of Compound 3

Compound 3-1 (7.0 g, 15.1 mmol) prepared in Step 1, Compound A (5.0 g, 16.6 mmol) prepared in Synthesis Example 1, 2M Na ₂ CO ₃ aqueous solution ( ₂₃ ml, 45.3 mmol) in a _three- necked flask , DME (30 ml), toluene (30 ml), Pd (PPh ₃ ) ₄ (1.7 g, 1.5 mmol) were added thereto, and the mixture was reacted under reflux under an argon atmosphere for 8 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, the resulting reaction solution was transferred to a separatory funnel, water (60 ml) was added thereto, and extracted with CH ₂ Cl ₂ . The resulting extract was dried over MgSO ₄ , filtered and concentrated, and the resulting sample was purified by silica gel column chromatography to give 4.9 g of compound 3 (substrate: 51%, MS through sublimation purification). [M + H] ⁺ = 641).

Preparation Example 4 Synthesis of Compound 4

Step 1) Synthesis of Compound 4

Compound A (5.0g, 16.6mmol) prepared in Synthesis Example 1, Compound C-4 (6.1g, 18.2mmol) prepared in Synthesis Example 3, 2M Na ₂ CO ₃ aqueous solution (25ml, 49.7mmol) in a _three- necked flask ), DME (33 ml), toluene (32 ml) and Pd (PPh ₃ ) ₄ (1.9 g, 1.7 mmol) were added thereto, and the mixture was reacted under reflux under an argon atmosphere for 8 hours. After the reaction was completed, after cooling to room temperature, the resulting reaction solution was transferred to a separatory funnel, water (66 ml) was added, and extracted with CH ₂ Cl ₂ . The resulting extract was dried over MgSO ₄ , filtered and concentrated, and the resulting sample was purified by silica gel column chromatography, and then 4.7 g of Compound 4 was obtained through sublimation purification (yield: 47%, MS). [M + H] ⁺ = 515).

Preparation Example 5 Synthesis of Compound 5

Step 1) Synthesis of Compound 5-1

Three-necked compound I (5.0g, 15.0mmol) in a flask, 3,6-dibromo-9-phenyl -9H- carbazole (6.0g, 15.0mmol), 2M Na 2 CO 3 aqueous solution (22ml, 44.9mmol), DME (30 ml), toluene (30 ml) and Pd (PPh ₃ ) ₄ (1.7 g, 1.5 mmol) were added thereto, and the mixture was reacted by stirring under reflux conditions under an argon atmosphere for 8 hours. After the reaction was completed, after cooling to room temperature, the resulting reaction solution was transferred to a separatory funnel, water (60 ml) was added and extracted with CH ₂ Cl ₂ . The extract was dried over MgSO ₄ , filtered and concentrated, and the resulting sample was purified by silica gel column chromatography to give 6.4 g of a white solid (yield: 70%, MS [M + H] ⁺ = 611). ).

Step 2) Synthesis of Compound 5

Compound 5-1 (6.2 g, 10.2 mmol) prepared in Step 1, Compound J (3.7 g, 11.2 mmol), 2M Na ₂ CO ₃ aqueous solution (15 ml, 30.5 mmol), DME (20 ml), Toluene (20 ml) and Pd (PPh ₃ ) ₄ (1.2 g, 1.0 mmol) were added thereto, and the mixture was reacted with stirring under reflux conditions for 8 hours under argon atmosphere. After the reaction was completed, after cooling to room temperature, the resulting reaction solution was transferred to a separatory funnel, water (40 ml) was added, and extracted with CH ₂ Cl ₂ . The resulting extract was dried over MgSO ₄ , filtered and concentrated, and the resulting sample was purified by silica gel column chromatography to give 3.9 g of compound 5 through sublimation purification (yield: 47%, MS). [M + H] ⁺ = 820).

Preparation Example 6 Synthesis of Compound 6

Step 1) Synthesis of Compound 6-1

Compound F (7.0 g, 18.5 mmol), 3-bromoiodobenzene (5.2 g, 18.5 mmol), 2M Na ₂ CO ₃ aqueous solution (28 ml, 55.5 mmol), DME (prepared in Synthesis Example 6) in a three neck flask 37 ml), toluene (37 ml) and Pd (PPh ₃ ) ₄ (2.1 g, 1.9 mmol) were added thereto, and the mixture was reacted by stirring under reflux conditions under an argon atmosphere for 8 hours. After the reaction was completed, after cooling to room temperature, the resulting reaction solution was transferred to a separatory funnel, water (80 ml) was added and extracted with CH ₂ Cl ₂ . The extract was dried over MgSO ₄ , filtered and concentrated, and the resulting sample was purified by silica gel column chromatography to give 6.0 g of a white solid (yield: 66%, MS [M + H] ⁺ = 489). ).

Step 2) Synthesis of Compound 6

Compound 6-1 (6.0 g, 12.3 mmol) prepared in Step 1, Compound K (4.8 g, 13.5 mmol), 2M Na ₂ CO ₃ aqueous solution (18 ml, 36.8 mmol), DME (25 ml), Toluene (25 ml) and Pd (PPh ₃ ) ₄ (1.4 g, 1.2 mmol) were added thereto, and the mixture was reacted with stirring under reflux for 8 hours under argon atmosphere. After the reaction was completed, after cooling to room temperature, the resulting reaction solution was transferred to a separatory funnel, water (50 ml) was added, and the mixture was extracted with CH ₂ Cl ₂ . The resulting extract was dried over MgSO ₄ , filtered and concentrated, and the resulting sample was purified by silica gel column chromatography to give 4.2 g of compound 6 through sublimation purification (yield: 48%, MS). [M + H] ⁺ = 719).

Device Fabrication Example

Example 1

A glass substrate coated with ITO (Indium Tin Oxide) having a thickness of 1,400Å was placed in distilled water dissolved in a detergent and washed ultrasonically. At this time, the detergent used was Fischer Co.'s Decon? CON705 was used, and distilled water was filtered using a 0.22 μm sterilizing filter manufactured by Millerpore Co., Ltd. After ITO was washed for 30 minutes, ultrasonic washing was performed twice with distilled water for 10 minutes. After the distilled water was washed, ultrasonic washing with a solvent of isopropyl alcohol, acetone and methanol for 10 minutes, dried and then transported to a plasma cleaner. In addition, the substrate was cleaned for 5 minutes using an oxygen plasma, and then the substrate was transferred to a vacuum evaporator.

A mixture of 95 wt% of HT-A and 5 wt% of P-DOPANT was thermally vacuum deposited to a thickness of 100 kPa on the prepared ITO transparent electrode. Then, only HT-A was deposited to a thickness of 1150 kPa to form a hole transport layer.

The following HT-B was thermally vacuum deposited to a thickness of 450 위에 on the hole transport layer to form an electron blocking layer.

Subsequently, a mixture of 95 wt% of the following Compound 1 and 5 wt% of the dopant GD was vacuum deposited to a thickness of 400 kPa on the electronic blocking layer to form a light emitting layer.

Further, the following ET-A was vacuum deposited to a thickness of 50 kPa on the light emitting layer to form a hole blocking layer.

Next, the following ET-B and Liq are mixed in a weight ratio of 2: 1 on the hole blocking layer to form a vacuum layer by thermal vacuum deposition at a thickness of 250 kPa, followed by mixing LiF and magnesium in a weight ratio of 1: 1. Vacuum deposition was carried out to a thickness of 30 kHz to form an electron injection layer.

The organic light emitting device was manufactured by mixing magnesium and silver on the electron injection layer in a weight ratio of 1: 4 and depositing the same at a thickness of 160 kPa to form a cathode.

Example  2 to 6, and Comparative example  1 to 4

The organic light emitting diodes of Examples 2 to 6 and Comparative Examples 1 to 4 were manufactured by the same method as Example 1, except that the host material was changed to the material shown in Table 1 below.

 Voltage, efficiency, and lifetime (T95) were measured by applying current to the organic light emitting device, and the results are shown in Table 1 below.

At this time, the voltage and efficiency were measured by applying a current density of 10mA / cm ² , the life (T95) means the time until the initial luminance is reduced to 95% at a current density of 20mA / cm ² .

Host substance @ 10ma / cm ² @ 20ma / cm ² Voltage (V) Efficiency (cd / A) Life (T95, hr) Example 1 Compound 1 4.46 59.55 120 Example 2 Compound 2 4.43 54.15 130 Example 3 Compound 3 4.48 56.43 110 Example 4 Compound 4 4.38 55.25 140 Example 5 Compound 5 4.46 57.39 130 Example 6 Compound 6 4.50 53.73 120 Comparative Example 1 GH-A 4.56 42.11 80 Comparative Example 2 GH-B 4.67 38.19 70 Comparative Example 3 GH-C 4.65 40.15 30 Comparative Example 4 GH-D 4.78 41.55 60

As a result, the organic light emitting diodes of Examples 1 to 6, which include the compounds of Preparation Examples 1 to 6 (compounds 1 to 6) containing two different heteroatomic-containing condensed ring structures in the molecule, are the same as each other. Compared with the organic electroluminescent device of Comparative Examples 1 to 4 containing a compound having heteroatomic-containing condensed rings having the same skeletal structure at both sides or the same, the efficiency was increased with low voltage characteristics and markedly improved in life characteristics. Effect.

1: substrate 2: anode
3: light emitting layer 4: cathode
5: hole injection layer 6: hole transport layer
7: light emitting layer 8: electron transport layer

Claims (11)

A compound of formula
[Formula 1]

In Chemical Formula 1,
L is a bond; Unsubstituted phenylene; Unsubstituted naphthalene-diyl; Phenyl substituted carbazole-diyl; And unsubstituted dibenzofurandiyl is selected from the group consisting of,
A and D are each independently any one of the functional groups of the formula 2-1 to 2-6, except that A and D are all one of the functional groups of the formula 2-1 to 2-6,
[Formula 2-1]

[Formula 2-2]

[Formula 2-3]

[Formula 2-4]

[Formula 2-5]

[Formula 2-6]

In Chemical Formulas 2-1 to 2-6,
X ₅ and X ₆ are each independently selected from the group consisting of O, S and CR ₁ R ₂ ,
R ₁ and R ₂ are each methyl,
Z is-[(L ₁ ) _m -Y] _n , where L ₁ is a bond,
Y is hydrogen or phenyl,
m and n are each an integer of 0 or 1.
delete delete The method of claim 1,
L is a bond,
A and D are each independently any one of the functional groups of Formulas 2-1 to 2-6, except that A and D are all one of the functional groups of Formulas 2-1 to 2-6,
In Formulas 2-1 to 2-6, X ₅ and X ₆ are any one of O, S, and CR ₁ R ₂ are the same as each other, Z is-[(L ₁ ) _m -Y] _n , m And n is 0 each.
The method of claim 1,
L is unsubstituted phenylene,
A and D are each independently any one of the functional groups of Formulas 2-1 to 2-6, except that A and D are all one of the functional groups of Formulas 2-1 to 2-6,
In Chemical Formulas 2-1 to 2-6, Z is-[(L ₁ ) _m -Y] _n , _wherein L ₁ is a bond,
Y is hydrogen or phenyl,
m and n are each an integer of 0 or 1;
The method of claim 5,
In Chemical Formulas 2-1 to 2-6, X ₅ and X ₆ are the same as O or CR ₁ R ₂ .
The method of claim 1,
L is an unsubstituted naphthalene-diyl group,
A and D are each independently any one of the functional groups of Formulas 2-1 to 2-6, except that A and D are all one of the functional groups of Formulas 2-1 to 2-6,
In Chemical Formulas 2-1 to 2-6, Z is-[(L ₁ ) _m -Y] _n , _wherein L ₁ is a bond,
Y is hydrogen or phenyl,
m and n are each an integer of 0 or 1;
The method of claim 1,
L is a phenyl substituted carbazole group,
A and D are each independently any one of the functional groups of Formulas 2-1 to 2-6, except that A and D are all one of the functional groups of Formulas 2-1 to 2-6,
In Chemical Formulas 2-1 to 2-6, Z is-[(L ₁ ) _m -Y] _n , _wherein m and n are each 0.
The method of claim 1,
Compound which is any one selected from the group consisting of the following compounds.

A first electrode; A second electrode provided to face the first electrode; And one or more organic material layers provided between the first electrode and the second electrode.
At least one layer of the organic material layer, the organic light emitting device comprising a compound according to any one of claims 1 and 4 to 9.
The method of claim 10,
The organic material layer containing the compound is a light emitting layer, an organic light emitting device.

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