KR102614656B1 - Novel compound and organic light emitting device comprising the same - Google Patents

Abstract

The present invention provides a novel compound and an organic light-emitting device using the same.

Description

Novel compounds and organic light-emitting devices using the same {NOVEL COMPOUND AND ORGANIC LIGHT EMITTING DEVICE COMPRISING THE SAME}

The present invention relates to novel compounds and organic light-emitting devices containing them.

In general, organic luminescence refers to a phenomenon that converts electrical energy into light energy using organic materials. Organic light-emitting devices using the organic light-emitting phenomenon have a wide viewing angle, excellent contrast, fast response time, and excellent luminance, driving voltage, and response speed characteristics, so much research is being conducted.

Organic light emitting devices generally have a structure including an anode, a cathode, and an organic layer between the anode and the cathode. The organic material layer is often composed of a multi-layer structure made of different materials to increase the efficiency and stability of the organic light-emitting device, for example, a hole injection layer, a hole transport layer, an electron suppression layer, a light-emitting layer, a hole blocking layer, an electron transport layer, and an electron layer. It may consist of an injection layer, etc. In the structure of this organic light-emitting device, when a voltage is applied between the two electrodes, holes are injected from the anode and electrons from the cathode into the organic material layer. When the injected holes and electrons meet, an exciton is formed, and this exciton is When it falls back to the ground state, it glows.

The development of new materials for organic materials used in organic light-emitting devices as described above is continuously required.

Korean Patent Publication No. 10-2000-0051826

The present invention relates to novel compounds and organic light-emitting devices containing them.

The present invention provides a compound represented by the following formula (1):

[Formula 1]

In Formula 1,

Y is O or S,

R ₁ is each independently hydrogen; heavy hydrogen; halogen; cyano; Substituted or unsubstituted C _1-60 alkyl; Substituted or unsubstituted C _1-60 alkoxy; Substituted or unsubstituted C _2-60 alkenyl; Substituted or unsubstituted C _2-60 alkynyl; Substituted or unsubstituted C _3-60 cycloalkyl; Substituted or unsubstituted C _6-60 aryl; or a substituted or unsubstituted C _2-60 heteroaryl containing one or more heteroatoms selected from the group consisting of N, O and S,

n1 is an integer from 0 to 6,

n2 is an integer from 0 to 3,

One of R ₂ is of the formula 2 below, and the other is hydrogen or deuterium,

[Formula 2]

In Formula 2,

L is a single bond; Or substituted or unsubstituted C _6-60 arylene,

X is N, or CH, provided that at least two of X are N,

Ar ₁ and Ar ₂ are each independently substituted or unsubstituted C _6-60 aryl; or substituted or unsubstituted C _2-60 heteroaryl containing one or more heteroatoms selected from the group consisting of N, O, and S.

In addition, the present invention includes a first electrode; a second electrode provided opposite to the first electrode; and an organic light-emitting device comprising at least one organic material layer provided between the first electrode and the second electrode, wherein at least one layer of the organic material layer includes a compound represented by Formula 1. to provide.

The compound represented by the above-mentioned formula 1 can be used as a material for the organic layer of an organic light-emitting device, and can improve efficiency, low driving voltage, and/or lifespan characteristics of the organic light-emitting device. In particular, the compound represented by the above-mentioned formula 1 can be used as a hole injection, hole transport, hole injection and transport, light emitting, electron transport, or electron injection material.

Figure 1 shows an example of an organic light emitting device consisting of a substrate 1, an anode 2, a light emitting layer 3, and a cathode 4.
Figure 2 shows the substrate (1), anode (2), hole injection layer (5), hole transport layer (6), electron blocking layer (6), light emitting layer (3), hole blocking layer (8), electron injection and transport layer ( 9) and a cathode 4. An example of an organic light-emitting device is shown.

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

In this specification, or means a bond connected to another substituent.

As used herein, the term “substituted or unsubstituted” refers to deuterium; halogen group; Nitrile group; nitro group; hydroxyl group; carbonyl group; ester group; imide group; amino group; Phosphine oxide group; Alkoxy group; Aryloxy group; Alkylthioxy group; Arylthioxy group; Alkyl sulphoxy group; Aryl sulfoxy group; silyl group; boron group; Alkyl group; Cycloalkyl group; alkenyl group; Aryl group; Aralkyl group; Aralkenyl group; Alkylaryl group; Alkylamine group; Aralkylamine group; heteroarylamine group; Arylamine group; Arylphosphine group; or substituted or unsubstituted with one or more substituents selected from the group consisting of heterocyclic groups containing one or more of N, O and S atoms, or substituted or unsubstituted with two or more of the above-exemplified substituents linked. . For example, “a substituent group in which two or more substituents are connected” may be a biphenyl group. That is, the biphenyl group may be an aryl group, or it may be interpreted as a substituent in which two phenyl groups are connected.

In this specification, the carbon number of the carbonyl group is not particularly limited, but is preferably 1 to 40 carbon atoms. Specifically, it may be a compound with the following structure, but is not limited thereto.

In the present specification, the oxygen of the ester group may be substituted with a straight-chain, branched-chain, or ring-chain alkyl group having 1 to 25 carbon atoms 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, the carbon number of the imide group is not particularly limited, but is preferably 1 to 25 carbon atoms. Specifically, it may be a compound with the following structure, but is not limited thereto.

In the present specification, the silyl group specifically includes trimethylsilyl group, triethylsilyl group, t-butyldimethylsilyl group, vinyldimethylsilyl group, propyldimethylsilyl group, triphenylsilyl group, diphenylsilyl group, phenylsilyl group, etc. However, it is not limited to this.

In the present specification, the boron group specifically includes trimethyl boron group, triethyl boron group, t-butyldimethyl boron group, triphenyl boron group, and phenyl boron group, but is not limited thereto.

In this specification, examples of halogen groups include fluorine, chlorine, bromine, or iodine.

In the present specification, the alkyl group may be straight chain or branched, and the number of carbon atoms is not particularly limited, but is preferably 1 to 40. According to one embodiment, the carbon number of the alkyl group is 1 to 20. According to another embodiment, the carbon number of the alkyl group is 1 to 10. According to another embodiment, the carbon number of the alkyl group is 1 to 6. Specific examples of alkyl groups 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, etc., but is not limited to these.

In the present specification, the alkenyl group may be straight chain or branched, and the number of carbon atoms is not particularly limited, but is preferably 2 to 40. According to one embodiment, the alkenyl group has 2 to 20 carbon atoms. According to another embodiment, the alkenyl group has 2 to 10 carbon atoms. According to another 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, etc., but are not limited to these.

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 embodiment, the carbon number of the cycloalkyl group is 3 to 20. According to another embodiment, the carbon number of the cycloalkyl group is 3 to 6. Specifically, cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,3-dimethylcyclohexyl, 3, Examples include, but are not limited to, 4,5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, and cyclooctyl.

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 one embodiment, the aryl group has 6 to 30 carbon atoms. According to one embodiment, the aryl group has 6 to 20 carbon atoms. The aryl group may be a monocyclic aryl group, such as a phenyl group, biphenyl group, or terphenyl 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, etc., but is not limited thereto.

In the present specification, the fluorenyl group may be substituted, and two substituents may be combined with each other to form a spiro structure. When the fluorenyl group is substituted, It can be etc. However, it is not limited to this.

In the present specification, the heterocyclic group is a heterocyclic group containing one or more of O, N, Si, and S as a heterogeneous element, and the number of carbon atoms is not particularly limited, but is preferably 2 to 60 carbon atoms. Examples of heterocyclic groups 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, and acridyl 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, benzooxazole group, benzoimidazole group, benzothiazole group, benzocarbazole group, benzothiophene group, dibenzothiophene group, benzofuranyl group, phenanthroline group, isoxazolyl group, thiadia These include, but are not limited to, a zolyl group, a phenothiazinyl group, and a dibenzofuranyl group.

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

The present invention provides a compound represented by Formula 1 above.

The compound represented by Formula 1 is a heterocycle containing two or more Ns bonded to a specific position of the parent core structure in which a fluoranthene ring and a two-ring heterocycle containing O or S are condensed, thereby using it. The characteristics of organic light emitting devices can be improved. In particular, the compound represented by Formula 1 uses a polycyclic aromatic core connecting a plurality of aromatic rings to increase the rigidity of the molecule, thereby increasing stability against electrons and holes and exhibiting better luminescence characteristics. This can improve quantum efficiency and lifespan.

In Formula 1, depending on the specific position at which the heterocycle containing two or more N is bonded, the compound represented by Formula 1 may be represented by the following Formula 1-1 or 1-2:

[Formula 1-1]

[Formula 1-2]

In Formulas 1-1 and 1-2,

Y, R ₁ , n1, n2, L, X, Ar ₁ and Ar ₂ are as defined in Formula 1 above.

Specifically, in Formula 1, Formula 1-1, and Formula 1-2, Y is O or S.

Specifically, in Formula 1, Formula 1-1, and Formula 1-2, R ₁ is each hydrogen, deuterium, halogen, or cyano, or substituted or unsubstituted C _1-20 alkyl, or C _1-12 Alkyl, or C _1-6 alkyl, or substituted or unsubstituted C _1-20 alkoxy, or C _1-12 alkoxy, or C _1-6 alkoxy, or substituted or unsubstituted C _2-20 alkenyl, or C _2-12 alkenyl, or C _2-6 alkenyl, or substituted or unsubstituted C _2-20 alkynyl, or C _2-12 alkynyl, or C _2-6 alkynyl, or substituted or Unsubstituted C _3-30 cycloalkyl, or C _3-25 cycloalkyl, or C _3-20 cycloalkyl, or substituted or unsubstituted C _6-30 aryl, or C _6-28 aryl, or C _{6- 25} aryl, or C _6-20 aryl, or substituted or unsubstituted C _3-30 heteroaryl, or C _5-28 heteroaryl, containing one or more heteroatoms selected from the group consisting of N, O and S. , or C _5-25 heteroaryl, or C _6-20 heteroaryl, or C _12-18 heteroaryl.

For example, R ₁ may each be hydrogen or deuterium. Additionally, all of R ₁ may be hydrogen.

Specifically, in Formula 1, Formula 1-1, and Formula 1-2, n1 and n2 may each be an integer of 0 to 2, or 0 or 1.

Specifically, in Formula 1, Formula 1-1, and Formula 1-2, L is a single bond; Or it may be substituted or unsubstituted C _6-30 arylene, or C _6-28 arylene, or C _6-25 arylene, or C _6-20 arylene. Preferably, L is a single bond; Or it may be phenylene, biphenylylene, terphenylylene, quarterphenylylene, or naphthylene.

For example, L is a single bond; Alternatively, it may be represented by any one selected from the group consisting of the following.

.

.

Specifically, in Formula 1, Formula 1-1, and Formula 1-2, two of X may be N and the remainder may be CH, or all of X may be N.

Specifically, in Formula 1, Formula 1-1, and Formula 1-2, Ar ₁ and Ar ₂ are each substituted or unsubstituted C _6-30 aryl, or C _6-28 aryl, or C _6-25 aryl, or C _6-20 aryl; or substituted or unsubstituted C _3-30 heteroaryl containing at least one heteroatom selected from the group consisting of N, O and S, or C _5-28 heteroaryl, or C _5-25 heteroaryl, or It may be C _6-20 heteroaryl, or C _12-18 heteroaryl.

More specifically, Ar ₁ and Ar ₂ are each phenyl, naphthyl substituted phenyl, dibenzofuranyl substituted phenyl, dibenzothiophenyl substituted phenyl, carbazolyl substituted phenyl, biphenyl, terphenyl, naphthyl, It may be phenyl substituted naphthyl, phenanthryl, dibenzofuranyl, dibenzothiophenyl, carbazolyl, or phenyl substituted carbazolyl.

In particular, at least one of Ar ₁ and Ar ₂ may be phenyl, naphthyl substituted phenyl, biphenyl, naphthyl, or phenyl substituted naphthyl.

Representative examples of the compound represented by Formula 1 are as follows.

.

Meanwhile, the compound represented by Chemical Formula 1 can be prepared by a production method such as Scheme 1 or Scheme 2 below. The manufacturing method may be further detailed in the synthesis examples described later.

[Scheme 1]

In Scheme 1, Y, R ₁ , R ₂ , n1, and n2 are as defined in Formula 1, and one of Q ₁ is BO ₂ C ₂ (CH ₃ ) ₄ or B(OH) ₂ , the remainder is hydrogen or deuterium, and Q ₂ is a halogen group, preferably Cl, Br, or I, more preferably Cl;

[Scheme 2]

In Scheme 2, Y, R ₁ , R ₂ , n1, and n2 are as defined in Formula 1, and one of Q ₃ is a halogen group, preferably Cl, Br, or I, and more preferably is Cl, the remainder of Q ₃ is hydrogen or deuterium, and Q ₄ is BO ₂ C ₂ (CH ₃ ) ₄ , or B(OH) ₂ .

Specifically, Scheme 1 and Scheme 2 introduce a heteroaryl substituent containing at least two N at a specific position in the parent core structure in which a fluoranthene ring and a two-ring hetero ring containing O or S are condensed. It is a reaction. In this reaction, when a leaving group such as BO ₂ C ₂ (CH ₃ ) ₄ or B(OH) ₂ is bonded to an intermediate compound containing a fluoranthene ring, the compound of Formula 1 can be prepared according to Scheme 1. In the case where a leaving group such as BO ₂ C ₂ (CH ₃ ) ₄ or B(OH) ₂ is bonded to an intermediate compound containing a heteroaryl substituent containing at least two or more N, Formula 1 according to Scheme 2 Compounds can be manufactured.

As an example, in Scheme 1, one of Q ₁ is a pinacolborane group, BO ₂ C ₂ (CH ₃ ) ₄ , or a boronic acid group, B(OH) ₂ , and a fluoranthene ring. A polycyclic ring compound in which a two-ring heterocycle containing O or S is condensed, and a heterocyclic compound containing Q ₂ which is a halogen group and containing at least two Ns, are reacted with a palladium catalyst (Pd) in the presence of a base. It is achieved by reacting with a catalyst. Through this reaction, the inacolborone group BO ₂ C ₂ (CH ₃ ) ₄ , or B(OH) among polycyclic ring compounds in which a fluoranthene ring and a bicyclic hetero ring containing O or S are condensed ) ₂ At the Q ₁ position, a heteroaryl group containing at least two N is introduced. Preferably, in Scheme 1, Q ₁ is BO ₂ C ₂ (CH ₃ ) ₄ and Q ₂ may be chlorine. The specific reaction conditions of Scheme 1 can be performed with reference to known reactions known in the field. The manufacturing method may be further detailed in the synthesis examples described later.

As another example, Scheme 2 shows a polycyclic ring compound in which one of Q ₃ is a halogen group and a fluoranthene ring and a bicyclic heterocycle containing O or S are condensed, and BO ₂ C ₂ (CH ₃ ) ₄ , or a heterocyclic compound containing Q ₄ , which is a boronic acid group, B(OH) ₂ , and containing at least two N, reacted with a palladium catalyst (Pd catalyst) in the presence of a base. It is done by doing what you are told. Through this reaction, a heteroaryl group containing at least two N is introduced into the Q ₃ position, which is a halogen group, in a polycyclic ring compound in which a fluoranthene ring and a two-ring hetero ring containing O or S are condensed. will be. Preferably, in Scheme 2, Q ₃ may be chlorine, and Q ₄ may be BO ₂ C ₂ (CH ₃ ) ₄ . The specific reaction conditions of Scheme 2 can be performed by referring to known reactions known in the field. The manufacturing method may be further detailed in the synthesis examples described later.

In addition, in Scheme 1 and Scheme 2, the base components include potassium carbonate (K ₂ CO ₃ ), sodium bicarbonate (NaHCO ₃ ), cesium carbonate (Cs ₂ CO ₃ ), and sodium. Sodium acetate (NaOAc), potassium acetate (KOAc), sodium tert-butoxide (NaOtBu), sodium ethoxide (NaOEt), or triethylamine (Et ₃ ) N), N,N-diisopropylethylamine (N,N-diisopropylethylamine, EtN(iPr) ₂ ), etc. can be used. Preferably, the base component is potassium carbonate (K ₂ CO ₃ ), cesium carbonate (Cs ₂ CO ₃ ), potassium acetate (KOAc), and sodium tert-butoxide. butoxide, NaOtBu), or N,N-diisopropylethylamine (EtN(iPr) ₂ ).

In addition, in Scheme 1 and Scheme 2, the palladium catalyst includes tetrakis(triphenylphosphine)palladium (0) (tetrakis(triphenylphosphine)palladium (0), tris(dibenzylideneacetone)dipalladium (0) ( tris(dibenzylideneacetone)-dipalladium (0), Pd ₂ (dba) ₃ ), bis(tri-(tert-butyl)phosphine)palladium (0) (bis(tri-(tert-butyl)phosphine)palladium(0) , Pd(P-tBu ₃ ) ₂ ), bis(dibenzylideneacetone)palladium (0) (bis(dibenzylideneacetone)palladium (0), Pd(dba) ₂ ), Pd(PPh ₃ ) ₄ ) or palladium(II ) Acetate (palladium(II) acetate, Pd(OAc) ₂ ), etc. can be used. Preferably, the palladium catalyst is tetrakis(triphenylphosphine)palladium (0) (tetrakis(triphenylphosphine)palladium (0), Pd(PPh ₃ ) ₄ ), bis(tri-(tert-butyl)phosphine) Palladium (0) (bis(tri-(tert-butyl)phosphine)palladium(0), Pd(P-tBu ₃ ) ₂ ), or bis(dibenzylideneacetone)palladium (0) (bis(dibenzylideneacetone)palladium ( 0), Pd(dba) ₂ ). In particular, in Scheme 1, tetrakis(triphenylphosphine)palladium (0) (tetrakis(triphenylphosphine)palladium (0), Pd(PPh ₃ ) ₄ ) can be used as a catalyst, and in Scheme 2, bis(tri- (tert-butyl)phosphine)palladium (0) (bis(tri-(tert-butyl)phosphine)palladium(0), Pd(P-tBu ₃ ) ₂ ) can be used as a catalyst.

In this specification, equivalent weight (eq.) means molar equivalent.

Meanwhile, the present invention provides an organic light-emitting device containing the compound represented by Formula 1 above. In one example, the present invention includes a first electrode; a second electrode provided opposite to the first electrode; and an organic light-emitting device comprising at least one organic material layer provided between the first electrode and the second electrode, wherein at least one layer of the organic material layer includes a compound represented by Formula 1. do.

The organic material layer of the organic light emitting device of the present invention may have a single-layer structure, or may have a multi-layer 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, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron transport layer, an electron injection layer, etc. as an organic material layer. However, the structure of the organic light emitting device is not limited to this and may include fewer organic layers.

In addition, the organic material layer may include a hole injection layer, a hole transport layer, or a layer that simultaneously performs hole injection and transport, and the hole injection layer, the hole transport layer, or a layer that simultaneously performs hole injection and transport is represented by Formula 1 Contains the indicated compounds.

Additionally, the organic material layer may include an electron blocking layer, and the electron blocking layer includes the compound represented by Chemical Formula 1.

Additionally, the organic layer may include a light-emitting layer, and the light-emitting layer includes the compound represented by Chemical Formula 1.

Additionally, the light emitting layer further includes a dopant compound.

Additionally, the light-emitting layer includes the compound of Formula 1 and a dopant.

For example, the light-emitting layer includes the compound of Formula 1 and a dopant, and includes the compound of Formula 1 and the dopant in an content ratio of 100:1 to 1:1.

Additionally, the light-emitting layer includes the compound of Formula 1 and a dopant, and includes the compound of Formula 1 and the dopant in an content ratio of 100:1 to 2:1.

In addition, the light-emitting layer includes the compound of Formula 1 and a dopant, and includes the compound of Formula 1 and the dopant in an content ratio of 100:1 to 5:1.

For example, the dopant is a metal complex.

Specifically, the dopant is an iridium-based metal complex.

Additionally, the organic material layer includes a light-emitting layer, the light-emitting layer includes a dopant, and the dopant material is selected from the structural formulas below.

.

.

The structure specified above is not limited to the dopant compound.

Additionally, the organic material layer may include a hole blocking layer, and the hole blocking layer includes the compound represented by Chemical Formula 1.

In addition, the organic material layer may include an electron transport layer, an electron injection layer, or a layer that simultaneously performs electron injection and transport, and the electron transport layer, the electron injection layer, or a layer that simultaneously performs electron injection and transport is represented by Formula 1 Contains the indicated compounds.

Additionally, the organic layer includes a light-emitting layer and a hole transport layer, and the light-emitting layer or the hole transport layer may include the compound represented by Formula 1.

Additionally, the organic light emitting device according to the present invention may be a normal type organic light emitting device in which an anode, one or more organic material layers, and a cathode are sequentially stacked on a substrate. Additionally, the organic light emitting device according to the present invention may be an inverted type organic light emitting device in which a cathode, one or more organic 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.

Figure 1 shows an example of an organic light emitting device consisting of a substrate 1, an anode 2, a light emitting layer 3, and a cathode 4. In this structure, the compound represented by Formula 1 may be included in the light-emitting layer.

Figure 2 shows the substrate (1), anode (2), hole injection layer (5), hole transport layer (6), electron blocking layer (6), light emitting layer (3), hole blocking layer (8), electron injection and transport layer ( 9) and a cathode 4. An example of an organic light-emitting device is shown. In this structure, the compound represented by Formula 1 may be included in one or more of the hole injection layer, hole transport layer, electron blocking layer, light emitting layer, hole blocking layer, and electron injection and transport layer. Specifically, the compound represented by Formula 1 may be included in the light-emitting layer or the hole transport layer, for example, as a host material of the light-emitting layer.

The organic light emitting device according to the present invention can be manufactured using materials and methods known in the art, except that at least one of the organic layers includes the compound represented by Formula 1 above. Additionally, 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 can be manufactured by sequentially stacking a first electrode, an organic material layer, and a second electrode on a substrate. At this time, an anode is formed by depositing a metal or a conductive metal oxide or an alloy thereof on the substrate using a PVD (physical vapor deposition) method such as sputtering or e-beam evaporation. Then, an organic material layer including a hole injection layer, a hole transport layer, an electron blocking layer, a light-emitting layer, a hole blocking layer, an electron transport layer, and an electron injection layer is formed thereon, and then a material that can be used as a cathode is deposited thereon. can do. In addition to this method, an organic light-emitting device can be made by sequentially depositing a cathode material, an organic material layer, and an anode material on a substrate.

In addition, the compound represented by Formula 1 may be formed as an organic layer by a solution coating method as well as a vacuum deposition method when manufacturing an organic light-emitting device. In particular, the compound represented by Formula 1 has excellent solubility in the solvent used in the solution application method, making it easy to apply the solution application method. Here, the solution application method refers to spin coating, dip coating, doctor blading, inkjet printing, screen printing, spraying, roll coating, etc., but is not limited to these.

Accordingly, the present invention provides a coating composition comprising the compound represented by Formula 1 and a solvent.

The solvent is not particularly limited as long as it is capable of dissolving or dispersing the compound according to the present invention, and examples include chloroform, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, chlorobenzene, o -Chlorine-based solvents such as dichlorobenzene; Ether-based solvents such as tetrahydrofuran and dioxane; Aromatic hydrocarbon solvents such as toluene, xylene, trimethylbenzene, and mesitylene; Aliphatic hydrocarbon solvents such as cyclohexane, methylcyclohexane, n-pentane, n-hexane, n-heptane, n-octane, n-nonane, and n-decane; Ketone-based solvents such as acetone, methyl ethyl ketone, and cyclohexanone; Ester solvents such as ethyl acetate, butyl acetate, and ethyl cellosolve acetate; Polyhydric acids such as ethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, dimethoxyethane, propylene glycol, diethoxymethane, triethylene glycol monoethyl ether, glycerin, 1,2-hexanediol, etc. alcohol and its derivatives; Alcohol-based solvents such as methanol, ethanol, propanol, isopropanol, and cyclohexanol; Sulfoxide-based solvents such as dimethyl sulfoxide; and amide-based solvents such as N-methyl-2-pyrrolidone and N,N-dimethylformamide; Benzoate-based solvents such as butyl benzoate and methyl-2-methoxybenzoate; tetralin; Solvents such as 3-phenoxy-toluene may be mentioned. In addition, the above-mentioned solvents may be used individually or two or more types of solvents may be mixed.

Additionally, the viscosity of the coating composition is preferably 1 cP to 10 cP, and coating is easy within this range. In addition, the concentration of the compound according to the present invention in the coating composition is preferably 0.1 wt/v% to 20 wt/v%.

Additionally, the present invention provides a method of forming a functional layer using the above-described coating composition. Specifically, coating the coating composition according to the present invention described above by a solution process; and heat treating the coated coating composition.

In the heat treatment step, the heat treatment temperature is preferably 150°C to 230°C. Additionally, the heat treatment time is 1 minute to 3 hours, and more preferably 10 minutes to 1 hour. Additionally, the heat treatment is preferably performed in an inert gas atmosphere such as argon or nitrogen.

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

The anode material is generally preferably a material with a large work function to facilitate hole injection into the organic layer. Specific examples of the anode 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), and indium zinc oxide (IZO); Combinations of metals and oxides 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 are included, but are not limited to these.

The cathode material is generally preferably a material with a small work function to facilitate electron injection into the organic 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; There are, but are not limited to, multi-layered materials such as LiF/Al or LiO ₂ /Al.

The hole injection layer is a layer that injects holes from an electrode. The hole injection material has the ability to transport holes, has an excellent hole injection effect at the anode, a light-emitting layer or a light-emitting material, and has an excellent hole injection effect on the light-emitting layer or light-emitting material. A compound that prevents movement of excitons to the electron injection layer or electron injection material and has excellent thin film forming ability is preferred. It is preferable that the highest occupied molecular orbital (HOMO) of the hole injection material is between the work function of the anode material and the HOMO of the surrounding organic material layer. Specific examples of hole injection materials include metal porphyrin, oligothiophene, arylamine-based organic substances, hexanitrilehexaazatriphenylene-based organic substances, quinacridone-based organic substances, and perylene-based organic substances. organic substances, anthraquinone, polyaniline, and polythiophene series conductive polymers, etc., but are not limited to these.

The hole transport layer is a layer that receives holes from the hole injection layer and transports holes to the light-emitting layer. It is a hole transport material that can receive holes from the anode or hole injection layer and transfer them to the light-emitting layer, and is a material with high mobility for holes. This is suitable. Specific examples include arylamine-based organic materials, conductive polymers, and block copolymers with both conjugated and non-conjugated portions, but are not limited to these.

The light-emitting material is a material capable of emitting light in the visible range by receiving and combining holes and electrons from the hole transport layer and the electron transport layer, respectively, and is preferably a material with good quantum efficiency for fluorescence or phosphorescence. Specific examples include 8-hydroxy-quinoline aluminum complex (Alq ₃ ); Carbazole-based compounds; dimerized styryl compounds; BAlq; 10-hydroxybenzoquinoline-metal compound; Compounds of the benzoxazole, benzthiazole and benzimidazole series; Poly(p-phenylenevinylene) (PPV) series polymer; Spiro compounds; Polyfluorene, rubrene, etc., but are not limited to these.

The light emitting layer may include a host material and a dopant material. Host materials include condensed aromatic ring derivatives or heterocyclic ring-containing compounds. Specifically, condensed aromatic ring derivatives include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, and fluoranthene compounds, and heterocycle-containing compounds include carbazole derivatives, dibenzofuran derivatives, and ladder-type compounds. These include, but are not limited to, furan compounds and pyrimidine derivatives. Preferably, a compound according to the present invention is used as the host material.

Dopant materials include aromatic amine derivatives, strylamine compounds, boron complexes, fluoranthene compounds, and metal complexes. Specifically, aromatic amine derivatives include condensed aromatic ring derivatives having a substituted or unsubstituted arylamino group, such as pyrene, anthracene, chrysene, and periplanthene, and styrylamine compounds include substituted or unsubstituted arylamino groups. It is a compound in which at least one arylvinyl group is substituted on the arylamine, and is substituted or unsubstituted with one or two or more substituents selected from the group consisting of aryl group, silyl group, alkyl group, cycloalkyl group, and arylamino group. Specifically, styrylamine, styryldiamine, styryltriamine, styryltetraamine, etc. are included, but are not limited thereto. Additionally, metal complexes include, but are not limited to, iridium complexes and platinum complexes. Preferably, an iridium-based metal complex is used as the dopant material.

The light-emitting layer may be a red light-emitting layer, and when the compound according to the present invention is used as a host material, the stability of electrons and holes increases, energy is transferred from the host to the red dopant well, and the driving voltage of the organic light-emitting device, Luminous efficiency and lifespan characteristics can be improved.

The electron transport layer is a layer that receives electrons from the electron injection layer and transports electrons to the light-emitting layer. The electron transport material is a material that can easily inject electrons from the cathode and transfer them to the light-emitting layer, and a material with high electron mobility is suitable. do. Specific examples include Al complex of 8-hydroxyquinoline; Complex containing Alq ₃ ; organic radical compounds; Hydroxyflavone-metal complexes, etc., but are not limited to these. 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 with a low work function followed by an aluminum or silver layer. Specifically, cesium, barium, calcium, ytterbium and samarium, in each case followed by an aluminum layer or a silver layer.

The electron injection layer is a layer that injects electrons from the electrode, has the ability to transport electrons, has an excellent electron injection effect from the cathode, a light-emitting layer or a light-emitting material, and hole injection of excitons generated in the light-emitting layer. A compound that prevents movement to the layer and has excellent thin film forming ability is preferred. Specifically, fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, preorenylidene methane, anthrone, etc. and their derivatives, metals. Complex compounds and nitrogen-containing five-membered ring derivatives are included, but are not limited thereto.

Examples of the metal complex compounds 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-naphtolato) aluminum, bis(2-methyl-8-quinolinato)(2-naphtolato) gallium, etc. It is not limited to this.

The organic light-emitting device according to the present invention may be a bottom-emitting device, a top-emitting device, or a double-sided light-emitting device. In particular, it may be a bottom-emitting device that requires relatively high luminous efficiency.

Additionally, the compound according to the present invention may be included in an organic solar cell or an organic transistor in addition to an organic light-emitting device.

The preparation of the compound represented by Formula 1 and an organic light-emitting device containing the same will be described in detail in the following Examples. However, the following examples are for illustrating the present invention, and the scope of the present invention is not limited thereto.

Synthesis Example A. Synthesis of intermediate compound a

1) Preparation of compound a-3

300 g (1.0 eq) of 2-bromo-1-chlorodibenzo[b,d]furan, 297.7 g (1.1 eq) of bis(pinacolato)diboron, [1,1′-bis(diphenylphosphino)ferrocene]dichloropalladium(II), [ Pd(dppf)Cl ₂ ] 15.6 g (0.02 eq) and 313.7 g (3.00 eq) of potassium acetate (KOAc) were added to 6000 mL of 1,4-dioxnae, refluxed, and stirred. When the reaction was completed after 3 hours, the pressure was reduced and the solvent was removed. The filtered solid was completely dissolved in CHCl ₃ and washed with water, and the solution containing the product was concentrated under reduced pressure to remove about 90% of the solvent. Ethanol was added again under reflux to drop crystals, cooled, and filtered to obtain 273.1 g of compound a-3 (yield 78%). [M+H] ⁺ =330.

2) Preparation of compound a-2

273.1 g (1.0 eq.) of compound a-3 and 347.4 g (1.1 eq.) of 1,8-diiodonaphthalene were added to 5462 mL of tetrahydrofuran (THF), stirred and refluxed. Afterwards, 344.6 g (3.0 eq.) of potassium carbonate (K ₂ CO ₃ ) was dissolved in 1034 mL of water, stirred sufficiently, and tetrakis(triphenylphosphine)palladium(0) [Pd(PPh ₃ ) ₄ ] 19.2 g (0.02 eq.) .) was input. After 5 hours of reaction, the reaction mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. Afterwards, it was completely dissolved in ethyl acetate, washed with water, and the pressure was reduced again to remove about 80% of the solvent. Hexane was added again under reflux, and the crystals were dropped, cooled, and then filtered. This was purified by silica gel column chromatography to obtain 238.1 g of compound a-2 (yield 63%). [M+H] ⁺ =456.

3) Preparation of compound a-1

Compound a-2 238.1 g (1.0 eq), bis(tri-tert-butylphosphine)palladium(0) [Pd(P-tBu ₃ ) ₂ ] 2.7 g (0.01 eq), potassium carbonate (K ₂ CO ₃ ) 144.7 g (2.00 eq) was added to 2.5 L of N,N-Dimethylacetamide (DMAC), refluxed, and stirred. After 3 hours, the reaction product was poured into water, crystals were dropped and filtered. The filtered solid was completely dissolved in 1,2-dichlorobenzene, washed with water, and the solution containing the product was concentrated under reduced pressure, the crystals were dropped, cooled, and then filtered. This was purified by silica gel column chromatography to obtain 78.7 g of compound a-1 (yield 46%). [M+H] ⁺ =328.

4) Preparation of compound a

78.7 g (1.0 eq.) of compound a-1 and 67.3 g (1.1 eq.) of bis(pinacolato)diboron were refluxed in 1,4-dioxane 1574 mL and stirred. Afterwards, 70.9 g (3.0 eq.) of potassium acetate (KOAc) was added and stirred sufficiently, followed by bis(dibenzylideneacetone)palladium (0) [Pd(dba) ₂ ] 4.2 g (0.03 eq.) and tricyclohexylphosphine ( 4.1 g (0.06 eq.) of PCy ₃ ) was added. After reacting for 3 hours, it was distilled under reduced pressure, dissolved in chloroform again, and washed twice with water. Afterwards, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 80.6 g of compound a (yield 80%). [M+H] ⁺ = 419.

Synthesis Example B. Synthesis of intermediate compound b

1) Preparation of compound b-5

Add 400.0 g (1.0 eq.) of 4-bromo-1-fluoro-2-iodobenzene and 229.1 g (1.0 eq.) of (2-chloro-6-hydroxyphenyl)boronic acid to 8000 mL of tetrahydrofuran (THF) and stir. It refluxed. Afterwards, 551.2 g (3.0 eq.) of potassium carbonate (K ₂ CO ₃ ) was dissolved in 1654 mL of water, stirred sufficiently, and tetrakis(triphenylphosphine)palladium(0) [Pd(PPh ₃ ) ₄ ] 30.7 g (0.02 eq.) .) was input. After 5 hours of reaction, the reaction mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. Afterwards, it was completely dissolved in ethyl acetate, washed with water, and the pressure was reduced again to remove about 80% of the solvent. Hexane was added again under reflux, and the crystals were dropped, cooled, and then filtered. This was purified by silica gel column chromatography to obtain 240.5 g of compound b-5 (yield 60%). [M+H] ⁺ =303.

2) Preparation of compound b-4

240.5 g (1.0 eq.) of compound b-5 and 330.7 g (3.0 eq.) of potassium carbonate (K ₂ CO ₃ ) were added to 2405 mL of N,N-Dimethylacetamide (DMAC), refluxed, and stirred. After 4 hours, the reaction product was poured into water, crystals were dropped and filtered. The filtered solid was completely dissolved in chloroform, washed with water, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 206.6 g of compound b-4 (yield 92%). [M+H] ⁺ = 283.

3) Preparation of compound b-3

Compound b-3 was synthesized in the same manner as the method for preparing compound a-3 described above, except that compound b-4 was used instead of 2-bromo-1-chlorodibenzo[b,d]furan.

4) Preparation of compound b-2

Compound b-2 was synthesized in the same manner as the method for preparing compound a-2 described above, except that compound b-3 was used instead of compound a-3.

5) Preparation of compound b-1

Compound b-1 was synthesized in the same manner as the method for preparing compound a-1 described above, except that compound b-2 was used instead of compound a-2.

6) Preparation of compound b

Compound b was synthesized in the same manner as the method for preparing compound a described above, except that compound b-1 was used instead of compound a-1.

Synthesis Example C. Synthesis of intermediate compound c

1) Preparation of compound c-1

The following compounds were produced in the same manner as the method for preparing compound a-1 described above, except that 2-bromo-1-chlorodibenzo[b,d]thiophene was used instead of 2-bromo-1-chlorodibenzo[b,d]furan. c-1 was synthesized.

2) Preparation of compound c

The following formula c was synthesized in the same manner as the method for preparing compound a described above, except that compound c-1 was used instead of compound a-1.

Synthesis Example D. Synthesis of intermediate compound d

1) Preparation of compound d-6

(4-bromo-2-iodophenyl)(methyl)sulfane 300.0 g (1.0 eq.) and (2-chlorophenyl)boronic acid 142.6 g (1.0 eq.) were added to 6000 mL of tetrahydrofuran (THF) and stirred and refluxed. . Afterwards, 378.1 g (3.0 eq.) of potassium carbonate (K ₂ CO ₃ ) was dissolved in 1134 mL of water, stirred sufficiently, and tetrakis(triphenylphosphine)palladium(0) [Pd(PPh ₃ ) ₄ ] 21.1 g (0.02 eq.) .) was input. After 2 hours of reaction, the reaction mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. Afterwards, it was completely dissolved in ethyl acetate, washed with water, and the pressure was reduced again to remove about 80% of the solvent. Hexane was added again under reflux, and the crystals were dropped, cooled, and then filtered. This was purified by silica gel column chromatography to obtain 214.5 g of compound d-6 (yield 75%). [M+H] ⁺ =315.

2) Preparation of compound d-5

To 214.5 g (1.0 eq) of compound d-6, 46.5 g (2.00 eq) of H ₂ O ₂ was added to 1 L of acetic acid (AcOH), refluxed, and stirred. After 1 hour, the reaction product was poured into water, crystals were dropped and filtered. The filtered solid was completely dissolved in ethyl acetate, washed with water, and the pressure was reduced again to remove about 80% of the solvent. Hexane was added again under reflux, and the crystals were dropped, cooled, and then filtered. This was purified by silica gel column chromatography to obtain 81.2 g of compound d-5 (yield 36%). [M+H] ⁺ =331.

3) Preparation of compound d-4

81.2 g (1.0 eq) of compound d-5 and 450 mL of H ₂ SO ₄ were added, refluxed, and stirred to dissolve. When the reaction was completed after 2 hours, the reactant was poured into water, crystals were dropped, and the mixture was filtered. The filtered solid was completely dissolved in CHCl ₃ and washed with water, and the solution containing the product was concentrated under reduced pressure to remove about 80% of the solvent. Hexane was added again under reflux, the crystals were dropped, cooled, and filtered to obtain 27.9 g of compound d-4 (yield 38%). [M+H] ⁺ =299.

4) Preparation of compound d-3

Compound d-3 was synthesized in the same manner as the preparation method of compound a-3 described above, except that compound d-4 was used instead of 2-bromo-1-chlorodibenzo[b,d]furan.

5) Preparation of compound d-2

Compound d-2 was synthesized in the same manner as the method for preparing compound a-2 described above, except that compound d-3 was used instead of compound a-3.

6) Preparation of compound d-1

Compound d-1 was synthesized in the same manner as the method for preparing compound a-1 described above, except that compound d-2 was used instead of compound a-2.

7) Preparation of compound d

Compound d was synthesized in the same manner as the preparation method of Chemical Formula a described above, except that Compound d-1 was used instead of Compound a-1.

Synthesis Example 1. Synthesis of Compound 1

Compound sub 1 (15 g, 38.1 mmol) and compound a (17.5 g, 41.9 mmol) were added to 300 mL of THF, stirred and refluxed. Afterwards, potassium carbonate (15.8 g, 114.3 mmol) was dissolved in 47 mL of water, stirred sufficiently, and then tetrakis(triphenylphosphine)palladium(0) (0.9 g, 0.8 mmol) was added. After reacting for 11 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 17.3 g of Compound 1. (Yield 70%, MS: [M+H] ⁺ = 651).

Synthesis Example 2. Synthesis of Compound 2

Compound sub 2 (15 g, 40.1 mmol) and compound a (18.5 g, 44.1 mmol) were added to 300 mL of THF, stirred and refluxed. Afterwards, potassium carbonate (16.6 g, 120.4 mmol) was dissolved in 50 mL of water, stirred sufficiently, and then tetrakis(triphenylphosphine)palladium(0) (0.9 g, 0.8 mmol) was added. After reacting for 12 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 15.2 g of Compound 2. (Yield 60%, MS: [M+H] ⁺ = 631).

Synthesis Example 3. Synthesis of Compound 3

Compound sub 3 (15 g, 42 mmol) and compound a (19.3 g, 46.2 mmol) were added to 300 mL of THF, stirred and refluxed. Afterwards, potassium carbonate (17.4 g, 126.1 mmol) was dissolved in 52 mL of water, stirred sufficiently, and then tetrakis(triphenylphosphine)palladium(0) (1 g, 0.8 mmol) was added. After reacting for 11 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 20.6 g of Compound 3. (80% yield, MS: [M+H] ⁺ = 614).

Synthesis Example 4. Synthesis of Compound 4

Compound sub 4 (15 g, 38.1 mmol) and compound a (17.5 g, 41.9 mmol) were added to 300 mL of THF, stirred, and refluxed. Afterwards, potassium carbonate (15.8 g, 114.3 mmol) was dissolved in 47 mL of water, stirred sufficiently, and then tetrakis(triphenylphosphine)palladium(0) (0.9 g, 0.8 mmol) was added. After reaction for 8 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 17.1 g of Compound 4. (Yield 69%, MS: [M+H] ⁺ = 651)

Synthesis Example 5. Synthesis of Compound 5

Compound sub 5 (15 g, 40.8 mmol) and compound a (18.8 g, 44.9 mmol) were added to 300 mL of THF, stirred and refluxed. Afterwards, potassium carbonate (16.9 g, 122.3 mmol) was dissolved in 51 mL of water, stirred sufficiently, and then tetrakis(triphenylphosphine)palladium(0) (0.9 g, 0.8 mmol) was added. After reacting for 11 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 20.3 g of Compound 5. (Yield 80%, MS: [M+H] ⁺ = 625)

Synthesis Example 6. Synthesis of Compound 6

Compound sub 6 (15 g, 30.9 mmol) and compound a-1 (10.1 g, 30.9 mmol) were added to 300 mL of THF, stirred and refluxed. Afterwards, potassium carbonate (12.8 g, 92.7 mmol) was dissolved in 38 mL of water, stirred sufficiently, and bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After reacting for 10 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.9 g of Compound 6. (Yield 69%, MS: [M+H] ⁺ = 651).

Synthesis Example 7. Synthesis of Compound 7

Compound sub 7 (15 g, 47.2 mmol) and compound b (21.7 g, 51.9 mmol) were added to 300 mL of THF, stirred, and refluxed. Afterwards, potassium carbonate (19.6 g, 141.6 mmol) was dissolved in 59 mL of water, stirred sufficiently, and then tetrakis(triphenylphosphine)palladium(0) (1.1 g, 0.9 mmol) was added. After reaction for 8 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 21.7 g of Compound 7. (80% yield, MS: [M+H] ⁺ = 575).

Synthesis Example 8. Synthesis of Compound 8

Compound sub 8 (15 g, 41.9 mmol) and compound b (19.3 g, 46.1 mmol) were added to 300 mL of THF, stirred and refluxed. Afterwards, potassium carbonate (17.4 g, 125.8 mmol) was dissolved in 52 mL of water, stirred sufficiently, and then tetrakis(triphenylphosphine)palladium(0) (1 g, 0.8 mmol) was added. After reaction for 9 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 18.5 g of Compound 8. (Yield 72%, MS: [M+H] ⁺ = 615).

Synthesis Example 9. Synthesis of Compound 9

Compound sub 9 (15 g, 38.1 mmol) and compound b (17.5 g, 41.9 mmol) were added to 300 mL of THF, stirred and refluxed. Afterwards, potassium carbonate (15.8 g, 114.3 mmol) was dissolved in 47 mL of water, stirred sufficiently, and then tetrakis(triphenylphosphine)palladium(0) (0.9 g, 0.8 mmol) was added. After reacting for 12 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 16.6 g of Compound 9. (Yield 67%, MS: [M+H] ⁺ = 651).

Synthesis Example 10. Synthesis of Compound 10

Compound sub 10 (15 g, 34.6 mmol) and compound b (15.9 g, 38.1 mmol) were added to 300 mL of THF, stirred and refluxed. Afterwards, potassium carbonate (14.4 g, 103.9 mmol) was dissolved in 43 mL of water, stirred sufficiently, and then tetrakis(triphenylphosphine)palladium(0) (0.8 g, 0.7 mmol) was added. After reacting for 10 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 16 g of compound 10. (Yield 67%, MS: [M+H] ⁺ = 690).

Synthesis Example 11. Synthesis of Compound 11

Compound sub 11 (15 g, 26.1 mmol) and b-1 (8.5 g, 26.1 mmol) were added to 300 mL of THF, stirred and refluxed. Afterwards, potassium carbonate (10.8 g, 78.2 mmol) was dissolved in 32 mL of water, stirred sufficiently, and bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After reaction for 8 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.1 g of compound 11. (Yield 73%, MS: [M+H] ⁺ = 741).

Synthesis Example 12. Synthesis of Compound 12

Compound sub 12 (15 g, 34.5 mmol) and compound b-1 (11.3 g, 34.5 mmol) were added to 300 mL of THF, stirred, and refluxed. Afterwards, potassium carbonate (14.3 g, 103.4 mmol) was dissolved in 43 mL of water, stirred sufficiently, and bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After reacting for 11 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.8 g of compound 12. (Yield 62%, MS: [M+H] ⁺ = 601).

Synthesis Example 13. Synthesis of Compound 13

Compound sub 13 (15 g, 56 mmol) and compound c (26.8 g, 61.6 mmol) were added to 300 mL of THF, stirred, and refluxed. Afterwards, potassium carbonate (23.2 g, 168.1 mmol) was dissolved in 70 mL of water, stirred sufficiently, and then tetrakis(triphenylphosphine)palladium(0) (1.3 g, 1.1 mmol) was added. After reacting for 12 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 23 g of Compound 13. (Yield 76%, MS: [M+H] ⁺ = 541).

Synthesis Example 14. Synthesis of Compound 14

Compound sub 14 (15 g, 35.9 mmol) and compound c (17.1 g, 39.5 mmol) were added to 300 mL of THF, stirred, and refluxed. Afterwards, potassium carbonate (14.9 g, 107.7 mmol) was dissolved in 45 mL of water, stirred sufficiently, and then tetrakis(triphenylphosphine)palladium(0) (0.8 g, 0.7 mmol) was added. After reaction for 8 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 18.3 g of compound 14. (Yield 74%, MS: [M+H] ⁺ = 691).

Synthesis Example 15. Synthesis of Compound 15

Compound sub 15 (15 g, 35.7 mmol) and compound c (17.1 g, 39.3 mmol) were added to 300 mL of THF, stirred and refluxed. Afterwards, potassium carbonate (14.8 g, 107.2 mmol) was dissolved in 44 mL of water, stirred sufficiently, and then tetrakis(triphenylphosphine)palladium(0) (0.8 g, 0.7 mmol) was added. After reaction for 9 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 18.8 g of compound 15. (Yield 76%, MS: [M+H] ⁺ = 693).

Synthesis Example 16. Synthesis of Compound 16

Compound sub 16 (15 g, 40.1 mmol) and compound c (19.2 g, 44.1 mmol) were added to 300 mL of THF, stirred and refluxed. Afterwards, potassium carbonate (16.6 g, 120.4 mmol) was dissolved in 50 mL of water, stirred sufficiently, and then tetrakis(triphenylphosphine)palladium(0) (0.9 g, 0.8 mmol) was added. After reaction for 8 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 16.3 g of compound 16. (Yield 63%, MS: [M+H] ⁺ = 647).

Synthesis Example 17. Synthesis of Compound 17

Compound sub 17 (15 g, 30.9 mmol) and compound c-1 (10.6 g, 30.9 mmol) were added to 300 mL of THF, stirred and refluxed. Afterwards, potassium carbonate (12.8 g, 92.7 mmol) was dissolved in 38 mL of water, stirred sufficiently, and bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After reacting for 12 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.3 g of compound 17. (Yield 60%, MS: [M+H] ⁺ = 667).

Synthesis Example 18. Synthesis of Compound 18

Compound sub 18 (15 g, 43.6 mmol) and compound d (20.8 g, 48 mmol) were added to 300 mL of THF, stirred, and refluxed. Afterwards, potassium carbonate (18.1 g, 130.9 mmol) was dissolved in 54 mL of water, stirred sufficiently, and then tetrakis(triphenylphosphine)palladium(0) (1 g, 0.9 mmol) was added. After reaction for 8 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 18.3 g of compound 18. (Yield 68%, MS: [M+H] ⁺ = 617).

Synthesis Example 19. Synthesis of Compound 19

Compound sub 19 (15 g, 41.9 mmol) and compound d (20 g, 46.1 mmol) were added to 300 mL of THF, stirred and refluxed. Afterwards, potassium carbonate (17.4 g, 125.8 mmol) was dissolved in 52 mL of water, stirred sufficiently, and then tetrakis(triphenylphosphine)palladium(0) (1 g, 0.8 mmol) was added. After reacting for 11 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 16.9 g of compound 19. (Yield 64%, MS: [M+H] ⁺ = 631).

Synthesis Example 20. Synthesis of Compound 20

Compound sub 20 (15 g, 35.7 mmol) and compound d (17.1 g, 39.3 mmol) were added to 300 mL of THF, stirred, and refluxed. Afterwards, potassium carbonate (14.8 g, 107.2 mmol) was dissolved in 44 mL of water, stirred sufficiently, and then tetrakis(triphenylphosphine)palladium(0) (0.8 g, 0.7 mmol) was added. After reacting for 11 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 18.8 g of compound 20. (Yield 76%, MS: [M+H] ⁺ = 693).

Synthesis Example 21. Synthesis of Compound 21

Compound sub 21 (15 g, 28 mmol) and compound d-1 (9.6 g, 28 mmol) were added to 300 mL of THF, stirred, and refluxed. Afterwards, potassium carbonate (11.6 g, 84 mmol) was dissolved in 35 mL of water, stirred sufficiently, and bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After reacting for 11 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 15.6 g of compound 21. (Yield 78%, MS: [M+H] ⁺ = 717).

Synthesis Example 22. Synthesis of Compound 22

Compound sub 22 (15 g, 34.6 mmol) and compound d (16.6 g, 38.1 mmol) were added to 300 mL of THF, stirred, and refluxed. Afterwards, potassium carbonate (14.4 g, 103.9 mmol) was dissolved in 43 mL of water, stirred sufficiently, and then tetrakis(triphenylphosphine)palladium(0) (0.8 g, 0.7 mmol) was added. After reacting for 11 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.9 g of Compound 22. (Yield 61%, MS: [M+H] ⁺ = 706).

Example 1

A glass substrate coated with a thin film of indium tin oxide (ITO) with a thickness of 1,000 Å was placed in distilled water with a detergent dissolved in it and washed ultrasonically. At this time, a detergent manufactured by Fischer Co. was used, and distilled water filtered secondarily using a filter manufactured by Millipore Co. was used as distilled water. After washing the ITO for 30 minutes, ultrasonic washing was repeated twice with distilled water for 10 minutes. After washing with distilled water, it was ultrasonic washed with solvents of isopropyl alcohol, acetone, and methanol, dried, and then transported to a plasma cleaner. Additionally, the substrate was cleaned for 5 minutes using oxygen plasma and then transported to a vacuum evaporator.

As a hole injection layer on the ITO transparent electrode prepared in this way, the following compound HI-1 was thermally vacuum deposited to a thickness of 1150 Å to form a hole injection layer, and the following compound A-1 was p-doped at a concentration of 1.5%. The following compound HT-1 was vacuum deposited on the hole injection layer to form a hole transport layer with a film thickness of 800 Å. Next, the following compound EB-1 was vacuum deposited on the hole transport layer to a film thickness of 150 Å to form an electron blocking layer. Next, Compound 1 below and Compound Dp-7 below were vacuum deposited on the EB-1 deposition film at a weight ratio of 98:2 to form a red light-emitting layer with a thickness of 400 Å. The following compound HB-1 was vacuum deposited on the light-emitting layer to a thickness of 30 Å to form a hole-blocking layer. Next, the following compound ET-1 and the following compound LiQ were vacuum deposited on the hole blocking layer at a weight ratio of 2:1 to form an electron injection and transport layer with a thickness of 300 Å. A cathode was formed by sequentially depositing lithium fluoride (LiF) to a thickness of 12 Å and aluminum to a thickness of 1,000 Å on the electron injection and transport layer.

.

.

In the above process, the deposition rate of organic materials was maintained at 0.4 Å/sec to 0.7 Å/sec, the deposition rate of lithium fluoride of the cathode was maintained at 0.3 Å/sec, and aluminum was maintained at 2 Å/sec, and the vacuum level during deposition was An organic light emitting device was manufactured by maintaining 2x10 ^-7 to 5x10 ^-6 torr.

Examples 2 to 22

An organic light emitting device was manufactured in the same manner as in Example 1, except that compounds 2 to 22 listed in Table 1 below were used instead of compound 1 in the organic light emitting device of Example 1.

.

.

Comparative Examples 1 to 8

An organic light-emitting device was manufactured in the same manner as Example 1, except that the compounds listed in Table 1 below were used instead of Compound 1 in the organic light-emitting device of Example 1. The compounds of C-1, C-2, C-3, C-4, C-5, C-6, C-7, and C-8 used in Table 1 below are as follows.

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.

When current was applied to the organic light emitting device manufactured in the above Examples and Comparative Examples, the voltage and efficiency were measured (15 mA/cm ² ), and the results are shown in Table 1 below. Lifespan T95 refers to the time it takes for luminance to decrease to 95% from the initial luminance (6000 nits).

division matter Driving voltage (V) Efficiency (cd/A) Life T95(hr) Luminous color Example 1 Compound 1 3.71 18.8 135 Red Example 2 compound 2 3.79 17.3 107 Red Example 3 Compound 3 3.78 17.0 114 Red Example 4 Compound 4 3.73 18.2 122 Red Example 5 Compound 5 3.68 18.7 105 Red Example 6 Compound 6 3.74 18.3 121 Red Example 7 Compound 7 3.68 19.0 134 Red Example 8 Compound 8 3.63 19.6 156 Red Example 9 Compound 9 3.65 19.3 123 Red Example 10 Compound 10 3.72 18.5 118 Red Example 11 Compound 11 3.70 18.2 106 Red Example 12 Compound 12 3.61 19.9 142 Red Example 13 Compound 13 3.82 17.3 125 Red Example 14 Compound 14 3.78 17.8 131 Red Example 15 Compound 15 3.76 18.0 117 Red Example 16 Compound 16 3.85 17.3 105 Red Example 17 Compound 17 3.89 17.0 103 Red Example 18 Compound 18 3.72 18.7 126 Red Example 19 Compound 19 3.80 17.8 101 Red Example 20 Compound 20 3.68 18.5 109 Red Example 21 Compound 21 4.76 17.7 106 Red Example 22 Compound 22 3.71 18.3 122 Red Comparative Example 1 C-1 4.20 14.9 84 Red Comparative Example 2 C-2 4.25 13.6 72 Red Comparative Example 3 C-3 4.01 15.3 79 Red Comparative Example 4 C-4 4.51 8.9 13 Red Comparative Example 5 C-5 4.59 7.8 10 Red Comparative Example 6 C-6 4.06 15.1 62 Red Comparative Example 7 C-7 3.97 16.4 93 Red Comparative Example 8 C-8 4.05 15.3 81 Red

When current was applied to the organic light-emitting devices manufactured in Examples 1 to 22 and Comparative Examples 1 to 8, the results shown in Table 1 were obtained. As described above, the red organic light emitting device of Example 1 used widely used materials and has a structure using compound EB-1 as an electron suppressing layer and compound 1 and compound Dp-7 as a red light emitting layer. Additionally, in Comparative Examples 1 to 8, organic light-emitting devices were manufactured using compounds C-1 to C-8 instead of compound 1.

As shown in Table 1, the compound represented by Formula 1 according to the present invention, that is, N is 2 at a specific position in the parent core structure in which a fluoranthene ring and a two-ring heterocycle containing O or S are condensed. The organic light-emitting devices of Examples 1 to 22 in which a compound having a specific polycyclic structure containing at least two heteroaryl substituents was used in the light-emitting layer were C-1, C-2, C-3, C-4, and C-5. , the driving voltage was significantly lowered compared to the organic light emitting devices of Comparative Examples 1 to 8 manufactured using compounds of C-6, C-7, and C-8, and efficiency was also significantly increased, indicating that the red dot plate in the host It was found that Tro's energy was transferred well. In addition, it was found that the organic light emitting devices of Examples 1 to 22 could significantly improve lifespan characteristics while maintaining high efficiency. This can ultimately be judged to be because the compounds of the examples according to the present invention have higher stability to electrons and holes than the compounds of the comparative examples. In conclusion, it can be confirmed that when the compound of the present invention is used as a host for a red light-emitting layer, the driving voltage, luminous efficiency, and lifespan characteristics of the organic light-emitting device can be improved.

1: Substrate 2: Anode
3: light emitting layer 4: cathode
5: hole injection layer 6: hole transport layer
7: electron blocking layer 8: hole blocking layer
9: Electron injection and transport layer

Claims (11)

Compound represented by Formula 1:
[Formula 1]

In Formula 1,
Y is O or S,
R ₁ is each independently hydrogen; or deuterium,
n1 is an integer from 0 to 6,
n2 is an integer from 0 to 3,
One of R ₂ is of the formula 2 below, and the other is hydrogen or deuterium,
[Formula 2]

In Formula 2,
L is a single bond; unsubstituted phenylene; or unsubstituted naphthylene,
All Xs are N,
Ar ₁ and Ar ₂ are each independently unsubstituted phenyl, naphthyl substituted phenyl, carbazolyl substituted phenyl, unsubstituted naphthyl, phenyl substituted naphthyl, unsubstituted biphenyl, unsubstituted terphenyl, unsubstituted phenanthryl, unsubstituted dibenzofuranyl, unsubstituted dibenzothiophenyl, unsubstituted carbazolyl, or phenyl substituted carbazolyl.
According to paragraph 1,
The compound represented by Formula 1 is represented by the following Formula 1-1 or 1-2,
[Formula 1-1]

[Formula 1-2]

In Formulas 1-1 and 1-2,
Y, R ₁ , n1, n2, L, X, Ar ₁ and Ar ₂ are as defined in clause 1.
delete delete According to paragraph 1,
L is a single bond; or is represented by any one selected from the group consisting of:
compound:

.
delete delete delete According to paragraph 1,
The compound represented by Formula 1 is any one selected from the group consisting of:
compound:

.
first electrode; a second electrode provided opposite to the first electrode; And an organic light-emitting device comprising at least one organic material layer provided between the first electrode and the second electrode, wherein at least one layer of the organic material layer is one of the organic material layers of claims 1, 2, 5, and 9. An organic light-emitting device comprising the compound according to any one of the preceding claims.
According to clause 10,
The organic material layer containing the compound is a light emitting layer,
Organic light emitting device.