KR20230147284A - 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 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 material 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, and may be composed of, for example, a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, and an electron injection layer. 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.

Meanwhile, recently, in order to reduce process costs, organic light-emitting devices have been developed using a solution process, especially an inkjet process, instead of the existing deposition process. In the beginning, attempts were made to develop organic light emitting devices by coating all organic light emitting device layers using a solution process, but there are limitations with the current technology, so only HIL, HTL, and EML were performed using a solution process, and future processes were hybrid processes using the existing deposition process. (hybrid) process is being studied.

Accordingly, the present invention provides a novel organic light-emitting device material that can be used in an organic light-emitting device and at the same time can be used in a solution process.

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,

D stands for deuterium,

L ₁ and L ₂ are each independently a single bond; or unsubstituted or deuterium-substituted phenylene,

L ₃ is unsubstituted or deuterium-substituted phenylene,

a and d are each independently integers from 0 to 7,

b is an integer from 0 to 8,

c is an integer from 0 to 6.

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. .

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, can also be used in a solution process, and can improve efficiency and lifespan characteristics of the organic light-emitting device.

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

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

(Definition of Terms)

In this specification, and means a bond connected to another substituent, and D means deuterium.

In this specification, the term "substituted or unsubstituted" refers to deuterium, halogen group, cyano group, nitro group, hydroxy group, carbonyl group, ester group, imide group, amino group, phosphine oxide group, alkoxy group, aryloxy group, alkyl group. Thioxy group, arylthioxy group, alkylsulfoxy group, arylsulfoxy group, silyl group, boron group, alkyl group, cycloalkyl group, alkenyl group, aryl group, aralkyl group, aralkenyl group, alkylaryl group, alkylamine group, aralkylamine substituted or unsubstituted with one or more substituents selected from the group consisting of a heteroarylamine group, an arylamine group, an arylphosphine group, or a heteroaryl containing one or more of N, O, and S atoms; It means that two or more of the substituents exemplified above are substituted or unsubstituted. 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. For example, the term "substituted or unsubstituted" means "unsubstituted or one or more selected from the group consisting of deuterium, halogen, C _1-10 alkyl, C _1-10 alkoxy, and C _6-20 aryl. , for example, may be understood as “substituted with 1 to 5 substituents.” In addition, the term “substituted with one or more substituents” as used herein will be understood to mean, for example, “substituted with 1 to 5 substituents,” or “substituted with 1 or 2 substituents.” You can.

In this specification, the carbon number of the carbonyl group is not particularly limited, but is preferably 1 to 40 carbon atoms. Specifically, the substituent may have the structure shown below, 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 substituent 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, the substituent may have the structure shown below, 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 fluoro, chloro, bromo, or iodo.

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, 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-ethylbutyl, pentyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, 1-ethyl-propyl, 1,1-dimethylpropyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl, n-heptyl, isohexyl, 1-methylhexyl, 2-methylhexyl, 3-methylhexyl, 4-methylhexyl, 5 -methylhexyl, cyclopentylmethyl, cyclohexylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2,4,4-trimethyl-1-pentyl, 2,4,4- Trimethyl-2-pentyl, 2-propylpentyl, n-nonyl, 2,2-dimethylheptyl, etc., but are not limited thereto.

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 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 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 with aromaticity. 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, a biphenyl group, or a terphenyl group, but is not limited thereto. The polycyclic aryl group may be a naphthyl group, anthracenyl group, phenanthrenyl group, triphenylenyl group, pyrenyl group, perylenyl group, chrysenyl group, etc., but is not limited thereto.

In the present specification, heteroaryl is a heteroaryl containing one or more of O, N, Si, and S as a heteroelement, and the number of carbon atoms is not particularly limited, but is preferably 2 to 60 carbon atoms. Examples of heteroaryl 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, 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, thiadiazolyl group group, phenothiazinyl group, and dibenzofuranyl group, but are not limited thereto.

In this specification, the aryl group among the aralkyl group, aralkenyl group, alkylaryl group, arylamine group, and arylsilyl 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 heteroaryl 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 heteroaryl 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 heteroaryl described above can be applied, except that the heterocycle is not monovalent and is formed by combining two substituents.

As used herein, the term “deuterated or substituted with deuterium” means that at least one available hydrogen in each chemical formula is replaced with deuterium. Specifically, substitution with deuterium in each chemical formula or definition of a substituent means that at least one of the positions in the molecule where hydrogen can be bonded is substituted with deuterium.

Additionally, as used herein, the term “deuterium substitution rate” refers to the percentage of the number of substituted deuteriums compared to the total number of hydrogens that may exist in each chemical formula.

(compound)

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

The compound represented by Formula 1 is a compound having a structure in which the 9th position of anthracene is substituted with a 1-naphthyl group and the 10th position is substituted with a (naphthylene)-(phenylene)-(naphthyl) substituent, The naphthylene linker is characterized as “2,8-naphthylene”. In other words, the compound represented by Formula 1 has a structure in which five moieties (1-naphthyl)-(anthracene)-(2,8-naphthylene)-(phenylene)-(naphthyl) are connected. Essentially, but optionally, further comprising a phenylene linker between (1-naphthyl)-(anthracene) and/or between (anthracene)-(2,8-naphthylene).

On the other hand, compounds consisting of one anthracene moiety and three or fewer moieties selected from phenylene and naphthalene in the molecule, that is, compounds having a structure with four or fewer moieties connected, have a low molecular weight and do not consider the conformation of the molecule. Even so, it can exhibit excellent solubility in the solvent used in the solution process. However, compounds with at least 5 moieties, for example, (naphthyl)-(anthracene)-(naphthylene)-(phenylene)-(naphthyl), have 5 moieties in the molecule in liner form. In the case of having only, the problem of not dissolving in the solvent used in the solution process occurs due to the increased molecular weight. Therefore, a compound with at least 5 moieties must have a structure that can induce a twist form within the molecule, considering the conformation of the molecule in terms of improving solubility.

Accordingly, from a molecular orbital perspective, the present inventors used a "naphthylene" linker for compounds having at least 5 moieties, such as (naphthyl)-(anthracene)-(naphthylene)-(phenylene)-(naphthyl). The present invention was completed by confirming that the twist form within the molecule can be effectively induced when the two sigma bonding orbitals are at an angle of 60 degrees.

In addition, in order for a compound with at least 5 moieties to exhibit not only solubility in solvents but also structural stability, an anthracene moiety is bound to the 2nd position of the “naphthylene” linker, and a phenylene moiety is bound to the 8th position. It must have a cohesive structure. The reason is that in the case of compound Because it may not be possible.

Therefore, the "naphthylene" linker has a structure in which an anthracene moiety is bonded to the 2-position and a phenylene moiety is bonded to the 8-position, that is, (naphthyl)-(anthracene) and (phenylene) The compound represented by Chemical Formula 1, which contains a "2,8-naphthylene" linker between -(naphthyl) substituents, effectively induces a twist form within the molecule and, unlike compounds that only show a liner form, is used in the solution process. Not only does it exhibit high solubility in solvents, but it also has excellent structural stability, which can improve the efficiency and lifespan characteristics of organic light-emitting devices.

Furthermore, when the compound represented by Formula 1 contains at least one deuterium in the molecule, the bond energy of the C-D bond is greater than the bond energy of the C-H bond, so compared to the compound not substituted with deuterium, the molecule It has stronger binding energy, which can increase material stability. Therefore, the compound represented by Formula 1 containing at least one deuterium can further improve the efficiency and stability of the organic light-emitting device.

In one embodiment, both L ₁ and L ₂ can be a single bond.

In other embodiments, L ₁ is a single bond and L ₂ is 1,2-phenylene, unsubstituted or substituted with 1 to 4 deuteriums; 1,3-phenylene unsubstituted or substituted with 1 to 4 deuteriums; or 1,4-phenylene, which is unsubstituted or substituted with 1 to 4 deuterium atoms; or

L ₁ is 1,2-phenylene that is unsubstituted or substituted with 1 to 4 deuterium atoms; 1,3-phenylene unsubstituted or substituted with 1 to 4 deuteriums; or 1,4-phenylene that is unsubstituted or substituted with 1 to 4 deuteriums, and L ₂ may be a single bond.

In another embodiment, L ₁ and L ₂ are each independently 1,2-phenylene, unsubstituted or substituted with 1 to 4 deuteriums; 1,3-phenylene unsubstituted or substituted with 1 to 4 deuteriums; Alternatively, it may be unsubstituted or 1,4-phenylene substituted with 1 to 4 deuteriums.

Additionally, L ₁ and L ₂ may be the same as each other.

Alternatively, L ₁ and L ₂ may be different.

Additionally, L ₃ is 1,2-phenylene that is unsubstituted or substituted with 1 to 4 deuterium atoms; 1,3-phenylene unsubstituted or substituted with 1 to 4 deuteriums; Alternatively, it may be unsubstituted or 1,4-phenylene substituted with 1 to 4 deuteriums.

In one embodiment, L ₃ can be 1,2-phenylene, 1,3-phenylene, or 1,4-phenylene.

In another embodiment, L ₃ is 1,2-phenylene substituted with 1 to 4 deuterium atoms; 1,3-phenylene substituted with 1 to 4 deuterium atoms; Alternatively, it may be 1,4-phenylene substituted with 1 to 4 deuterium atoms.

In addition, a, which means the number of deuterium, is 0, 1, 2, 3, 4, 5, 6, or 7, and b is 0, 1, 2, 3, 4, 5, 6, 7, or 8, c is 0, 1, 2, 3, 4, 5, or 6, and d is 0, 1, 2, 3, 4, 5, 6, or 7.

In one implementation, a+b+c+d is 0; Or it may be an integer from 22 to 28.

Additionally, the compound may not contain deuterium or may contain one or more deuterium.

For example, when the compound contains deuterium, the deuterium substitution rate of the compound may be 50% to 100%. Specifically, the deuterium substitution rate of the compound may be 60% or more, 70% or more, 80% or more, 85% or more, 87% or more, 88% or more, or 90% or more, but may be 100% or less. The deuterium substitution rate of these compounds is calculated as the number of substituted deuteriums compared to the total number of hydrogens that may exist in the chemical formula. In this case, the number of substituted deuteriums is calculated by MALDI-TOF MS (Matrix-Assisted Laser Desorption/Ionization Time-of-Flight Mass It can be obtained through spectrometer analysis.

Preferably, the deuterium substitution rate of the compound may be 0% or 80% or more.

Additionally, the compound 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,

a, b, c and d are as defined in Formula 1 above,

e, f and g are each independently integers from 0 to 4,

n1 and n2 are each independently 0 or 1.

In Formulas 1-1 and 1-2, e, f, and g also refer to the number of deuterium and are each independently 0, 1, 2, 3, or 4.

Specifically, in Formulas 1-1 and 1-2,

If n1 and n2 are both 0, then a+b+c+d+g is 0; or an integer from 1 to 32,

If n1 is 1 and n2 is 0, then a+b+c+d+e+g is 0; or an integer from 1 to 36,

If n1 is 0 and n2 is 1, then a+b+c+d+f+g is 0; or an integer from 1 to 36

If n1 and n2 are both 1, then a+b+c+d+e+f+g is 0; Or it is an integer from 1 to 40.

Preferably, in Formulas 1-1 and 1-2,

If n1 and n2 are both 0, then a+b+c+d+g is 0; or an integer from 28 to 32,

If n1 is 1 and n2 is 0, then a+b+c+d+e+g is 0; or an integer from 32 to 36,

If n1 is 0 and n2 is 1, then a+b+c+d+f+g is 0; or an integer from 32 to 36

If n1 and n2 are both 1, then a+b+c+d+e+f+g is 0; or an integer of 36 to 40.

Meanwhile, a representative example of the compound represented by Formula 1 is any one selected from the group consisting of compounds represented by the following formula:

In compounds 2, 4, 6, 8, 10 and 12, a+b+c+d+g is an integer from 1 to 32,

In compounds 14, 16, 18, 20, 22 and 24, a+b+c+d+e+g is an integer from 1 to 36,

In compounds 26, 28, 30, 32, 34 and 36, a+b+c+d+f+g is an integer from 1 to 36,

In compounds 38, 40, 42, 44, 46 and 48, a+b+c+d+e+f+g is an integer from 1 to 40.

Preferably,

In compounds 2, 4, 6, 8, 10 and 12, a+b+c+d+g is an integer from 28 to 32,

In compounds 14, 16, 18, 20, 22 and 24, a+b+c+d+e+g is an integer from 32 to 36,

In compounds 26, 28, 30, 32, 34 and 36, a+b+c+d+f+g is an integer from 32 to 36,

In compounds 38, 40, 42, 44, 46 and 48, a+b+c+d+e+f+g is an integer from 36 to 40.

Meanwhile, among the compounds represented by Chemical Formula 1, the compound represented by Chemical Formula 1-1 can be prepared by the production method shown in Scheme 1 below when a to g are all 0.

[Scheme 1]

In Scheme 1, the definition of each substituent is as described above, and BPin refers to a boronic pinacol ester group.

Specifically, the compound represented by Formula 1-1 may be prepared through steps a to c. First, step a is a step of preparing intermediate compound 1-3 through Suzuki coupling reaction of compounds A-1 and A-2. Next, in step b, Tf ₂ O (Trifluoromethanesulfonic anhydride) is used to prepare compound A-4, in which -OTf (-O ₃ SCF ₃ ) group, which is a reactive group for Suzuki coupling reaction, is introduced into compound A-3. It's a step. Next, step c is a step of preparing the compound represented by Formula 1 through the Suzuki coupling reaction of compounds A-4 and A-5. At this time, the Suzuki coupling reaction in steps a and c is preferably performed in the presence of a palladium catalyst and a base, respectively. Additionally, the reactor for the Suzuki coupling reaction may be modified appropriately.

Additionally, the compound represented by Chemical Formula 1-1 having at least one deuterium can be prepared by the production method shown in Scheme 2 below.

[Scheme 2]

In Scheme 2, the definition of each substituent is the same as previously described.

Specifically, a compound represented by Formula 1-1 having at least one deuterium can be prepared by deuterating a compound represented by Formula 1-1 that is not substituted with deuterium. At this time, the deuterium substitution reaction is performed by adding the compound represented by Formula 1-1, which is not substituted with deuterium, into a deuterated solvent such as benzene-D ₆ (C ₆ D ₆ ) solution and then reacting with TfOH (trifluoromethanesulfonic acid). It can be done.

Meanwhile, compounds represented by Formula 1-2 can be prepared by appropriately changing the reaction materials in Schemes 1 and 2, and their preparation methods can be more detailed in the preparation examples to be described later.

Meanwhile. The compound represented by Formula 1 has high solubility in organic solvents used in solution processes, such as cyclohexanone, and can be used in large-area solution processes such as inkjet coating using solvents with high boiling points. Suitable.

The organic layer containing the compound according to the present invention can be formed using various methods such as vacuum deposition and solution process, and the solution process will be described in detail below.

(Coating composition)

Meanwhile, the compound according to the present invention can form an organic layer, especially a light-emitting layer, of an organic light-emitting device through a solution process. Specifically, the compound can be used as a host material for the light-emitting layer. For this purpose, the present invention provides a coating composition comprising the compound and solvent according to the present invention described above.

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, mesitylene, 1-methylnaphthalene, and 2-methylnaphthalene; 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, methyl-2-methoxybenzoate, and ethyl benzoate; Phthalate-based solvents such as dimethyl phthalate, diethyl phthalate, and diphenyl phthalate; tetralin; Solvents such as 3-phenoxytoluene can be mentioned. In addition, the above-mentioned solvents may be used individually or two or more types of solvents may be mixed. Preferably, cyclohexanone can be used as the solvent.

Additionally, the coating composition may further include a compound used as a dopant material, and a description of the compound used as the dopant material will be provided later.

Additionally, the viscosity of the coating composition is preferably 1 cP or more. In addition, considering the ease of coating of the coating composition, the viscosity of the coating composition is preferably 10 cP or less. In addition, the concentration of the compound according to the present invention in the coating composition is preferably 0.1 wt/v% or more. In addition, so that the coating composition can be optimally coated, the concentration of the compound according to the present invention in the coating composition is preferably 20 wt/v% or less.

In addition, the solubility (wt%) of the compound represented by Formula 1 at room temperature/normal pressure may be 0.1 wt% or more, more specifically 0.1 wt% to 5 wt%, based on the solvent cyclohexanone. Accordingly, a coating composition containing the compound represented by Formula 1 and a solvent can be used in a solution process.

Additionally, the present invention provides a method of forming a light-emitting layer using the above-described coating composition. Specifically, coating the above-described light-emitting layer according to the present invention on the anode or on the hole transport layer formed on the anode by a solution process; and heat treating the coated coating composition.

The solution process uses the coating composition according to the present invention described above, and includes spin coating, dip coating, doctor blading, inkjet printing, screen printing, spraying, roll coating, etc., but is not limited to these.

In the heat treatment step, the heat treatment temperature is preferably 150 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.

(Organic light emitting device)

Meanwhile, the present invention provides an organic light-emitting device containing the compound represented by Formula 1 above. For 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. .

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, a light emitting 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 one embodiment, the organic material layer may include a light-emitting layer, and in this case, the organic material layer including the compound may be a light-emitting layer.

In another embodiment, the organic material layer may include a hole injection layer, a hole transport layer, a light-emitting layer, and an electron injection and transport layer, and in this case, the organic material layer containing the compound may be a light-emitting layer.

In another embodiment, the organic material layer may include a hole injection layer, a hole transport layer, an electron suppression layer, a light-emitting layer, and an electron injection and transport layer, and in this case, the organic material layer containing the compound may be a light-emitting layer.

In another embodiment, the organic material layer may include a hole injection layer, a hole transport layer, an electron suppression layer, a light emitting layer, an electron blocking layer, and an electron injection and transport layer, and in this case, the organic material layer containing the compound may be a light emitting layer.

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 is an organic material layer that, in addition to the light-emitting layer, further includes a hole injection layer and a hole transport layer between the first electrode and the light-emitting layer, and an electron transport layer and an electron injection layer between the light-emitting layer and the second electrode. It can have a structure that does. However, the structure of the organic light emitting device is not limited to this and may include fewer or more organic layers.

In addition, the organic light-emitting device according to the present invention is 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 in which the first electrode is an anode and the second electrode is a cathode. It can be. In addition, the organic light emitting device according to the present invention is an inverted type organic light emitting device in which a cathode, one or more organic material layers, and an anode are sequentially stacked on a substrate where the first electrode is a cathode and the second electrode is an anode. It can be. 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 is an example of an organic light emitting device consisting of a substrate (1), an anode (2), a hole injection layer (5), a hole transport layer (6), a light emitting layer (3), an electron injection and transport layer (7), and a cathode (4). It shows. In this structure, the compound represented by Formula 1 may be included in 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 the light emitting layer contains the compound according to the present invention and is manufactured according to the method described above.

For example, the organic light emitting device according to the present invention can be manufactured by sequentially stacking an anode, an organic material layer, and a cathode 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. It can be manufactured by forming an organic material layer including a hole injection layer, a hole transport layer, a light emitting layer, and an electron transport layer thereon, and then depositing a material that can be used as a cathode thereon.

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

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 multi-layer structure materials such as LiF/Al or LiO ₂ /Al, but they are not limited to these.

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. The hole transport material is a material that can receive holes from the anode or hole injection layer and transfer them to the light-emitting layer, and has high mobility for holes. The material is suitable. As the hole transport material, a compound represented by Formula 1 may be used, or an arylamine-based organic material, a conductive polymer, and a block copolymer having both a conjugated and non-conjugated portion may be used, but is not limited thereto. .

Meanwhile, the organic light emitting device may include an electron suppression layer between the hole transport layer and the light emitting layer. The electron blocking layer is formed on the hole transport layer, preferably in contact with the light emitting layer, to control hole mobility and prevent excessive movement of electrons to increase the probability of hole-electron coupling, thereby increasing the efficiency of the organic light emitting device. This refers to the layer that plays a role in improving. The electron blocking layer includes an electron blocking material, and examples of the electron blocking material include the compound represented by Chemical Formula 1, or an arylamine-based organic material, but are not limited thereto.

The light emitting layer may include a host material and a dopant material. As a host material, a compound represented by Formula 1 above may be used. Additionally, as the host material, a condensed aromatic ring derivative or a heterocyclic ring-containing compound may be used along with the compound represented by Formula 1. 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.

Additionally, 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.

Meanwhile, the organic light emitting device may include a hole blocking layer between the light emitting layer and the electron transport layer. The hole blocking layer is formed on the light-emitting layer, preferably in contact with the light-emitting layer, to improve the efficiency of the organic light-emitting device by controlling electron mobility and preventing excessive movement of holes to increase the probability of hole-electron coupling. It refers to the layer that plays a role. The hole blocking layer includes a hole blocking material. Examples of the hole blocking material include azine derivatives including triazine; triazole derivatives; Oxadiazole derivatives; phenanthroline derivatives; Compounds into which electron-withdrawing groups are introduced, such as phosphine oxide derivatives, may be used, but are not limited thereto.

The electron injection and transport layer is a layer that simultaneously performs the roles of an electron transport layer and an electron injection layer, injecting electrons from an electrode and transporting the received electrons to the light-emitting layer, and is formed on the light-emitting layer or the hole blocking layer. As such an electron injection and transport material, a material that can easily inject electrons from the cathode and transfer them to the light emitting layer, and a material with high mobility for electrons, is suitable. Specific examples of electron injection and transport materials include Al complex of 8-hydroxyquinoline; Complex containing Alq ₃ ; organic radical compounds; hydroxyflavone-metal complex; Triazine derivatives, etc., but are not limited to these. or fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, preorenylidene methane, anthrone, etc. and their derivatives, metal complex compounds. , or a nitrogen-containing 5-membered ring derivative, etc., but is not limited thereto.

The electron injection and transport layer may also be formed as separate layers such as an electron injection layer and an electron transport layer. In this case, the electron transport layer is formed on the light emitting layer or the hole blocking layer, and the electron injection and transport material described above may be used as the electron transport material included in the electron transport layer. In addition, an electron injection layer is formed on the electron transport layer, and electron injection materials included in the electron injection layer include LiF, NaCl, CsF, Li ₂ O, BaO, fluorenone, anthraquinodimethane, diphenoquinone, Thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, fluorenylidene methane, anthrone and their derivatives, metal complex compounds and nitrogen-containing five-membered ring derivatives can be used.

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-hydroxyquinolinato)chlorogallium, bis(2-methyl-8-hydroxyquinolinato) Nolinato) (o-cresolato) gallium, bis (2-methyl-8-hydroxyquinolinato) (1-naphtolato) aluminum, bis (2-methyl-8-hydroxyquinolinato) (2- Naphtolato) gallium, etc., but is not limited thereto.

In addition to the materials described above, the light emitting layer, hole injection layer, hole transport layer, electron transport layer, and electron injection layer may further include inorganic compounds or polymer compounds such as quantum dots.

The quantum dots may be, for example, colloidal quantum dots, alloy quantum dots, core-shell quantum dots, or core quantum dots. elements belonging to groups 2 and 16, elements belonging to groups 13 and 15, elements belonging to groups 13 and 17, elements belonging to groups 11 and 17, or elements belonging to groups 14 and 17. It may be a quantum dot containing elements belonging to group 15, including cadmium (Cd), selenium (Se), zinc (Zn), sulfur (S), phosphorus (P), indium (In), tellurium (Te), and lead. Quantum dots containing elements such as (Pb), gallium (Ga), and arsenic (As) may be used.

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.

Preparation Example 1: Preparation of Compound 1

Compound 1-a (1.0 eq.) and Compound 1-b (1.1 eq.) were placed in a round bottom flask and dissolved in THF. Inject Cs ₂ CO ₃ (5.0 eq.) dissolved in water. Pd(PPh ₃ ) ₄ (10 mol%) was added dropwise at a bath temperature of 80°C and stirred for 3 days. After reaction, the reactant was cooled at room temperature, diluted sufficiently with EtOAc, washed with water with EtOAc/brine, and the organic layer was separated. Water was removed with MgSO ₄ and passed through a Celite-Florisil-Silica pad. The passed solution was concentrated under reduced pressure and purified by column chromatography to prepare compound 1-c (73% yield).

Compound 1-c (1.0 eq.) was placed in a round bottom flask and dissolved in anhydrous CH ₂ Cl ₂ . Afterwards, pyridine (2.0 eq.) was added dropwise at room temperature, and the bath temperature was lowered to 0°C and stirred for 10 minutes. Afterwards, Tf ₂ O (1.2 eq.) dissolved in anhydrous CH ₂ Cl ₂ was slowly added dropwise to the mixture using a dropping funnel, the bath temperature was gradually raised from 0°C to room temperature, and the mixture was stirred overnight. After the reaction, the reactant was sufficiently diluted in CH ₂ Cl ₂ and washed with CH ₂ Cl ₂ /brine to separate the organic layer. Water was removed with MgSO ₄ and passed through a Celite-Florisil-Silica pad. The passed solution was concentrated under reduced pressure and purified by column chromatography to prepare compound 1-d (99% yield).

Compound 1-d (1.0 eq.) and Compound 1-e (1.1 eq.) were placed in a round bottom flask and dissolved in THF. Inject Na ₂ CO ₃ (3.0 eq.) dissolved in water. Pd(PPh ₃ ) ₄ (10 mol%) was added dropwise at a bath temperature of 80°C and stirred overnight. After reaction, the reactant was cooled at room temperature, diluted sufficiently with EtOAc, washed with water with EtOAc/brine, and the organic layer was separated. Water was removed with MgSO ₄ and passed through a Celite-Florisil-Silica pad. The passed solution was concentrated under reduced pressure and purified by column chromatography to prepare Compound 1 (83% yield).

m/z [M+H] ⁺ 633.3

Preparation Example 2: Preparation of Compound 2

Compound 1 (1.0 eq.) was placed in a round bottom flask under a nitrogen atmosphere and dissolved in benzene-D ₆ (150 eq.). TfOH (2.0 eq.) was slowly added dropwise to the reaction and stirred at 25°C for 2 hours. D ₂ O was added dropwise to the reactant to terminate the reaction, and potassium phosphate tribasic (30 wt% in aqueous solution, 2.4 eq.) was added dropwise to adjust the pH of the aqueous layer to 9-10. The organic layer was separated by washing with CH ₂ Cl ₂ /DI water. Water was removed with MgSO ₄ and passed through a Celite-Florisil-Silica pad. The passed solution was concentrated under reduced pressure and purified by column chromatography to prepare Compound 1 (a+b+c+d+g=28-32, 87% yield).

m/z [M+H] ⁺ 665.3

Preparation Example 3: Preparation of Compound 3

Compound 3 was synthesized in the same manner as Compound 1, except that Compound 3-a was used instead of Compound 1-e.

m/z [M+H] ⁺ 633.3

Preparation Example 4: Preparation of Compound 4

Compound 4 (a+b+c+d+g=28-32) was synthesized in the same manner as compound 2 except that compound 3 was used instead of compound 1.

m/z [M+H] ⁺ 665.3

Preparation Example 5: Preparation of Compound 5

Compound 5 was synthesized in the same manner as Compound 1, except that Compound 5-a was used instead of Compound 1-e.

m/z [M+H] ⁺ 633.3

Preparation Example 6: Preparation of Compound 6

Compound 6 (a+b+c+d+g=28-32) was synthesized in the same manner as compound 2 except that compound 5 was used instead of compound 1.

m/z [M+H] ⁺ 665.3

Preparation Example 7: Preparation of Compound 7

Compound 7 was synthesized in the same manner as Compound 1, except that Compound 7-a was used instead of Compound 1-e.

m/z [M+H] ⁺ 633.3

Preparation Example 8: Preparation of Compound 8

Compound 8 (a+b+c+d+g=28-32) was synthesized in the same manner as compound 2 except that compound 7 was used instead of compound 1.

m/z [M+H] ⁺ 665.3

Preparation Example 9: Preparation of Compound 9

Compound 9 was prepared in the same manner as Compound 1, except that Compound 9-a was used instead of Compound 1-e.

m/z [M+H] ⁺ 633.3

Preparation Example 10: Preparation of Compound 10

Compound 10 (a+b+c+d+g=28-32) was synthesized in the same manner as compound 2 except that compound 9 was used instead of compound 1.

m/z [M+H] ⁺ 665.3

Preparation Example 11: Preparation of Compound 11

Compound 11 was synthesized in the same manner as Compound 1, except that Compound 11-a was used instead of Compound 1-e.

m/z [M+H] ⁺ 633.3

Preparation Example 12: Preparation of Compound 12

Compound 8 (a+b+c+d+g=28-32) was synthesized in the same manner as compound 2 except that compound 7 was used instead of compound 1.

m/z [M+H] ⁺ 665.3

Preparation Example 13: Preparation of Compound 13

Compound 13 was synthesized in the same manner as Compound 1, except that Compound 13-a was used instead of Compound 1-b.

m/z [M+H] ⁺ 709.3

Manufacturing example 14: Preparation of compound 14

Compound 14 (a+b+c+d+e+g=32-36) was synthesized in the same manner as compound 2 except that compound 13 was used instead of compound 1.

m/z [M+H] ⁺ 745.3

Preparation Example 15: Preparation of Compound 15

Compound 15 was synthesized in the same manner as Compound 13, except that Compound 3-a was used instead of Compound 1-e.

m/z [M+H] ⁺ 709.3

Preparation Example 16: Preparation of Compound 16

Compound 16 (a+b+c+d+e+g=32-36) was synthesized in the same manner as compound 2 except that compound 15 was used instead of compound 1.

m/z [M+H] ⁺ 745.3

Preparation Example 17: Preparation of Compound 17

Compound 17 was synthesized in the same manner as Compound 13, except that Compound 5-a was used instead of Compound 1-e.

m/z [M+H] ⁺ 709.3

Preparation Example 18: Preparation of Compound 18

Compound 18 (a+b+c+d+e+g=32-36) was synthesized in the same manner as compound 2 except that compound 17 was used instead of compound 1.

m/z [M+H] ⁺ 745.3

Preparation Example 19: Preparation of Compound 19

Compound 19 was synthesized in the same manner as Compound 13, except that Compound 7-a was used instead of Compound 1-e.

m/z [M+H] ⁺ 709.3

Preparation Example 20: Preparation of Compound 20

Compound 20 (a+b+c+d+e+g=32-36) was synthesized in the same manner as compound 2 except that compound 19 was used instead of compound 1.

m/z [M+H] ⁺ 745.3

Preparation Example 21: Preparation of Compound 21

Compound 21 was synthesized in the same manner as Compound 13, except that Compound 9-a was used instead of Compound 1-e.

m/z [M+H] ⁺ 709.3

Preparation Example 22: Preparation of Compound 22

Compound 22 (a+b+c+d+e+g=32-36) was synthesized in the same manner as compound 2 except that compound 21 was used instead of compound 1.

m/z [M+H] ⁺ 745.3

Preparation Example 23: Preparation of Compound 23

Compound 23 was synthesized in the same manner as Compound 13, except that Compound 11-a was used instead of Compound 1-e.

m/z [M+H] ⁺ 709.3

Preparation Example 24: Preparation of Compound 24

Compound 24 (a+b+c+d+e+g=32-36) was synthesized in the same manner as compound 2 except that compound 23 was used instead of compound 1.

m/z [M+H] ⁺ 745.3

Preparation Example 25: Preparation of Compound 25

Compound 25 was synthesized in the same manner as Compound 1, except that Compound 25-a was used instead of Compound 1-b.

m/z [M+H] ⁺ 709.3

Preparation Example 26: Preparation of Compound 26

Compound 26 (a+b+c+d+f+g=32-36) was synthesized in the same manner as compound 2 except that compound 25 was used instead of compound 1.

m/z [M+H] ⁺ 745.3

Preparation Example 27: Preparation of Compound 27

Compound 27 was synthesized in the same manner as Compound 25 except that Compound 3-a was used instead of Compound 1-e.

m/z [M+H] ⁺ 709.3

Preparation Example 28: Preparation of Compound 28

Compound 28 (a+b+c+d+f+g=32-36) was synthesized in the same manner as compound 2 except that compound 27 was used instead of compound 1.

m/z [M+H] ⁺ 745.3

Preparation Example 29: Preparation of Compound 29

Compound 29 was synthesized in the same manner as Compound 25, except that Compound 5-a was used instead of Compound 1-e.

m/z [M+H] ⁺ 709.3

Preparation Example 30: Preparation of Compound 30

Compound 30 (a+b+c+d+f+g=32-36) was synthesized in the same manner as compound 2 except that compound 29 was used instead of compound 1.

m/z [M+H] ⁺ 745.3

Preparation Example 31: Preparation of Compound 31

Compound 31 was synthesized in the same manner as compound 25 except that compound 7-a was used instead of compound 1-e.

m/z [M+H] ⁺ 709.3

Preparation Example 32: Preparation of Compound 32

Compound 32 (a+b+c+d+f+g=32-36) was synthesized in the same manner as compound 2 except that compound 31 was used instead of compound 1.

m/z [M+H] ⁺ 745.3

Preparation Example 33: Preparation of compound 33

Compound 33 was synthesized in the same manner as compound 25, except that compound 9-a was used instead of compound 1-e.

m/z [M+H] ⁺ 709.3

Preparation Example 34: Preparation of Compound 34

Compound 34 (a+b+c+d+f+g=32-36) was synthesized in the same manner as compound 2 except that compound 33 was used instead of compound 1.

m/z [M+H] ⁺ 745.3

Preparation Example 35: Preparation of Compound 35

Compound 35 was synthesized in the same manner as Compound 25 except that Compound 11-a was used instead of Compound 1-e.

m/z [M+H] ⁺ 709.3

Preparation Example 36: Preparation of Compound 36

Compound 36 (a+b+c+d+f+g=32-36) was synthesized in the same manner as compound 2 except that compound 35 was used instead of compound 1.

m/z [M+H] ⁺ 745.3

Preparation Example 37: Preparation of compound 37

Compound 37 was synthesized in the same manner as Compound 1, except that Compound 37-a was used instead of Compound 1-b.

m/z [M+H] ⁺ 785.4

Preparation Example 38: Preparation of compound 38

Compound 38 (a+b+c+d+e+f+g=36-40) was synthesized in the same manner as compound 2 except that compound 37 was used instead of compound 1.

m/z [M+H] ⁺ 825.3

Preparation Example 39: Preparation of Compound 39

Compound 39 was synthesized in the same manner as Compound 37, except that Compound 3-a was used instead of Compound 1-e.

m/z [M+H] ⁺ 785.4

Preparation Example 40: Preparation of Compound 40

Compound 40 (a+b+c+d+e+f+g=36-40) was synthesized in the same manner as compound 2 except that compound 39 was used instead of compound 1.

m/z [M+H] ⁺ 825.3

Preparation Example 41: Preparation of Compound 41

Compound 41 was synthesized in the same manner as Compound 37, except that Compound 5-a was used instead of Compound 1-e.

m/z [M+H] ⁺ 785.4

Preparation Example 42: Preparation of Compound 42

Compound 42 (a+b+c+d+e+f+g=36-40) was synthesized in the same manner as compound 2 except that compound 41 was used instead of compound 1.

m/z [M+H] ⁺ 825.3

Preparation Example 43: Preparation of Compound 43

Compound 43 was synthesized in the same manner as Compound 37, except that Compound 7-a was used instead of Compound 1-e.

m/z [M+H] ⁺ 785.4

Preparation Example 44: Preparation of Compound 44

Compound 44 (a+b+c+d+e+f+g=36-40) was synthesized in the same manner as compound 2 except that compound 43 was used instead of compound 1.

m/z [M+H] ⁺ 825.3

Preparation Example 45: Preparation of Compound 45

Compound 45 was synthesized in the same manner as Compound 37, except that Compound 9-a was used instead of Compound 1-e.

m/z [M+H] ⁺ 785.4

Preparation Example 46: Preparation of Compound 46

Compound 46 (a+b+c+d+e+f+g=36-40) was synthesized in the same manner as compound 2 except that compound 45 was used instead of compound 1.

m/z [M+H] ⁺ 825.3

Preparation Example 47: Preparation of compound 47

Compound 47 was synthesized in the same manner as Compound 37, except that Compound 11-a was used instead of Compound 1-e.

m/z [M+H] ⁺ 785.4

Preparation Example 48: Preparation of compound 48

Compound 48 (a+b+c+d+e+f+g=36-40) was synthesized in the same manner as compound 2 except that compound 47 was used instead of compound 1.

m/z [M+H] ⁺ 825.3

Comparative Preparation Example 1: Preparation of Comparative Compound A

Compound Aa (1.0 eq.) and compound 1-b (1.1 eq.) were placed in a round bottom flask and dissolved in THF. Inject Cs ₂ CO ₃ (5.0 eq.) dissolved in water. Pd(PPh ₃ ) ₄ (10 mol%) was added dropwise at a bath temperature of 80°C and stirred for 3 days. After reaction, the reactant was cooled at room temperature, diluted sufficiently with EtOAc, washed with water with EtOAc/brine, and the organic layer was separated. Water was removed with MgSO ₄ and passed through a Celite-Florisil-Silica pad. The passed solution was concentrated under reduced pressure and purified by column chromatography to prepare compound Ab (71% yield).

Compound Ab (1.0 eq.) was placed in a round bottom flask and dissolved in anhydrous CH ₂ Cl ₂ . Afterwards, pyridine (2.0 eq.) was added dropwise at room temperature, and the bath temperature was lowered to 0°C and stirred for 10 minutes. Afterwards, Tf ₂ O (1.2 eq.) dissolved in anhydrous CH ₂ Cl ₂ was slowly added dropwise to the mixture using a dropping funnel, the bath temperature was gradually raised from 0°C to room temperature, and the mixture was stirred overnight. After the reaction, the reactant was sufficiently diluted in CH ₂ Cl ₂ and washed with CH ₂ Cl ₂ /brine to separate the organic layer. Water was removed with MgSO ₄ and passed through a Celite-Florisil-Silica pad. The passed solution was concentrated under reduced pressure and purified by column chromatography to prepare compound Ac (99% yield).

Compound Ac (1.0 eq.) and compound Ad (1.1 eq.) were placed in a round bottom flask and dissolved in THF. Inject Na ₂ CO ₃ (3.0 eq.) dissolved in water. Pd(PPh ₃ ) ₄ (10 mol%) was added dropwise at a bath temperature of 80°C and stirred overnight. After reaction, the reactant was cooled at room temperature, diluted sufficiently with EtOAc, washed with water with EtOAc/brine, and the organic layer was separated. Water was removed with MgSO ₄ and passed through a Celite-Florisil-Silica pad. The passed solution was concentrated under reduced pressure and purified by column chromatography to prepare Compound A (92% yield).

m/z [M+H] ⁺ 507.2

Comparative Preparation Example 2: Preparation of Comparative Compound B

Compound B (h+i+j+k=22-26) was synthesized in the same manner as Compound 2 except that Compound A was used instead of Compound 1.

m/z [M+H] ⁺ 533.2

Comparative Preparation Example 3: Preparation of Comparative Compound C

Compound Ca (1.0 eq.) and compound 1-b (1.1 eq.) were placed in a round bottom flask and dissolved in THF. Inject Cs ₂ CO ₃ (5.0 eq.) dissolved in water. Pd(PPh ₃ ) ₄ (10 mol%) was added dropwise at a bath temperature of 80°C and stirred for 3 days. After reaction, the reactant was cooled at room temperature, diluted sufficiently with EtOAc, washed with water with EtOAc/brine, and the organic layer was separated. Water was removed with MgSO ₄ and passed through a Celite-Florisil-Silica pad. The passed solution was concentrated under reduced pressure and purified by column chromatography to prepare Compound C (85% yield).

m/z [M+H] ⁺ 633.3

Comparative Preparation Example 4: Preparation of Comparative Compound D

Under a nitrogen atmosphere, compound 1 (1.0 eq.) was placed in a round bottom flask, benzene-D ₆ (150 eq.) was added dropwise, and dissolved at 80°C. TfOH (20.0 eq.) was slowly added dropwise to the reaction and stirred at 80°C for 2 hours. After the reactant is sufficiently cooled to room temperature, D ₂ O is added dropwise to the reactant to terminate the reaction. Potassium phosphate tribasic (30 wt% in aqueous solution, 2.4 eq.) was added dropwise to adjust the pH of the aqueous layer to 9-10, and the organic layer was separated by washing with CH ₂ Cl ₂ /DI water. Water was removed with MgSO ₄ and passed through a Celite-Florisil-Silica pad. The passed solution was concentrated under reduced pressure and purified by column chromatography to prepare compound D (h+i+j+k+l=28-32).

m/z [M+H] ⁺ 665.3

Comparative Preparation Example 5: Preparation of Comparative Compound E

Compound E was prepared in the same manner as Compound A, except that Compound E-a was used instead of Compound A-a, and E-d was used instead of Compound A-d.

m/z [M+H] ⁺ 557.2

Comparative Preparation Example 6: Preparation of Comparative Compound F

Compound F (h+i+j+k=24-28) was synthesized in the same manner as Compound 2 except that Compound E was used instead of Compound 1.

m/z [M+H] ⁺ 585.4

Comparative Preparation Example 7: Preparation of Comparative Compound G

Compound G was prepared in the same manner as Compound E except that Compound 3-a was used instead of Compound E-d.

m/z [M+H] ⁺ 633.4

Comparative Preparation Example 8: Preparation of Comparative Compound H

H(h+i+j+k+l=28-32) was synthesized in the same manner as Compound D except that Compound G was used instead of Compound C.

m/z [M+H] ⁺ 665.4

Comparative Preparation Example 9: Preparation of Comparative Compound I

Compound I was prepared in the same manner as Compound E except that Compound I-a was used instead of Compound E-a and 3-a was used instead of Compound E-d.

m/z [M+H] ⁺ 633.3

Comparative Preparation Example 10: Preparation of Comparative Compound J

Compound J (h+i+j+k+l=28-32) was synthesized in the same manner as Compound D except that Compound I was used instead of Compound C.

m/z [M+H] ⁺ 665.4

Experimental Example 1: Confirmation of deuterium substitution rate

For the compounds in which deuterium was substituted in Preparation Examples 1 to 48, the number of substituted deuteriums in the compounds was determined through MALDI-TOF MS (Matrix-Assisted Laser Desorption/Ionization Time-of-Flight Mass Spectrometer) analysis, and the chemical formula The deuterium substitution rate was calculated as a percentage of the number of substituted deuteriums compared to the total number of hydrogens that could be present, and this is shown in Table 1 below.

compound heavy hydrogen
Number of substitutions heavy hydrogen
Substitution rate (%) compound heavy hydrogen
Number of substitutions heavy hydrogen
Substitution rate (%) compound 2 28-32 87.5-100 Compound 26 32-36 88.9-100 Compound 4 28-32 87.5-100 Compound 28 32-36 88.9-100 Compound 6 28-32 87.5-100 Compound 30 32-36 88.9-100 Compound 8 28-32 87.5-100 Compound 32 32-36 88.9-100 Compound 10 28-32 87.5-100 Compound 34 32-36 88.9-100 Compound 12 28-32 87.5-100 Compound 36 32-36 88.9-100 Compound 14 32-36 88.9-100 Compound 38 36-40 90-100 Compound 16 32-36 88.9-100 Compound 40 36-40 90-100 Compound 18 32-36 88.9-100 Compound 42 36-40 90-100 Compound 20 32-36 88.9-100 Compound 44 36-40 90-100 Compound 22 32-36 88.9-100 Compound 46 36-40 90-100 Compound 24 32-36 88.9-100 Compound 48 36-40 90-100

Experiment example 2: Solubility measurement

It was confirmed whether Compounds 1 and 48 and Compounds A and J prepared in the above Preparation Example could each be dissolved in cyclohexanone at a concentration of 1.3 wt% at 25°C, and the results are shown in Table 2. At this time, the “O” mark means that the compound is easily dissolved in cyclohexanone, the “△” mark means that the compound is dissolved in cyclohexanone at 80°C, and the “X” mark means that the compound is dissolved in cyclohexanone. This means that it does not dissolve in

compound Solubility (1.3 wt%) compound Solubility (1.3 wt%) Compound 1 O Compound 30 O compound 2 O Compound 31 O Compound 3 O Compound 32 O Compound 4 O Compound 33 O Compound 5 O Compound 34 O Compound 6 O Compound 35 O Compound 7 O Compound 36 O Compound 8 O Compound 37 O Compound 9 O Compound 38 O Compound 10 O Compound 39 O Compound 11 O Compound 40 O Compound 12 O Compound 41 O Compound 13 O Compound 42 O Compound 14 O Compound 43 O Compound 15 O Compound 44 O Compound 16 O Compound 45 O Compound 17 O Compound 46 O Compound 18 O Compound 47 O Compound 19 O Compound 48 O Compound 20 O Compound A O Compound 21 O Compound B O Compound 22 O Compound C X Compound 23 O Compound D X Compound 24 O Compound E O Compound 25 O Compound F O Compound 26 O Compound G △ Compound 27 O Compound H △ Compound 28 O Compound I X Compound 29 O Compound J X

As can be seen in Table 2, all of the compounds represented by Formula 1 were soluble in cyclohexanone at a concentration of 1.3 wt%, but comparative compounds C, D, I and J were not soluble even at high temperatures. It can be seen that when the organic layer of an organic light emitting device is manufactured through a solution process, it cannot be used as a compound forming the organic layer.

This is 5 of (naphthyl)-(anthracene)-(phenylene)-(naphthylene)-(naphthyl) or (naphthyl)-(anthracene)-(naphthylene)-(phenylene)-(naphthyl) This is because the two sigma bonding orbitals of the "naphthylene" linker in the comparative compounds C, D, I, and J, which have two moieties, are angled at 180 degrees instead of 60 degrees, so that the twist form within the molecule is not effectively induced and only the linear form is induced. It is judged. In addition, comparative compounds G and H, which have five moieties of (naphthyl)-(anthracene)-(naphthylene)-(phenylene)-(naphthyl), have two sigma bonding orbitals of the “naphthylene” linker. Compared to comparative compounds C, D, I, and J, the twist form is induced within the molecule at an angle of 120 degrees, but it can be seen that the twist form is not induced to a sufficient extent to increase solubility.

Therefore, through the above solubility measurement, it is confirmed that in order to increase the solubility of compounds over a certain molecular weight, a twist form, rather than a linear form, must be effectively induced within the molecule, even if it has the same moiety structure.

Example 1

A glass substrate coated with a thin film of ITO (indium tin oxide) to a thickness of 500 Å was placed in distilled water with a detergent dissolved in it and washed ultrasonically. At this time, a detergent from Fischer Co. was used, and distilled water filtered secondarily using a filter from Millipore Co. was used as distilled water. After washing the ITO for 30 minutes, ultrasonic cleaning was repeated twice with distilled water for 10 minutes. After washing with distilled water, ultrasonic cleaning was performed using isopropyl and acetone solvents and drying, the substrate was washed for 5 minutes and then transported to a glove box.

On the ITO transparent electrode, a coating composition containing Compound O and Compound P (weight ratio of 2:8) dissolved in cyclohexanone at 20 wt/v% was spin coated (4000 rpm) and heat treated (cured) at 200° C. for 30 minutes. ) to form a hole injection layer with a thickness of 400 Å.

A coating composition containing 6 wt/v% of the compound Q (Mn: 27,900; Mw: 35,600; measured by GPC using PC Standard using Agilent 1200 series) dissolved in toluene was spin coated on the hole injection layer ( 4000 rpm) and heat treatment at 200°C for 30 minutes to form a hole transport layer with a thickness of 200 Å.

On the hole transport layer, a coating composition containing Compound 1 prepared in Preparation Example 1 as a light-emitting layer host and Compound R (98:2 weight ratio) as a light-emitting layer dopant dissolved in cyclohexanone at 1.3 wt/v% was spin-coated (4000 rpm). ) and heat treated at 180°C for 30 minutes to form a light emitting layer with a thickness of 400 Å.

After being transferred to a vacuum evaporator, the compound S was vacuum deposited to a thickness of 350 Å on the light emitting layer to form an electron injection and transport layer. A cathode was formed by sequentially depositing LiF to a thickness of 10 Å and aluminum to a thickness of 1000 Å on the electron injection and transport layer.

In the above process, the deposition rate of organic materials was maintained at 0.4 to 0.7 Å/sec, LiF was maintained at 0.3 Å/sec, and aluminum was maintained at 2 Å/sec, and the vacuum degree during deposition was 2*10 ^-7 to 5. *10 ^-8 torr was maintained.

Examples 2 to 48

An organic light-emitting device was manufactured in the same manner as Example 1, except that the compounds listed in Table 3 below were used instead of Compound 1 as the host of the light-emitting layer.

Comparative example 1 to Comparative example 6

An organic light-emitting device was manufactured in the same manner as Example 1, except that the compounds listed in Table 3 below were used instead of Compound 1 as the host of the light-emitting layer.

Experimental Example 3: Evaluation of characteristics of organic light-emitting device

When current is applied to the organic light emitting device manufactured in the examples and comparative examples, the driving voltage, external quantum efficiency (EQE), and lifespan at a current density of 10 mA/cm ² are measured. The results are as follows. It is shown in Table 3. At this time, the external quantum efficiency (EQE) was calculated as "(number of photons emitted)/(number of injected charge carriers)*100", and T90 is the time required for the luminance to decrease from the initial luminance (200 nit) to 90%. means.

division luminescent layer
host driving voltage
(V @10mA/cm ² ) EQE
(%@10mA/ ^cm2 ) Lifespan (hr)
(T90 @500 nits) Example 1 Compound 1 6.5 5.57 634 Example 2 compound 2 6.7 5.59 744 Example 3 Compound 3 6.5 5.56 648 Example 4 Compound 4 6.7 5.58 754 Example 5 Compound 5 6.5 5.51 642 Example 6 Compound 6 6.2 5.57 734 Example 7 Compound 7 6.0 5.64 676 Example 8 Compound 8 6.9 5.69 754 Example 9 Compound 9 6.3 5.35 657 Example 10 Compound 10 6.5 5.40 798 Example 11 Compound 11 6.2 5.95 674 Example 12 Compound 12 6.4 6.00 746 Example 13 Compound 13 6.8 5.47 679 Example 14 Compound 14 6.5 5.52 768 Example 15 Compound 15 6.3 5.85 654 Example 16 Compound 16 6.5 5.92 735 Example 17 Compound 17 6.2 5.58 652 Example 18 Compound 18 6.9 5.60 699 Example 19 Compound 19 7.0 5.49 625 Example 20 Compound 20 6.8 5.55 726 Example 21 Compound 21 6.3 5.56 668 Example 22 Compound 22 6.5 5.58 702 Example 23 Compound 23 6.2 5.47 639 Example 24 Compound 24 6.9 5.49 754 Example 25 Compound 25 7.2 5.36 698 Example 26 Compound 26 7.0 5.62 712 Example 27 Compound 27 6.3 5.85 657 Example 28 Compound 28 6.5 5.87 758 Example 29 Compound 29 6.3 5.56 658 Example 30 Compound 30 6.5 5.57 757 Example 31 Compound 31 6.2 5.62 668 Example 32 Compound 32 6.5 5.68 726 Example 33 Compound 33 6.3 5.54 700 Example 34 Compound 34 6.9 5.59 728 Example 35 Compound 35 6.9 5.62 702 Example 36 Compound 36 6.8 5.72 768 Example 37 Compound 37 6.7 5.44 659 Example 38 Compound 38 6.3 5.48 751 Example 39 Compound 39 6.5 5.45 665 Example 40 Compound 40 7.0 5.59 779 Example 41 Compound 41 6.8 5.59 668 Example 42 Compound 42 6.2 5.52 721 Example 43 Compound 43 6.3 5.68 654 Example 44 Compound 44 6.5 5.70 725 Example 45 Compound 45 7.0 5.35 678 Example 46 Compound 46 6.9 5.48 754 Example 47 Compound 47 6.5 5.46 687 Example 48 Compound 48 6.8 5.52 702 Comparative Example 1 Compound A 6.8 4.02 325 Comparative Example 2 Compound B 6.7 4.21 422 Comparative Example 3 Compound E 6.6 3.85 308 Comparative Example 4 Compound F 6.5 4.11 359 Comparative Example 5 Compound G 6.2 3.24 143 Comparative Example 6 Compound H 6.7 3.47 205

As shown in Table 3, it is confirmed that the organic light-emitting device containing the compound of the present invention as a host in the light-emitting layer shows improved efficiency and lifespan while exhibiting an equivalent level of voltage compared to the device of the comparative example.

Specifically, the organic light-emitting device of the example using the compound represented by Formula 1 as the host of the light-emitting layer is the organic light-emitting device of Comparative Examples 1 to 6 using the comparative compounds A, B, F, F, G, and H, respectively, as the host of the light-emitting layer. Compared to light emitting devices, efficiency and lifespan have been significantly improved. This is believed to be due to improved material stability due to the structural characteristics of the compound represented by Formula 1.

Therefore, it can be seen that when the compound represented by Formula 1 is used as the host material of the organic light-emitting device, the external quantum efficiency and lifespan characteristics of the organic light-emitting device can be improved simultaneously.

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

Claims (13)

Compound represented by Formula 1:
[Formula 1]

In Formula 1,
D stands for deuterium,
L ₁ and L ₂ are each independently a single bond; or unsubstituted or deuterium-substituted phenylene,
L ₃ is unsubstituted or deuterium-substituted phenylene,
a and d are each independently integers from 0 to 7,
b is an integer from 0 to 8,
c is an integer from 0 to 6.
According to paragraph 1,
L ₁ and L ₂ are both single bonds,
compound.
According to paragraph 1,
L ₁ is a single bond, L ₂ is 1,2-phenylene unsubstituted or substituted with 1 to 4 deuteriums; 1,3-phenylene unsubstituted or substituted with 1 to 4 deuteriums; or 1,4-phenylene, which is unsubstituted or substituted with 1 to 4 deuterium atoms; or
L ₁ is 1,2-phenylene that is unsubstituted or substituted with 1 to 4 deuterium atoms; 1,3-phenylene unsubstituted or substituted with 1 to 4 deuteriums; or 1,4-phenylene that is unsubstituted or substituted with 1 to 4 deuteriums, and L ₂ is a single bond,
compound.
According to paragraph 1,
L ₁ and L ₂ are each independently 1,2-phenylene that is unsubstituted or substituted with 1 to 4 deuterium atoms; 1,3-phenylene unsubstituted or substituted with 1 to 4 deuteriums; or 1,4-phenylene, which is unsubstituted or substituted with 1 to 4 deuteriums,
compound.
According to paragraph 1,
L ₁ and L ₂ are the same as each other,
compound.
According to paragraph 1,
L ₃ is 1,2-phenylene, 1,3-phenylene, or 1,4-phenylene,
compound.
According to paragraph 1,
L ₃ is 1,2-phenylene substituted with 1 to 4 deuterium atoms; 1,3-phenylene substituted with 1 to 4 deuterium atoms; or 1,4-phenylene substituted with 1 to 4 deuterium atoms,
compound.
According to paragraph 1,
a+b+c+d is 0; or an integer from 22 to 28,
compound.
According to paragraph 1,
The compound is represented by the following formula 1-1 or 1-2,
compound:
[Formula 1-1]

[Formula 1-2]

In Formulas 1-1 and 1-2,
a, b, c and d are as defined in paragraph 1,
e, f and g are each independently integers from 0 to 4,
n1 and n2 are each independently 0 or 1.
According to paragraph 1,
The deuterium substitution rate of the compound is 0% or 80% or more,
compound.
According to paragraph 1,
The compound is any one selected from the group consisting of compounds represented by the following formula,
compound:

In compounds 2, 4, 6, 8, 10 and 12, a+b+c+d+g is an integer from 1 to 32,
In compounds 14, 16, 18, 20, 22 and 24, a+b+c+d+e+g is an integer from 1 to 36,
In compounds 26, 28, 30, 32, 34 and 36, a+b+c+d+f+g is an integer from 1 to 36,
In compounds 38, 40, 42, 44, 46 and 48, a+b+c+d+e+f+g is an integer from 1 to 40.
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 the compound according to any one of claims 1 to 11. An organic light-emitting device.
According to clause 12,
The organic material layer containing the compound is a light emitting layer,
Organic light emitting device.