KR102210266B1 - An electroluminescent compound and an electroluminescent device comprising the same - Google Patents

Abstract

The present invention relates to an organic light-emitting compound represented by the following [Chemical Formula 1] and an organic electroluminescent device comprising the same, wherein the organic light-emitting compound according to the present invention increases the PL quantum efficiency of the emission spectrum and decreases the half value width. When used as a guest in the light emitting layer of a light emitting device, it is possible to obtain an improvement in color purity due to an increase in efficiency and a decrease in half width. In particular, when the resonance structure is applied, an additional efficiency improvement can be obtained compared to a material having a broad spectrum at half width.
[Formula 1]

Description

An electroluminescent compound and an electroluminescent device comprising the same}

The present invention relates to an organic light-emitting compound and an organic light-emitting device including the same, excellent in luminance and power efficiency, and capable of realizing long life characteristics.

The organic electroluminescent device has a plurality of organic thin films stacked between an anode as a hole injection electrode and a cathode as an electron injection electrode. When a voltage is applied between the anode and the cathode, electrons and holes are injected into the organic thin film, and the injected electrons and holes The silver is destroyed by forming a hole/electron pair in the emission layer and emitting light.

A plurality of organic thin films are composed of a multi-layered structure made of different materials in order to increase the efficiency and stability of the device, and a hole injection material, a hole transport material, an electron transport material, an electron injection material, etc. are several nanometers to hundreds of nanometers in front and behind the light emitting layer. It is stacked to have a thickness of nanometers to help charge transfer to the light emitting layer and increase the hole/electron bonding ratio.

In addition, when only one material is used as the light-emitting layer, the maximum light-emitting wavelength moves to a long wavelength due to the interaction between molecules, and the color purity decreases or the efficiency of the device decreases due to the light-emitting attenuation effect. In order to increase the luminous efficiency through energy transfer, a host/guest system is used as a light-emitting material, and is usually composed of 90 to 99% of host material and 1 to 10% of guest material by weight (or molar ratio). It is made by co-deposition. If necessary, two or more substances may be co-deposited. Mainly, after a hole/electron pair is made in the host, it is transferred to the guest to emit light, and the guest determines the light emission characteristics. In order to increase the efficiency of energy transfer, a material pair is selected so that the emission wavelength band of the host and the absorption wavelength band of the guest match.

Hole/electron pairs exist in singlet and triplet states. This is because the electron spin direction is strictly limited in the wave function of organic molecules. Usually, organic molecules consisting of only carbon and hydrogen emit light in a singlet at room temperature (fluorescence), and most of the triplet energy is converted into heat. On the other hand, when heavy metals are introduced (phosphorescence) or molecules are designed so that the energy difference between singlet and triplet is small (Delayed fluorescence), triplet energy can be used for light emission. For mobile displays, where actual power consumption is important, phosphorescent red (Dohan Kim et al, Adv. Mat. 2011, v23, 2271), which has an internal quantum efficiency of 90% or more, is already used, and phosphorescent green is also gradually applied. It is expanding.

However, in the case of phosphorescent blue, despite its high efficiency, it is not yet applicable, which is due to the instability of phosphorescent blue (Jang Hyuk Kwon et al, J. Mater. Chem. 2013, v1, 5008). It has a large band gap of 3.0 to 3.5 eV and has a triplet energy of about 2.8 eV or more, constraints on stable host synthesis, constraints on stable guest material synthesis, and charge accumulation due to a high energy barrier at the interface of the light emitting layer Symptoms can be cited as causes.

As a result, at present, stable blue fluorescence is the only means, and it is very important to improve the efficiency and color purity of fluorescence in order to lower power consumption and increase color reproducibility. Recently, the blue external quantum efficiency of about 8% at 0.01 mA/cm2 was announced by minimizing the energy difference between triplet and singlet in efficiency (Chihaya Adachi et al, Nature, 2012, v492, 236) Color purity, efficiency and light emission. Further improvements in stability are still needed.

Accordingly, in order to improve the efficiency of a stable fluorescent blue device, development of a light emitting material having high PL quantum efficiency is urgently required.

In addition, an important factor in improving the efficiency and color purity as well as improving the PL quantum efficiency is the full width at half maximum (FWHM, hereinafter referred to as “half width”) of the emission spectrum. Displays such as mobile and TV use a resonance structure in order to realize a high color gamut. If the path of light is designed so that resonance occurs at a specific wavelength (hereinafter referred to as'resonant filter'), the line width is narrowed and the color purity is increased (RH Jordan et al, Appl. Phys. Lett. 1996, v6, 1997 , Huajun Peng et al, Appl. Phys. Lett. 2005, v87, 173505). Since the half-width of the emission spectrum of organic materials is usually 30 to 100 nm (B. M. Krasovitskii et al. Organic luminescent materials, VCH publishers), a light-emitting material with a smaller half-width can expect an additional increase in efficiency in the resonant device.

When the spectrum of the guest material passes through the resonant filter, the relative intensity change at each wavelength is given by:

I(λ): The intensity of the wavelength transmitted through the resonance filter

I _Guest (λ): Intensity according to the wavelength of the emission spectrum of the guest material

R _filter (λ): Intensity ratio according to each wavelength of the resonance filter

The total area S of the guest emission spectrum transmitted through the resonance filter measured from the front side is as follows.

For example, when a resonance structure with a half width of 25 nm is applied (the more a resonance structure with a small half width is used, the higher the color purity is obtained).In the case of a guest material with the same quantum efficiency, the emission spectrum is larger than the half width of 25 nm. The more the material is, the smaller the S value and the overall efficiency decreases. That is, even if the two materials have the same photoluminescene (PL) quantum efficiency, a material having a narrow half-value width exhibits higher efficiency in an actual device.

Accordingly, development of a fluorescent material having a high PL quantum efficiency and a narrow half width is required.

1. US Patent Publication No. US 7233019 2. Korean Patent Publication No. 2006-0006760

1. Jang Hyuk Kwon et al, J. Mater. Chem. 2013, v1, 5008 2. Chihaya Adachi et al, Nature, 2012, v492, 236 3. R. H. Jordan et al, Appl. Phys. Lett. 1996, v6, 1997 4. Huajun Peng et al, Appl. Phys. Lett. 2005, v87, 173505

Accordingly, a problem to be solved by the present invention is to provide an organic light-emitting compound having a high photoluminescene (PL) quantum efficiency and a narrow light emission characteristic of a full width at half maximum (FWHM) of an emission spectrum.

In addition, by employing the organic light emitting compound according to the present invention to provide an organic light emitting device having excellent luminous efficiency and improved color purity.

The present invention provides an organic light emitting compound represented by the following [Chemical Formula 1], an organic thin film layer including the same, and an organic electroluminescent device including the organic thin film layer in order to solve the above problems.

[Formula 1]

Specific structural features and substituents of [Chemical Formula 1] will be described later.

The organic light-emitting compound according to the present invention increases the PL quantum efficiency of the emission spectrum and decreases the half-value width, and when it is used as a guest in the emission layer of an organic light-emitting device, the color purity can be improved due to an increase in efficiency and a decrease in the half-value width. In particular, when the resonance structure is applied, an additional efficiency improvement can be obtained compared to a material having a broad spectrum at half width.

1 is a conceptual diagram showing a multi-layered organic light emitting device according to an embodiment of the present invention.
2 is a spectrum comparison of Compound 1 according to the present invention and Comparative Compounds 1 and 2, FIG. 2A is a graph comparing relative quantum efficiency, and FIG. 2B is a graph in which the spectrum is overlapped based on the maximum emission wavelength for half-width comparison. to be.
3 is a graph of resonance filters for each wavelength in the case where Compound 1 and Comparative Compounds 1 and 2 according to the present invention have maximum resonance.
4 is a spectrum of Compound 1 and Comparative Compounds 1 and 2 according to the present invention to which a resonance filter is applied.
5 is a PL spectrum of compounds 2 and 3 according to the present invention.
6 is a PL spectrum of compounds 4, 5, 6, and 7 according to the present invention.
7 is a PL spectrum of compounds 8, 9, 10 and 11 according to the present invention.
8 is a PL spectrum of compounds 12, 13 and 14 according to the present invention.
9 is an EL spectrum (10 mA/cm 2) of Example 1 and Comparative Examples 1 to 2 according to the present invention.
10 is an EL spectrum (10 mA/cm 2) of Examples 2 to 6 according to the present invention.
11 is an EL spectrum (10 mA/cm 2) of Examples 7 to 10 according to the present invention.
12 is an EL spectrum (10 mA/cm 2) of Examples 11 to 14 according to the present invention.

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

The organic light-emitting compound according to the present invention is represented by the following [Chemical Formula 1], and is characterized by necessarily including a substituent at positions 2 and 6 of any one of the phenyl groups of the arylamine.

Due to these characteristics, the compound represented by [Chemical Formula 1] has higher PL quantum efficiency, and the organic electroluminescent device employing it has more improved luminous efficiency, and the half width of the emission spectrum is reduced so that it is a guest in the emission layer of the organic electroluminescent device. When used as a compound, it has excellent color purity due to an increase in luminous efficiency and a decrease in half width.

[Formula 1]

In the above [Formula 1],

A is a substituted or unsubstituted condensed aromatic cyclic group having 10 to 40 carbon atoms, and is naphthalene, phenanthrene, fluoranthene, anthracene, pyrene, perylene, coronene, chrysene, picene, diphenylanthracene, fluorene, tri It may be phenylene, rubicene, benzoanthracene, phenylanthracene, bisanthracene, dianthracenylbenzene or dibenzoanthracene, preferably anthracene, pyrene or chrysene.

X ₁ to X ₄ are the same as or different from each other, and each independently hydrogen, a halogen group, a cyano group, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, A substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted heterocycloalkyl group having 2 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 50 carbon atoms having O, N or S as a hetero atom, It may be selected from an alkyl group having 1 to 20 carbon atoms and an aryl group having 5 to 24 carbon atoms, preferably a halogen group, a cyano group, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted C 6 to 30 aryloxy group, a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted heterocycloalkyl group having 2 to 30 carbon atoms, a substituted or unsubstituted heterocycloalkyl group having O, N or S as a hetero atom, 3 to carbon atoms It may be selected from a 50 heteroaryl group, an alkyl group having 1 to 20 carbon atoms, and an aryl group having 5 to 24 carbon atoms.

More preferably, the compound of [Formula 1] according to the present invention is characterized in that it has a substituent at the position 2, 6 of any one of the phenyl groups of the arylamine, X ₁ and X ₂ Group and X ₃ and X ₄ One of the groups has a substituent at the same time, and the substituent is a halogen group, a cyano group, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted A cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted heterocycloalkyl group having 2 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 50 carbon atoms having O, N or S as a hetero atom, and 1 to 20 carbon atoms It may be selected from an alkyl group and an aryl group having 5 to 24 carbon atoms, more preferably an alkyl group having 1 to 20 carbon atoms.

R ₁ and R ₂ are the same as or different from each other, and each independently hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, a substituted or unsubstituted carbon number 2 to 30 alkynyl group, a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted heterocycloalkyl group having 2 to 30 carbon atoms, a substituted or unsubstituted cycloalkenyl group having 5 to 30 carbon atoms, a substituted or Unsubstituted C1-C30 alkoxy group, substituted or unsubstituted C6-C30 aryloxy group, substituted or unsubstituted C1-C30 alkylthioxy group, substituted or unsubstituted C5-C30 aryl Thioxy group, substituted or unsubstituted alkylamine group having 1 to 30 carbon atoms, substituted or unsubstituted arylamine group having 5 to 30 carbon atoms, substituted or unsubstituted aryl group having 5 to 50 carbon atoms, substituted or unsubstituted and heterogeneous Heteroaryl group having 3 to 50 carbon atoms having O, N or S as an atom, substituted or unsubstituted silyl group, substituted or unsubstituted germanium group, substituted or unsubstituted boron group, substituted or unsubstituted aluminum group, carbonyl group , Phosphoryl group, amino group, thiol group, cyano group, hydroxy group, nitro group, halogen group, selenium group, tellurium group, amide group, ether group and ester group.

m and n are each an integer of 0 to 3, p is an integer of 1 to 4, and when m, n and p are 2 or more, a plurality of R ₁ , R ₂ and *-[] may be the same or different from each other. have.

In addition, the plurality of adjacent substituents selected from R ₁ and R ₂ , X ₁ to X ₄ may be connected to each other to form an alicyclic hydrocarbon ring, a monocyclic or polycyclic aromatic hydrocarbon ring, and the formed alicyclic, aromatic Carbon atoms in the hydrocarbon ring are N, S, O, Se, Te, Po, NR _{10 ,} SiR ₁₁ R ₁₂ , GeR ₁₃ R ₁₄ , PR ₁₅ , PR ₁₆ (=O), C=O, S=O and BR ₁₇ It may be substituted with one or more substituted or unsubstituted heteroatoms selected from (R ₁₀ to R ₁₇ are the same as the definitions of R ₁ to R ₂ ).

As a preferred embodiment of [Chemical Formula 1] according to the present invention, when A is pyrene, it may be represented by the following [Chemical Formula 2], and the scope of the present invention is not limited thereto.

[Formula 2]

In the above [Formula 2],

R ₁ to R ₄ and Q ₁ to Q ₂ are the same as or different from each other, each independently the same as the definition of R ₁ to R ₂ in the [Formula 1], q is an integer of 0 to 4, m, n, r and s are each an integer of 0 to 3, and when q, m, n, r and s are 2 or more, a plurality of R ₁ to R ₄ and Q ₁ to Q ₂ are the same or different, respectively.

X ₁ to X ₈ are hydrogen, a halogen group, a cyano group, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted C 3 to 30 carbon number A cycloalkyl group, a substituted or unsubstituted heterocycloalkyl group having 2 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 50 carbon atoms having O, N or S as a hetero atom, an alkyl group having 1 to 20 carbon atoms, and 5 carbon atoms It may be selected from the aryl groups of to 24, except when all of X ₁ to X ₈ are hydrogen, preferably X ₁ to X ₈ Two or more of them are halogen groups, cyano groups, substituted or unsubstituted alkoxy groups having 1 to 30 carbon atoms, substituted or unsubstituted aryloxy groups having 6 to 30 carbon atoms, substituted or unsubstituted cycloalkyl groups having 3 to 30 carbon atoms , A substituted or unsubstituted heterocycloalkyl group having 2 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 50 carbon atoms having O, N or S as a hetero atom, an alkyl group having 1 to 20 carbon atoms, and a 5 to 24 carbon atoms It may be selected from aryl groups, and the rest may be hydrogen, and more preferably, 4 or more of X ₁ to X ₈ are halogen groups, cyano groups, substituted or unsubstituted alkoxy groups having 1 to 30 carbon atoms, substituted or An unsubstituted C6-C30 aryloxy group, a substituted or unsubstituted C3-C30 cycloalkyl group, a substituted or unsubstituted C2-C30 heterocycloalkyl group, a substituted or unsubstituted heterocycloalkyl group having O, N or S may be selected from a C3-C50 heteroaryl group, a C1-C20 alkyl group, and a C5-C24 aryl group, and the remainder may be hydrogen.

In addition, when X ₁ to X ₈ are not hydrogen, each of the phenyl ring positions 2 and 6 is simultaneously substituted with a substituent other than hydrogen, and X ₁ and X ₂ (first group), X ₃ and X ₄ (second Group) X ₅ and X ₆ (third group), X ₇ and X ₈ (fourth group) of at least one of each of X is a halogen group, a cyano group, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, A substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted heterocycloalkyl group having 2 to 30 carbon atoms, a substituted or unsubstituted heterocycloalkyl group having O, It may be selected from a C3-C50 heteroaryl group having N or S, a C1-C20 alkyl group, and a C5-C24 aryl group, and more preferably, each of two or more groups X is a halogen group, a cyano group , It may be selected from an alkyl group having 1 to 6 carbon atoms and an aryl group having 5 to 24 carbon atoms.

In addition, based on L---L', only one or more of the first group and the second group may have a substituent excluding hydrogen, and only one or more of the third group and the fourth group may have a substituent excluding hydrogen. have. Preferably, at least one of the first group and the second group, and at least one of the third group and the fourth group may each have a substituent excluding hydrogen.

In addition, the compound of [Formula 2] according to the present invention may be symmetric or asymmetric based on L---L' by R ₁ to R ₄ and Q ₁ to Q ₂ as well as X ₁ to X ₈ .

A, X ₁ to X ₈ , R ₁ to R ₄ , R ₁₀ described in the [Formula 1] to [Formula 2] To R ₁₇ and Q ₁ to Q ₂ are each independently deuterium, an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, an alkynyl group having 2 to 30 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, and 2 to 30 carbon atoms Heterocycloalkyl group, C5 to C30 cycloalkenyl group, C1 to C30 alkoxy group, C6 to C30 aryloxy group, C1 to C30 alkylthio group, C5 to C30 arylthioxy group, C5 1 to 30 alkylamine group, C 5 to C 30 arylamine group, C 5 to C 50 aryl group, C 3 to C 50 heteroaryl group having O, N or S as heteroatoms, silyl group, germanium group, boron Group, aluminum group, carbonyl group, phosphoryl group, amino group, thiol group, cyano group, hydroxy group, nitro group, halogen group, selenium group, tellurium group, amide group, ether group, and one or more selected from the group consisting of ester groups Substituted, the substituents may be bonded to each other to form a saturated or unsaturated ring, or may be attached or fused together in a pendant manner.

In addition, the range of carbon atoms in the present invention refers to the total number of carbon atoms constituting an alkyl group, an aryl group, and the like, as viewed as unsubstituted without considering the substituted part of the substituent. For a specific example, a phenyl group in which a butyl group is substituted in the para position corresponds to an aryl group having 6 carbon atoms substituted with a butyl group having 4 carbon atoms.

Specific examples of the alkyl group used in the present invention include methyl, ethyl, propyl, isopropyl, isobutyl, sec-butyl, tert-butyl, pentyl, iso-amyl, hexyl, heptyl, oxy And a butyl group, a stearyl group, a trichloromethyl group, a trifluoromethyl group, and the like. At least one hydrogen atom in the alkyl group is a deuterium atom, a halogen atom, a hydroxy group, a nitro group, a cyano group, a trifluoromethyl group, a silyl group (this In the case of "alkylsilyl group"), a substituted or unsubstituted amino group (-NH ₂ , -NH(R), -N(R')(R"), wherein R, R'and R" are each independently It is an alkyl group having 1 to 24 carbon atoms (referred to as "alkylamino group" in this case), an amidino group, a hydrazine group, a hydrazone group, a carboxyl group, a sulfonic acid group, a phosphoric acid group, an alkyl group having 1 to 24 carbon atoms, a halogenated group having 1 to 24 carbon atoms Alkyl group, an alkenyl group having 2 to 24 carbon atoms, an alkynyl group having 2 to 24 carbon atoms, a heteroalkyl group having 1 to 24 carbon atoms, an aryl group having 5 to 24 carbon atoms, an arylalkyl group having 6 to 24 carbon atoms, a heteroaryl group having 3 to 24 carbon atoms Or it may be substituted with a C3-C24 heteroarylalkyl group.

Specific examples of the alkoxy group used in the present invention include methoxy group, ethoxy group, propoxy group, isobutyloxy group, sec-butyloxy group, pentyloxy group, iso-amyloxy group, hexyloxy group, and the like. And may be substituted with the same substituent as in the case of the alkyl group.

Specific examples of the halogen group used in the present invention include fluorine (F), chlorine (Cl), and bromine (Br).

The aryloxy group used in the present invention refers to an -O- aryl radical, wherein the aryl group is as defined above, and specific examples include phenoxy, naphthoxy, anthracenyloxy, phenanthrenyloxy, fluorenyloxy, Indenyloxy, etc., and one or more hydrogen atoms contained in the aryloxy group may be further substituted.

Specific examples of the silyl group used in the present invention include trimethylsilyl, triethylsilyl, triphenylsilyl, trimethoxysilyl, dimethoxyphenylsilyl, diphenylmethylsilyl, silyl, diphenylvinylsilyl, methylcyclobutylsilyl, dimethyl Furylsilyl, etc. are mentioned.

The aryl group used in the present invention is an organic radical derived from an aromatic hydrocarbon by removing one hydrogen, and includes a single or fused ring system containing 5 to 7 members, preferably 5 or 6 members, and the aryl group If there is a substituent, it may be fused with neighboring substituents to further form a ring.

As a specific example of the aryl group, a phenyl group, o-biphenyl group, m-biphenyl group, p-biphenyl group, o-terphenyl group, m-terphenyl group, p-terphenyl group, naphthyl group, anthryl group, phenanthryl group , Pyrenyl group, indenyl, fluorenyl group, tetrahydronaphthyl group, peryleneyl, chrysenyl, naphthacenyl, fluoranthenyl, and the like.

In addition, the aryl group may also be further substituted with one or more substituents, and more specifically, at least one hydrogen atom in the aryl group is a deuterium atom, a halogen atom, a hydroxy group, a nitro group, a cyano group, a silyl group, an amino group (-NH ₂ , -NH(R), -N(R')(R"), R'and R" are each independently an alkyl group having 1 to 10 carbon atoms, in this case referred to as an "alkylamino group"), an amidino group, a hydrazine Group, hydrazone group, carboxyl group, sulfonic acid group, phosphoric acid group, alkyl group having 1 to 24 carbon atoms, halogenated alkyl group having 1 to 24 carbon atoms, alkenyl group having 1 to 24 carbon atoms, alkynyl group having 1 to 24 carbon atoms, hetero with 1 to 24 carbon atoms It may be substituted with an alkyl group, an aryl group having 6 to 24 carbon atoms, an arylalkyl group having 6 to 24 carbon atoms, a heteroaryl group having 2 to 24 carbon atoms, a heteroarylalkyl group having 2 to 24 carbon atoms, and the like.

The heteroaryl group used in the present invention may be any one selected from the following [Structural Formula 5] to [Structural Formula 14].

In the [Structural Formula 5] to [Structural Formula 14],

T ₁ to T ₁₂ are the same as or different from each other, and each independently, may be any one selected from C (R ₄₁ ), C (R ₄₂ ) (R ₄₃ ), N, N (R ₄₄ ), O and S And, T ₁ to T ₁₂ are not all carbon atoms at the same time, and R ₄₁ to R ₄₄ are the same as or different from each other, and each independently hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, substituted Or an unsubstituted C3-C30 cycloalkyl group, a substituted or unsubstituted C5-C30 aryl group, and a substituted or unsubstituted C2-C30 heteroaryl group having O, N, S or P as a hetero atom. Is selected.

In addition, the [Structural Formula 7] may include a compound represented by the following [Structural Formula 7-1] by a resonance structure according to the movement of electrons.

[Structural Formula 7-1]

In the [Structural Formula 7-1], T ₁ to T ₇ are the same as defined in [Structural Formula 5] to [Structural Formula 14].

According to a preferred embodiment of the present invention, the [Structural Formula 5] to [Structural Formula 14] may be selected from the following [Structural Formula 15].

[Structural Formula 15]

In [Structural Formula 15],

X is the same as the definition of R ₁ and R ₂ in the [Chemical Formula 1], m is an integer of 1 to 11, when m is 2 or more, a plurality of X are the same or different from each other, It may be connected with a substituent.

[Chemical Formula 1] according to the present invention may be more specifically selected from the following compounds, but the scope of [Chemical Formula 1] according to the present invention is not limited thereby.

In addition, the present invention relates to an organic electroluminescent device comprising an anode, a cathode, and one or more organic thin-film layers interposed between the anode and the cathode, wherein the organic light-emitting device according to the present invention represented by the above [Formula 1] It may contain at least one compound.

In addition, the organic thin film layer containing the organic light emitting compound of the present invention may include a hole injection layer, a hole transport layer, a functional layer having a hole injection function and a hole transport function at the same time, a light emitting layer, an electron transport layer, and an electron injection layer.

In this case, the organic thin film layer interposed between the anode and the cathode may include a light emitting layer, the light emitting layer is made of a host and a dopant, and the organic light emitting compound of the present invention may be used as a dopant of the light emitting layer.

Meanwhile, in the present invention, various host materials may be used for the light emitting layer in addition to the organic light emitting compound according to the present invention. When the light emitting layer includes a host and a dopant, the content of the dopant may be generally selected from about 0.01 to about 20 parts by weight based on about 100 parts by weight of the host.

The emission layer may further contain at least one host compound represented by the following [Chemical Formula 1A] in addition to the organic light emitting compound of [Chemical Formula 1] according to the present invention.

[Formula 1A]

In the above [Formula 1A],

X ₁ To X ₁₀ are the same as or different from each other, and each independently hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, a substituted or unsubstituted carbon number 3 to 30 Of a cycloalkyl group, a substituted or unsubstituted cycloalkenyl group having 5 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted C1-C30 alkylthioxy group, a substituted or unsubstituted C5-C30 arylthioxy group, a substituted or unsubstituted C1-C30 alkylamine group, a substituted or unsubstituted C5-C30 arylamine group , A substituted or unsubstituted aryl group having 5 to 50 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 50 carbon atoms having O, N or S as a hetero atom, a substituted or unsubstituted silicon group, a substituted or unsubstituted It is selected from a boron group, a substituted or unsubstituted silane group, a carbonyl group, a phosphoryl group, an amino group, a nitrile group, a hydroxy group, a nitro group, a halogen group, an amide group, and an ester group, and X ₁ Each of to X ₁₀ may form a condensed ring of an aliphatic, aromatic, aliphatic hetero or aromatic hetero with a group adjacent to each other.

[Chemical Formula 1A] may be specifically selected from compounds represented by the following [Chemical Formula 1Aa] to [Chemical Formula 1Ae].

[Formula 1Aa]

In the above [Formula 1Aa],

Ar ₇ and Ar ₈ are the same as or different from each other and are each independently selected from a substituted or unsubstituted aromatic linking group having 5 to 60 carbon atoms and a substituted or unsubstituted heteroaromatic linking group having 2 to 60 carbon atoms.

R ₂₁ to R ₃₀ are the same as or different from each other, and each independently the same as the definition in X ₁ to X ₁₀ , e and f are the same as or different from each other, and each independently an integer of 0 to 4.

[Formula 1Ab]

In the above [Formula 1Ab],

The Ar ₉ and Ar ₁₀ are the same as or different from each other and are each independently the same as the definition in Ar ₇ to Ar ₈ , and R ₃₁ to R ₄₀ are the same or different from each other and each independently the definition in the X ₁ to X ₁₀ And, g and h are the same as or different from each other, and are each independently an integer of 0 to 4.

Each of the substituents may be connected to an adjacent substituent to form a saturated or unsaturated cyclic structure, but in [Formula 1Ab], an independent substituent is bonded to each of the 9th and 10th half positions of the central anthracene. Groups that become symmetrical with respect to the phase are never combined.

[Formula 1Ac]

In the [Formula 1Ac],

Ar ₁₁ to Ar ₁₂ are the same as or different from each other, and each independently the same as defined in Ar ₇ to Ar ₈ , i and j are the same as or different from each other, and each independently an integer of 1 to 4.

One of the substituents of c1 to c4 is bonded to the *- moiety of [Formula 1Ac], and X is selected from -O-, -S-, -N(R ₅₀ )- and -N(R ₅₁ R ₅₂ ).

R ₄₁ To R ₄₉ are the same as or different from each other, and each independently the same as defined in X ₁ to X ₁₀ , k is an integer of 1 to 4, and when k is 2 or more, the two or more R ₄₂ to R ₄₉ are each The same or different.

[Formula 1Ad]

In [Chemical Formula 1Ad],

Ar ₁₃ and Ar ₁₄ are the same as or different from each other and are each independently the same as the definition in Ar ₇ to Ar ₈ , R ₅₃ and R ₅₄ are the same as the definition in X ₁ to X ₁₀ , and L and m are The same or different from each other, each independently an integer of 1 to 4, P and q are the same as or different from each other, and each independently an integer of 0 to 4.

[Formula 1Ae]

In the above [Formula 1Ae],

L ₂ is a single bond, -O-, -S-, -N(R ₅₅ )-, an alkylene group or an arylene group, and r is 2 or 3, and in this case, each of the [] may be the same or different from each other. And * parts are connected to each other.

Ar ₁₅ and Ar ₁₆ are the same as or different from each other and are each independently the same as the definition in Ar ₇ to Ar ₈ , and R ₅₆ to R ₅₉ are the same as or different from each other, and each independently the same as the definition in X ₁ to X ₁₀ And u is an integer of 1 to 4, v is an integer of 1 to 3, s and t are the same as or different from each other and are each independently an integer of 0 to 4, and s, t, u, and v are each independently In the case of 2 or more, Ar ₁₅ and Ar ₁₆ and R ₅₆ to R ₅₉ may be the same or different.

In addition, at least one or more host compounds represented by the following [Chemical Formula 1B] may be further contained.

[Formula 1B]

In the above [Formula 1B],

Ar ₁₇ to Ar ₂₀ are the same as or different from each other and are each independently selected from a substituted or unsubstituted aromatic linking group having 5 to 60 carbon atoms and a substituted or unsubstituted heteroaromatic linking group having 2 to 60 carbon atoms.

R ₆₀ to R ₆₃ are the same as or different from each other, and each independently hydrogen, deuterium, halogen atom, hydroxyl group, cyano group, nitro group, amino group, amidino group, hydrazine, hydrazone, carboxyl group or salt thereof, sulfonic acid group or its Salt, phosphoric acid or a salt thereof, a substituted or unsubstituted alkyl group having 1 to 60 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 60 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 60 carbon atoms, a substituted or unsubstituted A C1-C60 alkoxy group, a substituted or unsubstituted C3-C60 cycloalkyl group, a substituted or unsubstituted C5-C60 aryl group, a substituted or unsubstituted C5-C60 aryloxy group, a substituted or Unsubstituted C5-C60 arylthio group, substituted or unsubstituted C2-C60 heteroaryl group, -Si (R ₂₁ ) (R ₂₂ ) (R ₂₃ ) and -N (R ₂₄ ) (R ₂₅ ).

The R ₂₁ to R ₂₅ are the same as or different from each other, and each independently a substituted or unsubstituted alkyl group having 1 to 60 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 60 carbon atoms, and a substituted or unsubstituted C 2 to 60 carbon number. Alkynyl group, substituted or unsubstituted alkoxy group having 1 to 60 carbon atoms, substituted or unsubstituted cycloalkyl group having 3 to 60 carbon atoms, substituted or unsubstituted aryl group having 5 to 60 carbon atoms, substituted or unsubstituted 5 to 60 It is selected from an aryloxy group of, a substituted or unsubstituted arylthio group having 5 to 60 carbon atoms, and a substituted or unsubstituted heteroaryl group having 2 to 60 carbon atoms.

w and ww are the same as or different from each other, the x and xx are the same or different from each other, the w+ww and x+xx values are the same or different from each other, and are each independently an integer of 0 to 3, y and yy are They are the same as or different from each other, and z and zz are the same as or different from each other, and values of y+yy to z+zz are 2 or less, and are integers of 0 to 2, respectively.

In addition, it may further contain at least one or more host compounds represented by the following [Chemical Formula 1C].

[Formula 1C]

In the above [Formula 1C],

Ar ₂₁ to Ar ₂₄ are the same as or different from each other and are each independently selected from a substituted or unsubstituted aromatic linking group having 5 to 60 carbon atoms and a substituted or unsubstituted heteroaromatic linking group having 2 to 60 carbon atoms.

R ₆₄ to R ₆₇ are the same as or different from each other, and each independently hydrogen, deuterium, halogen atom, hydroxyl group, cyano group, nitro group, amino group, amidino group, hydrazine, hydrazone, carboxyl group or salt thereof, sulfonic acid group or its Salt, phosphoric acid or a salt thereof, a substituted or unsubstituted alkyl group having 1 to 60 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 60 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 60 carbon atoms, a substituted or unsubstituted A C1-C60 alkoxy group, a substituted or unsubstituted C3-C60 cycloalkyl group, a substituted or unsubstituted C5-C60 aryl group, a substituted or unsubstituted C5-C60 aryloxy group, a substituted or Unsubstituted C5-C60 arylthio group, substituted or unsubstituted C2-C60 heteroaryl group, -Si (R ₂₁ ) (R ₂₂ ) (R ₂₃ ) and -N (R ₂₄ ) (R ₂₅ ).

The R ₂₁ to R ₂₅ are the same as or different from each other, and each independently a substituted or unsubstituted alkyl group having 1 to 60 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 60 carbon atoms, and a substituted or unsubstituted C 2 to 60 carbon number. Alkynyl group, substituted or unsubstituted alkoxy group having 1 to 60 carbon atoms, substituted or unsubstituted cycloalkyl group having 3 to 60 carbon atoms, substituted or unsubstituted aryl group having 5 to 60 carbon atoms, substituted or unsubstituted 5 to 60 It is selected from an aryloxy group of, a substituted or unsubstituted arylthio group having 5 to 60 carbon atoms, and a substituted or unsubstituted heteroaryl group having 2 to 60 carbon atoms.

ee to hh are the same as or different from each other, and each independently an integer of 1 to 4, and ii to ll are the same or different from each other, and each independently an integer of 0 to 4.

In addition, it may further contain at least one or more host compounds represented by the following [Chemical Formula 1D].

[Formula 1D]

In the above [Formula 1D],

Ar ₂₅ to Ar ₂₇ are the same as or different from each other, and each independently selected from a substituted or unsubstituted aromatic linking group having 5 to 60 carbon atoms and a substituted or unsubstituted heteroaromatic linking group having 2 to 60 carbon atoms.

R ₆₈ to R ₇₃ are the same as or different from each other, and each independently hydrogen, deuterium, a halogen atom, a hydroxyl group, a cyano group, a nitro group, an amino group, an amidino group, a hydrazine, a hydrazone, a carboxyl group or a salt thereof, a sulfonic acid group or its Salt, phosphoric acid or a salt thereof, a substituted or unsubstituted alkyl group having 1 to 60 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 60 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 60 carbon atoms, a substituted or unsubstituted A C1-C60 alkoxy group, a substituted or unsubstituted C3-C60 cycloalkyl group, a substituted or unsubstituted C5-C60 aryl group, a substituted or unsubstituted C5-C60 aryloxy group, a substituted or Unsubstituted C5-C60 arylthio group, substituted or unsubstituted C2-C60 heteroaryl group, -Si (R ₂₁ ) (R ₂₂ ) (R ₂₃ ) and -N (R ₂₄ ) (R ₂₅ ).

The R ₂₁ to R ₂₅ are the same as or different from each other, and each independently a substituted or unsubstituted alkyl group having 1 to 60 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 60 carbon atoms, and a substituted or unsubstituted C 2 to 60 carbon number. Alkynyl group, substituted or unsubstituted alkoxy group having 1 to 60 carbon atoms, substituted or unsubstituted cycloalkyl group having 3 to 60 carbon atoms, substituted or unsubstituted aryl group having 5 to 60 carbon atoms, substituted or unsubstituted 5 to 60 It is selected from an aryloxy group of, a substituted or unsubstituted arylthio group having 5 to 60 carbon atoms, and a substituted or unsubstituted heteroaryl group having 2 to 60 carbon atoms.

Each of R ₂₁ to R ₂₅ may be connected to an adjacent substituent to form a saturated or unsaturated cyclic structure, and mm to ss are the same as or different from each other, and each independently an integer of 0 to 4.

Hereinafter, an embodiment of an organic light emitting diode according to the present invention will be described in more detail with reference to FIG. 1 below.

1 is a cross-sectional view showing the structure of an organic electroluminescent device of the present invention. The organic electroluminescent device according to the present invention includes an anode 20, a hole transport layer 40, an organic light emitting layer 50, an electron transport layer 60, and a cathode. Including 80, may further include a hole injection layer 30 and an electron injection layer 70 if necessary, it is also possible to further form an intermediate layer of one or two layers, and hole blocking layer Alternatively, an electron blocking layer may be further formed, and an organic layer having various functions may be further included according to characteristics of the device.

Referring to FIG. 1, an organic light emitting device of the present invention and a method of manufacturing the same will be described as follows.

First, an anode 20 is formed by coating a material for an anode electrode on the substrate 10. Here, as the substrate 10, a substrate used in a typical organic electroluminescent device is used, and an organic substrate or a transparent plastic substrate excellent in transparency, surface smoothness, ease of handling and waterproofness is preferable. In addition, as a material for the anode electrode, indium tin oxide (ITO), indium zinc oxide (IZO), tin oxide (SnO ₂ ), zinc oxide (ZnO), etc., which are transparent and have excellent conductivity, are used.

The hole injection layer 30 is formed by vacuum thermal evaporation or spin coating of a hole injection layer material on the anode 20 electrode. Then, the hole transport layer material is vacuum thermally evaporated or spin coated on the hole injection layer 30 to form the hole transport layer 40.

The hole injection layer material may be used without particular limitation as long as it is commonly used in the art, and as a specific example, 2-TNATA[4,4',4"-tris(2-naphthylphenyl-phenylamino)-triphenylamine] , NPD[N,N'-di(1-naphthyl)-N,N'-diphenylbenzidine)], TPD[N,N'-diphenyl-N,N'-bis(3-methylphenyl)-1,1'- biphenyl-4,4'-diamine], DNTPD[N,N'-diphenyl-N,N'-bis-[4-(phenyl-m-tolyl-amino)-phenyl]-biphenyl-4,4'-diamine ], etc. can be used.

In addition, as long as the material for the hole transport layer is not particularly limited as long as it is commonly used in the art, for example, N,N'-bis(3-methylphenyl)-N,N'-diphenyl-[1,1 -Biphenyl]-4,4'-diamine (TPD) or N,N'-di(naphthalen-1-yl)-N,N'-diphenylbenzidine (α-NPD), and the like can be used.

Subsequently, an organic light-emitting layer 50 is stacked on the hole transport layer 40, and a hole blocking layer (not shown) is selectively formed on the organic light-emitting layer 50 by vacuum deposition or spin coating to form a thin film. can do. The hole blocking layer plays a role of preventing such a problem by using a material having a very low HOMO (Highest Occupied Molecular Orbital) level because when holes pass through the organic light emitting layer and flow into the cathode, the life and efficiency of the device are reduced. . In this case, the hole blocking material to be used is not particularly limited, but must have an electron transport ability and an ionization potential higher than that of the light emitting compound, and representatively, BAlq, BCP, TPBI, etc. may be used.

As the material used for the hole blocking layer, any one selected from BAlq, BCP, Bphen, TPBI, NTAZ, BeBq ₂ , OXD-7, Liq, and [Formula 501] to [Formula 507] may be used, but limited thereto It does not become.

BAlq BCP Bphen

TPBI NTAZ BeBq ₂

OXD-7 Liq

[Formula 501] [Formula 502] [Formula 503]

[Formula 504] [Formula 505] [Formula 506]

[Chemical Formula 507]

After depositing the electron transport layer 60 on the hole blocking layer through a vacuum deposition method or a spin coating method, an electron injection layer 70 is formed, and a cathode-forming metal is vacuum-heated on the electron injection layer 70. The organic EL device is completed by vapor deposition to form the cathode 80 electrode. Here, the cathode-forming metal is lithium (Li), magnesium (Mg), aluminum (Al), aluminum-ridium (Al-Li), calcium (Ca), magnesium-indium (Mg-In), and magnesium-silver ( Mg-Ag) or the like may be used, and in order to obtain a top light emitting device, a transmissive cathode using ITO or IZO may be used.

As the material for the electron transport layer, a known electron transport material may be used as it has a function of stably transporting electrons injected from an electron injection electrode (Cathode). Examples of known electron transport materials include quinoline derivatives, in particular tris(8-quinolinolate)aluminum (Alq3), TAZ, Balq, beryllium bis(benzoquinolin-10-noate) (beryllium bis(benzoquinolin-10- olate: Bebq2), ADN, [Chemical Formula 401], [Chemical Formula 402], and oxadiazole derivatives such as PBD, BMD, BND, and the like may be used.

TAZ BAlq

[Compound 401] [Compound 402] BCP

In addition, as for the electron transport layer used in the present invention, an organometallic compound represented by the following [Chemical Formula C] may be used alone or in combination with the electron transport layer material.

[Formula C]

In [Chemical Formula C],

Y is a portion in which any one selected from C, N, O, and S is directly bonded to the M to form a single bond, and a portion in which any one selected from C, N, O, and S forms a coordination bond to the M. It includes, and is a ligand chelated by the single bond and the coordination bond. M is an alkali metal, alkaline earth metal, aluminum (Al) or boron (B) atom.

OA is a monovalent ligand capable of a single bond or coordination bond with M, wherein O is oxygen, and A is a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 5 to 50 carbon atoms, A substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 5 to 30 carbon atoms Any one selected from an alkenyl group and a substituted or unsubstituted heteroaryl group having 2 to 50 carbon atoms having O, N or S as a hetero atom.

In addition, when M is one metal selected from alkali metals, m=1, n=0, and when M is one metal selected from alkaline earth metals, m=1, n=1, or m =2, n=0, and when M is boron or aluminum, m=1 to 3, and n is any one of 0 to 2, satisfying m+n=3.

'Substituted' in the'substituted or unsubstituted' is deuterium, cyano group, halogen group, hydroxy group, nitro group, alkyl group, alkoxy group, alkylamino group, arylamino group, hetero arylamino group, alkylsilyl group, arylsilyl group, It means substituted with one or more substituents selected from the group consisting of aryloxy group, aryl group, heteroaryl group, germanium, phosphorus and boron.

In addition, each of Y is the same or different, and may be any one independently selected from the following [Structural Formula C1] to [Structural Formula C39], but is not limited thereto.

[Structural Formula C1] [Structural Formula C2] [Structural Formula C3]

[Structural Formula C4] [Structural Formula C5] [Structural Formula C6]

[Structural Formula C7] [Structural Formula C8] [Structural Formula C9] [Structural Formula C10]

[Structural Formula C11] [Structural Formula C12] [Structural Formula C13]

[Structural Formula C14] [Structural Formula C15] [Structural Formula C16]

[Structural Formula C17] [Structural Formula C18] [Structural Formula C19] [Structural Formula C20]

[Structural Formula C21] [Structural Formula C22] [Structural Formula C23]

[Structural Formula C24] [Structural Formula C25] [Structural Formula C26]

[Structural Formula C27] [Structural Formula C28] [Structural Formula C29] [Structural Formula C30]

[Structural Formula C31] [Structural Formula C32] [Structural Formula C33]

[Structural Formula C34] [Structural Formula C35] [Structural Formula C36]

[Structural Formula C37] [Structural Formula C38] [Structural Formula C39]

In the [Structural Formula C1] to [Structure C39]

R is the same as or different from each other, and each independently hydrogen, deuterium, halogen, cyano group, substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, substituted or unsubstituted aryl group having 6 to 30 carbon atoms, substituted or unsubstituted A heteroaryl group having 3 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, a substituted or Unsubstituted C1-C30 alkylamino group, substituted or unsubstituted C1-C30 alkylsilyl group, substituted or unsubstituted C6-C30 arylamino group, and substituted or unsubstituted C6-C30 arylsilyl It is selected from groups, and may be connected to an adjacent substituent with alkylene or alkenylene to form a spiro ring or a fused ring.

L is a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted C 5 to 30 carbon atom Selected from a heteroaryl group and a substituted or unsubstituted cycloalkyl group having 5 to 30 carbon atoms, wherein L is an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 40 carbon atoms, and 3 to 20 carbon atoms It is further substituted with one or more substituents selected from a heteroaryl group, a cyano group, a halogen group, deuterium and hydrogen, and may be connected to an adjacent substituent by alkylene or alkenylene to form a spiro ring or a fused ring.

In addition, one or more layers selected from the hole injection layer, the hole transport layer, the electron blocking layer, the light emitting layer, the hole blocking layer, the electron transport layer and the electron injection layer may be formed by a single molecule deposition method or a solution process, wherein the deposition method Means a method of forming a thin film by evaporating a material used as a material for forming each layer through heating in a vacuum or low pressure state, and the solution process is used as a material for forming each layer It refers to a method of forming a thin film through a method such as inkjet printing, roll-to-roll coating, screen printing, spray coating, dip coating, spin coating, and the like by mixing the material to be formed with a solvent.

In addition, the organic electroluminescent device according to the present invention may be used in a device selected from a flat panel display device, a flexible display device, a monochrome or white flat lighting device, and a single color or white flexible lighting device.

Hereinafter, the present invention will be described in more detail with reference to preferred embodiments. However, these examples are for explaining the present invention in more detail, and it will be apparent to those of ordinary skill in the art that the scope of the present invention is not limited thereto.

Synthesis example : Synthesis of organic light emitting compound according to the present invention

Synthesis Example 1: Synthesis of [Compound 1]

[Scheme 1-1] Synthesis of [Intermediate 1-a]

[Intermediate 1-a]

Bromobenzene (8.0 g, 0.050 mol), 2,6-dimethylaniline (6.2 g, 0.050 mol), palladium acetate (0.22 g, 1 mmol), 2,2'-bis(diphenylphosphino)-1- 1'-Binaphthyl (1.3 g, 2 mmol) and sodium turretoxide (12.2 g, 0.120 mol) were added to 100 mL of toluene and refluxed for 12 hours. After cooling to room temperature, extraction was performed with ethyl acetate, and separated by column chromatography to give [Intermediate 1-a] 7.3 g (73% yield).

[Scheme 1-2] Synthesis of [Compound 1]

[Compound 1]

1,6-dibromopyrene (4 g, 0.011 mol), [Intermediate 1-a] synthesized in [Scheme 1-1] (5.0 g, 0.025 mol), sodium tersher reviewoxide (5.3 g, 0.055 mol), palladium acetate (0.1 g, 0.44 mmol), and triteributylphosphine (0.36 g, 1.7 mmol) were added to 50 mL of toluene and refluxed for 24 hours. After lowering the temperature to room temperature, extraction was performed with ethyl acetate and then separated by column chromatography to give 3.1 g (yield 48%) of [Compound 1].

Synthesis Example 2: Synthesis of [Compound 2]

[Scheme 2-1] Synthesis of [Intermediate 2-a]

[Intermediate 2-a]

In the above [Scheme 1-1], 2,6-diethylaniline was used instead of 2,6-dimethylaniline, and [Intermediate 2-a] (yield 75%) was obtained by the same method.

[Scheme 2-2] Synthesis of [Compound 2]

[Compound 2]

Instead of [Intermediate 1-a] in [Scheme 1-2], [Intermediate 2-a] synthesized in [Scheme 2-1] was used, and [Compound 2] (yield 63%) was obtained by the same method.

Synthesis Example 3: Synthesis of [Compound 3]

[Scheme 3-1] Synthesis of [Intermediate 3-a]

[Intermediate 3-a]

In the above [Scheme 1-1], 2,6-diisopropylaniline was used instead of 2,6-dimethylaniline, and [Intermediate 3-a] (yield 75%) was obtained in the same manner.

[Scheme 3-2] Synthesis of [Compound 3]

[Compound 3]

[Intermediate 3-a] synthesized in [Scheme 3-1] was used instead of [Intermediate 1-a] in [Scheme 1-2], and [Compound 3] (yield 56%) was obtained by the same method.

Synthesis Example 4: Synthesis of [Compound 4]

[Scheme 4-1] Synthesis of [Intermediate 4-a]

[Intermediate 4-a]

In a nitrogen atmosphere, zinc chloride (42.5 g, 0.312 mol) and 500 mL of THF were added, cooled to 0 ℃, and 2 M isopropyl magnesium chloride (156 mL, 0.312 mol) was slowly added dropwise. 1,6-dibromopyrene (37.5 g, 0.104 mol) and 1,1'-bis-(diphenylphosphino)ferrocene palladium dichloride (1.12 g, 1.56 mmol) were added and then refluxed. After lowering the temperature to room temperature, the reaction solution was concentrated, dissolved in ethyl acetate, washed with an aqueous hydrochloric acid solution, and then the organic layer was extracted and separated by column chromatography to give 23.8 g (yield 80%) of [Intermediate 5-d].

[Scheme 4-2] Synthesis of [Intermediate 4-b]

[Intermediate 4-b]

[Intermediate 4-a] (23.8 g, 0.083 mol) is dissolved in 500 mL of dichlorobenzene, bromine (27.8 g, 0.174 mol) is dissolved in 50 mL of dichlorobenzene, and then slowly added dropwise. After 2 hours, the reaction solution was poured into 1 L of methanol and filtered to obtain [Intermediate 4-b] 22 g (yield 60%).

[Scheme 4-3] Synthesis of [Compound 4]

[Compound 4]

Instead of 1,6-dibromopyrene in [Scheme 1-2], [Intermediate 4-b] synthesized in [Scheme 2-2] was used, and [Compound 4] (72% yield) was prepared in the same manner. Got it.

Synthesis Example 5: Synthesis of [Compound 5]

[Scheme 5-1] Synthesis of [Intermediate 5-a]

[Intermediate 5-a]

After dissolving 2-fluoroaniline (10.0 g, 0.899 mol) in 80 mL of acetic acid, bromine (30 g, 0.188 mol) is dissolved in 20 mL of acetic acid and slowly added dropwise. After 2 hours, the reaction solution was washed with an aqueous sodium thiosulfate solution, extracted with ethyl acetate, and separated by column chromatography to give 20.5 g (yield 85%) of [Intermediate 5-a].

[Scheme 5-2] Synthesis of [Intermediate 5-b]

[Intermediate 5-b]

[Intermediate 5-a] (10.0 g, 0.037 mol), phenylboronic acid (11.3 g, 0.092 mol), tetrakis (triphenylphosphine) palladium (0.85 g, 0.74 mmol), potassium carbonate (15.4 g, 0.111 mol) was added to 100 mL of toluene and 50 mL of distilled water and refluxed for 12 hours. After cooling to room temperature, extraction with ethyl acetate, and separation by column chromatography to give [Intermediate 5-b] 7.8 g (80% yield).

[Scheme 5-3] Synthesis of [Intermediate 5-c]

[Intermediate 5-c]

[Intermediate 5-b] was used instead of 2,6-dimethylaniline in [Scheme 1-1], and [Intermediate 5-c] (yield 80%) was obtained by the same method.

[Scheme 5-4] Synthesis of [Compound 5]

[Compound 5]

[Intermediate 4-b] synthesized in [Scheme 4-2] was used instead of dibromopyrene in [Scheme 1-2], and synthesized in [Scheme 5-3] instead of [Intermediate 1-a] [Compound 5] (68% yield) was obtained by the same method using one [Intermediate 5-c].

Synthesis Example 6: Synthesis of [Compound 6]

[Scheme 6-1] Synthesis of [Intermediate 6-a]

[Intermediate 6-a]

In the above [Scheme 1-1], 1-bromo-4-trimethylsilyl benzene was used instead of bromobenzene, and [Intermediate 6-a] (yield 78%) was obtained in the same manner.

[Scheme 6-2] Synthesis of [Compound 6]

[Compound 6]

Instead of [Intermediate 1-a] in [Scheme 1-2], [Intermediate 6-a] synthesized in [Scheme 6-1] was used, and [Compound 6] (70% yield) was obtained by the same method.

Synthesis Example 7: Synthesis of [Compound 7]

[Scheme 7-1] Synthesis of [Intermediate 7-a]

[Intermediate 7-a]

In the above [Reaction Scheme 1-1], 1-bromo-4-tertiarybenzene was used instead of bromobenzene, and [Intermediate 7-a] (yield 77%) was obtained in the same manner.

[Scheme 7-2] Synthesis of [Compound 7]

[Compound 7]

[Intermediate 7-a] synthesized in [Scheme 7-1] was used instead of [Intermediate 1-a] in [Scheme 1-2], and [Compound 7] (75% yield) was obtained in the same manner.

Synthesis Example 8: Synthesis of [Compound 8]

[Scheme 8-1] Synthesis of [Intermediate 8-a]

[Intermediate 8-a]

1-tertiary-butyl-3,5-dimethylbenzene (40 g, 0.246 mol) was added to 60 mL of acetic acid and stirred. A 1:1 mixture of 40 mL of sulfuric acid and nitric acid was added dropwise over 20 minutes. After raising the temperature to 45 °C, it was slowly cooled to room temperature. The reaction was poured into water and extracted with ethyl acetate. The organic layer was washed 3 times with 1.0 M aqueous potassium hydroxide solution. The organic layer was condensed and crystals were formed with hexane to obtain [Intermediate 8-a] 30 g (59% yield).

[Scheme 8-2] Synthesis of [Intermediate 8-b]

[Intermediate 8-b]

[Intermediate 8-a] (15 g, 0.072 mol) and tin chloride (41 g, 0.216 mol) were added to 300 mL of ethanol and refluxed for 24 hours. After cooling to room temperature, potassium hydroxide aqueous solution was added and stirred. After extraction with ethyl acetate and separation by column chromatography, [Intermediate 8-b] 7g (yield 58%) was obtained.

[Scheme 8-3] Synthesis of [Intermediate 8-c]

[Intermediate 8-c]

1,3-dibromo-5-fluorobenzene (10 g, 0.039 mol), 1-naphthylboronic acid (6.7 g, 0.039 mol), tetrakis (triphenylphosphine) palladium (0.9 g, 0.78 mmol) ), potassium carbonate (16.2 g, 0.117 mol) was added to 150 mL of toluene and 50 mL of distilled water and refluxed for 12 hours. After cooling to room temperature, extraction with ethyl acetate, and separation by column chromatography to give 8.5 g (yield 72%) of [Intermediate 8-c].

[Scheme 8-4] Synthesis of [Intermediate 8-d]

[Intermediate 8-d]

[Intermediate 8-b] synthesized in [Scheme 11-2] was used instead of 2,6-dimethylaniline in [Scheme 1-1], and [Intermediate 8-b] synthesized in [Scheme 8-3] was used instead of bromobenzene. [Intermediate 8-d] (yield 74%) was obtained in the same manner using Intermediate 8-c].

[Scheme 8-5] Synthesis of [Compound 8]

[Compound 8]

[Intermediate 8-d] synthesized in [Scheme 8-4] was used instead of [Intermediate 1-a] in [Scheme 1-2], and [Compound 8] (yield 73%) was obtained by the same method.

Synthesis Example 9: Synthesis of [Compound 9]

[Scheme 9-1] Synthesis of [Intermediate 9-a]

[Intermediate 9-a]

4-trimethylsilyl-2,6-dimethylaniline (4 g, 0.02 mol), bromobenzene (3.2 g, 0.02 mol), palladium acetate (0.08 g, 0.4 mmol), tri-tertiary-butylphosphine (0.16 g, 0.8mmol), sodium tertiarybutoxide (5.8 g, 0.06 mol) was added to 60 mL of toluene and refluxed for 4 hours. After cooling to room temperature, extraction with ethyl acetate and separation by column chromatography to give [Intermediate 9-a] 3.8 g (74% yield).

[Scheme 9-2] Synthesis of [Compound 9]

[Compound 9]

1,6-dibromopyrene (2.2 g, 0.006 mol), [Intermediate 9-a] (3.8 g, 0.014 mol), sodium tersher reviewoxide (4.03 g, 0.042 mol), palladium acetate (0.06 g, 0.28 mmol) ), tri-tertiary-butylphosphine (0.056 g, 0.56 mmol) was added to 40 mL of toluene and refluxed for 4 hours. After lowering the temperature to room temperature, extraction was performed with ethyl acetate and then separated by column chromatography to give 2.7 g (yield 61%) of [Compound 9].

Synthesis Example 10: Synthesis of [Compound 10]

[Scheme 10-1] Synthesis of [Intermediate 10-a]

[Intermediate 10-a]

Dibenzofuran (35.0 g, 0.208 mol) was dissolved in 400 mL of toluene in a nitrogen atmosphere, cooled to -78 °C, and then 143 mL (0.228 mol) of 1.6 M normal butyl lithium was slowly added dropwise. After 2 hours, the temperature was raised to room temperature and stirred for 6 hours. After cooling to -78 ℃, iodine (58 g, 0.228 mol) was dissolved in 60 mL of THF, added dropwise over 1 hour, and the temperature was raised to room temperature. After extraction with ethyl acetate and separation by column chromatography, 45.8 g (75% yield) of [Compound 10-a] was obtained.

[Scheme 10-2] Synthesis of [Intermediate 10-b]

[Intermediate 10-b]

In the above [Scheme 1-1], 4-iododibenzofuran was used instead of bromobenzene, and [Intermediate 10-b] (yield 80%) was obtained by the same method.

[Scheme 10-3] Synthesis of [Compound 10]

[Compound 10]

[Intermediate 4-b] synthesized in [Scheme 4-2] was used instead of dibromopyrene in [Scheme 1-2], and synthesized in [Scheme 13-2] instead of [Intermediate 1-a] [Compound 10] (yield 52%) was obtained by the same method using one [Intermediate 11-b].

Synthesis Example: Synthesis of [Compound 11]

[Scheme 11-1] Synthesis of [Intermediate 11-a]

[Intermediate 11-a]

Dissolve 2-dimethylnitrobenzene (25 g, 0.165 mol), iron (III) bromide (0.97 g, 3.3 mmol), and iron (2.5 g, 44 mmol) in 75 mL of dichloromethane. Bromine (29 g, 0.181 mol) is dissolved in 50 mL of dichloromethane and slowly added dropwise. After 30 minutes, the reaction solution was washed with an aqueous sodium sulfite (19 g, 0.181 mol) aqueous solution, and the organic layer was extracted, moisture was removed with magnesium sulfate, and then concentrated to give 37.8 g (yield 99%) of [Intermediate 11-a].

[Scheme 11-2] Synthesis of [Intermediate 11-b]

[Intermediate 11-b]

[Intermediate 11-a] (37.8 g, 0.164 mol), tin chloride (93.5 g, 0.492 mol), 500 mL of ethanol, 10 mL of hydrochloric acid, and 10 mL of water were added and then refluxed. After 12 hours, the reaction solution was basified with an aqueous sodium hydroxide solution, and the organic layer was separated by column chromatography to obtain 14 g (yield 42%) of [Intermediate 11-b].

[Scheme 11-3] Synthesis of [Intermediate 11-c]

[Intermediate 11-c]

[Intermediate 11-b] was used instead of 2,6-dimethylaniline in [Scheme 1-1], and [Intermediate 11-c] (yield 32%) was obtained in the same manner.

[Scheme 11-4] Synthesis of [Intermediate 11-d]

[Intermediate 11-d]

Benzooxazole (2.7 g, 0.022 mol), [Intermediate 12-c] (6.1 g, 0.022 mol), palladium acetate (0.3 g, 1.1 mmol), tertiary butylphosphine (1.2 mL, 2.2 mmol), cesium carbonate (7.5 g, 0.022 mol) and cuperbromide (0.7 g, 4.5 mmol) were added to 60 mL of dimethylformamide and refluxed for 3 hours. After cooling to room temperature, extraction was performed with ethyl acetate, and separated by column chromatography to give 3.3 g (yield 47%) of [Intermediate 11-d].

[Scheme 11-5] Synthesis of [Compound 11]

[Compound 11]

[Intermediate 4-b] synthesized in [Scheme 4-2] was used instead of dibromopyrene in [Scheme 1-2], and synthesized in [Scheme 12-4] instead of [Intermediate 1-a] [Compound 11] (yield 80%) was obtained by the same method using one [Intermediate 12-d].

Synthesis Example 12: Synthesis of [Compound 12]

[Scheme 12-1] Synthesis of [Intermediate 12-a]

[Intermediate 12-a]

4-triethylsilyl-2,6-dimethylaniline (4 g, 0.02 mol), bromobenzene (3.2 g, 0.02 mol), palladium acetate (0.08 g, 0.4 mmol), tri-tertiary-butylphosphine (0.16 g, 0.8mmol), sodium tertiarybutoxide (5.8 g, 0.06 mol) was added to 60 mL of toluene and refluxed for 4 hours. After cooling to room temperature, extraction was performed with ethyl acetate, and then separated by column chromatography to obtain 3.6 g of [Intermediate 12-a] (71% yield).

[Scheme 12-2] Synthesis of [Compound 12]

[Compound 12]

1,6-dibromopyrene (2.3 g, 0.006 mol), [Intermediate 12-a] (4 g, 0.013 mol), sodium turretoxide (3.7 g, 0.039 mol), palladium acetate (0.06 g, 0.25 mmol) ), tri-tertiary-butylphosphine (0.1 g, 0.52 mmol) was added to 40 mL of toluene and refluxed for 4 hours. After lowering the temperature to room temperature, extraction was performed with ethyl acetate and then separated by column chromatography to give 2.8 g (62% yield) of [Compound 9].

Synthesis Example 13: Synthesis of [Compound 13]

[Scheme 13-1] Synthesis of [Intermediate 13-a]

[Intermediate 13-a]

4-dimethylisopropylsilyl-2,6-dimethylaniline (4 g, 0.018 mol), bromobenzene (2.8 g, 0.018 mol), palladium acetate (0.08 g, 0.36 mmol), tri-tertiary-butylphosphine (0.14 g, 0.72 mmol), sodium tertiarybutoxide (5.2 g, 0.054 mol) was added to 60 mL of toluene and refluxed for 4 hours. After cooling to room temperature, extraction with ethyl acetate and separation by column chromatography to give [Intermediate 13-a] 3.0 g (yield 55%).

[Scheme 13-2] Synthesis of [Compound 13]

[Compound 13]

1,6-dibromopyrene (1.8 g, 0.005 mol), [intermediate 13-a] (3 g, 0.01 mol), sodium turretoxide (2.9 g, 0.03 mol), palladium acetate (0.05 g, 0.2 mmol) ), tri-tertiary-butylphosphine (0.08 g, 0.4 mmol) was added to 40 mL of toluene and refluxed for 4 hours. After lowering the temperature to room temperature, extraction was performed with ethyl acetate and then separated by column chromatography to obtain 2.3 g (yield 58%) of [Compound 9].

Synthesis Example 14: Synthesis of [Compound 14]

[Scheme 14-1] Synthesis of [Intermediate 14-a]

[Intermediate 14-a]

[Intermediate 8-b] (10 g, 0.056 mol), bromobenzene (8.8 g, 0.056 mol), palladium acetate (0.24 g, 1.12 mmol), tri-tertiary-butylphosphine (0.45 g, 2.24 mmol) , Sodium tertiary butoxide (16.0 g, 0.168 mol) was added to 150 mL of toluene and refluxed for 4 hours. After cooling to room temperature, extraction with ethyl acetate and separation by column chromatography to give [Intermediate 13-a] 10.2 g (72% yield).

[Scheme 14-2] Synthesis of [Intermediate 14-b]

[Intermediate 14-b]

1,6-dibromopyrene (14 g, 0.039 mol), [Intermediate 14-a] (10 g, 0.039 mol), sodium tersher reviewoxide (2.9 g, 0.12 mol), palladium acetate (0.17 g, 0.78 mmol) ), tri-tertiary-butylphosphine (0.31 g, 1.56 mmol) was added to 200 mL of toluene and refluxed for 4 hours. After lowering the temperature to room temperature, extraction was performed with ethyl acetate and then separated by column chromatography to give 5.4 g (yield 26%) of [Intermediate 14-b].

[Scheme 14-3] Synthesis of [Compound 14]

[Compound 14]

[Intermediate 14-b] (5.4 g, 0.01 mol), [Intermediate 9-a] (2.7 g, 0.01 mol), sodium turretoxide (2.9 g, 0.03 mol), palladium acetate (0.05 g, 0.2 mmol) , Tri-tertiary-butylphosphine (0.08 g, 0.4 mmol) was added to 80 mL of toluene and refluxed for 4 hours. After lowering the temperature to room temperature, extraction was performed with ethyl acetate and then separated by column chromatography to give 3.46 g (yield 48%) of [Compound 14].

Experimental example One

The pyrene derivative compound according to the present invention is characterized in that it has a characteristic structure capable of effectively limiting the three-dimensional vibrational freedom of the molecule.

Molecules in the excited state are transferred to the ground state by light and heat, and the PL quantum efficiency decreases as the rate constant related to the vibration of the molecule increases, and the half-width of the molecule increases as the degree of freedom of vibration increases. Therefore, in order to have a high PL quantum efficiency and a narrow half width, it is necessary to effectively limit the three-dimensional vibration freedom of the molecule.

[Compound 1]

In [Compound 1], the amine bound to pyrene is an essential component to realize blue color, and pyrene has a stable skeleton and a rigid property, so it does not significantly affect the change in half width. However, since the phenyl group bonded to the amine has a relatively high degree of freedom of vibration, limiting this is effective in limiting the three-dimensional degree of freedom of vibration of the molecule.

Specifically, as in [Compound 1] according to the present invention, a matyl group was simultaneously introduced at positions 2 and 6 of the phenyl group, and the effects are shown in Table 1 and FIG. 2 below.

The PL measurement conditions of FIGS. 2A and 2B are as follows.

Solvent: toluene (anhydrous), temperature: 25 ℃, excitation wavelength: 350 ㎚, relative quantum efficiency reference substance: diphenyl anthracene (φ _L = 75%)

[Comparative Compound 1] is a pyrene derivative compound having an unsubstituted phenyl group, and [Comparative Compound 2] is a pyrene derivative compound having a trimethylsilyl group at the 4th position of the phenyl group, and their half widths are all 34 nm. However, [Compound 1] according to the present invention has improved efficiency of 15.4% and reduced half width of 8 nm compared to the comparative compound in terms of PL quantum efficiency and half width reduction.

[Comparative compound 1] [Comparative compound 2]

In the following [Table 1], the PL properties for [Compound 1], [Comparative Compound 1] and [Comparative Compound 2] according to the present invention are shown. Relative quantum efficiency is the relative quantum efficiency (toluene, excitation 350 ㎚) measured based on diphenylanthracene.

division Comparative compound 1 Comparative compound 2 Compound 1 Spectral half width (nm) 34 34 26 Maximum emission wavelength (nm) 457 460 454 Relative quantum efficiency 0.84 0.89 0.97

Measurement conditions for the relative quantum efficiency and wavelength in [Table 1] are as follows.

Solvent: toluene (anhydrous), temperature: 25 ℃, excitation wavelength: 350 ㎚, relative quantum efficiency reference substance: diphenyl anthracene (φ _L = 75%)

It can be confirmed that [Compound 1] according to the present invention has a limited degree of freedom due to the influence of the methyl group substituted at the 2nd and 6th positions of the phenyl group by changing the emission wavelength according to the substituent.

In general, when an alkyl group is introduced into the phenyl group of 1,8-diphenylaminopyrene, the HOMO energy level is raised to cause a long wavelength shift, the effect of which is greater than the trimethylsilyl group. In the case of [Comparative Compound 2] in which four trimethylsilyl groups were introduced into [Comparative Compound 1], it can be seen that the emission wavelength shifts from 457 nm to 460 nm. On the other hand, when t-butyl group is introduced at the same position, it shows a long wavelength shift of 468 ㎚. However, in the case of [Compound 1] according to the present invention, although a methyl group was introduced at positions 2 and 6, the wavelength shifted to 454 nm by 3 nm. This is due to the fact that the conjugation effect of the entire molecule is reduced due to the distortion of the substituted aryl group, and quantum calculation is performed through structure optimization (B3LYP DFT 6-41G* by Spartan '10) as in Experimental Example 2 below. ) And examine the wave function distribution of the HOMO.

Experimental example 2

In order to find out how the improvement of the efficiency of the compound of [Compound 1] according to the present invention and the reduction of the half width affect the actual resonance structure, the PL spectra of [Comparative Compound 1], [Comparative Compound 2] and [Compound 1] The efficiency change was calculated by applying to a resonance filter having a half width of 25 nm for each wavelength.

[Comparative compound 1] [Compound 1]

3 and 4 show the spectrum of the resonant filter for each wavelength and the compound to which the resonant filter is applied, and Table 2 shows the results of calculating the relative efficiency change and color coordinate change before and after applying the resonance filter.

division Comparative compound 1 Comparative compound 2 Compound 1 PL Relative quantum efficiency 0.84 0.89 0.97 CIE (x, y) 0.134, 0.094 0.130, 0.109 0.137, 0.080 Resonance application S in Equation 2 47.152 50.257 56.214 CIE (x, y) 0.142, 0.042 0.138, 0.049 0.145, 0.035

The measurement conditions for the relative quantum efficiency and wavelength in [Table 2] are as follows.

Solvent: toluene (anhydrous), temperature: 25 ℃, excitation wavelength: 350 ㎚, relative quantum efficiency reference substance: diphenyl anthracene (φ _L = 75%)

As shown in [Table 2], when considering only the PL quantum efficiency of a material, [Compound 1] according to the present invention improved the efficiency by 15% based on [Comparative Compound 1], but when the resonance structure was applied, about 19 % Efficiency improvement occurred, and based on [Comparative Compound 2], it can be seen that from 8.9% efficiency improvement before resonance application to 11.8% efficiency improvement after resonance structure application.

Experimental example 3

In the case of [Compound 2] to [Compound 14] according to the present invention, it was confirmed that the efficiency and half width were improved by limiting the degree of freedom of vibration of the molecule.

The PL spectra of [Compound 2] to [Compound 3] are shown in FIG. 5, and the PL characteristics of [Compound 1] to [Compound 3] are shown in Table 3 below.

PL measurement conditions of FIGS. 5 to 7 are as follows.

Solvent: toluene (anhydrous), temperature: 25 ℃, excitation wavelength: 350 ㎚, relative quantum efficiency reference substance: diphenyl anthracene (φ _L = 75%)

division Compound 1 Compound 2 Compound 3 Spectral half width (nm) 26 25.5 23.5 Maximum emission wavelength (nm) 454 457 458

The PL spectra of [Compound 4] to [Compound 7] in FIG. 6, the PL spectrum of [Compound 8] to [Compound 11] in FIG. 7, and the PL spectrum of [Compound 12] to [Compound 14] in FIG. It is shown in the following [Table 4] for the PL characteristics of [Compound 4] to [Compound 14].

Classification / compound 4 5 6 7 8 9 10 11 12 13 14 Spectral half width (nm) 27 29 27 28 29 26 29 27 27 28 28 Maximum emission wavelength (nm) 460 458 456 461 455 456 457 457 457 457 457

As shown in [Table 3] to [Table 4] and Figs. 5 to 8, it was confirmed that the half width is reduced by limiting the three-dimensional vibration freedom of the molecule in the same manner in the case of [Compound 2] to [Compound 11] .

Examples 1 to 14

After implementing the organic electroluminescent device employing the organic light-emitting compound of [Chemical Formula 1] according to the present invention having the above-described PL spectral characteristics, light emission characteristics were confirmed.

Example : Organic light emitting device Produce

Example 1

After loading ITO glass (active area: 2 mm × 2 mm) into a vacuum chamber (5 × 10 ^-7 torr) after UV Ozone treatment, DNTPD was 700 Å as a hole injection layer and α-NPD (300 Å) as a hole transport layer. ), α-ADN and [Compound 1] as a light emitting layer were co-deposited so that (3 wt%) was 200 Å, and [Chemical Formula E-1] and [Formula E-2] as an electron transfer layer were 300 at a ratio of 1:1. Å, [Chemical Formula E-1] was stacked by 5 Å as an electron injection layer and 1,000 Å of Al was deposited as a cathode to fabricate a device. After sealing in a glove box, the characteristics of the device were measured at a current density of 10 mA/cm 2. It is shown in [Table 5].

[Formula E-1]

[Formula E-2]

Examples 2 to 14

Except for using [Compound 2] to [Compound 14] instead of [Compound 1], which is the dopant compound of Example 1, it was prepared in the same manner as in Example 1, and the characteristics of the device were measured, and the following [Table 5] ].

Comparative Examples 1 to 2

Except for using [Comparative Compound 1] to [Comparative Compound 2] in place of [Compound 1], which is the dopant compound of Example 1, it was prepared in the same manner as in Example 1, and the characteristics of the device were measured and the following [ It is shown in Table 5].

In addition, EL spectra (10 mA/cm 2) of Examples 1 to 14 and Comparative Examples 1 to 2 are shown in FIGS. 9 to 12 below.

The measurement equipment was Spectroradiometer CS1000A (Konicha Minolta sensing Inc.).

division Q.E FWHM (nm) V Cd/A lm/W Cd/㎡ CIEx CIEy λ _max (nm) Comparative compound 1 9.53 36 3.90 8.38 6.74 837.6 0.130 0.124 461 Comparative compound 2 9.64 36 3.80 8.65 7.15 864.6 0.131 0.128 462 Compound 1 10.05 27 3.71 8.25 6.99 825.0 0.133 0.111 458 Compound 2 10.05 26 3.92 8.45 6.78 845.3 0.132 0.116 459 Compound 3 9.64 24 3.80 8.61 7.11 861.0 0.133 0.125 460 Compound 4 10.59 28 3.83 9.96 8.16 996.2 0.130 0.137 462 Compound 5 10.38 31 3.84 9.50 7.77 950.4 0.131 0.132 462 Compound 6 11.06 26 3.68 9.01 7.69 900.8 0.133 0.111 459 Compound 7 10.95 28 3.91 10.60 8.52 1060.0 0.128 0.144 463 Compound 8 10.85 31 3.80 8.20 6.79 819.9 0.136 0.099 456 Compound 9 10.09 27 3.81 8.57 7.07 856.6 0.132 0.117 459 Compound 10 10.20 32 3.71 8.88 7.53 888.4 0.133 0.121 459 Compound 11 10.18 27 3.83 9.27 7.60 927.2 0.134 0.128 461 Compound 12 10.77 27 3.97 9.04 7.16 904.2 0.132 0.116 459 Compound 13 11.08 27 3.85 9.30 7.59 929.9 0.133 0.114 459 Compound 14 11.10 28 3.84 9.45 7.74 945.2 0.132 0.118 460

As described above, the organic light-emitting compound according to the present invention is characterized by limiting the three-dimensional freedom of the aryl group of the amine substituted with pyrene, thereby further increasing the efficiency of the organic light-emitting device and reducing the half-width. Through this, the overall efficiency can be improved in the resonance structure.

In particular, the organic light-emitting compound according to the present invention increases the PL quantum efficiency of the emission spectrum and decreases the half value width, and when it is used as a guest in the emission layer of an organic light emitting device, the color purity can be improved due to an increase in efficiency and a decrease in the half value width . In particular, when the resonance structure is applied, an additional efficiency improvement can be obtained compared to a material having a broad spectrum at half width.

Claims (10)

Organic light-emitting compound represented by the following [Formula 2]:
[Formula 2]

[Formula 2] is symmetrical or asymmetric based on L---L',
X ₁ to X ₂ and X ₅ to X ₆ are the same as or different from each other, and each independently a halogen group, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms and a substituted Or it is selected from unsubstituted C6 to C30 aryl group,
All of X ₃ to X ₄ and X ₇ to X ₈ are each independently linked to the adjacent plurality of R ₂ and R ₄ to form an alicyclic hydrocarbon ring, a monocyclic or polycyclic aromatic hydrocarbon ring. Hydrogen or deuterium (the carbon atom of the formed alicyclic, aromatic hydrocarbon ring may be substituted with any one heteroatom selected from S, O and Se),
Q ₁ to Q ₂ are the same or different from each other, and each independently hydrogen, deuterium, a cyano group, a halogen group, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, A substituted or unsubstituted heterocycloalkyl group having 2 to 30 carbon atoms, a substituted or unsubstituted cycloalkenyl group having 5 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms and a substituted or unsubstituted heteroatom O, It is selected from a heteroaryl group having 3 to 30 carbon atoms having N or S (p and q are each an integer of 0 to 4, and when p and q are 2 or more, a plurality of Q ₁ to Q ₂ are the same or different, respectively) ,
R ₁ and R ₃ are the same as or different from each other, and each independently hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 24 carbon atoms, a substituted or unsubstituted and heterogeneous It is selected from a C3-C30 heteroaryl group and a substituted or unsubstituted silyl group having O, N or S as an atom,
m and r are each an integer of 0 to 3, when m and r are 2 or more, a plurality of R ₁ and R ₃ are each the same or different,
R ₂ and R ₄ are the same as or different from each other, and each independently hydrogen, deuterium, a halogen group, a cyano group, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, A substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted C 5 to 30 carbon atom A cycloalkenyl group, a substituted or unsubstituted alkylamine group having 1 to 30 carbon atoms, a substituted or unsubstituted arylamine group having 6 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, and a substituted or unsubstituted It is selected from a heteroaryl group having 3 to 30 carbon atoms having O, N or S as a hetero atom,
n and s are each an integer of 0 to 3, when n and s are 2 or more, a plurality of R ₂ and R ₄ are each the same or different,
When n and s are 2 or more, excluding a case in which all of a plurality of R ₂ and R ₄ are aryl groups,
When at least one of X ₁ to X ₂ and at least one of X ₅ to X ₆ are not an alkyl group, Q ₁ and Q ₂ are each a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms. . delete delete delete The method of claim 1,
The [Chemical Formula 1] is an organic light emitting compound, characterized in that selected from the following [Compound 1] to [Compound 82]:

An organic thin film layer for an organic light emitting device comprising at least one organic light emitting compound according to claim 1. An organic electroluminescent device comprising an anode, a cathode, and the organic thin film layer according to claim 6 interposed between the anode and the cathode. The method of claim 7,
The organic electroluminescent device further includes at least one layer selected from the group consisting of a light emitting layer, a hole injection layer, a hole transport layer, a hole blocking layer, an electron transport layer, an electron injection layer and an electron blocking layer between the anode and the cathode,
An organic electroluminescent device, characterized in that one of the emission layer, the hole injection layer, the hole transport layer, the hole blocking layer, the electron transport layer, the electron injection layer and the electron blocking layer is the organic thin film layer according to claim 6. The method of claim 8,
An organic electroluminescent device, wherein the emission layer is the organic thin film layer according to claim 6. The method of claim 7,
The organic light-emitting device is an organic light-emitting device, characterized in that it emits white light by including at least one light-emitting layer emitting blue, red, or green light.

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