KR102147235B1 - Heteroaryl compound exhibiting luminescent, ferroelectric and piezoelectric properties, and electronic device containing the same - Google Patents

Abstract

The present invention relates to a heteroaryl compound exhibiting luminescence, ferroelectricity and piezoelectricity, and an electronic device including the same. Since the heteroaryl compound may induce tautomerization by including a benzoimidazole group and/or a benzazaphosphole group having an asymmetric structure as a parent nucleus, excellent ferroelectricity and piezoelectricity may be implemented along with luminescence through this. In addition, since an electronic device having an organic layer including the compound can implement both luminescence, ferroelectricity and piezoelectricity, the luminous characteristics are easily controlled by controlling the AC power applied according to the polarity or size of the residual polarization generated in the organic layer. In addition to being possible, since it is not necessary to include a light-emitting material and a ferroelectric and/or piezoelectric material, respectively, there is an advantage of excellent workability and excellent durability.

Description

Heteroaryl compound exhibiting luminescent, ferroelectric and piezoelectric properties, and electronic device containing the same}

The present invention relates to a heteroaryl compound exhibiting luminescence, ferroelectricity and piezoelectricity, and an electronic device including the same.

Ferroelectric material is a material that was first discovered and known in 1920 in a material called Rochelle salt. Ferroelectrics are materials in which electric polarization occurs spontaneously without applying an electric field to the material, and can have electric polarization in a natural state. Materials exhibiting such spontaneous polarization exhibit piezoelectricity not only by an electric field, but also by changing the polarization even when pressure is applied.

In addition, unlike ordinary dielectrics, dielectric polarization is not proportional to the electric field, and the relationship between polarization and electric field has a hysteresis closed curve. Up to now, dozens of ferroelectric materials have been discovered. These materials not only have spontaneous polarization, but also have physical properties in which the spontaneous polarization is reversed by an electric field. The physical properties of ferroelectrics represent piezoelectric and pyroelectric properties due to the reversal of spontaneous polarization. Using these characteristics of ferroelectrics, personal portable night vision goggles or GPS, a location tracking device using satellites, secure night vision of cars. You can develop a device for In addition, since ferroelectrics have a large piezoelectric constant, they are widely used in acoustic machinery, and because of their high dielectric constant, they are also used as dielectrics for small capacitors.

Meanwhile, as the IoT (internet of things) industry develops and the demand for wearable electronic devices increases, the demand for light-emitting devices using flexible substrates such as electroluminescent devices that emit light with an applied AC electric field is increasing. The electroluminescent device can be applied to various fields such as interior lighting for automobiles, interior lighting, billboards, large displays, and wearable lighting. Luminescence is when a material becomes a stable state with low energy from an unstable state with high energy, and emits light with a wavelength corresponding to the difference in energy between them, maximizing the luminous efficiency of the electroluminescent device and easily controlling the luminescence characteristics. In order to do so, the research has been actively conducted centering on a luminescent material that emits light.

However, the conventional light-emitting material exhibits luminescence, but cannot implement ferroelectricity or piezoelectricity, and thus has a limitation in that it does not have synesthesia characteristics that sensitively respond to external environments. In addition, in order to improve this problem, a technology for using a luminescent material and a material exhibiting ferroelectricity and/or piezoelectricity together has been developed, but in this case, the materials mixed with the luminescent material are not uniformly dispersed or are sufficient to exhibit an effective effect. Since the amount is not used, the ferroelectricity and/or piezoelectricity that is realized is insignificant, and the durability is low.

Accordingly, there is a need for development of an electronic device capable of controlling luminescence characteristics through which the material has excellent luminescence properties, as well as excellent ferroelectricity and piezoelectricity, and can react sensitively to external environments such as sound or wind.

Republic of Korea Patent Publication No. 10-2017-0025335

An object of the present invention is to provide a material excellent in luminescence, ferroelectricity and piezoelectricity.

Another object of the present invention is to provide an electronic device including the material having excellent luminescence, ferroelectricity and piezoelectricity.

In order to achieve the above object, the present invention in one embodiment,

It provides a heteroaryl compound represented by Formula 1:

[Formula 1]

In Formula 1,

X is N or P,

R ₁ is hydrogen or a C1-6 alkyl group,

R ₂ is a C1 to 6 alkyl group, a C6 to 30 aryl group, or a 5 to 20 atom heteroaryl group,

R ₃ and R ₆ are each independently hydrogen or a halogen group, or together with the carbon atom to which R ₃ or R ₆ is bonded form a ketone group,

R ₄ is hydrogen, a halogen group, or a 5 to 20 atom heteroaryl group,

R ₅ is a halogen group, a carboxyl group, a 5 to 20 atom heteroaryl group, or a C6 to 30 aryl group,

Any one or more of the hydrogens present in the alkyl group, aryl group, and heteroaryl group of R ₁ to R ₆ is a halogen group, an amine group, a hydroxy group, an aldehyde group, a carboxyl group, or a C6 to 30 aryl substituted or unsubstituted with these Unsubstituted or substituted with a group or a 5 to 20 membered heteroaryl group.

In addition, the present invention in one embodiment,

A first electrode;

A second electrode opposite the first electrode; And

It is interposed between the first electrode and the second electrode, and provides an electronic device including an organic layer containing a heteroaryl compound represented by the following formula (1):

[Formula 1]

(In Formula 1, X, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , and R ₆ are as previously defined).

Further, the present invention provides an organic light emitting device, a transistor, or a capacitor including the electronic device in one embodiment.

Since the heteroaryl compound according to the present invention can induce tautomerization by including a benzoimidazole group and/or a benzazaphosphole group having an asymmetric structure as a parent nucleus, it is possible to implement excellent ferroelectricity and piezoelectricity along with luminescence.

In addition, since an electronic device having an organic layer including the compound can implement both luminescence, ferroelectricity and piezoelectricity, the luminous characteristics are easily controlled by controlling the AC power applied according to the polarity or size of the residual polarization generated in the organic layer. In addition to being possible, since it is not necessary to include a light-emitting material and a ferroelectric and/or piezoelectric material, respectively, there is an advantage of excellent workability and excellent durability.

1 is a graph showing the luminance of an electronic device manufactured in Example 33 measured using a UV-Vis spectrophotometer.
2 is a photograph showing the luminescence characteristics of the electronic device manufactured in Example 33, where A is a photograph of emitting fluorescence upon UV irradiation, and B is a photograph of emitting light under an electric field condition.

In the present invention, terms such as "comprises" or "have" are intended to designate the presence of features, numbers, steps, actions, components, parts, or a combination thereof described in the specification, but one or more other features. It is to be understood that the presence or addition of elements or numbers, steps, actions, components, parts, or combinations thereof, does not preclude in advance.

In addition, the accompanying drawings in the present invention should be understood as being enlarged or reduced for convenience of description.

Hereinafter, the present invention will be described in detail with reference to the drawings, and the same reference numerals are assigned to the same or corresponding components regardless of the reference numerals, and redundant descriptions thereof will be omitted.

In the present invention, the "alkyl group" means a functional group derived from a saturated hydrocarbon in a linear or branched form.

At this time, the "alkyl group" includes, for example, a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, and an n-butyl group (n -Butyl group), sec-butyl group (sec-butyl group), t-butyl group (tert-butyl group), n-pentyl group (n-pentyl group), 1,1-dimethylpropyl group (1,1- Dimethylpropyl group), 1,2-dimethylpropyl group (1,2-dimethylpropyl group), 2,2-dimethylpropyl group (2,2-dimethylpropyl group), 1-ethylpropyl group (1-ethylpropyl group) , 2-ethylpropyl group, n-hexyl group, 1-methyl-2-ethylpropyl group, 1-ethyl-2- Methylpropyl group (1-ethyl-2-methylpropyl group), 1,1,2-trimethylpropyl group (1,1,2-trimethylpropyl group), 1-propylpropyl group (1-propylpropyl group), 1-methyl Butyl group (1-methylbutyl group), 2-methylbutyl group (2-methylbutyl group), 1,1-dimethylbutyl group (1,1-dimethylbutyl group), 1,2-dimethylbutyl group (1 ,2-dimethylbutyl group), 2,2-dimethylbutyl group (2,2-dimethylbutyl group), 1,3-dimethylbutyl group (1,3-dimethylbutyl group), 2,3-dimethyl Butyl group (2,3-dimethylbutyl group), 2-ethylbutyl group (2-ethylbutyl group), 2-methylpentyl group (2-methylpentyl group), 3-methylpentyl group (3-methylpentyl group), etc. Can be mentioned.

In addition, the "alkyl group" may have 1 to 20 carbon atoms, for example, 1 to 12 carbon atoms, 1 to 6 carbon atoms, or 1 to 4 carbon atoms.

Further, in the present invention, the "alkylene group" may mean a divalent substituent derived from the above-described alkyl group.

In addition, in the present invention, the term "haloalkyl group" means that at least one of the hydrogen atoms included in the above-described alkyl group is a halogen element, for example, an element such as fluorine (F), chlorine (Cl), and bromine (Br). It may mean a substituted monovalent substituent.

In the present invention, "aryl group" means a monovalent substituent derived from an aromatic hydrocarbon.

In this case, the "aryl group" includes, for example, a phenyl group, a naphthyl group, an anthracenyl group, a phenanthryl group, a naphthacenyl group, and a pyrenyl group. (pyrenyl group), tolyl group, biphenyl group, terphenyl group, chrycenyl group, spirobifluorenyl group, fluorante Fluoranthenyl group, fluorenyl group, perylenyl group, indenyl group, azulenyl group, heptalenyl group, phenalenyl group group) and a phenanthrenyl group.

In addition, the "aryl group" may have 6 to 30 carbon atoms, for example, 6 to 10 carbon atoms, 6 to 14 carbon atoms, 6 to 18 carbon atoms, or 6 to 12 carbon atoms.

In the present invention, "heteroaryl group" means "aromatic heterocycle" or "heterocyclic" derived from a monocyclic or condensed ring. The "heteroaryl group" is at least one of nitrogen (N), sulfur (S), oxygen (O), phosphorus (P), selenium (Se), and silicon (Si) as a heteroatom, for example 1, 2 It may contain dogs, three or four.

At this time, the "heteroaryl group" includes, for example, a pyrrolyl group, a pyridyl group, a pyrimidinyl group, a pyrazinyl group, and a triazolyl group. , Benzotriazolyl group, pyrazolyl group, imidazolyl group, benzimidazolyl group, indolyl group, indolizinyl group group), indazolyl group, quinolyl group, carbazolyl group, carbazolinyl group, nitrogen-containing heteroaryl including pyrimidinyl group, etc. group; A sulfur-containing heteroaryl group including a thiophenyhl group, a thienyl group, a benzothienyl group, a dibenzothienyl group, and the like; An oxygen-containing heteroaryl group including a furyl group, a pyranyl group, a cyclopentapyranyl group, a benzofuranyl group, a dibenzofuranyl group, etc. And the like.

Further, the "heteroaryl group" may have 2 to 20 carbon atoms, for example, 4 to 19 carbon atoms, 4 to 15 carbon atoms, or 5 to 11 carbon atoms. For example, if a heteroatom is included, the heteroaryl group may have a ring member of 5 to 21 atoms.

In addition, in the present invention, the "heteroarylalkylene group" may mean a divalent substituent in which an alkylene group is bonded to the heteroaryl group described above.

The present invention relates to a heteroaryl compound exhibiting luminescence, ferroelectricity and piezoelectricity, and an electronic device including the same.

With the development of the IoT (internet of things) industry and increasing demand for wearable electronic devices, demand for light-emitting devices using flexible substrates such as electroluminescent devices that emit light with an applied alternating electric field is increasing. The electroluminescent device can be applied to various fields such as interior lighting for automobiles, interior lighting, billboards, large displays, and wearable lighting. Luminescence is the emission of light with a wavelength corresponding to the difference in energy between the material as it becomes a stable state with low energy from an unstable state with high energy, maximizing the luminous efficiency of the electroluminescent device, and easily controlling the luminescence characteristics. In order to do so, the research has been actively conducted centering on a luminescent material that emits light.

However, the conventional light-emitting material exhibits luminescence, but cannot implement ferroelectricity or piezoelectricity, and thus has a limitation in that it does not have synesthesia characteristics that sensitively respond to external environments. In addition, in order to improve this problem, a technology for using a luminescent material and a material exhibiting ferroelectricity and/or piezoelectricity together has been developed, but in this case, the materials mixed with the luminescent material are not uniformly dispersed or are sufficient to exhibit an effective effect. Since the amount is not used, the ferroelectricity and/or piezoelectricity that is realized is insignificant, and the durability is low.

Accordingly, the present invention provides a heteroaryl compound exhibiting luminescence, ferroelectricity and piezoelectricity, and an electronic device including the same.

Since the heteroaryl compound according to the present invention can induce tautomerization by including a benzoimidazole group and/or a benzazaphosphole group having an asymmetric structure as a parent nucleus, it is possible to implement excellent ferroelectricity and piezoelectricity along with luminescence. In addition, since an electronic device having an organic layer including the compound can implement both luminescence, ferroelectricity and piezoelectricity, the luminous characteristics are easily controlled by controlling the AC power applied according to the polarity or size of the residual polarization generated in the organic layer. In addition to being possible, since it is not necessary to include a light-emitting material and a ferroelectric and/or piezoelectric material, respectively, there is an advantage of excellent workability and excellent durability.

Hereinafter, the present invention will be described in detail.

In one embodiment, the present invention provides a heteroaryl compound represented by Formula 1:

In Formula 1,

X is N or P,

R ₁ is hydrogen or a C1-6 alkyl group,

R ₂ is a C1 to 6 alkyl group, a C6 to 30 aryl group, or a 5 to 20 atom heteroaryl group,

R ₃ and R ₆ are each independently hydrogen or a halogen group, or together with the carbon atom to which R ₃ or R ₆ is bonded form a ketone group,

R ₄ is hydrogen, a halogen group, or a 5 to 20 atom heteroaryl group,

R ₅ is a halogen group, a carboxyl group, a C6 to 30 aryl group or a 5 to 20 atom heteroaryl group,

Any one or more of the hydrogens present in the alkyl group, aryl group, and heteroaryl group of R ₁ to R ₆ is a halogen group, an amine group, a hydroxy group, an aldehyde group, a carboxyl group, or a C6 to 30 aryl substituted or unsubstituted with these Unsubstituted or substituted with a group or a 5 to 20 membered heteroaryl group.

Specifically, in Formula 1,

X is N or P,

R ₁ is hydrogen or a C1-4 alkyl group,

R ₂ is a C1-4 alkyl group, a C6-14 aryl group, or a 5-16 membered heteroaryl group,

R ₃ and R ₆ are each independently hydrogen or a halogen group, or together with the carbon atom to which R ₃ or R ₆ is bonded form a ketone group,

R ₄ is hydrogen, a halogen group, or a 5 to 16 membered heteroaryl group,

R ₅ is a halogen group, a carboxyl group, a 5 to 16 membered heteroaryl group, or a C6 to 30 aryl group,

Any one or more of the hydrogens present in the alkyl group, aryl group, and heteroaryl group of R ₁ to R ₆ are substituted or provided with a halogen group, an amine group, a hydroxy group, a C6-14 aryl group, or a 5-16 membered heteroaryl group It can be bright.

More specifically, in Chemical Formula 1,

X is N or P,

R ₁ is hydrogen, methyl group, ethyl group or propyl group,

또는

이고,R ₂ is a methyl group, ethyl group, propyl group, phenyl group, naphthyl group, pyrenyl group,

or

ego,

R ₃ and R ₆ are each independently hydrogen, a fluoro group, a chloro group, or a bromo group, or together with the carbon atom to which R ₃ or R ₆ is bonded constitute a ketone group,

R ₄ is hydrogen, a fluoro group, a chloro group, a bromo group, a thiophenyl group, a pyrrolyl group, a tetrazinyl group, an imidazolyl group, or a triazolyl group,

R ₅ is a fluoro group, a chloro group, a bromo group, a carboxyl group, a phenyl group, a naphthyl group, an anthracenyl group, a pyrenyl group, a thiophenyl group, a pyrrolyl group, a tetrazinyl group, an imidazolyl group, or a triazolyl group,

Any of the hydrogens present in the methyl group, ethyl group, propyl group, phenyl group, naphthyl group, anthracenyl group, pyrenyl group, thiophenyl group, pyrrolyl group, tetrazinyl group, imidazolyl group, and triazolyl group of R ₁ to R ₆ At least one may be unsubstituted or substituted with a halogen group, an amine group, a hydroxy group, a C6 to 30 aryl group, or a 5 to 20 atom heteroaryl group.

As an example, in Formula 1,

X is N,

R ₁ is hydrogen, methyl or ethyl,

R ₂ is a methyl group, an ethyl group or a propyl group,

R ₃ and R ₆ are hydrogen or halogen groups,

R ₄ is a halogen group,

R ₅ is a phenyl group, a naphthyl group, a pyrenyl group, an anthracenyl group, a thiophenyl group, a pyrrolyl group, a tetrazinyl group, an imidazolyl group, or a triazolyl group

Any one of hydrogen present in the methyl group, ethyl group, propyl group, phenyl group, naphthyl group, pyrenyl group, anthracenyl group, thiophenyl group, pyrrolyl group, tetrazinyl group, imidazolyl group and triazolyl group of R ₁ to R ₆ These are substituted or provided with a hydroxy group, an amine group, a fluoro group, a chloro group, a bromo group, a methyl group, an ethyl group, a phenyl group, a naphthyl group, a thiophenyl group, a pyrrolyl group, a tetrazinyl group, an imidazolyl group, or a triazolyl group. It can be bright.

Specifically, the compound represented by Formula 1 may be at least one selected from the following <Structure 1-1> to <Structure 1-12>:

<Structure 1-1>

<Structure 1-2>

<Structure 1-3>

<Structure 1-4>

<Structure 1-5>

<Structure 1-6>

<Structure 1-7>

<Structure 1-8>

<Structure 1-9>

<Structure 1-10>

<Structure 1-11>

.<Structure 1-12>

.

As another example, in Formula 1,

X is N,

R ₁ is hydrogen,

또는

이고,R ₂ is a methyl group, an ethyl group,

or

ego,

R ₃ and R ₆ are hydrogen or halogen groups,

R ₄ is hydrogen,

R ₅ is a carboxyl group, a phenyl group, a naphthyl group, an anthracenyl group, a pyrenyl group, a thiophenyl group, a pyrrolyl group, a tetrazinyl group, an imidazolyl group, or a triazolyl group,

At least one of hydrogen present in the methyl group, ethyl group, phenyl group, naphthyl group, anthracenyl group, pyrenyl group, thiophenyl group, pyrrolyl group, tetrazinyl group, imidazolyl group, or triazolyl group of R ₂ and R ₅ is It may be unsubstituted or substituted with an amine group, a fluoro group, a chloro group, a bromo group, a methyl group, an ethyl group, a phenyl group, or a naphthyl group.

Specifically, the compound represented by Formula 1 may be any one or more selected from the following <Structure 2-1> to <Structure 2-7>:

<Structure 2-1>

<Structure 2-2>

<Structure 2-3>

<Structure 2-4>

<Structure 2-5>

<Structure 2-6>

.<Structure 2-7>

.

As another example, in Formula 1,

X is P,

R ₁ is hydrogen,

R ₂ is a methyl group, an ethyl group, a propyl group or a butyl group,

R ₃ and R ₆ are hydrogen or halogen groups,

R ₄ is a fluoro group, a chloro group or a bromo group,

R ₅ is a chloro group, a bromo group, a phenyl group, a naphthyl group, an anthracenyl group, a pyrenyl group, a thiophenyl group, a pyrrolyl group, a tetrazinyl group, an imidazolyl group, or a triazolyl group,

Present in a methyl group, ethyl group, propyl group, butyl group, phenyl group, naphthyl group, anthracenyl group, pyrenyl group, thiophenyl group, pyrrolyl group, tetrazinyl group, imidazolyl group, or triazolyl group of R ₂ and R ₅ Any one or more of hydrogen may be unsubstituted or substituted with a phenyl group, naphthyl group, thiophenyl group, pyrrolyl group, tetrazinyl group, imidazolyl group, or triazolyl group.

Specifically, the compound represented by Formula 1 may be any one or more selected from the following <Structure 3-1> and <Structure 3-2>:

<Structure 3-1>

.<Structure 3-2>

.

As another example, the compound represented by Formula 1 may be a compound selected from the following <Structure 4-1>:

.<Structure 4-1>

.

The heteroaryl compound according to the present invention contains a benzoimidazole group and/or a benzazaphosphol group having an asymmetric structure as a parent nucleus, and the benzoimidazole group and a benzazaphosphole group having an asymmetric structure are nitrogen (N) as shown below. It may have a tautomer that achieves an equilibrium state by moving an atom and/or a phosphorus (P) atom and a hydrogen and/or a C1-4 lower alkyl group between molecules or by moving a bonding electron. As such, the tautomer-containing compound may exhibit ferroelectricity and/or antiferroelectricity at room temperature.

The heteroaryl compound represented by Formula 1 according to the present invention has excellent effects of implementing piezoelectricity together with ferroelectricity at room temperature by introducing an appropriate substituent to the parent nucleus including a benzoimidazole group and a benzazaphosphole group.

As an example, since the heteroaryl compound represented by Chemical Formula 1 has excellent ferroelectricity and piezoelectricity, it may exhibit a polarization characteristic of 0.1 μC/cm 2 to 100 μC/cm 2 under voltage conditions of 0.1 kV/cm to 500 kV/cm. Specifically, the compound is 0.1 μC/cm 2 to 100 μC/cm 2 under voltage conditions of 0.1 kV/cm to 500 kV/cm; 0.1 μC/cm 2 to 75 μC/cm 2; 0.1 μC/cm 2 to 50 μC/cm 2; 0.1 μC/cm 2 to 40 μC/cm 2; 0.1 μC/cm 2 to 30 μC/cm 2; 0.1 μC/cm 2 to 20 μC/cm 2; 0.1 μC/cm 2 to 20 μC/cm 2; 0.1 μC/cm 2 to 10 μC/cm 2 18 0.1 μC/cm 2 to 5 μC/cm 2; 1 μC/cm 2 to 5 μC/cm 2; 1.5 μC/cm 2 to 4.7 μC/cm 2; 5.3 μC/cm2 to 7 μC/cm2; 4 μC/cm 2 to 7 μC/cm 2; 10 μC/cm 2 to 20 μC/cm 2; 5 μC/cm 2 to 20 μC/cm 2; 12 μC/cm 2 to 19 μC/cm 2; 4 μC/cm 2 to 20 μC/cm 2; 15 μC/cm 2 to 25 μC/cm 2; 20 μC/cm 2 to 30 μC/cm 2; 15 μC/cm 2 to 25 μC/cm 2; 21 μC/cm 2 to 28 μC/cm 2; 25 μC/cm 2 to 30 μC/cm 2; It can exhibit a polarization characteristic of 30 μC/cm 2 to 40 μC/cm 2 or 35 μC/cm 2 to 40 μC/cm 2.

In addition, the heteroaryl compound according to the present invention may have excellent effect of emitting light under UV irradiation conditions as well as electric field conditions.

As an example, the heteroaryl compound has an absorption maximum in a wavelength range of 250 to 500 nm when evaluating the light emission characteristics at a wavelength of 200 to 800 nm using a UV-Vis spectrophotometer, and a wavelength range of 370 to 720 nm, specifically 370 ~650 nm; 370-600 nm; 370-550 nm; 370-500 nm; 370-450 nm; 370-400 nm; 380-420 nm; 400-450 nm; 400-500 nm; 400-550 nm; 400-590 nm; 420-480 nm; 430-470 nm; 450-490 nm; 460-590 nm; 480-560 nm; 370-390 nm; 530-590 nm; 400-720 nm; 450-720 nm; 500-720 nm; 550-720 nm; 600-720 nm; 650-720 nm; 630-710 nm; 670-700 nm; Alternatively, it was found to have a maximum emission in the 420 ~ 440 nm wavelength range. The wavelength of 370-700 nm includes regions corresponding to red (red, about 370-520 nm), green (green, about 520-620 nm), and blue (blue, about 620-720 nm), which is represented by Formula 1 When the heteroaryl compound shown is included in the organic layer, it can be seen that red, green, blue, or a mixed color thereof emit light depending on the type of substituent introduced into the parent nucleus.

In addition, the present invention in one embodiment,

A first electrode;

A second electrode opposite the first electrode; And

It is interposed between the first electrode and the second electrode, and provides an electronic device including a light emitting layer including a heteroaryl compound represented by the following formula (1):

[Formula 1]

In Formula 1,

X is N or P,

R ₁ is hydrogen or a C1-6 alkyl group,

R ₂ is a C1 to 6 alkyl group, a C6 to 30 aryl group, or a 5 to 20 atom heteroaryl group,

R ₃ and R ₆ are each independently hydrogen or a halogen group, or together with the carbon atom to which R ₃ or R ₆ is bonded form a ketone group,

R ₄ is hydrogen, a halogen group, or a 5 to 20 atom heteroaryl group,

R ₅ is a halogen group, a carboxyl group, a C6 to 30 aryl group or a 5 to 20 atom heteroaryl group,

Any one or more of the hydrogens present in the alkyl group, aryl group, and heteroaryl group of R ₁ to R ₆ is a halogen group, an amine group, a hydroxy group, an aldehyde group, a carboxyl group, or a C6 to 30 aryl substituted or unsubstituted with these Unsubstituted or substituted with a group or a 5 to 20 membered heteroaryl group.

The electronic device according to the present invention includes a heteroaryl compound represented by Formula 1 of the present invention in an organic layer positioned between the first electrode and the second electrode. As described above, the heteroaryl compound has a tautomer including a benzoimidazole group and/or a benzazaphosphole group having an asymmetric structure as a parent nucleus, and thus excellent luminescence, ferroelectricity and piezoelectricity at room temperature can be realized. Accordingly, the electronic device of the present invention includes the heteroaryl compound having both ferroelectricity and piezoelectricity as well as luminescence in an organic layer, and controls the AC power applied according to the polarity or size of the residual polarization generated in the organic layer to facilitate light emission characteristics. Can be controlled.

In addition, in the case of materials in which a luminescent material and a ferroelectric material and/or a piezoelectric material are mixed/combined as an electroluminescent material, the manufacturing process is complicated and uniform dispersion of each material is difficult, so the reliability of the material is low, in order to obtain an effective effect. There is a limit that a large amount of material must be used. However, the electronic device of the present invention can improve all of these problems by including an organic layer including the heteroaryl compound represented by Formula 1.

Meanwhile, the organic layer is polyvinylidene fluoride (PVDF), a copolymer of vinylidene fluoride and trifluoroethylene (PVDF-TrFE), vinylidene fluoride and hexafluoroethylene together with the heteroaryl compound represented by Chemical Formula 1 (PVDF-HFP), vinylidene cyanide and vinyl acetate copolymer (P(VDCN-VAc)), nylon-11 (nylon-11), polyurea-9 (polyurea-9), polyvinyl chloride (PVC), polyacrylonitrile (PAN), polyphthalazinone ether nitrile (PPEN), polyethylene oxide (PEO), and may further include one or more binders selected from the group consisting of polyether sulfone (PES) Specifically, polyvinylidene fluoride (PVDF), a copolymer of vinylidene fluoride and trifluoroethylene (PVDF-TrFE), a copolymer of vinylidene fluoride and hexafluoroethylene (PVDF-HFP), etc. It may further include a fluorine-based polymer. The binder may function as a medium in which the heteroaryl compound represented by Formula 1 is dispersed and a binder, and in some cases, may perform a function of reinforcing ferroelectricity and piezoelectricity of the organic layer implemented by the heteroaryl compound.

In addition, the organic layer may further include a host-guest material. For example, the host material is ZnS, ZnO, CaS, SrS, Y ₂ O ₂ , Y ₂ O ₂ S, Zn ₂ SiO ₄ , Y ₃ Al ₅ O ₁₂ , Y ₃ (AlGa) ₅ O ₁₂ , Y ₂ SiO ₅ , LaOCl, InBO ₃ , Gd ₂ O ₂ S, and may include at least one of ZnGa ₂ O ₄ , and the guest material is Mn, Cu, Ag, Eu, Cl, I, Tb, Al, Ce, It may contain one or more activators of Er and Pr. As an example, the host-guest material may be ZnS:Mn. The host-guest material may perform a function of improving the luminescence property of the organic layer formed by the heteroaryl compound when the electronic device emits light.

In addition, the first and second electrodes may be selectively used from materials used as electrodes of electronic devices. For example, the first and second electrodes are silver (Ag) nanowires, indium tin oxide (ITO), carbon nanotubes (CNT), graphene, gold (Au) nanorods, and Conductive polymers such as particles, metal mesh, PEDOT:Tos, and PEDOT:PSS can be used.

Furthermore, the electronic device may further include a hole transport layer between the first electrode and the organic layer. The hole transport layer may be used without particular limitation as long as it is a material having excellent hole transport capability, and for example, conductive polymers such as PEDOT:PSS, carbon nanotubes (CNT), graphene, 4,4-bis[N -(1-naphthyl)-N-phenyl-amine]biphenyl(α-NPD), N,N-diphenyl-N,N-bis(3-methylphenyl)-1,1-biphenyl-4,4 -Diamine (TPD), poly-(N-vinylcarbazole) (PVCz), and the like may be included alone or in combination of two or more.

Furthermore, in one embodiment, the present invention provides an organic light emitting device, a transistor, and a capacitor including the electronic device.

The organic light-emitting device, transistor, and capacitor according to the present invention are simple to manufacture by including the electronic devices described above, so that large-area devices can be easily manufactured, and can react sensitively to external environmental changes such as magnetic field, pressure, and friction. The luminance of the device can be easily controlled. In addition, when external pressure or friction is applied, energy can be generated by itself, so that energy required for driving the device can be saved, so that the device can be easily miniaturized and improved in efficiency, and applicable to wearable devices.

Hereinafter, the present invention will be described in more detail by examples and experimental examples.

However, the following examples and experimental examples are merely illustrative of the present invention, and the contents of the present invention are not limited to the following examples and experimental examples.

Example 1. Synthesis of <Structure 1-1> Compound

After dissolving 4-bromo-5-chlorobenzene-1,2-diamine (10 mmol) in a 4N aqueous hydrochloric acid solution (HCl, 15 ml), trifluoroacetic acid (10 mmol) was added, and for 24 hours Stir at reflux. Thereafter, the reaction solution was cooled to room temperature and neutralized with a 2N aqueous sodium hydroxide (NaOH) solution, and then the solid formed in the reaction solution was filtered and washed with water.

The washed solid (10 mmol) was dissolved in toluene (100 ml), triphenylphosphine palladium (Pd(PPh ₃ ) ₄ , 0.407 mmol) was added, and then tributyl (2-thienyl) stanane (10.1 mmol) was added and reacted for 24 hours. When the reaction was completed, the solid formed in the reaction solution was separated by filtration, and the separated solid was recrystallized from dimethylformamide (DMF) to obtain the target compound.

¹ H NMR, δ (ppm) = 7.86 (s, 1H), 7.77 (s, 1H), 7.2 (m, 1H), 7.0, (m, 2H), 5.0 (s, 1H).

Example 2. Synthesis of <Structure 1-2> compound

The compound (2.68 mmol) obtained in Example 1 was dissolved in dimethylformamide (20 ml), and a solution in which N-bromosuccinimide (5.64 mmol) was dissolved in dimethylformamide (8 ml) was slowly added dropwise. The mixture was stirred at 70° C. for 24 hours. When the reaction was completed, the solid in the reaction solution was separated by filtration, and the separated solid was recrystallized from dimethylformamide.

A solution in which the recrystallized solid (2.3 mmol) was dissolved in dimethylformamide (20 ml), and 3-bromo-1,2,4,5-tetrazine (4.9 mmol) was dissolved in dimethylformamide (5 ml). Was slowly added dropwise and stirred at 80° C. for 48 hours. When the reaction was completed, the solid in the reaction solution was separated by filtration, and the separated solid was washed with dimethylformamide and water to obtain the target compound.

¹ H NMR, δ (ppm) = 7.93 (s, 1H), 7.81 (s, 1H), 7.0 (m, 2H), 5.0 (s, 1H).

Example 3. Synthesis of <Structure 1-3> Compound

After dissolving 4,5-dibromobenzene-1,2-diamine (10 mmol) in a 4N aqueous hydrochloric acid solution (HCl, 15 ml), trifluoroacetic acid (10 mmol) was added, and for 24 hours Stir at reflux. Thereafter, the reaction solution was cooled to room temperature and neutralized with a 2N aqueous sodium hydroxide (NaOH) solution, and then the solid formed in the reaction solution was filtered and washed with water. The washed solid (10 mmol) was dissolved in toluene (100 ml), triphenylphosphine palladium (Pd(PPh3)4, 0.407 mmol) was added, and then 2-(tributylstannyl)-3H-pyrrole ( 10.1 mmol) was added and reacted for 24 hours. When the reaction was completed, the solid formed in the reaction solution was separated by filtration, and the separated solid was recrystallized from dimethylformamide.

The recrystallized solid (2.68 mmol) was dissolved in dimethylformamide (20 ml), and a solution in which N-bromosuccinimide (5.64 mmol) was dissolved in dimethylformamide (8 ml) was slowly added dropwise at 70°C. Stir for 24 hours. When the reaction was completed, the solid in the reaction solution was separated by filtration, and the separated solid was recrystallized from dimethylformamide.

The recrystallized solid (2 mmol) was dissolved in toluene (100 ml), triphenylphosphine palladium (Pd(PPh ₃ ) ₄ , 0.08 mmol) was added, and then tributyl (phenyl) stanane (2.2 mmol) was added. And reacted for 24 hours. When the reaction was completed, the solid formed in the reaction solution was separated by filtration, and the separated solid was recrystallized from dimethylformamide to obtain the target compound.

¹ H NMR, δ(ppm) = 8.23 (s,1H), 8.11 (s, 1H), 7.30 (d, 2H), 7.21 (t, 2H), 7.14 (m, 1H), 6.1 (t, 1H) , 5.0 (s, 1H), 2.0 (d, 1H).

Example 4. Synthesis of <Structure 1-4> Compound

The compound (2.68 mmol) obtained in Example 1 was dissolved in dimethylformamide (20 ml), and a solution in which N-bromosuccinimide (5.64 mmol) was dissolved in dimethylformamide (8 ml) was slowly added dropwise. The mixture was stirred at 70° C. for 24 hours. When the reaction was completed, the solid in the reaction solution was separated by filtration, and the separated solid was recrystallized from dimethylformamide.

The recrystallized solid (2 mmol) was dissolved in toluene (100 ml), triphenylphosphine palladium (Pd(PPh ₃ ) ₄ , 0.08 mmol) was added, and (3, 5-dibromophenyl) tributyl Stanan (2.2 mmol) was added and reacted for 24 hours. When the reaction was completed, the solid formed in the reaction solution was separated by filtration, and the separated solid was recrystallized from dimethylformamide to obtain the target compound.

¹ H NMR, δ (ppm) = 13.4 (s, 1H), 7.93 (s, 1H), 7.0 (d, 2H), 5.0 (s, 1H).

Example 5. Synthesis of <Structure 1-5> Compound

After dissolving 4,5-dibromobenzene-1,2-diamine (10 mmol) in a 4N aqueous hydrochloric acid solution (HCl, 15 ml), trifluoroacetic acid (12 mmol) was added, and for 24 hours Stir at reflux. Thereafter, the reaction solution was cooled to room temperature and neutralized with a 2N aqueous sodium hydroxide (NaOH) solution, and then the solid formed in the reaction solution was filtered and washed with water. The washed solid (10 mmol) was dissolved in toluene (100 ml), triphenylphosphine palladium (Pd(PPh ₃ ) ₄ , 0.407 mmol) was added, followed by 2 tributyl (2-thienyl) stanane ( 10.1 mmol) was added and reacted for 24 hours. When the reaction was completed, the solid formed in the reaction solution was separated by filtration, and the separated solid was recrystallized from dimethylformamide.

The recrystallized solid (2.68 mmol) was dissolved in dimethylformamide (20 ml), and a solution in which N-bromosuccinimide (5.64 mmol) was dissolved in dimethylformamide (8 ml) was slowly added dropwise at 70°C. Stir for 24 hours. When the reaction was completed, the solid in the reaction solution was separated by filtration, and the separated solid was recrystallized from dimethylformamide.

The recrystallized solid (2 mmol) was dissolved in toluene (100 ml), triphenylphosphine palladium (Pd(PPh ₃ ) ₄ , 0.08 mmol) was added, and 4,5-dibromo-2-(tri Butylstanyl)-1H-imidazole (2.2 mmol) was added and reacted for 24 hours. When the reaction was completed, the solid formed in the reaction solution was separated by filtration, and the separated solid was recrystallized from dimethylformamide to obtain the target compound.

¹ H NMR, δ (ppm) = 13.40 (s, 1H), 7.93 (s, 1H), 7.81 (s, 1H), 7.0 (d, 2H), 5.0 (s, 1H).

Example 6. Synthesis of <Structure 1-6> Compound

The compound (1.5 mmol) obtained in Example 5 was dissolved in bromomethanol (2 ml) and reacted at 60° C. for 24 hours. When the reaction was completed, the solid formed in the reaction solution was separated by filtration, and the separated solid was recrystallized from dimethylformamide to obtain the target compound.

¹ H NMR: δ (ppm) = 13.40 (s, 1H), 7.93 (s, 1H), 7.81 (s, 1H), 7.0 (d, 2H), 5.97 (s, 1H), 2.0 (s, 1H) .

Example 7. Synthesis of <Structure 1-7> Compound

The compound (1.5 mmol) obtained in Example 5 was dissolved in 1-bromo-2-chloroethane (1.6 ml), and reacted at 60° C. for 24 hours. When the reaction was completed, the solid formed in the reaction solution was separated by filtration, and the separated solid was recrystallized from dimethylformamide to obtain the target compound.

¹ H NMR, δ (ppm) = 13.40 (s, 1H), 7.93 (s, 1H), 7.81 (s, 1H), 7.0 (d, 2H), 4.01 (t, 2H), 3.86 (t, 2H) .

Example 8. Synthesis of <Structure 1-8> Compound

After dissolving 4,5-dibromobenzene-1,2-diamine (10 mmol) in a 4N aqueous hydrochloric acid solution (HCl, 15 ml), difluorochloroacetic acid (10 mmol) was added, and 24 hours Stir at reflux during. Thereafter, the reaction solution was cooled to room temperature and neutralized with a 2N aqueous sodium hydroxide (NaOH) solution, and then the solid formed in the reaction solution was filtered and washed with water.

The washed solid (1 eq) and 3-bromo-1,2,4,5-tetrazine (1 eq) were mixed and reacted at 70° C. for 24 hours. When the reaction was completed, the solid formed in the reaction solution was separated by filtration, and the separated solid was recrystallized from dimethylformamide.

¹ H NMR, δ (ppm) = 7.93 (s, 1H), 7.81 (s, 1H), 5.0 (s, 1H).

Example 9. Synthesis of <Structure 1-9> Compound

After dissolving 4-bromo-5-chlorobenzene-1,2-diamine (10 mmol) in 4N aqueous hydrochloric acid solution (HCl, 15 ml), 2-amino-2,2-difluoro acetic acid (15 mmol) was added and stirred under reflux for 24 hours. Thereafter, the reaction solution was cooled to room temperature and neutralized with a 2N aqueous sodium hydroxide (NaOH) solution, and then the solid formed in the reaction solution was filtered and washed with water.

The washed solid (1 eq) and 3-bromo-1,2,4,5-tetrazine (1 eq) were mixed and reacted at 70° C. for 24 hours. When the reaction was completed, the solid formed in the reaction solution was separated by filtration, and the separated solid was recrystallized from dimethylformamide.

¹ H NMR, δ (ppm) = 7.86 (s, 1H), 7.77 (s, 1H), 5.0 (s, 1H), 2.0 (s, 2H).

Example 10. Synthesis of <Structure 1-10> Compound

After dissolving 4,5-dibromobenzene-1,2-diamine (10 mmol) in a 4N aqueous hydrochloric acid solution (HCl, 15 ml), trifluoroacetic acid (19 mmol) was added, and for 24 hours Stir at reflux. Thereafter, the reaction solution was cooled to room temperature and neutralized with a 2N aqueous sodium hydroxide (NaOH) solution, and then the solid formed in the reaction solution was filtered and washed with water. The washed solid (10 mmol) was dissolved in toluene (100 ml), triphenylphosphine palladium (Pd(PPh ₃ ) ₄ , 0.407 mmol) was added, and then 4,5-dibromo-2-(tri Butylstanyl)-1H-imidazole (10.1 mmol) was added and reacted for 24 hours. When the reaction was completed, the solid formed in the reaction solution was separated by filtration, and the separated solid was recrystallized from dimethylformamide to obtain the target compound.

¹ H NMR, δ (ppm) = 13.4 (s, 1H), 7.93 (d, 1H), 7.81 (m, 3H), 5.0 (s, 1H).

Example 11. Synthesis of <Structure 1-11> Compound

After dissolving 4,5-dibromobenzene-1,2-diamine (10 mmol) in a 4N aqueous hydrochloric acid solution (HCl, 15 ml), trifluoroacetic acid (10 mmol) was added, and for 24 hours Stir at reflux. Thereafter, the reaction solution was cooled to room temperature and neutralized with a 2N aqueous sodium hydroxide (NaOH) solution, and then the solid formed in the reaction solution was filtered and washed with water. The washed solid (10 mmol) was dissolved in toluene (100 ml), triphenylphosphine palladium (Pd(PPh ₃ ) ₄ , 0.407 mmol) was added, and then tributyl (2-thienyl) stanane (10.1 mmol) was added and reacted for 24 hours. When the reaction was completed, the solid formed in the reaction solution was separated by filtration, and the separated solid was recrystallized from dimethylformamide to obtain the target compound.

¹ H NMR, δ (ppm) = 7.86 (s, 1H), 7.77 (s, 1H), 7.2 (m, 1H), 7.0, (m, 2H), 5.0 (s, 1H).

Example 12. Synthesis of <Structure 1-12> compound

After dissolving 4,5-dibromobenzene-1,2-diamine (10 mmol) in a 4N aqueous hydrochloric acid solution (HCl, 15 ml), trifluoroacetic acid (10 mmol) was added, and for 24 hours Stir at reflux. Thereafter, the reaction solution was cooled to room temperature and neutralized with a 2N aqueous sodium hydroxide (NaOH) solution, and then the solid formed in the reaction solution was filtered and washed with water. The washed solid (10 mmol) was dissolved in toluene (100 ml), triphenylphosphine palladium (Pd(PPh ₃ ) ₄ , 0.407 mmol) was added, and then naphthalen-1-yl-1-boronic acid (10.1 mmol) was added and reacted for 24 hours. When the reaction was completed, the solid formed in the reaction solution was separated by filtration, and the separated solid was recrystallized from dimethylformamide to obtain the target compound.

¹ H NMR, [delta](ppm) = 7.86-7.95 (m, 2H), 7.67-7.54 (m, 4H), 7.38-7.29 (m, 3H), 5.0 (s, 1H).

Example 13. Synthesis of <Structure 2-1> compound

After dissolving 4-bromobenzene-1,2-diamine (10 mmol) in a 4N aqueous hydrochloric acid solution (HCl, 15 ml), trifluoroacetic acid (10 mmol) was added, followed by reflux stirring for 24 hours. . Thereafter, the reaction solution was cooled to room temperature and neutralized with a 2N aqueous sodium hydroxide (NaOH) solution, and then the solid formed in the reaction solution was filtered and washed with water. The washed solid (10 mmol) was dissolved in toluene (100 ml), triphenylphosphine palladium (Pd(PPh ₃ ) ₄ , 0.407 mmol) was added, and then tributyl(thiophen-2-yl)stanan (10.1 mmol) was added and reacted for 24 hours. When the reaction was completed, the solid formed in the reaction solution was separated by filtration, and the separated solid was recrystallized from dimethylformamide.

The recrystallized solid (2.68 mmol) was dissolved in dimethylformamide (20 ml), and a solution in which N-bromosuccinimide (5.64 mmol) was dissolved in dimethylformamide (8 ml) was slowly added dropwise at 70°C. Stir for 24 hours. When the reaction was completed, the solid in the reaction solution was separated by filtration, and the separated solid was recrystallized from dimethylformamide.

The recrystallized solid (2 mmol) was dissolved in toluene (100 ml), triphenylphosphine palladium (Pd(PPh ₃ ) ₄ , 0.08 mmol) was added, and (3,5-dibromophenyl) tributyl Stanan (2.2 mmol) was added and reacted for 24 hours. When the reaction was completed, the solid formed in the reaction solution was separated by filtration, and the separated solid was recrystallized from dimethylacetamide to obtain the target compound.

¹ H NMR, δ (ppm) = 7.92 (s, 1H), 7.76 (d, 1H), 7.56-7.59 (m, 3H), 5.0 (s, 1H).

Example 14. Synthesis of <Structure 2-2> Compound

After dissolving 3,4-diaminobenzoic acid (10 mmol) in a 4N aqueous hydrochloric acid solution (HCl, 15 ml), trifluoroacetic acid (15 mmol) was added, followed by reflux stirring for 24 hours. Thereafter, the reaction solution was cooled to room temperature and neutralized with a 2N aqueous sodium hydroxide (NaOH) solution, and then the solid formed in the reaction solution was filtered and washed with water. The washed solid was recrystallized from dimethylacetamide to obtain the target compound.

¹ H NMR, δ (ppm) = 11.0 (s, 1H), 8.57 (s, 1H), 8.13 (d, 1H), 7.91 (d, 1H), 5.0 (s, 1H).

Example 15. Synthesis of <Structure 2-3> compound

After dissolving 4-bromobenzene-1,2-diamine (10 mmol) in a 4N aqueous hydrochloric acid solution (HCl, 15 ml), trifluoroacetic acid (20 mmol) was added, followed by reflux stirring for 24 hours. . Thereafter, the reaction solution was cooled to room temperature and neutralized with a 2N aqueous sodium hydroxide (NaOH) solution, and then the solid formed in the reaction solution was filtered and washed with water. The washed solid (10 mmol) was dissolved in toluene (100 ml), triphenylphosphine palladium (Pd(PPh ₃ ) ₄ , 0.407 mmol) was added, and then 6-(tributylstannyl)naphthalene-1- Amine (10.1 mmol) was added and reacted for 24 hours. When the reaction was completed, the solid formed in the reaction solution was separated by filtration, and the separated solid was recrystallized from dimethylformamide to obtain the target compound.

¹ H NMR, δ (ppm) = 7.92 (s, 1H), 7.83 (s, 1H), 7.72-7.76 (m, 2H), 7.48-7.53 (m, 2H), 7.15-7.16 (m, 2H), 6.55 (d, 1H), 5.0 (s, 1H), 4.0 (s, 1H).

Example 16. Synthesis of <Structure 2-4> Compound

After dissolving 4-bromobenzene-1,2-diamine (10 mmol) in a 4N aqueous hydrochloric acid solution (HCl, 15 ml), trifluoroacetic acid (10 mmol) was added, followed by reflux stirring for 24 hours. . Thereafter, the reaction solution was cooled to room temperature and neutralized with a 2N aqueous sodium hydroxide (NaOH) solution, and then the solid formed in the reaction solution was filtered and washed with water. The washed solid (10 mmol) was dissolved in toluene (100 ml), triphenylphosphine palladium (Pd(PPh ₃ ) ₄ , 0.407 mmol) was added, and then 9-sec-butyl-1-(tributyls Tanyl) pyrene-4-amine (10.1 mmol) was added and reacted for 24 hours. When the reaction was completed, the solid formed in the reaction solution was separated by filtration, and the separated solid was recrystallized from dimethylformamide to obtain the target compound.

¹ H NMR, δ (ppm) = 8.18 (d, 1H), 8.12 (d, 1H), 8.04 (m, 2H), 7.91-7.76 (m, 4H), 7.58 (d, 1H), 7.48 (d, 1H), 6.91 (s, 1H), 4.0 (s, 1H), 2.94 (m, 1H), 1.64 (m, 4H), 1.47 (d, 3H), 0.96 (t, 3H).

Example 17. Synthesis of <Structure 2-5> Compound

After dissolving 4-bromobenzene-1,2-diamine (10 mmol) in a 4N aqueous hydrochloric acid solution (HCl, 15 ml), trifluoroacetic acid (10 mmol) was added, followed by reflux stirring for 24 hours. . Thereafter, the reaction solution was cooled to room temperature and neutralized with a 2N aqueous sodium hydroxide (NaOH) solution, and then the solid formed in the reaction solution was filtered and washed with water. The washed solid (10 mmol) was dissolved in toluene (100 ml), triphenylphosphine palladium (Pd(PPh ₃ ) ₄ , 0.407 mmol) was added, and 2-(tributylstannyl)-3,4 -Dichloro-1H-pyrrole (10.1 mmol) was added and reacted for 24 hours. When the reaction was completed, the solid formed in the reaction solution was separated by filtration, and the separated solid was recrystallized from dimethylformamide to obtain the target compound.

¹ H NMR, δ (ppm) = 7.92 (s, 1H), 7.76 (d, 1H), 7.48 (d, 1H), 6.6 (s, 1H), 5.0 (s, 2H).

Example 18. Synthesis of <Structure 2-6> Compound

3,4-dihydrofuran-2,5-dione (28 mmol) and 5-bromo-1H-benzo[d]imidazol-2-amine (28 mmol) were added to distilled dimethylformamide (70 ml). Dissolve and stir under reflux for 24 hours. Thereafter, the temperature was cooled to room temperature, and the solid formed in the reaction solution was filtered and washed with methanol.

The washed solid was recrystallized with dimethylformamide, the recrystallized solid (10 mmol) was dissolved in toluene (100 ml), and triphenylphosphine palladium (Pd(PPh ₃ ) ₄ , 0.407 mmol) was added, followed by 2 -(Tributylstannyl)-3,4-dichloro-1H-pyrrole (10.1 mmol) was added and reacted for 24 hours. When the reaction was completed, the solid formed in the reaction solution was separated by filtration, and the separated solid was recrystallized from dimethylformamide to obtain the target compound.

¹ H NMR, δ (ppm) = 15.0 (s, 2H), 7.92 (s, 1H), 7.76 (d, 1H), 7.48 (d, 1H), 6.6 (s, 1H), 5.0 (s, 2H) .

Example 19. Synthesis of <Structure 2-7> compound

3,4-dihydrofuran-2,5-dione (28 mmol) and pyromellitic dianhydride (28 mmol) were dissolved in distilled dimethylformamide (70 ml) and stirred under reflux for 24 hours. Thereafter, the temperature was cooled to room temperature, and the solid formed in the reaction solution was filtered and washed with methanol.

The washed solid was recrystallized with dimethylformamide, and the recrystallized solid (20 mmol) and 4-(trifluoromethyl)benzeneamine (20 mmol) were dissolved in dimethylformamide (70 ml) and stirred under reflux for 24 hours. I did. Thereafter, the temperature was cooled to room temperature, and the solid formed in the reaction solution was filtered, washed with methanol, and recrystallized from dimethylformamide.

The recrystallized solid (10 mmol) was dissolved in toluene (100 ml), and triphenylphosphine palladium (Pd(PPh ₃ ) ₄ , 0.407 mmol) was added, followed by 2-(tributylstannyl)-3,4 -Dichloro-1H-pyrrole (10.1 mmol) was added and reacted for 24 hours. When the reaction was completed, the solid formed in the reaction solution was separated by filtration, and the separated solid was recrystallized from dimethylformamide to obtain the target compound.

¹ H NMR, δ (ppm) = 9.00 (s, 2H), 7.92 (s, 1H), 7.76 (d, 1H), 7.57 (d, 2H), 7.48-7.43 (m, 3H), 6.6 (s, 1H), 5.0 (s, 2H).

Example 20. Synthesis of <Structure 3-1> Compound

After dissolving 4,5-dibromobenzene-1-amino-2-phosphine (10 mmol) in a 4N aqueous hydrochloric acid solution (HCl, 15 ml), trifluoroacetic acid (10 mmol) was added, Stir at reflux for 24 hours. Thereafter, the reaction solution was cooled to room temperature and neutralized with a 2N aqueous sodium hydroxide (NaOH) solution, and the solid formed in the reaction solution was filtered and washed with water to obtain a target compound.

¹ H NMR, δ (ppm) = 7.1 (s, 1H), 6.5 (s, 1H), 4.0 (s, 1H).

Example 21. Synthesis of <Structure 3-2> Compound

After dissolving 4,5-dibromobenzene-1-amino-2-phosphine (10 mmol) in a 4N aqueous hydrochloric acid solution (HCl, 15 ml), 2,2,3,3,3-pentafluoro Propionic acid (10 mmol) was added and stirred under reflux for 24 hours. Thereafter, the reaction solution was cooled to room temperature and neutralized with a 2N aqueous sodium hydroxide (NaOH) solution, and then the solid formed in the reaction solution was filtered and washed with water. The washed solid (10 mmol) was dissolved in toluene (100 ml), triphenylphosphine palladium (Pd(PPh ₃ ) ₄ , 0.407 mmol) was added, and then tributyl (2-thienyl) stanane (10.1 mmol) was added and reacted for 24 hours. When the reaction was completed, the solid formed in the reaction solution was separated by filtration, and the separated solid was recrystallized from dimethylformamide.

The recrystallized solid (2.68 mmol) was dissolved in dimethylformamide (20 ml), and a solution in which N-bromosuccinimide (5.64 mmol) was dissolved in dimethylformamide (8 ml) was slowly added dropwise at 70°C. Stir for 24 hours. When the reaction was completed, the solid in the reaction solution was separated by filtration, and the separated solid was recrystallized from dimethylformamide.

The recrystallized solid (2 mmol) was dissolved in toluene (100 ml), triphenylphosphine palladium (Pd(PPh ₃ ) ₄ , 0.08 mmol) was added, and then 4,5-dibromo-2-(tri Butylstanyl)-1H-imidazole (2.2 mmol) was added and reacted for 24 hours. When the reaction was completed, the solid formed in the reaction solution was separated by filtration, and the separated solid was recrystallized from dimethylformamide to obtain the target compound.

¹ H NMR, δ (ppm) = 13.4 (s, 1H), 7.1 (s, 1H), 7.0 (d, 2H), 6.7 (s, 1H), 4.0 (s, 1H).

Example 22. Synthesis of <Structure 4-1> Compound

After dissolving 4,5-dibromobenzene-1,2-diamine (10 mmol) in a 4N aqueous hydrochloric acid solution (HCl, 15 ml), trifluoroacetic acid (10 mmol) was added, and for 24 hours Stir at reflux. Thereafter, the reaction solution was cooled to room temperature and neutralized with a 2N aqueous sodium hydroxide (NaOH) solution, and then the solid formed in the reaction solution was filtered and washed with water. The washed solid (10 mmol) was dissolved in toluene (100 ml), triphenylphosphine palladium (Pd(PPh ₃ ) ₄ , 0.407 mmol) was added, and then tributyl(thiophen-2-yl)stanan (10.1 mmol) was added and reacted for 24 hours. When the reaction was completed, the solid formed in the reaction solution was separated by filtration, and the separated solid was recrystallized from dimethylformamide.

The recrystallized solid (2.68 mmol) was dissolved in toluene (100 ml), triphenylphosphine palladium (Pd(PPh ₃ ) ₄ , 0.08 mmol) was added, and then tributyl(thiophen-2-yl)stanan (2.7 mmol) was added and reacted for 24 hours. When the reaction was completed, the solid formed in the reaction solution was separated by filtration, and the separated solid was recrystallized from dimethylformamide.

The recrystallized solid (1.5 mmol) was dissolved in dimethylformamide (20 ml), and a solution in which N-bromosuccinimide (5.64 mmol) was dissolved in dimethylformamide (8 ml) was slowly added dropwise at 70°C. Stir for 24 hours. When the reaction was completed, the solid in the reaction solution was separated by filtration, and the separated solid was recrystallized from dimethylformamide.

The recrystallized solid (1 mmol) was dissolved in toluene (100 ml), triphenylphosphine palladium (Pd(PPh ₃ ) ₄ , 0.04 mmol) was added, and then tributyl(thiophen-2-yl)stanan (2.1 mmol) was added and reacted for 24 hours. When the reaction was completed, the solid formed in the reaction solution was separated by filtration, and the separated solid was recrystallized from dimethylformamide to obtain the target compound.

¹ H NMR, δ (ppm) = 7.98 (s, 2H), 7.2 (d, 2H), 7.0 (m, 8H).

Example 23~44. Manufacture of electronic devices

After cleaning the ITO substrate with Hellamax and ethanol for 1 hour, hydrophobicizing the surface using oxygen (O2) plasma, trichloro (1H, 1H, 2H, 2H-perfluorooctyl) silane in a vacuum chamber And left for 50 minutes to treat the surface. A solution prepared by dissolving the compound (2.28 g) obtained in the Example in a solvent (10 ml) in which dimethylacetamide and acetone were mixed in a ratio of 1:1 (wt/wt) as shown in Table 1 below was prepared, The previously surface-treated ITO substrate was coated for 60±5 seconds at 1,200±10 rpm using a spin coater to form an organic layer having a thickness of 30±2 nm. An electronic device was manufactured by depositing gold (Au) having a thickness of 100±20 nm on the organic layer.

Types of compounds contained in the organic layer Types of compounds contained in the organic layer Example 23 Compound of Example 1 Example 34 Compound of Example 12 Example 24 Compound of Example 2 Example 35 Compound of Example 13 Example 25 Compound of Example 3 Example 36 Compound of Example 14 Example 26 Compound of Example 4 Example 37 Compound of Example 15 Example 27 Compound of Example 5 Example 38 Compound of Example 16 Example 28 Compound of Example 6 Example 39 Compound of Example 17 Example 29 Compound of Example 7 Example 40 The compound of Example 18 (70% by weight) and the compound of Example 22 (30% by weight) Example 30 Compound of Example 8 Example 41 Compound of Example 19 Example 31 Compound of Example 9 Example 42 Compound of Example 20 Example 32 Compound of Example 10 Example 43 Compound of Example 21 Example 33 Compound of Example 11 Example 44 The compound of Example 17 (10% by weight), the compound of Example 18 (70% by weight) and
Compound of Example 22 (20% by weight)

Example 45.

After cleaning the ITO substrate with Hellamax and ethanol for 1 hour, hydrophobicizing the surface using oxygen (O2) plasma, trichloro (1H, 1H, 2H, 2H-perfluorooctyl) silane in a vacuum chamber And left for 120 minutes to treat the surface. PVDF-HFP (3 g), the compound obtained in Example 11 (2.28 g), and ZnS:Mn (1 g) in a solvent (15 ml) in which dimethylacetamide and acetone were mixed in a ratio of 1:1 (wt/wt) ) Was prepared, and the solution was coated on the previously surface-treated ITO substrate at 1,800±50 rpm for 30±2 seconds using a spin coater to form an organic layer having a thickness of 35±0.2 μm. An electronic device was manufactured by depositing gold (Au) having a thickness of 100±5 nm on the organic layer.

Experimental example .

In order to evaluate the luminescence, ferroelectricity and piezoelectricity of the compound according to the present invention, the following experiment was performed.

First, absorbance and luminance in the range of 200 nm to 800 nm were measured after UV irradiation on the electronic devices prepared in Examples 23 to 44 using a UV-Vis spectrophotometer. In addition, the luminance and luminous efficiency of each electronic device were measured, and the luminous efficiency was measured based on a value when the luminance was 10 cd/A, and the unit of the measured value is %.

In addition, a polarization history curve was derived by applying an electric field of 0.1 to 500 kV/cm to the electronic devices of Examples 23 to 44 at room temperature for 10 to 20 minutes, and the piezoelectricity and residual polarization characteristics (Pr) from the derived hysteresis curve Was calculated.

The results are shown in FIGS. 1 and 2 and Table 2 below.

Absorption wavelength [nm] Emission wavelength [nm] Pr [μC/㎠] Example 23 307 411 5.5 Example 24 427 483 3.0 Example 25 315 470 5.4 Example 26 294 419 2.5 Example 27 261 432 4.1 Example 28 301 408 17.0 Example 29 308 431 3.7 Example 30 440 487 14.0 Example 31 437 486 2.9 Example 32 261 412 23.5 Example 33 267 393 4.6 Example 34 281 426 6.1 Example 35 340 442 4.5 Example 36 260 386 39.0 Example 37 321 468 32.0 Example 38 392 485 27.0 Example 39 270 420 5.0 Example 40 495 550 56.0 Example 41 490 587 3.0 Example 42 293 425 6.0 Example 43 310 459 26.0 Example 44 630 690 2.5 Example 45 267 393 4.6

Referring to Table 2 and FIGS. 1 and 2, it can be seen that an electronic device including the heteroaryl compound represented by Formula 1 according to the present invention in an organic layer has excellent luminescence, ferroelectricity and piezoelectricity.

Specifically, it was found that the organic layer containing the heteroaryl compound represented by Formula 1 has an absorption maximum in a wavelength range of 250 to 500 nm and a maximum emission in a wavelength range of 370 to 720 nm upon UV irradiation. The wavelength of 370 to 720 nm includes regions corresponding to red (red, about 370 to 520 nm), green (green, about 520 to 620 nm), and blue (blue, about 620 to 720 nm), which is represented by Formula 1 When the represented heteroaryl compound is included in the organic layer, it means that red, green, or blue light is emitted depending on the type of substituent introduced into the parent nucleus. In addition, it was confirmed that the luminance of each electronic device was about 5 cd/A or more, and the electronic device of Example 11 was found to have a luminance of about 10±2 cd/A. In addition, it was found that the luminous efficiency of the electronic device was 10% or more, and in particular, the electronic device of Example 12 was found to have a luminous efficiency of about 25±2%.

Further, it was found that the electronic devices of Examples 23 to 44 exhibit a nonlinear polarization history curve, and the residual polarization characteristic (Pr) is 2 to 58 μC/cm 2. This means that the heteroaryl compound represented by Formula 1 is ferroelectric and exhibits high piezoelectricity.

From these results, it can be seen that the heteroaryl compound represented by Formula 1 according to the present invention exhibits excellent luminescence, ferroelectricity and piezoelectricity, and an electronic device including the same can be usefully used in an organic light emitting device, a transistor, a capacitor, and the like.

Claims (16)

It exhibits a polarization characteristic of 0.1 μC/cm 2 to 100 μC/cm 2,
Heteroaryl compound represented by the following formula (1):
[Formula 1]

In Formula 1,
X is N or P,
R ₁ is hydrogen or a C1-6 alkyl group,
R ₂ is a C 1 to 6 alkyl group or a 5 to 20 atom heteroaryl group,
R ₃ and R ₆ are each independently hydrogen or a halogen group, or together with the carbon atom to which R ₃ or R ₆ is bonded form a ketone group,
R ₄ is hydrogen, a halogen group, or a 5 to 20 membered heteroaryl group,
R ₅ is a halogen group, a carboxyl group, a C6 to 30 aryl group, a thiophenyl group, a pyrrolyl group, a tetrazinyl group, an imidazolyl group, or a triazolyl group,
When R ₅ is an aryl group, the aryl group is substituted with an amine group or an amine group and an s-butyl group (s-Bu),
When R ₅ is a thiophenyl group, the thiophenyl group is substituted with a C6 to 30 aryl group or a 5 to 20 atom heteroaryl group;
At least one of the hydrogens present in the alkyl group, heteroaryl group, thiophenyl group, pyrrolyl group, tetrazinyl group, imidazolyl group or triazolyl group of R ₁ to R ₆ is a halogen group, amine group, hydroxy group, aldehyde group , A carboxyl group, or a C6 to 30 aryl group unsubstituted or substituted with these, or a 5 to 20 membered heteroaryl group, or unsubstituted.
The method of claim 1,
In the definition of a substituent in Formula 1,
X is N,
R ₁ is hydrogen, methyl or ethyl,
R ₂ is a methyl group, an ethyl group or a propyl group,
R ₃ and R ₆ are hydrogen or halogen groups,
R ₄ is a halogen group,
R ₅ is a thiophenyl group, a pyrrolyl group, a tetrazinyl group, an imidazolyl group, or a triazolyl group,
When R ₅ is a thiophenyl group, the thiophenyl group is substituted with a C6 to 30 aryl group or a 5 to 20 atom heteroaryl group;
At least one of the hydrogens present in the alkyl group, heteroaryl group, thiophenyl group, pyrrolyl group, tetrazinyl group, imidazolyl group or triazolyl group of R ₁ to R ₆ is a halogen group, amine group, hydroxy group, aldehyde group , A carboxyl group, or a heteroaryl compound unsubstituted or substituted with a C6 to 30 aryl group substituted or unsubstituted with these or a 5 to 20 membered heteroaryl group.
The method of claim 2,
The compound represented by Formula 1 is any one or more heteroaryl compounds selected from the following <Structure 1-2> to <Structure 1-10>:

<Structure 1-2>

<Structure 1-3>

<Structure 1-4>

<Structure 1-5>

<Structure 1-6>

<Structure 1-7>

<Structure 1-8>

<Structure 1-9>

<Structure 1-10>

.
The method of claim 1,
In the definition of a substituent in Formula 1,
X is N,
R ₁ is hydrogen,
R ₂ is a methyl group, an ethyl group,

or

ego,
R ₃ and R ₆ are hydrogen or halogen groups,
R ₄ is hydrogen,
R ₅ is a carboxyl group, a phenyl group, a naphthyl group, an anthracenyl group, a pyrenyl group, a thiophenyl group, a pyrrolyl group, a tetrazinyl group, an imidazolyl group, or a triazolyl group,
When R ₅ is a phenyl group, naphthyl group, anthracenyl group or pyrenyl group, the phenyl group, naphthyl group, anthracenyl group, or pyrenyl group is substituted with an amine group or an amine group and an s-butyl group (s-Bu),
When R ₅ is a thiophenyl group, the thiophenyl group is substituted with a C6 to 30 aryl group,
At least one of the hydrogens present in the alkyl group, heteroaryl group, thiophenyl group, pyrrolyl group, tetrazinyl group, imidazolyl group or triazolyl group of R ₁ to R ₆ is a halogen group, amine group, hydroxy group, aldehyde group , A carboxyl group, or a heteroaryl compound unsubstituted or substituted with a C6 to 30 aryl group substituted or unsubstituted with these or a 5 to 20 membered heteroaryl group.
The method of claim 4,
The compound represented by Formula 1 is any one or more heteroaryl compounds selected from the following <Structure 2-1> to <Structure 2-7>:
<Structure 2-1>

<Structure 2-2>

<Structure 2-3>

<Structure 2-4>

<Structure 2-5>

<Structure 2-6>

<Structure 2-7>

.
The method of claim 1,
In the definition of a substituent in Formula 1,
X is P,
R ₁ is hydrogen,
R ₂ is a methyl group, an ethyl group, a propyl group or a butyl group,
R ₃ and R ₆ are hydrogen or halogen groups,
R ₄ is a fluoro group, a chloro group or a bromo group,
R ₅ is a chloro group, a bromo group, a phenyl group, a naphthyl group, an anthracenyl group, a pyrenyl group, a thiophenyl group, a pyrrolyl group, a tetrazinyl group, an imidazolyl group, or a triazolyl group,
When R ₅ is a phenyl group, naphthyl group, anthracenyl group or pyrenyl group, the phenyl group, naphthyl group, anthracenyl group, or pyrenyl group is substituted with an amine group or an amine group and an s-butyl group (s-Bu),
When R ₅ is a thiophenyl group, the thiophenyl group is substituted with a C6 to 30 aryl group or a 5 to 20 atom heteroaryl group,
Any one or more of the hydrogens present in the methyl group, ethyl group, propyl group, butyl group, pyrrolyl group, tetrazinyl group, imidazolyl group, or triazolyl group of R ₂ and R ₅ are phenyl group, naphthyl group, thiophenyl group, pyrrolyl group , A tetrazinyl group, an imidazolyl group, or a heteroaryl compound unsubstituted or substituted with a triazolyl group.
The method of claim 6,
The compound represented by Formula 1 is any one or more heteroaryl compounds selected from the following <Structure 3-1> and <Structure 3-2>:
<Structure 3-1>

<Structure 3-2>

.
The method of claim 1,
The compound represented by Formula 1 is a heteroaryl compound selected from the following <Structure 4-1>:
<Structure 4-1>

.
The method of claim 1,
The heteroaryl compound is a heteroaryl compound having a maximum emission at 380 nm to 720 nm when measuring the luminance in the 200 nm to 800 nm range.
delete A first electrode;
A second electrode opposite the first electrode; And
Interposed between the first electrode and the second electrode, including an organic layer containing a heteroaryl compound represented by the following formula (1),
The heteroaryl compound is an electronic device exhibiting a polarization characteristic of 0.1 μC/cm 2 to 100 μC/cm 2:
[Formula 1]

In Formula 1,
X is N or P,
R ₁ is hydrogen or a C1-6 alkyl group,
R ₂ is a C 1 to 6 alkyl group or a 5 to 20 atom heteroaryl group,
R ₃ and R ₆ are each independently hydrogen or a halogen group, or together with the carbon atom to which R ₃ or R ₆ is bonded form a ketone group,
R ₄ is hydrogen, a halogen group, or a 5 to 20 membered heteroaryl group,
R ₅ is a halogen group, a carboxyl group, a C6 to 30 aryl group, a thiophenyl group, a pyrrolyl group, a tetrazinyl group, an imidazolyl group, or a triazolyl group,
When R ₅ is an aryl group, the aryl group is substituted with an amine group or an amine group and an s-butyl group (s-Bu),
When R ₅ is a thiophenyl group, the thiophenyl group is substituted with a C6 to 30 aryl group or a 5 to 20 atom heteroaryl group;
At least one of the hydrogens present in the alkyl group, heteroaryl group, thiophenyl group, pyrrolyl group, tetrazinyl group, imidazolyl group or triazolyl group of R ₁ to R ₆ is a halogen group, amine group, hydroxy group, aldehyde group , A carboxyl group, or a C6 to 30 aryl group unsubstituted or substituted with these, or a 5 to 20 membered heteroaryl group, or unsubstituted.
The method of claim 11,
The organic layer is polyvinylidene fluoride (PVDF), a copolymer of vinylidene fluoride and trifluoroethylene (PVDF-TrFE), a copolymer of vinylidene fluoride and hexafluoroethylene (PVDF-HFP), vinylidene. Copolymer of amide and vinyl acetate (P(VDCN-VAc)), nylon-11 (nylon-11), polyurea-9, polyvinyl chloride (PVC), polyacrylonitrile (PAN), An electronic device further comprising at least one binder selected from the group consisting of polyphthalazinone ether nitrile (PPEN), polyethylene oxide (PEO), and polyether sulfone (PES).
The method of claim 11,
An electronic device further comprising a hole transport layer between the first electrode and the organic layer.
An organic light-emitting device comprising the electronic device according to claim 11.
A transistor comprising the electronic device according to claim 11.
A capacitor comprising the electronic device according to claim 11.

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