KR20120078301A - Compound for organic photoelectric device and organic photoelectric device including the same - Google Patents

Abstract

PURPOSE: A compound for organic photoelectric device is provided to have high hole or electron transportability, a film stability, thermal stability, and triplet excitation energy. CONSTITUTION: A compound for organic photoelectric device is combinations of chemical formula 1, chemical formula 2, or chemical formula 3. An organic photoelectric device comprises a positive electrode, a negative electrode, and at least one or more layers of organic thin film layers inserted between the positive electrode and the negative electrode. The organic thin film layer comprises the compound for organic photoelectric device. The thin filmy layer is selected from a group selected from an electroluminescence layer, a hole transport layer, a hole injection layer, an electron transport layer, an electron injection layer, a hole block layer, and combinations thereof.

Description

Compound for organic photoelectric device and organic photoelectric device including same

The present invention relates to a compound for an organic photoelectric device and an organic photoelectric device including the same, which can provide an organic photoelectric device having excellent lifetime, efficiency, electrochemical stability, and thermal stability.

An organic photoelectric device refers to a device requiring charge exchange between an electrode and an organic material using holes or electrons.

The organic photoelectric device can be divided into two types according to the operation principle. First, excitons are formed in the organic material layer by photons introduced into the device from an external light source, and the excitons are separated into electrons and holes, and these electrons and holes are transferred to different electrodes to be used as current sources (voltage sources). It is an electronic device of the form.

The second is an electronic device in which holes or electrons are injected into an organic semiconductor forming an interface with the electrodes by applying voltage or current to two or more electrodes, and operated by the injected electrons and holes.

Examples of an organic photoelectric device include an organic light emitting device, an organic solar cell, an organic photo conductor drum, and an organic transistor, all of which are used for injecting or transporting holes, injecting or transporting electrons for driving the device. Or a luminescent material.

In particular, organic light emitting diodes (OLEDs) are attracting attention as the demand for flat panel displays increases. In general, organic light emission phenomenon refers to a phenomenon in which an organic material is used to convert electric energy into light energy.

Such an organic light emitting device converts electrical energy into light by applying a current to an organic light emitting material, and has a structure in which a functional organic material layer is inserted between an anode and a cathode. The organic material layer is often made of a multi-layered structure composed of different materials to increase the efficiency and stability of the organic photoelectric device, for example, it may be made of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer.

When the voltage is applied between the two electrodes in the structure of the organic light emitting device, holes are injected into the organic material layer in the anode and electrons in the cathode, and the injected holes and the electrons meet and recombine by recombination. High energy excitons are formed. At this time, the excitons formed are moved to the ground state, and light having a specific wavelength is generated.

Recently, it has been known that not only fluorescent light emitting materials but also phosphorescent light emitting materials may be used as light emitting materials of organic photoelectric devices. Such phosphorescent light emitting may be performed after the electrons transition from the ground state to the excited state, It is composed of a mechanism in which singlet excitons are non-luminescent transition into triplet excitons through intersystem crossing, and then triplet excitons emit light as they transition to the ground state.

As described above, the material used as the organic material layer in the organic light emitting device may be classified into a light emitting material and a charge transport material, such as a hole injection material, a hole transport material, an electron transport material, an electron injection material, and the like according to a function.

In addition, the light emitting materials may be classified into blue, green, and red light emitting materials and yellow and orange light emitting materials required to realize better natural colors according to light emission colors.

On the other hand, when only one material is used as the light emitting material, the maximum emission wavelength is shifted to a long wavelength due to the intermolecular interaction, and the color purity decreases or the efficiency of the device decreases due to the emission attenuation effect. In order to increase luminous efficiency and stability through the host / dopant system can be used as a light emitting material.

In order for the organic light emitting device to fully exhibit the above-described excellent features, materials constituting the organic material layer in the device, such as a hole injection material, a hole transport material, a light emitting material, an electron transport material, an electron injection material, a host and / or a dopant in the light emitting material, etc. Supported by this stable and efficient material should be preceded, and development of a stable and efficient organic material layer for an organic light emitting device has not been made yet, and therefore, development of new materials is continuously required. The need for such a material development is the same for the other organic photoelectric devices described above.

In addition, the low molecular weight organic light emitting diode is manufactured in the form of a thin film by vacuum evaporation method, so the efficiency and lifespan performance is good, and the high molecular weight organic light emitting diode using the inkjet or spin coating method has low initial investment cost. Large area has an advantage.

Both low molecular weight organic light emitting diodes and high molecular weight organic light emitting diodes are attracting attention as next-generation displays because they have advantages such as self-luminous, high-speed response, wide viewing angle, ultra-thin, high-definition, durability, and wide driving temperature range. Compared with crystal display, it is self-luminous type, so it is good for cyanity even in the dark or outside light, and it can reduce thickness and weight by 1/3 of LCD because it does not need backlight.

In addition, the response speed is 1000 times faster than the LCD in microseconds, it is possible to implement a perfect video without afterimages. Therefore, it is expected to be spotlighted as the most suitable display in line with the recent multimedia era. Based on these advantages, we have made rapid technological developments with efficiency of 80 times and lifespan over 100 times since the first development in the late 1980s. Increasingly, large-scaled developments are being made with the introduction of organic light emitting diode panels.

In order to increase the size, the luminous efficiency must be increased and the life of the device must be accompanied. In this case, the light emitting efficiency of the device should be smoothly coupled to the holes and electrons in the light emitting layer. However, since the electron mobility of the organic material is generally slower than the hole mobility, in order to efficiently combine holes and electrons in the light emitting layer, an efficient electron transport layer is used to increase the electron injection and mobility from the cathode, It should be able to block the movement of holes.

In addition, in order to improve the life, it is necessary to prevent the material from crystallizing due to Joule heat generated when the device is driven. Therefore, there is a need for development of organic compounds having excellent electron injection and mobility and high electrochemical stability.

An organic photoelectric device refers to a device requiring charge exchange between an electrode and an organic material using holes or electrons.

The organic photoelectric device can be divided into two types according to the operation principle. First, excitons are formed in the organic material layer by photons introduced into the device from an external light source, and the excitons are separated into electrons and holes, and these electrons and holes are transferred to different electrodes to be used as current sources (voltage sources). It is an electronic device of the form.

The second is an electronic device in which holes or electrons are injected into an organic semiconductor forming an interface with the electrodes by applying voltage or current to two or more electrodes, and operated by the injected electrons and holes.

Examples of an organic photoelectric device include an organic light emitting device, an organic solar cell, an organic photo conductor drum, and an organic transistor, all of which are used for injecting or transporting holes, injecting or transporting electrons for driving the device. Or a luminescent material.

In particular, organic light emitting diodes (OLEDs) are attracting attention as the demand for flat panel displays increases. In general, organic light emission phenomenon refers to a phenomenon in which an organic material is used to convert electric energy into light energy.

Such an organic light emitting device converts electrical energy into light by applying a current to an organic light emitting material, and has a structure in which a functional organic material layer is inserted between an anode and a cathode. The organic material layer is often made of a multi-layered structure composed of different materials to increase the efficiency and stability of the organic photoelectric device, for example, it may be made of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer.

When the voltage is applied between the two electrodes in the structure of the organic light emitting device, holes are injected into the organic material layer in the anode and electrons in the cathode, and the injected holes and the electrons meet and recombine by recombination. High energy excitons are formed. At this time, the excitons formed are moved to the ground state, and light having a specific wavelength is generated.

Recently, it has been known that not only fluorescent light emitting materials but also phosphorescent light emitting materials may be used as light emitting materials of organic photoelectric devices. Such phosphorescent light emitting may be performed after the electrons transition from the ground state to the excited state, It is composed of a mechanism in which singlet excitons are non-luminescent transition into triplet excitons through intersystem crossing, and then triplet excitons emit light as they transition to the ground state.

As described above, the material used as the organic material layer in the organic light emitting device may be classified into a light emitting material and a charge transport material, such as a hole injection material, a hole transport material, an electron transport material, an electron injection material, and the like according to a function.

In addition, the light emitting materials may be classified into blue, green, and red light emitting materials and yellow and orange light emitting materials required to realize better natural colors according to light emission colors.

On the other hand, when only one material is used as the light emitting material, the maximum emission wavelength is shifted to a long wavelength due to the intermolecular interaction, and the color purity decreases or the efficiency of the device decreases due to the emission attenuation effect. In order to increase luminous efficiency and stability through the host / dopant system can be used as a light emitting material.

In order for the organic light emitting device to fully exhibit the above-described excellent features, materials constituting the organic material layer in the device, such as a hole injection material, a hole transport material, a light emitting material, an electron transport material, an electron injection material, a host and / or a dopant in the light emitting material, etc. Supported by this stable and efficient material should be preceded, and development of a stable and efficient organic material layer for an organic light emitting device has not been made yet, and therefore, development of new materials is continuously required. The need for such a material development is the same for the other organic photoelectric devices described above.

In addition, the low molecular weight organic light emitting diode is manufactured in the form of a thin film by vacuum evaporation method, so the efficiency and lifespan performance is good, and the high molecular weight organic light emitting diode using the inkjet or spin coating method has low initial investment cost. Large area has an advantage.

Both low molecular weight organic light emitting diodes and high molecular weight organic light emitting diodes are attracting attention as next-generation displays because they have advantages such as self-luminous, high-speed response, wide viewing angle, ultra-thin, high-definition, durability, and wide driving temperature range. Compared with crystal display, it is self-luminous type, so it is good for cyanity even in the dark or outside light, and it can reduce thickness and weight by 1/3 of LCD because it does not need backlight.

In addition, the response speed is 1000 times faster than the LCD in microseconds, it is possible to implement a perfect video without afterimages. Therefore, it is expected to be spotlighted as the most suitable display in line with the recent multimedia era. Based on these advantages, we have made rapid technological developments with efficiency of 80 times and lifespan over 100 times since the first development in the late 1980s. Increasingly, large-scaled developments are being made with the introduction of organic light emitting diode panels.

In order to increase the size, the luminous efficiency must be increased and the life of the device must be accompanied. In this case, the light emitting efficiency of the device should be smoothly coupled to the holes and electrons in the light emitting layer. However, since the electron mobility of the organic material is generally slower than the hole mobility, in order to efficiently combine holes and electrons in the light emitting layer, an efficient electron transport layer is used to increase the electron injection and mobility from the cathode, It should be able to block the movement of holes.

In addition, in order to improve the life, it is necessary to prevent the material from crystallizing due to Joule heat generated when the device is driven. Therefore, there is a need for development of organic compounds having excellent electron injection and mobility and high electrochemical stability.

In one aspect of the invention, the formula 1; And it provides a compound for an organic photoelectric device represented by the combination of formula (2) or (3).

[Formula 1] [Formula 2] [Formula 3]

In Formulas 1 to 3, X is O, Se, S, SO 2 (O = S = O), PO (P = O) or CO (C = O), and Y is CR′R ′ or NR * Wherein a *, b *, R ', R', R ¹ , R ² and R * are the same as or different from each other, and independently hydrogen, deuterium, halogen, cyano group, hydroxyl group, amino group, substituted or Unsubstituted C1 to C20 amine group, nitro group, substituted or unsubstituted C2 to C10 carboxyl group, substituted or unsubstituted ferrocenyl group, substituted or unsubstituted C1 to C20 alkyl group, substituted or unsubstituted C6 to C30 aryl Groups, substituted or unsubstituted C2 to C30 heteroaryl groups, substituted or unsubstituted C1 to C20 alkoxy groups, substituted or unsubstituted C6 to C20 aryloxy groups, substituted or unsubstituted C3 to C40 silyloxy groups, substituted Or an unsubstituted C1 to C20 acyl group, a substituted or unsubstituted C2 to C20 alkoxycarbonyl group, a substituted or unsubstituted C2 to C20 acyloxy group, substituted Or an unsubstituted C2 to C20 acylamino group, a substituted or unsubstituted C2 to C20 alkoxycarbonylamino group, a substituted or unsubstituted C7 to C20 aryloxycarbonylamino group, a substituted or unsubstituted C1 to C20 sulfamoylamino group , Substituted or unsubstituted C1 to C20 sulfonyl group, substituted or unsubstituted C1 to C20 alkylthiol group, substituted or unsubstituted C6 to C20 arylthiol group, substituted or unsubstituted C1 to C20 heterocyclothiol group, A substituted or unsubstituted C1 to C20 ureide group, a substituted or unsubstituted C3 to C40 silyl group, or a combination thereof, and two adjacent * of Formula 1 are selected from two adjacent * of Formula 2 or 3 and Combine to form a fused ring, and at least one of the a *, b * or R * is a substituent represented by the following Chemical Formula 4,

[Formula 4]

In Chemical Formula 4, the ETU has an electronic property, a substituted or unsubstituted C6 to C30 aryl group; Or a substituted or unsubstituted C2 to C30 heteroaryl group having electronic properties, wherein L is a single bond, a substituted or unsubstituted C2 to C6 alkenylene group, a substituted or unsubstituted C2 to C6 alkynylene group, substituted Or an unsubstituted C6 to C30 arylene group, a substituted or unsubstituted heteroarylene group, or a combination thereof, wherein n is an integer of 0 to 2.

The compound for an organic photoelectric device may be represented by Formula 5 below.

[Chemical Formula 5]

In Formula 5, X is O, Se, S, SO 2 (O = S = O), PO (P = O) or CO (C = O), and Y is CR′R ′ or NR *, A *, b *, R ', R', R ¹ , R ² and R * are the same as or different from each other, and independently hydrogen, deuterium, a halogen group, a cyano group, a hydroxyl group, an amino group, a substituted or unsubstituted Substituted C1 to C20 amine group, nitro group, substituted or unsubstituted C2 to C10 carboxyl group, substituted or unsubstituted ferrocenyl group, substituted or unsubstituted C1 to C20 alkyl group, substituted or unsubstituted C6 to C30 aryl group, Substituted or unsubstituted C2 to C30 heteroaryl group, substituted or unsubstituted C1 to C20 alkoxy group, substituted or unsubstituted C6 to C20 aryloxy group, substituted or unsubstituted C3 to C40 silyloxy group, substituted or unsubstituted A substituted C1 to C20 acyl group, a substituted or unsubstituted C2 to C20 alkoxycarbonyl group, a substituted or unsubstituted C2 to C20 acyloxy group, a substituted or Substituted C2 to C20 acylamino group, substituted or unsubstituted C2 to C20 alkoxycarbonylamino group, substituted or unsubstituted C7 to C20 aryloxycarbonylamino group, substituted or unsubstituted C1 to C20 sulfamoylamino group, substituted Or unsubstituted C1 to C20 sulfonyl group, substituted or unsubstituted C1 to C20 alkylthiol group, substituted or unsubstituted C6 to C20 arylthiol group, substituted or unsubstituted C1 to C20 heterocyclothiol group, substituted or An unsubstituted C1 to C20 ureide group, a substituted or unsubstituted C3 to C40 silyl group, or a combination thereof, and at least one of the a *, b * or R * is a substituent represented by the following Chemical Formula 4,

[Formula 4]

In Chemical Formula 4, the ETU has an electronic property, a substituted or unsubstituted C6 to C30 aryl group; Or a substituted or unsubstituted C2 to C30 heteroaryl group having electronic properties, wherein L is a single bond, a substituted or unsubstituted C2 to C6 alkenylene group, a substituted or unsubstituted C2 to C6 alkynylene group, substituted Or an unsubstituted C6 to C30 arylene group, a substituted or unsubstituted heteroarylene group, or a combination thereof, wherein n is an integer of 0 to 2.

The compound for an organic photoelectric device may be represented by the following formula (6).

[Formula 6]

In Formula 6, X is O, Se, S, SO 2 (O = S = O), PO (P = O) or CO (C = O), and Y is CR′R ′ or NR *, R ′, R ′, R ¹ , R ² and R * are the same as or different from each other, and independently hydrogen, deuterium, a halogen group, a cyano group, a hydroxyl group, an amino group, a substituted or unsubstituted C1 to C20 amine group , Nitro group, substituted or unsubstituted C2 to C10 carboxyl group, substituted or unsubstituted ferrocenyl group, substituted or unsubstituted C1 to C20 alkyl group, substituted or unsubstituted C6 to C30 aryl group, substituted or unsubstituted C2 To C30 heteroaryl group, substituted or unsubstituted C1 to C20 alkoxy group, substituted or unsubstituted C6 to C20 aryloxy group, substituted or unsubstituted C3 to C40 silyloxy group, substituted or unsubstituted C1 to C20 ah Real, substituted or unsubstituted C2 to C20 alkoxycarbonyl group, substituted or unsubstituted C2 to C20 acyloxy group, substituted or unsubstituted Substituted C2 to C20 acylamino group, substituted or unsubstituted C2 to C20 alkoxycarbonylamino group, substituted or unsubstituted C7 to C20 aryloxycarbonylamino group, substituted or unsubstituted C1 to C20 sulfamoylamino group, substituted or Unsubstituted C1 to C20 sulfonyl group, substituted or unsubstituted C1 to C20 alkylthiol group, substituted or unsubstituted C6 to C20 arylthiol group, substituted or unsubstituted C1 to C20 heterocyclothiol group, substituted or unsubstituted A substituted C1 to C20 ureide group, a substituted or unsubstituted C3 to C40 silyl group, or a combination thereof, wherein the ETU has an electronic property, a substituted or unsubstituted C6 to C30 aryl group; Or a substituted or unsubstituted C2 to C30 heteroaryl group having electronic properties, wherein L is a single bond, a substituted or unsubstituted C2 to C6 alkenylene group, a substituted or unsubstituted C2 to C6 alkynylene group, substituted Or an unsubstituted C6 to C30 arylene group, a substituted or unsubstituted heteroarylene group, or a combination thereof, wherein n is an integer of 0 to 2.

The compound for an organic photoelectric device may be represented by the following Formula 7.

[Formula 7]

In Formula 7, X is O, Se, S, SO 2 (O = S = O), PO (P = O) or CO (C = O), and Y is CR′R ′ or NR *, R ′, R ′, R ¹ , R ² and R * are the same as or different from each other, and independently hydrogen, deuterium, a halogen group, a cyano group, a hydroxyl group, an amino group, a substituted or unsubstituted C1 to C20 amine group , Nitro group, substituted or unsubstituted C2 to C10 carboxyl group, substituted or unsubstituted ferrocenyl group, substituted or unsubstituted C1 to C20 alkyl group, substituted or unsubstituted C6 to C30 aryl group, substituted or unsubstituted C2 To C30 heteroaryl group, substituted or unsubstituted C1 to C20 alkoxy group, substituted or unsubstituted C6 to C20 aryloxy group, substituted or unsubstituted C3 to C40 silyloxy group, substituted or unsubstituted C1 to C20 ah Real, substituted or unsubstituted C2 to C20 alkoxycarbonyl group, substituted or unsubstituted C2 to C20 acyloxy group, substituted or unsubstituted Substituted C2 to C20 acylamino group, substituted or unsubstituted C2 to C20 alkoxycarbonylamino group, substituted or unsubstituted C7 to C20 aryloxycarbonylamino group, substituted or unsubstituted C1 to C20 sulfamoylamino group, substituted or Unsubstituted C1 to C20 sulfonyl group, substituted or unsubstituted C1 to C20 alkylthiol group, substituted or unsubstituted C6 to C20 arylthiol group, substituted or unsubstituted C1 to C20 heterocyclothiol group, substituted or unsubstituted A substituted C1 to C20 ureide group, a substituted or unsubstituted C3 to C40 silyl group, or a combination thereof, wherein the ETU has an electronic property, a substituted or unsubstituted C6 to C30 aryl group; Or a substituted or unsubstituted C2 to C30 heteroaryl group having electronic properties, wherein L is a single bond, a substituted or unsubstituted C2 to C6 alkenylene group, a substituted or unsubstituted C2 to C6 alkynylene group, substituted Or an unsubstituted C6 to C30 arylene group, a substituted or unsubstituted heteroarylene group, or a combination thereof, wherein n is an integer of 0 to 2.

The compound for an organic photoelectric device may be represented by the following formula (8).

[Formula 8]

In Formula 8, X is O, Se, S, SO 2 (O = S = O), PO (P = O) or CO (C = O), and Y is CR′R ′ or NR *, R ′, R ′, R ¹ , R ² and R * are the same as or different from each other, and independently hydrogen, deuterium, a halogen group, a cyano group, a hydroxyl group, an amino group, a substituted or unsubstituted C1 to C20 amine group , Nitro group, substituted or unsubstituted C2 to C10 carboxyl group, substituted or unsubstituted ferrocenyl group, substituted or unsubstituted C1 to C20 alkyl group, substituted or unsubstituted C6 to C30 aryl group, substituted or unsubstituted C2 To C30 heteroaryl group, substituted or unsubstituted C1 to C20 alkoxy group, substituted or unsubstituted C6 to C20 aryloxy group, substituted or unsubstituted C3 to C40 silyloxy group, substituted or unsubstituted C1 to C20 ah Real, substituted or unsubstituted C2 to C20 alkoxycarbonyl group, substituted or unsubstituted C2 to C20 acyloxy group, substituted or unsubstituted Substituted C2 to C20 acylamino group, substituted or unsubstituted C2 to C20 alkoxycarbonylamino group, substituted or unsubstituted C7 to C20 aryloxycarbonylamino group, substituted or unsubstituted C1 to C20 sulfamoylamino group, substituted or Unsubstituted C1 to C20 sulfonyl group, substituted or unsubstituted C1 to C20 alkylthiol group, substituted or unsubstituted C6 to C20 arylthiol group, substituted or unsubstituted C1 to C20 heterocyclothiol group, substituted or unsubstituted A substituted C1 to C20 ureide group, a substituted or unsubstituted C3 to C40 silyl group, or a combination thereof, wherein the ETU has an electronic property, a substituted or unsubstituted C6 to C30 aryl group; Or a substituted or unsubstituted C2 to C30 heteroaryl group having electronic properties, wherein L is a single bond, a substituted or unsubstituted C2 to C6 alkenylene group, a substituted or unsubstituted C2 to C6 alkynylene group, substituted Or an unsubstituted C6 to C30 arylene group, a substituted or unsubstituted heteroarylene group, or a combination thereof, wherein n is an integer of 0 to 2.

The substituted or unsubstituted C6 to C30 aryl group having the above electronic properties is a substituted or unsubstituted triphenylenyl group, a substituted or unsubstituted florenyl group, a substituted or unsubstituted spiroflorenyl group, a substituted or unsubstituted terphenyl group , Substituted or unsubstituted pyrenyl group, substituted or unsubstituted perenyl group, substituted or unsubstituted phenanthrenyl group, or a combination thereof.

Substituted or unsubstituted C2 to C30 heteroaryl group having the above electronic properties, substituted or unsubstituted imidazolyl group, substituted or unsubstituted triazolyl group, substituted or unsubstituted tetrazolyl group, substituted or unsubstituted Carbazolyl group, substituted or unsubstituted oxadiazolyl group, substituted or unsubstituted oxatriazolyl group, substituted or unsubstituted thiaziazolyl group, substituted or unsubstituted benzimidazolyl group, substituted or unsubstituted Benzotriazolyl group, substituted or unsubstituted pyridinyl group, substituted or unsubstituted pyrimidinyl group, substituted or unsubstituted triazinyl group, substituted or unsubstituted pyrazinyl group, substituted or unsubstituted pyridazinyl Groups, substituted or unsubstituted purinyl groups, substituted or unsubstituted quinolinyl groups, substituted or unsubstituted isoquinolinyl groups, substituted or unsubstituted phthalazinyl groups, substituted or unsubstituted naphthos Dinyl group, substituted or unsubstituted quinoxalinyl group, substituted or unsubstituted quinazolinyl group, substituted or unsubstituted acridinyl group, substituted or unsubstituted phenanthrolinyl group, substituted or unsubstituted phenazinyl group or theirs May be a combination.

The compound for an organic photoelectric device may be represented by any one of the following Formulas A-1 to A-55.

[Formula A-1] [Formula A-2] [Formula A-3]

[Formula A-4] [Formula A-5] [Formula A-6]

[Formula A-7] [Formula A-8] [Formula A-9]

[Formula A-10] [Formula A-11] [Formula A-12]

[Formula A-13] [Formula A-14] [Formula A-15]

[Formula A-16] [Formula A-17] [Formula A-18]

[화학식 A-19] [화학식 A-20] [화학식 A-21]

[Formula A-19] [Formula A-20] [Formula A-21]

[Formula A-22] [Formula A-23] [Formula A-24]

[Formula A-25] [Formula A-26] [Formula A-27]

[Formula A-28] [Formula A-29] [Formula A-30]

[Formula A-31] [Formula A-32] [Formula A-33]

[Formula A-34] [Formula A-35] [Formula A-36]

[Formula A-37] [Formula A-38] [Formula A-39]

[Formula A-40] [Formula A-41] [Formula A-42]

[Formula A-43] [Formula A-44] [Formula A-45]

[Formula A-46] [Formula A-47] [Formula A-48]

[Formula A-49] [Formula A-51] [Formula A-52]

[Formula A-53] [Formula A-54] [Formula A-55]

The compound for an organic photoelectric device may be represented by any one of the following Formulas B-1 to B-44.

[Formula B-1] [Formula B-2] [Formula B-3]

[Formula B-4] [Formula B-5] [Formula B-6]

[Formula B-7] [Formula B-8] [Formula B-9]

[Formula B-10] [Formula B-11]

[Formula B-12] [Formula B-13] [Formula B-14]

[Formula B-15] [Formula B-16] [Formula B-17]

[Formula B-18] [Formula B-19] [Formula B-20]

Formula B-21 Formula B-22

[Formula B-23] [Formula B-24] [Formula B-25]

[Formula B-26] [Formula B-27] [Formula B-28]

[Formula B-29] [Formula B-30] [Formula B-31]

Formula B-32 Formula B-33

[Formula B-34] [Formula B-35] [Formula B-36]

[Formula B-37] [Formula B-38] [Formula B-39]

[Formula B-40] [Formula B-41] [Formula B-42]

Formula B-43 Formula B-44

The compound for an organic photoelectric device may be represented by any one of the following Chemical Formulas C-1 to C-12.

[Formula C-1] [Formula C-2] [Formula C-3]

[Formula C-4] [Formula C-5] [Formula C-6]

[Formula C-7] [Formula C-8] [Formula C-9]

[Formula C-10] [Formula C-11] [Formula C-12]

[Formula C-13] [Formula C-14] [Formula C-15]

[Formula C-16] [Formula C-17] [Formula C-18]

Formula C-19 Formula C-20

The compound for an organic photoelectric device may be represented by any one of the following Formulas D-1 to D-6.

[Formula D-1] [Formula D-2] [Formula D-3]

[Formula D-4] [Formula D-5] [Formula D-6]

[Formula D-7] [Formula D-8]

The compound for an organic photoelectric device is a compound for an organic photoelectric device represented by any one of the following formulas E-1 to E-6.

[Formula E-1] [Formula E-2] [Formula E-3]

[Formula E-4] [Formula E-5] [Formula E-6]

[Formula E-7] [Formula E-8]

[Formula E-9]

The compound for an organic photoelectric device may be one that can be used as a light emitting material of the organic light emitting device.

The compound for an organic photoelectric device may be a triplet excitation energy (T1) of 2.0 eV or more.

The organic photoelectric device may be selected from the group consisting of an organic light emitting device, an organic solar cell, an organic transistor, an organic photosensitive drum, and an organic memory device.

In another aspect of the invention, in the organic light emitting device comprising an anode, a cathode and at least one organic thin film layer interposed between the anode and the cathode, at least any one of the organic thin film layer for the above organic photoelectric device It provides an organic light emitting device comprising a compound.

The organic thin film layer may be selected from the group consisting of a light emitting layer, a hole transport layer, a hole injection layer, an electron transport layer, an electron injection layer, a hole blocking layer and a combination thereof.

The compound for an organic photoelectric device may be included in a hole transport layer, a hole injection layer, an electron transport layer or an electron injection layer.

The compound for an organic photoelectric device may be included in a light emitting layer.

The compound for an organic photoelectric device may be used as a phosphorescent or fluorescent host material in the light emitting layer.

The compound for an organic photoelectric device may be used as a fluorescent blue dopant material in a light emitting layer.

In another aspect of the present invention, a display device including the organic light emitting diode described above is provided.

Compounds having high hole or electron transport properties, film stability thermal stability and high triplet excitation energy can be provided.

Such a compound may be used as a hole injection / transport material, a host material, or an electron injection / transport material for the light emitting layer. The organic photoelectric device using the same has excellent electrochemical and thermal stability and has excellent life characteristics, and may have high luminous efficiency even at a low driving voltage.

1 to 5 are cross-sectional views illustrating various embodiments of an organic photoelectric device that may be manufactured using the compound for an organic photoelectric device according to an embodiment of the present invention.

Hereinafter, embodiments of the present invention will be described in detail. However, it should be understood that the present invention is not limited thereto, and the present invention is only defined by the scope of the following claims.

As used herein, unless otherwise defined, “substituted” means that at least one hydrogen in a substituent or compound is a deuterium, a halogen group, a hydroxy group, an amino group, a substituted or unsubstituted C1 to C20 amine group, a nitro group, a substituted or unsubstituted C1 to C10 such as C3 to C40 silyl group, C1 to C30 alkyl group, C1 to C10 alkylsilyl group, C3 to C30 cycloalkyl group, C6 to C30 aryl group, C1 to C20 alkoxy group, fluoro group, trifluoromethyl group, etc. Substituted by a trifluoroalkyl group or a cyano group.

As used herein, unless otherwise defined, "hetero" means containing 1 to 3 heteroatoms selected from the group consisting of N, O, S, and P in one functional group, and the remainder is carbon.

In the present specification, "combination thereof" means that two or more substituents are bonded to a linking group or two or more substituents are condensed to each other unless otherwise defined.

As used herein, unless otherwise defined, an "alkyl group" means an aliphatic hydrocarbon group. The alkyl group may be a "saturated alkyl group" meaning that it does not contain any alkenes or alkyne groups. The alkyl group may be an "unsaturated alkyl group" meaning that it contains at least one alkene group or alkyne group. "Alkene group" means a functional group consisting of at least two carbon atoms of at least one carbon-carbon double bond, and "alkyne group" means at least two carbon atoms of at least one carbon-carbon triple bond It means a functional group formed. The alkyl group, whether saturated or unsaturated, may be branched, straight chain or cyclic.

The alkyl group may be an alkyl group that is C1 to C20. The alkyl group may be a medium sized alkyl group which is C1 to C10. The alkyl group may be a lower alkyl group which is C1 to C6.

For example, a C1 to C4 alkyl group has 1 to 4 carbon atoms in the alkyl chain, i.e., the alkyl chain is methyl, ethyl, propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl and t-butyl Selected from the group consisting of:

Typical alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, pentyl, hexyl, ethenyl, propenyl, butenyl, cyclopropyl, cyclobutyl and cyclo It means a functional group which may be substituted with one or more groups individually and independently selected from pentyl group, cyclohexyl group and the like.

"Aromatic group" means a functional group in which all elements of the functional group in the ring form have p-orbitals, and these p-orbitals form conjugation. Specific examples include an aryl group and a heteroaryl group.

An "aryl group" includes monocyclic or fused ring polycyclic (ie, rings that divide adjacent pairs of carbon atoms) functional groups.

"Heteroaryl group" means containing 1 to 3 heteroatoms selected from the group consisting of N, O, S and P in the aryl group, and the rest are carbon. When the heteroaryl group is a fused ring, each ring may include 1 to 3 heteroatoms.

In the present specification, the carbazole derivative refers to a structure in which a nitrogen atom of a substituted or unsubstituted carbazolyl group is substituted with a hetero atom instead of nitrogen. Specific examples thereof include dibenzofuran (dibenzofuranyl group), dibenzothiophene (dibenzothiophenyl group), and the like.

In the present specification, the hole characteristic means a characteristic that has conductivity characteristics along the HOMO level to facilitate injection of holes formed at the anode into the light emitting layer and movement in the light emitting layer.

In addition, an electronic characteristic means the characteristic which has electroconductive characteristic along LUMO level, and facilitates the injection of the electron formed in the cathode into the light emitting layer, and the movement in the light emitting layer.

The compound for an organic photoelectric device according to the exemplary embodiment of the present invention may have a core structure in which a substituent having electronic properties is bonded to a fused ring including at least one hetero atom.

The core structure may be used as a light emitting material, a hole injection material or a hole transport material of the organic light emitting device because it contains a substituent having excellent electronic properties in the hetero fused ring having excellent hole properties. In particular, it may be suitable for the light emitting material.

In addition, due to the fused ring there is an advantage in that the intramolecular symmetry may be reduced to lower the crystallinity of the compound and thus recrystallization is suppressed in the device.

At least one of the substituents bonded to the core may be a substituent having electronic properties. Therefore, the compound may satisfy the conditions required in the light emitting layer by reinforcing the electronic properties in the carbazole structure having excellent hole properties. More specifically, it can be used as a host material of the light emitting layer.

In addition, the compound for an organic photoelectric device may be a compound having various energy band gaps by introducing a variety of other substituents to the substituents substituted in the core portion and the core portion.

By using a compound having an appropriate energy level in the organic photoelectric device according to the substituent of the compound, the hole transfer ability or the electron transfer ability is enhanced to have an excellent effect in terms of efficiency and driving voltage, and has excellent electrochemical and thermal stability and is excellent in organic photoelectric It is possible to improve the life characteristics when driving the device.

According to one embodiment of the present invention, the compound for an organic photoelectric device is represented by the formula (1); And it may be a compound for an organic photoelectric device represented by a combination of formula (2) or (3).

[Formula 1] [Formula 2] [Formula 3]

In Formulas 1 to 3, X is O, Se, S, SO 2 (O = S = O), PO (P = O) or CO (C = O), and Y is CR′R ′ or NR * Wherein a *, b *, R ', R', R ¹ , R ² and R * are the same as or different from each other, and independently hydrogen, deuterium, halogen, cyano group, hydroxyl group, amino group, substituted or Unsubstituted C1 to C20 amine group, nitro group, substituted or unsubstituted C2 to C10 carboxyl group, substituted or unsubstituted ferrocenyl group, substituted or unsubstituted C1 to C20 alkyl group, substituted or unsubstituted C6 to C30 aryl Groups, substituted or unsubstituted C2 to C30 heteroaryl groups, substituted or unsubstituted C1 to C20 alkoxy groups, substituted or unsubstituted C6 to C20 aryloxy groups, substituted or unsubstituted C3 to C40 silyloxy groups, substituted Or an unsubstituted C1 to C20 acyl group, a substituted or unsubstituted C2 to C20 alkoxycarbonyl group, a substituted or unsubstituted C2 to C20 acyloxy group, substituted Or an unsubstituted C2 to C20 acylamino group, a substituted or unsubstituted C2 to C20 alkoxycarbonylamino group, a substituted or unsubstituted C7 to C20 aryloxycarbonylamino group, a substituted or unsubstituted C1 to C20 sulfamoylamino group , Substituted or unsubstituted C1 to C20 sulfonyl group, substituted or unsubstituted C1 to C20 alkylthiol group, substituted or unsubstituted C6 to C20 arylthiol group, substituted or unsubstituted C1 to C20 heterocyclothiol group, A substituted or unsubstituted C1 to C20 ureide group, a substituted or unsubstituted C3 to C40 silyl group, or a combination thereof, and two adjacent * of Formula 1 are selected from two adjacent * of Formula 2 or 3 and Combine to form a fused ring, and at least one of the a *, b * or R * is a substituent represented by the following Chemical Formula 4,

[Formula 4]

In Chemical Formula 4, the ETU has an electronic property, a substituted or unsubstituted C6 to C30 aryl group; Or a substituted or unsubstituted C2 to C30 heteroaryl group having electronic properties, wherein L is a single bond, a substituted or unsubstituted C2 to C6 alkenylene group, a substituted or unsubstituted C2 to C6 alkynylene group, substituted Or an unsubstituted C6 to C30 arylene group, a substituted or unsubstituted heteroarylene group, or a combination thereof, wherein n is an integer of 0 to 2.

By appropriate combination of the above formula, it is possible to prepare a compound for an organic photoelectric device having light emission, hole or electronic properties, film stability, thermal stability and high triplet excitation energy (T1).

The compound for an organic photoelectric device may be a compound represented by Formula 5 below.

[Chemical Formula 5]

In Formula 5, X is O, Se, S, SO 2 (O = S = O), PO (P = O) or CO (C = O), and Y is CR′R ′ or NR *, A *, b *, R ', R', R ¹ , R ² and R * are the same as or different from each other, and independently hydrogen, deuterium, a halogen group, a cyano group, a hydroxyl group, an amino group, a substituted or unsubstituted Substituted C1 to C20 amine group, nitro group, substituted or unsubstituted C2 to C10 carboxyl group, substituted or unsubstituted ferrocenyl group, substituted or unsubstituted C1 to C20 alkyl group, substituted or unsubstituted C6 to C30 aryl group, Substituted or unsubstituted C2 to C30 heteroaryl group, substituted or unsubstituted C1 to C20 alkoxy group, substituted or unsubstituted C6 to C20 aryloxy group, substituted or unsubstituted C3 to C40 silyloxy group, substituted or unsubstituted A substituted C1 to C20 acyl group, a substituted or unsubstituted C2 to C20 alkoxycarbonyl group, a substituted or unsubstituted C2 to C20 acyloxy group, a substituted or Substituted C2 to C20 acylamino group, substituted or unsubstituted C2 to C20 alkoxycarbonylamino group, substituted or unsubstituted C7 to C20 aryloxycarbonylamino group, substituted or unsubstituted C1 to C20 sulfamoylamino group, substituted Or unsubstituted C1 to C20 sulfonyl group, substituted or unsubstituted C1 to C20 alkylthiol group, substituted or unsubstituted C6 to C20 arylthiol group, substituted or unsubstituted C1 to C20 heterocyclothiol group, substituted or An unsubstituted C1 to C20 ureide group, a substituted or unsubstituted C3 to C40 silyl group, or a combination thereof, and at least one of the a *, b * or R * is a substituent represented by the following Chemical Formula 4,

[Formula 4]

In Chemical Formula 4, the ETU has an electronic property, a substituted or unsubstituted C6 to C30 aryl group; Or a substituted or unsubstituted C2 to C30 heteroaryl group having electronic properties, wherein L is a single bond, a substituted or unsubstituted C2 to C6 alkenylene group, a substituted or unsubstituted C2 to C6 alkynylene group, substituted Or an unsubstituted C6 to C30 arylene group, a substituted or unsubstituted heteroarylene group, or a combination thereof, wherein n is an integer of 0 to 2.

By appropriate combination of the above substituents, a compound having a structure excellent in thermal stability or resistance to oxidation can be prepared.

R ¹ and as above If any one of the substituents of R ² is any one of the above-described substituents other than hydrogen, finely control the electro-optic and thin film properties for optimizing performance as a material for an organic photoelectric device while maintaining the basic properties of the compound having no substituent. There are advantages to it.

In addition, in the case of the structure as shown in Formula 5 may be advantageous in terms of the synthesis of the compound, because the meta-linked to the main chain has the advantage of high triplet energy.

More specifically, the compound for an organic photoelectric device may be a compound represented by any one of Chemical Formulas 6, 7, or 8.

[Formula 6]

[Formula 7]

[Formula 8]

In Chemical Formulas 6, 7, and 8, X is O, Se, S, SO 2 (O = S = O), PO (P = O) or CO (C = O) e, and Y is CR'R ' Or NR *, wherein R ', R', R ¹ , R ² and R * are the same as or different from each other, and independently hydrogen, deuterium, a halogen group, a cyano group, a hydroxyl group, an amino group, a substituted or unsubstituted C1 to C20 amine group, nitro group, substituted or unsubstituted C2 to C10 carboxyl group, substituted or unsubstituted ferrocenyl group, substituted or unsubstituted C1 to C20 alkyl group, substituted or unsubstituted C6 to C30 aryl group, substituted Or an unsubstituted C2 to C30 heteroaryl group, a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C6 to C20 aryloxy group, a substituted or unsubstituted C3 to C40 silyloxy group, a substituted or unsubstituted Substituted C1 to C20 acyl group, substituted or unsubstituted C2 to C20 alkoxycarbonyl group, substituted or unsubstituted C2 to C20 acyloxy group, substituted or Unsubstituted C2 to C20 acylamino group, substituted or unsubstituted C2 to C20 alkoxycarbonylamino group, substituted or unsubstituted C7 to C20 aryloxycarbonylamino group, substituted or unsubstituted C1 to C20 sulfamoylamino group, Substituted or unsubstituted C1 to C20 sulfonyl group, substituted or unsubstituted C1 to C20 alkylthiol group, substituted or unsubstituted C6 to C20 arylthiol group, substituted or unsubstituted C1 to C20 heterocyclothiol group, substituted Or an unsubstituted C1 to C20 ureide group, a substituted or unsubstituted C3 to C40 silyl group, or a combination thereof, wherein the ETU has an electronic property, a substituted or unsubstituted C6 to C30 aryl group; Or a substituted or unsubstituted C2 to C30 heteroaryl group having electronic properties, wherein L is a single bond, a substituted or unsubstituted C2 to C6 alkenylene group, a substituted or unsubstituted C2 to C6 alkynylene group, substituted Or an unsubstituted C6 to C30 arylene group, a substituted or unsubstituted heteroarylene group, or a combination thereof, wherein n is an integer of 0 to 2.

When a substituent having an electronic property is bonded to the structure shown in Chemical Formula 6, the molecular structure is close to a spherical shape, and thus an amorphous thin film may be well formed, thereby improving device stability.

When substituents having electronic properties in the structures shown in Chemical Formulas 7 and 8 are combined, they can easily affect the electron density in the entire molecule, thereby easily changing the HOMO level and the LUMO level according to the type and size of the substituent. Can be given. Therefore, there is an advantage to improve the electrochemical stability, device efficiency and life through this.

By a suitable combination of the substituents can be prepared a structure of asymmetric bipolar (bipolar) characteristics, the structure of the asymmetric bipolar characteristics can be expected to improve the luminous efficiency and performance of the device by improving the hole and electron transfer ability.

In addition, the structure of the compound can be prepared in bulk by the control of the substituents, thereby lowering the crystallinity. If the crystallinity of the compound is lowered, the lifetime of the device may be longer.

The substituted or unsubstituted C6 to C30 aryl group having the above electronic properties is a substituted or unsubstituted triphenylenyl group, a substituted or unsubstituted florenyl group, a substituted or unsubstituted spiroflorenyl group, a substituted or unsubstituted terphenyl group , Substituted or unsubstituted pyrenyl group, substituted or unsubstituted perenyl group, substituted or unsubstituted phenanthrenyl group, or a combination thereof.

In addition, the substituted or unsubstituted C2 to C30 heteroaryl group having the above electronic properties is substituted or unsubstituted imidazolyl group, substituted or unsubstituted triazolyl group, substituted or unsubstituted tetrazolyl group, substituted or unsubstituted A substituted carbazolyl group, a substituted or unsubstituted oxadiazolyl group, a substituted or unsubstituted oxatriazolyl group, a substituted or unsubstituted cythiazolyl group, a substituted or unsubstituted benzimidazolyl group, a substituted or Unsubstituted benzotriazolyl group, substituted or unsubstituted pyridinyl group, substituted or unsubstituted pyrimidinyl group, substituted or unsubstituted triazinyl group, substituted or unsubstituted pyrazinyl group, substituted or unsubstituted pyri Dazinyl group, substituted or unsubstituted purinyl group, substituted or unsubstituted quinolinyl group, substituted or unsubstituted isoquinolinyl group, substituted or unsubstituted phthalazinyl group, substituted or unsubstituted b A pyridinyl group, a substituted or unsubstituted quinoxalinyl group, a substituted or unsubstituted quinazolinyl group, a substituted or unsubstituted acridinyl group, a substituted or unsubstituted phenanthrolinyl group, a substituted or unsubstituted phenazinyl group, or Combinations thereof. However, it is not limited to the substituent.

As described above, when Y is carbon, there is an advantage that can use the characteristics of the florene sulfide.

As described above, when Y is nitrogen, there is an advantage of using the properties of the carbazole compound.

By controlling the length of L of the general formula (4) is adjusted the total conjugation length (π-conjugation length), thereby adjusting the triplet energy bandgap so that it can be very usefully applied to the light emitting layer of the organic photoelectric device as a phosphorescent host Can play a role. In addition, when a heteroaryl group is introduced, bipolar characteristics are implemented in the molecular structure, thereby indicating high efficiency as a phosphorescent host.

Compound for an organic photoelectric device according to an embodiment of the present invention, the compound for an organic photoelectric device may be represented by any one of the formulas A-1 to A-55. In the case of the structure described below, the molecular structure is close to a spherical shape, the process temperature can be lowered, and an amorphous thin film can be made, thereby improving device stability.

[Formula A-1] [Formula A-2] [Formula A-3]

[Formula A-4] [Formula A-5] [Formula A-6]

[Formula A-7] [Formula A-8] [Formula A-9]

[Formula A-10] [Formula A-11] [Formula A-12]

[Formula A-13] [Formula A-14] [Formula A-15]

[Formula A-16] [Formula A-17] [Formula A-18]

[화학식 A-19] [화학식 A-20] [화학식 A-21]

[Formula A-19] [Formula A-20] [Formula A-21]

[Formula A-22] [Formula A-23] [Formula A-24]

[Formula A-25] [Formula A-26] [Formula A-27]

[Formula A-28] [Formula A-29] [Formula A-30]

[Formula A-31] [Formula A-32] [Formula A-33]

[Formula A-34] [Formula A-35] [Formula A-36]

[Formula A-37] [Formula A-38] [Formula A-39]

[Formula A-40] [Formula A-41] [Formula A-42]

[Formula A-43] [Formula A-44] [Formula A-45]

[Formula A-46] [Formula A-47] [Formula A-48]

[Formula A-49] [Formula A-51] [Formula A-52]

[Formula A-53] [Formula A-54] [Formula A-55]

Compound for an organic photoelectric device according to an embodiment of the present invention, the compound for an organic photoelectric device may be represented by any one of the following formula B-1 to B-44. In the case of the following structure, HOMO level and LUMO level can be easily changed according to the type and size of the substituent, which has the advantage of improving electrochemical stability, device efficiency and lifespan.

[Formula B-1] [Formula B-2] [Formula B-3]

[Formula B-4] [Formula B-5] [Formula B-6]

[Formula B-7] [Formula B-8] [Formula B-9]

[Formula B-10] [Formula B-11]

[Formula B-12] [Formula B-13] [Formula B-14]

[Formula B-15] [Formula B-16] [Formula B-17]

[Formula B-18] [Formula B-19] [Formula B-20]

Formula B-21 Formula B-22

[Formula B-23] [Formula B-24] [Formula B-25]

[Formula B-26] [Formula B-27] [Formula B-28]

[Formula B-29] [Formula B-30] [Formula B-31]

Formula B-32 Formula B-33

[Formula B-34] [Formula B-35] [Formula B-36]

[Formula B-37] [Formula B-38] [Formula B-39]

[Formula B-40] [Formula B-41] [Formula B-42]

Formula B-43 Formula B-44

[Formula B-1] [Formula B-2] [Formula B-3]

[Formula B-4] [Formula B-5] [Formula B-6]

[Formula B-7] [Formula B-8] [Formula B-9]

[Formula B-10] [Formula B-11]

[Formula B-12] [Formula B-13] [Formula B-14]

[Formula B-15] [Formula B-16] [Formula B-17]

[Formula B-18] [Formula B-19] [Formula B-20]

Formula B-21 Formula B-22

[Formula B-23] [Formula B-24] [Formula B-25]

[Formula B-26] [Formula B-27] [Formula B-28]

[Formula B-29] [Formula B-30] [Formula B-31]

Formula B-32 Formula B-33

[Formula B-34] [Formula B-35] [Formula B-36]

[Formula B-37] [Formula B-38] [Formula B-39]

[Formula B-40] [Formula B-41] [Formula B-42]

Formula B-43 Formula B-44

Compound for an organic photoelectric device according to an embodiment of the present invention, the compound for an organic photoelectric device may be represented by any one of the formulas C-1 to C-12. In the case of the following structure, HOMO level and LUMO level can be easily changed according to the type and size of the substituent, which has the advantage of improving electrochemical stability, device efficiency and lifespan.

[Formula C-1] [Formula C-2] [Formula C-3]

[Formula C-4] [Formula C-5] [Formula C-6]

[Formula C-7] [Formula C-8] [Formula C-9]

[Formula C-10] [Formula C-11] [Formula C-12]

[Formula C-13] [Formula C-14] [Formula C-15]

[Formula C-16] [Formula C-17] [Formula C-18]

Formula C-19 Formula C-20

Compound for an organic photoelectric device according to an embodiment of the present invention, the compound for an organic photoelectric device may be represented by any one of the following formula D-1 to D-6. In the following structure, the HOMO homo level and the LUMO level can be easily changed according to the type and size of the substituent, thereby improving the electrochemical stability, device efficiency, and lifespan.

[Formula D-1] [Formula D-2] [Formula D-3]

[Formula D-4] [Formula D-5] [Formula D-6]

[Formula D-7] [Formula D-8]

Compound for an organic photoelectric device according to an embodiment of the present invention, the compound for an organic photoelectric device may be represented by any one of the following formulas E-1 to E-6. In the following structure, the HOMO level and LUMO level can be easily changed according to the type and size of the substituent, thereby improving the electrochemical stability, device efficiency, and lifespan.

[Formula E-1] [Formula E-2] [Formula E-3]

[Formula E-4] [Formula E-5] [Formula E-6]

[Formula E-7] [Formula E-8]

[Formula E-9]

When the compound according to the embodiment of the present invention requires both electronic and hole characteristics, introducing a functional group having the electronic characteristics is effective for improving the lifespan and driving voltage of the organic light emitting diode.

Compound for an organic photoelectric device according to an embodiment of the present invention described above has a maximum emission wavelength of about 320 to 500 nm, triplet excitation energy (T1) is more than 2.0 eV, more specifically in the range of 2.0 to 4.0 eV The charge of the host having a high triplet excitation energy is well transferred to the dopant to increase the luminous efficiency of the dopant, and the driving voltage can be lowered by freely adjusting the HOMO and LUMO energy levels of the material. Because of the advantages it can be very useful as a host material or a charge transport material.

In addition, since the compound for an organic photoelectric device has photoactive and electrical activity, a nonlinear optical material, an electrode material, a color change material, an optical switch, a sensor, a module, a wave guide, an organic transistor, a laser, an optical absorber, a dielectric, and a separator It can also be very usefully applied to materials such as (membrane).

The compound for an organic photoelectric device including the compound as described above has a glass transition temperature of 90 ° C. or higher, and a thermal decomposition temperature of 400 ° C. or higher, which is excellent in thermal stability. This makes it possible to implement a high efficiency organic photoelectric device.

The compound for an organic photoelectric device including the compound as described above may serve as light emission, electron injection and / or transport, and may also serve as a light emitting host with an appropriate dopant. That is, the compound for an organic photoelectric device may be used as a host material of phosphorescence or fluorescence, a blue dopant material, or an electron transport material.

Compound for an organic photoelectric device according to an embodiment of the present invention is used in the organic thin film layer to improve the life characteristics, efficiency characteristics, electrochemical stability and thermal stability of the organic photoelectric device, it is possible to lower the driving voltage.

Accordingly, one embodiment of the present invention provides an organic photoelectric device comprising the compound for an organic photoelectric device. In this case, the organic photoelectric device means an organic light emitting device, an organic solar cell, an organic transistor, an organic photosensitive drum, or an organic memory device. In particular, in the case of an organic solar cell, a compound for an organic photoelectric device according to an exemplary embodiment of the present invention is included in an electrode or an electrode buffer layer to increase quantum efficiency, and in the case of an organic transistor, a gate, a source-drain electrode, and the like are used as electrode materials. Can be used.

Hereinafter, an organic photoelectric device will be described in detail.

Another embodiment of the present invention is an organic light emitting device comprising an anode, a cathode and at least one organic thin film layer interposed between the anode and the cathode, at least any one of the organic thin film layer is an embodiment of the present invention It provides an organic light emitting device comprising a compound for an organic photoelectric device according to.

The organic thin film layer which may include the compound for an organic photoelectric device may include a layer selected from the group consisting of a light emitting layer, a hole transport layer, a hole injection layer, an electron transport layer, an electron injection layer, a hole blocking layer, and a combination thereof. At least one of the layers includes the compound for an organic photoelectric device according to the present invention. In particular, the hole transport layer or the hole injection layer may include a compound for an organic photoelectric device according to an embodiment of the present invention. In addition, when the compound for an organic photoelectric device is included in a light emitting layer, the compound for an organic photoelectric device may be included as a phosphorescent or fluorescent host, and in particular, may be included as a fluorescent blue dopant material.

1 to 5 are cross-sectional views of an organic light emitting device including the compound for an organic photoelectric device according to an embodiment of the present invention.

1 to 5, the organic photoelectric device 100, 200, 300, 400, and 500 according to an embodiment of the present invention may be interposed between the anode 120, the cathode 110, and the anode and the cathode. It has a structure including at least one organic thin film layer 105.

The anode 120 includes a cathode material, and a material having a large work function is preferable as the anode material so that hole injection can be smoothly injected into the organic thin film layer. Specific examples of the positive electrode material include metals such as nickel, platinum, vanadium, chromium, copper, zinc, and gold or alloys thereof, and include zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO). And metal oxides such as ZnO and Al, or combinations of metals and oxides such as SnO ₂ and Sb, and poly (3-methylthiophene), poly [3,4- (ethylene-1, 2-dioxy) thiophene] (conductive polymers such as polyehtylenedioxythiophene (PEDT), polypyrrole and polyaniline, etc.), but is not limited thereto. Preferably, a transparent electrode including indium tin oxide (ITO) may be used as the anode.

The negative electrode 110 includes a negative electrode material, and the negative electrode material is preferably a material having a small work function to facilitate electron injection into the organic thin film layer. Specific examples of the negative electrode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, lead, cesium, barium, or alloys thereof, and LiF / Al. , Multilayer structure materials such as LiO ₂ / Al, LiF / Ca, LiF / Al, and BaF ₂ / Ca, and the like, but are not limited thereto. Preferably, a metal electrode such as aluminum may be used as the cathode.

First, referring to FIG. 1, FIG. 1 illustrates an organic photoelectric device 100 in which only a light emitting layer 130 exists as an organic thin film layer 105. The organic thin film layer 105 may exist only as a light emitting layer 130.

Referring to FIG. 2, FIG. 2 illustrates a two-layered organic photoelectric device 200 in which an emission layer 230 including an electron transport layer and a hole transport layer 140 exist as an organic thin film layer 105, as shown in FIG. 2. Likewise, the organic thin film layer 105 may be a two-layer type including the light emitting layer 230 and the hole transport layer 140. In this case, the light emitting layer 130 functions as an electron transporting layer, and the hole transporting layer 140 functions to improve bonding and hole transporting properties with a transparent electrode such as ITO.

Referring to FIG. 3, FIG. 3 is a three-layered organic photoelectric device 300 having an electron transport layer 150, an emission layer 130, and a hole transport layer 140 as an organic thin film layer 105, wherein the organic thin film layer 105 is formed. The light emitting layer 130 is in an independent form, and has a form in which a film (electron transport layer 150 and hole transport layer 140) having excellent electron transport properties or hole transport properties is stacked in separate layers.

Referring to FIG. 4, FIG. 4 is a four-layered organic photoelectric device 400 having an electron injection layer 160, a light emitting layer 130, a hole transport layer 140, and a hole injection layer 170 as an organic thin film layer 105. As a result, the hole injection layer 170 may improve adhesion to ITO used as an anode.

Referring to FIG. 5, FIG. 5 shows different functions such as the electron injection layer 160, the electron transport layer 150, the light emitting layer 130, the hole transport layer 140, and the hole injection layer 170 as the organic thin film layer 105. The five-layered organic photoelectric device 500 having five layers is present, and the organic photoelectric device 500 is effective for lowering the voltage by forming the electron injection layer 160 separately.

1 to 5, the electron transport layer 150, the electron injection layer 160, the light emitting layers 130 and 230, the hole transport layer 140, and the hole injection layer 170 forming the organic thin film layer 105 and their Any one selected from the group consisting of a combination includes the compound for an organic photoelectric device. In this case, the compound for an organic photoelectric device may be used in the electron transport layer 150 including the electron transport layer 150 or the electron injection layer 160, and among them, a hole blocking layer (not shown) when included in the electron transport layer. It is desirable to provide an organic photoelectric device having a simpler structure since it does not need to be separately formed.

In addition, when the compound for an organic photoelectric device is included in the light emitting layers 130 and 230, the compound for an organic photoelectric device may be included as a phosphorescent or fluorescent host, or may be included as a fluorescent blue dopant.

The above-described organic light emitting device includes a dry film method such as an evaporation, sputtering, plasma plating and ion plating after forming an anode on a substrate; Alternatively, the organic thin film layer may be formed by a wet film method such as spin coating, dipping, flow coating, or the like, followed by forming a cathode thereon.

According to another embodiment of the present invention, a display device including the organic photoelectric device is provided.

Hereinafter, specific embodiments of the present invention will be described. However, the embodiments described below are only intended to illustrate or explain the present invention, and thus the present invention should not be limited thereto.

( For organic photoelectric device  Preparation of compounds)

Synthesis of Intermediates

Synthesis of Intermediate M-1

Scheme 1

30 g (141.5 mmol) of (4-dibenzofuranyl) boronic acid, 37.1 g of methyl-2-bromo-5-chlorobenzoate (148.6 mmol) and tetrakistriphenylphosphinepalladium 8.2 g (7.1 mmol) were placed in a flask and dissolved in 550 ml of toluene under a nitrogen atmosphere. After addition, the mixture was stirred under reflux for 12 hours. After completion of the reaction, the mixture was extracted with ethyl acetate, the extract was dried over magnesium sulfate (magnesium sulphate), filtered and the filtrate was concentrated under reduced pressure. The product was purified by silica gel column chromatography with n-hexane / dichloromethane (7 '3 volume ratio) to give 38.2 g (yield 80%) of the target compound intermediate M-1 as a white solid.

LC-Mass (Theoretical value: 336.06 g / mol, Measured value: M + 1 = 336 g / mol)

Synthesis of Intermediate M-2

Scheme 2

38.18 g (113.37 mmol) of intermediate M-1 were placed in a flask, dissolved in 500 ml of anhydrous ether under a nitrogen atmosphere, and cooled to 0 ° C. and stirred. To this was slowly added 110 mL (in diethyl ether, 340.1 mmol) of 3M methylmagnesium bromide and stirred for 5 hours at room temperature under nitrogen atmosphere. After completion of the reaction, the solution was concentrated under reduced pressure to remove the solvent, followed by extraction with distilled water and dichloromethane. It was.

Synthesis of Intermediate M-3

Scheme 3

Intermediate M-3 was dissolved in 250 ml of dichloromethane, cooled to 0 ° C. and stirred. Borontrifluoride and diethyl ether complex 15.18 g (56.7 mmol) dissolved in 20 mL of dichloromethane were slowly added thereto, followed by stirring at room temperature for 5 hours. After completion of the reaction, the mixture was extracted with ethyl acetate, the extract was dried over magnesium sulfate (magnesium sulphate), filtered and the filtrate was concentrated under reduced pressure. The product was purified by silica gel column chromatography with 'n-Hexane' to give 29 mg (yield 80%) of the target compound, Intermediate M-3, as a white solid.

GC-Mass (Theoretical value: 318.8 μg / mol, Measured value: M + 1 = 318 μg / mol)

Synthesis of Intermediate M-4

Scheme 4

Intermediate (4-dibenzofuranyl) boronic acid 30g (141.5mmol), methyl-2-bromo-5-chlorobenzoateate37.1 g (148.6 mmol), tetrakistriphenylphosphine Palladium 8.2 g (7.1 mmol) was added to the flask and dissolved in 550 ml of toluene under a nitrogen atmosphere. Then, 353.8 ml of aqueous solution in which 104.2 g (707.51 mmol) of potassium carbonate was dissolved were added and stirred under reflux for 12 hours. After completion of the reaction, the mixture was extracted with ethyl acetate, the extract was dried over magnesium sulfate (magnesium sulphate), filtered and the filtrate was concentrated under reduced pressure. The product was purified by silica gel column chromatography with x-hexane / dichloromethane (7 x: 3 volume ratio) to give 38.2 xg (yield 80%) of the target compound Intermediate M-1 as a white solid.

LC-Mass (Theoretical value: 336.06 μg / mol, Measured value: M + 1 = 336 μg / mol)

Synthesis of Intermediate M-5

Scheme 5

38.2 g (113.37 mmol) of intermediate M-4 were placed in a flask, dissolved in 500 ml of anhydrous ether under a nitrogen atmosphere, and cooled to 0 ° C. and stirred. 3M methylmagnesium bromide 110mL (in diethyl ether, 324.63 mmol) was slowly added thereto, followed by stirring at room temperature under nitrogen atmosphere for 5 hours. After completion of the reaction, the solution was concentrated under reduced pressure to remove the solvent, followed by extraction with distilled water and dichloromethane. The extract was dried over magnesium sulphate, filtered, and the filtrate was concentrated under reduced pressure to obtain the intermediate compound M-2 having high viscosity. Obtained in liquid form.

Synthesis of Intermediate M-6

[Reaction Scheme 6]

Intermediate M-5 was dissolved in 250 ml of dichloromethane, cooled to 0 ° C. and stirred. 14.5 g (54.1 mmol) of borontrifluoride and diethyl ether (diethyl ether complex) dissolved in 20 mL of dichloromethane were slowly added thereto, followed by stirring at room temperature for 5 hours. After completion of the reaction, the mixture was extracted with ethyl acetate, the extract was dried over magnesium sulfate (magnesium sulphate), filtered and the filtrate was concentrated under reduced pressure. The product was purified by silica gel column chromatography with 'n-Hexane' to give 31 mg (yield 85.5%) of the target compound, Intermediate M-6, as a white solid.

GC-Mass (Theoretical value: 334.86 g / mol, Measured value: 335 g / mol)

Synthesis of Intermediate M-7

Scheme 7

Intermediate (4-dibenzofuranyl) boronic acid 23g (108.5 mmol), methyl-2-bromo-benzoate 24.5 g (113.9 mmol), tetrakistriphenylphosphinepalladium 6.3 g (5.47 mmol) was added to the flask and dissolved in 500 ml of toluene under a nitrogen atmosphere, and then 271.2 ml of an aqueous solution of 79.9 g (542.4 mmol) of potassium carbonate was added thereto, followed by stirring under reflux for 12 hours. After completion of the reaction, the mixture was extracted with ethyl acetate, the extract was dried over magnesium sulfate (magnesium sulphate), filtered and the filtrate was concentrated under reduced pressure. The product was purified by silica gel column chromatography with x-hexane / dichloromethane (7 x: 3 volume ratio) to give 31 mg (yield 94.5%) of the target compound Intermediate M-7 as a white solid.

LC-Mass (Theoretical value: 302.32 μg / mol, Measured value: M + 1 = 303 μg / mol)

Synthesis of Intermediate M-8

[Reaction Scheme 8]

29 g (95.92 mmol) of intermediate M-7 were placed in a flask, dissolved in 400 ml of anhydrous tetrahydrofuran (THF) under a nitrogen atmosphere, and then cooled to 0 ° C. and stirred. 9M mL (in diethyl ether, 287.8 mmol) of 3M methylmagnesium bromide was slowly added thereto, followed by stirring at room temperature under nitrogen atmosphere for 5 hours. After completion of the reaction, the solution was concentrated under reduced pressure to remove the solvent, followed by extraction with distilled water and dichloromethane. The extract was dried over magnesium sulphate, filtered, and the filtrate was concentrated under reduced pressure to obtain the intermediate compound M-8 having high viscosity. Obtained in liquid form.

Synthesis of Intermediate M-9

Scheme 9

Intermediate M-8 was dissolved in 250 ml of dichloromethane, cooled to 0 ° C. and stirred. To this, borontrifluoride and diethyl ether complex 12.84 g (47.5 mmol) dissolved in 20 mL of dichloromethane were slowly added, followed by stirring at room temperature for 5 hours. After completion of the reaction, the mixture was extracted with ethyl acetate, the extract was dried over magnesium sulfate (magnesium sulphate), filtered and the filtrate was concentrated under reduced pressure. The product was purified by silica gel column chromatography with 'n-Hexane' to give 22 mg (yield 71.9%) of the target compound Intermediate M-9 as a white solid.

LC-Mass (Theoretical value: 284.35 g / mol, Measured value: M + 1 = 284 g / mol)

Synthesis of Intermediate M-10

[Reaction Scheme 10]

10 g (59.5 mmol) of intermediate M-9 was added to a two-necked round bottom flask heated under vacuum under nitrogen atmosphere, 119 mL of anhydrous tetrahydrofuran was added thereto, and the mixture was cooled and stirred at -40 ° C. 26 mL (in Hexane, 65.5 mmol) of 1.6 M n-butyllithium was slowly added thereto, followed by stirring at room temperature under nitrogen atmosphere for 5 hours. After the reaction solution was cooled to -78 ° C, 22.4 g (119 mmol) of 1,2-dibromoethane dissolved in 10 mL of anhydrous tetrahydrofuran was slowly added thereto, followed by stirring at room temperature for 5 hours. After completion of the reaction, the solution was concentrated under reduced pressure to remove the solvent, extracted with distilled water and dichloromethane, the extract was dried over magnesium sulfate (magnesium sulphate), filtered and the filtrate was concentrated under reduced pressure. The reaction solution was recrystallized with n-hexane to give 11 g (yield 75%) of the intermediate compound M-10 as a white solid.

GC-Mass (Theoretical value: 245.97 g / mol, Measured value: 246 g / mol)

Synthesis of Intermediate M-11

[Reaction Scheme 11]

Intermediate M-10 11g (30.28mmol), 4-chlorophenylboronic acid acid5.0 g (31.8 mmol), tetrakistriphenylphosphinepalladium 1.8 g (1.5 mmol) was added to the flask and toluene under nitrogen atmosphere. After dissolving in 120 ml, 75.7ml of an aqueous solution of 22.3 g (151.4 mmol) of potassium carbonate was added thereto, followed by stirring under reflux for 12 hours. After completion of the reaction, the mixture was extracted with ethyl acetate, the extract was dried over magnesium sulfate (magnesium sulphate), filtered and the filtrate was concentrated under reduced pressure. The product was purified by silica gel column chromatography with x-hexane / dichloromethane (7 x: 3 volume ratio) to give 8.0 mg (yield 66.7%) of the target compound Intermediate M-11 as a white solid.

GC-Mass (Theoretical value: 394.89 g / mol, Measured value: 395 g / mol)

Synthesis of Intermediate M-12

[Reaction Scheme 12]

Intermediate (4-dibenzothiophenyl) boronic acid 25g (109.62 mmol), methyl-2-bromo-benzoate 24.8 g (115.1 mmol), tetrakistriphenylphosphinepalladium 6.3 g (5.48 mmol) was added to the flask and dissolved in 500 ml of toluene under a nitrogen atmosphere. Then, 274 ml of an aqueous solution of 80.7 g (548.1 mmol) dissolved in potassium carbonate was added thereto, followed by stirring under reflux for 12 hours. After completion of the reaction, the mixture was extracted with ethyl acetate, the extract was dried over magnesium sulfate (magnesium sulphate), filtered and the filtrate was concentrated under reduced pressure. The product was purified by silica gel column chromatography with x-hexane / dichloromethane (7 x: 3 volume ratio) to give 31 mg (yield 88.8%) of the target compound Intermediate M-12 as a white solid.

GC-Mass (Theoretical value: 318.39 g / mol, Measured value: M + 1 = 318 g / mol)

Synthesis of Intermediate M-13

Scheme 13

15.4 g (47.1 mmol) of intermediate M-12 were placed in a flask, dissolved in 400 ml of anhydrous tetrahydrofuran under a nitrogen atmosphere, and cooled to 0 ° C. and stirred. To this was slowly added 50 mL (in diethyl ether, 141.34 mmol) of 3M methylmagnesium bromide and stirred at room temperature under nitrogen atmosphere for 5 hours. After completion of the reaction, the solution was concentrated under reduced pressure to remove the solvent, followed by extraction with distilled water and dichloromethane. The extract was dried over magnesium sulphate, filtered and the filtrate was concentrated under reduced pressure to obtain the intermediate compound M-13 having high viscosity. Obtained in liquid form.

Synthesis of Intermediate M-14

[Reaction Scheme 14]

Intermediate M-13 was dissolved in 250 ml of dichloromethane, cooled to 0 ° C. and stirred. 12.6 g (47.1 mmol) of borontrifluoride and diethyl ether complex dissolved in 20 mL of dichloromethane were slowly added thereto, followed by stirring at room temperature for 5 hours. After completion of the reaction, the mixture was extracted with ethyl acetate, the extract was dried over magnesium sulfate (magnesium sulphate), filtered and the filtrate was concentrated under reduced pressure. The product was purified by silica gel column chromatography with n-hexane to give 10.5 g (yield 74.3%) of the target compound Intermediate M-14 as a white solid.

LC-Mass (Theoretical value: 300.42 μg / mol, Measured value: M + 1 = 300 μg / mol)

Intermediate M-15 Synthesis of

[Reaction Scheme 15]

9.6 g (31.79 mmol) of the intermediate M14 was added to a two-necked round bottom flask heated under vacuum under nitrogen atmosphere, and 100 mL of anhydrous tetrahydrofuran was added thereto to dissolve, followed by cooling and stirring at 40 ° C. 20.7 mL (in Hexane, 63.6 mmol) of 1.6 M nbutyllithium was slowly added thereto, followed by stirring at room temperature under nitrogen atmosphere for 5 hours. After the reaction solution was cooled to 78 ° C., 11.9 g (63.58 mmol) of 1,2 dibromoethane dissolved in 10 mL of anhydrous tetrahydrofuran was slowly added thereto, followed by stirring at room temperature for 5 hours. After completion of the reaction, the solution was concentrated under reduced pressure to remove the solvent, extracted with distilled water and dichloromethane, the extract was dried over magnesium sulphate, filtered and the filtrate was concentrated under reduced pressure. 9.5 g (yield 78.8%) of a phosphorus intermediate M15 was obtained as a white solid.

GCMass (Theoretical value: 379.31 / mol, Measured value: / mol)

Synthesis of Intermediate M-16

[Reaction Scheme 16]

Intermediate M-15 9.5g (26.4mmol), 4-chlorophenylboronic acid 4.3 g (27.7 mmol) and tetrakistriphenylphosphinepalladium 1.5 g (1.3 mmol) were added to the flask under nitrogen atmosphere. After dissolving in 150 ml of toluene, 64.9 ml of an aqueous solution of 19.4 g (130.9 mmol) of potassium carbonate was added thereto, followed by stirring under reflux for 12 hours. After completion of the reaction, the mixture was extracted with ethyl acetate, the extract was dried over magnesium sulfate (magnesium sulphate), filtered and the filtrate was concentrated under reduced pressure. The product was purified by silica gel column chromatography with x-hexane / dichloromethane (7 x: 3 volume ratio) to give 5.3 g (yield 48.5%) of the target compound Intermediate M-16 as a white solid.

GC-Mass (Theoretical value: 394.89 g / mol, Measured value: 395 g / mol)

Synthesis of Intermediate M-17

[Reaction Scheme 17]

Dibenzofuran boronic acid (15.0 g, 70.7 mmol), substance 1-bromo-2-nitrobenzene (19.38 g, 77.83 mmol), and tetrakistriphenylphosphinepalladium (2.46 g, 2.12 mmol) was dissolved in 200 mL toluene, and potassium acetate (19.56 g, 141 mmol) and 70 mL of water were added thereto, followed by stirring at 90 ° C. for 24 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, extracted with toluene and water, and the reaction product was dried with anhydrous magnesium sulfate, filtered, and then the solvent was removed. The solvent was removed, and then purified through a silica gel column with a methylene chloride / hexane (1: 1) mixed solvent to obtain 15 g of an intermediate M-17 (yield: 73.3%).

Synthesis of Intermediate M-18

[Reaction Scheme 18]

M-17 (15.0 g, 51.8 mmol) and triphenylphosphine (36 g, 137.5 mmol) were dissolved in dichlorobenzene in a 500 mL round-bottom flask-nitrogen atmosphere, followed by stirring at 160 ° C for 24 hours. After the reaction, the reaction was cooled to room temperature, and dichlorobenzene was removed under reduced pressure. The reaction was purified through a silica gel column with a methylene chloride / hexane (1: 1) mixed solvent to obtain 9.1 g of intermediate M-18 (yield: 68.2%).

Synthesis of Intermediate M-19

Scheme 19

In a 250 mL round-bottom flask, under nitrogen atmosphere, M-18 (9 g, 34.9 mmol), bromobenzene (10.9 g, 69.9 mmol), copper chloride (1.6 g, 17.4 mmol) and potassium hydroxide (20 g, 356.4 mmol) were added. After dissolving in 100 ml of xylene, the mixture was stirred at 150 ° C. for 48 hours, and then the reaction mass was cooled to room temperature and xylene was removed under reduced pressure. The remaining solid is dissolved in methylene chloride and washed several times with water, followed by removing water with anhydrous magnesium sulfate, filtering it, and then removing the solvent. After removing the solvent, silica gel column purification with a nucleic acid / methylene chloride (1: 2) solvent to give 10 g (86%) of the target compound M-19.

Synthesis of Intermediate M-20

[Reaction Scheme 20]

10.0 g (30.0 mmol) of Intermediate M-19 was added to a two-necked round bottom flask heated in vacuo under nitrogen atmosphere, and 100 mL of anhydrous tetrahydrofuran was added to dissolve it, followed by cooling and stirring at -40 ° C. 10.4 mL (in Hexane, 31.20 mmol) of 1.6 M n-butyllithium was slowly added thereto, followed by stirring at room temperature under nitrogen atmosphere for 5 hours. After the reaction solution was cooled to -78 ° C, 11.3 g (60.0 mmol) of 1,2-dibromoethane dissolved in 10 mL of anhydrous tetrahydrofuran was slowly added thereto, followed by stirring at room temperature for 5 hours. After completion of the reaction, the solution was concentrated under reduced pressure to remove the solvent, extracted with distilled water and dichloromethane, the extract was dried over magnesium sulfate (magnesium sulphate), filtered and the filtrate was concentrated under reduced pressure. The reaction solution was recrystallized with n-Hexane to give 9.7g (yield 78.4%) of the target compound intermediate M-20 as a white solid.

GC-Mass (Theoretical value: 412.28 g / mol, Measured value: 412 g / mol)

Synthesis of Intermediate M-21

Scheme 21

Intermediate M-20 9.7g (23.5mmol), 4-chlorophenylboronic acid 3.9 g (24.7mmol), tetrakistriphenylphosphinepalladium 1.4 g (1.2mmol) were placed in a flask and toluene 100 ml under nitrogen atmosphere. After dissolving in, 58.8 ml of an aqueous solution in which potassium carbonate was dissolved in 17.3 g (117.6 mmol) was added thereto, followed by stirring under reflux for 12 hours. After completion of the reaction, the mixture was extracted with ethyl acetate, the extract was dried over anhydrous magnesium sulfate, filtered, and the filtrate was concentrated under reduced pressure. The product was purified by silica gel column chromatography with n-hexane / methylene chloride (7 ': 3 vol. Ratio) to give 7.0 mg (yield: 67.0%) of the target compound, Intermediate M-21, as a white solid.

GC-Mass (Theoretical value: 443.92 g / mol, Measured value: 444 g / mol)

Synthesis of Intermediate M-22

[Reaction Scheme 22]

Dibenzofuran boronic acid (15.0 g, 65.7 mmol), substance 1-bromo-2-nitrobenzene (18.0 g, 72.3 mmol), and tetrakistriphenylphosphinepalladium (2.3 g, 1.97 mmol) was dissolved in 200 mL toluene, and potassium acetate (18.2 g, 131.5 mmol) and 70 mL of water were added thereto, followed by stirring at 90 ° C. for 24 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, extracted with toluene and water, and the reaction product was dried with anhydrous magnesium sulfate, filtered, and then the solvent was removed. The solvent was removed, and then purified through a silica gel column with a methylene chloride / hexane (1: 1) mixed solvent to obtain 14 g of an intermediate M-22 (yield: 69.7%).

Synthesis of Intermediate M-23

[Reaction Scheme 23]

M-22 (14.0 g, 45.8 mmol) and triphenylphosphine (36 g, 137.5 mmol) were dissolved in dichlorobenzene in a 500 mL round bottom flask nitrogen atmosphere, and then stirred at 160 ° C. for 24 hours. After the reaction, the reaction was cooled to room temperature, and dichlorobenzene was removed under reduced pressure. The reaction was purified through a silica gel column with a methylene chloride / hexane (1: 1) mixed solvent to obtain 9.7 g (yield: 77.6%) of intermediate M-23.

Synthesis of Intermediate M-24

Scheme 24

In a 250 ml round-bottom flask, under nitrogen atmosphere, M-23 (9.7 g, 35.4 mmol), bromobenzene (11.1 g, 70.9 mmol), copper chloride (1.6 g, 17.4 mmol), potassium hydroxide (20 g, 356.4 mmol) Was dissolved in 100 ml of xylene and stirred at 150 ° C. for 48 hours. The reaction was then cooled to room temperature and xylene was removed under reduced pressure. The remaining solid is dissolved in methylene chloride and washed several times with water, followed by removing water with anhydrous magnesium sulfate, filtering it, and then removing the solvent. The solvent was removed and silica gel column purification with a nucleic acid / methylene chloride (1: 2) solvent yielded 11 g (89%) of the target compound M-24.

Synthesis of Intermediate M-25

[Reaction Scheme 25]

10.0 g (28.6 mmol) of Intermediate M-24 was added to a two-necked round bottom flask heated in vacuo under nitrogen atmosphere, and 100 mL of anhydrous tetrahydrofuran was added to dissolve it, followed by cooling and stirring at -40 ° C. 9.92 mL (in Hexane, 29.76 mmol) of 1.6 M n-butyllithium was slowly added thereto, followed by stirring at room temperature under nitrogen atmosphere for 5 hours. After cooling the reaction solution to -78 ° C, 10.8 g (57.2 mmol) of 1,2-dibromoethane dissolved in 10 mL of anhydrous tetrahydrofuran was slowly added thereto, followed by stirring at room temperature for 5 hours. After completion of the reaction, the solution was concentrated under reduced pressure to remove the solvent, extracted with distilled water and dichloromethane, the extract was dried over magnesium sulfate (magnesium sulphate), filtered and the filtrate was concentrated under reduced pressure. The reaction solution was recrystallized with n-hexane to give 9.8 g (yield 79.9%) of the intermediate compound M-25 as a white solid.

GC-Mass (Theoretical value: 428.34 g / mol, Measured value: 428 g / mol)

Synthesis of Intermediate M-26

[Reaction Scheme 26]

Intermediate M-25 9.8g (22.9mmol), 4-chlorophenylboronic acid 3.8 g (24.0mmol) and tetrakistriphenylphosphinepalladium 1.3 g (1.1mmol) were added to the flask under nitrogen atmosphere. After dissolving in 100 ml of toluene, 57.2ml of an aqueous solution of 16.8 g (114.4 mmol) of potassium carbonate was added thereto, and the mixture was stirred under reflux for 12 hours. After completion of the reaction, the mixture was extracted with ethyl acetate, the extract was dried over magnesium sulfate (magnesium sulphate), filtered and the filtrate was concentrated under reduced pressure. The product was purified by silica gel column chromatography with x-hexane / dichloromethane (7 x: 3 volume ratio) to give 6.0 mg (yield: 57.0%) of the target compound Intermediate M-26 as a white solid.

GC-Mass (Theoretical value: 459.99 g / mol, Measured value: 460 g / mol)

Synthesis of Intermediate M-27

[Reaction Scheme 27]

In a 1 L round bottom flask, nitrogen atmosphere, substance dibenzofuran boronic acid (20.0 g, 94.3 mmol), substance 2-bromo-5-chloronitrobenzene (24.5 g, 103.7 mmol), and tetrakistriphenylphosphine Palladium (3.28 g, 2.83 mmol) was dissolved in 300 mL toluene, potassium acetate (26 g, 188.6 mmol) and 100 mL of water were added, followed by stirring at 90 ° C for 24 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, extracted with toluene and water, and the reaction product was dried with anhydrous magnesium sulfate, filtered, and then the solvent was removed. The solvent was removed, and then purified through a silica gel column with a methylene chloride / hexane (1: 1) mixed solvent to obtain 20 g of an intermediate M-27 (yield: 65.49%).

Synthesis of Intermediate M-28

[Reaction Scheme 28]

M-27 (20.0 g, 61.7 mmol) and triphenylphosphine (48.6 g, 185.3 mmol) were dissolved in dichlorobenzene in a 500 mL round-bottom flask-nitrogen atmosphere and stirred at 160 ° C. for 24 hours. After the reaction, the reaction was cooled to room temperature, and dichlorobenzene was removed under reduced pressure. The reaction was purified through a silica gel column with a methylene chloride / hexane (1: 1) mixed solvent to obtain 14.5 g of intermediate M-28 (yield: 81%).

Synthesis of Intermediate M-29

[Reaction Scheme 29]

In a 250 ml round-bottom flask, under nitrogen atmosphere, M-28 (14 g, 47.9 mmol), bromobenzene (15 g, 95.9 mmol), copper chloride (3.2g, 34.8 mmol), potassium hydroxide (30g, 535.7 mmol) Was dissolved in 200 ml of xylene and stirred at 150 ° C. for 48 hours. The reaction was then cooled to room temperature and xylene was removed under reduced pressure. The remaining solid is dissolved in methylene chloride and washed several times with water, followed by removing water with anhydrous magnesium sulfate, filtering it, and then removing the solvent. After removing the solvent, silica gel column purification with a nucleic acid / methylene chloride (1: 2) solvent to obtain 14 g (79.5%) of the target compound M-29.

Synthesis of Intermediate M-30

Scheme 30

In a 1 L round-bottom flask, nitrogen atmosphere, substance dibenzothiophene boronic acid (20.0 g, 87.6 mmol), substance 2-bromo-5-chloronitrobenzene (22.8 g, 96.4 mmol), and tetrakistriphenylphosphate Pinpalladium (3 g, 2.63 mmol) was dissolved in 300 mL toluene, and potassium acetate (24.2 g, 175.3 mmol) and 100 mL of water were added, followed by stirring at 90 ° C for 24 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, extracted with toluene and water, and the reaction product was dried with anhydrous magnesium sulfate, filtered, and then the solvent was removed. The solvent was removed, and then purified through a silica gel column with a methylene chloride / hexane (1: 1) mixed solvent to obtain 23 g of an intermediate M-27 (yield: 77.2%).

Synthesis of Intermediate M-31

Scheme 31

In a 500 mL round bottom flask: nitrogen atmosphere, M-30 (20.0 g, 58.8 mmol) and triphenylphosphine (48.6 g, 185.3 mmol) were dissolved in dichlorobenzene and stirred at 160 ° C. for 24 hours. After the reaction, the reaction was cooled to room temperature, and dichlorobenzene was removed under reduced pressure. The reaction was purified through a silica gel column with a methylene chloride / hexane (1: 1) mixed solvent to obtain 14 g of intermediate M-31 (yield: 77.3%).

Synthesis of Intermediate M-32

Scheme 32

In a 250 mL round-bottom flask, under nitrogen atmosphere, M-31 (14 g, 45.4 mmol), bromobenzene (14.2 g, 90.9 mmol), copper chloride (3.2g, 34.8 mmol), potassium hydroxide (30g, 535.7 mmol) Was dissolved in 200 ml of xylene and stirred at 150 ° C. for 48 hours. The reaction was then cooled to room temperature and xylene was removed under reduced pressure. The remaining solid is dissolved in methylene chloride and washed several times with water, followed by removing water with anhydrous magnesium sulfate, filtering it, and then removing the solvent. After removing the solvent, silica gel column purification with a nucleic acid / methylene chloride (1: 2) solvent to obtain 13 g (74.6%) of the target compound M-32.

Synthesis of Intermediate M-33

Scheme 33

In a 1 L round bottom flask, nitrogen atmosphere, substance dibenzofuran boronic acid (20.0 g, 94.3 mmol), substance 2-bromo-5-chloronitrobenzene (24.5 g, 103.7 mmol), and tetrakistriphenylphosphine Palladium (3.28 g, 2.83 mmol) was dissolved in 300 mL toluene, potassium acetate (26 g, 188.6 mmol) and 100 mL of water were added, followed by stirring at 90 ° C for 24 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, extracted with toluene and water, and the reaction product was dried with anhydrous magnesium sulfate, filtered, and then the solvent was removed. The solvent was removed, and then purified through a silica gel column with a methylene chloride / hexane (1: 1) mixed solvent to obtain 21 g of an intermediate M-33 (yield: 68.7%).

Synthesis of Intermediate M-34

Scheme 34

M-33 (20.0 g, 61.7 mmol) and triphenylphosphine (48.6 g, 185.3 mmol) were dissolved in dichlorobenzene in a 500 mL round-bottom flask-nitrogen atmosphere and stirred at 160 ° C. for 24 hours. After the reaction, the reaction was cooled to room temperature, and dichlorobenzene was removed under reduced pressure. The reaction product was purified through a silica gel column with a methylene chloride / hexane (1: 1) mixed solvent to obtain 14 g of an intermediate M-34 (yield: 77.7%).

Synthesis of Intermediate M-35

Scheme 35

In a 250 mL round-bottom flask, under nitrogen atmosphere, M-34 (14 g, 47.9 mmol), bromobenzene (15 g, 95.9 mmol), copper chloride (3.2g, 34.8 mmol), potassium hydroxide (30g, 535.7 mmol) Was dissolved in 200 ml of xylene and stirred at 150 ° C. for 48 hours. The reaction was then cooled to room temperature and xylene was removed under reduced pressure. The remaining solid is dissolved in methylene chloride and washed several times with water, followed by removing water with anhydrous magnesium sulfate, filtering it, and then removing the solvent. After removing the solvent, silica gel column purification with a nucleic acid / methylene chloride (1: 2) solvent to give 14.5 g (82.3%) of the target compound M-35.

Synthesis of Intermediate M-36

Scheme 36

In a 1 L round-bottom flask, nitrogen atmosphere, substance dibenzothiophene boronic acid (20.0 g, 87.6 mmol), substance 2-bromo-5-chloronitrobenzene (22.8 g, 96.4 mmol), and tetrakistriphenylphosphate Pinpalladium (3 g, 2.63 mmol) was dissolved in 300 mL toluene, and potassium acetate (24.2 g, 175.3 mmol) and 100 mL of water were added, followed by stirring at 90 ° C for 24 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, extracted with toluene and water, and the reaction product was dried with anhydrous magnesium sulfate, filtered, and then the solvent was removed. The solvent was removed, and then purified through a silica gel column with a methylene chloride / hexane (1: 1) mixed solvent to obtain 22 g of an intermediate M-36 (yield: 73.8%).

Synthesis of Intermediate M-37

Scheme 37

M-36 (20.0 g, 58.8 mmol) and triphenylphosphine (48.6 g, 185.3 mmol) were dissolved in dichlorobenzene in a 500 mL round-bottom flask-nitrogen atmosphere and stirred at 160 ° C for 24 hours. After the reaction, the reaction was cooled to room temperature, and dichlorobenzene was removed under reduced pressure. The reaction was purified through a silica gel column with a methylene chloride / hexane (1: 1) mixed solvent to obtain 14.5 g of an intermediate M-37 (yield: 80.5%).

Synthesis of Intermediate M-38

Scheme 38

In a 250 mL round-bottom flask, under nitrogen atmosphere, M-37 (14 g, 45.4 mmol), bromobenzene (14.2 g, 90.9 mmol), copper chloride (3.2g, 34.8 mmol), potassium hydroxide (30g, 535.7 mmol) Was dissolved in 200 ml of xylene and stirred at 150 ° C. for 48 hours. The reaction was then cooled to room temperature and xylene was removed under reduced pressure. The remaining solid is dissolved in methylene chloride and washed several times with water, followed by removing water with anhydrous magnesium sulfate, filtering it, and then removing the solvent. The solvent was removed and silica gel column purification with a nucleic acid / methylene chloride (1: 2) solvent yielded 13.5 g (77.5%) of the title compound M-38.

Synthesis of Intermediate M-39

Scheme 39

The target compound M-39 was synthesized in the same manner as in the synthesis of Intermediate M-2, except that phenylmagnesium bromide was used instead of methylmagnesium bromide.

Synthesis of Intermediate M-40

Scheme 40

20 g (82%) of the target compound M-40 was synthesized by the same method as the intermediate M-3.

Synthesis of Intermediate M-41

Scheme 41

The target compound M-41 was synthesized in the same manner as the synthesis of Intermediate M-5, except that phenylmagnesium bromide was used instead of methylmagnesium bromide.

Synthesis of Intermediate M-42

Scheme 42

22 g (81%) of the target compound M-42 was synthesized by the same method as the intermediate M-6.

Synthesis of Intermediate M-43

Scheme 42

M-11 M-43

In a 250 mL round bottom flask, M-11 (10 g, 25.3 mmol), 10 mg of I ₂ and magnesium (3.0 g, 126.6 mmol) were added to 50 mL of THF under a nitrogen atmosphere, and the temperature was raised to the presence of a reflux reactor. Stir at 75 ^o C for about 1 hour and then lower the temperature back to O ^o C. Trimethyl borate (2.9 g, 27.9 mmol) was added dropwise at 0 ^° C.

After raising the temperature to room temperature, the mixture was stirred for about 2 hours, 2N HCl was added dropwise to the reaction mixture, and after confirming that the reaction solution was acidic using a pH tester, only the organic layer was collected and concentrated under reduced pressure. The reaction product thus obtained was dissolved in a small amount of methylene chloride, and then precipitated in a hexane solvent. The precipitate was filtered off and the obtained solid was recrystallized under hexane / acetone to give 7.2 g (70.3%) of the desired compound M-43.

Synthesis of Intermediates M-44 to M-54

Using the synthesis method of the intermediate M-1 to M-43, the starting material was changed as shown in Table 1 to prepare intermediates M-44 to M-54. In the case of M-51 to M-53, the same method for synthesizing intermediate M-3, M-6, M-34 or M-37 synthesized using dibenzofuran or dibenzothiophene as starting material was used in the same manner. Synthesized.

Starting material product
Boronic acid yield

71%

69%

80%

85%

88%

73%

77%

M-51

M-52 65%

M-53

M-54 67%

Example  1: compound  A-4 Manufacturing

Scheme 43

M-43 W-1 A-4

In a 250 ml round bottom flask, boronic acid M-43 (6 g, 14.84 mmol), halogenated compound W-1 (4.4 g, 14.84 mmol), Pd ₂ (dba) ₃ (0.136 g, 1 mol%) under nitrogen atmosphere , KF, potassium fluoride (2.85 g, 48.98 mmol) was dissolved in 100 mL of THF, P (tBu) 3 (0.060 g, 2 mol%) was added in the presence of reflux and the temperature was increased to 75 ^° C. After stirring at 75 ^° C. for about 24 hours, the mixture was concentrated under reduced pressure. The remaining solid is dissolved in methylene chloride and washed several times with water, followed by removing water with anhydrous magnesium sulfate, filtering it, and then removing the solvent. The solvent was removed and silica gel column purification with a nucleic acid / methylene chloride (1: 2) solvent to give the target compound 7 g (88.7%, LC Mass M + H ⁺ = 591.4).

Example  2 to 26: preparation of compounds

Except for using the starting materials M-43 of Example 1 (corresponding to starting material 1 of Table 2) and W-1 (corresponding to starting material 2 of Table 2 below) instead of the two starting materials shown in Table 2 below. Compounds were prepared in the same manner as in all synthesis procedures.

Example Starting material 1 Starting material 2 product yield(%)
LC-Mass (M + H ⁺ ) 2

A-12 78%
756.31 3

A-21 80%
772.30 4

C-9 75%
680.27 5

C-10 68%
696.25 6

D-3 66%
729.27 7

D-4 78%
744.24 8

A-14 80%
756.30 9

A-23 82%
773.28 10

C-11 80%
681.27 11

C-12 75%
697.24 12

C-13 56%
693.27 13

C-14 60%
712.24 14

C-15 67%
745.19 15

C-16 91%
511.21 16

C-17 85%
756.31 17

C-18 78%
602.25 18

C-19 72%
618.23 19

C-20 70%
665.16 20

D-7 75%
651.25 21

D-8 77%
667.22 22

E-1 80%
729.27 23

E-5 75%
745.24 24

E-9 82%
793.19 25

E-3 77%
745.24 26

E-7 80%
793.19 27

B-3 87%
805.30

Example  28: Organic photoelectric device  Produce

An organic photoelectric device was manufactured by using the compound synthesized in Example 2 as a host and using Ir (PPy) ₃ as a dopant. ITO was used as a cathode of 1000 kPa, and aluminum (Al) was used as a cathode of 1000 kPa.

Specifically, the manufacturing method of the organic photoelectric device, the anode is 15 　 ITO glass substrate with sheet resistance of / cm ² was cut into 50 mm × 50 mm × 0.7 mm and ultrasonically cleaned in acetone, isopropyl alcohol and pure water for 15 minutes, and then UV ozone cleaning for 30 minutes. Was used.

N, N'-di (1-naphthyl) -N, N'-diphenylbenzidine (NPB) (70 nm) under conditions of vacuum degree 650 × 10 ^-7 Pa and deposition rate of 0.1 to 0.3 nm / s on the substrate. ) And 4,4 ', 4 "-tri (N-carbazolyl) triphenylamine (TCTA) (10 nm) were deposited to form an 800 kV hole transport layer.

Subsequently, using the compound synthesized in Example 1 under the same vacuum deposition conditions, a light emitting layer having a film thickness of 300 Å was formed, and at this time, a phosphorescent dopant Ir (PPy) ₃ was simultaneously deposited. At this time, by adjusting the deposition rate of the phosphorescent dopant, when the total amount of the light emitting layer is 100% by weight, the deposition rate of the phosphorescent dopant was deposited so as to be 7% by weight.

Bis (8-hydroxy-2-methylquinolinato) -aluminum biphenoxide (BAlq) was deposited on the light emitting layer using the same vacuum deposition conditions to form a hole blocking layer having a thickness of 50 kHz.

Subsequently, Alq ₃ was deposited under the same vacuum deposition conditions to form an electron transport layer having a film thickness of 200 GPa.

An organic photoelectric device was manufactured by sequentially depositing LiF and Al as a cathode on the electron transport layer.

The structure of the organic photoelectric device is ITO / NPB (70 nm) / TCTA (10 nm) / EML (compound of Example 1 (93% by weight) + Ir (PPy) ₃ (7% by weight), 30 nm) / Balq (5 nm) / Alq ₃ (20 nm) / LiF (1 nm) / Al (100 nm).

Example  29: Organic photoelectric device  Produce

An organic light emitting diode was manufactured according to the same method as Example 27 except for using Example 3 instead of Example 2.

Example  30: Organic photoelectric device  Produce

An organic light emitting diode was manufactured according to the same method as Example 27 except for using Example 4 instead of Example 2.

Example  31: Organic photoelectric device  Produce

An organic light emitting diode was manufactured according to the same method as Example 27 except for using Example 5 instead of Example 2.

Example  32: Organic photoelectric device  Produce

An organic light emitting diode was manufactured according to the same method as Example 27 except for using Example 6 instead of Example 2.

Example  33: Organic photoelectric device  Produce

An organic light emitting diode was manufactured according to the same method as Example 27 except for using Example 7 instead of Example 2.

Example  34: Organic photoelectric device  Produce

An organic light emitting diode was manufactured according to the same method as Example 27 except for using Example 10 instead of Example 2.

Example  35: Organic photoelectric device  Produce

An organic light emitting diode was manufactured according to the same method as Example 27 except for using Example 11 instead of Example 2.

Example  36: Organic photoelectric device  Produce

An organic light emitting diode was manufactured according to the same method as Example 27 except for using Example 12 instead of Example 2.

Example  37: Organic photoelectric device  Produce

An organic light emitting diode was manufactured according to the same method as Example 27 except for using Example 13 instead of Example 2.

Example  38: Organic photoelectric device  Produce

An organic light emitting diode was manufactured according to the same method as Example 27 except for using Example 14 instead of Example 2.

Example  39: Organic photoelectric device  Produce

An organic light emitting diode was manufactured according to the same method as Example 27 except for using Example 22 instead of Example 2.

Example  40: Organic photoelectric device  Produce

An organic light emitting diode was manufactured according to the same method as Example 27 except for using Example 27 instead of Example 2.

Comparative example  One : Organic photoelectric device  Produce

Except for using the compound synthesized in Example 2 as a host of the light emitting layer, the same as in Example 27 except that 4,4-N, N-dicarbazole biphenyl (CBP) was used as the host of the light emitting layer An organic photoelectric device was manufactured by the method.

(Performance Measurement of Organic Light Emitting Diode)

For each of the organic light emitting diodes manufactured in Examples 28 to 40 and Comparative Example 1, the current density change, luminance change, and luminous efficiency according to voltage were measured. Specific measurement methods are as follows, and the results are shown in Table 3 below.

(1) Measurement of change of current density according to voltage change

For the organic light emitting device manufactured, the current value flowing through the unit device was measured using a current-voltmeter (Keithley 2400) while increasing the voltage from 0 V to 10 V, and the measured current value was divided by the area to obtain a result.

(2) Measurement of luminance change according to voltage change

The resulting organic light emitting device was measured by using a luminance meter (Minolta Cs-1000A) while increasing the voltage from 0 V to 10 V to obtain a result.

(3) Measurement of luminous efficiency

The current efficiency (cd / A) of the same current density (10 mA / cm ² ) was calculated using the brightness, current density, and voltage measured from (1) and (2) above.

Example Emission Layer Host Material @ 1000 cd / m ² Driving voltage Luminous efficiency Power efficiency 27 Compound of Example 2
(A-12) 6.7 50.3 23.6 28 Compound of Example 3
(A-21) 7.0 49.2 22.1 29 Compound of Example 4
(C-9) 6.8 48.0 22.2 30 Compound of Example 5
(C-10) 6.6 55.2 26.3 31 Compound of Example 6
(D-3) 6.5 57.2 27.6 32 Compound of Example 7
(D-4) 6.3 60.1 30.0 33 Compound of Example 10
(C-11) 7.1 63.5 28.1 34 Compound of Example 11
(C-12) 7.2 49.3 21.5 35 Compound of Example 12
(C-13) 6.9 58.2 26.5 36 Compound of Example 13
(C-14) 7.3 59.3 25.5 37 Compound of Example 14
(C-15) 6.6 51.9 24.7 38 Compound of Example 22
(E-1) 6.5 58.4 28.2 40 Compound of Example 27
(B-3) 6.3 60.4 30.1 Comparative Example 1 CBP 7.6 42.7 17.6

Referring to Table 1, it can be seen that in Examples 27 to 38, the driving voltage and the efficiency are higher than those of the reference material CBP. This shows the possibility that the compounds prepared in Examples 2 to 7, 10 to 14 and 22 can be used as materials for good organic photoelectric devices.

The present invention is not limited to the above embodiments, but may be manufactured in various forms, and a person skilled in the art to which the present invention pertains has another specific form without changing the technical spirit or essential features of the present invention. It will be appreciated that the present invention may be practiced as. It is therefore to be understood that the above-described embodiments are illustrative in all aspects and not restrictive.

100: organic photoelectric device 110: cathode
120: anode 105: organic thin film layer
130: light emitting layer 140: hole transport layer
150: electron transport layer 160: electron injection layer
170: hole injection layer 230: light emitting layer + electron transport layer

Claims (21)

Formula 1; And a compound for an organic photoelectric device represented by the combination of Formula 2 or 3:
[Formula 1] [Formula 2] [Formula 3]

In the above Formulas 1 to 3,
X is O, Se, S, SO 2 (O = S = O), PO (P = O) or CO (C = O),
Y is CR'R 'or NR *,
A *, b *, R ', R', R ¹ , R ² and R * are the same as or different from each other, and independently hydrogen, deuterium, a halogen group, a cyano group, a hydroxyl group, an amino group, a substituted or unsubstituted Substituted C1 to C20 amine group, nitro group, substituted or unsubstituted C2 to C10 carboxyl group, substituted or unsubstituted ferrocenyl group, substituted or unsubstituted C1 to C20 alkyl group, substituted or unsubstituted C6 to C30 aryl group, Substituted or unsubstituted C2 to C30 heteroaryl group, substituted or unsubstituted C1 to C20 alkoxy group, substituted or unsubstituted C6 to C20 aryloxy group, substituted or unsubstituted C3 to C40 silyloxy group, substituted or unsubstituted A substituted C1 to C20 acyl group, a substituted or unsubstituted C2 to C20 alkoxycarbonyl group, a substituted or unsubstituted C2 to C20 acyloxy group, a substituted or unsubstituted C2 to C20 acylamino group, a substituted or unsubstituted C2 to C20 alkoxycarbonylamino group, A substituted or unsubstituted C7 to C20 aryloxycarbonylamino group, a substituted or unsubstituted C1 to C20 sulfamoylamino group, a substituted or unsubstituted C1 to C20 sulfonyl group, a substituted or unsubstituted C1 to C20 alkylthiol group, Substituted or unsubstituted C6 to C20 arylthiol group, substituted or unsubstituted C1 to C20 heterocyclothiol group, substituted or unsubstituted C1 to C20 ureide group, substituted or unsubstituted C3 to C40 silyl group or these Is a combination of
Adjacent two * of Chemical Formula 1, combine with two adjacent * of Chemical Formula 2 or 3 to form a fused ring,
At least one of the a *, b * or R * is a substituent represented by the following formula (4),
[Chemical Formula 4]

In Chemical Formula 4,
The ETU is a substituted or unsubstituted C6 to C30 aryl group having an electronic property; Or a substituted or unsubstituted C2 to C30 heteroaryl group having electronic properties,
L is a single bond, a substituted or unsubstituted C2 to C6 alkenylene group, a substituted or unsubstituted C2 to C6 alkynylene group, a substituted or unsubstituted C6 to C30 arylene group, a substituted or unsubstituted heteroarylene group or Combination of these,
N is an integer of any one of 0-2.
The method of claim 1,
The compound for an organic photoelectric device is a compound for an organic photoelectric device is represented by the following formula (5):
[Chemical Formula 5]

In Formula 5,
X is O, Se, S, SO 2 (O = S = O), PO (P = O) or CO (C = O),
Y is CR'R 'or NR *,
A *, b *, R ', R', R ¹ , R ² and R * are the same as or different from each other, and independently hydrogen, deuterium, a halogen group, a cyano group, a hydroxyl group, an amino group, a substituted or unsubstituted Substituted C1 to C20 amine group, nitro group, substituted or unsubstituted C2 to C10 carboxyl group, substituted or unsubstituted ferrocenyl group, substituted or unsubstituted C1 to C20 alkyl group, substituted or unsubstituted C6 to C30 aryl group, Substituted or unsubstituted C2 to C30 heteroaryl group, substituted or unsubstituted C1 to C20 alkoxy group, substituted or unsubstituted C6 to C20 aryloxy group, substituted or unsubstituted C3 to C40 silyloxy group, substituted or unsubstituted A substituted C1 to C20 acyl group, a substituted or unsubstituted C2 to C20 alkoxycarbonyl group, a substituted or unsubstituted C2 to C20 acyloxy group, a substituted or unsubstituted C2 to C20 acylamino group, a substituted or unsubstituted C2 to C20 alkoxycarbonylamino group, A substituted or unsubstituted C7 to C20 aryloxycarbonylamino group, a substituted or unsubstituted C1 to C20 sulfamoylamino group, a substituted or unsubstituted C1 to C20 sulfonyl group, a substituted or unsubstituted C1 to C20 alkylthiol group, Substituted or unsubstituted C6 to C20 arylthiol group, substituted or unsubstituted C1 to C20 heterocyclothiol group, substituted or unsubstituted C1 to C20 ureide group, substituted or unsubstituted C3 to C40 silyl group or these Is a combination of
At least one of the a *, b * or R * is a substituent represented by the following formula (4),
[Chemical Formula 4]

In Chemical Formula 4,
The ETU is a substituted or unsubstituted C6 to C30 aryl group having an electronic property; Or a substituted or unsubstituted C2 to C30 heteroaryl group having electronic properties,
L is a single bond, a substituted or unsubstituted C2 to C6 alkenylene group, a substituted or unsubstituted C2 to C6 alkynylene group, a substituted or unsubstituted C6 to C30 arylene group, a substituted or unsubstituted heteroarylene group or Combination of these,
N is an integer of any one of 0-2.
The method of claim 1,
The compound for an organic photoelectric device is a compound for an organic photoelectric device is represented by the following formula (6):
[Formula 6]

In Formula 6,
X is O, Se, S, SO 2 (O = S = O), PO (P = O) or CO (C = O),
Y is CR'R 'or NR *,
R ′, R ′, R ¹ , R ² and R * are the same as or different from each other, and independently hydrogen, deuterium, a halogen group, a cyano group, a hydroxyl group, an amino group, a substituted or unsubstituted C1 to C20 amine group , Nitro group, substituted or unsubstituted C2 to C10 carboxyl group, substituted or unsubstituted ferrocenyl group, substituted or unsubstituted C1 to C20 alkyl group, substituted or unsubstituted C6 to C30 aryl group, substituted or unsubstituted C2 To C30 heteroaryl group, substituted or unsubstituted C1 to C20 alkoxy group, substituted or unsubstituted C6 to C20 aryloxy group, substituted or unsubstituted C3 to C40 silyloxy group, substituted or unsubstituted C1 to C20 ah Real, substituted or unsubstituted C2 to C20 alkoxycarbonyl group, substituted or unsubstituted C2 to C20 acyloxy group, substituted or unsubstituted C2 to C20 acylamino group, substituted or unsubstituted C2 to C20 alkoxycarbonylamino group , Substitution Is an unsubstituted C7 to C20 aryloxycarbonylamino group, a substituted or unsubstituted C1 to C20 sulfamoylamino group, a substituted or unsubstituted C1 to C20 sulfonyl group, a substituted or unsubstituted C1 to C20 alkylthiol group, a substitution Or an unsubstituted C6 to C20 arylthiol group, a substituted or unsubstituted C1 to C20 heterocyclothiol group, a substituted or unsubstituted C1 to C20 ureide group, a substituted or unsubstituted C3 to C40 silyl group, or their Combination,
The ETU is substituted or unsubstituted C6 to C30 aryl group having an electronic property; Or a substituted or unsubstituted C2 to C30 heteroaryl group having electronic properties,
L is a single bond, a substituted or unsubstituted C2 to C6 alkenylene group, a substituted or unsubstituted C2 to C6 alkynylene group, a substituted or unsubstituted C6 to C30 arylene group, a substituted or unsubstituted heteroarylene group or Combination of these,
N is an integer of any one of 0-2.
The method of claim 1,
The compound for an organic photoelectric device is a compound for an organic photoelectric device is represented by the following formula (7):
[Formula 7]

In Chemical Formula 7,
X is O, Se, S, SO 2 (O = S = O), PO (P = O) or CO (C = O),
Y is CR'R 'or NR *,
R ′, R ′, R ¹ , R ² and R * are the same as or different from each other, and independently hydrogen, deuterium, a halogen group, a cyano group, a hydroxyl group, an amino group, a substituted or unsubstituted C1 to C20 amine group , Nitro group, substituted or unsubstituted C2 to C10 carboxyl group, substituted or unsubstituted ferrocenyl group, substituted or unsubstituted C1 to C20 alkyl group, substituted or unsubstituted C6 to C30 aryl group, substituted or unsubstituted C2 To C30 heteroaryl group, substituted or unsubstituted C1 to C20 alkoxy group, substituted or unsubstituted C6 to C20 aryloxy group, substituted or unsubstituted C3 to C40 silyloxy group, substituted or unsubstituted C1 to C20 ah Real, substituted or unsubstituted C2 to C20 alkoxycarbonyl group, substituted or unsubstituted C2 to C20 acyloxy group, substituted or unsubstituted C2 to C20 acylamino group, substituted or unsubstituted C2 to C20 alkoxycarbonylamino group , Substitution Is an unsubstituted C7 to C20 aryloxycarbonylamino group, a substituted or unsubstituted C1 to C20 sulfamoylamino group, a substituted or unsubstituted C1 to C20 sulfonyl group, a substituted or unsubstituted C1 to C20 alkylthiol group, a substitution Or an unsubstituted C6 to C20 arylthiol group, a substituted or unsubstituted C1 to C20 heterocyclothiol group, a substituted or unsubstituted C1 to C20 ureide group, a substituted or unsubstituted C3 to C40 silyl group, or their Combination,
The ETU is a substituted or unsubstituted C6 to C30 aryl group having an electronic property; Or a substituted or unsubstituted C2 to C30 heteroaryl group having electronic properties,
L is a single bond, a substituted or unsubstituted C2 to C6 alkenylene group, a substituted or unsubstituted C2 to C6 alkynylene group, a substituted or unsubstituted C6 to C30 arylene group, a substituted or unsubstituted heteroarylene group or Combination of these,
N is an integer of any one of 0-2.
The method of claim 1,
The compound for an organic photoelectric device is a compound for an organic photoelectric device is represented by the following formula (8):
[Chemical Formula 8]

In Chemical Formula 8,
X is O, Se, S, SO 2 (O = S = O), PO (P = O) or CO (C = O),
Y is CR'R 'or NR *,
R ′, R ′, R ¹ , R ² and R * are the same as or different from each other, and independently hydrogen, deuterium, a halogen group, a cyano group, a hydroxyl group, an amino group, a substituted or unsubstituted C1 to C20 amine group , Nitro group, substituted or unsubstituted C2 to C10 carboxyl group, substituted or unsubstituted ferrocenyl group, substituted or unsubstituted C1 to C20 alkyl group, substituted or unsubstituted C6 to C30 aryl group, substituted or unsubstituted C2 To C30 heteroaryl group, substituted or unsubstituted C1 to C20 alkoxy group, substituted or unsubstituted C6 to C20 aryloxy group, substituted or unsubstituted C3 to C40 silyloxy group, substituted or unsubstituted C1 to C20 ah Real, substituted or unsubstituted C2 to C20 alkoxycarbonyl group, substituted or unsubstituted C2 to C20 acyloxy group, substituted or unsubstituted C2 to C20 acylamino group, substituted or unsubstituted C2 to C20 alkoxycarbonylamino group , Substitution Is an unsubstituted C7 to C20 aryloxycarbonylamino group, a substituted or unsubstituted C1 to C20 sulfamoylamino group, a substituted or unsubstituted C1 to C20 sulfonyl group, a substituted or unsubstituted C1 to C20 alkylthiol group, a substitution Or an unsubstituted C6 to C20 arylthiol group, a substituted or unsubstituted C1 to C20 heterocyclothiol group, a substituted or unsubstituted C1 to C20 ureide group, a substituted or unsubstituted C3 to C40 silyl group, or their Combination,
The ETU is a substituted or unsubstituted C6 to C30 aryl group having an electronic property; Or a substituted or unsubstituted C2 to C30 heteroaryl group having electronic properties,
L is a single bond, a substituted or unsubstituted C2 to C6 alkenylene group, a substituted or unsubstituted C2 to C6 alkynylene group, a substituted or unsubstituted C6 to C30 arylene group, a substituted or unsubstituted heteroarylene group or Combination of these,
N is an integer of any one of 0-2.
The method of claim 1,
The substituted or unsubstituted C6 to C30 aryl group having the above electronic properties is a substituted or unsubstituted triphenylenyl group, a substituted or unsubstituted florenyl group, a substituted or unsubstituted spiroflorenyl group, a substituted or unsubstituted terphenyl group , Substituted or unsubstituted pyrenyl group, substituted or unsubstituted perenyl group, substituted or unsubstituted phenanthrenyl group, or a combination thereof.
The method of claim 1,
Substituted or unsubstituted C2 to C30 heteroaryl group having the above electronic properties, substituted or unsubstituted imidazolyl group, substituted or unsubstituted triazolyl group, substituted or unsubstituted tetrazolyl group, substituted or unsubstituted Carbazolyl group, substituted or unsubstituted oxadiazolyl group, substituted or unsubstituted oxatriazolyl group, substituted or unsubstituted thiaziazolyl group, substituted or unsubstituted benzimidazolyl group, substituted or unsubstituted Benzotriazolyl group, substituted or unsubstituted pyridinyl group, substituted or unsubstituted pyrimidinyl group, substituted or unsubstituted triazinyl group, substituted or unsubstituted pyrazinyl group, substituted or unsubstituted pyridazinyl Groups, substituted or unsubstituted purinyl groups, substituted or unsubstituted quinolinyl groups, substituted or unsubstituted isoquinolinyl groups, substituted or unsubstituted phthalazinyl groups, substituted or unsubstituted naphthos Dinyl group, substituted or unsubstituted quinoxalinyl group, substituted or unsubstituted quinazolinyl group, substituted or unsubstituted acridinyl group, substituted or unsubstituted phenanthrolinyl group, substituted or unsubstituted phenazinyl group or theirs Compound for an organic photoelectric device that is a combination.
The method of claim 1,
The compound for an organic photoelectric device is a compound for an organic photoelectric device represented by any one of the following formula A-1 to A-55.
[Formula A-1] [Formula A-2] [Formula A-3]

[Formula A-4] [Formula A-5] [Formula A-6]

[Formula A-7] [Formula A-8] [Formula A-9]

[Formula A-10] [Formula A-11] [Formula A-12]

[Formula A-13] [Formula A-14] [Formula A-15]

[Formula A-16] [Formula A-17] [Formula A-18]

[Formula A-19] [Formula A-20] [Formula A-21]

[Formula A-22] [Formula A-23] [Formula A-24]

[Formula A-25] [Formula A-26] [Formula A-27]

[Formula A-28] [Formula A-29] [Formula A-30]

[Formula A-31] [Formula A-32] [Formula A-33]

[Formula A-34] [Formula A-35] [Formula A-36]

[Formula A-37] [Formula A-38] [Formula A-39]

[Formula A-40] [Formula A-41] [Formula A-42]

[Formula A-43] [Formula A-44] [Formula A-45]

[Formula A-46] [Formula A-47] [Formula A-48]

[Formula A-49] [Formula A-51] [Formula A-52]

[Formula A-53] [Formula A-54] [Formula A-55]

The method of claim 1,
The compound for an organic photoelectric device is a compound for an organic photoelectric device represented by any one of the following formula B-1 to B-44.
[Formula B-1] [Formula B-2] [Formula B-3]

[Formula B-4] [Formula B-5] [Formula B-6]

[Formula B-7] [Formula B-8] [Formula B-9]

[Formula B-10] [Formula B-11]

[Formula B-12] [Formula B-13] [Formula B-14]

[Formula B-15] [Formula B-16] [Formula B-17]

[Formula B-18] [Formula B-19] [Formula B-20]

Formula B-21 Formula B-22

[Formula B-23] [Formula B-24] [Formula B-25]

[Formula B-26] [Formula B-27] [Formula B-28]

[Formula B-29] [Formula B-30] [Formula B-31]

Formula B-32 Formula B-33

[Formula B-34] [Formula B-35] [Formula B-36]

[Formula B-37] [Formula B-38] [Formula B-39]

[Formula B-40] [Formula B-41] [Formula B-42]

Formula B-43 Formula B-44

The method of claim 1,
The compound for an organic photoelectric device is a compound for an organic photoelectric device represented by any one of the following formula C-1 to C-20.
[Formula C-1] [Formula C-2] [Formula C-3]

[Formula C-4] [Formula C-5] [Formula C-6]

[Formula C-7] [Formula C-8] [Formula C-9]

[Formula C-10] [Formula C-11] [Formula C-12]

[Formula C-13] [Formula C-14] [Formula C-15]

[Formula C-16] [Formula C-17] [Formula C-18]

Formula C-19 Formula C-20

The method of claim 1,
The compound for an organic photoelectric device is a compound for an organic photoelectric device represented by any one of the following formula D-1 to D-8.
[Formula D-1] [Formula D-2] [Formula D-3]

[Formula D-4] [Formula D-5] [Formula D-6]

[Formula D-7] [Formula D-8]

The method of claim 1,
The compound for an organic photoelectric device is a compound for an organic photoelectric device represented by any one of the following formulas E-1 to E-9.
[Formula E-1] [Formula E-2] [Formula E-3]

[Formula E-4] [Formula E-5] [Formula E-6]

[Formula E-7] [Formula E-8]

[Formula E-9]

The method of claim 1,
The compound for an organic photoelectric device is a compound for an organic photoelectric device that can be used as a light emitting material of the organic light emitting device.
The method of claim 1,
The compound for an organic photoelectric device is a compound for an organic photoelectric device is triplet excitation energy (T1) 2.0 eV or more.
The method of claim 1,
The organic photoelectric device is a compound for an organic photoelectric device is selected from the group consisting of an organic light emitting device, an organic solar cell, an organic transistor, an organic photosensitive drum and an organic memory device.
In an organic light emitting device comprising an anode, a cathode and at least one organic thin film layer interposed between the anode and the cathode,
At least one of the organic thin film layer is an organic light emitting device comprising the compound for an organic photoelectric device according to claim 1.
17. The method of claim 16,
The organic thin film layer is selected from the group consisting of a light emitting layer, a hole transport layer, a hole injection layer, an electron transport layer, an electron injection layer, a hole blocking layer and a combination thereof.
17. The method of claim 16,
The compound for an organic photoelectric device is an organic light emitting device which is contained in a hole transport layer or a hole injection layer.
17. The method of claim 16,
The organic light emitting device compound is included in the light emitting layer.
17. The method of claim 16,
The compound for an organic photoelectric device is used in the light emitting layer as a phosphorescent or fluorescent host material.
A display device comprising the organic light emitting device of claim 16.

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