KR20240057705A - Compound for organic electric element, organic electric element using the same, and an electronic device thereof - Google Patents

Abstract

The present invention provides a compound represented by Formula 1, an organic electric device including a first electrode, a second electrode, and an organic material layer between the first electrode and the second electrode, and an electronic device including the organic electric device. do. By including the compound represented by Formula 1 in the organic material layer, the driving voltage of the organic electric device can be lowered and the luminous efficiency and lifespan can be improved.

Description

Compounds for organic electric devices, organic electric devices using the same, and their electronic devices {COMPOUND FOR ORGANIC ELECTRIC ELEMENT, ORGANIC ELECTRIC ELEMENT USING THE SAME, AND AN ELECTRONIC DEVICE THEREOF}

The present invention relates to compounds for organic electric devices, organic electric devices using the same, and electronic devices thereof.

In general, organic luminescence refers to a phenomenon that converts electrical energy into light energy using organic materials. Organic electric devices that utilize the organic light emission phenomenon usually have a structure including an anode, a cathode, and an organic material layer between them. Here, the organic material layer is often composed of a multi-layer structure composed of different materials to increase the efficiency and stability of the organic electric device, and may be composed of, for example, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer.

Materials used as organic layers in organic electric devices can be classified into light-emitting materials and charge transport materials, such as hole injection materials, hole transport materials, electron transport materials, and electron injection materials, depending on their function. In addition, the light-emitting materials can be classified into high-molecular and low-molecular types depending on their molecular weight, and can be classified into fluorescent materials derived from the singlet excited state of electrons and phosphorescent materials derived from the triplet excited state of electrons depending on the light-emitting mechanism. there is. In addition, light-emitting materials can be divided into blue, green, and red light-emitting materials depending on the color of the light, and yellow and orange light-emitting materials necessary to realize better natural colors.

On the other hand, when only one substance is used as a light-emitting material, the maximum emission wavelength is shifted to a longer wavelength due to intermolecular interactions, and color purity is reduced or the efficiency of the device is reduced due to the luminescence attenuation effect. This causes an increase in color purity and energy transfer. In order to increase luminous efficiency through , a host/dopant system can be used as a luminescent material. The principle is that when a small amount of a dopant with a smaller energy band gap than the host forming the light-emitting layer is mixed into the light-emitting layer, excitons generated in the light-emitting layer are transported to the dopant, producing highly efficient light. At this time, since the wavelength of the host moves to the wavelength of the dopant, light of the desired wavelength can be obtained depending on the type of dopant used.

Currently, the portable display market is increasing in size toward large-area displays, which requires greater power consumption than that required for existing portable displays. Therefore, power consumption has become a very important factor for portable displays that have a limited power source such as batteries, and issues of efficiency and lifespan must also be resolved.

Efficiency, lifespan, and driving voltage are related to each other. As efficiency increases, the driving voltage relatively decreases. As the driving voltage decreases, crystallization of organic substances due to Joule heating generated during driving decreases, resulting in less crystallization of organic substances. Life expectancy tends to increase. However, efficiency cannot be maximized simply by improving the organic layer. This is because long lifespan and high efficiency can be achieved at the same time when the energy level and T ₁ value between each organic layer and the intrinsic properties of the material (mobility, interface properties, etc.) are optimally combined. .

Therefore, there is a need to develop a light-emitting material that has high thermal stability and can efficiently achieve charge balance within the light-emitting layer. In other words, in order to fully demonstrate the excellent characteristics of organic electric devices, the materials that make up the organic layer within the device, such as hole injection materials, hole transport materials, light-emitting materials, electron transport materials, and electron injection materials, must be supported by stable and efficient materials. This must take precedence, and in particular, the development of a host material for the light-emitting layer is necessary.

The purpose of the present invention is to provide a compound for an organic electric device that can lower the driving voltage of the device and improve the luminous efficiency and lifespan of the device, an organic electric device using the same, and an electronic device thereof.

In one aspect, the present invention provides a compound represented by the formula:

In another aspect, the present invention provides a method for recovering a reusable compound represented by the above chemical formula by recovering the compound represented by the above chemical formula after deposition.

In another aspect, the present invention provides an organic electric device and an electronic device containing the compound represented by the above formula.

By using the compound according to the embodiment of the present invention, the driving voltage of the device can be lowered, the luminous efficiency and lifespan can be improved, and the compound used in the deposition process can be recovered and reused.

1 to 3 are exemplary diagrams of organic electroluminescent devices according to embodiments of the present invention.

The terms “aryl group” and “arylene group” used in the present invention each have 6 to 60 carbon atoms unless otherwise specified, and are not limited thereto. In the present invention, an aryl group or arylene group may include a single ring type, a ring aggregate, a fused multiple ring system, a spiro compound, etc.

As used in the present invention, the term "fluorenyl group" refers to a substituted or unsubstituted fluorenyl group, and the term "fluorenylene group" refers to a substituted or unsubstituted fluorenylene group, and the fluorenyl group or The fluorenylene group includes spiro compounds formed by R and R' bonded to each other in the structure below, and also includes compounds formed by adjacent R" bonded to each other to form a ring. "Substituted fluorenyl group", "substituted The fluorenylene group" means that at least one of R, R', and R" in the structure below is a substituent other than hydrogen, and in the formula below, R" may be 1 to 8. In the present specification, regardless of the valence, Fluorenyl group, fluorenylene group, etc. may be referred to as fluorene group or fluorene.

The term "spiro compound" used in the present invention has a 'spiro connection', and the spiro connection means a connection made by two rings sharing only one atom. At this time, the atom shared between the two rings is called a 'spiro atom', and depending on the number of spiro atoms in one compound, they are 'monospiro-', 'dispiro-', and 'trispiro-' respectively. 'It is called a compound.

The term “heterocyclic group” used in the present invention includes not only aromatic rings such as “heteroaryl group” or “heteroarylene group” but also non-aromatic rings, and unless otherwise specified, each carbon number containing one or more heteroatoms. It refers to a ring numbered from 2 to 60, but is not limited thereto. Unless otherwise specified, the term "heteroatom" used in this specification refers to an element other than carbon, such as N, O, S, P or Si, and instead of carbon forming a ring, SO ₂ , P= It may also contain heteroatom groups such as O. In the present specification, heterocyclic groups include single rings containing heteroatoms, ring aggregates, multiple fused ring systems, spiro compounds, etc.

The term "aliphatic ring" used in the present invention refers to cyclic hydrocarbons excluding aromatic hydrocarbons, and includes single rings, ring aggregates, fused multiple ring systems, spiro compounds, etc., and has the number of carbon atoms unless otherwise specified. It means 3 to 60 rings, but is not limited thereto. For example, even when benzene, an aromatic ring, and cyclohexane, a non-aromatic ring, are fused, it is an aliphatic ring.

In this specification, the 'group name' corresponding to the aryl group, arylene group, heterocyclic group, etc., as examples of each symbol and its substituent, may be written as the 'name of the group reflecting the valence', but is written as the 'name of the parent compound' You may. For example, in the case of 'phenanthrene', a type of aryl group, the name of the group may be written by distinguishing the valence, such as the monovalent 'group' is 'phenanthryl' and the divalent group is 'phenanthrylene'. Regardless, it can also be written as the parent compound name, ‘phenanthrene’. Similarly, in the case of pyrimidine, it can be written as 'pyrimidine' regardless of the valence, or it can be written as the 'name of the group' of the valence, such as pyrimidineyl group in the case of monovalent group, pyrimidineylene in the case of divalent group, etc. there is.

Additionally, in this specification, when describing compound names or substituent names, numbers or alphabets indicating positions may be omitted. For example, pyrido[4,3-d]pyrimidine to pyridopyrimidine, benzofuro[2,3-d]pyrimidine to benzofuropyrimidine, 9,9-dimethyl-9H-flu. Orene can be described as dimethylfluorene, etc. Therefore, both benzo[g]quinoxaline and benzo[f]quinoxaline can be described as benzoquinoxaline.

In addition, unless explicitly stated otherwise, the chemical formula used in the present invention is applied identically to the substituent definition according to the exponent definition of the following chemical formula.

Here, when a is an integer of 0, it means that the substituent R ¹ is absent. That is, when a is 0, it means that hydrogen is bonded to all carbons forming the benzene ring. In this case, the hydrogen bonded to the carbon is indicated as You can omit it and write the chemical formula or compound. In addition, when a is an integer of 1, one substituent R ¹ is bonded to any one of the carbons forming the benzene ring, and when a is an integer of 2 or 3, it can be bonded as follows, for example, and a is 4 to 6 Even when it is an integer, it is bonded to the carbon of the benzene ring in a similar way, and when a is an integer of 2 or more, R ¹ may be the same or different.

In addition, unless otherwise specified in the specification, a ring refers to an aryl ring, heteroaryl ring, fluorene ring, aliphatic ring, etc., a number-ring refers to a condensed ring, and a number-atom ring refers to the form of a ring. It can mean. For example, naphthalene corresponds to a 2-ring, anthracene corresponds to a 3-ring condensed ring, thiophene or furan corresponds to a 5-membered heterocycle, and benzene or pyridine corresponds to a 6-membered aromatic ring.

In addition, unless otherwise specified in the specification, the ring formed by combining adjacent groups is an aromatic ring group of C ₆ to C ₆₀ ; fluorenyl group; C ₂ ~ C ₆₀ heterocyclic group containing at least one hetero atom among O, N, S, Si and P; and an aliphatic ring group of C ₃ to C ₆₀ . Here, the aromatic ring group may include an aryl ring, and the heterocyclic group may include a heteroaryl ring.

Unless otherwise specified in the specification, 'neighboring groups' refers to groups R ₁ and R ₂ , R ₂ and R ₃ , R ₃ and R ₄ , and R ₅ using the following chemical formula as an example. and R ₆ , as well as R ₇ and R ₈ that share one carbon, and ring configurations that are not immediately adjacent, such as between R ₁ and R ₇ , between R ₁ and R ₈ , or between R ₄ and R ₅ , etc. Substituents bonded to elements (such as carbon or nitrogen) may also be included. In other words, if there are substituents on immediately adjacent ring elements such as carbon or nitrogen, they can become neighboring groups, but if no substituents are bonded to the immediately adjacent ring elements, they can be bonded to the next ring element. It can be a group adjacent to a substituent, and substituents bonded to carbons of the same ring can also be said to be neighboring groups. In the formula below, when substituents bonded to the same carbon, such as R ₇ and R ₈ , combine to form a ring, a compound containing a spiro moiety may be formed.

,

In addition, in this specification, the expression 'neighboring groups can combine with each other to form a ring' is used in the same meaning as 'neighboring groups can selectively form a ring by combining with each other', and at least one pair of This refers to a case where neighboring groups combine with each other to form a ring.

In addition, unless otherwise specified in the specification, an aryl group, arylene group, fluorenyl group, fluorenylene group, heterocyclic group, aliphatic ring group, alkyl group, alkenyl group, alkynyl group, alkoxy group, aryloxy group, alkylcy group. Substituents such as arylthio groups, arylthio groups, etc., rings formed by bonding adjacent groups, etc. are each deuterium; halogen; Cyano group; nitro group; siloxane group; C ₆ -C ₃₀ aryl group; fluorenyl group; A C ₂ -C ₃₀ heterocyclic group containing at least one heteroatom selected from the group consisting of O, N, S, Si and P; C ₃ -C ₃₀ aliphatic ring group; C ₁ -C ₂₀ alkyl group; C ₂ -C ₂₀ alkenyl group; C ₂ -C ₂₀ alkyne group; C ₁ -C ₂₀ alkoxy group; C ₆ -C ₂₀ aryloxy group; C ₁ -C ₂₀ alkylthio group; C ₆ -C ₂₀ arylthio group; Silane group substituted or unsubstituted with a C ₁ -C ₂₀ alkyl group or a C ₆ -C ₂₀ aryl group; and a phosphine oxide group unsubstituted or substituted with a C ₁ -C ₂₀ alkyl group or a C ₆ -C ₂₀ aryl group.

Hereinafter, the layered structure of an organic electric device containing the compound of the present invention will be described with reference to FIGS. 1 to 3.

When adding reference numerals to components in each drawing, it should be noted that identical components are given the same reference numerals as much as possible even if they are shown in different drawings. Additionally, in describing the present invention, if it is determined that a detailed description of a related known configuration or function may obscure the gist of the present invention, the detailed description will be omitted.

In describing the components of the present invention, terms such as first, second, A, B, (a), (b), etc. may be used. These terms are only used to distinguish the component from other components, and the nature, sequence, or order of the component is not limited by the term. When a component is described as being “connected,” “coupled,” or “connected” to another component, that component may be directly connected or connected to that other component, but there is another component between each component. It will be understood that elements may be “connected,” “combined,” or “connected.”

Additionally, when a component, such as a layer, membrane, region, plate, etc., is said to be "on" or "on" another component, it means not only that it is "directly above" the other component, but also that there is another component in between. It should be understood that it can also include cases. Conversely, when an element is said to be "right on top" of another part, it should be understood to mean that there is no other part in between.

1 to 3 are exemplary diagrams of organic electric devices according to embodiments of the present invention.

Referring to FIG. 1, the organic electric device 100 according to an embodiment of the present invention includes a first electrode 110, a second electrode 170, and a first electrode 110 formed on a substrate (not shown). and an organic material layer formed between the first electrode 110 and the second electrode 170, and an inorganic material layer may be included between the first electrode 110 and the second electrode 170, or the organic material layer may include an inorganic material.

For example, the first electrode 110 may be an anode, and the second electrode 170 may be a cathode. In the case of an inverted type, the first electrode may be a cathode and the second electrode may be an anode. .

The organic material layer refers to a layer containing at least one organic material. For example, the organic material layer may include a hole injection layer 120, a hole transport layer 130, a light emitting layer 140, an electron transport layer 150, and an electron injection layer 160. However, the electron injection layer 160 may be an inorganic material layer that does not contain organic materials.

Specifically, a hole injection layer 120, a hole transport layer 130, a light emitting layer 140, an electron transport layer 150, and an electron injection layer 160 may be formed sequentially on the first electrode 110.

Preferably, the luminous efficiency improvement layer 180 may be formed on one side of both sides of the first electrode 110 or both sides of the second electrode 170 that is not in contact with the organic material layer or the inorganic material layer, and the luminous efficiency improvement layer 180 ) is formed, the light efficiency of the organic electric device can be improved.

For example, the luminous efficiency improvement layer 180 may be formed on the second electrode 170. In the case of a top emission organic light emitting device, the luminous efficiency improvement layer 180 is formed to form the second electrode 170. ) can reduce optical energy loss due to SPPs (surface plasmon polaritons), and in the case of bottom emission organic light emitting devices, the light efficiency improvement layer 180 serves as a buffer for the second electrode 170. can do.

A buffer layer 210 or a light-emitting auxiliary layer 220 may be further formed between the hole transport layer 130 and the light-emitting layer 140, which will be described with reference to FIG. 2.

Referring to FIG. 2, the organic electric device 200 according to another embodiment of the present invention includes a hole injection layer 120, a hole transport layer 130, a buffer layer 210, and a hole injection layer 120 sequentially formed on the first electrode 110. It may include a light emitting auxiliary layer 220, a light emitting layer 140, an electron transport layer 150, an electron injection layer 160, and a second electrode 170, and a light efficiency improvement layer 180 is formed on the second electrode. It can be.

Although not shown in FIG. 2, an electron transport auxiliary layer may be further formed between the light emitting layer 140 and the electron transport layer 150.

Additionally, according to another embodiment of the present invention, the organic material layer may be formed in a plurality of stacks including a hole transport layer, a light emitting layer, and an electron transport layer. This will be explained with reference to FIG. 3 .

Referring to Figure 3, the organic electric device 300 according to another embodiment of the present invention has two stacks (ST1, ST2) of multi-layered organic material layers between the first electrode 110 and the second electrode 170. More than a set may be formed, and a charge generation layer (CGL) may be formed between the stacks of the organic material layers.

Specifically, the organic electric device according to an embodiment of the present invention includes a first electrode 110, a first stack (ST1), a charge generation layer (CGL), a second stack (ST2), and a second electrode. (170) and may include a light efficiency improvement layer (180).

The first stack (ST1) is an organic material layer formed on the first electrode 110, which includes a first hole injection layer 320, a first hole transport layer 330, a first light emitting layer 340, and a first electron transport layer 350. ) may include, and the second stack (ST2) may include a second hole injection layer 420, a second hole transport layer 430, a second light-emitting layer 440, and a second electron transport layer 450. . In this way, the first stack and the second stack may be organic material layers with the same stacked structure, or they may be organic material layers with different stacked structures.

A charge generation layer (CGL) may be formed between the first stack (ST1) and the second stack (ST2). The charge generation layer (CGL) may include a first charge generation layer 360 and a second charge generation layer 361. This charge generation layer (CGL) is formed between the first light emitting layer 340 and the second light emitting layer 440 to increase the current efficiency generated in each light emitting layer and serves to smoothly distribute charges.

The first light-emitting layer 340 may include a light-emitting material including a blue fluorescent dopant in a blue host, and the second light-emitting layer 440 may include a material doped with a greenish yellow dopant and a red dopant in a green host. However, the materials of the first light emitting layer 340 and the second light emitting layer 440 according to the embodiment of the present invention are not limited thereto.

In FIG. 3, n may be an integer between 1 and 5. When n is 2, a charge generation layer (CGL) and a third stack may be additionally stacked on the second stack (ST2).

When a plurality of light-emitting layers are formed using a multi-layer stack structure as shown in Figure 3, it is possible to manufacture an organic electroluminescent device that not only emits white light due to the mixing effect of the light emitted from each light-emitting layer, but also emits light of various colors. Organic electroluminescent devices that emit light can also be manufactured.

The compound represented by Formula 1 of the present invention may be included in the organic layer. For example, the compound represented by Formula 1 of the present invention includes a hole injection layer (120, 320, 420), a hole transport layer (130, 330, 430), a buffer layer (210), an auxiliary light emitting layer (220), an electron transport layer (150, It can be used as a material for the light emitting layer (140, 340, 440), the light emitting layer (140, 340, 440), or the light efficiency improvement layer (180), but is preferably used as a material for the light emitting layer (140, 340, 440) or/and the light efficiency improvement layer (180), More preferably, it can be used as a host for the light emitting layer (140, 340, 440).

Even if the core is identical, the band gap, electrical properties, and interface properties may vary depending on which substituent is attached to which position, so research on the selection of the core and the combination of sub-substituents attached to it is required, and in particular, when the energy level and T ₁ value between each organic layer and the intrinsic properties of the material (mobility, interface properties, etc.) are optimally combined, long lifespan and high efficiency can be achieved simultaneously.

Therefore, in the present invention, by using the compound represented by Formula 1 as a material for the light emitting layer (140, 340, 440), the energy level and T ₁ value between each organic material layer, and the intrinsic properties of the material (mobility, interface properties, etc.) By optimizing it, the lifespan and efficiency of organic electric devices can be improved simultaneously.

An organic electroluminescent device according to an embodiment of the present invention may be manufactured using various deposition methods. It can be manufactured using a deposition method such as PVD or CVD. For example, an anode 110 is formed by depositing a metal or a conductive metal oxide or an alloy thereof on a substrate, and a hole injection layer 120 is formed thereon. , It can be manufactured by forming an organic material layer including the hole transport layer 130, the light emitting layer 140, the electron transport layer 150, and the electron injection layer 160, and then depositing a material that can be used as the cathode 170 thereon. there is. In addition, a light-emitting auxiliary layer 220 may be formed between the hole transport layer 130 and the light-emitting layer 140, and an electron transport auxiliary layer (not shown) may be further formed between the light-emitting layer 140 and the electron transport layer 150. As shown, it can also be formed in a stack structure.

In addition, the organic material layer uses a variety of polymer materials, such as a solution process or solvent process rather than a deposition method, such as spin coating process, nozzle printing process, inkjet printing process, slot coating process, dip coating process, roll-to-roll process, and doctor bleed process. It can be manufactured with fewer layers by methods such as a printing process, screen printing process, or thermal transfer method. Since the organic material layer according to the present invention can be formed by various methods, the scope of the present invention is not limited by the formation method.

The organic electric device according to an embodiment of the present invention may be a front-emitting type, a rear-emitting type, or a double-sided emitting type depending on the material used.

Additionally, the organic electric device according to an embodiment of the present invention may be selected from the group consisting of organic electroluminescent devices, organic solar cells, organic photoreceptors, organic transistors, monochromatic lighting devices, and quantum dot display devices.

Another embodiment of the present invention may include a display device including the organic electric device of the present invention described above, and an electronic device including a control unit that controls the display device. At this time, the electronic device may be a current or future wired or wireless communication terminal, and includes all electronic devices such as mobile communication terminals such as mobile phones, navigation devices, game consoles, various TVs, and various computers.

Hereinafter, a compound according to one aspect of the present invention will be described.

The compound according to one aspect of the present invention is represented by the following formula (1).

<Formula 1>

In Formula 1, each symbol can be defined as follows.

X ¹ and X ² are each independently O or S.

L ¹ is single bond; C ₆ ~ C ₆₀ arylene group; fluorenylene group; C ₃ ~ C ₆₀ aliphatic ring group; and a C ₂ to C ₆₀ heterocyclic group containing at least one hetero atom selected from O, N, S, Si, and P.

L ² is an arylene group of C ₆ to C ₆₀ ; fluorenylene group; C ₃ ~ C ₆₀ aliphatic ring group; and a C ₂ to C ₆₀ heterocyclic group containing at least one hetero atom selected from O, N, S, Si, and P.

Ar is an aryl group of C ₆ to C ₆₀ ; fluorenyl group; C ₃ ~ C ₆₀ aliphatic ring group; and a C ₂ to C ₆₀ heterocyclic group containing at least one hetero atom selected from O, N, S, Si, and P.

R ¹ and R ² are independently hydrogen; heavy hydrogen; halogen; Cyano group; nitro group; Aryl group of C ₆ to C ₆₀ ; fluorenyl group; C ₂ ~ C ₆₀ heterocyclic group containing at least one hetero atom among O, N, S, Si and P; C ₃ ~ C ₆₀ aliphatic ring group; C ₁ ~ C ₂₀ alkyl group; C ₂ ~ C ₂₀ alkenyl group; C ₂ ~ C ₂₀ alkyne group; C ₁ ~ C ₂₀ alkoxy group; and aryloxy groups of C ₆ to C ₆₀ , and adjacent groups may be bonded to each other to form a ring.

R ³ is hydrogen; heavy hydrogen; halogen; Cyano group; nitro group; Aryl group of C ₆ to C ₆₀ ; fluorenyl group; C ₂ ~ C ₆₀ heterocyclic group containing at least one hetero atom among O, N, S, Si and P; C ₃ ~ C ₆₀ aliphatic ring group; C ₁ ~ C ₂₀ alkyl group; C ₂ ~ C ₂₀ alkenyl group; C ₂ ~ C ₂₀ alkyne group; C ₁ ~ C ₂₀ alkoxy group; and aryloxy groups of C ₆ to C ₆₀ , excluding cases where adjacent groups combine to form a ring.

a is an integer from 0 to 6, b and c are each an integer from 0 to 4, and when each of them is an integer of 2 or more, each of the plurality of R ¹ , each of the plurality of R ² , and each of the plurality of R ³ are the same or different from each other .

The ring formed by bonding adjacent groups, for example, adjacent R ¹ groups and adjacent R ² groups, is an aryl ring having C ₆ to C ₆₀ ; fluorenyl group; C ₃ ~ C ₆₀ aliphatic ring group; and a C ₂ to C ₆₀ heterocyclic group containing at least one hetero atom selected from O, N, S, Si, and P.

When adjacent groups combine with each other to form an aryl ring, the aryl ring is, for example, C ₆ ~ C ₂₀ , C ₆ ~ C ₁₈ , C ₆ ~ C ₁₆ , C ₆ ~ C ₁₄ , C ₆ ~ C ₁₃ , C It may be an aryl ring such as ₆ ~C ₁₂ , C ₆ ~C ₁₀ , C ₆ , C ₁₀ , C ₁₂ , C ₁₄ , C ₁₅ , C ₁₆ , C ₁₈ , specifically, benzene, naphthalene, anthracene, phenanthrene, It may be pyrene, etc.

At least one of Ar, R ¹ to R ³ may contain deuterium.

When at least one of R ¹ to R ³ and Ar is an aryl group, the aryl group is, for example, C ₆ to C ₃₀ , C ₆ to C ₂₉ , C ₆ to C ₂₈ , C ₆ to C ₂₇ , C ₆ to C _26. , C ₆ ~C ₂₅ , C ₆ ~C ₂₄ , C ₆ ~C ₂₃ , C ₆ ~C ₂₂ , C ₆ ~C ₂₁ , C ₆ ~C ₂₀ , C ₆ ~C ₁₉ , C ₆ ~C ₁₈ , C ₆ ~C ₁₇ , C ₆ ~C ₁₆ , C ₆ ~C ₁₅ , C ₆ ~C ₁₄ , C ₆ ~C ₁₃ , C ₆ ~C ₁₂ , C ₆ ~C ₁₁ , C ₆ ~C ₁₀ , C ₆ , It may be an aryl group such as C ₁₀ , C ₁₂ , C ₁₃ , C ₁₄ , C ₁₅ , C ₁₆ , C ₁₇ , C ₁₈ , and specifically, phenyl, biphenyl, naphthyl, terphenyl, phenanthrene, triphenylene. It may be, etc.

When at least one of L ¹ and L ² is an arylene group, the arylene group is, for example, C ₆ to C ₃₀ , C ₆ to C ₂₉ , C ₆ to C ₂₈ , C ₆ to C ₂₇ , C ₆ to C _26. , C ₆ ~C ₂₅ , C ₆ ~C ₂₄ , C ₆ ~C ₂₃ , C ₆ ~C ₂₂ , C ₆ ~C ₂₁ , C ₆ ~C ₂₀ , C ₆ ~C ₁₉ , C ₆ ~C ₁₈ , C ₆ ~C ₁₇ , C ₆ ~C ₁₆ , C ₆ ~C ₁₅ , C ₆ ~C ₁₄ , C ₆ ~C ₁₃ , C ₆ ~C ₁₂ , C ₆ ~C ₁₁ , C ₆ ~C ₁₀ , C ₆ , It may be an arylene group such as C ₁₀ , C ₁₂ , C ₁₃ , C ₁₄ , C ₁₅ , C ₁₆ , C ₁₇ , C ₁₈ , and specifically, phenylene, biphenyl, naphthylene, terphenyl, phenanthrene, tri. It may be phenylene, etc.

When at least one of R ¹ to R ³ , Ar, L ¹ and L ² is a heterocyclic group, the heterocyclic group is, for example, C ₂ to C ₃₀ , C ₂ to C ₂₉ , C ₂ to C ₂₈ , C ₂ to C ₂₇ , C ₂ ~C ₂₆ , C ₂ ~C ₂₅ , C ₂ ~C ₂₄ , C ₂ ~C ₂₃ , C ₂ ~C ₂₂ , C ₂ ~C ₂₁ , C ₂ ~C ₂₀ , C ₂ ~C ₁₉ , C ₂ ~C ₁₈ , C ₂ ~C ₁₇ , C ₂ ~C ₁₆ , C ₂ ~C ₁₅ , C ₂ ~C ₁₄ , C ₂ ~C ₁₃ , C ₂ ~C ₁₂ , C ₂ ~C ₁₁ , C ₂ ~C ₁₀ , C ₂ ~C ₉ , C ₂ ~C ₈ , C ₂ ~C ₇ , C ₂ ~C ₆ , C ₂ ~C ₅ , C ₂ ~C ₄ , C ₂ ~C ₃ , C ₂ , C ₃ , C ₄ , C ₅ , C ₆ , C ₇ , C ₈ , C ₉ , C ₁₀ , C ₁₁ , C ₁₂ , C ₁₃ , C ₁₄ , C ₁₅ , C ₁₆ , C ₁₇ , C ₁₈ , C ₁₉ , C ₂₀ , C ₂₁ , C ₂₂ , C ₂₃ , C ₂₄ , C ₂₅ , C ₂₆ , C ₂₇ , C ₂₈ , C ₂₉ , etc., and specifically, pyridine, pyrimidine, pyrazine, pyridazine. , triazine, furan, pyrrole, indene, indole, phenyl-indole, benzoindole, phenyl-benzoindole, pyrazinoindole, quinoline, isoquinoline, benzoquinoline, pyridoquinoline, quinazoline, benzoquinazoline, dibenzoquina. Joline, phenanthroquinazoline, quinoxaline, benzoquinoxaline, dibenzoquinoxaline, benzofuran, naphthobenzofuran, dibenzofuran, dinaphthofuran, thiophene, benzothiophene, dibenzothiophene, naphthobenzo Thiophene, dinaphthothiophene, carbazole, phenyl-carbazole, benzocarbazole, phenyl-benzocarbazole, naphthyl-benzocarbazole, dibenzocarbazole, indolocarbazole, benzofuropyridine, benzothiophene Enopyridine, benzofuropyridine, benzothienopyrimidine, benzofuropyrimidine, benzothienopyrazine, benzofuropyrazine, benzoimidazole, benzothiazole, benzoxazole, phenanthroline, die Hydro-phenylphenazine, 10-phenyl-10H-phenoxazine, phenoxazine, phenothiazine, dibenzodioxin, benzodibenzodioxin, cyanthrene, 9,9-dimethyl-9H-zanthrene, 9,9 -It may be dimethyl-9H-thioxanthrene, dihydrodimethylphenylacridine, spiro[fluorene-9,9'-xanthene], etc.

When at least one of R ¹ to R ³ and Ar is a fluorenyl group, or when one of L ¹ and L ² is a fluorenylene group, the fluorenyl group or fluorenylene group is 9,9-dimethyl-9H- Fluorene, 9,9-diphenyl-9H-fluorene, 9,9'-spirobifluorene, spiro[benzo[ b ]fluorene-11,9'-fluorene], benzo[ b ]fluorene It may be orene, 11,11-diphenyl-11 H -benzo[ b ]fluorene, 9-(naphthalen-2-yl)9-phenyl-9 H -fluorene, etc.

When at least one of R ¹ to R ³ is an alkyl group, the alkyl group is, for example, C ₁ to C ₂₀ , C ₁ to C ₁₀ , C ₁ to C ₄ , C ₁ , C ₂ , C ₃ , C _4, etc. It may be an alkyl group, for example, a methyl group, an ethyl group, a t-butyl group, etc.

The aryl group, arylene group, fluorenyl group, fluorenylene group, hetero ring group, aliphatic ring group, alkyl group, alkenyl group, alkynyl group, alkoxy group, aryloxy group, and the rings formed by bonding adjacent groups are each heavy hydrogen; halogen; A silane group unsubstituted or substituted with a C ₁ -C ₂₀ alkyl group or a C ₆ -C ₂₀ aryl group; Phosphine oxide substituted or unsubstituted with a C ₁ -C ₂₀ alkyl group or a C ₆ -C ₂₀ aryl group; siloxane group; Cyano group; nitro group; C ₁ -C ₂₀ alkylthio group; C ₁ -C ₂₀ alkoxy group; C ₆ -C ₃₀ aryloxy group; C ₆ -C ₃₀ arylthio group; C ₁ -C ₂₀ alkyl group; C ₂ -C ₂₀ alkenyl group; C ₂ -C ₂₀ alkyne group; C ₆ -C ₃₀ aryl group; fluorenyl group; A C ₂ -C ₃₀ heterocyclic group containing at least one heteroatom selected from the group consisting of O, N, S, Si and P; and C ₃ -C ₃₀ aliphatic ring groups.

The aryl group, fluorenyl group, heterocyclic group, aliphatic ring group, aromatic ring group, alkyl group, alkenyl group, alkynyl group, alkoxy group, aryloxy group, arylene group, fluorenylene group, and adjacent groups are bonded to each other. When at least one of the rings formed is substituted with an aryl group, the aryl group is, for example, C ₆ ~ C ₃₀ , C ₆ ~ C ₂₉ , C ₆ ~ C ₂₈ , C ₆ ~ C ₂₇ , C ₆ ~ C ₂₆ , C ₆ ~ C ₂₅ , C ₆ ~C ₂₄ , C ₆ ~C ₂₃ , C ₆ ~C ₂₂ , C ₆ ~C ₂₁ , C ₆ ~C ₂₀ , C ₆ ~C ₁₉ , C ₆ ~C ₁₈ , C ₆ ~C ₁₇ , C ₆ ~C ₁₆ , C ₆ ~C ₁₅ , C ₆ ~C ₁₄ , C ₆ ~C ₁₃ , C ₆ ~C ₁₂ , C ₆ ~C ₁₁ , C ₆ ~C ₁₀ , C ₆ , C ₁₀ , C It may be an aryl group such as ₁₂ , C ₁₃ , C ₁₄ , C ₁₅ , C ₁₆ , C ₁₇ , or C ₁₈ .

The aryl group, fluorenyl group, heterocyclic group, aliphatic ring group, aromatic ring group, alkyl group, alkenyl group, alkynyl group, alkoxy group, aryloxy group, arylene group, fluorenylene group, and adjacent groups are bonded to each other. When at least one of the rings formed is substituted with an aliphatic ring group, the aliphatic ring group is, for example, C ₃ ~ C ₃₀ , C ₃ ~ C ₂₉ , C ₃ ~ C ₂₈ , C ₃ ~ C ₂₇ , C ₃ ~ C ₂₆ , C ₃ ~C ₂₅ , C ₃ ~C ₂₄ , C ₃ ~C ₂₃ , C ₃ ~C ₂₂ , C ₃ ~C ₂₁ , C ₃ ~C ₂₀ , C ₃ ~C ₁₉ , C ₃ ~C ₁₈ , C ₃ ~ C ₁₇ , C ₃ ~C ₁₆ , C ₃ ~C ₁₅ , C ₃ ~C ₁₄ , C ₃ ~C ₁₃ , C ₃ ~C ₁₂ , C ₃ ~C ₁₁ , C ₃ ~C ₁₀ , C ₃ ~C ₈ , C ₃ ~ C ₆ , C ₆ , C ₁₀ , C ₁₁ , C ₁₂ , C ₁₃ , C ₁₄ , C ₁₅ , C ₁₆ , C ₁₇ , C _18, etc.

The aryl group, fluorenyl group, heterocyclic group, aliphatic ring group, aromatic ring group, alkyl group, alkenyl group, alkynyl group, alkoxy group, aryloxy group, arylene group, fluorenylene group, and adjacent groups are bonded to each other. When at least one of the rings formed is substituted with a fluorenyl group, the fluorenyl group is 9,9-dimethyl-9H-fluorene, 9,9-diphenyl-9H-fluorene, 9,9'-spy Robifluorene, spiro[benzo[ b ]fluorene-11,9'-fluorene], benzo[ b ]fluorene, 11,11-diphenyl-11 H -benzo[ b ]fluorene, 9- It may be (naphthalen-2-yl)9-phenyl- 9H -fluorene, etc.

The aryl group, fluorenyl group, heterocyclic group, aliphatic ring group, aromatic ring group, alkyl group, alkenyl group, alkynyl group, alkoxy group, aryloxy group, arylene group, fluorenylene group, and adjacent groups are bonded to each other. When at least one of the rings formed is substituted with an alkyl group, the alkyl group is, for example, an alkyl group such as C ₁ to C ₂₀ , C ₁ to C ₁₀ , C ₁ to C ₄ , C ₁ , C ₂ , C ₃ , C ₄ , etc. It may be, for example, a methyl group, an ethyl group, a t-butyl group, etc.

Formula 1 may be represented by one of the following Formulas 2-1 to 2-3 and Formulas 3-1 to 3-10.

<Formula 2-1> <Formula 2-2>

<Formula 2-3>

<Formula 3-1> <Formula 3-2>

<Formula 3-3> <Formula 3-4>

<Formula 3-5> <Formula 3-6>

<Formula 3-7> <Formula 3-8>

<Formula 3-9> <Formula 3-10>

^In Formulas ^2-1 to ^2-3 and Formulas ^3-1 to ^3-10 , X ¹ , , a' is an integer from 0 to 5, and b' is an integer from 0 to 3.

At least one of L ¹ and L ² may be selected from the group consisting of the following formulas L-1 to L-5.

<Formula L-1><Formula L-2><Formula L-3><Formula L-4><Formula L-5>

In the above formulas L-1 to L-5, each symbol may be defined as follows.

* indicates the binding position.

Y is O, S, N(R) or C(R _a )(R _b ).

R ⁴ to R ¹² , R, R _a and R _b are independently hydrogen; heavy hydrogen; halogen; A silane group unsubstituted or substituted with a C ₁ -C ₂₀ alkyl group or a C ₆ -C ₂₀ aryl group; Phosphine oxide substituted or unsubstituted with a C ₁ -C ₂₀ alkyl group or a C ₆ -C ₂₀ aryl group; siloxane group; Cyano group; nitro group; C ₁ -C ₂₀ alkylthio group; C ₁ -C ₂₀ alkoxy group; C ₆ -C ₃₀ aryloxy group; C ₆ -C ₃₀ arylthio group; C ₁ -C ₂₀ alkyl group; C ₂ -C ₂₀ alkenyl group; C ₂ -C ₂₀ alkyne group; C ₆ -C ₃₀ aryl group; fluorenyl group; A C ₂ -C ₃₀ heterocyclic group containing at least one heteroatom selected from the group consisting of O, N, S, Si and P; and C ₃ -C ₃₀ aliphatic ring groups, and adjacent groups may combine with each other to form a ring, and R _a and R _b may combine with each other to form a ring. When R _a and R _b combine with each other to form a ring, a spiro compound is formed.

d, e and f are each an integer from 0 to 4, g to i, k and l are each an integer from 0 to 3, j is an integer from 0 to 5, and when these are integers of 2 or more, a plurality of R ⁴ each to a plurality of R ¹² are the same as or different from each other.

Specifically, the compound represented by Formula 1 may be one of the following compounds, but is not limited thereto.

.

In another aspect, the present invention provides an organic electric device including a first electrode, a second electrode, and an organic material layer formed between the first electrode and the second electrode, wherein the organic material layer includes the compound represented by Formula 1 do.

The organic material layer includes a light-emitting layer between the first electrode and the second electrode, and the light-emitting layer includes the compound.

In another aspect, the present invention provides an electronic device including a display device including an organic electric device and a control unit for driving the display device, wherein the organic electric device includes the compound represented by Formula 1 above.

In another aspect, the present invention provides a compound represented by Formula 1, which is obtained by depositing an organic layer in the manufacturing process of an organic electric device, then recovering and purifying the material of the organic layer from deposition equipment. The purity of the compound obtained through recovery and purification is more than 99.9%.

In another aspect, the present invention includes the steps of depositing an organic layer material containing a compound represented by Formula 1, recovering the organic layer material attached to deposition equipment, and purifying the recovered organic layer material to a purity of 99.9% or more. A method for recovering the compound represented by Formula 1 is provided, including the step of obtaining the compound represented by Formula 1.

The purification step may include recrystallizing the recovered organic layer material using a recrystallization solvent, adsorption separation using an adsorbent, and sublimation purification.

The recrystallization step may include a preliminary purification process to obtain the compound represented by Formula 1 with a purity of 98% using a recrystallization solvent.

As a recrystallization solvent, a polar solvent with a polarity index (PI) of 5.5 to 7.2 may be used, or a mixture of a polar solvent with a polarity index (PI) of 5.5 to 7.2 and a non-polar solvent with a polarity index of 2.0 to 4.7 may be used.

When using a mixture of a polar solvent and a non-polar solvent as a recrystallization solvent, the non-polar solvent may be used in a ratio of 15% (v/v) or less compared to the polar solvent.

In addition, the recrystallization solvent is preferably a single solvent of methylpyrrolidone (N-methylpyrrolidone: NMP); Or the methyl pyrrolidone, dimethyl imidazolidinone (1,3-dimethyl-2-imidazolidinone), 2-pyrrolidone, dimethyl formamide (N, N-dimethyl formamide), dimethyl acetate A mixed polar solvent containing any one selected from the group consisting of amide (dimethyl acetamide) and dimethyl sulfoxide, or toluene, DCM (Dichloromethane), DCE (dichloroethane), THF (tetrahydrofuran), chloroform ( A single or mixed nonpolar solvent selected from the group consisting of chloroform, ethyl acetate, and butanone can be used, or a mixture of polar and nonpolar solvents can be used.

The preliminary purification process may include dissolving the crude organic light-emitting material recovered from the deposition equipment in a polar solvent at 90°C to 120°C, and then cooling to 0°C to 5°C to precipitate crystals.

In the preliminary purification process, the crude organic light-emitting material recovered from the deposition equipment is dissolved in a polar solvent at 90°C to 120°C, then cooled to 35°C to 40°C, a non-polar solvent is added, and then the temperature is heated to 0°C to 5°C. It may include cooling to precipitate crystals.

The preliminary purification process may include dissolving the crude organic light-emitting material recovered from the deposition equipment in a non-polar solvent, concentrating the solvent, and precipitating crystals while removing the non-polar solvent.

The preliminary purification process may include first recrystallizing from a polar solvent and then recrystallizing again from a non-polar solvent.

In the adsorption separation step using the adsorbent, activated carbon, silica gel, alumina, or known materials for adsorption may be used as the adsorbent.

Hereinafter, the synthesis example of the compound represented by Formula 1 and the manufacturing example of the organic electric device according to the present invention will be described in detail through examples, but the present invention is not limited to the following examples.

[Synthesis example]

The compound represented by Formula 1 according to the present invention can be synthesized by reacting Sub 1 and Sub 2 as shown in Scheme 1 below, but is not limited thereto.

<Scheme 1>

Ⅰ. Synthesis example of Sub 1

1. Synthesis example of Sub 1-8

After dissolving Sub 1-8a (10.0 g, 33.7 mmol) in Toluene (110 mL), bis(pinacolato)diboron(BPDB) (12.8 g, 50.5 mmol), PdCl ₂ (dppf) (0.7 g, 1.0 mmol), Add KOAc (9.9 g, 101.0 mmol) and proceed with the reaction at 120°C. When the reaction is completed, the extract is extracted with CH ₂ Cl ₂ and water, and the organic layer is dried over MgSO ₄ and concentrated. Afterwards, the concentrate was separated using a silica gel column and recrystallized to obtain 9.8 g of product. (yield 84.0%)

2. Synthesis example of Sub 1-17

1) Synthesis example of Sub 1-17-1

After dissolving Sub 1-17-1a (20.0 g, 67.3 mmol) in THF (168 mL) and water (56 mL), Sub 1-17-1b (10.5 g, 67.3 mmol), Pd(PPh ₃ ) ₄ ( 2.3 g, 2.0 mmol) and K ₂ CO ₃ (18.6 g, 134.6 mmol) were added and the reaction was carried out at 60°C. When the reaction is completed, the extract is extracted with CH ₂ Cl ₂ and water, and the organic layer is dried over MgSO ₄ and concentrated. Afterwards, the concentrate was separated using a silica gel column and recrystallized to obtain 18 g of product. (yield 81.3%)

2) Synthesis example of Sub 1-17

After dissolving Sub 1-17-1 (18.0 g, 54.7 mmol) in Toluene (182 mL), bis(pinacolato)diboron(BPDB) (27.8 g, 109.5 mmol), Pd ₂ (dba) ₃ (1.0 g, 1.1 mmol), x-phos (1.0 g, 2.2 mmol), and KOAc (16.1 g, 164.2 mmol) were added and the reaction was carried out at 120°C. When the reaction is completed, the extract is extracted with CH ₂ Cl ₂ and water, and the organic layer is dried over MgSO ₄ and concentrated. Afterwards, the concentrate was separated using a silica gel column and recrystallized to obtain 17.4 g of product. (yield 75.6%)

3. Synthesis example of Sub 1-26

1) Synthesis example of Sub 1-26-1

After dissolving Sub 1-26-1a (20.0 g, 76.3 mmol) in THF and water, Sub 1-26-1b (20.4 g, 76.3 mmol), Pd(PPh ₃ ) ₄ (2.6 g, 2.3 mmol), K ₂ CO ₃ (21.1 g, 152.6 mmol) was added, and synthesis was performed in the same manner as in the synthesis example of Sub 1-17-1, to obtain 25.6 g of product. (yield 82.9%)

2) Synthesis example of Sub 1-26

After dissolving Sub 1-26-1 (25.6 g, 63.2 mmol) in toluene, bis(pinacolato)diboron(BPDB) (32.1 g, 126.5 mmol), Pd ₂ (dba) ₃ (1.2 g, 1.3 mmol), x -phos (1.2 g, 2.5 mmol) and KOAc (18.6 g, 189.7 mmol) were added, and synthesis was performed in the same manner as in the synthesis example of Sub 1-17, to obtain 22.4 g of product. (yield 71.4%)

4. Synthesis example of Sub 1-31

1) Synthesis example of Sub 1-31-1

After dissolving Sub 1-31-1a (20.0 g, 76.3 mmol) in THF and water, Sub 1-31-1b (18.4 g, 76.3 mmol), Pd(PPh ₃ ) ₄ (2.6 g, 2.3 mmol), K ₂ CO ₃ (21.1 g, 152.6 mmol) was added, and synthesis was performed in the same manner as in the synthesis example of Sub 1-17-1, to obtain 20.3 g of product. (yield 70.2%)

2) Synthesis example of Sub 1-31

After dissolving Sub 1-31-1 (20.3 g, 53.6 mmol) in toluene, bis(pinacolato)diboron(BPDB) (27.2 g, 107.2 mmol), Pd ₂ (dba) ₃ (1.0 g, 1.1 mmol), x -phos (1.0 g, 2.1 mmol) and KOAc (15.8 g, 160.7 mmol) were added, and synthesis was performed in the same manner as in the synthesis example of Sub 1-17, to obtain 18.2 g of product. (yield 72.2%)

5. Synthesis example of Sub 1-35

1) Synthesis example of Sub 1-35-1

After dissolving Sub 1-35-1a (20.0 g, 76.3 mmol) in THF and water, Sub 1-35-1b (25.6 g, 76.3 mmol), Pd(PPh ₃ ) ₄ (2.6 g, 2.3 mmol), K ₂ CO ₃ (21.1 g, 152.6 mmol) was added, and synthesis was performed in the same manner as in the synthesis example of Sub 1-17-1, to obtain 18 g of product. (yield 49.8%)

2) Synthesis example of Sub 1-35

After dissolving Sub 1-35-1 (18 g, 38.0 mmol) in toluene, bis(pinacolato)diboron(BPDB) (19.3 g, 76.1 mmol), Pd ₂ (dba) ₃ (0.7 g, 0.8 mmol), x -phos (0.7 g, 1.5 mmol) and KOAc (11.2 g, 114.1 mmol) were added, and synthesis was performed in the same manner as in the synthesis example of Sub 1-17, to obtain 14.3 g of product. (yield 72.3%)

6. Synthesis example of Sub 1-39

1) Synthesis example of Sub 1-39-1

After dissolving Sub 1-39-1a (20.0 g, 71.9 mmol) in THF and water, Sub 1-39-1b (20.2 g, 71.9 mmol), Pd(PPh ₃ ) ₄ (2.5 g, 2.2 mmol), K ₂ CO ₃ (19.9 g, 143.8 mmol) was added, and synthesis was performed in the same manner as in the synthesis example of Sub 1-17-1, to obtain 26.8 g of product. (yield 85.7%)

2) Synthesis example of Sub 1-39

After dissolving Sub 1-39-1 (26.8 g, 61.6 mmol) in toluene, bis(pinacolato)diboron(BPDB) (31.3 g, 123.2 mmol), Pd ₂ (dba) ₃ (1.1 g, 1.2 mmol), x -phos (1.2 g, 2.5 mmol) and KOAc (18.1 g, 184.9 mmol) were added, and synthesis was performed in the same manner as in the synthesis example of Sub 1-17, to obtain 24.5 g of product. (yield 75.5%)

Compounds belonging to Sub 1 may be, but are not limited to, the following compounds, and the FD-MS (Field Desorption-Mass Spectrometry) values of the following compounds are shown in Table 1.

compound FD-MS compound FD-MS Sub 1-1 m/z=262.07(C ₁₆ H ₁₁ BO ₃ =262.08) Sub 1-2 m/z=262.07(C ₁₆ H ₁₁ BO ₃ =262.08) Sub 1-3 m/z=278.06(C ₁₆ H ₁₁ BO ₂ S=278.13) Sub 1-4 m/z=262.07(C ₁₆ H ₁₁ BO ₃ =262.08) Sub 1-5 m/z=262.07(C ₁₆ H ₁₁ BO ₃ =262.08) Sub 1-6 m/z=262.07(C ₁₆ H ₁₁ BO ₃ =262.08) Sub 1-7 m/z=278.06(C ₁₆ H ₁₁ BO ₂ S=278.13) Sub 1-8 m/z=262.07(C ₁₆ H ₁₁ BO ₃ =262.08) Sub 1-9 m/z=262.07(C ₁₆ H ₁₁ BO ₃ =262.08) Sub 1-10 m/z=262.07(C ₁₆ H ₁₁ BO ₃ =262.08) Sub 1-11 m/z=420.19(C ₂₈ H ₂₅ BO ₃ =420.32) Sub 1-12 m/z=424.21(C ₂₈ H ₂₁ D ₄ BO ₃ =424.34) Sub 1-13 m/z=420.19(C ₂₈ H ₂₅ BO ₃ =420.32) Sub 1-14 m/z=420.19(C ₂₈ H ₂₅ BO ₃ =420.32) Sub 1-15 m/z=420.19(C ₂₈ H ₂₅ BO ₃ =420.32) Sub 1-16 m/z=420.19(C ₂₈ H ₂₅ BO ₃ =420.32) Sub 1-17 m/z=420.19(C ₂₈ H ₂₅ BO ₃ =420.32) Sub 1-18 m/z=445.22(C ₂₈ H ₁₆ D ₉ BO ₂ S=445.43) Sub 1-19 m/z=420.19(C ₂₈ H ₂₅ BO ₃ =420.32) Sub 1-20 m/z=436.17(C ₂₈ H ₂₅ BO ₂ S=436.38) Sub 1-21 m/z=496.22(C ₃₄ H ₂₉ BO ₃ =496.41) Sub 1-22 m/z=436.17(C ₂₈ H ₂₅ BO ₂ S=436.38) Sub 1-23 m/z=420.19(C ₂₈ H ₂₅ BO ₃ =420.32) Sub 1-24 m/z=420.19(C ₂₈ H ₂₅ BO ₃ =420.32) Sub 1-25 m/z=420.19(C ₂₈ H ₂₅ BO ₃ =420.32) Sub 1-26 m/z=496.22(C ₃₄ H ₂₉ BO ₃ =496.41) Sub 1-27 m/z=496.22(C ₃₄ H ₂₉ BO ₃ =496.41) Sub 1-28 m/z=505.28(C ₃₄ H ₂₀ D ₉ BO ₃ =505.47) Sub 1-29 m/z=496.22(C ₃₄ H ₂₉ BO ₃ =496.41) Sub 1-30 m/z=486.18(C ₃₂ H ₂₇ BO ₂ S=486.44) Sub 1-31 m/z=470.21(C ₃₂ H ₂₇ BO ₃ =470.38) Sub 1-32 m/z=470.21(C ₃₂ H ₂₇ BO ₃ =470.38) Sub 1-33 m/z=470.21(C ₃₂ H ₂₇ BO ₃ =470.38) Sub 1-34 m/z=536.20(C ₃₆ H ₂₉ BO ₂ S=536.50) Sub 1-35 m/z=520.22(C ₃₆ H ₂₉ BO ₃ =520.44) Sub 1-36 m/z=536.25(C ₃₇ H ₃₃ BO ₃ =536.48) Sub 1-37 m/z=510.20(C ₃₄ H ₂₇ BO ₄ =510.40) Sub 1-38 m/z=526.18(C ₃₄ H ₂₇ BO ₃ S=526.46) Sub 1-39 m/z=526.18(C ₃₄ H ₂₇ BO ₃ S=526.46) Sub 1-40 m/z=526.18(C ₃₄ H ₂₇ BO ₃ S=526.46)

Ⅱ. Synthesis example of Sub 2

1. Synthesis example of Sub 2-9

After dissolving Sub 2-9a (10.0 g, 41.8 mmol) in THF (105 mL) and water (35 mL), Sub 2-9b (18.9 g, 83.7 mmol), Pd(PPh ₃ ) ₄ (1.5 g, 1.3 mmol), K ₂ CO ₃ (11.6 g, 83.7 mmol) and proceed with the reaction at 80°C. When the reaction is completed, the extract is extracted with CH ₂ Cl ₂ and water, and the organic layer is dried over MgSO ₄ and concentrated. Afterwards, the concentrate was separated using a silica gel column and recrystallized to obtain 11.6 g of product. (yield 72.0%)

2. Synthesis example of Sub 2-30

1) Synthesis example of Sub 2-30-1

After dissolving Sub 2-30-1a (20.0 g, 65.4 mmol) in Toluene (218 mL), bis(pinacolato)diboron(BPDB) (33.2 g, 130.8 mmol), Pd ₂ (dba) ₃ (1.2 g, 1.3 mmol), x-phos (1.2 g, 2.6 mmol), and KOAc (19.3 g, 196.2 mmol) were added and the reaction was performed at 120°C. When the reaction is completed, the extract is extracted with CH ₂ Cl ₂ and water, and the organic layer is dried over MgSO ₄ and concentrated. Afterwards, the concentrate was separated using a silica gel column and recrystallized to obtain 18.4 g of product. (yield 70.8%)

2) Synthesis example of Sub 2-30

After dissolving Sub 2-30-1 (18.4 g, 46.3 mmol) in THF and water, Sub 2-30b (20.9 g, 92.6 mmol), Pd(PPh ₃ ) ₄ (1.6 g, 1.4 mmol), K ₂ CO ₃ (12.8 g, 92.6 mmol) was added, and synthesis was performed in the same manner as in the synthesis example of Sub 2-9, to obtain 12 g of product. (yield 56.2%)

3. Synthesis example of Sub 2-38

1) Synthesis example of Sub 2-38-1

After dissolving Sub 2-38-1a (20.0 g, 71.5 mmol) in toluene, bis(pinacolato)diboron(BPDB) (36.3 g, 143.0 mmol), Pd ₂ (dba) ₃ (1.3 g, 1.4 mmol), x-phos (1.4 g, 2.9 mmol) and KOAc (21.1 g, 214.5 mmol) were added, and synthesis was performed in the same manner as in the synthesis example of Sub 2-30-1, to obtain 19.7 g of product. (yield 74.2%)

2) Synthesis example of Sub 2-38

After dissolving Sub 2-38-1 (19.7 g, 53.1 mmol) in THF and water, Sub 2-38b (32.1 g, 106.1 mmol), Pd(PPh ₃ ) ₄ (1.8 g, 1.6 mmol), K ₂ CO ₃ (14.7 g, 106.1 mmol) was added, and synthesis was performed in the same manner as in the synthesis example of Sub 2-9, to obtain 14.3 g of product. (yield 52.7%)

4. Synthesis example of Sub 2-50

1) Synthesis example of Sub 2-50-1

After dissolving Sub 1-50-1a (20.0 g, 54.9 mmol) in Toluene (183 mL), bis(pinacolato)diboron(BPDB) (20.9 g, 82.4 mmol), PdCl ₂ (dppf) (1.2 g, 1.6 mmol) ), KOAc (16.2 g, 164.7 mmol) were added, and synthesis was performed in the same manner as in the synthesis example of Sub 2-30-1, to obtain 16.8 g of product. (yield 74.4%)

2) Synthesis example of Sub 2-50

After dissolving Sub 2-50-1 (16.8 g, 40.9 mmol) in THF and water, Sub 2-50b (18.5 g, 81.7 mmol), Pd(PPh ₃ ) ₄ (1.4 g, 1.2 mmol), K ₂ CO ₃ (11.3 g, 81.7 mmol) was added, and synthesis was performed in the same manner as in the synthesis example of Sub 2-9, to obtain 9.7 g of product. (yield 50.0%)

Compounds belonging to Sub 2 may be, but are not limited to, the following compounds, and the FD-MS values of the following compounds are shown in Table 2.

compound FD-MS compound FD-MS Sub 2-1 m/z=384.08(C ₂₂ H ₁₃ ClN ₄ O=384.82) Sub 2-2 m/z=400.05(C ₂₂ H ₁₃ ClN ₄ S=400.88) Sub 2-3 m/z=460.11(C ₂₈ H ₁₇ ClN ₄ O=460.92) Sub 2-4 m/z=460.11(C ₂₈ H ₁₇ ClN ₄ O=460.92) Sub 2-5 m/z=434.09(C ₂₆ H ₁₅ ClN ₄ O=434.88) Sub 2-6 m/z=500.09(C ₃₀ H ₁₇ ClN ₄ S=501.00) Sub 2-7 m/z=566.10(C ₃₄ H ₁₉ ClN ₄ OS=567.06) Sub 2-8 m/z=466.16(C ₂₈ H ₂₃ ClN ₄ O=466.97) Sub 2-9 m/z=384.08(C ₂₂ H ₁₃ ClN ₄ O=384.82) Sub 2-10 m/z=393.13(C ₂₂ H ₄ D ₉ ClN ₄ O=393.88) Sub 2-11 m/z=400.05(C ₂₂ H ₁₃ ClN ₄ S=400.88) Sub 2-12 m/z=460.11(C ₂₈ H ₁₇ ClN ₄ O=460.92) Sub 2-13 m/z=434.09(C ₂₆ H ₁₅ ClN ₄ O=434.88) Sub 2-14 m/z=490.07(C ₂₈ H ₁₅ ClN ₄ OS=490.97) Sub 2-15 m/z=490.07(C ₂₈ H ₁₅ ClN ₄ OS=490.97) Sub 2-16 m/z=500.09(C ₃₀ H ₁₇ ClN ₄ S=501.00) Sub 2-17 m/z=409.07(C ₂₃ H ₁₂ ClN ₅ O=409.83) Sub 2-18 m/z=516.17(C ₃₂ H ₂₅ ClN ₄ O=517.03) Sub 2-19 m/z=384.08(C ₂₂ H ₁₃ ClN ₄ O=384.82) Sub 2-20 m/z=400.05(C ₂₂ H ₁₃ ClN ₄ S=400.88) Sub 2-21 m/z=465.14(C ₂₈ H ₁₂ D ₅ ClN ₄ O=465.95) Sub 2-22 m/z=526.10(C ₃₂ H ₁₉ ClN ₄ S=527.04) Sub 2-23 m/z=460.11(C ₂₈ H ₁₇ ClN ₄ O=460.92) Sub 2-24 m/z=490.07(C ₂₈ H ₁₅ ClN ₄ OS=490.97) Sub 2-25 m/z=549.14(C ₃₄ H ₂₀ ClN ₅ O=550.02) Sub 2-26 m/z=550.10(C ₃₄ H ₁₉ ClN ₄ S=551.06) Sub 2-27 m/z=460.11(C ₂₈ H ₁₇ ClN ₄ O=460.92) Sub 2-28 m/z=460.11(C ₂₈ H ₁₇ ClN ₄ O=460.92) Sub 2-29 m/z=476.09(C ₂₈ H ₁₇ ClN ₄ S=476.98) Sub 2-30 m/z=460.11(C ₂₈ H ₁₇ ClN ₄ O=460.92) Sub 2-31 m/z=510.12(C ₃₂ H ₁₉ ClN ₄ O=510.98) Sub 2-32 m/z=576.17(C ₃₇ H ₂₅ ClN ₄ O=577.08) Sub 2-33 m/z=476.09(C ₂₈ H ₁₇ ClN ₄ S=476.98) Sub 2-34 m/z=450.07(C ₂₆ H ₁₅ ClN ₄ S=450.94) Sub 2-35 m/z=506.13(C ₃₀ H ₂₃ ClN ₄ S=507.05) Sub 2-36 m/z=434.09(C ₂₆ H ₁₅ ClN ₄ O=434.88) Sub 2-37 m/z=434.09(C ₂₆ H ₁₅ ClN ₄ O=434.88) Sub 2-38 m/z=510.12(C ₃₂ H ₁₉ ClN ₄ O=510.98) Sub 2-39 m/z=434.09(C ₂₆ H ₁₅ ClN ₄ O=434.88) Sub 2-40 m/z=556.06(C ₃₂ H ₁₇ ClN ₄ S ₂ =557.09) Sub 2-41 m/z=484.11(C ₃₀ H ₁₇ ClN ₄ O=484.94) Sub 2-42 m/z=500.09(C ₃₀ H ₁₇ ClN ₄ S=501.00) Sub 2-43 m/z=484.11(C ₃₀ H ₁₇ ClN ₄ O=484.94) Sub 2-44 m/z=500.09(C ₃₀ H ₁₇ ClN ₄ S=501.00) Sub 2-45 m/z=474.09(C ₂₈ H ₁₅ ClN ₄ O ₂ =474.90) Sub 2-46 m/z=490.07(C ₂₈ H ₁₅ ClN ₄ OS=490.97) Sub 2-47 m/z=549.14(C ₃₄ H ₂₀ ClN ₅ O=550.02) Sub 2-48 m/z=638.13(C ₄₁ H ₂₃ ClN ₄ S=639.17) Sub 2-49 m/z=540.08(C ₃₂ H ₁₇ ClN ₄ OS=541.03) Sub 2-50 m/z=474.09(C ₂₈ H ₁₅ ClN ₄ O ₂ =474.90) Sub 2-51 m/z=388.10(C ₂₂ H ₉ D ₄ ClN ₄ O=388.85) Sub 2-52 m/z=494.09(C ₂₈ H ₁₁ D ₄ ClN ₄ OS=494.99)

Ⅲ. Synthesis example of final compound

1. Synthesis example of P-33

After dissolving Sub 1-17 (10.0 g, 23.8 mmol) in THF (60 mL) and water (20 mL), Sub 2-9 (9.2 g, 23.8 mmol), Pd(PPh ₃ ) ₄ (0.8 g, 0.7 mmol), NaOH (1.9 g, 47.6 mmol) and proceed with the reaction at 80°C. When the reaction is completed, the extract is extracted with CH ₂ Cl ₂ and water, and the organic layer is dried over MgSO ₄ and concentrated. Afterwards, the concentrate was separated using a silica gel column and recrystallized to obtain 12.1 g of product. (yield 79.1%)

2. Synthesis example of P-41

After dissolving Sub 1-18 (10.0 g, 22.5 mmol) in THF and water, Sub 2-45 (10.7 g, 22.5 mmol), Pd(PPh ₃ ) ₄ (0.8 g, 0.7 mmol), NaOH (1.8 g, 44.9 mmol) was added, and synthesis was performed in the same manner as in the synthesis example of P-33, to obtain 14.2 g of product. (yield 83.5%)

3. Synthesis example of P-66

After dissolving Sub 1-26 (10.0 g, 20.1 mmol) in THF and water, Sub 2-24 (9.9 g, 20.1 mmol), Pd(PPh ₃ ) ₄ (0.7 g, 0.6 mmol), NaOH (1.6 g, 40.3 mmol) was added, and synthesis was performed in the same manner as in the synthesis example of P-33, to obtain 13 g of product. (yield 78.2%)

4. Synthesis example of P-86

After dissolving Sub 1-31 (10.0 g, 21.3 mmol) in THF and water, Sub 2-33 (10.1 g, 21.3 mmol), Pd(PPh ₃ ) ₄ (0.7 g, 0.6 mmol), NaOH (1.7 g, 42.5 mmol) was added, and synthesis was performed in the same manner as in the synthesis example of P-33, to obtain 12.7 g of product. (yield 76.1%)

5. Synthesis example of P-94

After dissolving Sub 1-36 (10.0 g, 18.6 mmol) in THF and water, Sub 2-23 (8.6 g, 18.6 mmol), Pd(PPh ₃ ) ₄ (0.6 g, 0.6 mmol), NaOH (1.5 g, 37.3 mmol) was added, and synthesis was performed in the same manner as in the synthesis example of P-33, to obtain 11.8 g of product. (yield 75.8%)

The FD-MS values of compounds P-1 to P-100 of the present invention synthesized according to the above synthesis examples are shown in Table 3 below.

compound FD-MS compound FD-MS P-1 m/z=582.15(C ₃₈ H ₂₂ N ₄ OS=582.68) P-2 m/z=672.16(C ₄₄ H ₂₄ N ₄ O ₂ S=672.76) P-3 m/z=566.17(C ₃₈ H ₂₂ N ₄ O ₂ =566.62) P-4 m/z=598.13(C ₃₈ H ₂₂ N ₄ S ₂ =598.74) P-5 m/z=672.16(C ₄₄ H ₂₄ N ₄ O ₂ S=672.76) P-6 m/z=632.17(C ₄₂ H ₂₄ N ₄ OS=632.74) P-7 m/z=642.21(C ₄₄ H ₂₆ N ₄ O ₂ =642.72) P-8 m/z=658.18(C ₄₄ H ₂₆ N ₄ OS=658.78) P-9 m/z=698.16(C ₄₆ H ₂₆ N ₄ S ₂ =698.86) P-10 m/z=692.22(C ₄₈ H ₂₈ N ₄ O ₂ =692.78) P-11 m/z=732.20(C ₅₀ H ₂₈ N ₄ OS=732.86) P-12 m/z=648.25(C ₄₄ H ₃₂ N ₄ O ₂ =648.77) P-13 m/z=642.21(C ₄₄ H ₂₆ N ₄ O ₂ =642.72) P-14 m/z=784.23(C ₅₄ H ₃₂ N ₄ OS=784.94) P-15 m/z=662.21(C ₄₄ H ₂₂ D ₄ N ₄ OS=662.80) P-16 m/z=692.22(C ₄₈ H ₂₈ N ₄ O ₂ =692.78) P-17 m/z=658.18(C ₄₄ H ₂₆ N ₄ OS=658.78) P-18 m/z=718.24(C ₅₀ H ₃₀ N ₄ O ₂ =718.82) P-19 m/z=732.22(C ₅₀ H ₂₈ N ₄ O ₃ =732.80) P-20 m/z=692.22(C ₄₈ H ₂₈ N ₄ O ₂ =692.78) P-21 m/z=718.24(C ₅₀ H ₃₀ N ₄ O ₂ =718.82) P-22 m/z=667.20(C ₄₅ H ₂₅ N ₅ O ₂ =667.73) P-23 m/z=692.22(C ₄₈ H ₂₈ N ₄ O ₂ =692.78) P-24 m/z=748.19(C ₅₀ H ₂₈ N ₄ O ₂ S=748.86) P-25 m/z=658.18(C ₄₄ H ₂₆ N ₄ OS=658.78) P-26 m/z=724.18(C ₄₈ H ₂₈ N ₄ S ₂ =724.90) P-27 m/z=658.18(C ₄₄ H ₂₆ N ₄ OS=658.78) P-28 m/z=814.19(C ₅₄ H ₃₀ N ₄ OS ₂ =814.98) P-29 m/z=658.18(C ₄₄ H ₂₆ N ₄ OS=658.78) P-30 m/z=807.26(C ₅₆ H ₃₃ N ₅ O ₂ =807.91) P-31 m/z=742.24(C ₅₂ H ₃₀ N ₄ O ₂ =742.84) P-32 m/z=692.22(C ₄₈ H ₂₈ N ₄ O ₂ =692.78) P-33 m/z=642.21(C ₄₄ H ₂₆ N ₄ O ₂ =642.72) P-34 m/z=718.24(C ₅₀ H ₃₀ N ₄ O ₂ =718.82) P-35 m/z=748.19(C ₅₀ H ₂₈ N ₄ O ₂ S=748.86) P-36 m/z=718.24(C ₅₀ H ₃₀ N ₄ O ₂ =718.82) P-37 m/z=692.22(C ₄₈ H ₂₈ N ₄ O ₂ =692.78) P-38 m/z=718.24(C ₅₀ H ₃₀ N ₄ O ₂ =718.82) P-39 m/z=683.22(C ₄₄ H ₁₇ D ₉ N ₄ S ₂ =683.89) P-40 m/z=676.30(C ₄₄ H ₈ D ₁₈ N ₄ OS=676.89) P-41 m/z=757.25(C ₅₀ H ₁₉ D ₉ N ₄ O ₂ S=757.91) P-42 m/z=783.25(C ₅₂ H ₂₁ D ₉ N ₄ S ₂ =784.01) P-43 m/z=718.24(C ₅₀ H ₃₀ N ₄ O ₂ =718.82) P-44 m/z=718.24(C ₅₀ H ₃₀ N ₄ O ₂ =718.82) P-45 m/z=774.19(C ₅₂ H ₃₀ N ₄ S ₂ =774.96) P-46 m/z=708.20(C ₄₈ H ₂₈ N ₄ OS=708.84) P-47 m/z=734.21(C ₅₀ H ₃₀ N ₄ OS=734.88) P-48 m/z=768.25(C ₅₄ H ₃₂ N ₄ O ₂ =768.88) P-49 m/z=734.21(C ₅₀ H ₃₀ N ₄ OS=734.88) P-50 m/z=658.18(C ₄₄ H ₂₆ N ₄ OS=658.78) P-51 m/z=748.19(C ₅₀ H ₂₈ N ₄ O ₂ S=748.86) P-52 m/z=734.21(C ₅₀ H ₃₀ N ₄ OS=734.88) P-53 m/z=824.22(C ₅₆ H ₃₂ N ₄ O ₂ S=824.96) P-54 m/z=692.22(C ₄₈ H ₂₈ N ₄ O ₂ =692.78) P-55 m/z=708.20(C ₄₈ H ₂₈ N ₄ OS=708.84) P-56 m/z=896.26(C ₆₃ H ₃₆ N ₄ OS=897.07) P-57 m/z=718.24(C ₅₀ H ₃₀ N ₄ O ₂ =718.82) P-58 m/z=764.26(C ₅₂ H ₃₆ N ₄ OS=764.95) P-59 m/z=642.21(C ₄₄ H ₂₆ N ₄ O ₂ =642.72) P-60 m/z=814.19(C ₅₄ H ₃₀ N ₄ OS ₂ =814.98) P-61 m/z=658.18(C ₄₄ H ₂₆ N ₄ OS=658.78) P-62 m/z=723.27(C ₅₀ H ₂₅ D ₅ N ₄ O ₂ =723.85) P-63 m/z=768.25(C ₅₄ H ₃₂ N ₄ O ₂ =768.88) P-64 m/z=732.22(C ₅₀ H ₂₈ N ₄ O ₃ =732.80) P-65 m/z=718.24(C ₅₀ H ₃₀ N ₄ O ₂ =718.82) P-66 m/z=824.22(C ₅₆ H ₃₂ N ₄ O ₂ S=824.96) P-67 m/z=768.25(C ₅₄ H ₃₂ N ₄ O ₂ =768.88) P-68 m/z=734.21(C ₅₀ H ₃₀ N ₄ OS=734.88) P-69 m/z=834.25(C ₅₈ H ₃₄ N ₄ OS=835.00) P-70 m/z=734.21(C ₅₀ H ₃₀ N ₄ OS=734.88) P-71 m/z=768.25(C ₅₄ H ₃₂ N ₄ O ₂ =768.88) P-72 m/z=874.24(C ₆₀ H ₃₄ N ₄ O ₂ S=875.02) P-73 m/z=803.32(C ₅₆ H ₂₅ D ₉ N ₄ O ₂ =803.97) P-74 m/z=833.28(C ₅₆ H ₂₃ D ₉ N ₄ O ₂ S=834.01) P-75 m/z=827.32(C ₅₈ H ₂₅ D ₉ N ₄ O ₂ =827.99) P-76 m/z=777.31(C ₅₄ H ₂₃ D ₉ N ₄ O ₂ =777.93) P-77 m/z=850.33(C ₆₀ H ₄₂ N ₄ O ₂ =851.02) P-78 m/z=784.23(C ₅₄ H ₃₂ N ₄ OS=784.94) P-79 m/z=890.22(C ₆₀ H ₃₄ N ₄ OS ₂ =891.08) P-80 m/z=718.24(C ₅₀ H ₃₀ N ₄ O ₂ =718.82) P-81 m/z=708.20(C ₄₈ H ₂₈ N ₄ OS=708.84) P-82 m/z=800.21(C ₅₄ H ₃₂ N ₄ S ₂ =801.00) P-83 m/z=784.23(C ₅₄ H ₃₂ N ₄ OS=784.94) P-84 m/z=798.21(C ₅₄ H ₃₀ N ₄ O ₂ S=798.92) P-85 m/z=742.24(C ₅₂ H ₃₀ N ₄ O ₂ =742.84) P-86 m/z=784.23(C ₅₄ H ₃₂ N ₄ OS=784.94) P-87 m/z=864.20(C ₅₈ H ₃₂ N ₄ OS ₂ =865.04) P-88 m/z=692.22(C ₄₈ H ₂₈ N ₄ O ₂ =692.78) P-89 m/z=857.28(C ₆₀ H ₃₅ N ₅ O ₂ =857.97) P-90 m/z=802.23(C ₅₄ H ₂₆ D ₄ N ₄ O ₂ S=802.94) P-91 m/z=774.19(C ₅₂ H ₃₀ N ₄ S ₂ =774.96) P-92 m/z=758.21(C ₅₂ H ₃₀ N ₄ OS=758.90) P-93 m/z=818.27(C ₅₈ H ₃₄ N ₄ O ₂ =818.94) P-94 m/z=834.30(C ₅₉ H ₃₈ N ₄ O ₂ =834.98) P-95 m/z=732.22(C ₅₀ H ₂₈ N ₄ O ₃ =732.80) P-96 m/z=858.26(C ₆₀ H ₃₄ N ₄ O ₃ =858.96) P-97 m/z=798.21(C ₅₄ H ₃₀ N ₄ O ₂ S=798.92) P-98 m/z=764.17(C ₅₀ H ₂₈ N ₄ OS ₂ =764.92) P-99 m/z=764.17(C ₅₀ H ₂₈ N ₄ OS ₂ =764.92) P-100 m/z=748.19(C ₅₀ H ₂₈ N ₄ O ₂ S=748.86)

Manufacturing evaluation of organic electric devices

[Example 1] Green organic electroluminescent device (phosphorescent host)

N1-(naphthalen-2-yl)-N4,N4-bis(4-(naphthalen-2-yl(phenyl)amino)phenyl)-N1-phenylbenzene-1,4-diamine (hereinafter referred to as Abbreviated as 2-TNATA) was vacuum deposited to a thickness of 60 nm to form a hole injection layer, and then N,N'-bis(1-naphthalenyl)-N,N'-bis-phenyl-( 1,1'-biphenyl)-4,4'-diamine (hereinafter abbreviated as NPB) was vacuum deposited to a thickness of 60 nm to form a hole transport layer.

Next, on the hole transport layer, compound P-1 of the present invention was used as a host material, and tris(2-phenylpyridine)-iridium (hereinafter abbreviated as Ir(ppy) ₃ ) was used as a dopant material, with a weight ratio of 95:5. A 30 nm thick light-emitting layer was formed by doping with a dopant.

Afterwards, (1,1'-biphenyl-4-olato)bis(2-methyl-8-quinolinolato)aluminum (hereinafter abbreviated as BAlq) was vacuum deposited to a thickness of 10 nm on the emitting layer to form a hole blocking layer. , tris-(8-hydroxyquinoline)aluminum (hereinafter abbreviated as Alq ₃ ) was vacuum deposited to a thickness of 40 nm on the hole blocking layer to form an electron transport layer.

Afterwards, LiF was deposited to a thickness of 0.2 nm on the electron transport layer to form an electron injection layer, and Al was deposited to a thickness of 150 nm on the electron injection layer to form a cathode.

[Example 2] to [Example 18]

An organic electroluminescent device was manufactured in the same manner as Example 1, except that the compounds of the present invention shown in Table 4 below were used as host materials instead of the compound P-1 of the present invention.

[Comparative Example 1] and [Comparative Example 2]

An organic electroluminescent device was manufactured in the same manner as Example 1, except that Comparative Compound 1 or Comparative Compound 2 below was used instead of Compound P-1 of the present invention as a host material.

<Comparative compound 1> <Comparative compound 2>

Electroluminescence (EL) characteristics were obtained using PR-650 from Photoresearch by applying a forward bias direct current voltage to the organic electroluminescent devices manufactured in Examples 1 to 18 and Comparative Examples 1 and 2 of the present invention. The T95 lifespan was measured using a lifespan measuring device manufactured by McScience at a standard luminance of 5000 cd/m ² . The measurement results are shown in Table 4 below.

compound driving voltage
(V) current density
(mA/ ^cm2 ) efficiency
(cd/A) life span
T(95) Comparative example (1) Comparative compound 1 5.8 25.8 19.4 69.6 Comparative example (2) Comparative compound 2 5.5 22.0 22.7 78.4 Example (1) P-1 4.9 13.8 36.2 93.3 Example (2) P-2 5.0 13.6 36.7 95.1 Example (3) P-6 5.0 13.4 37.2 94.6 Example (4) P-15 4.9 11.6 43.2 116.5 Example (5) P-23 5.1 11.8 42.3 114.8 Example (6) P-28 5.1 11.7 42.6 113.7 Example (7) P-33 4.8 10.7 46.7 117.6 Example (8) P-34 5.1 10.8 46.2 115.8 Example (9) P-40 4.7 10.7 46.8 118.2 Example (10) P-48 5.1 11.5 43.6 112.3 Example (11) P-55 5.0 12.1 41.2 110.4 Example (12) P-65 5.1 12.0 41.6 107.2 Example (13) P-79 5.2 11.7 42.6 108.7 Example (14) P-85 5.0 12.3 40.7 105.6 Example (15) P-88 5.0 12.7 39.4 102.1 Example (16) P-93 5.4 12.9 38.9 98.8 Example (17) P-95 5.3 13.1 38.3 97.6 Example (18) P-98 5.2 12.8 39.1 96.1

Looking at Table 4, when the material for an organic electroluminescent device of the present invention is used as a phosphorescent host material, the driving voltage of the organic light emitting device can be lowered, and the efficiency and lifespan can be reduced compared to the case where Comparative Compound 1 or Comparative Compound 2 is used. It can be seen that it can be significantly improved.

Comparative Compound 1 and Comparative Compound 2 and the compound of the present invention are similar in that the benzooxazole-substituted triazine is substituted with a substituent containing a dibenzofuran moiety, but the compound of the present invention is dibenzofuran 3, While benzonaphthofuran with benzene fused at position 4 is substituted, comparative compound 1 is substituted with dibenzofuran, and comparative compound 2 is benzonaphtho with benzene fused at positions 2 and 3 of dibenzofuran. The difference is that it is furan.

Therefore, it can be seen that even if a compound has a similar skeleton, the properties of the device are different when a compound different in whether or not benzene is fused and the fusion position is used as a host. In particular, Comparative Compound 2 and the compound of the present invention differ only in the fusion position of benzene. However, the characteristics of the device change, which appears to be due to differences in the physical properties of these compounds.

Table 5 below shows the T1 values of Comparative Compound 2 and Compound P-2 of the present invention.

Comparative compound 2 P-2 structure T1 (eV) 2.29 2.58

Looking at Table 5, Compound P-2 of the present invention, in which benzene is fused to positions 3 and 4 of dibenzofuran, has a T1 energy level compared to Comparative Compound 2, in which benzene is fused to positions 2 and 3 of dibenzofuran. You can see that this is higher.

As the compound of the present invention has a high T1 energy level, energy transfer to the green phosphorescent dopant having a high T1 energy level is easier than that of Comparative Compound 2, thereby improving luminous efficiency.

Therefore, even if the basic skeleton of the compound used as a host material is similar, the hole characteristics, light efficiency characteristics, energy level (HOMO, LUMO), hole injection and It can be seen that the properties of the compound, such as mobility characteristics, charge balance of holes and electrons, etc., can vary, and when compounds with different compound characteristics are used as host materials, the properties of the device can also vary significantly.

In addition, it can be seen that among the compounds of the present invention, the lifespan is better when a compound in which deuterium is introduced as a substituent is used as a host. This appears to have improved the stability of the material and its lifespan characteristics by lowering the zero-point electromagnetic vibration energy of the compound substituted with deuterium compared to the compound not substituted with deuterium.

The above description is merely an illustrative description of the present invention, and those skilled in the art will be able to make various modifications without departing from the essential characteristics of the present invention. The scope of protection of the present invention should be interpreted in accordance with the claims below, and all technologies within the equivalent scope should be interpreted as being included in the scope of the present invention.

100, 200, 300: Organic electric element 110: First electrode
120: hole injection layer 130: hole transport layer
140: light emitting layer 150: electron transport layer
160: electron injection layer 170: second electrode
180: Light efficiency improvement layer 210: Buffer layer
220: Light-emitting auxiliary layer 320: First hole injection layer
330: first hole transport layer 340: first light emitting layer
350: first electron transport layer 360: first charge generation layer
361: second charge generation layer 420: second hole injection layer
430: second hole transport layer 440: second light emitting layer
450: Second electron transport layer CGL: Charge generation layer
ST1: first stack ST2: second stack

Claims (17)

Compound represented by Formula 1:
<Formula 1>

In Formula 1,
X ¹ and X ² are independently O or S,
L ¹ is single bond; C ₆ ~ C ₆₀ arylene group; fluorenylene group; C ₃ ~ C ₆₀ aliphatic ring group; and a C ₂ to C ₆₀ heterocyclic group containing at least one hetero atom selected from O, N, S, Si and P,
L ² is an arylene group of C ₆ to C ₆₀ ; fluorenylene group; C ₃ ~ C ₆₀ aliphatic ring group; and a C ₂ to C ₆₀ heterocyclic group containing at least one hetero atom selected from O, N, S, Si and P,
Ar is an aryl group of C ₆ to C ₆₀ ; fluorenyl group; C ₃ ~ C ₆₀ aliphatic ring group; and a C ₂ to C ₆₀ heterocyclic group containing at least one hetero atom selected from O, N, S, Si and P,
R ¹ to R ³ are independently hydrogen; heavy hydrogen; halogen; Cyano group; nitro group; Aryl group of C ₆ to C ₆₀ ; fluorenyl group; C ₂ ~ C ₆₀ heterocyclic group containing at least one hetero atom selected from O, N, S, Si and P; C ₃ ~ C ₆₀ aliphatic ring group; C ₁ ~ C ₂₀ alkyl group; C ₂ ~ C ₂₀ alkenyl group; C ₂ ~ C ₂₀ alkyne group; C ₁ ~ C ₂₀ alkoxy group; and aryloxy groups of C ₆ to C ₆₀ , and adjacent R ¹ groups or adjacent R ² groups may bond to each other to form a ring;
a is an integer from 0 to 6, b and c are each an integer from 0 to 4,
The aryl group, arylene group, fluorenyl group, fluorenylene group, hetero ring group, aliphatic ring group, alkyl group, alkenyl group, alkynyl group, alkoxy group, aryloxy group, and the rings formed by bonding adjacent groups are each heavy hydrogen; halogen; A silane group unsubstituted or substituted with a C ₁ -C ₂₀ alkyl group or a C ₆ -C ₂₀ aryl group; Phosphine oxide substituted or unsubstituted with a C ₁ -C ₂₀ alkyl group or a C ₆ -C ₂₀ aryl group; siloxane group; Cyano group; nitro group; C ₁ -C ₂₀ alkylthio group; C ₁ -C ₂₀ alkoxy group; C ₆ -C ₃₀ aryloxy group; C ₆ -C ₃₀ arylthio group; C ₁ -C ₂₀ alkyl group; C ₂ -C ₂₀ alkenyl group; C ₂ -C ₂₀ alkyne group; C ₆ -C ₃₀ aryl group; fluorenyl group; A C ₂ -C ₃₀ heterocyclic group containing at least one heteroatom selected from the group consisting of O, N, S, Si and P; and C ₃ -C ₃₀ aliphatic ring groups. According to clause 1,
The compound of Formula 1 is characterized in that it is represented by one of the following Formulas 2-1 to 2-3:
<Formula 2-1><Formula2-2>

<Formula 2-3>

^In Formulas ^{2-1 to} 2-3 ^, X ^{1 ,} It is an integer of 5, and b' is an integer of 0 to 3. According to clause 1,
The above Chemical Formula 1 is a compound characterized in that it is represented by one of the following Chemical Formulas 3-1 to 3-10:
<Formula 3-1><Formula3-2>

<Formula 3-3><Formula3-4>

<Formula 3-5><Formula3-6>

<Formula 3-7><Formula3-8>

<Formula 3-9><Formula3-10>

^{In Formulas 3-1 to} 3-10, X ^{1 ,} It is an integer of 5, and b' is an integer of 0 to 3. According to clause 1,
A compound characterized in that at least one of L ¹ and L ² is selected from the group consisting of the following formulas L-1 to formula L-5:
<Formula L-1><FormulaL-2><FormulaL-3><FormulaL-4><FormulaL-5>

In Formula L-1 to Formula L-5,
Y is O, S, N(R) or C(R _a )(R _b ),
R ⁴ to R ¹² , R, R _a and R _b are independently hydrogen; heavy hydrogen; halogen; A silane group unsubstituted or substituted with a C ₁ -C ₂₀ alkyl group or a C ₆ -C ₂₀ aryl group; Phosphine oxide substituted or unsubstituted with a C ₁ -C ₂₀ alkyl group or a C ₆ -C ₂₀ aryl group; siloxane group; Cyano group; nitro group; C ₁ -C ₂₀ alkylthio group; C ₁ -C ₂₀ alkoxy group; C ₆ -C ₃₀ aryloxy group; C ₆ -C ₃₀ arylthio group; C ₁ -C ₂₀ alkyl group; C ₂ -C ₂₀ alkenyl group; C ₂ -C ₂₀ alkyne group; C ₆ -C ₃₀ aryl group; fluorenyl group; A C ₂ -C ₃₀ heterocyclic group containing at least one heteroatom selected from the group consisting of O, N, S, Si and P; and C ₃ -C ₃₀ aliphatic ring groups, and adjacent groups may combine with each other to form a ring;
d, e and f are each an integer from 0 to 4, g to i, k and l are each an integer from 0 to 3, and j is an integer from 0 to 5. According to clause 1,
A compound characterized in that at least one of Ar, R ¹ to R ³ contains deuterium. According to clause 1,
The compound represented by Formula 1 is characterized in that it is one of the following compounds:

























. In an organic electric device comprising a first electrode, a second electrode, and an organic material layer formed between the first electrode and the second electrode,
The organic material layer is an organic electric device containing the compound of any one of claims 1 to 6. According to clause 7,
The organic material layer includes a light-emitting layer between the first electrode and the second electrode, and the light-emitting layer includes the compound. According to clause 7,
The organic material layer is an organic electric device comprising two or more stacks including a hole transport layer, a light emitting layer, and an electron transport layer sequentially formed on the first electrode. According to clause 9,
The organic material layer is an organic electric device further comprising a charge generation layer formed between the two or more stacks. According to clause 7,
The organic electric device further includes a light efficiency improvement layer, wherein the light efficiency improvement layer is formed on one side of both sides of the first electrode or both sides of the second electrode that is not in contact with the organic material layer. A display device including the organic electric element of claim 7; and
An electronic device including a control unit that drives the display device. According to clause 12,
The organic electric device is an electronic device selected from the group consisting of organic electroluminescent devices, organic solar cells, organic photoreceptors, organic transistors, monochromatic lighting devices, and quantum dot display devices. A compound obtained by depositing an organic layer in the manufacturing process of an organic electric device, then recovering and purifying the material of the organic layer from deposition equipment,
The compound is characterized in that it is a compound represented by the formula (1) of claim 1. According to clause 14,
A compound characterized in that the purity of the compound is 99.9% or more. Depositing an organic layer material containing the compound represented by Formula 1 of claim 1;
Recovering the organic layer material attached to deposition equipment; and
A method for recovering a compound represented by Formula 1, comprising the step of purifying the recovered organic layer material to obtain a compound represented by Formula 1 with a purity of 99.9% or more. According to clause 16,
The purification step includes the steps of recrystallizing the recovered organic layer material using a recrystallization solvent, adsorption separation using an adsorbent, and sublimation purification.