WO2022225340A1 - Compound for organic optoelectronic element, composition for organic optoelectronic element including same, organic optoelectronic element, and display device - Google Patents

Abstract

The present invention relates to: a compound for an organic optoelectronic element, wherein the compound is represented by chemical formula 1; a composition for an organic optoelectronic element, wherein the composition includes the compound; an organic optoelectronic element; and a display device. Chemical formula 1 is as defined in the specification.

Description

Compound for organic optoelectronic device, composition for organic optoelectronic device, organic optoelectronic device and display device

It relates to a compound for an organic optoelectronic device, a composition for an organic optoelectronic device, an organic optoelectronic device, and a display device.

An organic optoelectronic diode is a device capable of converting electrical energy and optical energy.

Organic optoelectronic devices can be roughly divided into two types according to their operating principles. One is a photoelectric device that generates electrical energy as excitons formed by light energy are separated into electrons and holes, and electrons and holes are transferred to different electrodes, and the other is electrical energy by supplying voltage or current to the electrode It is a light emitting device that generates light energy from

Examples of the organic optoelectronic device include an organic optoelectronic device, an organic light emitting device, an organic solar cell, and an organic photo conductor drum.

Among them, organic light emitting diodes (OLEDs) have recently attracted much attention due to an increase in demand for flat panel display devices. An organic light emitting device is a device that converts electrical energy into light, and the performance of the organic light emitting device is greatly affected by an organic material positioned between electrodes.

One embodiment provides a compound for an organic optoelectronic device capable of realizing a high-efficiency and long-life organic optoelectronic device.

Another embodiment provides a composition for an organic optoelectronic device comprising the compound.

Another embodiment provides an organic optoelectronic device including the compound.

Another embodiment provides a display device including the organic optoelectronic device.

According to one embodiment, there is provided a compound for an organic optoelectronic device represented by the following formula (1).

[Formula 1]

In Formula 1,

Z ¹ to Z ³ are each independently N or CR ^a ,

At least two of Z ¹ to Z ³ are N,

L ¹ to L ³ are each independently a single bond, or a substituted or unsubstituted C6 to C30 arylene group,

Ar ¹ and Ar ² are each independently a substituted or unsubstituted C6 to C30 aryl group or a substituted or unsubstituted C2 to C30 heterocyclic group,

R ^a and R ¹ to R ⁴ are each independently hydrogen, deuterium, a substituted or unsubstituted C1 to C20 alkyl group, or a substituted or unsubstituted C6 to C20 aryl group,

n1 is one of integers from 1 to 3,

n2 and n3 are each independently an integer of 1 or 2,

n4 is one of integers from 1 to 4.

According to another embodiment, there is provided a composition for an organic optoelectronic device comprising a first compound and a second compound.

The first compound may be the compound for an organic optoelectronic device described above, and the second compound may be represented by Formula 2 below.

[Formula 2]

In Formula 2,

X ¹ is O, S, NR ^b , CR ^c R ^d or SiR ^e R ^f ,

R ^b , R ^c , R ^d , ^Re , R ^f , R ⁷ and R ⁸ are each independently hydrogen, deuterium, a substituted or unsubstituted amine group, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted a C6 to C30 aryl group or a substituted or unsubstituted C2 to C30 heterocyclic group,

n5 is one of integers from 1 to 4,

Ring A is any one selected from the rings listed in Group II,

[Group II]

In group II,

* is the connection point,

X ² is O, S, NR ^g , CR ^h R ⁱ or SiR ^j R ^k ,

R ^g , R ^h , R ⁱ , R ^j , R ^k , and R ⁶ to R ¹⁰ are each independently hydrogen, deuterium, a substituted or unsubstituted amine group, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted a cyclic C6 to C30 aryl group or a substituted or unsubstituted C2 to C30 heterocyclic group,

n6, n8 and n10 are each independently one of an integer of 1 to 4,

n7 and n9 are each independently an integer of 1 or 2,

At least one of R ⁵ to R ¹⁰ is a group represented by the following formula (a),

[Formula a]

In the above formula (a),

L ⁴ To L ⁶ are each independently a single bond, or a substituted or unsubstituted C6 to C30 arylene group,

Ar ³ and Ar ⁴ are each independently a substituted or unsubstituted amine group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C2 to C30 heterocyclic group,

* is the connection point.

According to another embodiment, it includes an anode and a cathode facing each other, and at least one organic layer positioned between the anode and the cathode, wherein the organic layer comprises the compound for an organic optoelectronic device or a composition for an organic optoelectronic device An organic optoelectronic device is provided.

According to another embodiment, a display device including the organic optoelectronic device is provided.

A high-efficiency, long-life organic optoelectronic device can be realized.

1 is a cross-sectional view illustrating an organic light emitting diode according to an exemplary embodiment.

<Explanation of code>

100: organic light emitting device

105: organic layer

110: cathode

120: positive electrode

130: light emitting layer

140: hole transport region

150: electron transport region

Hereinafter, embodiments of the present invention will be described in detail. However, this is provided as an example, and the present invention is not limited thereto, and the present invention is only defined by the scope of the claims to be described later.

As used herein, unless otherwise defined, at least one hydrogen in a substituent or compound is deuterium, a halogen group, a hydroxyl group, an amino group, a substituted or unsubstituted C1 to C30 amine group, a nitro group, a substituted or Unsubstituted C1 to C40 silyl group, C1 to C30 alkyl group, C1 to C10 alkylsilyl group, C6 to C30 arylsilyl group, C3 to C30 cycloalkyl group, C3 to C30 heterocycloalkyl group, C6 to C30 aryl group, C2 to C30 It means substituted with a heteroaryl group, a C1 to C20 alkoxy group, a C1 to C10 trifluoroalkyl group, a cyano group, or a combination thereof.

In one embodiment of the present invention, "substitution" means that at least one hydrogen in a substituent or compound is deuterium, C1 to C30 alkyl group, C1 to C10 alkylsilyl group, C6 to C30 arylsilyl group, C3 to C30 cycloalkyl group, C3 to C30 It means substituted with a heterocycloalkyl group, a C6 to C30 aryl group, a C2 to C30 heteroaryl group, or a cyano group. In addition, in a specific embodiment of the present invention, "substitution" means that at least one hydrogen in a substituent or compound is substituted with deuterium, a C1 to C20 alkyl group, a C6 to C30 aryl group, or a cyano group. In addition, in a specific embodiment of the present invention, "substitution" means that at least one hydrogen in a substituent or compound is substituted with deuterium, a C1 to C5 alkyl group, a C6 to C18 aryl group, or a cyano group. In addition, in a specific example of the present invention, "substitution" means that at least one hydrogen in a substituent or compound is substituted with deuterium, a cyano group, a methyl group, an ethyl group, a propyl group, a butyl group, a phenyl group, a biphenyl group, a terphenyl group or a naphthyl group means it has been

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

As used herein, the term "aryl group" is a concept that encompasses a group having one or more hydrocarbon aromatic moieties, and all elements of the hydrocarbon aromatic moiety have p-orbitals, and these p-orbitals are conjugated. It contains a form that forms, for example, a phenyl group, a naphthyl group, etc., and includes a form in which two or more hydrocarbon aromatic moieties are connected through a sigma bond, such as a biphenyl group, a terphenyl group, a quaterphenyl group, etc., and two or more hydrocarbon aromatic moieties They may include a fused non-aromatic fused ring, such as a fluorenyl group, directly or indirectly.

Aryl groups include monocyclic, polycyclic or fused ring polycyclic (ie, rings that share adjacent pairs of carbon atoms) functional groups.

In the present specification, "heterocyclic group" is a higher concept including a heteroaryl group, and instead of carbon (C), N, O, It means containing at least one hetero atom selected from the group consisting of S, P and Si. When the heterocyclic group is a fused ring, the entire heterocyclic group or each ring may include one or more heteroatoms.

For example, "heteroaryl group" means containing at least one hetero atom selected from the group consisting of N, O, S, P and Si in the aryl group. Two or more heteroaryl groups may be directly connected through a sigma bond, or when the heteroaryl group includes two or more rings, the two or more rings may be fused to each other. When the heteroaryl group is a fused ring, each ring may include 1 to 3 heteroatoms.

More specifically, a substituted or unsubstituted C6 to C30 aryl group includes a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted anthracenyl group, a substituted or unsubstituted phenanthrenyl group, a substituted or Unsubstituted naphthacenyl group, substituted or unsubstituted pyrenyl group, substituted or unsubstituted biphenyl group, substituted or unsubstituted p-terphenyl group, substituted or unsubstituted m-terphenyl group, substituted or unsubstituted o- Terphenyl group, substituted or unsubstituted chrysenyl group, substituted or unsubstituted triphenylene group, substituted or unsubstituted perylenyl group, substituted or unsubstituted fluorenyl group, substituted or unsubstituted indenyl group, substituted or unsubstituted It may be a cyclic furanyl group, or a combination thereof, but is not limited thereto.

More specifically, a substituted or unsubstituted C2 to C30 heterocyclic group is a substituted or unsubstituted thiophenyl group, a substituted or unsubstituted pyrrolyl group, a substituted or unsubstituted pyrazolyl group, a substituted or unsubstituted imidazolyl group, A substituted or unsubstituted triazolyl group, a substituted or unsubstituted oxazolyl group, a substituted or unsubstituted thiazolyl group, a substituted or unsubstituted oxadiazolyl group, a substituted or unsubstituted thiadiazolyl group, a substituted or unsubstituted A substituted or unsubstituted pyrimidinyl group, a substituted or unsubstituted pyrazinyl group, a substituted or unsubstituted triazinyl group, a substituted or unsubstituted benzofuranyl group, a substituted or unsubstituted benzothiophenyl group, A substituted or unsubstituted benzimidazolyl group, a substituted or unsubstituted indolyl group, a substituted or unsubstituted quinolinyl group, a substituted or unsubstituted isoquinolinyl group, a substituted or unsubstituted quinazolinyl group, a substituted or unsubstituted quinoxalinyl group, substituted or unsubstituted naphthyridinyl group, substituted or unsubstituted benzoxazinyl group, substituted or unsubstituted benzthiazinyl group, substituted or unsubstituted acridinyl group, substituted or unsubstituted phenazine A diyl group, a substituted or unsubstituted phenothiazinyl group, a substituted or unsubstituted phenoxazinyl group, a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted dibenzothiophenyl group , a substituted or unsubstituted benzonaphthofuranyl group, a substituted or unsubstituted benzonaphthothiophenyl group, a substituted or unsubstituted dibenzosilolyl group, or a combination thereof, but is not limited thereto.

As used herein, "hydrogen substitution (-H)" may include "deuterium substitution (-D)" or "tritium substitution (-T)".

As used herein, the hole property refers to a property capable of forming a hole by donating electrons when an electric field is applied. It refers to a property that facilitates the movement of holes formed in the anode and in the light emitting layer.

In addition, the electronic property refers to a property that can receive electrons when an electric field is applied. It has conduction properties along the LUMO level, so electrons formed in the cathode are injected into the light emitting layer, electrons formed in the light emitting layer are moved to the cathode, and in the light emitting layer. properties that facilitate movement.

Hereinafter, a compound for an organic optoelectronic device according to an embodiment will be described.

The compound for an organic optoelectronic device according to an embodiment is represented by the following Chemical Formula 1.

[Formula 1]

In Formula 1,

Z ¹ to Z ³ are each independently N or CR ^a ,

At least two of Z ¹ to Z ³ are N,

L ¹ to L ³ are each independently a single bond, or a substituted or unsubstituted C6 to C30 arylene group,

Ar ¹ and Ar ² are each independently a substituted or unsubstituted C6 to C30 aryl group or a substituted or unsubstituted C2 to C30 heterocyclic group,

R ^a and R ¹ to R ⁴ are each independently hydrogen, deuterium, a substituted or unsubstituted C1 to C20 alkyl group, or a substituted or unsubstituted C6 to C20 aryl group,

n1 is one of integers from 1 to 3,

n2 and n3 are each independently an integer of 1 or 2,

n4 is one of integers from 1 to 4.

The compound represented by Formula 1 has a structure in which pyrimidine or triazine is substituted in the core to which phenyl is further fused at positions 1 and 2 of phenanthrene.

By further fusion of phenyl to phenanthrene, it has a more stable T1 energy level, so that long-life characteristics can be realized.

In particular, by fusion at positions 1 and 2 of phenanthrene, a stable T1 energy level is obtained, and the formed polyfused ring is not in a perfectly planar state but is twisted by about 17°, so crystallinity is reduced and Tg is improved. . In addition, the processability during deposition is improved by decreasing crystallinity.

In addition, as pyrimidine or triazine is substituted for the fused phenanthrene, it has high electron mobility and thus the driving voltage can be lowered.

Moreover, as pyrimidine or triazine is substituted at the end of the fused phenanthrene, the length of the conjugation becomes longer compared to that linked to the center, and thus the molecule is stabilized, thereby having the effect of long life.

Formula 1 may be represented by any one of the following Formulas 1-1 to 1-4 according to a specific substitution point of the triazine.

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

In Formulas 1-1 to 1-4,

Z ¹ to Z ³ , L ¹ to L ³ , Ar ¹ , Ar ² , R ¹ to R ⁴ and n1 to n4 are the same as described above.

In an embodiment, L ¹ to L ³ may each independently be a single bond, a substituted or unsubstituted phenylene group, or a substituted or unsubstituted naphthylene group.

In one embodiment, Ar ¹ and Ar ² are each independently a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted phenanthrenyl group, a substituted or unsubstituted A substituted or unsubstituted carbazolyl group, a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted dibenzothiophenyl group, a substituted or unsubstituted dibenzosilolyl group, or a substituted or unsubstituted It may be a benzonaphthofuranyl group.

In a specific embodiment, Ar ¹ and Ar ² are each independently a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted dibenzofuranyl group, It may be a substituted or unsubstituted dibenzothiophenyl group or a substituted or unsubstituted benzonaphthofuranyl group.

In a more specific example, *-L ² -Ar ¹ and *-L ³ -Ar ² may each independently be selected from the substituents listed in Group I below.

[Group I]

In group I,

D means deuterium,

n11 is one of integers from 1 to 5,

n12 is one of integers from 1 to 4,

n13 is one of integers from 1 to 3,

* is the connection point.

For example, the compound for an organic optoelectronic device represented by Formula 1 may be one selected from the compounds listed in Group 1 below, but is not limited thereto.

[Group 1]

[1] [2] [3] [4]

[5] [6] [7] [8]

[9] [10] [11] [12]

[13] [14] [15] [16]

[17] [18] [19] [20]

[21] [22] [23] [24]

[25] [26] [27] [28]

[29] [30] [31] [32]

[33] [34] [35] [36]

[37] [38] [39] [40]

[41] [42] [43] [44]

[45] [46] [47] [48]

[49] [50] [51] [52]

[52] [54] [55] [56]

[57] [58] [59] [60]

[61] [62] [63] [64]

[65] [66] [67] [68]

[69] [70] [71] [72]

[73] [74] [75] [76]

[77] [78] [79] [80]

[81] [82] [83] [84]

[85] [86] [87] [88]

[89] [90] [91] [92]

[93] [94] [95] [96]

[97] [98] [99] [100]

[101] [102] [103] [104]

[105] [106] [107] [108]

[109] [110] [111] [112]

[113] [114] [115] [116]

[117] [118] [119] [120]

[121] [122] [123] [124]

[125] [126] [127] [128]

The composition for an organic optoelectronic device according to another embodiment includes a first compound and a second compound, wherein the first compound is the above-described compound for an organic optoelectronic device, and the second compound may be represented by the following Chemical Formula 2 have.

[Formula 2]

In Formula 2,

X ¹ is O, S, NR ^b , CR ^c R ^d or SiR ^e R ^f ,

R ^b , R ^c , R ^d , R ^e , R ^f and R ⁵ are each independently hydrogen, deuterium, a substituted or unsubstituted amine group, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C6 to a C30 aryl group or a substituted or unsubstituted C2 to C30 heterocyclic group,

n5 is one of integers from 1 to 4,

Ring A is any one selected from the rings listed in Group II,

[Group II]

In group II,

* is the connection point,

X ² is O, S, NR ^g , CR ^h R ⁱ or SiR ^j R ^k ,

R ^g , R ^h , R ⁱ , R ^j , R ^k , and R ⁶ to R ¹⁰ are each independently hydrogen, deuterium, a substituted or unsubstituted amine group, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted a cyclic C6 to C30 aryl group or a substituted or unsubstituted C2 to C30 heterocyclic group,

n6, n8 and n10 are each independently one of an integer of 1 to 4,

n7 and n9 are each independently an integer of 1 or 2,

At least one of R ⁵ to R ¹⁰ is a group represented by the following formula (a),

[Formula a]

In the above formula (a),

L ⁴ To L ⁶ are each independently a single bond, or a substituted or unsubstituted C6 to C30 arylene group,

Ar ³ and Ar ⁴ are each independently a substituted or unsubstituted amine group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C2 to C30 heterocyclic group,

* is the connection point.

The second compound may have a structure in which an amine is substituted for carbazole / fused carbazole / fused dibenzofuran / fused dibenzothiophene / fused dibenzosilol, depending on the type and fusion position of the additional benzene ring, for example, the following formula It may be represented by any one of 2-I to Formula 2-X.

[Formula 2-Ⅰ] [Formula 2-Ⅱ]

[Formula 2-Ⅲ] [Formula 2-IV]

[Formula 2-V] [Formula 2-VI]

[Formula 2-VII] [Formula 2-VIII]

[Formula 2-IX] [Formula 2-X]

In Formula 2-I to Formula 2-X,

X ¹ , X ² , R ⁵ to R ¹⁰ and n5 to n10 are the same as described above.

In addition, depending on the substitution direction of the amine group, the second compound may be represented by any one of the following Chemical Formulas 2-IA to 2-XA, Formula 2-IIB to Formula 2-IVB, and Formula 2-IIC to Formula 2-IXC have.

[Formula 2-IA] [Formula 2-IIA]

[Formula 2-ⅢA] [Formula 2-IVA]

[Formula 2-VIA] [Formula 2-VIA]

[Formula 2-VIIA] [Formula 2-VIIIA]

[Formula 2-XA] [Formula 2-XA]

In Formula 2-IA to Formula 2-XA,

X ¹ , X ² , L ⁴ to L ⁶ , Ar ³ , Ar ⁴ , and n6 to n10 are the same as described above,

n5 is one of integers from 1 to 3.

[Formula 2-IIB]

[Formula 2-ⅢB] [Formula 2-IVB]

In Formulas 2-IIB to Formula 2-IVB,

X ¹ , L ⁴ to L ⁶ , Ar ³ , Ar ⁴ , n5 and n7 are the same as described above,

n8 is one of integers from 1 to 3.

[Formula 2-IIC] [Formula 2-IIIC]

[Formula 2-IVC]

In the formula 2-IIC to formula 2-IVC,

X ¹ , L ⁴ To L ⁶ , Ar ³ , Ar ⁴ , n5 and n8 are the same as described above,

n7 is 1.

[Formula 2-VC] [Formula 2-VIC]

[Formula 2-VIIC] [Formula 2-VIIIC]

[Formula 2-ⅨC]

In Formula 2-VC to Formula 2-IXC,

X ¹ , X ² , L ⁴ to L ⁶ , Ar ³ , Ar ⁴ , n5 and n10 are the same as described above,

n9 is 1.

For example, R ⁵ to R ¹⁰ are each independently hydrogen, deuterium, a substituted or unsubstituted C1 to C30 alkyl group, or a substituted or unsubstituted C6 to C30 aryl group.

The second compound according to an embodiment may be represented by Formula 2-IVB or Formula 2-VIIIB.

For example, X ¹ in Formula 2-IVB may be NR ^b .

For example, in Formula 2-XA, X ¹ may be CR ^c R ^d or SiR ^e R ^f , and X ² may be O or S.

Here, R ^b , R ^c , R ^d , R ^e and R ^f may each independently represent a substituted or unsubstituted C1 to C10 alkyl group, or a substituted or unsubstituted C6 to C20 aryl group.

The second compound according to a specific embodiment may be represented by the following Chemical Formula 2-IVB-2 or 2-VIIIB-2.

[Formula 2-IVB-2] [Formula 2-VIIIA-2]

In Formula 2-IVB-2 and Formula 2-VIIIA-2,

L ⁴ To L ⁶ are each independently a single bond or a substituted or unsubstituted phenylene group,

wherein Ar ³ and Ar ⁴ are each independently a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, or a substituted or unsubstituted naphthyl group,

R ⁵ , and R ⁷ to R ¹⁰ are each independently hydrogen, deuterium, a substituted or unsubstituted C1 to C30 alkyl group, or a substituted or unsubstituted C6 to C30 aryl group,

n7 and n9 are each independently an integer of 1 or 2,

n8 and n10 are each independently one of an integer of 1 to 3,

In Formula 2-IVB-2, X ¹ is NR ^b , O or S,

n5 of Formula 2-IVB-2 is one of integers from 1 to 4,

In Formula 2-VIIIA-2, X ¹ is CR ^c R ^d or SiR ^e R ^f ,

X ² of Formula 2-VIIIA-2 is O or S,

n5 in Formula 2-VIIIA-2 is one of integers from 1 to 3,

R ^b , R ^c , R ^d , R ^e and R ^f are each independently a substituted or unsubstituted C1 to C30 alkyl group, or a substituted or unsubstituted C6 to C30 aryl group.

For example, L ⁵ and L ⁶ may each independently represent a single bond, a substituted or unsubstituted phenylene group, or a substituted or unsubstituted biphenylene group.

For example, Ar ³ and Ar ⁴ are each independently a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted terphenyl group, a substituted or unsubstituted naphthyl group, or a substituted or unsubstituted phenantre A nyl group, a substituted or unsubstituted triphenylene group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted dibenzothiophenyl group, It may be a substituted or unsubstituted benzofuranofluorenyl group, or a substituted or unsubstituted benzothiophenefluorenyl group.

For example, the second compound may be one selected from the compounds listed in Group 2, but is not limited thereto.

[Group 2]

[2-1] [2-2] [2-3] [2-4]

[2-5] [2-6] [2-7]

[2-8] [2-9]

[2-10] [2-11] [2-12]

[2-13] [2-14] [2-15]

[2-16] [2-17]

[2-18] [2-19] [2-20]

[2-21] [2-22]

[2-23] [2-24] [2-25] [2-26]

[2-27] [2-28] [2-29] [2-30]

[2-31] [2-32] [2-33] [2-34]

[2-35] [2-36] [2-37] [2-38]

[2-39] [2-40]

[2-41] [2-42] [2-43] [2-44]

[2-45] [2-46] [2-47] [2-48]

[2-49] [2-50]

[2-51] [2-52]

[2-53] [2-54] [2-55] [2-56] [2-57]

[2-58] [2-59] [2-60]

[2-61] [2-62] [2-63] [2-64]

[2-65] [2-66] [2-67] [2-68]

[2-69] [2-70] [2-71] [2-72]

[2-73] [2-74] [2-75] [2-76]

[2-77] [2-78] [2-79] [2-80]

[2-81] [2-82] [2-83]

[2-84] [2-85] [2-86]

[2-87] [2-88] [2-89]

[2-90] [2-91]

[2-92] [2-93]

[2-94] [2-95] [2-96] [2-97]

[2-98] [2-99] [2-100] [2-101]

[2-102] [2-103] [2-104] [2-105]

[2-106] [2-107] [2-108] [2-109]

[2-110] [2-111] [2-112] [2-113]

[2-114] [2-115] [2-116] [2-117]

[2-118] [2-119] [2-120] [2-121]

[2-122] [2-123] [2-124] [2-125]

[2-126] [2-127] [2-128] [2-129]

[2-130] [2-131] [2-132] [2-133]

[2-134] [2-135] [2-136] [2-137]

[2-138] [2-139] [2-140] [2-141]

[2-142] [2-143] [2-144] [2-145]

[2-146] [2-147] [2-148] [2-149]

[2-150] [2-151] [2-152] [2-153]

[2-154] [2-155] [2-156] [2-157]

[2-158] [2-159] [2-160] [2-161]

[2-162] [2-163] [2-164] [2-165]

[2-166] [2-167] [2-168] [2-169]

[2-170] [2-171] [2-172] [2-173]

[2-174] [2-175] [2-176] [2-177]

[2-178] [2-179] [2-180] [2-181]

[2-182] [2-183] [2-184] [2-185]

[2-186] [2-187] [2-188] [2-189]

[2-190] [2-191] [2-192] [2-193]

[2-194] [2-195] [2-196] [2-197]

[2-198] [2-199] [2-200] [2-201]

[2-202] [2-203] [2-204] [2-205]

[2-206] [2-207] [2-208] [2-209]

[2-210] [2-211] [2-212] [2-213]

[2-214] [2-215] [2-216] [2-217]

[2-218] [2-219] [2-220] [2-221]

[2-222] [2-223]

The first compound and the second compound may be included, for example, in a weight ratio of 1:99 to 99:1. By being included in the above range, it is possible to implement bipolar characteristics by matching an appropriate weight ratio using the electron transport ability of the first compound and the hole transport ability of the second compound to improve efficiency and lifespan. Within the above range, for example, it may be included in a weight ratio of about 10:90 to 90:10, about 20:80 to 80:20, such as about 20:80 to about 70:30, about 20:80 to about 60:40, And it may be included in a weight ratio of about 30:70 to about 60:40. As a specific example, it may be included in a weight ratio of 40:60, 50:50, or 60:40.

It may further include one or more compounds in addition to the first compound and the second compound described above.

The compound for an organic optoelectronic device or the composition for an organic optoelectronic device described above may be a composition further comprising a dopant.

The dopant may be for example a phosphorescent dopant, for example a red, green or blue phosphorescent dopant, for example a red or green phosphorescent dopant.

A dopant is a material that emits light by being mixed in a small amount in a compound or composition for an organic optoelectronic device. In general, a material such as a metal complex that emits light by multiple excitation excitation to a triplet state or more may be used. can The dopant may be, for example, an inorganic, organic, or organic-inorganic compound, and may include one or two or more kinds.

Examples of the dopant include a phosphorescent dopant, and examples of the phosphorescent dopant include Ir, Pt, Os, Ti, Zr, Hf, Eu, Tb, Tm, Fe, Co, Ni, Ru, Rh, Pd, or a combination thereof. and organometallic compounds containing them. The phosphorescent dopant may be, for example, a compound represented by the following Chemical Formula Z, but is not limited thereto.

[Formula Z]

L ⁷ MX ³

In Formula Z, M is a metal, and L ⁷ and X ³ are the same as or different from each other and are ligands forming a complex with M.

M may be, for example, Ir, Pt, Os, Ti, Zr, Hf, Eu, Tb, Tm, Fe, Co, Ni, Ru, Rh, Pd or a combination thereof, and L ⁷ and X ³ are, for example, bi It may be a dentate ligand.

Examples of the ligands represented by L ⁷ and X ³ may be selected from the formulas listed in Group A, but are not limited thereto.

[Group A]

In group A,

R ³⁰⁰ to R ³⁰² are each independently hydrogen, deuterium, a halogen substituted or unsubstituted C1 to C30 alkyl group, a C1 to C30 alkyl substituted or unsubstituted C6 to C30 aryl group or halogen,

R ³⁰³ to R ³²⁴ are each independently hydrogen, deuterium, halogen, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted C3 to C30 cycloalkyl group, substituted or an unsubstituted C2 to C30 alkenyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C1 to C30 heteroaryl group, a substituted or unsubstituted C1 to C30 amino group, a substituted or unsubstituted C6 to C30 arylamino group, SF ₅ , a trialkylsilyl group having a substituted or unsubstituted C1 to C30 alkyl group, a dialkylarylsilyl group having a substituted or unsubstituted C1 to C30 alkyl group and a C6 to C30 aryl group, or It is a triarylsilyl group having a substituted or unsubstituted C6 to C30 aryl group.

For example, it may include a dopant represented by the following Chemical Formula V.

[Formula V]

In the above formula (V),

R ¹⁰¹ to R ¹¹⁶ are each independently hydrogen, deuterium, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C6 to C20 aryl group, or —SiR ¹³² R ¹³³ R ¹³⁴ ;

wherein R ¹³² to R ¹³⁴ are each independently a C1 to C6 alkyl group,

At least one of R ¹⁰¹ to R ¹¹⁶ is a functional group represented by the following formula IV-1,

L ¹⁰⁰ is a bidentate ligand of a monovalent anion, and is a ligand that coordinates to iridium through a lone pair of electrons of carbon or heteroatom,

m1 and m2 are each independently any one of an integer of 0 to 3, m1 + m2 is any one of an integer of 1 to 3,

[Formula V-1]

In Formula V-1,

R ¹³⁵ to R ¹³⁹ are each independently hydrogen, deuterium, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C6 to C20 aryl group, or —SiR ¹³² R ¹³³ R ¹³⁴ ;

* means a part connected to a carbon atom.

For example, a dopant represented by the following Chemical Formula Z-1 may be included.

[Formula Z-1]

In the above formula (Z-1), rings A, B, C, and D each independently represent a 5- or 6-membered carbocyclic or heterocyclic ring;

R ^A , ^{RB , R C ,} and R ^D each independently represent mono-, di-, tri-, or tetra-substituted, or unsubstituted;

L ^B , L ^C , and L ^D are each a direct bond, BR, NR, PR, O, S, Se, C=O, S=O, SO ₂ , CRR′, SiRR′, GeRR′, and combinations thereof independently selected from the group consisting of;

When nA is 1, L ^E is a direct bond, BR, NR, PR, O, S, Se, C=O, S=O, SO ₂ , CRR', SiRR', GeRR', and combinations thereof. is selected from; when nA is 0, L ^E is absent;

R ^A , ^{RB , R C ,} R ^D , R , and R' are each hydrogen, deuterium, halogen, an alkyl group, a cycloalkyl group, a heteroalkyl group, an arylalkyl group, an alkoxy group, an aryloxy group, an amino group, a silyl group, an alkenyl group , cycloalkenyl group, heteroalkenyl group, alkynyl group, aryl group, heteroaryl group, acyl group, carbonyl group, carboxylic acid group, ester group, nitrile group, isonitrile group, sulfanyl group, sulfinyl group, sulfonyl group, phosphino group independently selected from the group consisting of , and combinations thereof; any adjacent R ^A , R ^B , R ^C , R ^D , R , and R′ are optionally joined to form a ring; X ^B , X ^C , X ^D , and X ^E are each independently selected from the group consisting of carbon and nitrogen; Q ¹ , Q ² , Q ³ , and Q ⁴ each represent oxygen or a direct bond.

The dopant according to an embodiment may be a platinum complex, for example, it may be represented by the following Chemical Formula VI.

[Formula Ⅵ]

In the above formula (VI),

X ¹⁰⁰ is selected from O, S and NR ¹³¹ ,

R ¹¹⁷ to R ¹³¹ are each independently hydrogen, deuterium, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C6 to C20 aryl group, or —SiR ¹³² R ¹³³ R ¹³⁴ ;

wherein R ¹³² to R ¹³⁴ are each independently a C1 to C6 alkyl group,

At least one of R ¹¹⁷ to R ¹³¹ is -SiR ¹³² R ¹³³ R ¹³⁴ or a tert-butyl group.

Hereinafter, an organic optoelectronic device to which the above-described compound for an organic optoelectronic device or a composition for an organic optoelectronic device is applied will be described.

The organic optoelectronic device is not particularly limited as long as it is a device capable of converting electrical energy and optical energy, and examples thereof include an organic photoelectric device, an organic light emitting device, an organic solar cell, and an organic photosensitive drum.

Herein, an organic light emitting device, which is an example of an organic optoelectronic device, will be described with reference to the drawings.

1 is a cross-sectional view illustrating an organic light emitting diode according to an exemplary embodiment.

Referring to FIG. 1 , an organic light emitting device 100 according to an embodiment includes an anode 120 and a cathode 110 facing each other, and an organic layer 105 positioned between the anode 120 and the cathode 110 . include

The anode 120 may be made of, for example, a conductor having a high work function to facilitate hole injection, and may be made of, for example, a metal, a metal oxide, and/or a conductive polymer. The anode 120 may include, for example, a metal such as nickel, platinum, vanadium, chromium, copper, zinc, gold, or an alloy thereof; metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); combinations of metals and oxides such as ZnO and Al or SnO ₂ and Sb; conductive polymers such as poly(3-methylthiophene), poly(3,4-(ethylene-1,2-dioxy)thiophene) (polyehtylenedioxythiophene: PEDOT), polypyrrole, and polyaniline, but the present invention is not limited thereto. it is not

The cathode 110 may be made of, for example, a conductor having a low work function to facilitate electron injection, and may be made of, for example, a metal, a metal oxide, and/or a conductive polymer. The negative electrode 110 may include, for example, a metal such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, lead, cesium, barium, or an alloy thereof; and a multilayer structure material such as LiF/Al, LiO ₂ /Al, LiF/Ca, LiF/Al, and BaF ₂ /Ca, but is not limited thereto.

The organic layer 105 may include the aforementioned compound for an organic optoelectronic device or a composition for an organic optoelectronic device.

The organic layer 105 may include the emission layer 130 , and the emission layer 130 may include the aforementioned compound for an organic optoelectronic device or a composition for an organic optoelectronic device.

The composition for an organic optoelectronic device further comprising a dopant may be, for example, a red light-emitting composition.

The emission layer 130 may include, for example, the above-described first compound for an organic optoelectronic device and the second compound for an organic optoelectronic device, respectively, as a phosphorescent host.

The organic layer may further include a charge transport region in addition to the emission layer.

The charge transport region may be, for example, the hole transport region 140 .

The hole transport region 140 may further increase hole injection and/or hole mobility between the anode 120 and the emission layer 130 and block electrons. Specifically, the hole transport region 140 may include a hole transport layer between the anode 120 and the light emitting layer 130 and a hole transport auxiliary layer between the light emitting layer 130 and the hole transport layer. At least one of the listed compounds may be included in at least one of the hole transport layer and the hole transport auxiliary layer.

[Group E]

In the hole transport region 140, in addition to the compounds described above, known compounds described in US5061569A, JP1993-009471A, WO1995-009147A1, JP1995-126615A, JP1998-095973A, and the like, and compounds having a similar structure may also be used.

Also, the charge transport region may be, for example, the electron transport region 150 .

The electron transport region 150 may further increase electron injection and/or electron mobility between the cathode 110 and the emission layer 130 and block holes.

Specifically, the electron transport region 150 may include an electron transport layer between the cathode 110 and the light emitting layer 130, and an electron transport auxiliary layer between the light emitting layer 130 and the electron transport layer. At least one of the listed compounds may be included in at least one of the electron transport layer and the electron transport auxiliary layer.

[Group F]

One embodiment may be an organic light emitting device including a light emitting layer as an organic layer.

Another embodiment may be an organic light emitting device including a light emitting layer and a hole transport region as an organic layer.

Another embodiment may be an organic light emitting device including a light emitting layer and an electron transport region as an organic layer.

As shown in FIG. 1 , the organic light emitting device according to an embodiment of the present invention may include a hole transport region 140 and an electron transport region 150 in addition to the emission layer 130 as the organic layer 105 .

On the other hand, the organic light emitting device may further include an electron injection layer (not shown), a hole injection layer (not shown), etc. in addition to the light emitting layer as the above-described organic layer.

After forming an anode or cathode on a substrate, the organic light emitting device 100 forms an organic layer by a dry film deposition method such as vacuum deposition, sputtering, plasma plating and ion plating, etc., and then a cathode or a It can be manufactured by forming an anode.

The above-described organic light emitting device may be applied to an organic light emitting display device.

The above-described embodiment will be described in more detail through the following examples. However, the following examples are for illustrative purposes only and do not limit the scope of rights.

Hereinafter, unless otherwise specified, starting materials and reactants used in Examples and Synthesis Examples were purchased from Sigma-Aldrich, TCI, Tokyo chemical industry, or P&H tech, or synthesized through a known method.

(Production of compounds for organic optoelectronic devices)

The compound presented as a more specific example of the compound of the present invention was synthesized through the following steps.

Synthesis Example 1: Synthesis of Intermediate A

[Scheme 1]

Step 1: Synthesis of Intermediate A-1

In a round bottom flask, 40.0 g (182.27 mmol) of 2-bromo-3-chlorobenzaldehyde, 34.48 g (200.49 mmol) of naphthalen-1-ylboronic acid, 8.93 g (10.94 mmol) of Pd(dppf)Cl ₂ , 75.57 g of K ₂ CO ₃ (546.80 mmol) was suspended in 400 m of Dioxane/200 ml of distilled water and stirred at room temperature for 12 hours. After completion of the reaction, the reaction was concentrated, extracted with methylene chloride, and the organic layer was subjected to silicagel column to obtain 41.41 g (yield 85%) of intermediate A-1.

Step 2: Synthesis of Intermediate A-2

Intermediate A-1 41.4 g (155.29 mmol) and (methoxymethyl)triphenylphosphonium chloride 58.55 g (170.82 mmol) were suspended in 400 ml of THF, and 20.91 g (186.34 mmol) of Potassium tert-Butoxide was added thereto, followed by stirring at room temperature for 12 hours. . After completion of the reaction, 500 ml of distilled water was added, followed by extraction, and the organic layer was concentrated and re-extracted with Methylene Chloride. Magnesium Sulfate was added to the organic layer, stirred for 30 minutes, filtered, and the filtrate was concentrated. After adding 100 ml of Methylene Chloride to the concentrated filtrate, 20 ml of Methanesulfonic acid was added, followed by stirring for 1 hour. After completion of the reaction, the resulting solid was filtered, washed with distilled water and methyl alcohol, and dried to obtain 20.5 g (50% yield) of Intermediate A-2.

Step 3: Synthesis of Intermediate A

Intermediate A-2 10.0 g (38.06 mmol), Bis(pinacolato)diboron 12.56 g (49.48 mmol), Pd ₂ (dba) ₃ 2.09 g (2.28 mmol), P(Cy) ₃ 2.56 g (9.13 mmol), and KOAc 11.21 g (114.18 mmol) was suspended in 100 ml of Xylene and stirred under reflux for 12 hours. After completion of the reaction, the reaction solvent was removed with a rotary evaporator, extracted with methylene chloride, and the organic layer was columned with Hexane: EA = 4 : 1 (v/v) to obtain 13 g (96% Yield) of Intermediate A.

Intermediate B, Intermediate C, and Intermediate D were prepared by using 2-bromo-4-chlorobenzaldehyde, 2-bromo-5-chlorobenzaldehyde, and 2-bromo-6-chlorobenzaldehyde instead of 2-bromo-3-chlorobenzaldehyde in step 1 of Synthesis Example 1. It was synthesized in the same manner as in Synthesis Example 1, except that the reaction was carried out using each.

Synthesis Example 2: Synthesis of compound 12

[Scheme 2]

Intermediate A 10.42 g (26.48 mmol), int-1 9.00 g (22.07 mmol), Pd(PPh ₃ ) ₄ 0.76 g (0.66 mmol), and K ₂ CO ₃ 9.15 g (66.20 mmol) were placed in a round bottom flask and THF After dissolving in 150 mL and 75 mL of distilled water, it is heated to reflux under nitrogen atmosphere. After 12 hours, the reaction solution is cooled, the water layer is removed, and the organic layer is dried under reduced pressure. After washing the obtained solid with water and methanol, the solid was recrystallized with 200 mL of Toluene to obtain 10.0 g (76% yield) of Compound 12.

LC/MS calculated for: C43H25N3O Exact Mass: 599.20 found for 599.84 [M+H]

Synthesis Examples 3 to 15

In Synthesis Example 2, each compound according to Table 1 was synthesized by reacting in the same manner as in Synthesis Example 2 using Int A and/or Int B instead of Intermediate A and/or int-1, respectively.

Synthesis example	Int A	Int B	final product	yield (transference number)	of the final product physical data
Synthesis Example 3	Intermediate B	int-2	compound 32	7.94 g, (75%)	LC/MS calculated for: C43H27N3 Exact Mass: 585.22 found for 585.86 [M+H]
Synthesis Example 4	Intermediate B	int-3	compound 33	8.38 g, (69%)	LC/MS calculated for: C39H23N3O Exact Mass: 549.18 found for 549.85 [M+H]
Synthesis Example 5	Intermediate B	int-4	compound 36	8.69 g, (71%)	LC/MS calculated for: C39H24N4 Exact Mass: 548.20 found for 548.75 [M+H]
Synthesis Example 6	Intermediate B	int-1	compound 40	7.64 g, (76%)	LC/MS calculated for: C43H25N3O Exact Mass: 599.20 found for 599.68 [M+H]
Synthesis Example 7	Intermediate B	int-5	compound 43	5.41 g, (70%)	LC/MS calculated for: C43H27N3 Exact Mass: 585.22 found for 585.73 [M+H]
Synthesis Example 8	Intermediate C	int-2	compound 60	6.81 g, (75%)	LC/MS calculated for: C43H27N3 Exact Mass: 585.22 found for 585.87 [M+H]
Synthesis Example 9	Intermediate C	int-3	compound 61	7.51 g, (65%)	LC/MS calculated for: C39H23N3O Exact Mass: 549.18 found for 549.65 [M+H]
Synthesis Example 10	Intermediate D	int-2	compound 88	6.43 g, (75%)	LC/MS calculated for: C43H27N3 Exact Mass: 585.22 found for 585.89 [M+H]
Synthesis Example 11	Intermediate D	int-3	compound 89	6.09 g, (68%)	LC/MS calculated for: C39H23N3O Exact Mass: 549.18 found for 549.76 [M+H]
Synthesis Example 12	Intermediate D	int-4	compound 92	7.47 g, (79%)	LC/MS calculated for: C39H24N4 Exact Mass: 548.20 found for 549.24 [M+H]
Synthesis Example 13	Intermediate D	int-6	compound 97	5.74 g, (77%)	LC/MS calculated for: C43H27N3 Exact Mass: 585.22 found for 586.13 [M+H]
Synthesis Example 14	Intermediate D	int-5	compound 99	7.42 g, (77%)	LC/MS calculated for: C43H27N3 Exact Mass: 585.22 found for 586.15 [M+H]
Synthesis Example 15	Intermediate D	int-7	compound 103	8.55 g, (77%)	LC/MS calculated for: C49H29N3O Exact Mass: 675.23 found for 676.11 [M+H]

<Int A>

<Int B>

Comparative Synthesis Example 1: Synthesis of Compound V1

[Scheme 3]

Step 1: Synthesis of Intermediate V1-1

In a round-bottom flask, 40.0 g (216.19 mmol) of 2-bromobenzaldehyde, 40.90 g (237.81 mmol) of naphthalen-1-ylboronic acid, 10.59 g (12.97 mmol) of Pd(dppf)Cl ₂ , and 89.64 g (648.58 mmol) of K ₂ CO ₃ . ) was suspended in 500 m of Dioxane/250 ml of distilled water and stirred at room temperature for 12 hours. After completion of the reaction, the reaction was concentrated, extracted with methylene chloride, and the organic layer was subjected to silicagel column to obtain 41.01 g (yield 82%) of intermediate V1-1.

Step 2: Synthesis of Intermediate V1-2

Intermediate V1-1 40.70 g (175.22mmol) and (methoxymethyl)triphenylphosphonium chloride 66.07 g (192.74 mmol) were suspended in 600 ml of THF, 23.59 g (210.26 mmol) of Potassium tert-Butoxide was added thereto, followed by stirring at room temperature for 12 hours. . After completion of the reaction, 500 ml of distilled water was added, followed by extraction, and the organic layer was concentrated and re-extracted with Methylene Chloride, and the organic layer was stirred for 30 minutes after addition of Magnesium Sulfate, filtered and the filtrate was concentrated. To the concentrated filtrate, 350 ml of methylene chloride was added, 23 ml of methanesulfonic acid was added, and the mixture was stirred for 1 hour. After completion of the reaction, the resulting solid was filtered, washed with distilled water and methyl alcohol, and dried to obtain 20.0 g (50% yield) of intermediate V1-2.

Step 3: Synthesis of intermediate V1-3

9.0 g (39.42 mmol) of intermediate V1-2 is dissolved in chloroform solvent (300 mL). 4.45 mL (86.72 mmol) of Br ₂ is slowly added dropwise. After 5 hours, water was added to terminate the reaction, and anhydrous magnesium sulfate was added to the organic layer obtained by extraction with dichloromethane to remove water, followed by silica filtration. After removing the obtained organic solvent through distillation under reduced pressure, it was recrystallized from dichloromethane (100 mL) and methanol (300 mL) to obtain 12.94 g (85 % Yield) of Intermediate V1-3.

Step 4: Synthesis of Intermediate V1-4

Intermediate V1-3 15.2 g (39.37 mmol), Bis(pinacolato)diboron 23.99 g (94.49 mmol), Pd ₂ (dba) ₃ 2.16 g (2.36 mmol), P(Cy) ₃ 2.65 g (9.45 mmol), and KOAc 11.59 g (118.11 mmol) was suspended in 100 ml of Xylene and stirred under reflux for 12 hours. After completion of the reaction, the reaction solvent was removed with a rotary evaporator, extracted with methylene chloride, and the organic layer was columned with Hexane: EA = 4 : 1 (v/v) to obtain 16.0 g (85% Yield) of intermediate V1-4.

Step 5: Synthesis of compound V1

In a round bottom flask, 16.00 g (33.32 mmol) of intermediate V1-4, 9.41 g (73.30 mmol) of 2-chloro-1,3,5-triazine, 1.16 g (1.00 mmol) of Pd(PPh ₃ ) ₄ , and K ₂ CO ₃ Add 13.81 g (99.95 mmol), dissolve in 150 mL of THF and 75 mL of distilled water, and heat to reflux under nitrogen atmosphere. After 12 hours, the reaction solution is cooled, the water layer is removed, and the organic layer is dried under reduced pressure. After washing the obtained solid with water and methanol, the solid was recrystallized with 100 mL of Toluene to obtain 9.0 g (70% Yield) of Compound V1.

LC/MS calculated for: C24H14N6 Exact Mass: 386.13 found for 386.89 [M+H]

Comparative Synthesis Example 2: Synthesis of Compound V2

[Scheme 4]

In a round bottom flask, 10.00 g (20.82 mmol) of intermediate V1-4, 15.79 g (45.81 mmol) of 4-bromo-2,6-diphenylpyridine, 0.72 g (0.62 mmol) of Pd(PPh ₃ ) ₄ , and 8.63 of K ₂ CO ₃ g (62.47 mmol) is added, dissolved in 100 mL of THF and 50 mL of distilled water, and then heated to reflux under nitrogen atmosphere. After 12 hours, the reaction solution is cooled, the water layer is removed, and the organic layer is dried under reduced pressure. After washing the obtained solid with water and methanol, the solid was recrystallized with 100 mL of Toluene to obtain 10.0 g (70% Yield) of Compound V2.

LC/MS calculated for: C52H34N2 Exact Mass: 686.27 found for 686.84 [M+H]

Comparative Synthesis Example 3: Synthesis of Compound V3

[Scheme 5]

Step 1: Synthesis of intermediate V3-1

In a round-bottom flask, 9.50 g (19.78 mmol) of intermediate V1-4, 3.32 g (19.78 mmol) of bromobenzene, 0.69 g (0.59 mmol) of Pd(PPh ₃ ) ₄ , and 8.20 g (59.35 mmol) of K ₂ CO ₃ were placed in THF After dissolving in 100 mL of distilled water and 50 mL of distilled water, heat to reflux under nitrogen atmosphere. After completion of the reaction, the reaction solvent was removed with a rotary evaporator, extracted with methylene chloride, and the organic layer was columned with Hexane: EA = 4 : 1 (v/v) to obtain 6.5 g (76% Yield) of intermediate V3-1.

Step 2: Synthesis of compound V3

In a round bottom flask, 6.5 g (15.10 mmol) of intermediate V3-1, 2.68 g (15.86 mmol) of 2-bromopyridine, 0.52 g (0.45 mmol) of Pd(PPh ₃ ) ₄ , and 6.26 g (45.31 mmol) of K ₂ CO ₃ were added to a round bottom flask. After dissolving in 100 mL of THF and 50 mL of distilled water, heat to reflux under nitrogen atmosphere. After 12 hours, the reaction solution is cooled, the water layer is removed, and the organic layer is dried under reduced pressure. After washing the obtained solid with water and methanol, the solid was recrystallized with 100 mL of toluene to obtain 4.5 g (78% yield) of compound V3.

LC/MS calculated for: C29H19N Exact Mass: 381.15 found for 381.95 [M+H]

Synthesis Example 16: Synthesis of compound A-84

[Scheme 7]

a) Synthesis of intermediate 2-1a

Put phenylhydrazinehydrochloride (70.0 g, 484.1 mmol) and 7-bromo-3,4-dihydro-2H-naphthalen-1-one (108.9 g, 484.1 mmol) in a round-bottom flask and dissolve in ethanol (1200 ml). After slowly adding 60 mL of hydrochloric acid dropwise at room temperature, the mixture was stirred at 90° C. for 12 hours. When the reaction is complete, the solvent is removed under reduced pressure, followed by extraction with an excess of EA. The organic solvent was removed under reduced pressure, stirred in a small amount of methanol, and filtered to obtain 95.2 g (66%) of Intermediate 2-1a.

b) synthesis of intermediate 2-1b

Intermediate 2-1a (95.2 g, 319.3 mmol), and 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (108.7 g, 478.9 mmol) were placed in a round-bottom flask and dissolved in toluene (600 ml). Stir at 80° C. for 12 hours. When the reaction was completed, 41.3 g (44%) of Intermediate 2-1b was obtained by using column chromatography after removing the reaction solvent.

c) synthesis of intermediate 2-1c

Intermediate 2-1b (41.3 g, 139.0 mmol), iodobenzene (199.2 g, 976.0 mmol), CuI (5.31 g, 28.0 mmol), K ₂ CO ₃ (28.9 g, 209.0 mmol), and 1,10-phenanthroline (5.03) g, 28.0 mmol) in a round bottom flask and dissolved in DMF (500 ml). Stir at 180° C. for 12 hours. When the reaction is completed, the reaction solvent is removed under reduced pressure, dissolved in dichloromethane, and filtered through silica gel. After concentration in dichloromethane and recrystallization from hexane, 39.0 g (75%) of Intermediate 2-1c was obtained.

d) Synthesis of compound A-84

5.0 g (13.46 mmol) of intermediate 2-1c and 4.41 g (13.46 mmol) of amine intermediate 2-1d, 1.94 g (20.19 mmol) of sodium t-butoxide, and Tri-tert-butylphosphine ( butylphosphine) 0.54 g (1.35 mmol) was dissolved in 100 ml of toluene, 0.37 g (0.4 mmol) of Pd(dba) ₂ was added, and the mixture was stirred under reflux for 12 hours under a nitrogen atmosphere. After completion of the reaction, extraction was performed with toluene and distilled water, the organic layer 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 / dichloromethane (2: 1 volume ratio) to obtain 6.4 g (yield 82.0%) of Compound A-84.

Synthesis Example 17: Synthesis of compound 2-92

[Scheme 8]

a) Synthesis of intermediate 2-92a

It was synthesized with reference to the KR10-1423173 B1 patent.

b) synthesis of compound 2-92

5.0 g (16.93 mmol) of intermediate 2-92a and 5.4 g (16.93 mmol) of amine intermediate 2-92b, 2.44 g (25.39 mmol) of sodium t-butoxide, and Tri-tert-butylphosphine ( butylphosphine) 0.68 g (1.69 mmol) was dissolved in 100 ml of toluene, 0.47 g (0.51 mmol) of Pd(dba) ₂ was added, and the mixture was stirred under reflux for 12 hours under a nitrogen atmosphere. After completion of the reaction, extraction was performed with toluene and distilled water, the organic layer 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 normal hexane/dichloromethane (2:1 volume ratio) to obtain 8.2 g (yield 84.0%) of the target compound 2-92.

(Production of organic light emitting device)

Example 1

A glass substrate coated with a thin film of ITO (Indium tin oxide) was washed with distilled water and ultrasonic waves. After washing with distilled water, ultrasonic cleaning was performed with a solvent such as isopropyl alcohol, acetone, methanol, etc., dried and transferred to a plasma cleaner. After cleaning the substrate using oxygen plasma for 10 minutes, the substrate was transferred to a vacuum evaporator. Using the prepared ITO transparent electrode as an anode, compound A doped with 3% NDP-9 (commercially available from Novaled) was vacuum-deposited on the top of the ITO substrate to form a hole injection layer with a thickness of 100 Å, and Compound A was deposited thereon to a thickness of 1300 Å to form a hole transport layer. Compound B was deposited on the hole transport layer to a thickness of 700 Å to form a hole transport auxiliary layer. Compound 32 obtained in Synthesis Example 3 was used as a host on the hole transport auxiliary layer, and [Ir(piq) ₂ acac] was doped at 2 wt% as a dopant to form an emission layer with a thickness of 400 Å by vacuum deposition. Then, compound C was deposited on the light emitting layer to a thickness of 50 Å to form an electron transport auxiliary layer, and compound D and Liq were simultaneously vacuum deposited at a weight ratio of 1:1 to form an electron transport layer having a thickness of 300 Å. An organic light emitting diode was manufactured by sequentially vacuum-depositing 15 Å of LiQ and 1,200 Å of Al on the electron transport layer to form a cathode.

The organic light emitting device has a structure having a five-layer organic thin film layer, specifically as follows.

ITO / Compound A (3% NDP-9 doping, 100 Å) / Compound A (1300 Å) / Compound B (700 Å) / EML [Compound 32: [Ir(piq) ₂ acac] = 98: 2 (w/w]] (400 Å) / Compound C (50 Å) / Compound D: Liq (300 Å) / LiQ (15 Å) / Al (1200 Å) was prepared.

Compound A: N-(biphenyl-4-yl)-9,9-dimethyl-N-(4-(9-phenyl-9H-carbazol-3-yl)phenyl)-9H-fluoren-2-amine

Compound B: N,N-di([1,1'-biphenyl]-4-yl)-7,7-dimethyl-7H-fluoreno[4,3-b]benzofuran-10-amine

Compound C: 2-(3-(3-(9,9-dimethyl-9H-fluoren-2-yl)phenyl)phenyl)-4,6-diphenyl-1,3,5-triazine

Compound D: 8-(4-(4,6-di(naphthalen-2-yl)-1,3,5-triazin-2-yl)phenyl)quinoline

Examples 2 to 8 and Comparative Examples 1 to 3

Devices of Examples 2 to 8 and Comparative Examples 1 to 3 were manufactured in the same manner as in Example 1, except that the host was changed as shown in Table 2 below.

Examples 9 to 20 and Comparative Examples 4 to 6

The host was changed as shown in Table 3 below, and the first host and the second host were mixed in a weight ratio of 5:5, and in Examples 9 to 20 and Comparative Examples 4 to 6 in the same manner as in Example 1 above. The device was fabricated.

evaluation

The luminous efficiency and lifespan characteristics of the organic light emitting diodes according to Examples 1 to 20 and Comparative Examples 1 to 6 were evaluated. Specific measurement methods are as follows, and the results are shown in Tables 2 and 3.

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

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

(2) Measurement of luminance change according to voltage change

For the manufactured organic light emitting device, the luminance was measured at that time using a luminance meter (Minolta Cs-1000A) while increasing the voltage from 0V to 10V, and results were obtained.

(3) Measurement of luminous efficiency

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

Relative values based on the luminous efficiency of Comparative Examples 1 and 4 were calculated and shown in Tables 2 and 3 below.

(4) Lifetime measurement

For the manufactured organic light emitting device, the devices of Examples 1 to 20 and Comparative Examples 1 to 6 emit light at an initial luminance (cd/m ² ) of 6,000 cd/m ² using a polaronics lifetime measurement system, and time elapses The time when the luminance decreased to 95% compared to the initial luminance was measured as the T95 lifetime.

The relative values based on the T95 lifetime of Comparative Examples 1 and 4 were calculated and shown in Tables 2 and 3 below.

division	sole host	T95 Lifetime (%)	efficiency (%)
Example 1	32	195	118
Example 2	33	220	120
Example 3	36	198	118
Example 4	43	180	120
Example 5	61	160	116
Example 6	89	185	122
Example 7	92	180	118
Example 8	99	154	123
Comparative Example 1	103	152	121
Comparative Example 2	V1	100	100
Comparative Example 3	V2	105	107
Comparative Example 4	V3	100	75

division	host		T95 Life (%)	efficiency(%)
	first host	second host
Example 9	33	A-84	250	118
Example 10	36	A-84	235	115
Example 11	43	A-84	196	117
Example 12	61	A-84	187	115
Example 13	89	A-84	192	120
Example 14	92	A-84	186	116
Example 15	33	2-92	192	120
Example 16	36	2-92	180	118
Example 17	43	2-92	161	122
Example 18	61	2-92	175	115
Example 19	89	2-92	182	121
Example 20	92	2-92	180	116
Comparative Example 4	V1		A-84	100	100
Comparative Example 5	V2	A-84	106	107
Comparative Example 6	V2	2-92	84	108

Referring to Tables 2 and 3, when the compound according to the present invention is used as a host in combination with a single host and a second host, it can be confirmed that the efficiency and lifespan are significantly improved compared to that using the comparative compound.

Although the embodiments have been described in detail, the scope of the present invention is not limited thereto, and various modifications and improvements by those skilled in the art using the basic concept of the present invention defined in the following claims also fall within the scope of the present invention. will be.

Claims (14)

1. A compound for an organic optoelectronic device represented by the following Chemical Formula 1:

   [Formula 1]

   

   In Formula 1,

   Z ¹ to Z ³ are each independently N or CR ^a ,

   At least two of Z ¹ to Z ³ are N,

   L ¹ to L ³ are each independently a single bond, or a substituted or unsubstituted C6 to C30 arylene group,

   Ar ¹ and Ar ² are each independently a substituted or unsubstituted C6 to C30 aryl group or a substituted or unsubstituted C2 to C30 heterocyclic group,

   R ^a and R ¹ to R ⁴ are each independently hydrogen, deuterium, a substituted or unsubstituted C1 to C20 alkyl group, or a substituted or unsubstituted C6 to C20 aryl group,

   n1 is one of integers from 1 to 3,

   n2 and n3 are each independently an integer of 1 or 2,

   n4 is one of integers from 1 to 4.
2. According to claim 1,

   Formula 1 is a compound for an organic optoelectronic device, which is represented by any one of the following Formulas 1-1 to 1-4:

   [Formula 1-1]

   

   [Formula 1-2]

   

   [Formula 1-3]

   

   [Formula 1-4]

   

   In Formulas 1-1 to 1-4,

   Z ¹ to Z ³ , L ¹ to L ³ , Ar ¹ , Ar ² , R ¹ to R ⁴ and n1 to n4 are the same as in claim 1 .
3. According to claim 1,

   The L ¹ to L ³ are each independently a single bond, a substituted or unsubstituted phenylene group, or a substituted or unsubstituted naphthylene group, a compound for an organic optoelectronic device.
4. According to claim 1,

   Wherein Ar ¹ and Ar ² are each independently a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted phenanthrenyl group, a substituted or unsubstituted fluorenyl group , A substituted or unsubstituted carbazolyl group, a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted dibenzothiophenyl group, a substituted or unsubstituted dibenzosilolyl group, or a substituted or unsubstituted benzonaphthofuran Illyin, a compound for an organic optoelectronic device.
5. According to claim 1,

   The *-L ² -Ar ¹ and *-L ³ -Ar ² are each independently one selected from the substituents listed in Group I: A compound for an organic optoelectronic device:

   [Group I]

   

   In group I,

   D means deuterium,

   n11 is one of integers from 1 to 5,

   n12 is one of integers from 1 to 4,

   n13 is one of integers from 1 to 3,

   * is the connection point.
6. The method of claim 1

   A compound for an organic optoelectronic device, which is one selected from the compounds listed in Group 1:

   [Group 1]

   [1] [2] [3] [4]

   

   [5] [6] [7] [8]

   

   [9] [10] [11] [12]

   

   [13] [14] [15] [16]

   

   [17] [18] [19] [20]

   

   [21] [22] [23] [24]

   

   [25] [26] [27] [28]

   

   [29] [30] [31] [32]

   

   [33] [34] [35] [36]

   

   [37] [38] [39] [40]

   

   [41] [42] [43] [44]

   

   [45] [46] [47] [48]

   

   [49] [50] [51] [52]

   

   [52] [54] [55] [56]

   

   [57] [58] [59] [60]

   

   [61] [62] [63] [64]

   

   [65] [66] [67] [68]

   

   [69] [70] [71] [72]

   

   [73] [74] [75] [76]

   

   [77] [78] [79] [80]

   

   [81] [82] [83] [84]

   

   [85] [86] [87] [88]

   

   [89] [90] [91] [92]

   

   [93] [94] [95] [96]

   

   [97] [98] [99] [100]

   

   [101] [102] [103] [104]

   

   [105] [106] [107] [108]

   

   [109] [110] [111] [112]

   

   [113] [114] [115] [116]

   

   [117] [118] [119] [120]

   

   [121] [122] [123] [124]

   

   [125] [126] [127] [128]

   

   .
7. a first compound, and a second compound;

   The first compound is a compound for an organic optoelectronic device according to claim 1,

   The second compound is a compound for an organic optoelectronic device represented by the following formula (2), a composition for an organic optoelectronic device:

   [Formula 2]

   

   In Formula 2,

   X ¹ is O, S, NR ^b , CR ^c R ^d or SiR ^e R ^f ,

   R ^b , R ^c , R ^d , ^Re , R ^f , R ⁷ and R ⁸ are each independently hydrogen, deuterium, a substituted or unsubstituted amine group, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted a C6 to C30 aryl group or a substituted or unsubstituted C2 to C30 heterocyclic group,

   n5 is one of integers from 1 to 4,

   Ring A is any one selected from the rings listed in Group II,

   [Group II]

   

   In group II,

   * is the connection point,

   X ² is O, S, NR ^g , CR ^h R ⁱ or SiR ^j R ^k ,

   R ^g , R ^h , R ⁱ , R ^j , R ^k , and R ⁶ to R ¹⁰ are each independently hydrogen, deuterium, a substituted or unsubstituted amine group, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted a cyclic C6 to C30 aryl group or a substituted or unsubstituted C2 to C30 heterocyclic group,

   n6, n8 and n10 are each independently one of an integer of 1 to 4,

   n7 and n9 are each independently an integer of 1 or 2,

   At least one of R ⁵ to R ¹⁰ is a group represented by the following formula (a),

   [Formula a]

   

   In the above formula (a),

   L ⁴ To L ⁶ are each independently a single bond, or a substituted or unsubstituted C6 to C30 arylene group,

   Ar ³ and Ar ⁴ are each independently a substituted or unsubstituted amine group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C2 to C30 heterocyclic group,

   * is the connection point.
8. 8. The method of claim 7,

   Formula 2 is a composition for an organic optoelectronic device represented by any one of Formula 2-I to Formula 2-X:

   [Formula 2-Ⅰ] [Formula 2-Ⅱ]

   

   [Formula 2-Ⅲ] [Formula 2-IV]

   

   [Formula 2-V] [Formula 2-VI]

   

   [Formula 2-VII] [Formula 2-VIII]

   

   [Formula 2-IX] [Formula 2-X]

   

   In Formula 2-I to Formula 2-X,

   X ¹ , X ² , R ⁵ to R ¹⁰ and n5 to n10 are the same as in claim 7.
9. 8. The method of claim 7,

   The second compound is a composition for an organic optoelectronic device represented by any one of Formulas 2-IA to 2-XA, Formula 2-IIB to Formula 2-IVB, and Formula 2-IIC to Formula 2-IXC:

   [Formula 2-IA] [Formula 2-IIA]

   

   [Formula 2-ⅢA] [Formula 2-IVA]

   

   [Formula 2-VIA] [Formula 2-VIA]

   

   [Formula 2-VIIA] [Formula 2-VIIIA]

   

   [Formula 2-XA] [Formula 2-XA]

   

   In Formula 2-IA to Formula 2-XA,

   X ¹ , X ² , L ⁴ to L ⁶ , Ar ³ , Ar ⁴ , and n6 to n10 are as defined in claim 7,

   n5 is one of integers from 1 to 3.

   [Formula 2-IIB]

   

   [Formula 2-ⅢB] [Formula 2-IVB]

   

   In Formulas 2-IIB to Formula 2-IVB,

   X ¹ , L ⁴ to L ⁶ , Ar ³ , Ar ⁴ , n5 and n7 are as defined in claim 7,

   n8 is one of integers from 1 to 3.

   [Formula 2-IIC] [Formula 2-IIIC]

   

   [Formula 2-IVC]

   

   In the formula 2-IIC to formula 2-IVC,

   X ¹ , L ⁴ to L ⁶ , Ar ³ , Ar ⁴ , n5 and n8 are as defined in claim 7,

   n7 is 1.

   [Formula 2-VC] [Formula 2-VIC]

   

   [Formula 2-VIIC] [Formula 2-VIIIC]

   

   [Formula 2-ⅨC]

   

   In Formula 2-VC to Formula 2-IXC,

   X ¹ , X ² , L ⁴ to L ⁶ , Ar ³ , Ar ⁴ , n5 and n10 are as defined in claim 7,

   n9 is 1.
10. 8. The method of claim 7,

    Wherein R ⁵ To R ¹⁰ are each independently hydrogen, deuterium, a substituted or unsubstituted C1 to C30 alkyl group, or a substituted or unsubstituted C6 to C30 aryl group, the composition for an organic optoelectronic device.
11. 8. The method of claim 7,

    The second compound is a composition for an organic optoelectronic device, which is represented by Formula 2-IVB-2 or Formula 2-VIIIA-2:

    [Formula 2-IVB-2] [Formula 2-VIIIA-2]

    

    In Formula 2-IVB-2 and Formula 2-VIIIA-2,

    L ⁴ To L ⁶ are each independently a single bond or a substituted or unsubstituted phenylene group,

    wherein Ar ³ and Ar ⁴ are each independently a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, or a substituted or unsubstituted naphthyl group,

    R ⁵ , and R ⁷ to R ¹⁰ are each independently hydrogen, deuterium, a substituted or unsubstituted C1 to C30 alkyl group, or a substituted or unsubstituted C6 to C30 aryl group,

    n7 and n9 are each independently an integer of 1 or 2,

    n8 and n10 are each independently one of an integer of 1 to 3,

    In Formula 2-IVB-2, X ¹ is NR ^b , O or S,

    n5 of Formula 2-IVB-2 is one of integers from 1 to 4,

    In Formula 2-VIIIA-2, X ¹ is CR ^c R ^d or SiR ^e R ^f ,

    X ² of Formula 2-VIIIA-2 is O or S,

    n5 in Formula 2-VIIIA-2 is one of integers from 1 to 3,

    R ^b , R ^c , R ^d , R ^e and R ^f are each independently a substituted or unsubstituted C1 to C30 alkyl group, or a substituted or unsubstituted C6 to C30 aryl group.
12. positive and negative poles facing each other,

    At least one organic layer positioned between the anode and the cathode,

    The organic layer includes a light emitting layer,

    The light emitting layer is a compound for an organic optoelectronic device according to any one of claims 1 to 6; Or an organic optoelectronic device comprising the composition for an organic optoelectronic device according to any one of claims 7 to 11.
13. 13. The method of claim 12,

    The compound for an organic optoelectronic device or the composition for an organic optoelectronic device is an organic optoelectronic device included as a host of the light emitting layer.
14. A display device comprising the organic optoelectronic device according to claim 12 .

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