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

Abstract

Provided are a compound for an organic photoelectric device, a composition for an organic photoelectric device, an organic photoelectric device, and a display device, wherein the compound is represented by Chemical Formula 1, and the composition comprises the compound. The details of Chemical Formula 1 are as defined in the specification.

Description

[0001] Citations of Related Applications

[0002] This application claims priority to and the benefit of Korean Patent Application No. 10-2021-0089278 filed in the Korean Intellectual Property Office on July 7, 2021, and Korean Patent Application No. 10-2022-0075164 filed in the Korean Intellectual Property Office on June 20, 2022, the entire contents of which are incorporated herein by reference. Technical Field

[0003] Disclosed are a compound for an organic optoelectronic device, an organic optoelectronic device, an organic optoelectronic device, and an organic optoelectronic device, a composition for an organic optoelectronic device, an organic optoelectronic device, and a display device. Background Art

[0004] An organic photoelectric device (organic photodiode) is a device capable of converting electrical energy and light energy into each other.

[0005] Organic photoelectric devices can be mainly divided into two types according to the operating principle. One is a photoelectric device that generates electrical energy by separating excitons formed by light energy into electrons and holes and transferring the electrons and holes to different electrodes, respectively, and the other is a light-emitting device that generates light energy from electrical energy by supplying voltage or current to electrodes.

[0006] Examples of the organic optoelectronic device include an organic optoelectronic device, an organic light emitting diode, an organic solar cell, and an organic photosensitive drum.

[0007] Among them, organic light emitting diodes (OLEDs) have attracted much attention in recent years due to the increasing demand for flat panel display devices. An organic light emitting diode is a device that converts electrical energy into light, and the performance of an organic light emitting diode is greatly affected by the organic material between electrodes. Summary of the invention

[0008] One embodiment provides a compound for an organic photoelectric device, which can realize an organic photoelectric device with high efficiency and long lifetime.

[0009] Another embodiment provides a composition for an organic photoelectric device, including the compound.

[0010] Another embodiment provides an organic photoelectric device including the compound.

[0011] Another embodiment provides a display device including an organic optoelectronic device.

[0012] According to one embodiment, a compound for an organic photoelectric device represented by Chemical Formula 1 is provided.

[0013] [Chemical formula 1]

[0014]

[0015] In Chemical Formula 1,

[0016] X 1 is O or S,

[0017] Z 1 To Z 3 Each independently is N or CR a ,

[0018] Z 1 To Z 3 At least two of them are N,

[0019] L 1 To L 3 are each independently a single bond or a substituted or unsubstituted C6 to C30 arylene group,

[0020] 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,

[0021] R a and R 1 To R 5 are each independently hydrogen, deuterium, substituted or unsubstituted C1 to C20 alkyl, or substituted or unsubstituted C6 to C20 aryl,

[0022] R 6 and R 7 are each independently a substituted or unsubstituted C1 to C20 alkyl group or a substituted or unsubstituted C6 to C20 aryl group,

[0023] m1 and m2 are each independently an integer from 2 to 4,

[0024] m3 and m4 are each independently an integer from 1 to 4, and

[0025] n1 and n2 are each independently an integer of 0 or 1.

[0026] According to another embodiment, a composition for an organic photoelectric device includes a first compound and a second compound.

[0027] The first compound may be the compound for an organic photoelectric device described above, and the second compound may be represented by Chemical Formula 2.

[0028] [Chemical formula 2]

[0029]

[0030] In chemical formula 2,

[0031] X 2 O, S, NR b , CR c R d or SiR e R f ,

[0032] R b , R c , R d , R e , R f and R 8 are each independently hydrogen, deuterium, substituted or unsubstituted amine, substituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C6 to C30 aryl, or substituted or unsubstituted C2 to C30 heterocyclic, and

[0033] m5 is an integer from 1 to 4, and

[0034] Ring A is any one selected from the rings of Group II,

[0035] [Group II]

[0036]

[0037] Among them, in Group II,

[0038] * is the connection point,

[0039] X 3 O, S, NR g , CR h R i or SiR j R k ,

[0040] R g , R h , R i , R j , R k and R 9 To R 16 are each independently hydrogen, deuterium, substituted or unsubstituted amine, substituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C6 to C30 aryl, or substituted or unsubstituted C2 to C30 heterocyclic,

[0041] m6, m8, m11 and m13 are each independently an integer from 1 to 4,

[0042] m7, m9, m10 and m12 are each independently an integer of 1 or 2, and

[0043] R 8 To R 16 At least one of them is a group represented by chemical formula a,

[0044] [Chemical formula a]

[0045]

[0046] Among them, in chemical formula a,

[0047] L 4 To L 6 are each independently a single bond, or a substituted or unsubstituted C6 to C30 arylene group,

[0048] 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, and

[0049] * is the connection point.

[0050] According to another embodiment, an organic photoelectric device includes an anode and a cathode facing each other, and at least one organic layer between the anode and the cathode, wherein the organic layer includes a compound for an organic photoelectric device or a composition for an organic photoelectric device.

[0051] According to another embodiment, a display device including an organic optoelectronic device is provided.

[0052] An organic photoelectric device with high efficiency and long life can be realized. BRIEF DESCRIPTION OF THE DRAWINGS

[0053] Figure 1 is a cross-sectional view showing an organic light emitting diode according to an embodiment.

[0054] <Description of Reference Numerals>

[0055] 100: Organic light-emitting diode

[0056] 105: Organic layer

[0057] 110: cathode

[0058] 120: Anode

[0059] 130: Luminous layer

[0060] 140: Hole transport region

[0061] 150: Electron transport region DETAILED DESCRIPTION

[0062] Hereinafter, embodiments of the present invention are described in detail. However, these embodiments are exemplary, the present invention is not limited thereto, and the present invention is defined by the scope of the claims.

[0063] As used herein, when no definition is otherwise provided, "substituted" means that at least one hydrogen of the substituent or compound is replaced with deuterium, halogen, hydroxyl, amino, substituted or unsubstituted C1 to C30 amine, nitro, substituted or unsubstituted C1 to C40 silyl (silyl, silyl), C1 to C30 alkyl, C1 to C10 alkylsilyl (alkylsilyl, alkylsilyl), C6 to C30 arylsilyl (arylsilyl, arylsilyl), C3 to C30 cycloalkyl, C3 to C30 heterocycloalkyl, C6 to C30 aryl, C2 to C30 heteroaryl, C1 to C20 alkoxy, C1 to C10 trifluoroalkyl, cyano, or a combination thereof.

[0064] In one example of the present invention, "substituted" means that at least one hydrogen of a substituent or a compound is replaced by deuterium, C1 to C30 alkyl, C1 to C10 alkylsilyl, C6 to C30 arylsilyl, C3 to C30 cycloalkyl, C3 to C30 heterocycloalkyl, C6 to C30 aryl, C2 to C30 heteroaryl or cyano. In addition, in a specific example of the present invention, "substituted" means that at least one hydrogen of a substituent or a compound is replaced by deuterium, C1 to C20 alkyl, C6 to C30 aryl or cyano. In addition, in a specific example of the present invention, "substituted" means that at least one hydrogen of a substituent or a compound is replaced by deuterium, C1 to C5 alkyl, C6 to C18 aryl or cyano. In addition, in a specific example of the present invention, "substituted" means that at least one hydrogen of a substituent or a compound is replaced by deuterium, cyano, methyl, ethyl, propyl, butyl, phenyl, biphenyl, terphenyl or naphthyl.

[0065] "Unsubstituted" means that a hydrogen atom is not replaced by another substituent and that a hydrogen atom remains.

[0066] In the present specification, a "hydrogen substituent (—H)" may include a "deuterium substituent (—D)" or a "tritium substituent (—T)".

[0067] As used herein, when no definition is otherwise provided, "hetero" means containing one to three heteroatoms selected from N, O, S, P and Si and the remaining carbon in one functional group.

[0068] As used herein, "aryl" refers to a group containing at least one hydrocarbon aromatic portion, and may include a group in which all elements of the hydrocarbon aromatic portion have p orbitals forming a conjugation, such as phenyl, naphthyl, etc., a group in which two or more hydrocarbon aromatic portions can be linked by a σ bond, such as biphenyl, terphenyl, quaterphenyl, etc., and a group in which two or more hydrocarbon aromatic portions are directly or indirectly fused to provide a non-aromatic fused ring, such as fluorenyl, etc.

[0069] Aryl groups can include monocyclic, polycyclic, or fused-ring polycyclic (ie, rings which share adjacent pairs of carbon atoms) functional groups.

[0070] As used herein, "heterocyclic group" is a general concept of heteroaryl, and may contain at least one heteroatom selected from N, O, S, P and Si instead of carbon (C) in a cyclic compound such as an aryl group, a cycloalkyl group, a condensed ring thereof, or a combination thereof. When the heterocyclic group is a condensed ring, the entire ring or each ring of the heterocyclic group may contain one or more heteroatoms.

[0071] For example, "heteroaryl" refers to an aryl group containing at least one heteroatom selected from N, O, S, P and Si. Two or more heteroaryls are directly connected by a sigma bond, or when the heteroaryl includes two or more rings, the two or more rings can be fused. When the heteroaryl is a fused ring, each ring can contain 1 to 3 heteroatoms.

[0072] More specifically, the substituted or unsubstituted C6 to C30 aryl group may be 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 naphthyl group, a substituted or unsubstituted pyrenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted p-terphenyl group, a substituted or unsubstituted m-terphenyl group, a substituted or unsubstituted o-terphenyl group, a substituted or unsubstituted The invention may include, but is not limited to, a substituted or unsubstituted triphenylene group, a substituted or unsubstituted peryl group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted indenyl group, a substituted or unsubstituted furanyl group, or a combination thereof.

[0073] More specifically, the substituted or unsubstituted C2 to C30 heterocyclic group may be a substituted or unsubstituted thienyl, a substituted or unsubstituted pyrrolyl, a substituted or unsubstituted pyrazolyl, a substituted or unsubstituted imidazolyl, a substituted or unsubstituted triazolyl, a substituted or unsubstituted oxazolyl, a substituted or unsubstituted thiazolyl, a substituted or unsubstituted oxadiazolyl, a substituted or unsubstituted thiadiazolyl, a substituted or unsubstituted pyridyl, a substituted or unsubstituted pyrimidinyl, a substituted or unsubstituted pyrazinyl, a substituted or unsubstituted triazinyl, a substituted or unsubstituted benzofuranyl, a substituted or unsubstituted benzothiophenyl, a substituted or unsubstituted benzimidazolyl, a substituted or unsubstituted indolyl, or a substituted or unsubstituted quinolyl. , substituted or unsubstituted isoquinolyl, substituted or unsubstituted quinazoline, substituted or unsubstituted quinoxalinyl, substituted or unsubstituted naphthyridinyl, substituted or unsubstituted benzoxazinyl, substituted or unsubstituted benzothiazinyl, substituted or unsubstituted acridinyl, substituted or unsubstituted phenazinyl, substituted or unsubstituted phenothiazinyl, substituted or unsubstituted phenoxazinyl, substituted or unsubstituted carbazolyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothiophenyl, substituted or unsubstituted benzonaphthofuranyl, substituted or unsubstituted benzonaphthothiophenyl, substituted or unsubstituted dibenzosilolyl, or a combination thereof, but are not limited thereto.

[0074] In this specification, hole characteristics refer to the ability to donate electrons to form holes when an electric field is applied, and due to the conductive characteristics according to the highest occupied molecular orbital (HOMO) energy level, the holes formed in the anode can be easily injected into the light-emitting layer and transported in the light-emitting layer.

[0075] In addition, electronic properties refer to the ability to accept electrons when an electric field is applied, and electrons formed in the cathode can be easily injected into the light-emitting layer and transported in the light-emitting layer due to conductive properties according to the lowest unoccupied molecular orbital (LUMO) energy level.

[0076] Hereinafter, a compound for an organic photoelectric device according to one embodiment is described.

[0077] The compound for an organic photoelectric device according to one embodiment is represented by Chemical Formula 1.

[0078] [Chemical formula 1]

[0079]

[0080] In Chemical Formula 1,

[0081] X 1 is O or S,

[0082] Z 1 To Z 3Each independently is N or CR a ,

[0083] Z 1 To Z 3 At least two of them are N,

[0084] L 1 To L 3 are each independently a single bond or a substituted or unsubstituted C6 to C30 arylene group,

[0085] 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,

[0086] R a and R 1 To R 5 are each independently hydrogen, deuterium, substituted or unsubstituted C1 to C20 alkyl, or substituted or unsubstituted C6 to C20 aryl,

[0087] R 6 and R 7 are each independently a substituted or unsubstituted C1 to C20 alkyl group or a substituted or unsubstituted C6 to C20 aryl group,

[0088] m1 and m2 are each independently an integer from 2 to 4,

[0089] m3 and m4 are each independently an integer from 1 to 4, and

[0090] n1 and n2 are each independently an integer of 0 or 1.

[0091] The compound represented by Chemical Formula 1 has a structure in which a benzene ring is at the center of a skeleton, in which benzosilole is further condensed at the 3rd and 4th positions of dibenzofuran (or dibenzothiophene) and is substituted with pyrimidine or triazine.

[0092] Since the polycyclic condensed ring formed by further condensing the benzosilole has a twisted structure instead of a completely planar state, the crystallinity is reduced and the Tg is increased. In addition, due to the reduced crystallinity, the processability during the deposition process can be improved.

[0093] In addition, since it is substituted with pyrimidine or triazine, it has high electron mobility and thus can reduce the driving voltage.

[0094] In particular, when the central benzene ring is substituted with pyrimidine or triazine, the LUMO electrons smoothly expand to the left and right to improve the stability of the pair electrons, thereby improving the lifetime of the device.

[0095] Furthermore, since it includes a silicon-containing condensed ring, heat resistance is improved compared with a carbon condensed ring.

[0096] According to the specific substitution position of the triazine, Chemical Formula 1 may be represented by Chemical Formula 1A or Chemical Formula 1B.

[0097] [Chemical Formula 1A]

[0098]

[0099] [Chemical formula 1B]

[0100]

[0101] In Chemical Formula 1A and Chemical Formula 1B,

[0102] X 1 , Z 1 To Z 3 , L 1 To L 3 ,Ar 1 ,Ar 2 , R 1 To R 7 , m1 to m4, n1 and n2 are the same as described above.

[0103] In addition, depending on whether the terminal of the condensed ring is further condensed, it may be represented by any one of Chemical Formula 1-1 to Chemical Formula 1-7.

[0104]

[0105]

[0106]

[0107] In Chemical Formula 1-1 to Chemical Formula 1-7,

[0108] X 1 , Z 1 To Z 3 , L 1 To L 3 ,Ar 1 ,Ar 2 , R 1 To R 7 And m1 to m4 are the same as described above.

[0109] In an exemplary embodiment, L 1 To L 3 Each may independently be a single bond, a substituted or unsubstituted phenylene group, or a substituted or unsubstituted naphthylene group.

[0110] In a specific embodiment, L 1 can be a single bond, and L 2 and L 3 Each independently may be a single bond or a substituted or unsubstituted phenylene group.

[0111] In an exemplary embodiment, Ar 1 and Ar 2 Each of them may independently be a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted phenanthryl group, a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted dibenzothiophenyl group, or a substituted or unsubstituted dibenzosilyl group.

[0112] In a specific embodiment, Ar 1 and Ar 2 Each of them independently may be a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted dibenzofuranyl group, or a substituted or unsubstituted dibenzothiophenyl group.

[0113] As a more specific example, *-L 2 -Ar 1 and *-L 3 -Ar 2 Each may be independently selected from the substituents of Group I.

[0114] [Group I]

[0115]

[0116] In Group I,

[0117] D is deuterium,

[0118] m14 is an integer from 0 to 5,

[0119] m15 is an integer from 0 to 4,

[0120] m16 is an integer from 0 to 7,

[0121] m17 is an integer from 0 to 3,

[0122] m18 is an integer from 0 to 6,

[0123] m19 is an integer from 0 to 2, and

[0124] * is the connection point.

[0125] In the definitions of m14 to m19, 0 means that all hydrogen atoms are not replaced by deuterium and remain as hydrogen atoms, that is, “unsubstituted”.

[0126] In an exemplary embodiment, R 1 To R 5 and may each independently be hydrogen, deuterium, a substituted or unsubstituted C1 to C10 alkyl group, or a substituted or unsubstituted C6 to C12 aryl group.

[0127] In a specific embodiment, R 1 To R 5 may each independently be hydrogen or deuterium.

[0128] In one embodiment, R 6 and R 7 Each may independently be a substituted or unsubstituted C1 to C10 alkyl group or a substituted or unsubstituted C6 to C12 aryl group.

[0129] In a specific embodiment, R 6 and R 7 Each may independently be a substituted or unsubstituted methyl group or a substituted or unsubstituted phenyl group.

[0130] For example, the compound for an organic photoelectric device represented by Chemical Formula 1 may be one of the compounds selected from Group 1, but is not limited thereto.

[0131] [Group 1]

[0132]

[0133]

[0134]

[0135]

[0136]

[0137]

[0138]

[0139]

[0140]

[0141]

[0142]

[0143] A composition for an organic photoelectric device according to another embodiment includes a first compound and a second compound, wherein the first compound may be the above-mentioned compound for an organic photoelectric device, and the second compound may be represented by Chemical Formula 2.

[0144] [Chemical formula 2]

[0145]

[0146] In chemical formula 2,

[0147] X 2 O, S, NR b , CR c R d or SiR e R f ,

[0148] R b , R c , R d , R e , R f and R 8 are each independently hydrogen, deuterium, substituted or unsubstituted amine, substituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C6 to C30 aryl, or substituted or unsubstituted C2 to C30 heterocyclic, and

[0149] m5 is an integer from 1 to 4, and

[0150] Ring A is any one selected from the rings of Group II,

[0151] [Group II]

[0152]

[0153] In Group II,

[0154] * is the connection point,

[0155] X 3 O, S, NR g , CR h R i or SiR j R k ,

[0156] R g , R h , R i , R j , R k and R 9 To R 16are each independently hydrogen, deuterium, substituted or unsubstituted amine, substituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C6 to C30 aryl, or substituted or unsubstituted C2 to C30 heterocyclic,

[0157] m6, m8, m11 and m13 are each independently an integer from 1 to 4,

[0158] m7, m9, m10 and m12 are each independently an integer of 1 or 2, and

[0159] R 8 To R 16 At least one of them is a group represented by chemical formula a,

[0160] [Chemical formula a]

[0161]

[0162] Among them, in chemical formula a,

[0163] L 4 To L 6 are each independently a single bond, or a substituted or unsubstituted C6 to C30 arylene group,

[0164] 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, and

[0165] * is the connection point.

[0166] The second compound may have a structure in which carbazole / fused carbazole / fused dibenzofuran / fused dibenzothiophene / fused dibenzosilole is substituted with amine. Depending on the type and fusion position of the additional benzene ring, for example, the second compound may be represented by any one of Formula 2-I to Formula 2-IX.

[0167]

[0168]

[0169] In Chemical Formulae 2-I to 2-IX,

[0170] X 2 , X 3 , R 8 To R 11 , R 15 , R 16 , m5 to m8, m12 and m13 are the same as described above.

[0171] In addition, the second compound may be represented by any one of Chemical Formulae 2-IA to 2-IXA, Chemical Formulae 2-IIB to 2-IXB, and Chemical Formulae 2-IIC to 2-IXC according to the substitution direction of the amine group.

[0172]

[0173]

[0174] In Chemical Formulae 2-IA to 2-IXA,

[0175] X 2 , X 3 , L 4 To L 6 ,Ar 3 ,Ar 4 , R 8 To R 11 , R 15 , R 16 , m6 to m8, m12 and m13 are the same as described above, and

[0176] m5' is one of integers from 1 to 3.

[0177]

[0178]

[0179] In Chemical Formulae 2-IIB to 2-IXB,

[0180] X 2 , X 3 , L 4 To L 6 , R 8 , R 10 , R 11 , R 15 , R 16 ,Ar 3 ,Ar 4 , m5, m7 and m12 are the same as described above, and

[0181] m8′ and m13′ are each independently one of integers from 1 to 3.

[0182]

[0183]

[0184] In Chemical Formulae 2-IIC to 2-IXC,

[0185] X 2, X 3 , L 4 To L 6 ,Ar 3 ,Ar 4 , R 8 , R 10 , R 11 , R 15 , R 16 , m5, m8, and m13 are the same as described above.

[0186] For example, R 8 To R 16 Each is independently hydrogen, deuterium, a substituted or unsubstituted amine group, a substituted or unsubstituted C1 to C30 alkyl group, or a substituted or unsubstituted C6 to C30 aryl group.

[0187] The second compound according to one embodiment may be represented by Chemical Formula 2-IVB or Chemical Formula 2-VIIIB.

[0188] For example, X in formula 2-IVB 2 It can be NR b .

[0189] For example, in Formula 2-VIIIB, X 2 Can be O or S, and X 3 Can be CR h R i or SiR j R k .

[0190] R b , R h , R i , R j and R k Each may independently be a substituted or unsubstituted C1 to C10 alkyl group, or a substituted or unsubstituted C6 to C20 aryl group.

[0191] According to a specific embodiment, the second compound can be represented by chemical formula 2-IVB-2 or chemical formula 2-IVB-3.

[0192] It is represented by formula 2-VIIIB-2.

[0193]

[0194] In Chemical Formula 2-IVB-2 and Chemical Formula 2-VIIIB-2,

[0195] L 4 To L 6 are each independently a single bond or a substituted or unsubstituted phenylene group,

[0196] Ar3 and Ar 4 are each independently a substituted or unsubstituted phenyl, a substituted or unsubstituted biphenyl, or a substituted or unsubstituted naphthyl,

[0197] X 2 YesNR b , O or S,

[0198] X 3 Yes CR h R i or SiR j R k ,

[0199] R b , R h , R i , R j and R k are each independently a substituted or unsubstituted C1 to C10 alkyl group, or a substituted or unsubstituted C6 to C20 aryl group,

[0200] R 8 , R 10 , R 11 , R 15 and R 16 are each independently hydrogen, deuterium, substituted or unsubstituted C1 to C30 alkyl, or substituted or unsubstituted C6 to C30 aryl,

[0201] m5 is an integer from 1 to 4,

[0202] m7 and m12 are each independently an integer of 1 or 2, and

[0203] m8′ and m13′ are each independently one of integers from 1 to 3.

[0204] For example, L 4 To L 6 Each independently may be a single bond, a substituted or unsubstituted phenylene group, or a substituted or unsubstituted biphenylene group.

[0205] For example, Ar 3 and Ar 4 Each of them may independently be a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted terphenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted phenanthryl 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 dibenzothienyl group, a substituted or unsubstituted benzofuranofluorenyl group, or a substituted or unsubstituted benzothienofluorenyl group.

[0206] For example, the second compound may be one of the compounds selected from Group 2, but is not limited thereto.

[0207] [Group 2]

[0208]

[0209]

[0210]

[0211]

[0212]

[0213]

[0214]

[0215]

[0216]

[0217]

[0218]

[0219]

[0220]

[0221]

[0222]

[0223] For example, the first compound and the second compound can be included in a weight ratio of about 1:99 to about 99:1. Within this range, the electron transport ability of the first compound and the hole transport ability of the second compound can be used to adjust the desired weight ratio to achieve bipolar characteristics and thus improve efficiency and lifespan. Within this range, they can be included, for example, with a weight ratio of about 10:90 to about 90:10 or about 20:80 to about 80:20, such as about 20:80 to about 70:30, about 20:80 to about 60:40 and about 30:70 to about 60:40. As a specific example, they can be included with a weight ratio of about 40:60, about 50:50 or about 60:40.

[0224] In addition to the above-mentioned first and second compounds, one or more compounds may be contained.

[0225] The above-mentioned compound for an organic photoelectric device or the composition for an organic photoelectric device may be a composition further including a dopant.

[0226] The dopant may be, for example, a phosphorescent dopant, such as a red, green, or blue phosphorescent dopant, and may be, for example, a red or green phosphorescent dopant.

[0227] The dopant is a material mixed in a small amount with a compound or composition for an organic photoelectric device to cause light emission, and generally may be a material such as a metal complex that emits light by multiple excitation to a triplet state or more. The dopant may be, for example, an inorganic, organic, or organic-inorganic compound, and one or more types thereof may be used.

[0228] Examples of the dopant may be a phosphorescent dopant, and examples of the phosphorescent dopant may be an organic metal compound including Ir, Pt, Os, Ti, Zr, Hf, Eu, Tb, Tm, Fe, Co, Ni, Ru, Rh, Pd, or a combination thereof. The phosphorescent dopant may be, for example, a compound represented by the chemical formula Z, but is not limited thereto.

[0229] [Chemical formula Z]

[0230] L 7 MX 4

[0231] In the chemical formula Z, M is a metal and L 7 and X 4 They are the same as or different from each other and are ligands that form a complex with M.

[0232] M can 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 4 This may be, for example, a bidentate ligand.

[0233] By L 7 and X 4 Examples of the ligand represented by may be selected from the chemical formulae of Group A, but are not limited thereto.

[0234] [Group A]

[0235]

[0236] In Group A,

[0237] R 300 To R 302 are each independently hydrogen, deuterium, C1 to C30 alkyl which may be substituted by halogen, C6 to C30 aryl which may be substituted by C1 to C30 alkyl, or halogen, and

[0238] R 303 To R 324 Each is independently hydrogen, deuterium, halogen, substituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C1 to C30 alkoxy, substituted or unsubstituted C3 to C30 cycloalkyl, substituted or unsubstituted C2 to C30 alkenyl, substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C1 to C30 heteroaryl, substituted or unsubstituted C1 to C30 amino, substituted or unsubstituted C6 to C30 arylamino, SF5, 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 a triarylsilyl group having a substituted or unsubstituted C6 to C30 aryl group.

[0239] As an example, it may include a dopant represented by Chemical Formula V.

[0240] [Chemical Formula V]

[0241]

[0242] In chemical formula V,

[0243] R 101 To R 116 are each independently hydrogen, deuterium, substituted or unsubstituted C1 to C10 alkyl, substituted or unsubstituted C6 to C20 aryl, or -SiR 132 R 133 R 134 ,

[0244] R 132 To R 134 are each independently C1 to C6 alkyl,

[0245] R 101 To R 116 At least one of them is a functional group represented by the chemical formula V-1,

[0246] L 100 It is a bidentate ligand of a monovalent anion and is coordinated to iridium through the lone pair of electrons of carbon or heteroatoms.

[0247] m15 and m16 are each independently any one of integers from 0 to 3, and

[0248] m15+m16 is any integer from 1 to 3,

[0249] [Chemical formula V-1]

[0250]

[0251] Among them, in chemical formula V-1,

[0252] R 135 To R 139 are each independently hydrogen, deuterium, substituted or unsubstituted C1 to C10 alkyl, substituted or unsubstituted C6 to C20 aryl, or -SiR 132 R 133 R 134 ,

[0253] R 132 To R 134 are each independently C1 to C6 alkyl, and

[0254] * means the moiety attached to the carbon atom.

[0255] As an example, a dopant represented by Chemical Formula Z-1 may be included.

[0256] [Chemical formula Z-1]

[0257]

[0258] In the chemical formula Z-1, rings A, B, C and D each independently represent a 5-membered or 6-membered carbocyclic or heterocyclic ring;

[0259] R A , R B , R C and R D each independently represents mono-, di-, tri-, or tetra-substituted, or unsubstituted;

[0260] L B , L C and L D Each is independently selected from direct bond, BR, NR, PR, O, S, Se, C=O, S=O, SO2, CRR', SiRR', GeRR' and combinations thereof;

[0261] When nA is 1, L E is selected from the group consisting of direct bond, BR, NR, PR, O, S, Se, C=O, S=O, SO2, CRR', SiRR', GeRR' and combinations thereof; when nA is 0, L E does not exist; and

[0262] R A , R B , R C , R DR, R and R' are each independently selected from hydrogen, deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silanyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino and combinations thereof; any adjacent R A , R B , R C , R D , R and R' are optionally linked to each other to provide a ring; X B , X C , X D and X E are each independently selected from carbon and nitrogen; and Q 1 , Q 2 , Q 3 and Q 4 Each represents oxygen or a direct bond.

[0263] The dopant according to one embodiment may be a platinum complex, and may be represented, for example, by Chemical Formula VI.

[0264] [Chemical Formula VI]

[0265]

[0266] In Chemical Formula VI,

[0267] X 100 Selected from O, S and NR 131 ,

[0268] R 117 To R 131 are each independently hydrogen, deuterium, substituted or unsubstituted C1 to C10 alkyl, substituted or unsubstituted C6 to C20 aryl, or -SiR 132 R 133 R 134 ,

[0269] R 132 To R 134 are each independently C1 to C6 alkyl, and

[0270] R 117 To R 131 At least one of them is -SiR 132 R 133 R 134 or tert-butyl.

[0271] Hereinafter, an organic photoelectric device including the above-mentioned compound for an organic photoelectric device or the composition for an organic photoelectric device is described.

[0272] The organic photoelectric device may be any device that converts electrical energy into light energy, or vice versa, without particular limitation, and may be, for example, an organic optoelectronic device, an organic light emitting diode, an organic solar cell, and an organic photosensitive drum.

[0273] Herein, an organic light emitting diode as one example of an organic photoelectric device is described with reference to the accompanying drawings.

[0274] Figure 1 is a cross-sectional view showing an organic light emitting diode according to one embodiment.

[0275] Reference Figure 1 , an organic light emitting diode 100 according to one embodiment includes an anode 120 and a cathode 110 facing each other, and an organic layer 105 disposed between the anode 120 and the cathode 110 .

[0276] The anode 120 may be made of a conductor having a large work function to facilitate hole injection, and may be, for example, a metal, a metal oxide, and / or a conductive polymer. The anode 120 may be, for example, a metal such as nickel, platinum, vanadium, chromium, copper, zinc, gold, or the like, or an alloy thereof; a metal oxide such as zinc oxide, indium oxide, indium tin oxide (ITO), indium zinc oxide (IZO), or the like; a combination of a metal and an oxide such as ZnO and Al or SnO2 and Sb; a conductive polymer such as poly(3-methylthiophene), poly(3,4-(ethylene-1,2-dioxy)thiophene) (PEDOT), polypyrrole, and polyaniline, but is not limited thereto.

[0277] The cathode 110 may be made of a conductor having a small work function to facilitate electron injection, and may be, for example, a metal, a metal oxide, and / or a conductive polymer. The cathode 110 may be, for example, a metal such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, lead, cesium, barium, etc., or an alloy thereof; a multilayer structure material such as LiF / Al, LiO2 / Al, LiF / Ca, and BaF2 / Ca, but is not limited thereto.

[0278] The organic layer 105 may include the above-described compound for an organic photoelectric device or the composition for an organic photoelectric device.

[0279] The organic layer 105 may include a light emitting layer 130 , and the light emitting layer 130 may include the above-described compound for an organic photoelectric device or composition for an organic photoelectric device.

[0280] For example, the composition for an organic photoelectric device further including a dopant may be a composition emitting red light.

[0281] The light emitting layer 130 may include, for example, the above-described first compound and second compound, respectively serving as phosphorescent hosts.

[0282] In addition to the light-emitting layer, the organic layer may further include a charge transport region.

[0283] The charge transport region may be, for example, a hole transport region 140 .

[0284] The hole transport region 140 may further increase hole injection and / or hole mobility between the anode 120 and the light emitting 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, and at least one of the compounds of group B may be included in at least one of the hole transport layer and the hole transport auxiliary layer.

[0285] [Group B]

[0286]

[0287]

[0288]

[0289]

[0290]

[0291] In the hole transporting region 140, in addition to this compound, known compounds disclosed in US5061569A, JP1993-009471A, WO1995-009147A1, JP1995-126615A, JP1998-095973A, etc., and compounds similar thereto can be used.

[0292] In addition, the charge transport region may be, for example, the electron transport region 150 .

[0293] The electron transport region 150 may further increase electron injection and / or electron mobility between the cathode 110 and the light emitting layer 130 and block holes.

[0294] 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, and at least one of the compounds of group C may be included in at least one of the electron transport layer and the electron transport auxiliary layer.

[0295] [Group C]

[0296]

[0297]

[0298]

[0299]

[0300] One embodiment may be an organic light emitting diode including a light emitting layer as an organic layer.

[0301] Another embodiment may provide an organic light emitting diode including a light emitting layer and a hole transport region as an organic layer.

[0302] Another embodiment may provide an organic light emitting diode including a light emitting layer and an electron transport region as an organic layer.

[0303] like Figure 1 As shown, as the organic layer 105 , the organic light emitting diode according to the embodiment of the present invention may further include a hole transport region 140 and an electron transport region 150 in addition to the light emitting layer 130 .

[0304] On the other hand, as the above-mentioned organic layer, the organic light emitting diode may further include an electron injection layer (not shown), a hole injection layer (not shown), and the like in addition to the light emitting layer.

[0305] The organic light emitting diode 100 may be manufactured by forming an anode or a cathode on a substrate, forming an organic layer using a dry film forming method such as vacuum deposition (evaporation), sputtering, plasma plating, and ion plating, and forming a cathode or an anode thereon.

[0306] The organic light emitting diode may be applied to an organic light emitting display device.

[0307] Hereinafter, the embodiments are described in more detail with reference to Examples. However, these Examples are exemplary, and the present scope is not limited thereto.

[0308] Hereinafter, starting materials and reactants used in Examples and Synthesis Examples were purchased from Sigma-Aldrich Co. Ltd., TCI Inc., Tokyo chemical industry, or P&H tech unless specifically noted or synthesized by a known method.

[0309] (Preparation of compounds for organic optoelectronic devices)

[0310] The compound presented as a more specific example of the compound of the present invention is synthesized by the following steps.

[0311] Synthesis Example 1: Synthesis of Compound 64

[0312] [Reaction Scheme 1]

[0313]

[0314] Step 1: Synthesis of Intermediate 64-1

[0315] 4-bromo-1-chlorodibenzofuran (50.0 g, 178 mmol) and triisopropyl borate (40.1 g, 213 mmol) were dissolved in 1 L of anhydrous THF and then stirred at -78 ° C. After 30 minutes, 2.5 M n-butyl lithium solution (85.2 mL, 213 mmol) was slowly added dropwise thereto and then stirred for 12 hours. When the reaction was complete, a small amount of dilute hydrochloric acid was added thereto and then stirred for 1 hour. After separating the organic layer by extracting twice with a mixed solvent of distilled water and dichloromethane, the organic solvent of the organic layer was concentrated by using a rotary evaporator. The concentrated organic layer was slurry stirred / purified with n-hexane to obtain 34.6 g (79.0%) of intermediate 64-1.

[0316] Step 2: Synthesis of Intermediate 64-2

[0317] Intermediate 64-1 (34.6 g, 140 mmol), 1-bromo-2-iodobenzene (41.7 g, 147 mmol), Pd(PPh3)4 (8.1 g, 7 mmol) and K2CO3 (58.2 g, 421 mmol) were dissolved in 700 mL of a mixed solvent of tetrahydrofuran: distilled water = 2:1, and then stirred and refluxed at 80° C. for 12 hours. When the reaction was completed, the product was recrystallized from a mixed solvent of dichloromethane and n-hexane to obtain 41.2 g (82.1%) of intermediate 64-2.

[0318] Step 3: Synthesis of Intermediate 64-3

[0319] Intermediate 64-2 (41.2 g, 115 mmol) was dissolved in 600 mL of anhydrous THF and then stirred at -78 ° C. After 30 minutes, 2.5 M n-butyl lithium solution (55.2 mL, 138 mmol) was slowly added thereto in a dropwise manner. After 30 minutes, dichlorodimethylsilane (12.0 g, 127 mmol) was slowly added thereto in a dropwise manner and then stirred for 12 hours. When the reaction was complete, the product was extracted twice with a mixed solvent of ethyl acetate and distilled water to separate the organic layer, and the organic layer was purified by silica gel column chromatography to obtain 23.1 g (59.4%) of intermediate 64-3.

[0320] Step 4: Synthesis of Intermediate 64-4

[0321] Intermediate 64-3 (23.1 g, 69 mmol) and tris(triphenylphosphine)rhodium chloride (I) (1.3 g, 1 mmol) were dissolved in 300 mL of 1,4-dioxane and stirred at reflux for 12 hours at 110° C. When the reaction was complete, the product was purified by column chromatography with a mixed solvent of dichloromethane: n-hexane to obtain 15.5 g (67.5%) of intermediate 64-4.

[0322] Step 5: Synthesis of Intermediate 64-5

[0323] Intermediate 64-4 (15.5 g, 46 mmol), bis(pinacol)diboron (15.3 g, 60 mmol), potassium acetate (13.6 g, 139 mmol), tricyclohexylphosphine (2.6 g, 9 mmol) and [1,1'-bis(diphenylphosphino)ferrocene]-dichloropalladium(II) (1.9 g, 2 mmol) were added to 250 mL of N,N-dimethylformamide and then stirred and refluxed at 150 °C for 12 hours. When the reaction was complete, the solution was placed in excess DIW to form a precipitate. The precipitate was filtered, dissolved in toluene by boiling, and filtered again through silica gel. The filtered solution was recrystallized as it was to obtain 17.7 g (89.7%) of intermediate 64-5.

[0324] Step 6: Synthesis of compound 64

[0325] Compound 64 was synthesized / purified in the same manner as Intermediate 64-2 in Step 2 of Synthesis Example 1, except that Intermediate 64-5 and 2-chloro-4-(dibenzo[b,d]furan-1-yl)-6-phenyl-1,3,5-triazine were used as starting materials. LC / MS calculated: C41H27N3O2Si Exact mass: 621.19, measured: 622.30 [M+H]

[0326] Synthesis Example 2: Synthesis of Compound 84

[0327] [Reaction Scheme 2]

[0328]

[0329] a) Synthesis of Compound 84

[0330] Compound 84 was synthesized in the same manner as in step 2 of Synthesis Example 1, except that intermediate 64-5 and 2-([1,1'-diphenyl]-4-yl)-4-chloro-6-phenyl-1,3,5-triazine were used as starting materials. LC / MS calculated: C41H29N3OSi Exact mass: 607.21, measured: 608.27 [M+H]

[0331] Synthesis Example 3: Synthesis of Compound 85

[0332] [Reaction Scheme 3]

[0333]

[0334] a) Synthesis of Compound 85

[0335] Compound 85 was synthesized / purified in the same manner as in Step 2 of Synthesis Example 1, except that Intermediate 64-5 and 2-([1,1'-diphenyl]-3-yl)-4-chloro-6-phenyl-1,3,5-triazine were used as starting materials. LC / MS calculated: C41H29N3OSi Exact mass: 607.21, measured: 608.43 [M+H]

[0336] Synthesis Example 4: Synthesis of Compound 134

[0337] [Reaction Scheme 4]

[0338]

[0339] Intermediate 134-5 was synthesized in the same manner as in Steps 1 to 5 of Synthesis Example 1, except that 2,3-dibromonaphthalene was put in place of 1-bromo-2-iodobenzene to carry out the reaction in Step 2 of Synthesis Example 1, and Intermediate 134-5 and 2-chloro-4,6-diphenyl-1,3,5-triazine were used as starting materials to synthesize / purify Compound 134 in the same manner as in Step 2 of Synthesis Example 1. LC / MS calculated: C39H27N3OSi exact mass: 581.19, measured: 582.20 [M+H]

[0340] Synthesis Example 5: Synthesis of Compound 142

[0341] [Reaction Scheme 5]

[0342]

[0343] Step 1: Synthesis of Intermediate 142-1

[0344] 7-Chloro-naphtho[1,2-b]benzofuran (50.0 g, 198 mmol) was dissolved in 1 L of anhydrous THF and then stirred at -78 ° C. After 30 minutes, 2.5 M n-butyl lithium solution (95.0 mL, 237 mmol) was slowly added thereto, and then stirred for another 8 hours at room temperature. After 8 hours, the product was cooled to -78 ° C again, and triisopropyl borate (44.7 g, 237 mmol) was slowly added thereto, and then stirred for 12 hours. When the reaction was complete, a small amount of dilute hydrochloric acid was added thereto, and then stirred for 1 hour. After separating the organic layer by extracting twice with a mixed solvent of distilled water and dichloromethane, the organic solvent of the organic layer was concentrated by using a rotary evaporator. The concentrated organic layer was slurry stirred / purified with n-hexane to obtain 36.2 g (74.3%) of intermediate 142-1.

[0345] Step 2: Synthesis of compound 142

[0346] Intermediate 142-5 was synthesized in the same manner as in Steps 1 to 5 of Synthesis Example 1, except that Intermediate 142-1 was put in place of Intermediate 64-1 for reaction, and Compound 142 was synthesized / purified in the same manner as in Step 2 of Synthesis Example 1, except that Intermediate 142-5 and 2-chloro-4,6-diphenyl-1,3,5-triazine were used as starting materials. LC / MS calculated: C39H27N3OSi exact mass: 581.19, measured: 582.10 [M+H]

[0347] Comparative Synthesis Example 1: Synthesis of Compound C-1

[0348] [Reaction Scheme 6]

[0349]

[0350] Step 1: Synthesis of intermediate C-1-1

[0351] Intermediate C-1-1 was synthesized / purified in the same manner as in Step 2 of Synthesis Example 1, except that 4-bromo-1-chlorodibenzofuran and (2-(methoxycarbonyl)phenyl)boronic acid were used as starting materials.

[0352] Step 2: Synthesis of intermediate C-1-2

[0353] Intermediate C-1-1 (85.4 g, 254 mmol) was dissolved in 500 mL of anhydrous THF, and methylmagnesium bromide solution (211.8 mL, 634 mmol) was slowly added thereto in a dropwise manner at -78 ° C. After 12 hours, when the reaction was complete, the solution was slowly poured into ice water. The resulting mixture was extracted twice with ethyl acetate and distilled water, and then filtered through silica gel. The organic layer therefrom was completely evaporated and dried (without further purification), thereby obtaining 72.6 g (85.0%) of intermediate C-1-2.

[0354] c) Synthesis of intermediate C-1-3

[0355] Intermediate C-1-2 (72.6 g, 216 mmol) was dissolved in 400 mL of MC, and trifluoride boron etherate (29.3 mL, 237 mmol) was slowly added thereto in a dropwise manner at 0 ° C. After 12 hours, when the reaction was complete, the solution was slowly poured into distilled water. The mixture was extracted twice with dichloromethane and distilled water, and then filtered with silica gel. The organic layer therefrom was completely evaporated, and then recrystallized with toluene to obtain 37.3 g (54.3%) of intermediate C-1-3.

[0356] d) Synthesis of intermediate C-1-4

[0357] Intermediate C-1-4 was synthesized / purified in the same manner as in Step 5 of Synthesis Example 1, except that Intermediate C-1-3 was used as a starting material.

[0358] e) Synthesis of Compound C-1

[0359] Compound C-1 was synthesized in the same manner as in step 2 of Synthesis Example 1, except that intermediate C-1-4 and 2-chloro-4,6-diphenylpyrimidine were used as starting materials. LC / MS calculated: C37H26N2O Exact mass: 514.20, measured: 515.43 [M+H]

[0360] Comparative Synthesis Example 2: Synthesis of Compound C-2

[0361] [Reaction Scheme 7]

[0362]

[0363] Step 1: Synthesis of intermediate C-2-1

[0364] Intermediate C-2-1 was synthesized / purified in the same manner as in step 2 of Example 1, except that Intermediate C-1-4 and 1-bromo-4-chlorobenzene were used as starting materials.

[0365] Step 2: Synthesis of intermediate C-2-2

[0366] Intermediate C-2-2 was synthesized / purified in the same manner as in Step 5 of Synthesis Example 1, except that Intermediate C-2-1 was used as a starting material.

[0367] c) Synthesis of Compound C-2

[0368] Compound C-2 was synthesized / purified in the same manner as in step 2 of Synthesis Example 1, except that intermediate C-2-2 and 2-chloro-4,6-diphenyltriazine were used as starting materials. LC / MS calculated: C42H29N3O Exact mass: 591.23, measured: 592.40 [M+H]

[0369] Comparative Synthesis Example 3: Synthesis of Compound C-3

[0370] [Reaction Scheme 8]

[0371]

[0372] Step 1: Synthesis of intermediate C-3-1

[0373] Intermediate C-3-1 was synthesized / purified in the same manner as in step 2 of Comparative Synthesis Example 1, except that Intermediate C-1-1 and phenylmagnesium bromide were used as starting materials.

[0374] Step 2: Synthesis of intermediate C-3-2

[0375] Intermediate C-3-2 was synthesized / purified in the same manner as in Step 3 of Comparative Synthesis Example 1, except that Intermediate C-3-1 was used as a starting material.

[0376] Step 3: Synthesis of intermediate C-3-3

[0377] Intermediate C-3-3 was synthesized / purified in the same manner as in step 4 of Comparative Synthesis Example 1, except that Intermediate C-3-2 was used as a starting material.

[0378] Step 4: Synthesis of compound C-3

[0379] Compound C-3 was synthesized / purified in the same manner as in step 2 of Synthesis Example 1, except that intermediate C-3-3 and 2-chloro-4,6-diphenyltriazine were used as starting materials. LC / MS calculated: C46H29N3O Exact mass: 639.23, measured: 640.33 [M+H]

[0380] Comparative Synthesis Example 4: Synthesis of Compound C-4

[0381] [Reaction Scheme 9]

[0382]

[0383] Step 1: Synthesis of compound C-4

[0384] Intermediate C-4-4 was synthesized in the same manner as in Steps 1 to 4 of Comparative Synthesis Example 1, except that 4-bromo-1-chlorodibenzothiophene was used instead of 4-bromo-1-chlorodibenzofuran for the reaction in Step 1 of Comparative Synthesis Example 1, and compound C-4 was synthesized / purified in the same manner as in Step 2 of Synthesis Example 1, except that intermediate C-4-4 and 2-chloro-4,6-diphenylpyrimidine were used as starting materials. LC / MS calculated: C37H26N2S exact mass: 530.18, measured: 531.22 [M+H]

[0385] Comparative Synthesis Example 5: Synthesis of Compound C-5

[0386] [Reaction Scheme 10]

[0387]

[0388] Intermediate C-5-2 was synthesized in the same manner as in Steps 1 and 2 of Comparative Synthesis Example 2, except that intermediate C-4-4 was put into the reaction in Step 1 of Comparative Synthesis Example 2 instead of intermediate C-1-4, and compound C-5 was synthesized / purified in the same manner as in Step 2 of Synthesis Example 1, except that intermediate C-5-2 and 2-chloro-4,6-diphenyltriazine were used as starting materials. LC / MS calculated: C42H29N3S exact mass: 607.21, measured: 608.47 [M+H]

[0389] Comparative Synthesis Example 6: Synthesis of Compound C-6

[0390] [Reaction Scheme 11]

[0391]

[0392] Step 1: Synthesis of intermediate C-6-1

[0393] 1-Chloro-4-fluorobenzene (103.7 g, 794 mmol), 2,6-dibromophenol (50.0 g, 199 mmol) and K2CO3 (82.3 g, 596 mmol) were dissolved in 1 L of NMP and then stirred at 180 ° C. After 12 hours, when the reaction was complete, the solution was slowly poured into distilled water. The mixture was extracted twice with dichloromethane and distilled water and then filtered with silica gel. The organic layer therefrom was completely evaporated and then slurry purified with methanol to obtain 62.7 g (87.2%) of intermediate C-6-1.

[0394] Step 2: Synthesis of intermediate C-6-2

[0395] Intermediate C-6-1 (62.7 g, 173 mmol), Pd(OAc)2 (1.9 g, 9 mmol), PCy3HBF4 (10.0 g, 26 mmol) and K2CO3 (47.8 g, 346 mmol) were dissolved in 800 mL of DMAc and then stirred at 180 ° C. After 12 hours, when the reaction was complete, the solution was slowly poured into distilled water. The mixture was extracted twice with dichloromethane and distilled water, and then filtered with silica gel. The organic layer therefrom was completely evaporated and recrystallized with a mixed solution of dichloromethane: n-hexane to obtain 20.0 g (41.1%) of intermediate C-6-2.

[0396] Step 3: Synthesis of intermediate C-6-3

[0397] Intermediate C-6-3 was synthesized / purified in the same manner as in Synthesis Example 1, except that Intermediate C-6-2 was used as a starting material.

[0398] Step 4: Synthesis of intermediate C-6-4

[0399] Intermediate C-6-4 was synthesized / purified in the same manner as in Step 2 of Synthesis Example 1, except that Intermediate C-6-3 was used as a starting material.

[0400] Step 5: Synthesis of Intermediate C-6-5

[0401] Intermediate C-6-5 was synthesized / purified in the same manner as in Step 3 of Synthesis Example 1, except that Intermediate C-6-4 was used as a starting material.

[0402] Step 6: Synthesis of Intermediate C-6-6

[0403] Intermediate C-6-6 was synthesized / purified in the same manner as in Step 4 of Synthesis Example 1, except that Intermediate C-6-5 was used as a starting material.

[0404] Step 7: Synthesis of Intermediate C-6-7

[0405] Intermediate C-6-7 is synthesized / purified in the same manner as in Step 5 of Synthesis Example 1, except that Intermediate C-6-6 is used as a starting material.

[0406] Step 8: Synthesis of Compound C-6

[0407] Compound C-6 was synthesized / purified in the same manner as in step 2 of Synthesis Example 1, except that intermediate C-6-7 and 2-chloro-4,6-diphenyltriazine were used as starting materials. LC / MS calculated: C35H25N3OSi Exact mass: 531.18, measured: 532.22 [M+H]

[0408] Synthesis Example 6: Synthesis of Compound A-84

[0409] [Reaction Scheme 12]

[0410]

[0411] Step 1: Synthesis of intermediate 2-1a

[0412] In a round-bottom flask, phenylhydrazine hydrochloride (70.0 g, 484.1 mmol) and 7-bromo-3,4-dihydro-2H-naphthalene-1-one (108.9 g, 484.1 mmol) were dissolved in ethanol (1200 ml). 60 mL of hydrochloric acid was slowly added dropwise at room temperature, and then stirred at 90 ° C for 12 hours. When the reaction was complete, after removing the solvent under reduced pressure, an excess of EA was used for extraction. After removing the organic solvent therefrom under reduced pressure, the residue was stirred in a small amount of methanol and then filtered to obtain 95.2 g (66%) of intermediate 2-1a.

[0413] Step 2: Synthesis of intermediate 2-1b

[0414] In a round-bottom flask, 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 dissolved in 600 ml of toluene. The solution was stirred at 80° C. for 12 hours. When the reaction was complete, 41.3 g (44%) of intermediate 2-1b was obtained by column chromatography after removing the reaction solvent.

[0415] Step 3: Synthesis of intermediate 2-1c

[0416] In a round-bottom flask, intermediate 2-1b (41.3 g, 139.0 mmol), iodobenzene (199.2 g, 976.0 mmol), CuI (5.31 g, 28.0 mmol), K2CO3 (28.9 g, 209.0 mmol) and 1,10-phenanthroline (5.03 g, 28.0 mmol) were dissolved in 500 ml of DMF. The solution was stirred at 180 ° C for 12 hours. When the reaction was completed, after removing the reaction solvent therefrom under reduced pressure, the residue was dissolved in dichloromethane and then filtered with silica gel. The product filtered therefrom was concentrated with dichloromethane and recrystallized with hexane to obtain 39.0 g (75%) of intermediate 2-1c.

[0417] Step 4: Synthesis of Compound A-84

[0418] 5.0g (13.46mmol) intermediate 2-1c, 4.41g (13.46mmol) amine intermediate 2-1d, 1.94g (20.19mmol) sodium tert-butoxide and 0.54g (1.35mmol) tri-tert-butylphosphine were dissolved in 100ml toluene, and 0.37g (0.4mmol) Pd (dba) 2 was added thereto, and then stirred and refluxed for 12 hours under a nitrogen atmosphere. When the reaction was completed, after extraction with toluene and distilled water, the organic layer was dried with anhydrous magnesium sulfate and filtered, and the filtrate was concentrated under reduced pressure. The product from it was purified by silica gel column chromatography with n-hexane / dichloromethane (volume ratio of 2: 1), and 6.4g (yield: 82.0%) of compound A-84 was obtained.

[0419] Synthesis Example 7: Synthesis of Compound 2-92

[0420] [Reaction Scheme 13]

[0421]

[0422] Step 1: Synthesis of intermediate 2-92a

[0423] It was synthesized with reference to KR10-1423173B1.

[0424] Step 2: Synthesis of Compound 2-92

[0425] 5.0g (16.93mmol) of intermediate 2-92a, 5.4g (16.93mmol) of amine intermediate 2-92b, 2.44g (25.39mmol) of sodium tert-butoxide and 0.68g (1.69mmol) of tri-tert-butylphosphine were dissolved in 100ml of toluene, and 0.47g (0.51mmol) of Pd (dba) 2 was added thereto, and then stirred and refluxed for 12 hours under a nitrogen atmosphere. When the reaction was completed, after extraction with toluene and distilled water, the organic layer was dried with anhydrous magnesium sulfate and filtered, and the filtrate was concentrated under reduced pressure. The product obtained therefrom was purified by silica gel column chromatography with n-hexane / dichloromethane (volume ratio of 2: 1), and 8.2g (yield: 84.0%) of compound 2-92 was obtained.

[0426] (Manufacturing of organic light-emitting diodes)

[0427] Example 1

[0428] Wash with distilled water the A glass substrate of ITO (indium tin oxide) was prepared. After washing with distilled water, the glass substrate was ultrasonically washed with a solvent such as isopropyl alcohol, acetone, methanol, etc. and dried, then moved to a plasma cleaner, cleaned with oxygen plasma for 10 minutes, and moved to a vacuum depositor. The obtained ITO transparent electrode was used as an anode, and compound A doped with 3% NDP-9 (available from Novaled) was vacuum deposited on the ITO substrate to form A thick hole injection layer is formed, and compound A is deposited on the hole transport layer to form On the hole transport layer, Compound B was deposited to a thickness of 1000 to form a hole transport auxiliary layer. On the hole transport auxiliary layer, a 20%-doped 20%-doped 1 ... Then, on the light-emitting layer, Compound C is deposited at a thickness of 1:1 to form an electron transport auxiliary layer, and compound D and LiQ are simultaneously vacuum deposited at a weight ratio of 1:1 to form On the electron transport layer, Liq and Al are vacuum deposited sequentially to Thick and harmonious thick, thereby manufacturing an organic light emitting diode.

[0429] The organic light emitting diode has a structure of five organic thin film layers, as follows.

[0430] ITO / Compound A (3% NDP-9 doping, ) / Compound A / Compound B / EML[Compound 64:Ir(piq)2acac=98:2(w / w)] / Compound C / Compound D:Liq / LiQ / Al

[0431] Compound A: N-(biphenyl-4-yl)-9,9-dimethyl-N-(4-(9-phenyl-9H-carbazol-3-yl)phenyl)-9H-fluoren-2-amine

[0432] Compound B: N,N-di([1,1'-biphenyl]-4-yl)-7,7-dimethyl-7H-fluoren[4,3-b]benzofuran-10-amine

[0433] Compound C: 2-(3-(3-(9,9-dimethyl-9H-fluoren-2-yl)phenyl)phenyl)-4,6-diphenyl-1,3,5-triazine

[0434] Compound D: 8-(4-(4,6-di(naphthalen-2-yl)-1,3,5-triazine-2-yl)phenyl)quinoline

[0435] Example 2 to 5 and Comparative Examples 1 to 6

[0436] The diodes of Examples 2 to 5 and Comparative Examples 1 to 6 were respectively manufactured according to the same method as Example 1, except that the body was changed as shown in Table 1.

[0437] Examples 6 to 15 and Comparative Examples 7 to 12

[0438] Diodes of Examples 6 to 15 and Comparative Examples 7 to 12 were respectively manufactured according to the same method as Example 1, except that the host was changed as shown in Table 2 and the first host and the second host were mixed at a weight ratio of 5:5.

[0439] evaluate

[0440] The luminous efficiency and lifespan characteristics of the organic light emitting diodes according to Examples 1 to 15 and Comparative Examples 1 to 12 were evaluated. The specific measurement method is as follows, and the results are shown in Tables 1 and 2.

[0441] (1) Measurement of current density changes according to voltage changes

[0442] While increasing the voltage from 0 V to 10 V using a current-voltage meter (Keithley 2400), a current value flowing through the unit device in the obtained organic light emitting diode was measured, and the measured current value was divided by the area to provide a result.

[0443] (2) Measurement of brightness changes based on voltage changes

[0444] While the voltage of the organic light emitting diode was increased from 0V to 10V, the luminance was measured by using a luminance meter (Minolta Cs-1000A).

[0445] (3) Measurement of luminous efficiency

[0446] Using the luminance, current density, and voltage measured from (1) and (2), calculate the 2 )’s current efficiency (cd / A).

[0447] Relative values ​​of the luminous efficiency based on Comparative Example 1 and Comparative Example 7 were calculated and shown in Tables 1 and 2.

[0448] (4) Lifespan measurement

[0449] The T95 lifetimes of the diodes according to Examples 1 to 15 and Comparative Examples 1 to 12 were measured at 6,000 cd / m 2 As the initial brightness (cd / m 2 ) after emitting light, their brightness is relative to the initial brightness (cd / m 2 ) to 95%, and their brightness reduction over time was measured using the Polanonix lifetime measurement system.

[0450] Relative values ​​of T95 life based on Comparative Examples 1 and 7 were calculated and shown in Tables 1 and 2.

[0451] (5) Measurement of driving voltage

[0452] An ampere-voltmeter (Keithley 2400) was used at 15 mA / cm 2 The driving voltage of each diode is measured and the results are obtained.

[0453] The relative values ​​of the driving voltages based on Comparative Example 1 and Comparative Example 7 were calculated and shown in Tables 1 and 2.

[0454] (Table 1)

[0455] Single Subject Driving voltage (%) efficiency(%) Example 1 Compound 64 88 115 Example 2 Compound 84 88 115 Example 3 Compound 85 90 113 Example 4 Compound 134 90 113 Example 5 Compound 142 90 115 Comparative Example 1 Compound C-1 100 100 Comparative Example 2 Compound C-2 92 103 Comparative Example 3 Compound C-3 93 110 Comparative Example 4 Compound C-4 101 101 Comparative Example 5 Compound C-5 93 103 Comparative Example 6 Compound C-6 97 103

[0456] (Table 2)

[0457]

[0458] Referring to Table 1 and Table 2, when the compound according to the present invention is used as a single host and a mixed host in combination with a second host, the driving voltage, efficiency, and lifespan are significantly improved compared to using the comparative compound.

[0459] While the invention has been described in conjunction with what are presently considered to be practical exemplary embodiments, it is to be understood that the invention is not limited to the disclosed embodiments, but is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims.

Claims

1. A compound for an organic optoelectronic device, the compound being represented by Chemical Formula 1: [Chemical formula 1] in, In Chemical Formula 1, X 1 is O or S, Z 1 To Z 3 Each independently is N or CR a , Z 1 To Z 3 At least two of them are N, L 1 is a single key, L 2 and L 3 are each independently a single bond, a substituted or unsubstituted phenylene group, or a substituted or unsubstituted naphthylene group, Ar 1 and Ar 2 are each independently a substituted or unsubstituted phenyl, a substituted or unsubstituted biphenyl, a substituted or unsubstituted naphthyl, a substituted or unsubstituted phenanthryl, a substituted or unsubstituted carbazolyl, a substituted or unsubstituted dibenzofuranyl, a substituted or unsubstituted dibenzothiophenyl or a substituted or unsubstituted dibenzosilyl, R a and R 1 To R 5 are each independently hydrogen, deuterium or substituted or unsubstituted C1 to C10 alkyl, R 6 and R 7 are each independently a substituted or unsubstituted C1 to C10 alkyl group or a substituted or unsubstituted C6 to C12 aryl group, m1 and m2 are each independently an integer from 2 to 4, m3 and m4 are each independently an integer from 1 to 4, n1 and n2 are each independently an integer of 0 or 1, and "Substituted" means that at least one hydrogen of the substituent is replaced by deuterium, C1 to C5 alkyl, C6 to C18 aryl, or cyano.

2. The compound for an organic optoelectronic device according to claim 1, wherein Chemical Formula 1 is represented by Chemical Formula 1A or Chemical Formula 1B: [Chemical Formula 1A] [Chemical formula 1B] Wherein, in Chemical Formula 1A and Chemical Formula 1B, X 1 , Z 1 To Z 3 , L 1 To L 3 ,Ar 1 ,Ar 2 , R 1 To R 7 , m1 to m4, n1 and n2 are the same as those defined in claim 1.

3. The compound for an organic optoelectronic device according to claim 1, wherein Chemical Formula 1 is represented by any one of Chemical Formula 1-1 to Chemical Formula 1-7: Among them, in Chemical Formula 1-1 to Chemical Formula 1-7, X 1 , Z 1 To Z 3 , L 1 To L 3 ,Ar 1 ,Ar 2 , R 1 To R 7 And m1 to m4 are the same as defined in claim 1.

4. The compound for an organic optoelectronic device according to claim 1, wherein *-L 2 -Ar 1 and *-L 3 -Ar 2 Substituents independently selected from Group I: [Group I] Among them, in group I, D is deuterium, m14 is one of integers from 0 to 5, m15 is one of integers from 0 to 4, m16 is one of integers from 0 to 7, m17 is one of integers from 0 to 3, m18 is one of integers from 0 to 6, m19 is an integer from 0 to 2, and * is a connection point.

5. The compound for an organic optoelectronic device according to claim 1, wherein The compound is selected from the group consisting of: [Group 1] Wherein, D is deuterium.

6. A composition for an organic optoelectronic device, comprising a first compound and a second compound, in, The first compound is the compound for an organic optoelectronic device according to claim 1, and The second compound is a compound for an organic photoelectric device represented by Chemical Formula 2: [Chemical formula 2] Wherein, in Chemical Formula 2, X 2 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 8 are each independently hydrogen, deuterium, substituted or unsubstituted amine, substituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C6 to C30 aryl, or substituted or unsubstituted C2 to C30 heterocyclic, m5 is an integer from 1 to 4, and Ring A is any one selected from the rings of Group II, [Group II] Among them, in Group II, * is the connection point, X 3 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 9 To R 16 are each independently hydrogen, deuterium, substituted or unsubstituted amine, substituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C6 to C30 aryl, or substituted or unsubstituted C2 to C30 heterocyclic, m6, m8, m11 and m13 are each independently an integer from 1 to 4, m7, m9, m10 and m12 are each independently an integer of 1 or 2, and R 8 To R 16 At least one of them is a group represented by chemical formula a, [Chemical formula a] Among them, in chemical 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 a connection point, and "Substituted" means that at least one hydrogen of the substituent is replaced by deuterium, C1 to C5 alkyl, C6 to C18 aryl, or cyano.

7. The composition for an organic optoelectronic device according to claim 6, wherein: Chemical Formula 2 is represented by any one of Chemical Formula 2-I to Chemical Formula 2-IX: Among them, in Chemical Formula 2-I to Chemical Formula 2-IX, X 2 , X 3 , R 8 To R 11 , R 15 , R 16 , m5 to m8, m12 and m13 are the same as those defined in claim 6.

8. The composition for an organic optoelectronic device according to claim 6, wherein: The second compound is represented by any one of Formula 2-IA to Formula 2-IXA, Formula 2-IIB to Formula 2-IXB, and Formula 2-IIC to Formula 2-IXC: Among them, in Chemical Formula 2-IA to Chemical Formula 2-IXA, X 2 , X 3 , L 4 To L 6 ,Ar 3 ,Ar 4 , R 8 To R 11 , R 15 , R 16 , m6 to m8, m12 and m13 are the same as those defined in claim 6, and m5' is an integer from 1 to 3; Among them, in Chemical Formula 2-IIB to Chemical Formula 2-IXB, X 2 , X 3 , L 4 To L 6 , R 8 , R 10 , R 11 , R 15 , R 16 ,Ar 3 ,Ar 4 , m5, m7 and m12 are the same as those defined in claim 6, and m8' and m13' are each independently an integer from 1 to 3; Among them, in Chemical Formulae 2-IIC to 2-IXC, X 2 , X 3 , L 4 To L 6 ,Ar 3 ,Ar 4 , R 8 , R 10 , R 11 , R 15 , R 16 , m5, m8 and m13 are the same as those defined in claim 6.

9. The composition for an organic optoelectronic device according to claim 6, wherein: R 8 To R 16 Each is independently hydrogen, deuterium, a substituted or unsubstituted amine group, a substituted or unsubstituted C1 to C30 alkyl group, or a substituted or unsubstituted C6 to C30 aryl group.

10. The composition for an organic optoelectronic device according to claim 7, wherein: The second compound is represented by Chemical Formula 2-IVB-2 or Chemical Formula 2-VIIIB-2: Among them, in Chemical Formula 2-IVB-2 and Chemical Formula 2-VIIIB-2, L 4 To L 6 are each independently a single bond or a substituted or unsubstituted phenylene group, Ar 3 and Ar 4 are each independently a substituted or unsubstituted phenyl, a substituted or unsubstituted biphenyl, or a substituted or unsubstituted naphthyl, X 2 YesNR b , O, or S, X 3 Yes CR h R i or SiR j R k , R b , R h , R i , R j and R k are each independently a substituted or unsubstituted C1 to C10 alkyl group, or a substituted or unsubstituted C6 to C20 aryl group, R 8 , R 10 , R 11 , R 15 and R 16 are each independently hydrogen, deuterium, substituted or unsubstituted C1 to C30 alkyl, or substituted or unsubstituted C6 to C30 aryl, m5 is an integer from 1 to 4, m7 and m12 are each independently an integer of 1 or 2, and m8′ and m13′ are each independently one of integers from 1 to 3.

11. An organic optoelectronic device comprising an anode and a cathode facing each other, and at least one organic layer between the anode and the cathode, in, The organic layer includes a light-emitting layer, and The light-emitting layer comprises the compound for an organic optoelectronic device according to any one of claims 1 to 5; or The composition for an organic optoelectronic device according to any one of claims 6 to 10.

12. The organic optoelectronic device according to claim 11, wherein: The compound for an organic photoelectric device or the composition for an organic photoelectric device is included as a host of the light-emitting layer. 13 . A display device comprising the organic optoelectronic device according to claim 11 .

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