TWI644912B - Compound and organic electronic device using the same - Google Patents

Abstract

The invention provides a compound and an organic electronic device using the same. The compound is represented by the following formula (I), Y is an oxygen atom or a sulfur atom, and X ¹ and X ² are each independently C (R ^a ), and the two (R ^a ) the same or different from each other, the two (R ^a ) are connected to each other to form a first aromatic ring; X ³ and X ⁴ are each independently C (R ^b ), the two (R ^b ) are the same or different from each other, and the two ( R ^b ) are connected to each other to form a second aromatic ring or a heteroaromatic ring. <TABLE border = "1" borderColor = "# 000000" width = "85%"><TBODY><tr><td><img wi = "180" he = "166" file = "01_image002.gif" img- format = "jpg"></img></td></tr><tr><td> Formula (I) </ td></tr></TBODY></TABLE>

Description

Compound and organic electronic device using the same

The present invention relates to a novel compound and an organic electronic device using the same, and more particularly, to a novel compound for an electron transport layer and an organic electronic device using the same.

With the advancement of technology, various organic electronic devices made of organic materials have flourished. Common organic electronic devices such as organic light emitting devices (OLEDs), organic phototransistors, and organic photovoltaic devices Battery (organic photovoltaic cell) and organic photodetector (organic photodetector).

OLED was originally invented and proposed by Eastman Kodak. Dr. Deng Qingyun and Steven Van Slyke of Eastman Kodak used a vacuum evaporation method to form organic aromatic diamines. An electron transporting material is deposited on the transparent indium tin oxide (ITO) glass of the hole transporting layer {such as tris (8-hydroxyquinoline) aluminum (III), abbreviated as Alq ₃ ] }; Then, a metal electrode is deposited on the electron transport layer to complete the fabrication of the OLED. OLEDs have attracted much attention because they have the advantages of fast response rate, light weight, thinness, wide viewing angle, high brightness, high contrast, no need to set up a backlight, and low energy consumption, but OLEDs still have low efficiency and short life. problem.

In order to overcome the problem of low efficiency, one of the improvement methods is to provide an intermediate layer between the cathode and the anode. As shown in FIG. 1, the improved OLED is sequentially provided with a substrate 11, an anode 12, and a hole injection layer 13 (hole injection layer (HIL), a hole transport layer (HTL), an emitting layer 15 (EL), and an electron transport layer 16 (electron A transport layer (ETL), an electron injection layer 17 (EIL), and a cathode 18. When a voltage is applied to the anode 12 and the cathode 18, the holes emitted by the anode 12 will pass through the HIL and HTL and move to the EL, and the electrons emitted from the cathode 18 will move through the EIL and ETL to the EL, causing the holes The electrons and electrons recombine excitons in the EL layer, and light can be generated when the excitons decay from the excited state back to the ground state.

Another improvement method is to improve the ETL material in the OLED, so that the electron transport material exhibits hole blocking ability. The traditional electron transport material includes 3,3 ' -[5 ' -[3- (3-pyridyl) phenyl] [1,1 ' : 3 ' , 1 " -terphenyl] -3,3 " -diyl] dipyridine {(3,3 ' -[5 ' -[3- (3-pyridinyl) phenyl] [1, 1 ' : 3 ' , 1 " -terphenyl] -3,3 " -diyl] bispyridine, TmPyPb}, 1,3,5-tris (1-phenyl-1H-benzimidazol-2-yl) benzene [1 , 3,5-tris (1-phenyl-1H-benzimidazol-2-yl) benzene, TPBi], tris (2,4,6-trimethyl-3- (3-pyridyl) phenyl) borane [ tris (2,4,6-trimethyl-3- (pyridin-3-yl) phenyl) borane, 3TPYMB], 1,3-bis (3,5-dipyridin-3-yl-phenyl) benzene [1, 3-bis (3,5-dipyrid-3-yl-phenyl) benzene, BmPyPb] and 9,10-bis (3- (3-pyridyl) phenyl) anthracene [9,10-bis (3- (pyridin -3-yl) phenyl) anthracene, DPyPA].

However, even if the electron-transporting material is used, the current efficiency of the OLED has room for improvement, and therefore, the present invention provides a novel compound to overcome the problem of the conventional low current efficiency.

The object of the present invention is to provide a novel compound which can be used in organic electronic devices.

Another object of the present invention is to provide an organic electronic device using the novel compound, thereby reducing the driving voltage of the organic electronic device.

Furthermore, another object of the present invention is to provide an organic electronic device using the novel compound, thereby improving the efficiency of the organic electronic device.

To achieve the above object, the novel compound of the present invention is represented by formula (I): In formula (I), Y is an oxygen atom or a sulfur atom; in formula (I), X ¹ and X ² are each independently C (R ^a ), and the two (R ^a ) are the same or different from each other, and the two ( R ^a ) are connected to each other to form a first aromatic ring; in formula (I), X ³ and X ⁴ are each independently C (R ^b ), the two (R ^b ) are the same or different from each other, and the two (R ^b ) Interconnected to form a second aromatic ring or a heteroaromatic ring; in Formula (I), Z ¹ to Z ¹⁰ are each independently selected from the group consisting of hydrogen atom, deuterium atom, halo group, cyanide Radical, nitro, trifluoromethyl, alkyl having 1 to 40 carbons, alkenyl having 2 to 40 carbons, alkynyl having 2 to 40 carbons, ring having 3 to 60 carbons on the ring Alkyl, heterocycloalkyl having 3 to 60 carbons on the ring, aromatic group having 6 to 60 carbons on the ring, heteroaryl having 3 to 60 carbons on the ring, and 1 to 40 carbons Oxygen, aryloxy having 6 to 60 carbons on the ring, silyl having 1 to 40 carbons, arylsilyl having 6 to 60 carbons on the ring, boryl having 1 to 40 carbons, Arylboryl groups having 6 to 60 carbon atoms on the ring, phosphine groups having 1 to 40 carbon atoms, and phosphine oxide groups having 1 to 40 carbon atoms.

Preferably, the first aromatic ring formed by the extension of X ¹ and X ² and the second aromatic ring formed by the extension of X ³ and X ^{4 in} formula (I) are independently a substituted or unsubstituted and Carbocyclic ring having 6 to 60 carbon atoms. More preferably, the first aromatic ring formed by the extension of X ¹ and X ² and the second aromatic ring formed by the extension of X ³ and X ⁴ in the formula (I) are each independently a substituted or unsubstituted and A carbon ring having 6 to 20 carbon atoms.

For example, the substituted or unsubstituted carbon ring having 6 to 60 carbon atoms can be selected from the group consisting of a substituted or unsubstituted benzene ring structure, a substituted or unsubstituted Naphthalene ring structure, a substituted or unsubstituted anthracene ring structure, a substituted or unsubstituted phenanthrene ring structure, a substituted or unsubstituted fluorene ring structure, a substituted or unsubstituted fluoranthene ring structure, The substituted and unsubstituted benzofluoranthene ring structure and the substituted or unsubstituted fluorene ring structure are not limited thereto. More preferably, the substituted or unsubstituted carbocyclic ring having 6 to 60 carbon atoms is a substituted or unsubstituted benzene ring structure, a substituted or unsubstituted naphthalene ring structure, or a substituted or unsubstituted Substituted pyrene ring structure. The substituent on the carbon ring having 6 to 20 carbon atoms may be, but is not limited to, a halo group, a cyano group, a nitro group, an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, or a carbon Alkynyl having a number of 2 to 12.

Preferably, the heteroaryl ring formed by the extension of X ³ and X ⁴ in formula (I) may include at least one furan group or at least one thiophene group. For example, the heteroaryl ring may be, but is not limited to, a substituted or unsubstituted dibenzofuran ring, a substituted or unsubstituted dibenzothiophene ring, a substituted or An unsubstituted benzofuran ring, a substituted or unsubstituted isobenzofuran ring, a substituted or unsubstituted benzothiophene ring, or a substituted or unsubstituted A substituted isobenzothiophene ring.

Preferably, Z ¹ to Z ¹⁰ are independently selected from the group consisting of hydrogen atom, deuterium atom, halo group, cyano group, nitro group, trifluoromethyl group, and carbon number 1 to 12 Alkyl, alkenyl having 2 to 12 carbons, alkynyl having 2 to 12 carbons, cycloalkyl having 3 to 30 carbons on the ring, heterocycloalkyl having 3 to 30 carbons on the ring, Aromatic groups with 6 to 30 carbons on the ring, heteroaryl groups with 3 to 30 carbons on the ring, alkoxy groups with 1 to 12 carbons, aryloxy groups with 6 to 30 carbons on the ring, carbon Silyl groups of 1 to 12, arylsilyl groups of 6 to 30 carbon rings, boryl groups of 1 to 12 carbon atoms, arylboryl groups of 6 to 30 carbon rings, 1 carbon number Phosphino to 12 and oxophosphine having 1 to 12 carbons.

When Y is an oxygen atom, the compound may be represented by any of the following general formulas, for example:

When Y is a sulfur atom, the compound may be represented by any of the following general formulas, for example:

According to the present invention, the above A ¹ and A ² are independently C (R ^c ), the two (R ^c ) are the same or different from each other, and the two (R ^c ) are connected to each other to form an aromatic structure, and the aromatic structure is included in By the second aromatic ring or the heteroaromatic ring. According to the present invention, each of the aforementioned Z ¹¹ is selected from the group consisting of monomethyl, monoethyl, monopropyl, monobutyl, monopentyl, monohexyl, and monophenyl.

Preferably, the aromatic structure formed by connecting di (R ^c ) to each other may be a substituted or unsubstituted aromatic ring structure having 6 to 20 carbon atoms, such as, but not limited to, a substituted or unsubstituted Benzene ring structure, substituted or unsubstituted naphthalene ring structure, substituted or unsubstituted anthracene ring structure, substituted or unsubstituted phenanthrene ring structure, substituted or unsubstituted fluorene ring structure, once substituted Or an unsubstituted fluoranthene ring structure, a substituted or unsubstituted benzofluoranthene ring structure, or a substituted or unsubstituted fluorene ring structure; the substituted or unsubstituted and the carbon number is 6 to The substituent on the aromatic cyclic structure of 20 may be: monohalo, monocyano, mononitro, trifluoromethyl, alkyl having 1 to 12 carbons, and olefin having 2 to 12 carbons Or an alkynyl group having 2 to 12 carbons, but is not limited thereto.

Preferably, at least one of Z ¹ to Z ⁸ in formula (I) is selected from the group consisting of an alkyl group having at least one functional group and 1 to 40 carbon atoms, having at least one Alkenyl groups having 2 to 40 carbon atoms, functional groups, alkynyl groups having at least one functional group and 2 to 40 carbon atoms, cycloalkyl groups having at least one functional group and 3 to 60 carbon atoms on the ring, having at least Heterocycloalkyl having one functional group and 3 to 60 carbon atoms on the ring, aromatic group having at least one functional group and 6 to 60 carbon atoms on the ring, having at least one functional group and 3 to 60 carbon atoms on the ring Heteroaryl, alkoxy having at least one functional group and 1 to 40 carbon atoms, aryloxy having at least one functional group and 6 to 60 carbon atoms in the ring, having at least one functional group and carbon number 1 to 40 silyl groups, aryl silyl groups having at least one functional group and 6 to 60 carbons on the ring, boryl groups having at least one functional group and 1 to 40 carbons, having at least one functional group and a ring An arboryl group having 6 to 60 carbon atoms, a phosphine group having at least one functional group and 1 to 40 carbon atoms, and an phosphine group having at least one functional group and 1 to 40 carbon atoms. Whereas the others in Z ¹ to Z ⁸ in formula (I) may be the remaining substituents mentioned in the specification, and the functional group is selected from the group consisting of cyano, nitro, trifluoromethyl, fluoro and chloro Group.

More preferably, at least one of Z ¹ to Z ⁸ is a specific aromatic substituent, and the specific aromatic substituent is selected from the group consisting of: Among them, R ¹ to R ⁷ are each independently selected from the group consisting of hydrogen atom, deuterium atom, halo group, cyano group, nitro group, trifluoromethyl group, and alkyl group having 1 to 12 carbon atoms. Alkenyl with 2 to 12 carbons, alkynyl with 2 to 12 carbons, cycloalkyl with 3 to 30 carbons on the ring, heterocycloalkyl with 3 to 30 carbons on the ring, An aromatic group having 6 to 30 carbons, a heteroaryl group having 3 to 20 carbons on the ring, an alkoxy group having 1 to 40 carbons, an aryloxy group having 6 to 30 carbons on the ring, and a carbon number of Silyl groups of 1 to 40, arylsilyl groups of 6 to 30 carbons on the ring, boryl groups of 1 to 40 carbons, arylboryl groups of 6 to 30 carbons on the ring, 1 to 30 carbons And a phosphine group having 1 to 30 carbon atoms; wherein n is an integer from 0 to 4; m is an integer from 0 to 3; o is an integer from 0 to 3; the sum of m and o is less than or equal to 5 .

Preferably, the R ¹ to R ⁷ are each independently, but not limited to: phenyl, pyridine group, pyrimidine group, pyrazine group, pyridazine group ), Phenylpyridine group, phenylpyrimidine group, phenylpyrazine group, or phenylpyridazine group.

Preferably, at least one of Z ¹ , Z ² , Z ³ , Z ⁶ , Z ⁷ and Z ⁸ in the formula (I) is the specific aromatic substituent, and Z ⁴ and Z ⁵ are each independently selected from the group consisting of A group consisting of: hydrogen, deuterium, halo, cyano, nitro, alkyl having 1 to 12 carbons, alkenyl having 2 to 12 carbons, and alkyne having 2 to 12 carbons base. Alternatively, at least one of Z ² , Z ³ , Z ^6, and Z ⁷ in formula (I) is the specific aromatic substituent, and Z ¹ , Z ⁴ , Z ^5, and Z ⁸ are each independently selected from the following Groups formed: hydrogen atom, deuterium atom, alkyl group having 1 to 12 carbon atoms, alkenyl group having 2 to 12 carbon atoms, and alkynyl group having 2 to 12 carbon atoms.

Preferably, at least one of Z ² , Z ³ , Z ⁶ and Z ⁷ in formula (I) is selected from the group consisting of:

More preferably, at least one of Z ¹ , Z ² , Z ³ , Z ⁶ , Z ⁷ and Z ⁸ in formula (I) is a diphenyl, dipyridyl, dipyrimidinyl, dipyrazinyl, di Pyridazinyl, dibenzopyridyl, dibenzopyrimidyl, dibenzopyrazinyl or dibenzopyrazinyl-substituted triazine group.

Preferably, Z ⁹ and Z ¹⁰ in the formula (I) may be independently selected from the group consisting of a hydrogen atom, a deuterium atom, a halo group, a cyano group, a nitro group, and a carbon number of 1 to 12. Alkyl, alkenyl having 2 to 12 carbons, and alkynyl having 2 to 12 carbons.

According to the present invention, Z ¹ and Z ⁸ in formula (I) may be the same or different, Z ² and Z ⁷ may be the same or different, Z ³ and Z ⁶ may be the same or different; For example, any one of Z ¹ , Z ² , Z ³ , Z ⁶ , Z ⁷ and Z ⁸ may be the same substituent as described above, and Z ¹ , Z ² , Z ³ , Z ⁶ , Z ⁷ and Z ^The others in ⁸ may be selected from the group consisting of a hydrogen atom, a deuterium atom, a halogen group, a cyano group, a nitro group, an alkyl group having 1 to 12 carbon atoms, and an alkenyl group having 2 to 12 carbon atoms. And alkynyl having 2 to 12 carbons.

For example, the compound may be selected from the group consisting of: Compound 206, compound 207, compound 208, compound 209,

The invention further provides an organic electronic device, which includes a first electrode, a second electrode, and an organic layer disposed between the first electrode and the second electrode, and the organic layer includes the compound.

Preferably, the organic electronic device is an organic light emitting diode (OLED). More preferably, the novel compound can be used as a material for forming the electron transporting layer or the hole blocking layer.

Specifically, the organic light emitting diode includes a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer; the hole injection layer is formed on the first electrode; The hole transport layer is formed on the hole injection layer; the light emitting layer is formed on the hole transmission layer; the electron transport layer is formed on the light emitting layer; the organic layer is the electron transport layer; the electron injection layer Formed between the electron transport layer and the second electrode. In one embodiment, the organic layer may be an electron transport layer, that is, the electron transport layer includes the compound.

Preferably, the hole injection layer may have a double-layer structure, that is, the OLED has a first hole injection layer and a second hole injection layer, and the first hole injection layer and the second hole injection layer are disposed. Between the first electrode and the hole transport layer.

Similarly, the hole transmission layer may also have a double-layer structure, that is, the OLED has a first hole injection layer and a second hole injection layer, and the first hole injection layer and the second hole injection layer are disposed. Between the double-layer structure of the hole injection layer and the light emitting layer.

Preferably, the electron transport layer is made of the novel compound (such as the compounds 1 to 257). The OLED of the present invention has better current efficiency than the commercial OLED, and the commercial OLED is used Compounds such as 2- {4- [9,10-bis (2-naphthyl) -2-anthyl] phenyl} -1-phenyl-1H-benzo [d] imidazole {2- [4- ( 9,10-di (naphthalen-2-yl) anthracen-2-yl) phenyl] -1-phenyl-1H-benzo [d] imidazole}, bis (2-methyl-8-hydroxyquinoline) (p- Phenylphenol) aluminum [bis (2-methyl-8-quinolinolato) (p-phenylphenolato) aluminum] or 2- (4-biphenyl) -5- (tert-butylphenyl) -1,3,4-ox Diazole [2- (4-biphenylyl) -5- (4-tert-butylphenyl) -1,3,4-oxadiazole), PBD].

Preferably, the OLED includes a hole blocking layer formed between the electron transporting layer and the light emitting layer, which can prevent the hole from moving from the light emitting layer to the electron transporting layer. Compound, 2,9-dimethyl-4,7-biphenyl-1,10-o-phenanthroline (2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline, BCP) or 2 , 3,5,6-tetramethyl-1-phenyl-1,4-phthalimide [2,3,5,6-tetramethyl-phenyl-1,4- (bis-phthalimide), TMPP], but it is not limited to this. In another embodiment, the organic layer may be a hole blocking layer, and the hole blocking layer has the aforementioned novel compound.

Preferably, the OLED includes an electron blocking layer formed between the hole transporting layer and the light emitting layer, which can prevent electrons from moving from the light emitting layer to the hole transporting layer. The electron blocking layer may be 4,4 '-Bis (9-oxazole) biphenyl [9,9'-(1,1'-biphenyl) -4,4'-diylbis-9H-carbazole, CBP] or 4,4 ', 4 "-tris ( N-oxazolyl) triphenylamine [4,4 ', 4 "-tri (N-carbazolyl) -triphenylamine, TCTA] is formed, but it is not limited to this.

When the OLED is provided with a hole blocking layer or an electron blocking layer, the OLED of the present invention has higher luminous efficiency than the conventional OLED.

Said first and second hole transport layer may be N, N '- (4,4'- biphenyl two) bis (N ¹ - (1- naphthyl)) - N, N'- phenyl biphenyl -1,4-diamine [N ¹ , N ^{1 '} -(biphenyl-4,4'-diyl) bis (N ^1- (naphthalen-1-yl) -N ⁴ , N ^4' -diphenylbenzene-1,4 -diamine)] or N, N'-biphenyl-N, N'-bis (1-naphthyl) -1,1'-biphenyl-4,4'-diamine [N ⁴ , N ^{4 '} -di (naphthalen-1-yl) -N ⁴ , N ^{4 '} -diphenylbiphenyl-4,4'-diamine (NPB)].

The first and second hole injection layers may be made of polyaniline or polyethylenedioxythiophene, but are not limited thereto.

The light-emitting layer may be made of a light-emitting material. The light-emitting material includes a host and a dopant. The material of the host is, for example, 9- [4- (1-naphthyl) benzene. The group] -10- (2-naphthyl) anthracene [9- (4- (naphthalen-1-yl) phenyl) -10- (naphthalen-2-yl) anthracene], but is not limited thereto.

For red OLED, the dopant in the light-emitting layer may be a divalent iridium organometallic compound having a perylene ligand, a fluoranthene ligand, or a perinflanthene ligand, but It is not limited to this. For green OLEDs, the dopants in the light-emitting layer can be diaminoflourenes, diaminoanthracenes, or divalent iridium organometallic compounds with phenylpyridine ligands, but not limited to them this. For blue OLEDs, the dopants in the light-emitting layer may be diaminofluorene, anthracenediamine, diaminopyrenes, or a divalent iridium organometallic compound having a phenylpyridine ligand, but it is not limited thereto. With different materials for the main emitter, OLEDs can emit red, green or blue light.

The electron injection layer may be made of an electron injection material, for example, 8-oxonaphthalen-1-yl lithium [(8-oxidonaphthalen-1-yl) lithium (II)], but is not limited thereto.

The first electrode may be an indium-doped tin oxide electrode, but it is not limited thereto.

A work function of the second electrode is lower than a work function of the first electrode. Therefore, the second electrode may be, but is not limited to, an aluminum electrode, an indium electrode, or a magnesium electrode.

Other objects, effects and technical features of the present invention will be described in more detail with reference to drawings, examples and comparative examples.

11‧‧‧ substrate

12‧‧‧Anode

13‧‧‧ Hole injection layer

14‧‧‧ Hole Transmission Layer

15‧‧‧Light-emitting layer

16‧‧‧ electron transmission layer

17‧‧‧ Electron injection layer

18‧‧‧ cathode

FIG. 1 is a side sectional view of an OLED.

2 to 18 are proton nuclear magnetic resonance spectra of compounds 1 to 17, respectively.

Several examples are listed below as examples to illustrate the embodiments of the compounds of the present invention and their organic electronic devices, so as to highlight the differences of the present invention compared to the prior art; those skilled in the art can easily understand what the present invention can do through the content of this specification. The advantages and effects achieved, and various modifications and changes can be made without departing from the spirit of the invention to implement or apply the content of the invention.

Synthesis of intermediate A1

Intermediate A1 is used to prepare a novel compound. Intermediate A1 can be synthesized by the steps in the following synthetic mechanism A1.

Step 1: Synthesis of Intermediate A1-1

86 grams (1.0 equivalent) of 3-bromodibenzo [a, d] cyclohepten-5-one (3-bromodibenzo [a, d] cyclohepten-5-one, CAS No.3973-53-3) , 106 g (2.0 equivalents) of N-bromosuccinimide (NBS) and 0.7 g (0.01 equivalents) of benzyl peroxide in four times five volumes of the starting material In carbon tetrachloride (CCl ₄ ), the reaction was heated to 65 ° C to 70 ° C. During the reaction, monitoring was performed by high performance liquid chromatography (HPLC); when the reaction was completed The precipitate produced by the reaction was separated by filtration, washed with methanol and purified by recrystallization, and then concentrated and dried to obtain 123 g of a white solid product with a yield of 92.3%.

It was determined by field desorption mass spectroscopy (FD-MS) analysis that the white solid product was the intermediate A1-1. FD-MS analysis results: C ₁₅ H ₉ Br ₃ O, theoretical 444.94, detected 444.94.

Step 2: Synthesis of intermediate A1

The intermediate A1-1 (1.0 equivalent) was dissolved in dimethyl sulfoxide (DMSO) (w / v = 1/3 with respect to the reactant) and heated to 70 ° C., and monitored by HPLC during the reaction. After the reaction was completed, the solution was rapidly cooled in ice water and the precipitate was filtered and purified by silica gel column chromatography to obtain a pale yellow solid product intermediate A1 with a yield of 93%. FD-MS analysis confirmed that the result of FD-MS analysis: C ₁₅ H ₉ BrO, theoretical value 285.14, detection value 285.14.

FD-MS analysis confirmed that the light yellow solid product was the intermediate A1-2. FD-MS analysis results: C ₁₉ H ₁₁ BrO ₂ , theoretical value 351.19, detected value 351.19.

Synthesis of intermediate A2

Intermediate A2 (Intermediate A2) is used to prepare a novel compound. Intermediate A2 is synthesized in steps 1 and 2 similar to the synthesis of intermediate A1. The difference lies in the starting material 3-bromodibenzo [a, d] Cyclohepten-5-one is 2-bromodibenzo [a, d] cyclohepten-5-one (2-bromodibenzo [a, d] cyclohepten-5-one, CAS No. 198707-82- 3) Instead, the synthesis path of intermediate A2 is integrated in synthesis mechanism A2. The analysis method of all intermediates in synthesis mechanism A2 is the same as described above, and the analysis results are listed in Table 1 below.

Synthesis of intermediate A3

Intermediate A3 (Intermediate A3) is used to prepare a novel compound. Intermediate A3 is synthesized similar to Step 1 to Step 4 of Synthetic Intermediate A1. The difference is that the starting material 3-bromodibenzo [a, d) cyclohepten-5-one (3,7-dibromodibenzo [a, d] cyclohepten-5-one (3,7-dibromodibenzo [a, d] cyclohepten-5-one) (CAS No. 226946-20-9) Instead, the synthetic pathway of intermediate A3 is integrated in synthesis mechanism A3. The analysis methods of all intermediates in synthesis mechanism A3 are the same as described above, and the analysis results are listed in Table 1 below.

Modification of intermediates A1 to A3

In addition to the intermediates A1 to A3, those with ordinary knowledge in the art can substitute the starting materials in the synthetic mechanisms A1 to A3 and synthesize other intermediates in a synthetic path similar to the synthetic mechanisms A1 to A3, for example, the following The intermediates A4 to A15 come out:

Synthesis of intermediates B1 to B4

Intermediates B1 to B4 are obtained by reacting 1-fluoro-2-nitrobenzene with a phenol derivative (Ar ¹ -OH, ie, reactant An). The synthesis route of intermediate Bn This is shown in Synthesis Mechanism B-1. In Synthesis Mechanism B-1, "Reactant An" is selected from any one of the reactants A1 to A4 in Table 2-1, and "Intermediate Bn" is selected from the group consisting of Any one of the aforementioned groups of intermediates B1 to B4. According to the synthesis mechanism B-1, the intermediates B1 to B4 are synthesized according to the following steps 1 to 3.

Step 1: Synthesis of intermediate Bn-1

Mix 1.0 equivalent of a phenol derivative (Reactant An), 50 g (1 equivalent) of 1-fluoro-2-nitrobenzene, and 230.9 g (2 equivalents) of cesium carbonate (Cs ₂ CO ₃ ) in 2080 ml of 0.17 volume mole concentration (M) in dimethylformamide (DMF), and stirred in an argon atmosphere at 90 ° C, and then cooled with water, extracted with ethyl acetate, dried over magnesium sulfate, and then filtered. Concentrated under low pressure environment, the crude product was purified by silica gel column chromatography, and determined as intermediate Bn-1 by FD-MS analysis; taking B1-1 as an example, the analysis result of FD-MS was C ₁₂ H ₉ NO ₃ , The theoretical molecular weight is 215.2 and the measured molecular weight is 215.2.

Step 2: Synthesis of intermediate Bn-2

Add 1.0 equivalent of intermediate Bn-1 and 10 g of 5% palladium-carbon catalyst (Pd / C, 0.015 equivalent) to 680 ml of 0.5M ethanol and stir at 70 ° C. 31.6 g (2.0 equivalent) of Hydrazine monohydrate was slowly added to the solution. After the reaction was completed, the product was filtered through a celite pad and concentrated under a low pressure environment to obtain the product, which was identified as the intermediate Bn-2 by FD-MS analysis. Taking B1-2 as an example, the analysis result of FD-MS is C ₁₂ H ₁₁ NO, the theoretical molecular weight is 185.22, and the measured molecular weight is 185.22.

Step 3: Synthesis of intermediate Bn

Mix 1.0 equivalent of intermediate Bn-2 and 172.5 g (3.0 equivalents) of p-toluenesulfonic acid hydrate (PTSA * H ₂ O) in 224 ml of 1.3M acetonitrile (ACN) solution and cool to 5 in an ice bath. ℃, 41.7 g (2 equivalents) of sodium nitrite (NaNO ₂ ) was dissolved in 240 ml of water and added dropwise. After the dropwise addition was completed, the ice bath was maintained at 5 ° C. for 1 hour. It was treated with a 300 ml aqueous solution in which 100 g (2 equivalents) of potassium iodide (KI) was dissolved, followed by extraction with ethyl acetate. After the organic phases were combined, the organic phase was washed with a 10% sodium sulfite aqueous solution and dried over sodium sulfate, and then filtered under a low pressure environment to obtain The crude product was purified by silica gel column chromatography to obtain intermediate Bn. The chemical structural formula of the reactant An used to synthesize the intermediate Bn (especially intermediates B1 to B4), and the chemical structural formulas and yields of the intermediates Bn-1, Bn-2, and Bn are listed in Table 2-1. Intermediates B1 to B4 were determined by FD-MS analysis, and the analysis results are listed in Table 2-1.

Synthesis of intermediates B5 to B8

Unlike intermediates B1 to B4, intermediates B5 to B8 are synthesized by the reaction of 2-bromobenznenthiol and an aryl iodide. Therefore, intermediate Bn can be another synthetic mechanism B -2 to synthesize. In the synthesis mechanism B-2, the "reactant An" may be any one of the reactants A5 to A8 in Table 2-2 or an analogue thereof, and the "intermediate Bn" may be an intermediate Any of B5 to B8.

According to the synthetic mechanism B-2, 0.5% equivalent of tris (dibenzylideneacetone) dipalladium (tris (dibenzylideneacetone) dipalladium, Pd ₂ (dba) ₃ ), 0.01 equivalent of bis (2-diphenyl-o-phenyl) Ether (Bis (2-diphenylphosphinophenyl) ether, DPEphos), 1.5 equivalents of sodium tert-butoxide (Na-OtBu) were added to the screw-top vial, and then toluene and a stirrer were added to the screw-top Vial, add 1.05 equivalent of 2-bromothiophenol and 1.0 equivalent of aryl iodide derivative (reactant An); seal the screw-top vial again and stir at 100 ° C for 1 hour to obtain the crude product, The product was filtered through a pad of diatomaceous earth, concentrated, and then purified using a short silica gel column using heptane as an eluent to obtain the intermediate Bn. The chemical structural formula of the reactant An used to synthesize the intermediate Bn (especially intermediates B5 to B8), and the chemical structure formula and yield of the intermediate Bn are listed in Table 2-2. The intermediates B5 to B8 are all represented by FD. -MS analysis confirmed, and the analysis results are listed in Table 2-2.

Modification of intermediates B1 to B4

In addition to the intermediates B1 to B4, those skilled in the art can choose any phenol derivative other than 1-fluoro-2-nitrobenzene halonitrobenzene and other phenols except the reactants A1 to A4 As a reactant, other intermediates Bn are synthesized in a similar manner to the synthesis mechanism B-1, such as the following intermediates B9 to B20:

Modification of intermediates B5 to B8

In addition to the intermediates B5 to B8, those skilled in the art can choose any halobenzenethiol except 2-bromothiophenol and other aryl iodine derivatives except for the reactants A5 to A8. Reactant An, and other intermediates Bn are synthesized in a similar procedure to synthetic mechanism B-2, such as the following intermediates B21 to B36:

Synthesis of intermediate Cn

The aforementioned intermediates B1 to B36 (Intermediate Bn), especially the intermediates B1 to B8, can be further used to synthesize the intermediate Cn (Intermediate Cn). The synthesis path of the intermediate Cn is shown in the synthesis mechanism C-1. In Synthesis Mechanism C-1, "Intermediate An" is selected from any one of the group including intermediates A1 to A15 and the like, and "Intermediate Bn" is selected from the group consisting of Any one of the groups of intermediates B1 to B36 and their analogs, and "intermediate Cn" is any one selected from the group including intermediates C1 to C10 and their analogs in Table 3-1 ; Intermediates C1 to C10 were synthesized in the following steps, respectively.

Step 1: Synthesis of intermediate Cn-1

1.0 equivalent of intermediate Bn was dissolved in 120 ml of 0.4M anhydrous tetrahydrofuran (THF), and the temperature was reduced to -78 ° C, and n-butyllithium (n-BuLi) (2.5M, 1.0 equivalent) was slowly added to form a reaction The solution was stirred for 1 hour. Next, an intermediate An (0.7 equivalent) was added to the reaction solution and stirred at 25 ° C for another 3 hours. After the reaction was completed, the reaction solution was cooled with a saturated ammonium chloride aqueous solution, and the organic phase was separated by extraction with an organic solvent. After concentration, it was recrystallized using petroleum ether to obtain a white solid product. The white solid product was determined through analysis by FD-MS. The chemical structural formulas, yields, and molecular formulas and masses determined by FD-MS analysis of each intermediate are listed in Table 3-1.

Step 2: Synthesis of intermediate Cn

Mix 1 equivalent of intermediate Cn-1, acetic acid (HOAc) (compared to the reactant, w / v = 1/3) and 5 drops of sulfuric acid (H ₂ SO ₄ ) and stir at 110 ° C for 6 hours, then at The solvent was removed under a low-pressure environment. After purification by column chromatography, the product was recrystallized from toluene to obtain a white solid product.

Modification of intermediates C1 to C10

In addition to the intermediates C1 to C10, those skilled in the art may choose any intermediate An except the intermediates A1 to A3 and any intermediate Bn except the intermediates B1 to B8, according to the synthesis mechanism C-1. Synthesis of intermediates Cn, such as but not limited to the following intermediates C11 to C50:

Synthesis of intermediate Cn-B

The aforementioned intermediate Cn can be further modified into the intermediate Cn-B by the Miyaura borylation reaction. "Intermediate Cn-B" is the intermediate Cn The bromine group of (Intermediate Cn) is substituted with a (pinacolato) boron group, and the intermediate Cn-B can be synthesized by a synthetic route in the following synthesis mechanism C1-B.

1.2 equivalents of bis (pinacolato) diboron, 1.0 equivalents of intermediate Cn, 0.015 equivalents of [1,1-bis (diphenylphosphino) ferrocene] palladium dichloride [1 , 1-bis (diphenylphosphino) -ferrocene dichloropalladium (II), PdCl ₂ (dppf)] and 3.0 equivalents of potassium acetate (KOAc) in 0.3M anhydrous 1,4-dioxane (1,4-dioxane) A mixed solution was formed and stirred under a nitrogen environment at 110 ° C. for 8 hours. After cooling to room temperature, the solvent was removed under a low-pressure environment, and the residue was purified by column chromatography to obtain a pale yellow product. The chemical structure formula and yield of the pale yellow product, and the molecular formula and mass results analyzed by FD-MS are listed in Table 3-2.

Modification of intermediate Cn-B

In addition to the above-mentioned intermediates Cn and Cn-B, those skilled in the art may choose from any of the groups formed by the foregoing intermediates Cn and perform tasks in a manner similar to the synthesis mechanism C1-B. An intermediate Cn is subjected to a boronation reaction of Suzuki to synthesize the intermediate Cn-B.

Synthesis of novel compounds

Each of the intermediates Cn and Cn-B can be separately synthesized with a different reactant (Claimed Compound), and the novel compound can be synthesized through the steps in Synthesis Mechanism I described below. In Synthesis Mechanism I, "Reactant Bn" is selected from any one of the groups including reactants B1 to B30 in Table 4; "Intermediate C" is selected from the foregoing It includes any one of the group consisting of intermediate Cn, intermediate Cn-B, and the like.

1.0 equivalent of intermediate C, 0.01 equivalent of palladium acetate ((Pd (OAc) ₂ ), 0.04 equivalent of dicyclohexylphosphine (2-biphenyl), P (Cy) ₂ (2 -biPh)), toluene / ethanol (0.5M, v / v = 10/1), 3.0M potassium carbonate aqueous solution (K ₂ CO ₃ ), and 2.1 equivalents of the reactant Bn were mixed under a nitrogen atmosphere at 100 Reflux for 12 hours at a temperature of ℃. After the reaction is completed, add water and toluene to the solution. Then, extract the organic phase with a solvent and dry it with sodium sulfate. After the solvent is evaporated under low pressure, use silica gel column chromatography. The residue was purified and recrystallized from toluene to give a white solid product as the novel compound.

The reactants Bn and intermediates Cn used to synthesize compounds 1 to 17 are listed in Table 5. Each compound 1 to 17 was determined by proton nuclear magnetic resonance spectroscopy (H ¹ -NMR) and FD-MS analysis. Each compound 1 to 17 The proton nuclear magnetic resonance spectra are sequentially shown in FIGS. 2 to 18, and the chemical structural formulas, yields, molecular formulas, and masses of compounds 1 to 17 are listed in Table 5.

Modifications of compounds 1 to 17

In addition to the aforementioned compounds 1 to 17, those skilled in the art can substitute different intermediates C (ie, intermediates Cn or Cn-B) and reactants Bn and synthesize them by a synthetic pathway similar to synthetic mechanism I Other novel compounds.

Preparation of OLED device

A glass substrate (hereinafter referred to as an ITO substrate) coated with a 1500Å thick indium tin oxide (ITO) layer was placed in distilled water (filtered with a filter from Millipore Co.) containing a detergent (brand: Fischer Co.) Distilled water obtained from the second time), and oscillated with ultrasound for 30 minutes; after the distilled water was replaced, oscillated with ultrasound for 10 minutes to clean the ITO substrate, and the washing step was repeated once; after washing, the front The ITO substrate was washed with isopropyl alcohol, acetone, and methanol by ultrasonic vibration and dried; then, the ITO substrate was placed in a plasma surface cleaning machine, and the ITO substrate was cleaned with an oxygen plasma 5 After that, the cleaned ITO substrate was placed in a vacuum evaporation machine.

After that, the vacuum degree of the vacuum evaporation machine was maintained at 1x10 ^-6 torr to 3x10 ^-7 torr, and various organic materials and metal materials were sequentially deposited on the ITO substrate, and Examples 1 to 35 (E1 to E35 ) And OLED devices of Comparative Examples 1 to 6 (C1 to C6). Here, a first hole injection layer (HIL-1), a second hole injection layer (HIL-2), a hole transmission layer (HTL), a blue / A green / red light emitting layer (BEL / GEL / REL), an electron transport layer (ETL), an electron injection layer (EIL), and a cathode (Cthd).

Among the layers of the above OLED device, HI is a material for forming HIL-1 and HIL-2; HI-D is a material for forming HIL-1; HT is a material for forming HTL; the novel compound of the present invention And commercial electron transport materials (BCP and TPBi) are materials used to form ETL; Liq is a material used to form ETL and EIL; RH / GH / BH are matrix materials used to form REL / GEL / BEL; RD / GD / BD can be used as a dopant for REL / GEL / BEL.

The main difference between the OLED device of the example and the OLED device of the comparative example is that the ETL in the OLED device of the comparative example is made of BCP or TPBi, and the ETL in the OELD device of the example is made of the novel compounds listed in Table 5. . The detailed chemical structural formulas of the commercial materials are listed in Table 6.

Preparation of red light OLED device

The red light OLED device includes a plurality of organic layers. Each organic layer is sequentially deposited on the ITO substrate. The material and thickness of each organic layer are listed in Table 7.

Manufacturing of green OLED devices

The green OLED device includes a plurality of organic layers, which are sequentially deposited on the ITO substrate. The materials and thicknesses of the organic layers are listed in Table 8.

Preparation of blue light OLED device

The blue light OLED device includes a plurality of organic layers, which are sequentially deposited on the ITO substrate. The materials and thicknesses of the organic layers are listed in Table 9 respectively.

Performance of OLED devices

In order to evaluate the performance of OLED devices, red, green and blue OLED devices were connected to a power supply (brand: Keithley; model: 2400) and tested with a PR650 photometer. The measured chromaticity is considered international The chromaticity coordinates (x, y) developed by the Commission for Illumination (Commission Internationale de L'Eclairage 1931, CIE) are shown, and the test results are listed in Table 10 below. Among them, blue and red OLED devices are detected at a brightness of 1000 nits (1nit = 1cd / m ² ); green OLED devices are detected at a brightness of 3000 nits.

The ETL materials and characteristics of the OLED devices in Examples 1 to 35 and Comparative Examples 1 to 6 are listed in Table 10 below.

According to the results in Table 10, compared with the materials used in commercial OLEDs, the present invention can reduce the driving voltage and improve the current efficiency of red, green or blue OLED devices by adding compounds 1 to 15 to the electron transport layer. And external quantum efficiency, it is confirmed that the novel compound of the present invention is suitable for adding to various color OLED devices, and can achieve the effects of reducing driving voltage and improving current efficiency and external quantum efficiency.

The above embodiments are merely an illustration for explaining this creation, and do not limit the scope of the rights claimed in this creation in any way. Those with ordinary knowledge in the technical field to which they belong can follow the spirit of this creation. Adjustments are made, for example, to the number, position or arrangement of the substituents. The scope of the rights claimed in this creation should be based on the scope of the patent application, and not limited to the specific embodiments described above.

Claims (16)

A compound represented by the following formula (I): X ¹ and X ² are each independently C (R ^a ), the two (R ^a ) are the same or different from each other, and the two (R ^a ) are connected to each other to form a first aromatic ring; X ³ and X ⁴ are each independently C (R ^b ), the two (R ^b ) are the same or different from each other, the two (R ^b ) are connected to each other to form a second aromatic ring or a heteroaromatic ring; Y is an oxygen atom or a sulfur atom; wherein Z ¹ to At least one of Z ⁸ is selected from the group consisting of: Among them, R ¹ to R ⁷ are each independently selected from the group consisting of hydrogen atom, deuterium atom, halo group, cyano group, nitro group, trifluoromethyl group, and alkyl group having 1 to 12 carbon atoms. Alkenyl with 2 to 12 carbons, alkynyl with 2 to 12 carbons, cycloalkyl with 3 to 30 carbons on the ring, heterocycloalkyl with 3 to 30 carbons on the ring, An aromatic group having 6 to 30 carbons, a heteroaryl group having 3 to 20 carbons on the ring, an alkoxy group having 1 to 40 carbons, an aryloxy group having 6 to 30 carbons on the ring, and a carbon number of Silyl groups of 1 to 40, arylsilyl groups of 6 to 30 carbons on the ring, boryl groups of 1 to 40 carbons, arylboryl groups of 6 to 30 carbons on the ring, 1 to 30 carbons Phosphine and phosphine of 1 to 30; n is an integer of 0 to 4; m is an integer of 0 to 3; o is an integer of 0 to 3; the sum of m and o is less than or equal to 5; The rest of Z ¹ to Z ⁸ and Z ⁹ to Z ¹⁰ are independently selected from the group consisting of hydrogen atom, deuterium atom, halo group, cyano group, nitro group, trifluoromethyl group, carbon Alkyl groups of 1 to 40, alkenyl groups of 2 to 40 carbons, alkynyl groups of 2 to 40 carbons, cycloalkyl groups of 3 to 60 carbons on the ring, ring Heterocycloalkyl with 3 to 60 carbons, aromatic with 6 to 60 carbons on the ring, heteroaryl with 3 to 60 carbons on the ring, alkoxy with 1 to 40 carbons, ring Aryloxy group with 6 to 60 carbon atoms, silyl group with 1 to 40 carbon atoms, arylsilyl group with 6 to 60 carbon atoms on the ring, boryl group with 1 to 40 carbon atoms, carbon number on the ring An arboryl group having 6 to 60, a phosphine group having 1 to 40 carbon atoms, and an phosphine group having 1 to 40 carbon atoms. The compound according to claim 1, wherein the compound is represented by the following formulae (II) to (I-XXII): Wherein, A ¹ and A ² are each independently C (R ^c ), the two (R ^c ) are the same or different from each other, the two (R ^c ) are connected to each other to form an aromatic structure, and the aromatic structure is included in the second aromatic Ring or the heteroaryl ring; each Z ¹¹ is selected from the group consisting of methyl, ethyl, propyl, butyl, pentyl, hexyl, and phenyl. The compound according to claim 2, wherein the aromatic structure formed by extending A ¹ and A ² is a substituted or unsubstituted aromatic ring structure having 6 to 20 carbon atoms. The compound according to claim 3, wherein the substituted or unsubstituted aromatic ring structure having 6 to 20 carbon atoms is selected from the group consisting of: a substituted or unsubstituted benzene Ring structure, substituted or unsubstituted naphthalene ring structure, substituted or unsubstituted anthracene ring structure, substituted or unsubstituted phenanthrene ring structure, substituted or unsubstituted fluorene ring structure, substituted or An unsubstituted fluoranthene ring structure, a substituted or unsubstituted benzofluoranthene ring structure, and a substituted and unsubstituted fluorene ring structure. The compound according to claim 1, wherein the first aromatic ring formed by the extension of X ¹ and X ² is a substituted or unsubstituted carbocyclic ring having 6 to 60 carbon atoms. The compound according to claim 5, wherein the substituted or unsubstituted carbon ring having 6 to 60 carbon atoms is selected from the group consisting of a substituted or unsubstituted benzene ring structure , A substituted or unsubstituted naphthalene ring structure, a substituted or unsubstituted anthracene ring structure, a substituted or unsubstituted phenanthrene ring structure, a substituted or unsubstituted fluorene ring structure, a substituted or unsubstituted A substituted fluoranthene ring structure, a substituted and unsubstituted benzofluoranthene ring structure, and a substituted or unsubstituted fluorene ring structure. The compound according to claim 6, wherein the substituted or unsubstituted carbocyclic ring having 6 to 60 carbon atoms is a substituted or unsubstituted benzene ring structure. The compound according to any one of claims 1 to 7, wherein the remaining Z ¹ to Z ⁸ are selected from the group consisting of: a compound having at least one functional group and a carbon number of 1 to 40; Alkyl, alkenyl having at least one functional group and 2 to 40 carbons, alkynyl having at least one functional group and 2 to 40 carbons, alkenyl having at least one functional group and 3 to 60 carbons on the ring Cycloalkyl, heterocycloalkyl having at least one functional group and 3 to 60 carbons on the ring, aromatic group having at least one functional group and 6 to 60 carbons on the ring, having at least one functional group on the ring Heteroaryl having 3 to 60 carbons, alkoxy having at least one functional group and 1 to 40 carbons, aryloxy having at least one functional group and 6 to 60 carbons on the ring, having at least one Functional groups and silane groups having 1 to 40 carbons, aryl groups having at least one functional group and 6 to 60 carbons on the ring, boryl groups having at least one functional group and 1 to 40 carbons, having An arboryl group having at least one functional group and having 6 to 60 carbons on the ring, a phosphine group having at least one functional group and having 1 to 40 carbons, and one having at least one functional group and having 1 to 40 carbons Phosphine group; wherein said functional group is selected from consisting of cyano, nitro, trifluoromethyl, fluoro and chloro group consisting of. The compound according to any one of claims 1 to 7, wherein at least one of Z ² , Z ³ , Z ⁶ and Z ⁷ is selected from the group consisting of: Among them, Z ¹ , Z ⁴ , Z ⁵ and Z ⁸ may be independently selected from the group consisting of hydrogen atom, deuterium atom, halo group, cyano group, nitro group, and alkyl group having 1 to 12 carbon atoms. Alkenyl groups having 2 to 12 carbons and alkynyl groups having 2 to 12 carbons. The compound according to any one of claims 1 to 7, wherein at least one of Z ² , Z ³ , Z ⁶ and Z ⁷ is selected from the group consisting of: The compound according to any one of claims 1 to 7, wherein the Z ⁹ and Z ^{10 are} independently selected from the group consisting of a hydrogen atom, a deuterium atom, a halo group, a cyano group, a nitro group, Alkyl having 1 to 12 carbons, alkenyl having 2 to 12 carbons, and alkynyl having 2 to 12 carbons. The compound according to claim 1, wherein the compound is selected from the group consisting of: Compound 10, compound 11, compound 12, An organic electronic device includes a first electrode, a second electrode, and an organic layer disposed between the first electrode and the second electrode, wherein the organic layer includes the substrate according to any one of claims 1 to 12. Describing compounds. The organic electronic device according to claim 13, wherein the organic electronic device is an organic light emitting diode. The organic electronic device according to claim 14, wherein the organic light emitting diode includes: a hole injection layer formed on the first electrode; and a hole transmission layer formed on the hole injection layer. A light emitting layer formed on the hole transport layer, an electron transport layer formed on the light emitting layer, the organic layer being the electron transport layer, and an electron injection layer formed on the electron transport layer And the second electrode. The organic electronic device according to claim 14, wherein the organic light emitting diode includes: a hole injection layer formed on the first electrode; and a hole transmission layer formed on the hole injection layer. A light emitting layer formed on the hole transport layer; a hole blocking layer formed on the light emitting layer, the organic layer being the hole blocking layer; an electron transport layer formed on the hole On the barrier layer; and an electron injection layer formed between the electron transport layer and the second electrode.