KR102674465B1 - Compounds containing boron as a spiro atom and their high molecular compounds - Google Patents

Abstract

An excellent organic EL device is provided by a novel compound using boron as a spiro atom and its high molecular weight compound represented by the following general formula (1).

Rings A to D are optionally substituted aryl rings or heteroaryl rings, etc., provided that acridine-based substituents are excluded as substituents for ring A and D alone, and X ¹ to X ⁴ are each independently, C or N, and Z ¹ and Z ² are a single bond or a linking group such as alkylene that may be partially substituted, provided that Z ¹ and Z ² do not form a single bond at the same time, and are represented by formula (1) At least one hydrogen in the compound may be substituted with cyano, halogen, or deuterium.

Description

Compounds containing boron as a spiro atom and their high molecular compounds

The present invention relates to compounds with boron as a spiro atom and polymer compounds with boron as a repeating unit, organic electroluminescent devices using these compounds, organic field effect transistors and organic thin-film solar cells, and display devices and lighting devices.

Conventionally, display devices using light-emitting elements that emit electroluminescence have been studied in various ways because they can reduce power consumption and be thinner, and organic electroluminescent elements made of organic materials have been actively studied because they can easily be made lighter or larger. In particular, regarding the development of organic materials with luminescent properties such as blue, one of the three primary colors of light, and the development of organic materials with charge transport capabilities such as holes and electrons (with the potential to become semiconductors or superconductors), polymers Both compounds and low-molecular-weight compounds have been actively studied so far.

An organic EL element has a structure consisting of a pair of electrodes consisting of an anode and a cathode, and one or multiple layers disposed between the pair of electrodes and containing an organic compound. Layers containing organic compounds include a light-emitting layer and a charge transport/injection layer that transports or injects charges such as holes and electrons. Various organic materials suitable for these layers are being developed.

As materials for the light-emitting layer, for example, benzofluorene-based compounds have been developed (International Publication No. 2004/061047). Additionally, as hole transport materials, for example, triphenylamine-based compounds have been developed (Japanese Patent Application Laid-Open No. 2001-172232). Additionally, as electron transport materials, for example, anthracene-based compounds have been developed (Japanese Patent Application Laid-Open No. 2005-170911).

Recently, materials improved from triphenylamine derivatives have been reported as materials for use in organic EL devices and organic thin-film solar cells (International Publication No. 2012/118164). This material was made with reference to N,N'-diphenyl-N,N'-bis(3-methylphenyl)-1,1'-biphenyl-4,4'-diamine (TPD), which had already been put into practical use. It is a material characterized by improved planarity by connecting the aromatic rings that make up phenylamine. There are other examples of such compounds (International Publication No. 2011/107186, International Publication No. 2015/102118), and compounds having a conjugate structure with a large triplet exciton energy (T1) have shorter wavelengths. Since it can emit phosphorescence, it is useful as a material for a blue light-emitting layer. In addition, there is also a report in which the same study was conducted on compounds having a heteroborine ring containing a boron atom and an oxygen atom or a sulfur atom (International Publication No. 2015/072537).

International Publication No. 2004/061047 Japanese Patent Publication No. 2001-172232 Japanese Patent Publication No. 2005-170911 International Publication No. 2012/118164 International Publication No. 2011/107186 International Publication No. 2015/102118 International Publication No. 2015/072537

As mentioned above, various materials have been developed as materials for use in organic devices such as organic EL elements. However, in order to increase the selection of materials for organic devices, there is a demand for the development of materials made of compounds different from those of the past. .

As a result of careful study to solve the above problems, the present inventors discovered a novel compound using boron as a spiro atom and succeeded in producing it. Furthermore, it was discovered that an excellent organic EL device could be obtained by disposing a layer containing this compound between a pair of electrodes to form an organic EL device, and the present invention was completed. That is, the present invention provides the following compounds or polymer compounds using them as repeating units, and materials for organic devices containing these compounds.

Paragraph 1.

A compound represented by the following general formula (1), or a polymer compound having the structure represented by the general formula (1) as a repeating unit.

(In equation (1) above,

Ring A, ring C, and ring D are each independently an aryl ring or heteroaryl ring, and ring B is a heteroaryl ring, and ring A and ring B and/or ring C and ring D may be combined to form a ring structure, and these rings may be combined to form a ring structure. At least one hydrogen in the ring may be substituted, provided that acridine-based substituents are excluded as substituents for the A ring alone and the D ring alone,

X ¹ to X ⁴ are each independently C or N,

Z ¹ and Z ² are each independently a single bond, alkylene, alkenylene, alkynylene, or arylene, and any -CH ₂ - in these is -C(=CR ₂ )-, -C( =C(=O))-, -C(=O)-, -C(=S)-, -C(=O)O-, -C(=S)O-, -C(=O)S -, -C(=S)S-, -C(=O)NR-, -O-, -S-, -Se-, -Po-, -P(=O)-, -P(=S) It may be substituted with -, -S(=O)-, -S(=O) ₂ -, -SiR ₂ -, -NR-, or -N=N-, where R is each independently, hydrogen, aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, alkyl, cycloalkyl, alkenyl, alkynyl, alkoxy or aryloxy, and at least one hydrogen in R is aryl, heteroaryl. It may be substituted with aryl, alkyl, or cycloalkyl, and may form a ring structure by combining with adjacent R, A ring, B ring, C ring, and/or D ring, provided that Z ¹ and Z ² are simultaneously It does not form a single bond,

At least one hydrogen in the compound or structure represented by formula (1) may be substituted with cyano, halogen, or deuterium.)

Paragraph 2.

Ring A, ring C, and ring are each independently an aryl ring having 6 to 30 carbon atoms or a heteroaryl ring having 2 to 30 carbon atoms, and ring B is a heteroaryl ring having 2 to 30 carbon atoms, and ring A and ring B and/or The C ring and the D ring may be combined to form a ring structure, and at least one hydrogen in these rings may be substituted, provided that acridine-based substituents are excluded as substituents for the A ring alone and the D ring alone,

X ¹ to X ⁴ are each independently C or N,

Z ¹ and Z ² are each independently a single bond, -(CR ₂ ) _n - (n is 1 to 12), -CR=CR-, -C≡C-, -(CR=CR-CR ₂ ) _n -(n is 1 to 4), -C(=CR ₂ )-, -C(=C(=O))-, -C(=O)-, -C(=S)-, -C( =O)O-, -C(=S)O-, -C(=O)S-, -C(=S)S-, -C(=O)NR-, -C(=O)C( =O)-, -C(=O)OC(=O)-, -(CR ₂ -O)n-(n is 1 to 12), -(CR ₂ ) _n -O-(n is 1 to 12) ), -(CR ₂ -CR ₂ -O)n- (n is 1 to 6), -O-, -S-, -SS-, -Se-, -Po-, -P(=O)-, -P(=S)-, -S(=O)-, -S(=O) ₂ -, -SiR ₂ -, -NR-, -N=N-, or phenylene, where R is , each independently hydrogen, aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, alkyl, cycloalkyl, alkenyl, alkynyl, alkoxy or aryloxy, and at least one hydrogen in R may be substituted with aryl, heteroaryl, alkyl, or cycloalkyl, and may form a ring structure by combining with adjacent R, A ring, B ring, C ring, and/or D ring, provided that Z ¹ and Z ² do not form a single bond at the same time,

At least one hydrogen in the compound or structure represented by formula (1) may be substituted with cyano, halogen, or deuterium.

The compound or polymer compound described in item 1.

Clause 3.

Ring A, ring C, and ring are each independently a benzene ring, naphthalene ring, indan ring, indene ring, furan ring, thiophene ring, benzofuran ring, or benzothiophene ring, and ring B is a pyrrole ring and a pyridine ring. , a pyrazine ring, a pyrimidine ring, a pyridazine ring, a quinoline ring, or an isoquinoline ring, and ring A and ring B and/or ring C and ring D may be combined to form a ring structure, and at least one hydrogen in these rings may be substituted. may be present, provided that acridine-based substituents are excluded as substituents on the A ring alone and the D ring alone,

X ¹ ∼X ⁴ is C,

Z ¹ and Z ² are each independently a single bond, -CR ₂ -, -CR=CR-, -C(=O)-, -C(=S)-, -O-, -S-, - Se-, -P(=O)-, -P(=S)-, -S(=O)-, -SiR ₂ -, -NR-, or phenylene, where R is each independently , hydrogen, aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, alkyl, cycloalkyl, alkenyl, alkynyl, alkoxy or aryloxy, and at least one hydrogen in R is aryl, It may be substituted with heteroaryl, alkyl, or cycloalkyl, and may form a ring structure by combining with adjacent R, A ring, B ring, C ring, and/or D ring, provided that Z ¹ and Z ² At the same time, they do not form single bonds,

At least one hydrogen in the compound represented by formula (1) may be substituted with cyano, halogen, or deuterium.

Compound according to item 1 or 2.

Paragraph 4.

The compound according to any one of Items 1 to 3, which is represented by the following general formula (2).

(In equation (2) above,

Z ¹ and Z ² are each independently a single bond, -O-, -S-, -Se-, -NR-, or 1,2-phenylene, where R is hydrogen, aryl, hetero aryl, diarylamino, diheteroarylamino, arylheteroarylamino, alkyl, cycloalkyl, alkenyl, alkynyl, alkoxy or aryloxy, and at least one hydrogen in R is aryl, heteroaryl, alkyl or cyclo It may be substituted with alkyl, provided that Z ¹ and Z ² do not form a single bond at the same time,

R ¹ to R ¹⁶ are each independently hydrogen, aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, alkyl, cycloalkyl, alkenyl, alkynyl, alkoxy or aryloxy, and At least one hydrogen may be substituted with aryl, heteroaryl, alkyl, or cycloalkyl, provided that R ¹ to R ⁴ and R ¹³ to R ¹⁶ exclude acridine-based substituents,

Additionally, adjacent groups among R ¹ to R ⁴ and R ⁹ to R ¹⁶ may be combined to form an aryl ring with 9 to 30 carbon atoms or a heteroaryl ring with 6 to 30 carbon atoms together with the a ring, c ring or d ring. , adjacent groups among R ⁵ to R ⁸ may be combined to form a heteroaryl ring having 6 to 30 carbon atoms together with the b ring, and at least one hydrogen in the formed ring is aryl, heteroaryl, diarylamino, di. may be substituted with heteroarylamino, arylheteroarylamino, alkyl, cycloalkyl, alkoxy or aryloxy, and at least one hydrogen therein may be substituted with aryl, heteroaryl, alkyl or cycloalkyl, provided that a As a substituent on a ring or a ring formed including a d ring, an acridine-based substituent is excluded,

At least one hydrogen in the compound represented by formula (2) may be substituted with cyano, halogen, or deuterium.)

Clause 5.

In equation (2) above,

Z ¹ and Z ² are each independently a single bond, -O-, -S-, -Se-, -NR-, or 1,2-phenylene, where R is hydrogen, aryl, hetero Aryl, alkyl, or cycloalkyl, provided that Z ¹ and Z ² are not a single bond at the same time,

R ¹ to R ¹⁶ are each independently hydrogen, aryl, heteroaryl, diarylamino, alkyl, cycloalkyl, alkoxy, or aryloxy, and at least one hydrogen therein is aryl, heteroaryl, alkyl, or cyclo. It may be substituted with alkyl, provided that R ¹ to R ⁴ and R ¹³ to R ¹⁶ exclude acridine-based substituents,

Additionally, adjacent groups among R ¹ to R ⁴ and R ⁹ to R ¹⁶ may be combined to form an aryl ring with 9 to 16 carbon atoms or a heteroaryl ring with 6 to 15 carbon atoms together with the a ring, c ring, or d ring. , adjacent groups of R ⁵ to R ⁸ may be combined to form a heteroaryl ring having 6 to 15 carbon atoms together with the b ring, and at least one hydrogen in the formed ring is aryl, heteroaryl, diarylamino, or alkyl. , may be substituted with cycloalkyl, alkoxy, or aryloxy, and at least one hydrogen thereof may be substituted with aryl, heteroaryl, alkyl, or cycloalkyl, provided that it is a ring formed including the a ring or the d ring. As a substituent, an acridine-based substituent is excluded,

At least one hydrogen in the compound represented by formula (2) may be substituted with cyano, halogen, or deuterium.

The compound described in item 4.

Clause 6.

In equation (2) above,

Z ¹ and Z ² are each independently a single bond, -O-, -S-, -Se-, -NR-, or 1,2-phenylene, where R is hydrogen and has 6 to 16 carbon atoms. aryl, heteroaryl with 2 to 15 carbon atoms, alkyl with 1 to 6 carbon atoms, or cycloalkyl with 3 to 12 carbon atoms, provided that Z ¹ and Z ² do not form a single bond at the same time,

R ¹ to R ¹⁶ are each independently hydrogen, aryl with 6 to 16 carbon atoms, heteroaryl with 2 to 15 carbon atoms, diarylamino (where aryl is aryl with 6 to 12 carbon atoms), alkyl with 1 to 6 carbon atoms, Cycloalkyl with 3 to 12 carbon atoms, alkoxy with 1 to 6 carbon atoms, or aryloxy with 6 to 16 carbon atoms, where at least one hydrogen is aryl with 6 to 16 carbon atoms, heteroaryl with 2 to 15 carbon atoms, or 1 carbon atom. It may be substituted with alkyl of ∼6 or cycloalkyl of 3 to 12 carbon atoms, provided that R ¹ to R ⁴ and R ¹³ to R ¹⁶ exclude acridine-based substituents,

Additionally, adjacent groups among R ¹ to R ⁴ and R ⁹ to R ¹⁶ may be combined to form an aryl ring with 9 to 12 carbon atoms or a heteroaryl ring with 6 to 10 carbon atoms together with the a ring, c ring or d ring. , adjacent groups among R ⁵ to R ⁸ may be combined to form a heteroaryl ring having 6 to 10 carbon atoms together with ring b, and at least one hydrogen in the formed ring is aryl having 6 to 16 carbon atoms, or aryl having 2 to 10 carbon atoms. 15 heteroaryl, diarylamino (however, aryl is aryl with 6 to 12 carbon atoms), alkyl with 1 to 6 carbon atoms, cycloalkyl with 3 to 12 carbon atoms, alkoxy with 1 to 6 carbon atoms, or aryloxy with 6 to 16 carbon atoms. It may be substituted, and at least one hydrogen therein may be substituted with aryl with 6 to 16 carbon atoms, heteroaryl with 2 to 15 carbon atoms, alkyl with 1 to 6 carbon atoms, or cycloalkyl with 3 to 12 carbon atoms, provided that As a substituent for a ring formed including the a ring or the d ring, an acridine-based substituent is excluded,

At least one hydrogen in the compound represented by formula (2) may be substituted with cyano, halogen, or deuterium.

Compound according to item 4 or 5.

Clause 7.

In equation (2) above,

Z ¹ and Z ² are each independently a single bond, -O-, -S-, -Se-, -NR-, or 1,2-phenylene, where R is hydrogen and has 6 to 6 carbon atoms. Aryl with 16 carbon atoms, heteroaryl with 2 to 15 carbon atoms, alkyl with 1 to 6 carbon atoms, or cycloalkyl with 3 to 12 carbon atoms, provided that Z ¹ and Z ² do not form a single bond at the same time,

R ¹ to R ⁴ and R ⁹ to R ¹⁶ are hydrogen,

R ⁵ to R ⁸ are each independently hydrogen, aryl with 6 to 16 carbon atoms, heteroaryl with 2 to 15 carbon atoms, diarylamino (where aryl is aryl with 6 to 12 carbon atoms), alkyl with 1 to 6 carbon atoms, Cycloalkyl with 3 to 12 carbon atoms, alkoxy with 1 to 6 carbon atoms, or aryloxy with 6 to 16 carbon atoms, where at least one hydrogen is aryl with 6 to 16 carbon atoms, heteroaryl with 2 to 15 carbon atoms, or 1 carbon atom. It may be substituted with alkyl of ∼6 or cycloalkyl of 3 to 12 carbon atoms,

Additionally, adjacent groups among R ⁵ to R ⁸ may be combined to form a heteroaryl ring having 6 to 10 carbon atoms together with the b ring, and at least one hydrogen in the formed ring is aryl with 6 to 16 carbon atoms or 2 carbon atoms. Heteroaryl with ~15 carbon atoms, diarylamino (where aryl is aryl with 6-12 carbon atoms), alkyl with 1-6 carbon atoms, cycloalkyl with 3-12 carbon atoms, alkoxy with 1-6 carbon atoms, or aryloxy with 6-16 carbon atoms. may be substituted, and at least one hydrogen therein may be substituted with aryl with 6 to 16 carbon atoms, heteroaryl with 2 to 15 carbon atoms, alkyl with 1 to 6 carbon atoms, or cycloalkyl with 3 to 12 carbon atoms,

At least one hydrogen in the compound represented by formula (2) may be substituted with cyano, halogen, or deuterium.

The compound according to any one of claims 4 to 6.

Clause 8.

The compound according to item 1, represented by the following chemical structural formula.

Clause 9.

In equation (2) above,

Z ¹ and Z ² are each independently a single bond, -O-, -S-, -Se-, -NR-, or 1,2-phenylene, where R is aryl, heteroaryl or is cycloalkyl, and at least one hydrogen in R may be substituted with aryl, heteroaryl, alkyl, or cycloalkyl, provided that at least one of Z ¹ or Z ² is -NR-, and R and R ¹ , R ⁸ , R ⁹ and/or R ¹⁶ are a single bond, -CR ₂ -, -CR=CR-, -C(=O)-, -C(=S)-, -O-, -S- , -Se-, -P(=O)-, -P(=S)-, -S(=O)-, -SiR ₂ -, -NR-, or bonded with phenylene to form a ring structure , where R is each independently hydrogen, aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, alkyl, cycloalkyl, alkenyl, alkynyl, alkoxy or aryloxy, and in R At least one hydrogen may be substituted with aryl, heteroaryl, alkyl, or cycloalkyl,

R ¹ to R ¹⁶ are each independently hydrogen, aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, alkyl, cycloalkyl, alkenyl, alkynyl, alkoxy or aryloxy, and At least one hydrogen may be substituted with aryl, heteroaryl, alkyl, or cycloalkyl, provided that R ¹ to R ⁴ and R ¹³ to R ¹⁶ exclude acridine-based substituents,

Additionally, adjacent groups among R ¹ to R ⁴ and R ⁹ to R ¹⁶ may be combined to form an aryl ring with 9 to 30 carbon atoms or a heteroaryl ring with 6 to 30 carbon atoms together with the a ring, c ring or d ring. , adjacent groups among R ⁵ to R ⁸ may be combined to form a heteroaryl ring having 6 to 30 carbon atoms together with the b ring, and at least one hydrogen in the formed ring is aryl, heteroaryl, diarylamino, di. may be substituted with heteroarylamino, arylheteroarylamino, alkyl, cycloalkyl, alkoxy or aryloxy, and at least one hydrogen therein may be substituted with aryl, heteroaryl, alkyl or cycloalkyl, provided that a As a substituent on a ring or a ring formed including a d ring, an acridine-based substituent is excluded,

At least one hydrogen in the compound represented by formula (2) may be substituted with cyano, halogen, or deuterium.

The compound described in item 4.

Article 10.

In equation (2) above,

Z ¹ and Z ² are each independently a single bond, -O-, -S-, -Se- or -NR-, where R is aryl, and at least one hydrogen in R is aryl, It may be substituted with heteroaryl, alkyl, or cycloalkyl, provided that at least one of Z ¹ or Z ² is -NR-, and R, R ¹ , R ⁸ , R ⁹ and/or R ¹⁶ are a single bond. , -CR ₂ -, -O-, -S- or -NR- are bonded to form a ring structure, where R is each independently hydrogen, aryl, alkyl or cycloalkyl, and at least 1 in R The two hydrogens may be substituted with aryl, alkyl, or cycloalkyl,

R ¹ to R ¹⁶ are each independently hydrogen, aryl, heteroaryl, diarylamino, alkyl, cycloalkyl, alkoxy, or aryloxy, and at least one hydrogen therein is aryl, heteroaryl, alkyl, or cyclo. It may be substituted with alkyl, provided that R ¹ to R ⁴ and R ¹³ to R ¹⁶ exclude acridine-based substituents,

Additionally, adjacent groups among R ¹ to R ⁴ and R ⁹ to R ¹⁶ may be combined to form an aryl ring with 9 to 16 carbon atoms or a heteroaryl ring with 6 to 15 carbon atoms together with the a ring, c ring or d ring. , adjacent groups among R ⁵ to R ⁸ may be combined to form a heteroaryl ring having 6 to 15 carbon atoms together with the b ring, and at least one hydrogen in the formed ring is aryl, heteroaryl, diarylamino, or alkyl. , may be substituted with cycloalkyl, alkoxy, or aryloxy, and at least one hydrogen thereof may be substituted with aryl, heteroaryl, alkyl, or cycloalkyl, provided that it is a ring formed including the a ring or the d ring. As a substituent, an acridine-based substituent is excluded,

At least one hydrogen in the compound represented by formula (2) may be substituted with cyano, halogen, or deuterium.

The compound described in item 4.

Article 11.

In equation (2) above,

Z ¹ and Z ² are each independently a single bond, -O-, -S-, -Se-, or -NR-, where R is aryl having 6 to 16 carbon atoms, and at least one of R Hydrogen may be substituted with aryl with 6 to 16 carbon atoms, heteroaryl with 2 to 15 carbon atoms, alkyl with 1 to 6 carbon atoms, or cycloalkyl with 3 to 12 carbon atoms, provided that at least one of Z ¹ or Z ² is - NR-, and R, R ¹ , R ⁸ , R ⁹ and/or R ¹⁶ are single bonds, -CR ₂ -, -O-, -S- or -NR- bonded to form a ring structure, , where R is each independently hydrogen, aryl with 6 to 16 carbon atoms, alkyl with 1 to 6 carbon atoms, or cycloalkyl with 3 to 12 carbon atoms, and at least one hydrogen in R is aryl with 6 to 16 carbon atoms. , may be substituted with alkyl having 1 to 6 carbon atoms or cycloalkyl having 3 to 12 carbon atoms,

R ¹ to R ¹⁶ are each independently hydrogen, aryl with 6 to 16 carbon atoms, heteroaryl with 2 to 15 carbon atoms, diarylamino (where aryl is aryl with 6 to 12 carbon atoms), alkyl with 1 to 6 carbon atoms, Cycloalkyl with 3 to 12 carbon atoms, alkoxy with 1 to 6 carbon atoms, or aryloxy with 6 to 16 carbon atoms, where at least one hydrogen is aryl with 6 to 16 carbon atoms, heteroaryl with 2 to 15 carbon atoms, or 1 carbon atom. It may be substituted with alkyl of ∼6 or cycloalkyl of 3 to 12 carbon atoms, provided that R ¹ to R ⁴ and R ¹³ to R ¹⁶ exclude acridine-based substituents,

Additionally, adjacent groups among R ¹ to R ⁴ and R ⁹ to R ¹⁶ may be combined to form an aryl ring with 9 to 12 carbon atoms or a heteroaryl ring with 6 to 10 carbon atoms together with the a ring, c ring or d ring. , adjacent groups among R ⁵ to R ⁸ may be combined to form a heteroaryl ring having 6 to 10 carbon atoms together with ring b, and at least one hydrogen in the formed ring is aryl having 6 to 16 carbon atoms, or aryl having 2 to 10 carbon atoms. 15 heteroaryl, diarylamino (however, aryl is aryl with 6 to 12 carbon atoms), alkyl with 1 to 6 carbon atoms, cycloalkyl with 3 to 12 carbon atoms, alkoxy with 1 to 6 carbon atoms, or aryloxy with 6 to 16 carbon atoms. It may be substituted, and at least one hydrogen therein may be substituted with aryl with 6 to 16 carbon atoms, heteroaryl with 2 to 15 carbon atoms, alkyl with 1 to 6 carbon atoms, or cycloalkyl with 3 to 12 carbon atoms, provided that As a substituent for a ring formed including the a ring or the d ring, an acridine-based substituent is excluded,

At least one hydrogen in the compound represented by formula (2) may be substituted with cyano, halogen, or deuterium.

The compound described in item 4.

Article 12.

In equation (2) above,

Z ¹ is a single bond, -O-, -S-, -Se- or -NR-, Z ² is -NR-, where R is aryl having 6 to 16 carbon atoms, and at least one of R Hydrogen may be substituted with aryl with 6 to 16 carbon atoms, heteroaryl with 2 to 15 carbon atoms, alkyl with 1 to 6 carbon atoms, or cycloalkyl with 3 to 12 carbon atoms, and R in -NR- of Z ² and R ⁸ or R ⁹ is a single bond, -CR ₂ -, -O-, -S- or -NR- combined to form a ring structure, where R is each independently hydrogen, a ring having 6 to 16 carbon atoms Aryl, alkyl with 1 to 6 carbon atoms or cycloalkyl with 3 to 12 carbon atoms,

The compound according to any one of items 9 to 11.

Article 13.

The compound according to item 1, represented by the following chemical structural formula.

Article 14.

The compound or polymer compound according to any one of Items 1 to 13, wherein at least one of the substituents on the C ring or R ⁹ to R ¹² is a group represented by the partial structural formula (TSG1) below.

At least one hydrogen in the group represented by the formula (TSG1) may be substituted with aryl, heteroaryl, diarylamino, alkyl, cycloalkyl, alkoxy, or aryloxy,

Y is a single bond, -O-, -S-, -Se-, -NR-, >CR ₂ , or, >SiR ₂ , where R is each independently hydrogen, aryl, heteroaryl, dia It may be rylamino, alkyl, cycloalkyl, alkoxy or aryloxy, and adjacent groups among R may be bonded to form an aryl ring having 6 to 15 carbon atoms.

Article 15.

The group represented by the partial structural formula (TSG1) is represented by the following partial structural formula (TSG100), formula (TSG110), formula (TSG111), formula (TSG112), formula (TSG113), formula (TSG120), or formula (TSG121). The compound or polymer compound described in item 14.

At least one hydrogen in the above structural formula may be substituted with aryl, heteroaryl, diarylamino, alkyl, cycloalkyl, alkoxy, or aryloxy.

Article 16.

The compound according to item 14, which is represented by the following chemical structural formula.

Article 17.

The compound or polymer compound according to any one of Items 14 to 16, which satisfies the following formula.

ΔE _ST ≤ 0.20eV

Article 18.

A material for an organic device containing the compound or polymer compound according to any one of items 1 to 17.

Article 19.

The organic device material according to item 18, wherein the organic device material is a material for an organic electroluminescent element, a material for an organic field effect transistor, or a material for an organic thin film solar cell.

Article 20.

An organic electroluminescent device comprising a pair of electrodes consisting of an anode and a cathode, and an organic layer disposed between the pair of electrodes and containing the material for an organic electroluminescent device according to item 19.

Article 21.

It further has an electron transport layer and/or an electron injection layer, wherein at least one of the electron transport layer and the electron injection layer is selected from the group consisting of a quinolinol-based metal complex, a pyridine derivative, a phenanthroline derivative, a borane derivative, and a benzimidazole derivative. The organic electroluminescent element according to item 20, containing at least one selected element.

Article 22.

The electron transport layer and/or the electron injection layer is an alkali metal, an alkaline earth metal, a rare earth metal, an oxide of an alkali metal, a halide of an alkali metal, an oxide of an alkaline earth metal, a halide of an alkaline earth metal, an oxide of a rare earth metal, The organic electroluminescent device according to item 21, further comprising at least one selected from the group consisting of a halide of a rare earth metal, an organic complex of an alkali metal, an organic complex of an alkaline earth metal, and an organic complex of a rare earth metal.

Article 23.

An organic electroluminescent device having a light-emitting layer, wherein the light-emitting layer includes:

As a first component, at least one host compound,

As a second component, it includes at least one heat-activated delayed phosphor,

An organic electroluminescent device comprising, as the first component or the second component, a compound represented by the following general formula (1), or a polymer compound having the structure represented by the general formula (1) as a repeating unit.

(In equation (1) above,

Ring A, ring C, and ring D are each independently an aryl ring or heteroaryl ring, and ring B is a heteroaryl ring, and ring A and ring B and/or ring C and ring D may be combined to form a ring structure, and these rings may be combined to form a ring structure. At least one hydrogen in the ring may be substituted, provided that acridine-based substituents are excluded as substituents for the A ring alone and the D ring alone,

X ¹ to X ⁴ are each independently C or N,

Z ¹ and Z ² are each independently a single bond, alkylene, alkenylene, alkynylene, or arylene, and any -CH ₂ - in these is -C(=CR ₂ )-, -C( =C(=O))-, -C(=O)-, -C(=S)-, -C(=O)O-, -C(=S)O-, -C(=O)S -, -C(=S)S-, -C(=O)NR-, -O-, -S-, -Se-, -Po-, -P(=O)-, -P(=S) It may be substituted with -, -S(=O)-, -S(=O) ₂ -, -SiR ₂ -, -NR-, or -N=N-, where R is each independently, hydrogen, aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, alkyl, cycloalkyl, alkenyl, alkynyl, alkoxy or aryloxy, and at least one hydrogen in R is aryl, heteroaryl. It may be substituted with aryl, alkyl, or cycloalkyl, and may form a ring structure by combining with adjacent R, A ring, B ring, C ring, and/or D ring, provided that Z ¹ and Z ² are simultaneously It does not form a single bond,

At least one hydrogen in the compound or structure represented by formula (1) may be substituted with cyano, halogen, or deuterium.)

Article 24.

The organic electroluminescent device according to item 23, comprising as a first component a compound represented by the general formula (1), or a polymer compound having the structure represented by the general formula (1) as a repeating unit.

Article 25.

The organic electroluminescent device according to item 23, comprising as a second component a compound represented by the general formula (1), or a polymer compound having the structure represented by the general formula (1) as a repeating unit.

Article 26.

A display device including the organic electroluminescent element according to any one of items 20 to 25.

Article 27.

A lighting device comprising the organic electroluminescent element according to any one of items 20 to 25.

According to a preferred aspect of the present invention, it is possible to provide a novel compound with boron as a spiro atom or a polymer compound with boron as a repeating unit that can be used as a material for organic devices such as organic EL elements, and these By using the compound, an excellent organic EL device can be provided.

1 is a schematic cross-sectional view showing an organic EL device according to this embodiment.

1. Compounds containing boron as a spiro atom and their high molecular compounds

The present invention relates to a compound represented by the following general formula (1), or a polymer compound having a structure represented by the general formula (1) as a repeating unit, preferably a compound represented by the following general formula (2), or It is a polymer compound that has the structure represented by formula (2) as a repeating unit. Hereinafter, polymer compounds are also collectively referred to simply as “compounds.”

The compound represented by general formula (1) of the present invention uses a spiro structure centered on a boron atom or cross-linking of the C ring and D ring by the boron atom to separate the donor structure and the acceptor structure within the molecule. It has high triplet energy.

In particular, when HOMO and LUMO are completely separated by separation of the donor structure and the acceptor structure, the high triplet energy can be used for the host or surrounding materials of the light emitting layer. In this case, for example, HOMO and LUMO are centered on a spiro structure centered on a boron atom, HOMO is localized on the A ring and/or D ring, and B ring and/or Alternatively, it has a molecular orbital in which LUMO is localized on the C ring. When used as a host, it may be used as one component of a host compound used in two or more types, or may be used as one component of a host compound used in a multilayered light emitting layer that may be adjacent.

In addition, especially in the case of a heat-activated delayed fluorescence molecule (referred to as “D-A type TADF compound”), it can be used as a TADF light-emitting material (emitting dopant) or as an assisting dopant in a TAF (TADF Assisting Fluorescence) device. . In this case, for example, HOMO and LUMO are localized on the donor structure in which HOMO is substituted by C ring and/or C ring using crosslinking of C ring and D ring by boron atom, and LUMO is It has a molecular orbital localized on the B ring, but for LUMO, some of it may seep out to the C ring. When used as an assisting dopant, the emitting dopant and the assisting dopant may be contained in different adjacent layers.

Additionally, when it does not have heat-activated delayed fluorescence (referred to as a “fluorescent compound”), it can be used as a light-emitting material (dopant) in TTF (Triplet-Triplet Fusion) or an emitting dopant in a TAF (TADF Assisting Fluorescence) device. there is. In this case, for example, the substituents of Z ¹ and/or Z ² are molecules that form a cyclic structure with the A ring, B ring, C ring, and/or D ring, and the HOMO and LUMO partially overlap to a large extent. It has molecular orbitals. When used as an emitting dopant, the emitting dopant and assisting dopant may be contained in different adjacent layers.

First, in equation (1) above,

Ring A, ring C, and ring D are each independently an aryl ring or heteroaryl ring, and ring B is a heteroaryl ring, and ring A and ring B and/or ring C and ring D may be combined to form a ring structure, and these rings may be combined to form a ring structure. At least one hydrogen in the ring may be substituted, provided that acridine-based substituents are excluded as substituents for the A ring alone and the D ring alone,

X ¹ to X ⁴ are each independently C or N,

Z ¹ and Z ² are each independently a single bond, alkylene, alkenylene, alkynylene, or arylene, and any -CH ₂ - in these is -C(=CR ₂ )-, -C( =C(=O))-, -C(=O)-, -C(=S)-, -C(=O)O-, -C(=S)O-, -C(=O)S -, -C(=S)S-, -C(=O)NR-, -O-, -S-, -Se-, -Po-, -P(=O)-, -P(=S) It may be substituted with -, -S(=O)-, -S(=O) ₂ -, -SiR ₂ -, -NR-, or -N=N-, where R is each independently, hydrogen, aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, alkyl, cycloalkyl, alkenyl, alkynyl, alkoxy or aryloxy, and at least one hydrogen in R is aryl, heteroaryl. It may be substituted with aryl, alkyl, or cycloalkyl, and may form a ring structure by combining with adjacent R and the A ring, B ring, C ring, and/or D ring, provided that Z ¹ and Z ² are simultaneously There is no single bond,

At least one hydrogen in the compound or structure represented by formula (1) may be substituted with cyano, halogen, or deuterium.

Additionally, in equation (2) above,

Z ¹ and Z ² are each independently a single bond, -O-, -S-, -Se-, -NR-, or 1,2-phenylene, where R is hydrogen, aryl, hetero aryl, diarylamino, diheteroarylamino, arylheteroarylamino, alkyl, cycloalkyl, alkenyl, alkynyl, alkoxy or aryloxy, and at least one hydrogen in R is aryl, heteroaryl, alkyl or cyclo It may be substituted with alkyl, provided that Z ¹ and Z ² do not form a single bond at the same time,

R ¹ to R ¹⁶ are each independently hydrogen, aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, alkyl, cycloalkyl, alkenyl, alkynyl, alkoxy or aryloxy, and At least one hydrogen may be substituted with aryl, heteroaryl, alkyl, or cycloalkyl, provided that R ¹ to R ⁴ and R ¹³ to R ¹⁶ exclude acridine-based substituents,

Additionally, adjacent groups among R ¹ to R ⁴ and R ⁹ to R ¹⁶ may be combined to form an aryl ring with 9 to 30 carbon atoms or a heteroaryl ring with 6 to 30 carbon atoms together with the a ring, c ring or d ring. , adjacent groups among R ⁵ to R ⁸ may be combined to form a heteroaryl ring having 6 to 30 carbon atoms together with the b ring, and at least one hydrogen in the formed ring is aryl, heteroaryl, diarylamino, di. may be substituted with heteroarylamino, arylheteroarylamino, alkyl, cycloalkyl, alkoxy or aryloxy, and at least one hydrogen therein may be substituted with aryl, heteroaryl, alkyl or cycloalkyl, provided that a As a substituent on a ring or a ring formed including a d ring, an acridine-based substituent is excluded,

At least one hydrogen in the compound represented by formula (2) may be substituted with cyano, halogen, or deuterium.

And, in the formula (2), at least one of Z ¹ or Z ² is -NR-, and R, R ¹ , R ⁸ , R ⁹ and/or R ¹⁶ are a single bond, -CR ₂ -, -CR=CR-, -C(=O)-, -C(=S)-, -O-, -S-, -Se-, -P(=O)-, -P(=S) -, -S(=O)-, -SiR ₂ -, -NR-, or bonded with phenylene to form a ring structure, where R is each independently hydrogen, aryl, heteroaryl, diaryl amino, diheteroarylamino, arylheteroarylamino, alkyl, cycloalkyl, alkenyl, alkynyl, alkoxy or aryloxy, and at least one hydrogen in R is substituted with aryl, heteroaryl, alkyl or cycloalkyl You can stay.

Hereinafter, general formula (2) is a preferred form included in general formula (1), so the explanation common to the forms is represented by the explanation of general formula (1), and the explanation of general formula (2) is omitted. There is also.

Ring A, ring C, and ring D are each independently an aryl ring or heteroaryl ring. Ring B is a heteroaryl ring containing at least one nitrogen.

As the “aryl ring” as the A ring, C ring, and D ring, for example, there is an aryl ring with 6 to 30 carbon atoms, an aryl ring with 6 to 16 carbon atoms is preferable, an aryl ring with 6 to 12 carbon atoms is more preferable, and an aryl ring with 6 to 12 carbon atoms is more preferable. Aryl rings of 6 to 10 are particularly preferred. And, this “aryl ring” is a carbon number of 9 to 30 formed together with the a ring, c ring or d ring by bonding adjacent groups of “R ¹ to R ⁴ and R ⁹ to R ^16” defined in general formula (2). Since the a-ring (or c-ring, d-ring) is already composed of a benzene ring with 6 carbon atoms, the total carbon number of the 5-membered ring condensed here is 9, which is the lower limit.

Specific examples of “aryl rings” include monocyclic benzene rings, bicyclic biphenyl rings, condensed bicyclic naphthalene rings, and tricyclic terphenyl rings (m-terphenyl, o-terphenyl, p-terphenyl), and condensed rings. Tricyclic ring, acenaphthylene ring, fluorene ring, phenalene ring, phenanthrene ring, condensed tetracyclic ring, triphenylene ring, pyrene ring, naphthacene ring, benzofluorene ring, condensed pentacyclic ring, perylene ring, pentacene ring, etc. An example is given. Additionally, the fluorene ring or benzofluorene ring also includes structures in which the fluorene ring or benzofluorene ring is spiro bonded.

As the “heteroaryl ring” as the A ring to the D ring, for example, there is a heteroaryl ring having 2 to 30 carbon atoms, a heteroaryl ring having 2 to 25 carbon atoms is preferable, and a heteroaryl ring having 2 to 20 carbon atoms is more preferable, A heteroaryl ring having 2 to 15 carbon atoms is more preferable, and a heteroaryl ring having 2 to 10 carbon atoms is particularly preferable. Additionally, examples of the “heteroaryl ring” include heterocycles containing 1 to 5 heteroatoms selected from oxygen, sulfur, and nitrogen in addition to carbon as ring constituent atoms. And, this “heteroaryl ring” is a ring having 6 to 6 carbon atoms formed together with the a ring, c ring or d ring by bonding adjacent groups among “R ¹ to R ⁴ and R ⁹ to R ^16” defined in General Formula (2). It corresponds to “heteroaryl ring with 30 carbon atoms” or “heteroaryl ring with 6 to 30 carbon atoms formed together with ring b by bonding adjacent groups among R ⁵ to R ⁸ ,” and since ring b is already composed of a pyridine ring with 5 carbon atoms. , the total carbon number of 6 condensed rings formed by condensing 5-membered rings is the lower limit.

Specific "heteroaryl rings" include, for example, pyrrole ring, oxazole ring, isoxazole ring, thiazole ring, isothiazole ring, imidazole ring (unsubstituted, substituted with alkyl such as methyl or aryl substituted such as phenyl), oxa Diazole ring, thiadiazole ring, triazole ring, tetrazole ring, pyrazole ring, pyridine ring, pyrimidine ring, pyridazine ring, pyrazine ring, triazine ring, indole ring, isoindole ring, 1H-indazole ring, benzimidazole ring, Benzoxazole ring, benzothiazole ring, 1H-benzotriazole ring, quinoline ring, isoquinoline ring, cinnoline ring, quinazoline ring, quinoxaline ring, phthalazine ring, naphthyridine ring, purine ring, pteridine ring, carbamate. Zol ring, acridine ring, phenoxathiin ring, phenoxazine ring, phenothiazine ring, phenazine ring, indolizine ring, furan ring, benzofuran ring, isobenzofuran ring, dibenzofuran ring, naphthobenzofuran ring, tea ophen ring, benzothiophene ring, dibenzothiophene ring, naphthobenzothiophene ring, benzophosphor ring, dibenzophosphor ring, benzophosphoroxide ring, dibenzophosphoroxide ring, furazane ring, There are oxadiazole pills and thiantrene pills.

The A ring and the B ring and/or the C ring and the D ring may be bonded to form a ring structure, and examples of the bonding group in this case include the same groups as Z ¹ and Z ² , and may also be a single bond.

At least one hydrogen in the ring structure formed by combining the “aryl ring” or “heteroaryl ring” as the A ring to the D ring, or the A ring and the B ring and/or the C ring and the D ring, may be substituted with the first substituent, The first substituent may be further substituted with a second substituent. Examples of the first substituent include aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, alkyl, cycloalkyl, alkenyl, alkynyl, alkoxy, or aryloxy, and as the second substituent, , aryl, heteroaryl, alkyl, or cycloalkyl. In General Formula (2), the first substituent is an aryl ring formed by combining adjacent groups among substituents “R ¹ to R ¹⁶ ” or “R ¹ to R ^16” with the a ring, b ring, c ring or d ring. or heteroaryl ring”, and the second substituent also corresponds to new substituents thereto.

“aryl” or “heteroaryl” as the first substituent, aryl of “diarylamino”, heteroaryl of “diheteroarylamino”, aryl and heteroaryl of “arylheteroarylamino”, aryl of “aryloxy”, Examples of “aryl” and “heteroaryl” as the second substituent include the monovalent group of “aryl ring” or “heteroaryl ring” described above.

The "alkyl" as the first and second substituent may be either straight chain or branched, and examples include straight chain alkyl with 1 to 24 carbon atoms or branched chain alkyl with 3 to 24 carbon atoms. Alkyl with 1 to 18 carbon atoms (branched chain alkyl with 3 to 18 carbon atoms) is preferable, alkyl with 1 to 12 carbon atoms (branched chain alkyl with 3 to 12 carbon atoms) is more preferable, and alkyl with 1 to 6 carbon atoms (branched chain alkyl with 3 to 12 carbon atoms) is more preferable. Branched-chain alkyl with ~6 carbon atoms) is more preferable, and alkyl with 1-4 carbon atoms (branched-chain alkyl with 3-4 carbon atoms) is particularly preferable.

Specific alkyls include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, n-hexyl, 1- Methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, n-heptyl, 1-methylhexyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2-dimethylheptyl, 2,6-dimethyl-4-heptyl, 3,5,5-trimethylhexyl, n-decyl, n-undecyl, 1-methyldecyl, n Examples include -dodecyl, n-tridecyl, 1-hexylheptyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, and n-eicosyl.

Examples of “cycloalkyl” as the first and second substituents include cycloalkyl consisting of one ring, cycloalkyl consisting of multiple rings, cycloalkyl containing a double bond that is not conjugated within the ring, and cycloalkyl containing a branch outside the ring. It may be any of cycloalkyl, for example, cycloalkyl with 3 to 20 carbon atoms, cycloalkyl with 3 to 14 carbon atoms, cycloalkyl with 3 to 12 carbon atoms, cycloalkyl with 5 to 10 carbon atoms, cycloalkyl with 6 to 10 carbon atoms. Alkyl, etc. Among these, cycloalkyl with 5 to 10 carbon atoms is preferable, and cycloalkyl with 6 to 10 carbon atoms is more preferable.

Specific cycloalkyl examples include cyclopropyl, methylcyclopropyl, cyclobutyl, methylcyclobutyl, cyclopentyl, methylcyclopentyl, cyclohexyl, methylcyclohexyl, cycloheptyl, methylcycloheptyl, cyclooctyl, methylcyclooctyl, cyclononyl, Methylcyclononyl, cyclodecyl, methylcyclodecyl, bicyclo[1.0.1]butyl, bicyclo[1.1.1]pentyl, bicyclo[2.0.1]pentyl, bicyclo[1.2.1]hexyl, bicyclo[ 3.0.1]hexyl, bicyclo[2.2.1]heptyl, bicyclo[2.1.2]heptyl, bicyclo[2.2.2]octyl, decahydronaphthyl, adamantyl, diamantyl, decahydroazule Examples include Neal and others.

Examples of “alkenyl” as the first substituent include groups in which one or more -CH ₂ -CH ₂ - in the above-mentioned “alkyl” is substituted with -C=C-, preferably one or two. Examples include groups in which two groups are substituted, and more preferably, one group is substituted.

Examples of “alkynyl” as the first substituent include groups in which one or more -CH ₂ -CH ₂ - in the above “alkyl” is substituted with -C≡C-, preferably one or two. Examples include groups in which two groups are substituted, and more preferably, one group is substituted.

Examples of “alkoxy” as the first substituent include straight-chain alkoxy with 1 to 24 carbon atoms or branched chain alkoxy with 3 to 24 carbon atoms. Alkoxy with 1 to 18 carbon atoms (branched chain alkoxy with 3 to 18 carbon atoms) is preferable, alkoxy with 1 to 12 carbon atoms (branched chain alkoxy with 3 to 12 carbon atoms) is more preferable, and alkoxy with 1 to 6 carbon atoms (branched chain alkoxy with 3 to 12 carbon atoms) is more preferable. Branched chain alkoxy with 3 to 6 carbon atoms) is more preferable, and alkoxy with 1 to 4 carbon atoms (branched chain alkoxy with 3 to 4 carbon atoms) is particularly preferable.

Specific examples of alkoxy include methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, etc. there is.

However, as a substituent for the A ring (a ring) alone and the D ring (d ring) alone, an acridine-based substituent is excluded. This acridine-based substituent is a monovalent group of acridine and acridine derivatives. An acridine derivative is acridine having a substituent, and examples of the substituent include an alkyl group and an aryl group. In addition, the substituent for the A ring (a ring) alone and the D ring (d ring) alone is preferably not only an acridine-based substituent, but also a substituent having a nitrogen atom, where the nitrogen atom is used for the A ring (a ring) alone and D Groups (for example, amino groups, etc.) directly bonded to the ring (d ring) alone are also excluded, and more preferably, substituents having a nitrogen atom are also excluded.

Additionally, it is preferable that at least one of the substituents on the C ring or R ⁹ to R ¹² is a group represented by the partial structural formula (TSG1) below.

At least one hydrogen in the group represented by the formula (TSG1) may be substituted with aryl, heteroaryl, diarylamino, alkyl, cycloalkyl, alkoxy, or aryloxy. Details of these groups are described above. The description of the first and second substituents may be cited.

Y in the group represented by the above formula (TSG1) is a single bond, -O-, -S-, -Se-, -NR-, >CR ₂ , or >SiR ₂ , where R is each independent , hydrogen, aryl, heteroaryl, diarylamino, alkyl, cycloalkyl, alkoxy or aryloxy, and for details of these groups, the description of the above-mentioned first and second substituents can be referred to. Additionally, adjacent groups among R may be bonded to form an aryl ring having 6 to 15 carbon atoms, and for details of this aryl ring, the description of the A to D rings described above can be cited.

Specific examples of the group represented by the partial structural formula (TSG1) include the following partial structural formula (TSG100), formula (TSG110), formula (TSG111), formula (TSG112), formula (TSG113), formula (TSG120), or formula (TSG121). The displayed flags can be mentioned. “Me” in the formula is a methyl group.

At least one hydrogen in the above structural formula may be substituted with aryl, heteroaryl, diarylamino, alkyl, cycloalkyl, alkoxy, or aryloxy. For details of these groups, refer to the above-mentioned first and second substituents. Explanations may be cited.

Alkylene, alkenylene, alkynylene, or arylene as Z ¹ and Z ² are monovalent groups, and examples include the divalent groups of “alkyl,” “alkenyl,” “alkynyl,” or “aryl” described above. . Any -CH ₂ - in these is -CR ₂ -, -C(=CR ₂ )-, -CR=CR-, -C(=C(=O))-, -C(=O)- , -C(=S)-, -C(=O)O-, -C(=S)O-, -C(=O)S-, -C(=S)S-, -C(=O )NR-, -O-, -S-, -Se-, -Po-, -P(=O)-, -P(=R)-, -P(=O)(-R)-, -P It may be substituted with (=S)-, -S(=O)-, -S(=O) ₂ -, -SiR ₂ -, -NR-, or -N=N-.

「-CR ₂ -」, 「-C(=CR ₂ )-」, 「-CR=CR-」, 「-C(=O)NR-」, 「-P(=R) in Z ¹ and Z ² )-”, “-P(=O)(-R)-”, “-SiR ₂ -”, or “-NR-” each independently represents hydrogen, aryl, heteroaryl, diarylamino, di Heteroarylamino, arylheteroarylamino, alkyl, cycloalkyl, alkenyl, alkynyl, alkoxy or aryloxy, and at least one hydrogen in R may be substituted with aryl, heteroaryl, alkyl or cycloalkyl. Descriptions of these groups may refer to the descriptions of the above-described first and second substituents.

In addition, when the above R and the A ring, B ring, C ring and/or D ring (a ring, b ring, c ring and/or D ring) are adjacent, they may be combined to form a ring structure, Examples of this linking group include an alkylene bond in addition to a single bond, and some of -CH ₂ - in the above linking group may be substituted with -NR-, -O- or -S-, and -CH ₂ - or -CH= If the neighbor of is not a hetero atom, -CH ₂ - or -CH= may be substituted with a hetero atom. For details of the above “-NR-”, the above description can be cited.

More specifically, for example, in the above formula (2), R (preferably R of “-NR-”), R ¹ , R ⁸ , R ⁹ and/or R ¹⁶ are a single bond. , -CR ₂ -, -CR=CR-, -C(=O)-, -C(=S)-, -O-, -S-, -Se-, -P(=O)-, -P (=S)-, -S(=O)-, -SiR ₂ -, -NR-, or bonded with phenylene to form a ring structure, where R is each independently hydrogen, aryl, hetero Aryl, diarylamino, diheteroarylamino, arylheteroarylamino, alkyl, cycloalkyl, alkenyl, alkynyl, alkoxy or aryloxy (the description of these groups refers to the description of the first and second substituents above) can), and at least one hydrogen in R is substituted with aryl, heteroaryl, alkyl or cycloalkyl (the description of these groups may refer to the description of the first and second substituents described above) You can stay. Preferably, R (preferably R of "-NR-"), R ¹ , R ⁸ , R ⁹ and/or R ¹⁶ are a single bond, -CR ₂ -, -O-, -S- or -NR- to form a ring structure, where R is each independently hydrogen, aryl, alkyl, or cycloalkyl (the description of these groups refers to the description of the first and second substituents described above). may be substituted), and at least one hydrogen in R may be substituted with aryl, alkyl, or cycloalkyl (the description of these groups may refer to the description of the first and second substituents described above). The specific ring structure formed will be described later.

In addition, in the compound of the present invention, Z ¹ and Z ² are not simultaneously a single bond.

In addition, all or part of hydrogen in the chemical structure of the compound of the present invention and its polymer compound may be substituted with cyano, halogen, or deuterium. Halogen is fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine, more preferably fluorine or chlorine.

Next, the structure of the compound of the present invention will be described in more detail. In addition, the symbols in all structural formulas used in the following description are the same as the above definitions unless otherwise specified.

1-1. About changes in the basic skeleton of a compound

In the compound of the present invention, the condensed ring portion containing the A ring and D ring (a ring and d ring) and the condensed ring portion including the B ring and C ring (b ring and c ring) convert boron into a spiro atom to form a spiro atom. It is a combined compound. A substituent may be bonded to each ring or to Z ¹ and Z ² , but first, the basic skeleton of the spiro compound will be described below. In the following, only the basic skeleton and accompanying matters will be described, so basically, description or explanation of substituents that are not involved in this change in the structural formula (R ¹ to R ¹⁶ , etc., if mentioned in formula (2)) will be omitted. , Write or explain only when necessary. In addition, since general formula (2) is a preferred form included in general formula (1), the explanation common to the forms is represented by the explanation of general formula (1), and the explanation of general formula (2) is also omitted. there is.

In the compound or repeating structure (hereinafter collectively referred to simply as “compound”) represented by general formula (1), boron “B”, which is a spiro atom, is represented by carbon in the A ring, C ring, and D ring, respectively (in the formula: (the notation of "C" is omitted) and coordinates with one nitrogen "N" in ring B. ^{X 1 to ​}

As an example, the following general formula (1-C) is a structural formula in which X ¹ to X ⁴ are C (carbon), and general formula ( ¹ -N) is a structural formula in which X ¹ to X ^{1 to}

Examples of Z ¹ and Z ² include the following partial structural formulas (a) to (v).

R in the partial structural formula is each independently hydrogen, aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, alkyl, cycloalkyl, alkoxy or aryloxy, and at least one hydrogen in these is It may be substituted with aryl, heteroaryl, alkyl, or cycloalkyl.

Preferably it is formula (e) to formula (q), formula (u) or formula (v), more preferably formula (g) to formula (j), formula (n) to formula (q), formula ( u) or formula (v), more preferably formula (g), formula (h), formula (q) or formula (u), especially preferably formula (g), formula (q) or formula ( u).

More specifically, Z ¹ is formula (g), formula (q), or formula (u), preferably formula (g) or formula (u), and more preferably formula (g).

Combinations of Z ¹ and Z ² include formula (g), formula (g) and formula (q), formula (g) and formula (u), formula (u) and formula (g), or formula (u). ) and formula (q), and preferably, they are all formula (g), formula (g) and formula (q), formula (g) and formula (u), or formula (u) and formula (g). .

Examples of the A ring, C ring, and D ring include the following partial structural formulas (P) to (Xb). In the partial structural formula below, the bond interrupted by the broken line represents the bonding site of the spiro atom "B", Z ¹ or Z ² in General Formula (1). In addition, it is preferable that all partial structures in General Formula (1) have the same partial structure, but different types of partial structures may be used. Even in the partial structural formulas below, illustration of substituents is omitted.

R in the partial structural formula is each independently hydrogen, aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, alkyl, cycloalkyl, alkoxy or aryloxy, and at least one hydrogen in these is It may be substituted with aryl, heteroaryl, alkyl, or cycloalkyl.

Preferably, formula (P), formula (F), formula (Na), formula (Nb), formula (Ra), formula (BR), formula (Y), formula (Yb), formula (Z), formula ( BZ), Equation(S), Equation(BS), Equation(T), Equation(BT), Equation(E), Equation(BE), Equation(L), Equation(BL), Equation(G) and Equation( BG), and more preferably formula (P), formula (Na), formula (Ra), formula (Y), formula (Yb), formula (Z), formula (S), formula (T), formula ( E) and formula (G), more preferably formula (P), formula (Na) and formula (S), and most preferably formula (P) and formula (Na).

Examples of the B ring include a pyridine ring, pyridazine ring, pyrimidine ring, or triazine ring, and in these rings, one nitrogen is coordinated to the spiro atom “B.” Structural formulas containing such a B ring include, for example, the following general formulas (10) to (145) as modified examples of the above formula (1-C). The same applies to the above formula (1-N) or to other combinations of X ¹ to ^{X 4} .

The structural formula is preferably formula (10), formula (15), or formula (135), and more preferably formula (10).

In the above formulas (10) to (145), when the A ring, C ring, and D ring have a partial structural formula (P), for example, they are represented by the following general formula.

For example, when the same structure as the A ring, C ring, and D ring is selected from any one of the partial structural formulas (P) to (Xb) above, the structure of general formula (10) is represented by the following chemical formula.

The A ring, C ring, and D ring may have the same structure or may have different structures. In the above formula (10), when the A ring, C ring, and D ring have different structures, they are expressed by the following general formula.

Z ¹ and Z ² may have the same structure or may be different. An example in which partial structural formulas (a) to (v) are each independently selected as Z ¹ and Z ² is given below.

Among these, the general formula (10P-ge-1), formula (10P-gf-1), formula (10P-g-1), formula (10P-gh-1), formula (10P-gi- 1), Equation (10P-gj-1), Equation (10P-gk-1), Equation (10P-gm-1), Equation (10P-gn-1), Equation (10P-gp-1), Equation ( 10P-gq-1), formula (10P-gu-1), formula (10P-qe-1), formula (10P-qf-1), formula (10P-qg-1), formula (10P-qh-1) ), Equation (10P-qi-1), Equation (10P-qj-1), Equation (10P-qk-1), Equation (10P-qm-1), Equation (10P-qn-1), Equation (10P -qp-1), formula (10P-q-1), formula (10P-qu-1), formula (10P-ue-1), formula (10P-uf-1), formula (10P-ug-1) , Equation (10P-uh-1), Equation (10P-ui-1), Equation (10P-uj-1), Equation (10P-uk-1), Equation (10P-um-1), Equation (10P- un-1), formula (10P-up-1) and formula (10P-uq-1), and more preferably, general formula (10P-g-1), formula (10P-gh-1), formula ( 10P-gi-1), formula (10P-gj-1), formula (10P-gn-1), formula (10P-gp-1), formula (10P-gq-1), formula (10P-gu-1) ), Equation (10P-qg-1), Equation (10P-qh-1), Equation (10P-qi-1), Equation (10P-qj-1), Equation (10P-qn-1), Equation (10P -qp-1), formula (10P-q-1), formula (10P-qu-1), formula (10P-ug-1), formula (10P-uh-1), formula (10P-ui-1) , formula (10P-uj-1), formula (10P-un-1), formula (10P-up-1) and formula (10P-uq-1), and more preferably, the general formula (10P-g- 1), Equation (10P-gh-1), Equation (10P-gq-1), Equation (10P-gu-1), Equation (10P-qg-1), Equation (10P-qh-1), Equation ( 10P-q-1), formula (10P-qu-1), formula (10P-ug-1), formula (10P-uh-1) and formula (10P-uq-1), and especially preferably, general Equation (10P-g-1), Equation (10P-gq-1), Equation (10P-gu-1), Equation (10P-qg-1), Equation (10P-q-1), Equation (10P-qu -1), the formula (10P-ug-1) and the formula (10P-uq-1).

In addition, general formula (10P-Z-1), formula (12P-Z-1), formula (13P-Z-1), formula (14P-Z-1), formula (15P-Z-1), formula ( 123P-Z-1), formula (124P-Z-1), formula (125P-Z-1), formula (134P-Z-1), formula (135P-Z-1), or formula (145P-Z-1) ), the case where the ether bond of partial structural formula (g) is selected as Z ¹ and Z ² is shown below.

Z ¹ and Z ² may have different structures, and may be represented by the general formula (10P-Z-1), formula (12P-Z-1), formula (13P-Z-1), formula (14P-Z-1), formula ( 15P-Z-1), formula (123P-Z-1), formula (124P-Z-1), formula (125P-Z-1), formula (134P-Z-1), formula (135P-Z-1) ) or in the formula (145P-Z-1), the case where the ether bond of partial structural formula (g) and the amine bond of formula (q) are selected as Z ¹ and Z ² , respectively, are shown below.

Z ¹ and Z ² may have different structures, and may be represented by the general formula (10P-Z-1), formula (12P-Z-1), formula (13P-Z-1), formula (14P-Z-1), formula ( 15P-Z-1), formula (123P-Z-1), formula (124P-Z-1), formula (125P-Z-1), formula (134P-Z-1), formula (135P-Z-1) ) or in the formula (145P-Z-1), the case where the ether bond of partial structural formula (g) and the single bond of formula (u) are selected as Z ¹ and Z ² , respectively, are shown below.

Z ¹ and Z ² may have different structures, and may be represented by the general formula (10P-Z-1), formula (12P-Z-1), formula (13P-Z-1), formula (14P-Z-1), formula ( 15P-Z-1), formula (123P-Z-1), formula (124P-Z-1), formula (125P-Z-1), formula (134P-Z-1), formula (135P-Z-1) ) or in the formula (145P-Z-1), the case where a single bond of partial structural formula (u) and an ether bond of formula (g) are selected as Z ¹ and Z ² , respectively, are shown below.

Z ¹ and Z ² may have different structures, and may be represented by the general formula (10P-Z-1), formula (12P-Z-1), formula (13P-Z-1), formula (14P-Z-1), formula ( 15P-Z-1), formula (123P-Z-1), formula (124P-Z-1), formula (125P-Z-1), formula (134P-Z-1), formula (135P-Z-1) ) or in the formula (145P-Z-1), the case where a single bond of partial structural formula (u) and an amine bond of formula (q) are selected as Z ¹ and Z ² , respectively, are shown below.

「-CR ₂ -」, 「-C(=CR ₂ )-」, 「-CR=CR-」, 「-C(=O)NR-」, 「-P(=R) in Z ¹ and Z ² )-”, “-P(=O)(-R)-”, “-SiR ₂ -”, or “-NR-”, specifically, R is the following partial structural formula (J1) to formula (J74) . In each formula, “Me” is a methyl group and “tBu” is a tert-butyl group.

Among these, partial structural formula (J1) to formula (J3), formula (J11), formula (J12), formula (J38) or formula (J41) to formula (J44) are preferable, and more preferably formula (J1) ), Formula (J3), Formula (J11), Formula (J12), Formula (J41), or Formula (J44), and more preferably Formula (J11).

For example, partial structural formulas as Z ¹ and Z ² in general formula (10P-j-1), formula (10P-k-1), formula (10P-p-1) or formula (10P-q-1) (j), formula (k), formula (p), or formula (q) is selected, and R in this partial structural formula is hydrogen, partial structural formula (J1), formula (J3), formula (J6), or formula (J9). ), formula (J11), or formula (J21), it is expressed by the following structural formula. In each structural formula, “Me” is a methyl group and “tBu” is a tert-butyl group, and the same applies to all subsequent structural formulas.

For example, in the general formula (10P-gq-1), formula (10P-qg-1), formula (10P-qu-1), formula (10P-uq-1), or formula (10P-q-1) A partial structural formula (q) is selected as Z ¹ and Z ² of , and R in this partial structural formula is hydrogen, partial structural formula (J1), formula (J3), formula (J6), formula (J9), formula (J11) ) or formula (J21), it is expressed by the following structural formula.

Also, for example, a partial structural formula (q) is selected as Z2 in the general formula (10P-gq-1), formula (10P-q-1), or formula (10P-uq-1), and one of the partial structural formulas is selected as Z2. R is a partial structural formula (J11), and when adjacent R and B ring (b ring) combine to form a ring structure, it is represented by the following structural formula.

Also, for example, a partial structural formula (q) is selected as Z ² in the general formula (10P-gq-1), formula (10P-q-1) or formula (10P-uq-1), and this partial structural formula R in it is the partial structural formula (J11), and when adjacent R and C ring (c ring) combine to form a ring structure, it is represented by the following structural formula.

Also, for example, a partial structural formula (q) is selected as Z2 in the general formula (10P-gq-1), formula (10P-q-1), or formula (10P-uq-1), and one of the partial structural formulas is selected as Z2. R is a partial structural formula (J11), and when adjacent R and the B ring (b ring) and C ring (c ring) combine to form a ring structure, it is represented by the following structural formula.

In addition, for example, a partial structural formula (q) is selected as Z ¹ in the general formula (10P-q-1) or formula (10P-qg-1), and R in this partial structural formula is the partial structural formula (J11) , when adjacent R and the A ring (a ring) or D ring (d ring) combine to form a ring structure, it is represented by the following structural formula.

In addition, for example, a partial structural formula (q) is selected as Z ¹ in the general formula (10P-q-1) or formula (10P-qg-1), and R in this partial structural formula is the partial structural formula (J11) , when adjacent R and the A ring (a ring) and D ring (d ring) combine to form a ring structure, it is represented by the following structural formula.

In general formula (10P-Z-1), partial structural formula (q) is selected as Z ¹ or Z ² and partial structural formula (J11) is selected as R in partial structural formula (q), adjacent R and ring A (a ring), B ring (b ring), C ring (c ring), and/or D ring (d ring) are combined to form a ring structure, from the viewpoint of ease of synthesis, the general formula (10P-gq -21-J11), formula (10P-gq-22-J11), formula (10P-gq-23-J11), formula (10P-gq-24-J11), formula (10P-gq-25-J11), Formula (10P-q-21-J11), Formula (10P-q-22-J11), Formula (10P-q-23-J11), Formula (10P-q-24-J11), Formula (10P-q- 25-J11), equation (10P-uq-21-J11), equation (10P-uq-22-J11), equation (10P-uq-23-J11), equation (10P-uq-24-J11) and equation (10P-uq-25-J11) is preferred.

1-2. About substituents on the basic skeleton of a compound

Next, substituents for the basic skeleton in the above-described specific examples will be explained.

The "aryl ring" or "heteroaryl ring" as the A ring to the D ring, and the substituent for at least one hydrogen in the ring structure formed by combining the A ring and the B ring and/or the C ring and the D ring are specifically, These are partial structural formulas (J1) to formula (J74) and formulas (J81) to formula (J91). In each formula, “Me” is a methyl group and “tBu” is a tert-butyl group.

Among these, partial structural formula (J1) to formula (J3), formula (J11), formula (J12), formula (J38) or formula (J41) to formula (J44) are preferable, and more preferably formula (J1) ), Formula (J3), Formula (J11), Formula (J12), Formula (J41), or Formula (J44), and more preferably Formula (J11).

In addition, when partial structural formula (g), partial structural formula (q), or partial structural formula (u) is selected as Z ¹ or Z ² in general formula (10P-Z-1), as a substituent for the a ring and the d ring Using partial structural formulas (J81) to (J91), HOMO and LUMO can be separated between the a ring and d ring and the substituents on the a ring and d ring. On the other hand, if partial structural formulas (J32) to (J46) are used as substituents for the b ring and c ring, HOMO and LUMO can be separated between the b ring and c ring and the substituents for the b ring and c ring.

For example, some of the hydrogen atoms in the a ring and d ring in the general formula (10P-g-1) are substituted, or adjacent substituents are combined to form an aryl ring or heteroaryl ring together with the a ring or d ring. In one case, it is expressed by the structural formula below. Listed together with unsubstituted compounds of formula (10P-g-100). In each structural formula, “Me” is a methyl group and “tBu” is a tert-butyl group, and the same applies to all subsequent structural formulas.

In addition, for example, when some of the hydrogen atoms in the c ring in the general formula (10P-g-1) are substituted, or when adjacent substituents combine with each other to form an aryl ring or heteroaryl ring with the c ring, It is expressed by the structural formula below.

In addition, for example, when some of the hydrogen atoms in the b ring in the general formula (10P-g-1) are substituted, or when adjacent substituents are combined to form an aryl ring or heteroaryl ring with the b ring, It is expressed by the structural formula below.

Hydrogen atoms in rings a to d in general formula (10P-g-1) may each independently be substituted with the same structure or a different structure. For example, it is represented by the following structural formula.

In addition, for example, some of the hydrogen atoms in the a ring and d ring in the general formula (10P-gq-1) are substituted, or adjacent substituents are bonded together to form an aryl ring or heteroaryl ring together with the a ring or d ring. When formed, it is represented by the structural formula below. Listed together with unsubstituted compounds of the formula (10P-gq-100).

In addition, for example, when some of the hydrogen atoms in the c ring in the general formula (10P-gq-1) are substituted, or when adjacent substituents combine with each other to form an aryl ring or heteroaryl ring with the c ring, It is expressed by the structural formula below.

In addition, for example, when some of the hydrogen atoms in the b ring in the general formula (10P-gq-1) are substituted or adjacent substituents are combined to form an aryl ring or heteroaryl ring with the b ring, It is expressed by the structural formula below.

The hydrogen atoms in rings a to d in general formula (10P-gq-1) may each independently be substituted with the same structure or a different structure. For example, it is represented by the following structural formula.

In addition, for example, when R in the general formula (10P-gq-1) is the formula (J11), it is expressed by the following structural formula.

The hydrogen atoms in rings a to d in general formula (10P-gq-21-J11) and the hydrogen atom of phenyl as R in NR may each independently be substituted with the same structure or a different structure. From the viewpoint of ease of synthesis, it is preferable that the substituent for phenyl, which is R of the b ring, c ring, and NR, is substituted so as to be symmetrical with respect to the b ring-Z ² bond. For example, it is represented by the following structural formula.

The hydrogen atoms in rings a to d in general formula (10P-gq-23-J11) and the hydrogen atom of phenyl R in NR may each independently be substituted with the same structure or a different structure. From the viewpoint of ease of synthesis, it is preferable that the substituent for phenyl as R in the b ring, c ring, and NR is substituted so as to be symmetrical with respect to the b ring-Z ² bond. For example, it is represented by the following structural formula.

The hydrogen atoms in rings a to d in general formula (10P-gq-25-J11) and the hydrogen atom of phenyl as R in NR may each independently be substituted with the same structure or a different structure. From the viewpoint of ease of synthesis, it is preferable that the substituent for phenyl as R in the b ring, c ring, and NR is substituted so as to be symmetrical with respect to the b ring-Z ² bond. For example, it is represented by the following structural formula.

For example, some of the hydrogen atoms in the a ring and d ring in the general formula (10P-gu-1) are substituted, or adjacent substituents are combined to form an aryl ring or heteroaryl ring together with the a ring or d ring. In one case, it is expressed by the structural formula below. Listed together with the unsubstituted compound of the formula (10P-gu-100).

In addition, for example, when some of the hydrogen atoms in the c ring in the general formula (10P-gu-1) are substituted, or when adjacent substituents are combined to form an aryl ring or heteroaryl ring with the c ring, It is expressed by the structural formula below.

In addition, for example, when some of the hydrogen atoms in the b ring in the general formula (10P-gu-1) are substituted or adjacent substituents are combined to form an aryl ring or heteroaryl ring with the b ring, It is expressed by the structural formula below.

The hydrogen atoms in the a to d rings in the general formula (10P-gu-1) may each independently be substituted with the same structure or a different structure. For example, it is represented by the following structural formula.

For example, some of the hydrogen atoms in the a ring and d ring in the general formula (10P-ug-1) are substituted, or adjacent substituents are combined to form an aryl ring or heteroaryl ring together with the a ring or d ring. In one case, it is expressed by the structural formula below. Listed together with unsubstituted compounds of the formula (10P-ug-100).

In addition, for example, when some of the hydrogen atoms in the c ring in the general formula (10P-ug-1) are substituted, or when adjacent substituents are combined to form an aryl ring or heteroaryl ring with the c ring, It is expressed by the structural formula below.

In addition, for example, when some of the hydrogen atoms in the b ring in the general formula (10P-ug-1) are substituted or adjacent substituents are combined to form an aryl ring or heteroaryl ring with the b ring, It is expressed by the structural formula below.

The hydrogen atoms in the a to d rings in the general formula (10P-ug-1) may each independently be substituted with the same structure or a different structure. For example, it is represented by the following structural formula.

In addition, for example, some of the hydrogen atoms in the a ring and d ring in the general formula (10P-uq-1) are substituted, or adjacent substituents are bonded together to form an aryl ring or heteroaryl ring together with the a ring or d ring. When formed, it is represented by the structural formula below. Listed together with unsubstituted compounds of the formula (10P-uq-100).

In addition, for example, when some of the hydrogen atoms in the c ring in the general formula (10P-uq-1) are substituted or adjacent substituents are combined to form an aryl ring or heteroaryl ring with the c ring, It is expressed by the structural formula below.

In addition, for example, when some of the hydrogen atoms in the b ring in the general formula (10P-uq-1) are substituted or adjacent substituents are combined to form an aryl ring or heteroaryl ring with the b ring, It is expressed by the structural formula below.

Hydrogen atoms in rings a to d in general formula (10P-uq-1) may each independently be substituted with the same structure or a different structure. For example, it is represented by the following structural formula.

In general formula (10), the A ring, C ring, and D ring may each independently have the same structure or different structures, and the hydrogen atoms in the A ring, C ring, D ring, and b ring each independently have the same structure or It may be substituted with a group of a different structure. For example, it is represented by the following structural formula.

1-3. About the excitation energy of compounds

The difference ΔE _ST (=E _S -E _T ) between the singlet excitation energy (E _S ) and triplet excitation energy (E _T ) of the compound of the present invention is preferably 0.20 eV or less, and more preferably 0.02 eV or less. This energy difference is small enough to obtain thermally activated delayed fluorescence.

The singlet excitation energy (E _S ) is calculated as E _S = 1240/B from the maximum emission wavelength B (nm) of the fluorescence spectrum. Additionally, the triplet excitation energy (E _T ) is calculated as E _T =1240/C from the maximum emission wavelength C (nm) of the phosphorescence spectrum.

In addition, ΔE _ST is, for example, “Purely organic electroluminescent material realizing 100% conversion from electricity to light”, H. Kaji, H. Suzuki, T. Fukushima, K. Shizu, K. Katsuaki, S. Kubo, T Komino, H. Oiwa, F. Suzuki, A. Wakamiya, Y. Murata, C. Adachi, Nat. It can also be calculated using the method described in Commun.2015, 6, 8476.

“Thermal activation type delayed phosphor” refers to a compound that absorbs heat energy, causes reverse intersystem crossing from the excited singlet state to the excited singlet state, and emits delayed fluorescence by radiation deactivation from the excited singlet state. do. However, “heat-activated delayed fluorescence” also includes passing through a higher-order triplet during the excitation process from the triplet excited state to the singlet excited state. For example, a paper by Monkman et al. at Durham University (NATURE COMMUNICATIONS, 7: 13680, DOI: 10.1038/ncomms13680), a paper by Hosokai et al. at the Institute of Industrial Technology (Hosokai et al., Sci. Adv.2017 ;3: e1603282), a paper by Sato et al. at Kyoto University (Scientific Reports, 7: 4820, DOI: 10.1038/s41598-017-05007-7), and the same conference presentation by Sato et al. at Kyoto University (Japanese version) The Society's 98th Spring Banquet, presentation number: 2I4-15, Mechanism for high-efficiency light emission in organic EL using DABNA as a light-emitting molecule, Kyoto University Graduate School of Engineering, etc.

2. Method for producing the compound of the present invention and its polymer compound

Basically, the compounds represented by general formula (1) or (2) are first made of ring A (a ring), ring D (d ring), ring B (b ring), and ring C (c ring). An intermediate is prepared by linking with a linking group (a group containing Z ¹ or Z ² ) (first reaction), and then A ring (a ring), B ring (b ring), C ring (c ring) and D The final product can be prepared by combining the ring (d ring) with a boron atom (second reaction) (Scheme (1) and Scheme (2)).

In the first reaction, for example, if it is an etherification reaction, a general reaction such as a nucleophilic substitution reaction or Ullman reaction can be used, and if it is an amination reaction, a general reaction such as the Buchwald-Hartwig reaction can be used. Available. Additionally, in the second reaction, a metal-boron metal exchange reaction can be used.

The second reaction is a reaction that combines the A ring (a ring), B ring (b ring), C ring (c ring), and D ring (d ring) by introducing a boron atom, and is shown in Scheme (1) and Scheme ( 2) shows, for example, a case where an intermediate substituted by halogen (Hal) such as chlorine, bromine, or iodine is used as the intermediate. Intermediate (1-A) or intermediate (2-A), which is a dihalogen compound, is ortho-metalized to the halogen atom with n-butyllithium, sec-butyllithium, or tert-butyllithium to obtain intermediate (1-C) or intermediate. (2-C) (M in the formula is a metal such as lithium). On the one hand, the halogen atom of the intermediate (1-B) or intermediate (2-B), which is a halogen compound, is first metalized with n-butyllithium, sec-butyllithium, or tert-butyllithium, and then with boron trichloride or tert-butyllithium. Boron tribromide or the like is added to perform metal-boron exchange to obtain intermediate (1-D) or intermediate (2-D). By adding the previously prepared intermediate (1-C) or intermediate (2-C) to metal-boron exchange of the intermediate (1-D) or intermediate (2-D), the general formula (1) or formula The compound of (2) can be obtained.

In addition, by using an intermediate having a hydrogen atom with high metalization activity, it is possible to produce compounds represented by the general formula (1) or (2) even if the intermediate does not introduce a halogen atom through selective metalation. (Scheme(3), Scheme(4)).

In this second reaction, the hydrogen atom of intermediate (1-E) or intermediate (2-E) is ortho-metalated to produce intermediate (1-C) or intermediate (2-C) (M in the formula is lithium, etc. of metal). On the one hand, the hydrogen atom of the intermediate (1-F) or intermediate (2-F) is metalized, and then boron trichloride, boron tribromide, etc. are added to perform metal-boron metal exchange to produce the intermediate (1-D) ) or intermediate (2-D). By adding the previously prepared intermediate (1-C) or intermediate (2-C) to metal-boron exchange of the intermediate (1-D) or intermediate (2-D), the general formula (1) or formula The compound of (2) can be obtained.

And, as the ortho metalation reagent used in Scheme (1) to Scheme (4), alkyl lithium such as methyl lithium, n-butyl lithium, sec-butyl lithium, and tert-butyl lithium, lithium diisopropylamide, and lithium. Examples include organic alkali compounds such as tetramethylpiperidide, lithium hexamethyldisilazide, and potassium hexamethyldisilazide.

Reactivity can be improved by adding a coordinating additive during metallization to break down the association. Examples of the coordinating additive include N,N',N,N'-tetramethylethylenediamine (TMEDA), hexamethylphosphoramide (HMPA), and dimethylpropylene urea (DMPU).

In addition, as the metal-boron metal exchange reagent used in the above Schemes (1) to Scheme (4), halides of boron such as boron trifluoride, boron trichloride, boron tribromide, and boron triiodide, as well as trimethyl borate, etc. Examples include alkoxyborane compounds such as 4,4,5,5-tetramethyl-1,3,2-dioxaborolane, and aryloxy compounds such as triphenyl borate.

In addition, examples of the form of a polymer compound having the structure represented by the general formula (1) as a repeating unit include schematic diagrams (I) to schematic diagrams (III), and for a form of a polymer compound, especially a dimer, the schematic diagram ( Examples include i) and schematic diagram (ii). In the following description, the same applies to the polymer compound of general formula (2).

The polymer compound (I) is a polymer compound formed by sharing a part of the structure of formula (1) (for example, any one of the A ring to the D ring, etc.),

Polymer compound (II) is a polymer compound formed by linking the structures of formula (1) through the cross-linked structure XL, provided that EC is the terminal structure,

Polymer compound (III) is a polymer compound having the structure of formula (1) as a side chain of a linear polymer, where EC is the terminal structure, MU is a monomer unit polymerized by a polymerizable group,

Dimer (i) is a dimer formed by sharing a part of the structure of formula (1) (for example, one of the A ring to the D ring, etc.),

Dimer (ii) is a dimer formed by linking the structures of formula (1) through the cross-linked structure XL.

The structures of formula (1), which are partial structures in polymer compounds (I) to compounds (III) and dimers (i) and dimers (ii), may be the same structure or different structures. In addition, in the polymer compound (I) and dimer (i), the partial structures of formula (1) are A ring (a ring), B ring (b ring), C ring (c ring), and D ring. (d ring) or Z ¹ (Z ² ) using the aryl ring of NR (R = aryl ring). This bonding mode may be a form in which these rings are bonded by sharing a plurality of partial structures, or it can be a form in which these rings are bonded by condensing with each other. In addition, in polymer compound (II), polymer compound (III) and dimer (ii), the form in which the partial structure of formula (1), the cross-linked structure XL, the terminal structure EC and the monomer unit MU are combined is as described above. It may be in the form of a bond formed by sharing or condensation of one ring, as well as a single bond or a linking group such as an alkylene group with 1 to 3 carbon atoms, a phenylene group, or a naphthylene group.

For example, when polymer compound (I) is formed by sharing the a ring and d ring in the partial structure of formula (10P-g-100), it is represented by the following formula (I-1).

For example, when forming polymer compound (I) by sharing the a ring and the aryl ring (phenyl ring) of N-R in the partial structure of formula (10P-gq-100-J11), the formula (I- It is displayed as 2).

For example, when the a ring and the d ring in the partial structure of formula (10P-gq-100-J11) form polymer compound (II) using the cross-linked structure XL (m-phenylene ring) as a linking group, It is expressed as formula (II-1). And the terminal structure EC is a phenyl group.

For example, the a ring in the partial structure of the formula (10P-gq-100-J11) and the d ring in the partial structure of the formula (10P-g-100) form a dimer ( When forming ii), it is expressed by the following formula (ii-1).

For example, the aryl ring (phenyl ring) of N-R in the partial structure of formula (10P-gq-100-J11) and the aryl ring (phenyl ring) of N-R in the partial structure of formula (10P-gq-100-J11) ) When dimer (ii) is formed using crosslinked structure XL (single bond) as a linking group, it is represented by the following formula (ii-2).

The terminal structure EC in the polymer compound (II) is hydrogen or a monovalent aryl ring or heteroaryl ring having 6 to 30 carbon atoms, and is preferably hydrogen or a monovalent aryl ring having 6 to 18 carbon atoms.

The crosslinked structure XL in polymer compound (II) and dimer (ii) is a single bond or a divalent aryl ring or heteroaryl ring having 6 to 30 carbon atoms, preferably a single bond or a divalent aryl ring having 6 to 18 carbon atoms. It is an aryl ring, and more preferably, it is a single bond or a divalent aryl ring having 6 to 12 carbon atoms.

Specific “aryl rings” in structures EC and XL include monocyclic benzene rings, dicyclic biphenyl rings, condensed bicyclic naphthalene rings, and tricyclic terphenyl rings (m-terphenyl, o-terphenyl, p -terphenyl), condensed tricyclic ring, acenaphthylene ring, fluorene ring, phenarene ring, phenanthrene ring, condensed tetracyclic ring, triphenylene ring, pyrene ring, naphthacene ring, benzofluorene ring, condensed pentacyclic ring, peryl Examples include ren ring and pentacene ring. Additionally, the fluorene ring or benzofluorene ring also includes structures in which the fluorene ring or benzofluorene ring is spiro bonded.

Specific “heteroaryl rings” in structures EC and XL include, for example, pyrrole ring, oxazole ring, isoxazole ring, thiazole ring, isothiazole ring, imidazole ring (unsubstituted, alkyl substituted such as methyl or phenyl, etc. aryl substitution), oxadiazole ring, thiadiazole ring, triazole ring, tetrazole ring, pyrazole ring, pyridine ring, pyrimidine ring, pyridazine ring, pyrazine ring, triazine ring, indole ring, isoindole ring, 1H-indazole ring , benzimidazole ring, benzoxazole ring, benzothiazole ring, 1H-benzotriazole ring, quinoline ring, isoquinoline ring, cinnoline ring, quinazoline ring, quinoxaline ring, phthalazine ring, naphthyridine ring, purine ring, Pteridine ring, carbazole ring, acridine ring, phenoxathiin ring, phenoxazine ring, phenothiazine ring, phenazine ring, indolizine ring, furan ring, benzofuran ring, isobenzofuran ring, dibenzofuran ring, naph. Tobenzofuran ring, thiophene ring, benzothiophene ring, dibenzothiophene ring, naphthobenzothiophene ring, benzophosphor ring, dibenzophosphor ring, benzophosphoroxide ring, dibenzophosphoroxide There are seed pills, furazane pills, oxadiazole pills, and thiantrene pills.

For polymer compound (I), polymer compound (II), dimer (i) and dimer (ii), as in the synthesis method of Scheme (1) to Scheme (4), A ring (a ring) -Z ¹ After synthesizing the -D ring (d ring) linking structure and the B ring (b ring) -Z ² -C ring (c ring) linking structure, boron is introduced, or a halogenated aryl of the structure of formula (1) Using derivatives and arylboronic acid derivatives as starting materials, or using halogenated arylboronic acid derivatives, halogenated aryl derivatives, and arylboronic acid derivatives as starting materials, Suzuki-Miyaura coupling, Kumada )·Tamao·Corriu coupling, Negishi coupling, halogenation reaction, or boronation reaction can be appropriately combined to synthesize it. In addition, for the polymer compound (III), a (meth)acrylate derivative, a meta(acrylamide) derivative, an epoxy derivative, an oxetane derivative, a norbornene derivative having the structure of formula (1) is prepared using a known method. It can be synthesized using a dicyclopentadiene derivative or indene derivative as a starting material, using radical polymerization, cationic polymerization, anionic polymerization, or ring-opening metathesis polymerization.

Regarding the above-described coupling reaction, the reactive functional groups of the halide and boronic acid derivative in the Suzuki-Miyaura coupling may be replaced as appropriate, and are the same in the Kumada-Tamao-Koryu coupling and the Negishi coupling. Accordingly, the functional groups involved in these reactions may be replaced. Additionally, when converting to Grignard reagent, metallic magnesium and isopropyl Grignard reagent may be replaced appropriately. Boronic acid ester may be used as is, or may be hydrolyzed with acid to form boronic acid. When used as a boronic acid ester, alkyl groups other than those exemplified may be used as the alkyl group of the ester portion.

Specific examples of palladium catalysts used in the coupling reaction include tetrakis(triphenylphosphine)palladium(0): Pd(PPh ₃ ) ₄ , bis(triphenylphosphine)palladium(II) dichloride: PdCl ₂ (PPh) ₃ ) ₂ , palladium(II) acetate: Pd(OAc) ₂ , tris(dibenzylideneacetone)2palladium(0): Pd ₂ (dba) ₃ , tris(dibenzylideneacetone)2palladium(0)chloroform complex : Pd ₂ (dba) ₃ ·CHCl ₃ , bis(dibenzylideneacetone)palladium(0): Pd(dba)2, bis(tritert-butylphosphino)palladium(0): Pd(t-Bu ₃ P ) ₂ , [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II): Pd(dppf)Cl ₂ , [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II) ) Dichloromethane complex (1:1): Pd(dppf)Cl ₂ ·CH ₂ Cl ₂ , PdCl ₂ {P(t-Bu) ₂ -(p-NMe ₂ -Ph)}2: (A- ^ta Phos) ₂ PdCl ₂ , palladium bis (dibenzylidene), [1,3-bis (diphenylphosphino) propane] nickel (II) dichloride, PdCl ₂ [P(t-Bu) ₂ -(p-NMe ₂ - Ph)] ₂ : (A ^-ta Phos) ₂ PdCl ₂ (Pd-132: trademark; manufactured by Johnson-Matt. Co., Ltd.).

Additionally, in order to promote the coupling reaction, a phosphine compound may be added to the palladium catalyst in some cases. Specific examples of the phosphine compound include tri(tert-butyl)phosphine, tricyclohexylphosphine, 1-(N,N-dimethylaminomethyl)-2-(di-tert-butylphosphino)ferrocene, 1- (N,N-dibutylaminomethyl)-2-(di-tert-butylphosphino)ferrocene, 1-(methoxymethyl)-2-(di-tert-butylphosphino)ferrocene, 1,1'- Bis(di-tert-butylphosphino)ferrocene, 2,2'-bis(di-tert-butylphosphino)-1,1'-binaphthyl, 2-methoxy-2'-(di-tert- butylphosphino)-1,1'-binaphthyl, or 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl, etc.

Specific examples of bases used in the coupling reaction include sodium carbonate, potassium carbonate, cesium carbonate, sodium bicarbonate, sodium hydroxide, potassium hydroxide, barium hydroxide, sodium ethoxide, sodium tert-butoxide, sodium acetate, potassium acetate, Examples include tripotassium phosphate and potassium fluoride.

The base may be added as an aqueous solution and allowed to react in a two-phase system. When reacting in a two-phase system, a phase transfer catalyst such as quaternary ammonium salt may be added as needed.

In addition, polymerizable groups capable of radical polymerization, cationic polymerization, or anionic polymerization used in the synthesis of polymer compound (III) include (meth)acrylic group, allyl group, vinyl group, epoxide group, and oxetane. As for the polymerization initiator of radical polymerization, cationic polymerization, and anionic polymerization, a radical generator is preferably used in the case of radical polymerization, and an acid generator and a base generator are preferably used in the case of cationic polymerization and anionic polymerization. The polymerization initiator may be one type of compound or a mixture of two or more types of compounds.

In addition, examples of the polymerizable group capable of ring-opening metathesis polymerization used in the synthesis of polymer compound (III) include a cyclic alkene structure and a cyclic alkyne structure, and specifically include a norbornene structure, a dicyclopentadiene structure, Examples include indene structure and cyclopentene structure. As a catalyst used in ring-opening metathesis polymerization, complexes such as ruthenium, molybdenum, and tungsten are used, and examples include Grubbs catalyst.

In addition, specific examples of solvents used in the coupling reaction or polymerization reaction include benzene, toluene, xylene, 1,2,4-trimethylbenzene, anisole, acetonitrile, dimethyl sulfoxide, N, N-dimethylformamide, Examples include tetrahydrofuran, diethyl ether, tert-butyl methyl ether, 1,4-dioxane, methanol, ethanol, tert-butyl alcohol, cyclopentyl methyl ether, or isopropyl alcohol. These solvents can be appropriately selected and may be used individually or as a mixed solvent.

When producing a polymer compound, it may be produced in one step or may be produced through multiple steps. In addition, it may be carried out by a batch polymerization method in which the reaction is started after putting all the raw materials into the reaction vessel, or by a drop polymerization method in which the raw materials are added dropwise to the reaction vessel, or by precipitation polymerization in which the product precipitates as the reaction progresses. It may be carried out by a polymerization method, or it can be synthesized by appropriately combining them. For example, in the case of one-step synthesis, the target product is obtained by performing a reaction while adding a partial structure compound of formula (1) having a polymerizable group and a compound having a terminal structure (EC) to a reaction vessel. Additionally, in the case of multi-step synthesis, the target product is obtained by polymerizing the monomer unit (MU) to the desired molecular weight and then adding and reacting a compound having a terminal structure (EC).

Additionally, the primary structure of the polymer can be controlled by selecting the polymerizable group of the monomer unit (MU). For example, as shown in Scheme (5) 1 to 3, a polymer with a random primary structure (1 in Scheme (5)), a polymer with a regular primary structure (2 and 2 in Scheme (5)) 3), etc. can be synthesized and used in appropriate combinations depending on the target.

In particular, in dimer (i) and dimer (ii), it is preferable that the dipole moments formed by each of the two partial structures of formula (1) and the linking group (XL) cancel each other. In this case, dimer (i) and dimer (ii) have high symmetry.

3. Organic devices

The compound according to the present invention and its polymer compound can be used as a material for organic devices. Examples of organic devices include organic electroluminescent elements, organic field effect transistors, and organic thin-film solar cells.

3-1. Organic electroluminescent device

The compound according to the present invention and its polymer compound can be used, for example, as a material for an organic electroluminescent device. Below, the organic EL device according to this embodiment will be described in detail based on the drawings. 1 is a schematic cross-sectional view showing an organic EL device according to this embodiment.

<Structure of organic electroluminescent device>

The organic electroluminescent device 100 shown in FIG. 1 includes a substrate 101, an anode 102 installed on the substrate 101, a hole injection layer 103 provided on the anode 102, and a hole injection layer. A hole transport layer 104 provided on (103), a light-emitting layer 105 provided on the hole transport layer 104, an electron transport layer 106 provided on the light-emitting layer 105, and an electron transport layer 106 installed on the electron transport layer 106. It has an injection layer 107 and a cathode 108 provided on the electron injection layer 107.

Then, the organic electroluminescent device 100 is manufactured by reversing the manufacturing order, for example, a substrate 101, a cathode 108 provided on the substrate 101, and an electron injection layer provided on the cathode 108. (107), an electron transport layer 106 provided on the electron injection layer 107, a light emitting layer 105 provided on the electron transport layer 106, a hole transport layer 104 provided on the light emitting layer 105, and a hole transport layer 106 provided on the electron injection layer 107. It may be configured to include a hole injection layer 103 provided on the transport layer 104 and an anode 102 provided on the hole injection layer 103.

All of the above-mentioned layers are not necessary, and the minimum structural unit is composed of an anode 102, a light-emitting layer 105, and a cathode 108, and a hole injection layer 103, a hole transport layer 104, and an electron transport layer ( 106), the electron injection layer 107 is a layer installed arbitrarily. In addition, each of the above-mentioned layers may be a single layer or may be a plurality of layers.

As aspects of the layers constituting the organic electroluminescent element, in addition to the above-mentioned “substrate/anode/hole injection layer/hole transport layer/light-emitting layer/electron transport layer/electron injection layer/cathode”, “substrate/anode/hole transport layer/cathode” Light-emitting layer/electron transport layer/electron injection layer/cathode”, 「Substrate/anode/hole injection layer/light-emitting layer/electron transport layer/electron injection layer/cathode」, 「Substrate/anode/hole injection layer/hole transport layer/light-emitting layer/electron injection layer /cathode”, “substrate/anode/hole injection layer/hole transport layer/light emitting layer/electron transport layer/cathode”, “substrate/anode/light emitting layer/electron transport layer/electron injection layer/cathode”, “substrate/anode/hole transport layer/light emitting layer” /electron injection layer/cathode”, “substrate/anode/hole transport layer/light-emitting layer/electron transport layer/cathode”, “substrate/anode/hole injection layer/light-emitting layer/electron injection layer/cathode”, “substrate/anode/hole injection layer” /light emitting layer/electron transport layer/cathode”, “substrate/anode/light emitting layer/electron transport layer/cathode”, “substrate/anode/light emitting layer/electron injection layer/cathode” may be used.

<Substrate in organic electroluminescent device>

The substrate 101 is a support for the organic electroluminescent element 100, and usually quartz, glass, metal, plastic, etc. are used. The substrate 101 is formed in a plate shape, a film shape, or a sheet shape depending on the purpose, and for example, a glass plate, a metal plate, a metal foil, a plastic film, a plastic sheet, etc. are used. Among them, glass plates and plates made of transparent synthetic resins such as polyester, polymethacrylate, polycarbonate, and polysulfone are preferable. If it is a glass substrate, soda lime glass, alkali-free glass, etc. are used, and the thickness just needs to be sufficient to maintain mechanical strength, so for example, it can be 0.2 mm or more. The upper limit of the thickness is, for example, 2 mm or less, and preferably 1 mm or less. Regarding the material of glass, alkali-free glass is preferable since it is better to have fewer ions eluted from the glass. However, soda lime glass coated with a barrier such as SiO ₂ is also commercially available, so this can be used. . Additionally, in order to increase gas barrier properties, a gas barrier film such as a dense silicon oxide film may be formed on at least one side of the substrate 101. In particular, a plate, film or sheet made of synthetic resin with low gas barrier properties may be used as the substrate ( 101), it is desirable to form a gas barrier film.

<Anode in organic electroluminescent device>

The anode 102 serves to inject holes into the light emitting layer 105. Additionally, when the hole injection layer 103 and/or the hole transport layer 104 are provided between the anode 102 and the light emitting layer 105, holes are injected into the light emitting layer 105 through these.

Examples of materials forming the anode 102 include inorganic compounds and organic compounds. Inorganic compounds include, for example, metals (aluminum, gold, silver, nickel, palladium, chromium, etc.), metal oxides (indium oxide, tin oxide, indium-tin oxide (ITO), indium-zinc oxide (IZO) etc.), halogenated metals (copper iodide, etc.), copper sulfide, carbon black, ITO glass, and Nesa glass. Examples of organic compounds include polythiophenes such as poly(3-methylthiophene), and conductive polymers such as polypyrrole and polyaniline. In addition, the material can be appropriately selected and used as an anode for organic electroluminescent devices.

The resistance of the transparent electrode is not limited as long as it can supply sufficient current for light emission of the light-emitting element, but it is preferably low in resistance from the viewpoint of power consumption of the light-emitting element. For example, an ITO substrate of 300 Ω/□ or less functions as a device electrode, but currently, it is also possible to supply a substrate of about 10 Ω/□, for example, 100 to 5 Ω/□, preferably 50 to 50 Ω/□. It is particularly desirable to use a low-resistance material of 5 Ω/□. The thickness of ITO can be arbitrarily selected according to the resistance value, but is usually between 50 and 300 nm.

<Hole injection layer, hole transport layer in organic electroluminescent device>

The hole injection layer 103 serves to efficiently inject holes moving from the anode 102 into the light emitting layer 105 or the hole transport layer 104. The hole transport layer 104 serves to efficiently transport holes injected from the anode 102 or holes injected from the anode 102 through the hole injection layer 103 to the light emitting layer 105. The hole injection layer 103 and the hole transport layer 104 are each formed by laminating or mixing one or two or more types of hole injection/transport materials, or a mixture of a hole injection/transport material and a polymer binder. is formed by Additionally, the layer can be formed by adding an inorganic salt such as iron(III) chloride to the hole injection/transport material.

As a hole injection/transport material, it is necessary to efficiently inject and transport holes from the anode between electrodes to which an electric field is applied, and it is desirable to have high hole injection efficiency and efficiently transport the injected holes. For this purpose, it is desirable to use a material that has a small ionization potential, high hole mobility, excellent stability, and does not easily produce impurities that become traps during manufacture and use.

As a material for forming the hole injection layer 103 and the hole transport layer 104, the compound according to the present invention and its polymer compound can be used. In addition, in the photoconductive material, any compound may be selected from compounds conventionally used as hole charge transport materials and known compounds used in the hole injection layer and hole transport layer of p-type semiconductors and organic electroluminescent devices. You can select and use it. Specific examples of these include carbazole derivatives (N-phenylcarbazole, polyvinylcarbazole, etc.), biscarbazole derivatives such as bis(N-arylcarbazole) or bis(N-alkylcarbazole), and triarylamine. Derivatives (polymers having aromatic tertiary amino in the main or side chain, 1,1-bis(4-di-p-tolylaminophenyl)cyclohexane, N,N'-diphenyl-N,N'-di(3 -methylphenyl)-4,4'-diaminophenyl, N,N'-diphenyl-N,N'-ditaphthyl-4,4'-diaminophenyl, N,N'-diphenyl-N,N '-di(3-methylphenyl)-4,4'-diphenyl-1,1'-diamine, N,N'-dinaphthyl-N,N'-diphenyl-4,4'-diphenyl-1 ,1'-diamine, N ⁴ ,N ^{4 '} -diphenyl-N ⁴ ,N ^{4 '} -bis(9-phenyl-9 H-carbazol-3-yl)-[1,1'-biphenyl]- 4,4'-diamine, N ⁴ ,N ⁴ ,N ^{4 '} ,N ^4' -tetra[1,1'-biphenyl]-4-yl)-[1,1'-biphenyl]-4,4 Triphenylamine derivatives such as '-diamine, 4,4',4"-tris(3-methylphenyl(phenyl)amino)triphenylamine, starburst amine derivatives, etc.), stilbene derivatives, phthalocyanine derivatives (metal-free, copper phthalocyanine, etc.), pyrazoline derivatives, hydrazine-based compounds, benzofuran derivatives, thiophene derivatives, oxadiazole derivatives, quinoxaline derivatives (e.g., 1,4,5,8,9,12-hexaazatriphenylene) -2,3,6,7,10,11-hexacarbonitrile, etc.), heterocyclic compounds such as porphylline derivatives, polysilanes, polycarbonate and styrene derivatives having the above-mentioned monomers in the side chain, and polyvinyl. Carbazole, polysilane, etc. are preferable, but there is no particular limitation as long as it is a compound that forms a thin film necessary for manufacturing a light-emitting device, can inject holes from the anode, and can transport holes.

Additionally, it is known that the conductivity of an organic semiconductor is strongly influenced by its doping. Such an organic semiconductor matrix material is composed of a compound with good electron donating properties or a compound with good electron accepting properties. For doping of electron-donating materials, strong electron acceptors such as tetracyanoquinonedimethane (TCNQ) or 2,3,5,6-tetrafluorotetracyano-1,4-benzoquinonedimethane (F4TCNQ) are used. It is known (e.g., M. Pfeiffer, A. Beyer, T. Fritz, K. Leo, Appl. Phys. Lett., 73(22), 3202-3204 (1998) and J. Blochwitz, M. Pheiffer, T. Fritz, K. Leo, Appl. Lett., 73(6), 729-731 (1998)). The conductivity of the base material changes significantly depending on the number and mobility of holes through the transfer process. Examples of matrix materials with hole transport properties include benzidine derivatives (TPD, etc.). Alternatively, starburst amine derivatives (TDATA, etc.), or specific metal phthalocyanines (particularly, zinc phthalocyanine (ZnPc), etc.) are known (Japanese Patent Application Laid-Open No. 2005-167175).

<Emitting layer in organic electroluminescent device>

The light-emitting layer 105 is a layer that emits light by recombining holes injected from the anode 102 and electrons injected from the cathode 108 between electrodes to which an electric field is applied. The material forming the light-emitting layer 105 may be any compound (luminescent compound) that is excited and emits light by recombination of holes and electrons, and can form a stable thin film shape and have strong luminescence (fluorescence) efficiency in the solid state. It is preferable that it is a compound that represents In the present invention, the compound according to the present invention and its polymer compound can be used as the material for the light-emitting layer.

The light-emitting layer may be a single layer, may be composed of multiple layers, or may be any, and is formed of materials for the light-emitting layer (host material and dopant material). The host material and the dopant material may be of one type, a combination of multiple types, or any of them. The dopant material may be included in the entire host material, or may be included partially, or any of them may be used. As a doping method, it can be formed by co-deposition with the host material, but may be deposited simultaneously after mixing with the host material in advance.

The amount of host material used varies depending on the type of host material, and can be determined according to the characteristics of the host material. The standard for the usage amount of the host material is preferably 50 to 99.999% by weight of the total light emitting layer material, more preferably 80 to 99.95% by weight, and even more preferably 90 to 99.9% by weight. The compound according to the present invention and its polymer compound can also be used as a host material.

The amount of dopant material used varies depending on the type of dopant material, and can be determined according to the characteristics of the dopant material. The standard for the amount of dopant used is preferably 0.001 to 50% by weight of the total light emitting layer material, more preferably 0.05 to 20% by weight, and even more preferably 0.1 to 10% by weight. The above range is preferable because, for example, concentration quenching phenomenon can be prevented. The compound according to the present invention and its polymer compound can also be used as a dopant material.

On the other hand, in organic electroluminescent devices using thermally activated delayed fluorescence dopant materials, a low concentration of the dopant material is preferable in that it can prevent concentration quenching, but a high concentration of the dopant material is preferable for the thermally activated delayed fluorescence. This is desirable in terms of mechanism efficiency. In addition, in an organic electroluminescent device using a thermally activated delayed fluorescence assist dopant material, it is preferable that the amount of the dopant material used is low in concentration compared to the amount of the assist dopant material used, in terms of the efficiency of the thermally activated delayed fluorescence mechanism of the assist dopant material.

In the case where the assist dopant material is used, the standards for the usage amounts of the host material, assist dopant material, and dopant material are 40 to 99.999% by weight, 59 to 1% by weight, and 20 to 0.001% by weight, respectively, of the total material for the emitting layer. , preferably 60 to 99.99% by weight, 39 to 5% by weight, and 10 to 0.01% by weight, respectively, and more preferably 70 to 99.95% by weight, 29 to 10% by weight, and 5 to 0.05% by weight. The compound according to the present invention and its polymer compound can also be used as an assist dopant material.

Host materials that can be used in combination with the compound according to the present invention and its polymer compound include condensed ring derivatives such as anthracene and pyrene, which have previously been known as light emitters, bistyryl derivatives such as bistyryl anthracene derivatives and distyrylbenzene derivatives, and tetramethylene. Examples include phenylbutadiene derivatives, cyclopentadiene derivatives, fluorene derivatives, and benzofluorene derivatives.

In addition, the dopant material that can be used in combination with the compound according to the present invention and its polymer compound is not particularly limited, and known compounds can be used, and can be selected from various materials depending on the desired luminescent color. Specifically, for example, condensed ring derivatives such as phenanthrene, anthracene, pyrene, tetracene, pentacene, perylene, naphthopyrene, dibenzopyrene, rubrene, and chrysene, benzoxazole derivatives, and benzothiazole. Derivatives, benzoimidazole derivatives, benzotriazole derivatives, oxazole derivatives, oxadiazole derivatives, thiazole derivatives, imidazole derivatives, thiadiazole derivatives, triazole derivatives, pyrazoline derivatives, stilbene derivatives, thiophene derivatives, Tetraphenylbutadiene derivatives, cyclopentadiene derivatives, bistyryl derivatives such as bistyryl anthracene derivatives and distyrylbenzene derivatives (Japanese Patent Application Laid-Open No. 1-245087), bistyrylarylene derivatives (Japanese Patent Application Laid-Open No. 2) -247278 Publication), diazindacene derivatives, furan derivatives, benzofuran derivatives, phenylisobenzofuran, dimethylisobenzofuran, di(2-methylphenyl)isobenzofuran, di(2-trifluoromethylphenyl)iso Isobenzofuran derivatives such as benzofuran and phenylisobenzofuran, dibenzofuran derivatives, 7-dialkylaminocoumarin derivatives, 7-piperidinocoumarin derivatives, 7-hydroxycoumarin derivatives, 7-methoxycoumarin derivatives, 7 -Coumarin derivatives such as acetoxycoumarin derivatives, 3-benzothiazolylcoumarin derivatives, 3-benzimidazolylcoumarin derivatives, and 3-benzoxazolylcoumarin derivatives, dicyanomethylenepyran derivatives, dicyanomethylenethiopyran derivatives, polymethine Derivatives, cyanine derivatives, oxobenzanthracene derivatives, xanthene derivatives, rhodamine derivatives, fluorescein derivatives, pyrylium derivatives, carbostyryl derivatives, acridine derivatives, oxazine derivatives, phenylene oxide derivatives, quinaclidone derivatives , quinazoline derivatives, pyrrolopyridine derivatives, furopyridine derivatives, 1,2,5-thiadiazolopyrene derivatives, pyromethene derivatives, perinone derivatives, pyrrolopyrrole derivatives, squaryllium derivatives, violanthrone derivatives, phenazine There are derivatives, acridone derivatives, deazaflavin derivatives, fluorene derivatives, and benzofluorene derivatives.

For example, blue to blue-green dopant materials include aromatic hydrocarbon compounds such as naphthalene, anthracene, phenanthrene, pyrene, triphenylene, perylene, fluorene, indene, and chrysene, and their derivatives, furan, pyrrole, Thiophene, silol, 9-silafluorene, 9,9'-spirobicilafluorene, benzothiophene, benzofuran, indole, dibenzothiophene, dibenzofuran, imidazopyridine, phenanthroline, pyrazine, Aromatic heterocyclic compounds such as naphthyridine, quinoxaline, pyrrolopyridine, and thioxanthene, or their derivatives, distyrylbenzene derivatives, tetraphenylbutadiene derivatives, stilbene derivatives, aldazine derivatives, coumarin derivatives, imidazole, thiazole, Azole derivatives such as thiadiazole, carbazole, oxazole, oxadiazole, and triazole, and metal complexes thereof, and N,N'-diphenyl-N,N'-di(3-methylphenyl)-4,4'- There are aromatic amine derivatives such as diphenyl-1,1'-diamine.

Additionally, green to yellow dopant materials include coumarin derivatives, phthalimide derivatives, naphthalimide derivatives, perinone derivatives, pyrrolopyrrole derivatives, cyclopentadiene derivatives, acridone derivatives, quinacridone derivatives, rubrene, etc. Examples include naphthacene derivatives, and compounds in which a substituent that enables a longer wavelength, such as aryl, heteroaryl, arylvinyl, amino, and cyano, are introduced into the compounds exemplified as blue to blue-green dopant materials. An example can be given.

Additionally, as orange to red dopant materials, naphthalimide derivatives such as bis(diisopropylphenyl)perylenetetracarboxylic acid imide, perinone derivatives, and Eu with acetylacetone, benzoylacetone, and phenanthroline as ligands. Rare earth complexes such as complexes, 4-(dicyanomethylene)-2-methyl-6-(p-dimethylaminostyryl)-4H-pyran and its analogs, metal phthalocyanine derivatives such as magnesium phthalocyanine and aluminum chlorophthalocyanine. , rhodamine compounds, deazaflavin derivatives, coumarin derivatives, quinaclidone derivatives, phenoxazine derivatives, oxazine derivatives, quinazoline derivatives, pyrrolopyridine derivatives, squaryllium derivatives, violanthrone derivatives, phenazine derivatives, pe Examples include noxazone derivatives and thiadiazolopyrene derivatives, and the compounds exemplified as blue to blue green and green to yellow dopant materials can be extended to longer wavelengths such as aryl, heteroaryl, arylvinyl, amino, and cyano. Compounds into which substituents have been introduced can also be cited as preferred examples.

In addition, as the dopant, it can be appropriately selected and used from among the compounds described in the June 2004 issue of Chemical Industry, page 13, and the references cited therein.

Among the above-mentioned dopant materials, amines, perylene derivatives, borane derivatives, aromatic amine derivatives, coumarin derivatives, pyran derivatives or pyrene derivatives having a stilbene structure are particularly preferable.

Amines having a stilbene structure are, for example, represented by the following formula.

In the above formula, Ar ¹ is an m-valent group derived from aryl having 6 to 30 carbon atoms, and Ar ² and Ar ³ are each independently aryl having 6 to 30 carbon atoms, but at least one of Ar ¹ to ^{Ar 3} is steel. It has a Venn structure, Ar ¹ to Ar ³ may be substituted, and m is an integer of 1 to 4.

As for the amine having a stilbene structure, diaminostilbene represented by the following formula is more preferable.

In the above formula, Ar ² and Ar ³ are each independently aryl having 6 to 30 carbon atoms, and Ar ² and Ar ³ may be substituted.

Specific examples of aryl having 6 to 30 carbon atoms include benzene, naphthalene, acenaphthylene, fluorene, phenalene, phenanthrene, anthracene, fluoranthene, triphenylene, pyrene, chrysene, naphthacene, perylene, and steel. Examples include ben, distyrylbenzene, distyryl biphenyl, and distyryl fluorene.

Specific examples of amines having a stilbene structure include N,N,N',N'-tetra(4-biphenylyl)-4,4'-diaminostilbene, N,N,N',N'- Tetra(1-naphthyl)-4,4'-diaminostilbene, N,N,N',N'-Tetra(2-naphthyl)-4,4'-diaminostilbene, N,N' -di(2-naphthyl)-N,N'-diphenyl-4,4'-diamino stilbene, N,N'-di(9-phenanthryl)-N,N'-diphenyl-4, 4'-diaminostilbene, 4,4'-bis[4"-bis(diphenylamino)styryl]biphenyl, 1,4-bis[4'-bis(diphenylamino)styryl]-benzene , 2,7-bis[4'-bis(diphenylamino)styryl]-9,9-dimethylfluorene, 4,4'-bis(9-ethyl-3-carbazovinylene)-biphenyl, 4,4'-bis(9-phenyl-3-carbazovinylene)-biphenyl, etc. are mentioned.

Additionally, amines having a stilbene structure described in Japanese Patent Application Laid-Open No. 2003-347056, Japanese Patent Application Laid-Open No. 2001-307884, etc. can also be used.

Perylene derivatives include, for example, 3,10-bis(2,6-dimethylphenyl)perylene, 3,10-bis(2,4,6-trimethylphenyl)perylene, and 3,10-diphenylphene. Rylene, 3,4-diphenylperylene, 2,5,8,11-tetra-tert-butylperylene, 3,4,9,10-tetraphenylperylene, 3-(1'-pyrenyl)- 8,11-di(tert-butyl)perylene, 3-(9'-anthryl)-8,11-di(tert-butyl)perylene, 3,3'-bis(8,11-di(tert) -butyl)perylenyl), etc.

In addition, Japanese Patent Laid-Open No. 11-97178, Japanese Patent Laid-Open No. 2000-133457, Japanese Patent Laid-Open No. 2000-26324, Japanese Patent Laid-Open No. 2001-267079, and Japanese Patent Laid-Open No. 2001-267078. Perylene derivatives described in Japanese Patent Application Publication No. 2001-267076, Japanese Patent Application Publication No. 2000-34234, Japanese Patent Application Publication No. 2001-267075, and Japanese Patent Application Publication No. 2001-217077 may also be used. there is.

Examples of borane derivatives include 1,8-diphenyl-10-(dimethylboryl)anthracene, 9-phenyl-10-(dimethylboryl)anthracene, and 4-(9'-anthryl)dimesylene. Tilborylnaphthalene, 4-(10'-phenyl-9'-anthryl)dimethylborylnaphthalene, 9-(dimethylboryl)anthracene, 9-(4'-biphenylyl)-10-(dimesyl) Tilboryl)anthracene, 9-(4'-(N-carbazolyl)phenyl)-10-(dimesitylboryl)anthracene, etc.

Additionally, borane derivatives described in the pamphlet of International Publication No. 2000/40586, etc. can also be used.

Aromatic amine derivatives are, for example, represented by the following formula.

In the above formula, Ar ⁴ is an n-valent group derived from aryl having 6 to 30 carbon atoms, Ar ⁵ and Ar ⁶ are each independently an aryl having 6 to 30 carbon atoms, Ar ⁴ to Ar ⁶ may be substituted, and , n is an integer from 1 to 4.

In particular, Ar ⁴ is a divalent group derived from anthracene, chrysene, fluorene, benzofluorene or pyrene, Ar ⁵ and Ar ⁶ are each independently aryl having 6 to 30 carbon atoms, and Ar ⁴ to Ar ⁶ are substituted. may be used, and an aromatic amine derivative in which n is 2 is more preferable.

Specific examples of aryl having 6 to 30 carbon atoms include benzene, naphthalene, acenaphthylene, fluorene, phenalene, phenanthrene, anthracene, fluoranthene, triphenylene, pyrene, chrysene, naphthacene, perylene, and penta. Sen, etc. can be mentioned.

As aromatic amine derivatives, chrysene series include, for example, N,N,N',N'-tetraphenylchrysene-6,12-diamine, N,N,N',N'-tetra(p-tolyl) Chrysene-6,12-diamine, N,N,N',N'-tetra(m-tolyl)chrysene-6,12-diamine, N,N,N',N'-tetrakis(4-iso Propylphenyl)chrysene-6,12-diamine, N,N,N',N'-tetra(naphthalen-2-yl)chrysene-6,12-diamine, N,N'-diphenyl-N,N '-di(p-tolyl)chrysene-6,12-diamine, N,N'-diphenyl-N,N'-bis(4-ethylphenyl)chrysene-6,12-diamine, N,N' -Diphenyl-N,N'-bis(4-ethylphenyl)chrysene-6,12-diamine, N,N'-diphenyl-N,N'-bis(4-isopropylphenyl)chrysene-6 ,12-diamine, N,N'-diphenyl-N,N'-bis(4-tert-butylphenyl)chrysene-6,12-diamine, N,N'-bis(4-isopropylphenyl)- N,N'-di(p-tolyl)chrysene-6,12-diamine, etc.

In addition, examples of the pyrene series include N,N,N',N'-tetraphenylpyrene-1,6-diamine, N,N,N',N'-tetra(p-tolyl)pyrene-1, 6-diamine, N,N,N',N'-tetra(m-tolyl)pyrene-1,6-diamine, N,N,N',N'-tetrakis(4-isopropylphenyl)pyrene-1 ,6-diamine, N,N,N',N'-tetrakis(3,4-dimethylphenyl)pyrene-1,6-diamine, N,N'-diphenyl-N,N'-di(p- Tolyl) pyrene-1,6-diamine, N, N'-diphenyl-N, N'-bis (4-ethylphenyl) pyrene-1,6-diamine, N, N'-diphenyl-N, N' -bis(4-ethylphenyl)pyrene-1,6-diamine, N,N'-diphenyl-N,N'-bis(4-isopropylphenyl)pyrene-1,6-diamine, N,N'- Diphenyl-N,N'-bis(4-tert-butylphenyl)pyrene-1,6-diamine, N,N'-bis(4-isopropylphenyl)-N,N'-di(p-tolyl) Pyrene-1,6-diamine, N,N,N',N'-tetrakis(3,4-dimethylphenyl)-3,8-diphenylpyrene-1,6-diamine, N,N,N,N -Tetraphenylpyrene-1,8-diamine, N,N'-bis(biphenyl-4-yl)-N,N'-diphenylpyrene-1,8-diamine, N ¹ ,N ⁶ -diphenyl- N ¹ , N ⁶ -bis-(4-trimethylsilanyl-phenyl)-1H,8H-pyrene-1,6-diamine, etc.

Additionally, examples of anthracene series include N,N,N,N-tetraphenylanthracene-9,10-diamine, N,N,N',N'-tetra(p-tolyl)anthracene-9,10- Diamine, N,N,N',N'-tetra(m-tolyl)anthracene-9,10-diamine, N,N,N',N'-tetrakis(4-isopropylphenyl)anthracene-9,10 -Diamine, N,N'-diphenyl-N,N'-di(p-tolyl)anthracene-9,10-diamine, N,N'-diphenyl-N,N'-di(m-tolyl)anthracene -9,10-diamine, N,N'-diphenyl-N,N'-bis(4-ethylphenyl)anthracene-9,10-diamine, N,N'-diphenyl-N,N'-bis( 4-ethylphenyl)anthracene-9,10-diamine, N,N'-diphenyl-N,N'-bis(4-isopropylphenyl)anthracene-9,10-diamine, N,N'-diphenyl- N,N'-bis(4-tert-butylphenyl)anthracene-9,10-diamine, N,N'-bis(4-isopropylphenyl)-N,N'-di(p-tolyl)anthracene-9 ,10-diamine, 2,6-di-tert-butyl-N,N,N',N'-tetra(p-tolyl)anthracene-9,10-diamine, 2,6-di-tert-butyl-N ,N'-diphenyl-N,N'-bis(4-isopropylphenyl)anthracene-9,10-diamine, 2,6-di-tert-butyl-N,N'-bis(4-isopropylphenyl) )-N,N'-di(p-tolyl)anthracene-9,10-diamine, 2,6-dicyclohexyl-N,N'-bis(4-isopropylphenyl)-N,N'-di( p-Tolyl)anthracene-9,10-diamine, 2,6-dicyclohexyl-N,N'-bis(4-isopropylphenyl)-N,N'-bis(4-tert-butylphenyl)anthracene- 9,10-diamine, 9,10-bis(4-diphenylamino-phenyl)anthracene, 9,10-bis(4-di(1-naphthylamino)phenyl)anthracene, 9,10-bis(4- Di(2-naphthylamino)phenyl)anthracene, 10-di-p-tolylamino-9-(4-di-p-tolylamino-1-naphthyl)anthracene, 10-diphenylamino-9-(4 -Diphenylamino-1-naphthyl)anthracene, 10-diphenylamino-9-(6-diphenylamino-2-naphthyl)anthracene, etc.

In addition, [4-(4-diphenylamino-phenyl)naphthalen-1-yl]-diphenylamine, [6-(4-diphenylamino-phenyl)naphthalen-2-yl]-diphenylamine , 4,4'-bis[4-diphenylaminonaphthalen-1-yl]biphenyl, 4,4'-bis[6-diphenylaminonaphthalen-2-yl]biphenyl, 4,4"-bis[ Examples include 4-diphenylaminonaphthalen-1-yl]-p-terphenyl, 4,4"-bis[6-diphenylaminonaphthalen-2-yl]-p-terphenyl, etc.

Additionally, aromatic amine derivatives described in Japanese Patent Application Laid-Open No. 2006-156888 and the like can also be used.

Examples of coumarin derivatives include coumarin-6 and coumarin-334.

Additionally, coumarin derivatives described in Japanese Patent Laid-Open No. 2004-43646, Japanese Patent Laid-Open No. 2001-76876, and Japanese Patent Laid-Open No. 6-298758 can also be used.

Examples of pyran derivatives include the following DCM and DCJTB.

In addition, Japanese Patent Laid-open No. 2005-126399, Japanese Patent Laid-Open No. 2005-097283, Japanese Patent Laid-Open No. 2002-234892, Japanese Patent Laid-Open No. 2001-220577, and Japanese Patent Laid-Open No. 2001-081090. The pyran derivatives described in the publication, Japanese Patent Application Laid-Open No. 2001-052869, etc. can also be used.

<Electron injection layer and electron transport layer in organic electroluminescent devices>

The electron injection layer 107 serves to efficiently inject electrons moving from the cathode 108 into the light emitting layer 105 or the electron transport layer 106. The electron transport layer 106 serves to efficiently transport electrons injected from the cathode 108 or electrons injected from the cathode 108 through the electron injection layer 107 to the light emitting layer 105. The electron transport layer 106 and the electron injection layer 107 are formed by laminating or mixing one or two or more types of electron transport/injection material, or a mixture of an electron transport/injection material and a polymer binder, respectively.

The electron injection/transport layer is a layer responsible for injecting and transporting electrons from the cathode. It is desirable for the electron injection efficiency to be high and the injected electrons to be transported efficiently. For this purpose, it is desirable to use a material that has high electron affinity, high electron mobility, excellent stability, and does not easily produce impurities that become traps during manufacture and use. However, when considering the transport balance between holes and electrons, if the role is mainly to efficiently prevent holes from the anode from flowing to the cathode without recombining, the luminous efficiency is improved even if the electron transport ability is not that high. The effect is equivalent to that of materials with high electron transport ability. Accordingly, the electron injection/transport layer in this embodiment may also include a function of a layer that can efficiently prevent the movement of holes.

As the material (electron transport material) forming the electron transport layer 106 or the electron injection layer 107, the compound according to the present invention and its polymer compound can be used. In addition, compounds conventionally used as electron transport compounds in photoconductive materials and known compounds used in the electron injection layer and electron transport layer of organic electroluminescent devices can be arbitrarily selected and used.

Materials used in the electron transport layer or electron injection layer include compounds consisting of an aromatic or heteroaromatic ring composed of one or more atoms selected from carbon, hydrogen, oxygen, sulfur, silicon, and phosphorus, pyrrole derivatives, and condensed ring derivatives thereof, and It is preferable to contain at least one type selected from metal complexes having electron-accepting nitrogen. Specifically, condensed ring aromatic ring derivatives such as naphthalene and anthracene, styryl aromatic ring derivatives such as 4,4'-bis(diphenylethenyl)biphenyl, perinone derivatives, coumarin derivatives, and naphthalimide derivatives. , quinone derivatives such as anthraquinone and diphenoquinone, phosphorus derivatives, carbazole derivatives, and indole derivatives. Examples of metal complexes having electron-accepting nitrogen include hydroxyazole complexes such as hydroxyphenyloxazole complex, azomethine complex, tropolone metal complex, flavonol metal complex, and benzoquinoline metal complex. These materials can be used alone, but may be used in combination with different materials.

Additionally, specific examples of other electron transfer compounds include pyridine derivatives, naphthalene derivatives, anthracene derivatives, phenanthroline derivatives, perinone derivatives, coumarin derivatives, naphthalimide derivatives, anthraquinone derivatives, diphenoquinone derivatives, and diphenylquinone. Derivatives, perylene derivatives, oxadiazole derivatives (1,3-bis[(4-tert-butylphenyl)1,3,4-oxadiazolyl]phenylene, etc.), thiophene derivatives, triazole derivatives (N- (naphthyl-2,5-diphenyl-1,3,4-triazole, etc.), thiadiazole derivatives, metal complexes of auxin derivatives, quinolinol-based metal complexes, quinoxaline derivatives, polymers of quinoxaline derivatives, benzazoles Compounds, gallium complex, pyrazole derivative, perfluorinated phenylene derivative, triazine derivative, pyrazine derivative, benzoquinoline derivative (2,2'-bis(benzo[h]quinolin-2-yl)-9,9' -spirobifluorene, etc.), imidazopyridine derivatives, borane derivatives, benzoimidazole derivatives (tris(N-phenylbenzoimidazol-2-yl)benzene, etc.), benzoxazole derivatives, benzothiazole derivatives, quinoline derivatives , oligopyridine derivatives such as terpyridine, bipyridine derivatives, terpyridine derivatives (1,3-bis(4'-(2,2': 6'2"-terpyridinyl))benzene, etc.), naphthyridine derivatives ( Bis(1-naphthyl)-4-(1,8-naphthyridin-2-yl)phenylphosphine oxide, etc.), aldazine derivatives, carbazole derivatives, indole derivatives, in oxide derivatives, bistyryl derivatives, etc. can be mentioned.

Additionally, a metal complex having an electron-accepting nitrogen can also be used, for example, quinolinol-based metal complex, hydroxyazole complex such as hydroxyphenyloxazole complex, azomethine complex, tropolone metal complex, and flavonol metal complex. and benzoquinoline metal complexes.

The above-mentioned materials can be used alone, but may be used in combination with different materials.

Among the above-mentioned materials, quinolinol-based metal complexes, bipyridine derivatives, phenanthroline derivatives, or borane derivatives are preferable.

The quinolinol-based metal complex is a compound represented by the following general formula (E-1).

In the formula, R ¹ to R ⁶ are hydrogen or a substituent, M is Li, Al, Ga, Be or Zn, and n is an integer of 1 to 3.

Specific examples of quinolinol-based metal complexes include 8-quinolinol lithium, tris (8-quinolinolate) aluminum, tris (4-methyl-8-quinolinolate) aluminum, and tris (5-methyl-8- Quinolinolate) aluminum, tris(3,4-dimethyl-8-quinolinolate) aluminum, tris(4,5-dimethyl-8-quinolinolate) aluminum, tris(4,6-dimethyl-8) -Quinolinolate) aluminum, bis(2-methyl-8-quinolinolate)(phenolate) aluminum, bis(2-methyl-8-quinolinolate)(2-methylphenolate) aluminum, bis (2-methyl-8-quinolinolate)(3-methylphenolate)aluminum, bis(2-methyl-8-quinolinolate)(4-methylphenolate)aluminum, bis(2-methyl-8) -Quinolinolate)(2-phenylphenolate)aluminum, bis(2-methyl-8-quinolinolate)(3-phenylphenolate)aluminum, bis(2-methyl-8-quinolinoleate) (4-phenylphenolate)aluminum, bis(2-methyl-8-quinolinolate)(2,3-dimethylphenolate)aluminum, bis(2-methyl-8-quinolinolate)(2,6 -Dimethyl phenolate) aluminum, bis (2-methyl-8-quinolinolate) (3,4-dimethyl phenolate) aluminum, bis (2-methyl-8-quinolinolate) (3,5-dimethyl Phenolate) aluminum, bis (2-methyl-8-quinolinolate) (3,5-di-tert-butyl phenolate) aluminum, bis (2-methyl-8-quinolinolate) (2,6 -Diphenylphenolate) aluminum, bis(2-methyl-8-quinolinolate) (2,4,6-triphenylphenolate) aluminum, bis(2-methyl-8-quinolinolate) (2 ,4,6-trimethylphenolate)aluminum, bis(2-methyl-8-quinolinolate)(2,4,5,6-tetramethylphenolate)aluminum, bis(2-methyl-8-quinoli) Nolate) (1-naphtholate) aluminum, bis (2-methyl-8-quinolinolate) (2-naphtolate) aluminum, bis (2,4-dimethyl-8-quinolinolate) (2- Phenylphenolate) aluminum, bis(2,4-dimethyl-8-quinolinolate)(3-phenylphenolate) aluminum, bis(2,4-dimethyl-8-quinolinolate)(4-phenylphenol) Late) aluminum, bis (2,4-dimethyl-8-quinolinolate) (3,5-dimethyl phenolate) aluminum, bis (2,4-dimethyl-8-quinolinolate) (3,5- di-tert-butylphenolate) aluminum, bis(2-methyl-8-quinolinolate) aluminum-μ-oxo-bis(2-methyl-8-quinolinolate) aluminum, bis(2,4- Dimethyl-8-quinolinoleate) aluminum-μ-oxo-bis(2,4-dimethyl-8-quinolinoleate) aluminum, bis(2-methyl-4-ethyl-8-quinolinolate) aluminum -μ-oxo-bis(2-methyl-4-ethyl-8-quinolinolate)aluminum, bis(2-methyl-4-methoxy-8-quinolinoleate)aluminum-μ-oxo-bis( 2-methyl-4-methoxy-8-quinolinolate) aluminum, bis(2-methyl-5-cyano-8-quinolinoleate) aluminum-μ-oxo-bis(2-methyl-5- Cyano-8-quinolinolate) aluminum, bis (2-methyl-5-trifluoromethyl-8-quinolinolate) aluminum-μ-oxo-bis (2-methyl-5-trifluoromethyl -8-quinolinolate)aluminum, bis(10-hydroxybenzo[h]quinoline)beryllium, etc.

A bipyridine derivative is a compound represented by the following general formula (E-2).

In the formula, G simply represents a bond or an n-valent linking group, and n is an integer of 2 to 8. Additionally, carbons not used in the pyridine-pyridine or pyridine-G bond may be substituted.

For example, G in general formula (E-2) has the following structural formula. In the structural formula below, R is each independently hydrogen, methyl, ethyl, isopropyl, cyclohexyl, phenyl, 1-naphthyl, 2-naphthyl, biphenylyl, or terphenylyl.

Specific examples of pyridine derivatives include 2,5-bis(2,2'-pyridin-6-yl)-1,1-dimethyl-3,4-diphenylsilol, 2,5-bis(2,2'-pyridine) -6-yl)-1,1-dimethyl-3,4-dimethylsilol, 2,5-bis(2,2'-pyridin-5-yl)-1,1-dimethyl-3,4-di Phenylsilol, 2,5-bis(2,2'-pyridin-5-yl)-1,1-dimethyl-3,4-dimethylsilol, 9,10-di(2,2'-pyridin-6 -yl)anthracene, 9,10-di(2,2'-pyridin-5-yl)anthracene, 9,10-di(2,3'-pyridin-6-yl)anthracene, 9,10-di(2) ,3'-pyridin-5-yl)anthracene, 9,10-di(2,3'-pyridin-6-yl)-2-phenylanthracene, 9,10-di(2,3'-pyridin-5- 1)-2-phenylanthracene, 9,10-di(2,2'-pyridin-6-yl)-2-phenylanthracene, 9,10-di(2,2'-pyridin-5-yl)-2 -Phenylanthracene, 9,10-di(2,4'-pyridin-6-yl)-2-phenylanthracene, 9,10-di(2,4'-pyridin-5-yl)-2-phenylanthracene, 9,10-di(3,4'-pyridin-6-yl)-2-phenylanthracene, 9,10-di(3,4'-pyridin-5-yl)-2-phenylanthracene, 3,4- Diphenyl-2,5-di(2,2'-pyridin-6-yl)thiophene, 3,4-diphenyl-2,5-di(2,3'-pyridin-5-yl)thiophene, 6',6"-di(2-pyridyl)2,2':4',4":2",2"'-quarterpyridine, etc.

Phenanthroline derivatives are compounds represented by the following general formula (E-3-1) or (E-3-2).

In the formula, R ¹ to R ⁸ are hydrogen or a substituent, adjacent groups may combine with each other to form a condensed ring, G simply represents a bond or an n-valent linking group, and n is an integer of 2 to 8. In addition, G in the general formula (E-3-2) is, for example, the same structural formula as G described in the section on bipyridine derivatives.

Specific examples of phenanthroline derivatives include 4,7-diphenyl-1,10-phenanthroline, 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline, and 9,10-di( 1,10-phenanthroline-2-yl)anthracene, 2,6-di(1,10-phenanthroline-5-yl)pyridine, 1,3,5-tri(1,10-phenanthroline- 5-yl)benzene, 9,9'-difluoro-bis(1,10-phenanthroline-5-yl), vasocuproin or 1,3-bis(2-phenyl-1,10-phenene Trolin-9-yl)benzene, etc. can be mentioned.

In particular, the case where a phenanthroline derivative is used in the electron transport layer and electron injection layer will be described. In order to obtain stable light emission over a long period of time, a material with excellent thermal stability and thin film formation is desirable. Among phenanthroline derivatives, the substituent itself has a three-dimensional target three-dimensional structure, or is connected to the phenanthroline skeleton or with an adjacent substituent. A derivative having a three-dimensional structure due to steric repulsion, or a derivative in which a plurality of phenanthroline skeletons are linked is preferable. Additionally, when connecting multiple phenanthroline skeletons, a compound containing a conjugate bond, a substituted or unsubstituted aromatic hydrocarbon, or a substituted or unsubstituted aromatic heterocycle in the connecting unit is more preferable.

Borane derivatives are compounds represented by the following general formula (E-4), and details are disclosed in Japanese Patent Application Laid-Open No. 2007-27587.

In the formula, R ¹¹ and R ¹² are each independently at least one of hydrogen, alkyl, optionally substituted aryl, substituted silyl, optionally substituted nitrogen-containing heterocycle, or cyano, and R ¹³ to R ¹⁶ is each independently optionally substituted alkyl or optionally substituted aryl, , or carbazolyl which may be substituted, and n is each independently an integer of 0 to 3.

Among the compounds represented by the above general formula (E-4), there are compounds represented by the following general formula (E-4-1), and furthermore, the following general formulas (E-4-1-1) to (E-4) Compounds represented by -1-4) are preferred. Specific examples include 9-[4-(4-dimesitylborylnaphthalen-1-yl)phenyl]carbazole, 9-[4-(4-dimesitylborylnaphthalen-1-yl)naphthalen-1-yl] Carbazole, etc. can be mentioned.

In the formula, R ¹¹ and R ¹² are each independently at least one of hydrogen, alkyl, optionally substituted aryl, substituted silyl, optionally substituted nitrogen-containing heterocycle, or cyano, and R ¹³ ~R ¹⁶ are each independently optionally substituted alkyl or optionally substituted aryl, and R ²¹ and R ²² are each independently hydrogen, alkyl, optionally substituted aryl, substituted silyl, or substituted is at least ^one of an optional nitrogen-containing heterocycle or cyano ring, It is independently an integer from 0 to 4.

In each formula, R ³¹ to R ³⁴ are each independently any of methyl, isopropyl, or phenyl, and R ³⁵ and R ³⁶ are each independently any of hydrogen, methyl, isopropyl, or phenyl. .

Among the compounds represented by the above general formula (E-4), compounds represented by the following general formula (E-4-2) and further compounds represented by the following general formula (E-4-2-1) are preferred. .

In the formula, R ¹¹ and R ¹² are each independently at least one of hydrogen, alkyl, optionally substituted aryl, substituted silyl, optionally substituted nitrogen-containing heterocycle, or cyano, and R ¹³ to R ¹⁶ is each independently optionally substituted alkyl or optionally substituted aryl, X ¹ is optionally substituted arylene with 20 or less carbon atoms, and n is each independently an integer of 0 to 3. am.

In the formula, R ³¹ to R ³⁴ are each independently any of methyl, isopropyl, or phenyl, and R ³⁵ and R ³⁶ are each independently any of hydrogen, methyl, isopropyl, or phenyl.

Among the compounds represented by the general formula (E-4), compounds represented by the following general formula (E-4-3), and furthermore, compounds represented by the following general formula (E-4-3-1) or general formula (E-4) The compound represented by -3-2) is preferable.

In the formula, R ¹¹ and R ¹² are each independently at least one of hydrogen, alkyl, optionally substituted aryl, substituted silyl, optionally substituted nitrogen-containing heterocycle, or cyano, and R ¹³ to R ¹⁶ is each independently optionally substituted alkyl or optionally substituted aryl, X ¹ is optionally substituted arylene with 10 or less carbon atoms, and Y ¹ is optionally substituted with 14 or less carbon atoms. It is aryl, and n is each independently an integer of 0 to 3.

In each formula, R ³¹ to R ³⁴ are each independently any of methyl, isopropyl, or phenyl, and R ³⁵ and R ³⁶ are each independently any of hydrogen, methyl, isopropyl, or phenyl. .

A benzimidazole derivative is a compound represented by the following general formula (E-5).

In the formula, Ar ¹ to Ar ³ each independently represent hydrogen or optionally substituted aryl having 6 to 30 carbon atoms. In particular, a benzimidazole derivative in which Ar ¹ is an optionally substituted anthryl is preferred.

Specific examples of aryl having 6 to 30 carbon atoms include phenyl, 1-naphthyl, 2-naphthyl, acenaphthylene-1-yl, acenaphthylen-3-yl, acenaphthylene-4-yl, and acenaphthylene. -5-yl, fluoren-1-yl, fluoren-2-yl, fluoren-3-yl, fluoren-4-yl, fluoren-9-yl, phenalen-1-yl, phenalen- 2-yl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl, 9-phenanthryl, 1-anthryl, 2-anthryl, 9-anthryl, fluoranthene-1- 1, fluoranthen-2-yl, fluoranthen-3-yl, fluoranthen-7-yl, fluoranthen-8-yl, triphenylen-1-yl, triphenylen-2-yl, Pyrene-1-yl, pyrene-2-yl, pyrene-4-yl, chrysen-1-yl, chrysen-2-yl, chrysen-3-yl, chrysen-4-yl, chrysen-5 -yl, chrysene-6-yl, naphthacene-1-yl, naphthacene-2-yl, naphthacene-5-yl, perylene-1-yl, perylene-2-yl, perylene-3- 1, pentacene-1-yl, pentacene-2-yl, pentacene-5-yl, pentacene-6-yl.

Specific examples of benzoimidazole derivatives include 1-phenyl-2-(4-(10-phenylanthracen-9-yl)phenyl)-1H-benzo[d]imidazole, 2-(4-(10-(naphthalene) -2-yl)anthracen-9-yl)phenyl)-1-phenyl-1H-benzo[d]imidazole, 2-(3-(10-(naphthalen-2-yl)anthracen-9-yl)phenyl) -1-phenyl-1H-benzo[d]imidazole, 5-(10-(naphthalen-2-yl)anthracen-9-yl)-1,2-diphenyl-1H-benzo[d]imidazole, 1 -(4-(10-(naphthalen-2-yl)anthracen-9-yl)phenyl)-2-phenyl-1H-benzo[d]imidazole, 2-(4-(9,10-di(naphthalene- 2-yl)anthracen-2-yl)phenyl)-1-phenyl-1H-benzo[d]imidazole, 1-(4-(9,10-di(naphthalen-2-yl)anthracen-2-yl) Phenyl)-2-phenyl-1H-benzo[d]imidazole, 5-(9,10-di(naphthalen-2-yl)anthracen-2-yl)-1,2-diphenyl-1H-benzo[d ]It is imidazole.

The electron transport layer or electron injection layer may further include a material capable of reducing the material forming the electron transport layer or electron injection layer. As for this reducible substance, various materials are used as long as it has a certain reducing property, for example, alkali metal, alkaline earth metal, rare earth metal, oxide of alkali metal, halide of alkali metal, oxide of alkaline earth metal, alkali metal. One or more selected from the group consisting of halides of earth metals, oxides of rare earth metals, halides of rare earth metals, organic complexes of alkali metals, organic complexes of alkaline earth metals and organic complexes of rare earth metals can be preferably used.

Preferred reducing substances include alkali metals such as Na (work function 2.36 eV), K (work function 2.28 eV), Rb (work function 2.16 eV), or Cs (work function 1.95 eV), Ca (work function 2.9 eV), Examples include alkaline earth metals such as Sr (work function 2.0-2.5 eV) or Ba (work function 2.52 eV), and materials with a work function of 2.9 eV or less are particularly preferable. Among these, more preferable reducing substances are alkali metals of K, Rb or Cs, more preferably Rb or Cs, and most preferable is Cs. These alkali metals have a particularly high reducing ability, and by adding a relatively small amount to the material forming the electron transport layer or electron injection layer, the luminance of the organic EL device can be improved and its lifespan can be improved. In addition, as a reducing material with a work function of 2.9 eV or less, a combination of two or more of these alkali metals is also preferred, especially a combination containing Cs, for example, Cs and Na, Cs and K, Cs and Rb, or Cs and A combination of Na and K is preferred. By including Cs, the reducing ability can be efficiently exerted, and by adding it as a material forming the electron transport layer or electron injection layer, the luminance of the organic EL device can be improved and its lifespan can be improved.

<Cathode in organic electroluminescent device>

The cathode 108 serves to inject electrons into the light emitting layer 105 through the electron injection layer 107 and the electron transport layer 106.

The material forming the cathode 108 is not particularly limited as long as it is a material that can efficiently inject electrons into the organic layer, but the same material as the material forming the anode 102 can be used. Among them, metals such as tin, indium, calcium, aluminum, silver, copper, nickel, chromium, gold, platinum, iron, zinc, lithium, sodium, potassium, cesium and magnesium, or alloys thereof (magnesium-silver alloy, magnesium -Indium alloy, aluminum-lithium alloy such as lithium fluoride/aluminum, etc.) are preferable. In order to improve device characteristics by increasing electron injection efficiency, lithium, sodium, potassium, cesium, calcium, magnesium, or alloys containing these low work function metals are effective. However, these low work function metals are generally unstable in air. To improve this point, there is a known method of using a highly stable electrode by doping a trace amount of lithium, cesium or magnesium into the organic layer, for example. As other dopants, inorganic salts such as lithium fluoride, cesium fluoride, lithium oxide, and cesium oxide can also be used. However, it is not limited to these.

In addition, to protect the electrode, metals such as platinum, gold, silver, copper, iron, tin, aluminum and indium, or alloys using these metals, inorganic substances such as silica, titania and silicon nitride, polyvinyl alcohol, and vinyl chloride , hydrocarbon-based polymer compounds, etc. are laminated as a preferable example. The manufacturing method of these electrodes is not particularly limited as long as conduction can be achieved, such as resistance heating evaporation, electron beam evaporation, sputtering, ion plating, and coating.

<Binder that can be used in each layer>

The materials used for the above hole injection layer, hole transport layer, light-emitting layer, electron transport layer, and electron injection layer can form each layer independently, but may be used as a polymer binder such as polyvinyl chloride, polycarbonate, polystyrene, or poly(N-vinylcarboxylic acid). Bazole), polymethyl methacrylate, polybutyl methacrylate, polyester, polysulfone, polyphenylene oxide, polybutadiene, hydrocarbon resin, ketone resin, phenoxy resin, polyamide, ethyl cellulose, vinyl acetate resin, It is used by dispersing in solvent-soluble resins such as ABS resin, polyurethane resin, and curable resins such as phenol resin, xylene resin, petroleum resin, urea resin, melamine resin, unsaturated polyester resin, alkyd resin, epoxy resin, and silicone resin. It is also possible.

<Method for manufacturing organic electroluminescent devices>

Each layer constituting the organic electroluminescent device is formed by using a method such as deposition, resistance heating deposition, electron beam deposition, sputtering, molecular stacking, printing, spin coating or casting, or coating. It can be formed by making it a thin film. The film thickness of each layer formed in this way is not particularly limited and can be set appropriately depending on the properties of the material, but is usually in the range of 2 nm to 5000 nm. The film thickness can usually be measured using a crystal oscillation type film thickness measuring device or the like. When thinning a film using a vapor deposition method, the deposition conditions vary depending on the type of material, the target crystal structure and association structure of the film, etc. Deposition conditions are generally boat heating temperature +50 to +400 ℃, vacuum degree 10 ^-6 to 10 ^{- 3} Pa, deposition rate 0.01 to 50 nm/sec, substrate temperature -150 to +300 ℃, film thickness 2 nm to 5 ㎛. It is desirable to set it appropriately within the range.

Next, as an example of a method of manufacturing an organic electroluminescent device, a method of manufacturing an organic electroluminescent device composed of an anode/hole injection layer/hole transport layer/host material and a light emitting layer/electron transport layer/electron injection layer/cathode composed of a dopant material is described. Explain. An anode is manufactured by forming a thin film of an anode material on an appropriate substrate by a vapor deposition method or the like, and then a thin film of a hole injection layer and a hole transport layer is formed on the anode. A thin film is formed by co-depositing a host material and a dopant material thereon to form a light-emitting layer, an electron transport layer and an electron injection layer are formed on this light-emitting layer, and a thin film made of a cathode material is formed by a deposition method or the like to form a cathode, thereby forming the desired An organic electroluminescent device is obtained. In addition, in manufacturing the above-mentioned organic electroluminescent device, the manufacturing order can be reversed and the cathode, electron injection layer, electron transport layer, light emitting layer, hole transport layer, hole injection layer, and anode can be manufactured in that order.

When applying a direct current voltage to the organic electroluminescent device obtained in this way, it can be applied with the anode as + and the cathode as -, and when a voltage of about 2 to 40 V is applied, the transparent or translucent electrode side (anode) Alternatively, light emission can be observed from the cathode and both sides). Additionally, this organic electroluminescent element emits light even when pulse current or alternating current is applied. And, the waveform of the applied alternating current may be arbitrary.

<Application examples of organic electroluminescent devices>

Additionally, the present invention can be applied to a display device equipped with an organic electroluminescent device, a lighting device provided with an organic electroluminescent device, etc.

A display device or lighting device equipped with an organic electroluminescent element can be manufactured by known methods such as connecting the organic electroluminescent element according to the present embodiment and a known driving device, and can be manufactured using direct current driving, pulse driving, or alternating current driving. It can be driven by appropriately using a known driving method such as driving.

Examples of display devices include panel displays such as color flat displays, flexible displays such as flexible color organic electroluminescence (EL) displays, etc. (e.g., Japanese Patent Laid-Open No. 10-335066, Japanese Patent Laid-Open No. 10-335066). (See Publication No. 2003-321546, Japanese Patent Laid-Open No. 2004-281806, etc.). Additionally, examples of display methods include matrix and/or segment methods. Additionally, the matrix display and segment display may coexist in the same panel.

In a matrix, pixels for display are arranged two-dimensionally, such as in a grid or mosaic pattern, and characters or images are displayed as a set of pixels. The shape and size of the pixel are determined depending on the purpose. For example, in the image and text display of PCs, monitors, and televisions, square pixels with a side of 300 μm or less are usually used, and in the case of large displays such as display panels, pixels with a side of the mm order are used. . In the case of black-and-white display, it is desirable to arrange pixels of the same color, but in the case of color display, red, green, and blue pixels are arranged and displayed. In this case, typically there are delta types and stripe types. The driving method for this matrix may be either a linear sequential driving method or an active matrix driving method. Line-sequential drive has the advantage of a simple structure, but when considering operation characteristics, active matrix is sometimes superior, so it is necessary to use it separately depending on the purpose.

In the segment method (type), a pattern is formed to display predetermined information, and the determined area is emitted. For example, there are time and temperature displays in digital clocks and thermometers, operating status displays in audio devices and electric cookers, and panel displays in automobiles.

Examples of lighting devices include lighting devices such as indoor lighting, backlights of liquid crystal displays, etc. (e.g., Japanese Patent Laid-Open No. 2003-257621, Japanese Patent Laid-Open No. 2003-277741, Japanese Patent Laid-Open). (See Patent No. 2004-119211 Publication, etc.). Backlights are mainly used for the purpose of improving the visibility of display devices that do not emit light themselves, and are used in liquid crystal displays, clocks, audio devices, automobile panels, display boards, and signs. In particular, considering that it is difficult to reduce the thickness of a backlight for a liquid crystal display device, especially a PC, where thickness reduction is an issue because the conventional method consists of a fluorescent lamp or a light guide plate, a backlight using the light emitting element according to the present embodiment is used. It is thin and lightweight.

3-2. Other organic devices

The compound according to the present invention and its polymer compound can be used in the production of organic field effect transistors or organic thin film solar cells in addition to the organic electroluminescent devices described above.

An organic field effect transistor is a transistor that controls current by an electric field generated by voltage input, and is provided with a gate electrode in addition to the source and drain electrodes. When voltage is applied to the gate electrode, an electric field is generated, and the current can be controlled by arbitrarily blocking the flow of electrons (or holes) flowing between the source electrode and the drain electrode. Field-effect transistors are easier to miniaturize than simple transistors (bipolar transistors), and are often used as elements constituting integrated circuits, etc.

The structure of an organic field-effect transistor usually has a source electrode and a drain electrode formed in contact with an organic semiconductor active layer formed using the compound according to the present invention and its polymer compound, and an insulating layer (dielectric layer) in contact with the organic semiconductor active layer. All that is required is for the gate electrode to be installed across the . Examples of the device structure include the following structure.

(1) Substrate/gate electrode/insulator layer/source electrode/drain electrode/organic semiconductor active layer

(2) Substrate/gate electrode/insulator layer/organic semiconductor active layer/source electrode/drain electrode

(3) Substrate/organic semiconductor active layer/source electrode/drain electrode/insulator layer/gate electrode

(4) Substrate/source electrode/drain electrode/organic semiconductor active layer/insulator layer/gate electrode

The organic field effect transistor configured in this way can be applied as a pixel driving switching element of an active matrix driving type liquid crystal monitor or organic light emitting device display.

Organic thin film solar cells have a structure in which an anode such as ITO, a hole transport layer, a photoelectric conversion layer, an electron transport layer, and a cathode are stacked on a transparent substrate such as glass. The photoelectric conversion layer has a p-type semiconductor layer on the anode side and an n-type semiconductor layer on the cathode side. The compound according to the present invention and its polymer compound can be used as a material for a hole transport layer, a p-type semiconductor layer, an n-type semiconductor layer, and an electron transport layer, depending on its physical properties. The compound according to the present invention and its polymer compound can function as a hole transport material or electron transport material in an organic thin film solar cell. The organic thin film solar cell may be appropriately provided with a hole blocking layer, an electron blocking layer, an electron injection layer, a hole injection layer, a smoothing layer, etc. in addition to the above. For organic thin film solar cells, known materials used in organic thin film solar cells can be appropriately selected and used.

[Example]

Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited to these examples at all. The following are compounds synthesized in examples.

Synthesis example (1)

Compound of formula (10P-g-101): 2,8'-dimethyl-5 ^{λ4,6 λ4} -spiro[benzo[e]pyrido[2,1-b][1,3,4]oxazaborinine Synthesis of -6,10'-dibenzo[b,e][1,4]oxaborinine]

1st process

1,3-dibromo-5,5-dimethylhydantoin (DBH: 55.9 g, 200 mmol) was added to di-para-tolyl ether (10.1 g) and dimethylformamide (200 ml), and incubated at 70°C for 2 hours. Heated and stirred. The reaction solution was cooled to room temperature, water (500 ml) was added, and then extracted with toluene (200 ml x 5 times). The solvent was distilled off by distillation at 140°C under normal pressure. The crude product was filtered through a silica gel short pass column, and the solvent was distilled off under reduced pressure to obtain the crude product. Afterwards, by washing with hexane, 1,1'-oxybis(2-bromo-4-methylbenzene) was obtained as a white solid (10.8 g, yield 61%).

The structure of the obtained compound was confirmed by NMR measurement.

¹ H-NMR (CDCl ₃ , 400 MHz); 2.31(s, 6H), 6.71(d, 2H), 7.02(d, 2H), 7.35(s, 2H).

¹³ C-NMR (CDCl ₃ , 101 MHz); 20.4(2C), 113.7(2C), 119.1(2C), 129.1(2C), 134.1(2C), 134.8(2C), 151.2(2C).

2nd process

2-iodopyridine (3.20 ml, 30 mmol), copper iodide (0.573 g, 3.0 mmol), 2-picolinic acid (0.745 g, 61 mmol), tripotassium phosphate (12.9 g, 60 mmol) and dimethyl sulfoxide (150 ml). Under a nitrogen atmosphere, 2-bromophenol (3.80 ml, 36 mmol) was added at room temperature, and the mixture was heated and stirred at 100°C for 14 hours. The reaction solution was cooled to room temperature, water (500 ml) was added, and then extracted with ethyl acetate (250 ml x 3 times). The crude product was filtered through a silica gel short pass column, and the solvent was distilled off to obtain the crude product. Afterwards, by washing with hexane, 2-(2-bromophenoxy)pyridine was obtained as a white solid (4.88 g, yield 65%).

The structure of the obtained compound was confirmed by NMR measurement.

¹ H-NMR (CDCl ₃ , 400 MHz); 6.96-7.00(m, 2H), 7.12(t, 1H), 7.21(d, 1H), 7.36(t, 1H), 7.63(d, 1H), 7.71(t, 1H), 8.15(t, 1H) .

¹³ C-NMR (CDCl ₃ , 101 MHz); 111.4(1C), 116.7(1C), 118.7(1C), 123.9(1C), 126.5(1C), 128.7(1C), 133.8(1C), 139.6(1C), 147.7(1C), 151.1(1C), 163.1(1C).

3rd process

Butyllithium (245 ml, 3.9 mmol) was added to 2-(2-bromophenoxy)pyridine (0.971 g, 3.9 mmol) and toluene (50 ml) at -78°C under a nitrogen atmosphere, and stirred at 0°C for 1 hour. . Additionally, boron tribromide (0.380 ml, 0.50 mmol) was added at -78°C and stirred at 0°C for 15 minutes to prepare a boron intermediate. Also, at the same time, 1,1'-oxybis(2-bromo-4-methylbenzene) (1.36 g, 3.8 mmol) and diethyl ether (50 ml) were added to butyllithium (4.90 ml, 4.90 ml) at -78°C under a nitrogen atmosphere. 7.8 mmol) was added and stirred at 0°C for 1 hour to prepare a lithium intermediate. This was added to the boron intermediate at -78°C and stirred at 0°C for 1 hour. The reaction solution was filtered through a silica gel short pass column, and the solvent was distilled off under reduced pressure to obtain a crude product. Afterwards, by washing with hexane, the compound of the formula (10P-g-101) was obtained as a light yellow solid (0.224 mg, yield 16%).

The structure of the obtained compound was confirmed by NMR measurement.

¹ H-NMR (CDCl ₃ , 400 MHz); 2.13(s, 6H), 6.80(s, 2H), 6.93(t, 1H), 6.98-7.08(m, 6H), 7.18(t, 2H), 7.23(d, 1H), 7.70(d, 1H) , 7.79(t, 1H).

¹³ C-NMR (CDCl ₃ , 101 MHz); 20.8(2C), 114.2(1C), 115.0(1C), 115.4(2C), 118.9(1C), 125.5(1C), 126.7(1C), 128.7(2C), 130.9(2C), 134.8(2C), 135.1(1C), 141.8(1C), 144.4(1C), 152.5(1C), 154.9(2C), 157.6(1C).

Synthesis example (2)

Synthesis of compounds of formula (10P-g-101) (alternative methods)

The yield is improved by performing the second and third steps of Synthesis Example (1) using the following method.

2nd process

2-Bromopyridine (2.90 ml, 30 mmol), copper iodide (0.557 g, 2.9 mmol), 2-picolinic acid (0.372 g, 3.0 mmol), tripotassium phosphate (12.5 g, 59 mmol) and dimethyl sulfoxide (200 ml) ), phenol (3.20 ml, 36 mmol) was added at room temperature under a nitrogen atmosphere, and the mixture was heated and stirred at 90°C for 4 hours. The reaction solution was cooled to room temperature, dichloromethane (200 ml) was added, and then extracted with 1N aqueous sodium hydroxide solution (150 ml x 2 times) and water (150 ml x 2 times). By washing the obtained crude product with hexane, 2-phenoxypyridine was obtained as a white solid (4.88 g, yield 65%).

The structure of the obtained compound was confirmed by NMR measurement.

¹ H-NMR (CDCl ₃ , 400 MHz); 6.96-7.00(m, 2H), 7.12(t, 1H), 7.21(d, 1H), 7.36(t, 1H), 7.63(d, 1H), 7.71(t, 1H), 8.15(t, 1H) .

¹³ C-NMR (CDCl ₃ , 101 MHz); 111.4(1C), 116.7(1C), 118.7(1C), 123.9(1C), 126.5(1C), 128.7(1C), 133.8(1C), 139.6(1C), 147.7(1C), 151.1(1C), 163.1(1C).

3rd process

Butyllithium (6.00ml, 9.6mmol) was added to 1,1'-oxybis(2-bromo-4-methylbenzene) (1.70g, 4.8mmol) and diethyl ether (30ml) at -78°C under nitrogen atmosphere. was added and stirred at 0°C for 1 hour to prepare a lithium intermediate. Meanwhile, boron tribromide (0.451ml, 4.8mmol) was added to 2-phenoxypyridine (0.812g, 4.8mmol) and toluene (20ml) at room temperature under a nitrogen atmosphere, and heated and stirred at 90°C for 1 hour to produce a boron intermediate. It was prepared. This was added to the reaction solution containing the lithium intermediate at -78°C, and stirred at 0°C for 1 hour. The reaction solution was filtered through a silica gel short pass column, and the solvent was distilled off under reduced pressure to obtain a crude product. Afterwards, by washing with hexane, the compound of the formula (10P-g-101) was obtained as a yellow solid (0.710 g, yield 40%).

The structure of the obtained compound was confirmed by NMR measurement.

¹ H-NMR (CDCl ₃ , 400 MHz); 2.13(s, 6H), 6.80(s, 2H), 6.93(t, 1H), 6.98-7.08(m, 6H), 7.18(t, 2H), 7.23(d, 1H), 7.70(d, 1H) , 7.79(t, 1H).

¹³ C-NMR (CDCl ₃ , 101 MHz); 20.8(2C), 114.2(1C), 115.0(1C), 115.4(2C), 118.9(1C), 125.5(1C), 126.7(1C), 128.7(2C), 130.9(2C), 134.8(2C), 135.1(1C), 141.8(1C), 144.4(1C), 152.5(1C), 154.9(2C), 157.6(1C).

Synthesis example (3)

Compound of formula (10P-gq-101-J11): 2,8'-dimethyl-11-phenyl-11H-5 ^{λ4,6 λ4} -spiro[benzo[c]pyrido[2,1-f][1, Synthesis of 5,2]diazaborinine-6,10'-dibenzo[b,e][1,4]oxaborinine]

Diphenylamine (5.06g, 30mmol), palladium(II) acetate (65.3mg, 0.29mmol), 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl (SPhos: 0.128g, 0.31mmol) , 2-bromopyridine (3.00ml, 31mmol) was added to sodium-tert-butoxide (3.48g, 36mmol) and toluene (150ml) at room temperature under a nitrogen atmosphere, and heated and stirred at 90°C for 1 hour. The reaction solution was cooled to room temperature, filtered through a silica gel short pass column, and the solvent was distilled off under reduced pressure to obtain a crude product. Afterwards, by washing with hexane, N,N-diphenylpyridin-2-amine was obtained as a white solid (6.52 g, yield 88%).

The structure of the obtained compound was confirmed by NMR measurement.

¹ H-NMR (CDCl ₃ , 400 MHz); 6.74-6.79(m, 2H), 7.12(t, 2H), 7.18(d, 4H), 7.32(t, 4H), 7.44(dd, 1H), 8.23(d, 1H).

¹³ C-NMR (CDCl ₃ , 101 MHz); 13.8(1C), 116.1(1C), 124.5(2C), 126.3(4C), 129.3(4C), 137.2(1C), 146.1(2C), 148.3(1C), 159.0(1C).

Butyllithium (3.80ml, 6.1mmol) was added to 1,1'-oxybis(2-bromo-4-methylbenzene) (1.04g, 2.9mmol) and diethyl ether (20ml) at -78°C under nitrogen atmosphere. was added and stirred at 0°C for 1 hour to prepare a lithium intermediate. Meanwhile, boron tribromide (0.285ml, 3.0mmol) was added to N,N-diphenylpyridin-2-amine (0.724g, 2.9mmol) and toluene (20ml) at room temperature under a nitrogen atmosphere, and incubated at 90°C for 1 hour. After preparing the boron intermediate by heating and stirring, the reaction solution was concentrated under reduced pressure until the volume was reduced to about 2/3 of the total. This was added to the reaction solution containing the lithium intermediate at -78°C, and stirred at 0°C for 1 hour. The reaction solution was filtered through a silica gel short pass column, and the solvent was distilled off under reduced pressure to obtain a crude product. Afterwards, by washing with hexane, the compound of the formula (10P-gq-101-J11) was obtained as a yellow solid (0.813 mg, yield 61%).

The structure of the obtained compound was confirmed by NMR measurement.

¹ H-NMR (CDCl ₃ , 400 MHz); 2.20(s, 6H), 6.27(d, 1H), 6.38(d, 1H), 6.57(dd, 1H), 6.90(dd, 1H), 6.94(dd, 1H), 6.98-7.01(m, 3H) , 7.04-7.06(m, 4H), 7.32(dd, 1H), 7.51(d, 2H), 7.64(t, 1H), 7.70(d, 1H), 7.75(t, 2H).

¹³ C-NMR (CDCl ₃ , 126 MHz); 21.0(2C), 113.4(1C), 114.3(1C), 114.9(1C), 115.2(2C), 123.9(1C), 125.5(1C), 128.2(2C), 129.5(1C), 130.3(2C), 130.7(2C), 131.5(2C), 134.8(2C), 135.1(1C), 138.8(1C), 140.0(1C), 141.3(1C), 145.1(1C), 151.2(1C), 154.5(2C).

Synthesis example (4)

Compound of formula (10P-gq-100-J11): 11-phenyl-11H-5 ^{λ4,6 λ4} -spiro[benzo[c]pyrido[2,1-f][1,5,2]diaza barley Synthesis of nin-6,10'-dibenzo[b,e][1,4]oxaborinine]

Butyllithium (13.7ml, 21.2mmol) was added to 2,2'-oxybis(bromobenzene) (3.46g, 10.6mmol) and diethyl ether (30ml) at -78°C under a nitrogen atmosphere, and the mixture was cooled to 0°C. A lithium intermediate was prepared by stirring for 1 hour. Meanwhile, boron tribromide (1.01 ml, 10.6 mmol) was added to N,N-diphenylpyridin-2-amine (2.67 g, 10.8 mmol) and toluene (30 ml) at room temperature under a nitrogen atmosphere, and incubated at 90°C for 1 hour. After preparing the boron intermediate by heating and stirring, the reaction solution was concentrated under reduced pressure until the volume was reduced to about 2/3 of the total. This was added to the reaction solution containing the lithium intermediate at -78°C, and stirred at 0°C for 1 hour. The reaction solution was filtered through a silica gel short pass column, and the solvent was distilled off under reduced pressure to obtain a crude product. Afterwards, by washing with hexane, the compound of the formula (10P-gq-100-J11) was obtained as a light yellow solid (1.87 g, yield 42%).

The structure of the obtained compound was confirmed by NMR measurement.

¹ H-NMR (CDCl ₃ , 500 MHz); 6.26(d, 1H), 6.37(d, 1H), 6.57(dd, 1H), 6.85-6.97(m, 5H), 7.16(d, 2H), 7.21(dd, 2H), 7.28(d, 2H) , 7.32(dd, 1H), 7.49(d, 2H), 7.64(t, 1H), 7.70(d, 1H), 7.74(dd, 2H).

¹³ C-NMR (CDCl ₃ , 128 MHz); 113.4(1C), 114.3(1C), 114.8(1C), 115.6(2C), 122.3(2C), 124.0(1C), 125.6(1C), 127.4(2C), 129.5(1C), 130.3(2C), 131.5(2C), 134.7(2C), 135.1(1C), 138.9(1C), 139.9(1C), 141.2(1C), 145.0(1C), 151.2(1C), 156.3(2C).

Synthesis example (5)

Compound of formula (10P-g-100): 5 ^{λ4,6 λ4} -spiro[benzo[c]pyrido[2,1-f][1,5,2]diazaborinine-6,10'-di Synthesis of benzo[b,e][1,4]oxaborinine]

1st process

2-Bromophenol (6.30 ml, 59.7 mmol), potassium carbonate (10.3 g, 77.4 mmol) and 1,3-dimethyl-2-imidazolidinone (DMI: 150 ml) were mixed with 1-bromophenol at room temperature under nitrogen atmosphere. Parent-2-fluorobenzene (5.50 ml, 50.3 mmol) was added, and the mixture was heated and stirred at 200°C for 24 hours. The reaction solution was cooled to room temperature, toluene (200 ml) was added, and extracted with water (150 ml x 3 times). The crude product was distilled at 70°C under 4.6×10 ^-2 Pa to obtain 2,2'-oxybis(bromobenzene) as a colorless liquid (3.46 g, yield 23%).

2nd process

Butyllithium (14.0 ml) was added to 2,2'-oxybis(bromobenzene) (3.52 g, 10.7 mmol) and diethyl ether (30 ml) at -78°C under a nitrogen atmosphere, and stirred at 0°C for 1 hour. By doing so, a lithium intermediate was prepared. Meanwhile, boron tribromide (1.02ml, 10.7mmol) was added to 2-phenoxypyridine (1.75g, 10.2mmol) and toluene (30ml) at room temperature under a nitrogen atmosphere, and stirred at 90°C for 1 hour to prepare a boron intermediate. Then, the reaction solution was concentrated under reduced pressure until its volume was reduced to about 2/3 of the total volume. This was added to the reaction solution containing the lithium intermediate at -78°C, and stirred at 0°C for 1 hour. The reaction solution was filtered through a silica gel short pass column, and the solvent was distilled off under reduced pressure to obtain a crude product. Afterwards, by washing with hexane, the compound of the formula (10P-g-100) was obtained as a light yellow solid (1.84 g, yield 52%).

The structure of the obtained compound was confirmed by NMR measurement.

¹ H-NMR (CDCl ₃ , 500 MHz); 6.89(t, 2H), 6.92(dd, 1H), 7.00(d, 1H), 7.04-7.07(m, 3H), 7.16-7.18(m, 3H), 7.20-7.25(m, 4H), 7.70( d, 1H), 7.78(t, 1H).

¹³ C-NMR (CDCl ₃ , 128 MHz); 114.2(1C), 115.1(1C), 115.8(2C), 118.9(1C), 122.3(2C), 125.6(1C), 126.8(1C), 127.9(2C), 134.7(2C), 135.0(1C), 141.9(1C), 144.2(1C), 152.5(1C), 156.7(2C), 157.7(1C).

Synthesis example (6)

Compound of formula (10P-gq-303-J11): 2-methyl-11-phenyl-11H-5 ^{λ4,6 λ4} -spiro[benzo[c]pyrido[2,1-f][1,5,2 ]Synthesis of diazaborinine-6,10'-dibenzo[b,e][1,4]oxaborinine]

Diphenylamine (9.31 g, 5 mmol), palladium(II) acetate (0.113 g, 0.51 mmol), SPhos (0.208 g, 0.51 mmol), sodium-tert-butoxide (5.58 g, 60 mmol) and toluene (150 ml). Under a nitrogen atmosphere, 2-bromo-4-methylpyridine (5.65 ml, 50 mmol) was added at room temperature, and the mixture was heated and stirred at 90°C for 1 hour. The reaction solution was cooled to room temperature, filtered through a silica gel short pass column, and the solvent was distilled off under reduced pressure to obtain a crude product. Afterwards, by washing with hexane, 4-methyl-N,N-diphenylpyridin-2-amine (7.82 g, yield 61%) was obtained as a white solid.

The structure of the obtained compound was confirmed by NMR measurement.

¹ H-NMR (CDCl ₃ , 400 MHz); 2.19(s, 3H), 6.58(s, 1H), 6.63(d, 1H), 7.11(t, 2H), 7.16(d, 4H), 7.31(t, 4H), 8.10(d, 1H).

¹³ C-NMR (CDCl ₃ , 101 MHz); 21.2(1C), 114.4(1C), 117.7(1C), 124.3(2C), 126.2(4C), 129.3(4C), 146.3(2C), 148.0(1C), 148.4(1C), 159.2(1C).

Butyllithium (12.9ml, 20.0mmol) was added to 2,2'-oxybis(bromobenzene) (3.27g, 10.0mmol) and diethyl ether (30ml) at -78°C under a nitrogen atmosphere, and the mixture was cooled to 0°C. A lithium intermediate was prepared by stirring for 1 hour. Meanwhile, boron tribromide (0.946ml, 10.0mmol) was added to 4-methyl-N,N-diphenylpyridin-2-amine (2.60g, 10.0mmol) and toluene (30ml) at room temperature under a nitrogen atmosphere, and 90% After preparing the boron intermediate by heating and stirring at ℃ for 1 hour, the reaction solution was concentrated under reduced pressure until the volume was reduced to about 2/3 of the total. This was added to the reaction solution containing the lithium intermediate at -78°C, and stirred at 0°C for 1 hour. The reaction solution was filtered through a silica gel short pass column, and the solvent was distilled off under reduced pressure to obtain a crude product. Afterwards, by washing with hexane, the compound of the formula (10P-gq-303-J11) (0.52 g, yield 12%) was obtained as a light yellow solid.

The structure of the obtained compound was confirmed by NMR measurement.

¹ H-NMR (CDCl ₃ , 400 MHz); 2.17(s, 3H), 6.13(s, 1H), 6.21(d, 1H), 6.39(d, 1H), 6.85∼6.95(m, 5H), 7.15(d, 2H), 7.20(t, 2H) , 7.26(d, 2H), 7.48(d, 2H), 7.56(d, 1H), 7.64(t, 1H), 7.74(t, 2H).

¹³ C-NMR (CDCl ₃ , 101 MHz); 21.5(1C), 112.8(1C), 114.5(1C), 115.5(2C), 116.7(1C), 122.2(2C), 123.7(1C), 125.5(1C), 127.3(2C), 129.4(1C), 130.4(2C), 131.5(2C), 134.7(2C), 135.1(1C), 140.0(1C), 141.3(1C), 144.3(2C), 151.0(1C), 156.3(1C), 207.0(1C).

Synthesis example (7)

Compound of formula (10P-gq-301-J11): 4-methyl-11-phenyl-11H-5 ^{λ4,6 λ4} -spiro[benzo[c]pyrido[2,1-f][1,5,2 ]Synthesis of diazaborinine-6,10'-dibenzo[b,e][1,4]oxaborinine]

Diphenylamine (9.38 g, 55 mmol), palladium(II) acetate (0.116 g, 0.52 mmol), SPhos (0.214 g, 0.52 mmol), sodium-tert-butoxide (6.34 g, 66 mmol) and toluene (200 ml). Under a nitrogen atmosphere, 2-bromo-6-methylpyridine (5.68 ml, 50 mmol) was added at room temperature, and the mixture was heated and stirred at 90°C for 2 hours. The reaction solution was cooled to room temperature, filtered through a silica gel short pass column, and the solvent was distilled off under reduced pressure to obtain a crude product. Afterwards, by washing with hexane, 6-methyl-N,N-diphenylpyridin-2-amine (7.80 g, yield 60%) was obtained as a white solid.

The structure of the obtained compound was confirmed by NMR measurement.

¹ H-NMR (CDCl ₃ , 400 MHz); 2.38(s, 3H), 6.50(d, 1H), 6.66(d, 1H), 7.09(t, 2H), 7.16(d, 4H), 7.28(t, 4H), 7.33(t, 1H).

¹³ C-NMR (CDCl ₃ , 101 MHz); 24.4(1C), 111.4(1C), 115.9(1C), 123.9(2C), 126.0(4C), 129.1(4C), 137.5(1C), 146.3(2C), 157.2(1C), 159.2(1C).

Butyllithium (38.2ml, 60mmol) was added to 2,2'-oxybis(bromobenzene) (9.97g, 30mmol) and diethyl ether (100ml) at -78°C under nitrogen atmosphere, and incubated at 0°C for 1 hour. A lithium intermediate was prepared by stirring. Meanwhile, boron tribromide (2.85ml, 30.0mmol) was added to 6-methyl-N,N-diphenylpyridin-2-amine (7.82g, 30.0mmol) and toluene (100ml) at room temperature under a nitrogen atmosphere, and 90% After preparing the boron intermediate by heating and stirring at ℃ for 1 hour, the reaction solution was concentrated under reduced pressure until the volume was reduced to about 2/3 of the total. This was added to the reaction solution containing the lithium intermediate at -78°C, and stirred at 0°C for 1 hour. The reaction solution was filtered through a silica gel short pass column, and the solvent was distilled off under reduced pressure to obtain a crude product. Afterwards, by washing with hexane, the compound of the formula (10P-gq-301-J11) (3.08 g, yield 24%) was obtained as a light yellow solid.

The structure of the obtained compound was confirmed by NMR measurement.

¹ H-NMR (CDCl ₃ , 400 MHz); 2.01(s, 3H), 5.99(dt, 1H), 6.41(d, 1H), 6.48(d, 1H), 6.71∼6.76(m, 3H), 6.88(t, 2H), 7.09∼7.10(m, 4H), 7.14(t, 2H), 7.31(dd, 1H), 7.45(d, 2H), 7.62(t, 1H), 7.73(t, 2H).

¹³ C-NMR (CDCl ₃ , 101 MHz); 25.4(1C), 112.4(1C), 113.8(1C), 115.3(2C), 118.5(1C), 122.4(2C), 123.7(1C), 124.9(1C), 126.8(2C), 129.2(1C), 130.3(2C), 131.6(2C), 133.3(2C), 135.1(1C), 138.1(1C), 139.0(1C), 141.2(1C), 153.4(1C), 154.9(2C), 156.1(1C).

Synthesis example (8)

Compound of formula (10P-gq-342-J11): 3,11-diphenyl-11H-5 ^{λ4,6 λ4} -spiro[benzo[c]pyrido[2,1-f][1,5,2] Synthesis of diazaborinine-6,10'-dibenzo[b,e][1,4]oxaborinine]

Phenylboronic acid (2.93g, 24mmol), tetrakis(triphenylphosphine)palladium(0)(Pd(PPh ₃ ) ₄ : 1.74g, 1.5mmol), potassium carbonate (8.30g, 60mmol), water (80ml) And 5-bromo-2-chloropyridine (3.87 g, 20 mmol) was added to 1,4-dioxane (80 ml) at room temperature under a nitrogen atmosphere, and stirred at room temperature for 45 hours. After the solvent in the reaction solution was distilled off under reduced pressure, extraction was performed with toluene (100 ml x 3 times), and the solvent was distilled off under reduced pressure to obtain a crude product. Afterwards, it was washed with hexane and purified using a silica gel short pass column to obtain 2-chloro-5-phenylpyridine as a white solid (1.69 g, yield 44%).

Diphenylamine (0.934 g, 5.5 mmol), palladium(II) acetate (22.4 mg, 0.10 mmol), SPhos (82.2 mg, 0.20 mmol), sodium-tert-butoxide (0.579 g, 6.0 mmol) and o-xylene. To (20 ml), 2-chloro-5-phenylpyridine (0.948 g, 5.0 mmol) was added at room temperature under a nitrogen atmosphere, and the mixture was heated and stirred at 130°C for 6 hours. The reaction solution was filtered through a Florisil short pass column, and the solvent was distilled off under reduced pressure to obtain a crude product. Afterwards, N,N,5-triphenylpyridin-2-amine was obtained as a white solid by purification using a silica gel short pass column (1.55 g, yield 96%).

The structure of the obtained compound was confirmed by NMR measurement.

¹ H-NMR (CDCl ₃ , 400 MHz); 6.83(d, 1H), 7.15(t, 2H), 7.22(d, 4H), 7.34(m, 5H), 7.43(t, 2H), 7.53(d, 2H), 7.67(dd, 1H), 8.48 (s, 1H).

¹³ C-NMR (CDCl ₃ , 101 MHz); 113.6(1C), 124.6(2C), 126.3(4C), 126.4(2C), 127.2(1C), 128.9(2C), 129.1(1C), 129.4(4C), 135.8(1C), 138.0(1C), 146.0(2C), 146.5(1C), 158.2(1C).

Butyllithium (6.50ml, 10mmol) was added to 2,2'-oxybis(bromobenzene) (1.70g, 5.2mmol) and diethyl ether (20ml) at -78°C under a nitrogen atmosphere, and then incubated at 0°C for 3 hours. A lithium intermediate was prepared by stirring for a while. Meanwhile, boron tribromide (0.480ml, 5.1mmol) was added to N,N,5-triphenylpyridin-2-amine (1.65g, 5.1mmol) and toluene (30ml) at room temperature under a nitrogen atmosphere, and the mixture was heated to 90°C. After preparing the boron intermediate by heating and stirring for 4 hours, the reaction solution was concentrated under reduced pressure at 0°C until the volume was reduced to about 1/3 of the total. This was added to the reaction solution containing the lithium intermediate at -78°C, and stirred at 0°C for 1 hour and at room temperature for 19 hours. The reaction solution was filtered through a silica gel short pass column, and the solvent was distilled off under reduced pressure to obtain a crude product. Afterwards, by purifying using a silica gel short pass column, the compound of the formula (10P-gq-342-J11) was obtained as a light yellow solid (0.548 g, yield 21%).

The structure of the obtained compound was confirmed by NMR measurement.

¹ H-NMR (CDCl ₃ , 400 MHz); 6.28(d, 1H), 6.47(d, 1H), 6.91(dd, 1H), 6.95(dd, 1H), 6.97(dd, 2H), 7.01(dd, 1H), 7.10(dd, 2H), 7.18 (dd, 2H), 7.22(m, 2H), 7.26(m, 1H), 7.29(d, 2H), 7.33(dd, 2H), 7.53(dd, 2H), 7.55(dd, 1H), 7.65( t, 1H), 7.76(t, 2H), 7.92(s, 1H).

¹³ C-NMR (CDCl ₃ , 101 MHz); 113.7(1C), 114.4(1C), 115.7(2C), 122.3(2C), 124.0(1C), 125.7(1C), 126.0(2C), 127.5(2C), 128.0(1C), 128.1(1C), 129.1(2C), 129.5(1C), 130.2(2C), 131.5(2C), 134.6(2C), 135.1(1C), 135.3(1C), 137.7(1C), 140.0(1C), 141.2(1C), 142.5(1C), 150.2(1C), 156.4(2C).

Synthesis example (9)

Compound of formula (10P-gq-23-J11): 5 ^λ4 , 10 ^λ4 -spiro[dibenzo[b,e][1,4]oxaborinine-10,6'-pyrido[1',2' :1,6][1,5,2]diazaborinino[3,4,5-kl]phenoxazine] synthesis

Phenoxazine (6.00 g, 33 mmol), palladium(II) acetate (79.6 mg, 0.35 mmol), SPhos (0.122 g, 0.30 mmol), sodium-tert-butoxide (3.88 g, 40 mmol) and nitrogen in toluene (100 ml). 2-Bromopyridine (2.90 ml, 30 mmol) was added at room temperature under an atmosphere, and the mixture was heated and stirred at 60°C for 2 hours. The reaction solution was cooled to room temperature, filtered through a silica gel short pass column, and the solvent was distilled off under reduced pressure to obtain a crude product. Afterwards, by washing with hexane, a phenoxazine derivative was obtained as a white solid (6.15 g, yield 79%).

¹ H-NMR (CDCl ₃ , 400 MHz); 6.42(d, 2H), 6.69-6.81(m, 6H), 7.28(dd, 1H), 7.36(d, 1H), 7.84(dt, 1H), 8.68(dd, 1H).

¹³ C-NMR (CDCl ₃ , 101 MHz); 115.8(2C), 116.0(2C), 122.1(1C), 122.3(1C), 122.7(1C), 123.2(2C), 132.9(2C), 139.4(1C), 145.6(2C), 150.6(1C), 153.9(1C).

Butyllithium (12.7ml, 19.9mmol) was added to 2,2'-oxybis(bromobenzene) (3.28g, 10.0mmol) and diethyl ether (25ml) at -78°C under a nitrogen atmosphere, and the mixture was cooled to 0°C. A lithium intermediate was prepared by stirring for 2 hours. Meanwhile, boron tribromide (1.00ml, 10.5mmol) was added to the phenoxazine derivative (2.63g, 10.1mmol) and toluene (30ml) at room temperature under a nitrogen atmosphere, and then heated and stirred at 90°C for 4 hours to prepare a boron intermediate. , the reaction solution was concentrated under reduced pressure until the volume was reduced to about 2/3 of the total. This was added to the reaction solution containing the lithium intermediate at -78°C, and stirred at 0°C for 1 hour. The reaction solution was filtered through a silica gel short pass column, and the solvent was distilled off under reduced pressure to obtain a crude product. Afterwards, by washing with hexane, the compound of the formula (10P-gq-23-J11) was obtained as a yellow solid (3.30 g, yield 75%).

¹ H-NMR (CDCl ₃ , 400 MHz); 6.76-6.80(m, 3H), 6.88(dd, 1H), 7.00-7.06(m, 2H), 7.08-7.12(m, 3H), 7.21-7.27(m, 5H), 7.30(d, 1H), 7.36(dt, 1H), 7.60(dt, 1H), 7.66-7.70(m, 2H).

¹³ C-NMR (CDCl ₃ , 101 MHz); 113.2(1C), 114.0(1C), 115.9(1C), 116.1(1C), 117.3(1C), 118.4(1C), 118.9(1C), 122.3(1C), 122.4(1C), 123.6(1C), 126.0(1C), 126.7(1C), 127.6(1C), 128.3(1C), 128.3(1C), 128.5(1C), 129.0(1C), 133.3(1C), 135.2(1C), 139.5(1C), 145.0(1C), 145.1(1C), 149.4(1C), 149.7(1C), 155.3(1C), 158.7(1C).

By appropriately changing the raw material compounds, the compound according to the present invention and its polymer compound can be synthesized by a method similar to the above-described synthesis example.

<Evaluation of basic properties>

When evaluating the absorption characteristics and luminescence characteristics (fluorescence and phosphorescence) of a compound to be evaluated, the compound may be dissolved in a solvent and evaluated in the solvent, or may be evaluated in a thin film state. In addition, when evaluating in a thin film state, depending on the type of use of the compound in an organic EL device, only the compound is thinned and evaluated (single-component vapor deposition film), or the compound is dispersed in an appropriate matrix material and thinned (co-deposited film). There are cases where it happens.

Fabrication of dispersion membrane

As a matrix material, commercially available PMMA (polymethyl methacrylate) or the like can be used. A thin film sample dispersed in PMMA can be produced, for example, by dissolving PMMA and the compound to be evaluated in toluene and then forming a thin film on a quartz transparent support substrate (10 mm x 10 mm) by spin coating. .

Fabrication of single-component deposited films

The manufacturing method of the single-component vapor deposition film is described below. A transparent support substrate made of quartz or glass is fixed to the substrate holder of a commercially available vapor deposition apparatus (manufactured by Showa Vacuum Co., Ltd.), and a molybdenum deposition boat containing the compound to be evaluated is mounted. Next, the pressure of the vacuum tank is reduced to 5×10 ^-4 Pa, and the deposition boat containing the compound is heated to deposit the compound to an appropriate film thickness to form a single component vapor deposition film.

Production of co-deposited film

The manufacturing method of the thin film sample when the matrix material is the host material is described below. A transparent support substrate made of quartz or glass is fixed to the substrate holder of a commercially available vapor deposition device (manufactured by Showa Vacuum Co., Ltd.), and a molybdenum deposition boat containing a host material and a molybdenum deposition boat containing a dopant material are installed. Install it. Next, the pressure of the vacuum bath is reduced to ⁵ forms. The deposition rate is controlled according to the set weight ratio of the host material and the dopant material.

Evaluation of absorption and luminescence properties

The absorption spectrum is measured using an ultraviolet-visible-near-infrared spectrophotometer (Shimadzu Corporation, UV-2600). In addition, the measurement of the fluorescence spectrum or phosphorescence spectrum is performed using a spectrofluorometer (F-7000, manufactured by Hitachi Hi-Tech Co., Ltd.). For measurement of the fluorescence spectrum, photoluminescence is measured by excitation with an appropriate excitation wavelength at room temperature. For the measurement of the phosphorescence spectrum, the sample is immersed in liquid nitrogen (temperature 77K) using the attached cooling unit. To observe the phosphorescence spectrum, the delay time from excitation light irradiation to the start of measurement is adjusted using an optical chopper. The sample is excited with an appropriate excitation wavelength to measure photoluminescence.

<Evaluation as an organic EL device>

Hereinafter, the compound according to the present invention was evaluated as an organic EL device.

<Example 1>

A transparent support substrate made of glass on which ITO was deposited and a molybdenum deposition boat containing the compound (10P-gq-101-J11) were fixed to a commercially available deposition apparatus (manufactured by Showa Vacuum Co., Ltd.), and the vacuum chamber was heated for 5 minutes. The pressure was reduced to ×10 ^-4 Pa, and compound (10P-gq-101-J11) was heated and deposited to a film thickness of 50 nm, thereby forming a single component deposited film. The photoelectron quantity spectrum, absorption spectrum in the visible region, fluorescence spectrum, and phosphorescence spectrum of the obtained single-component deposited film were measured. The ionization potential (Ip) is determined from the photoelectron quantity spectrum, the energy gap (Eg) is determined from the end of the long wavelength side of the fluorescence peak, the electron affinity (Ea) is determined from the ionization potential, and the singlet energy (S) is determined from the peak top of the fluorescence spectrum. ₁ ), and the triplet energy (T ₁ ) was obtained from the peak top of the phosphorescence spectrum, respectively. The results were expressed as the difference with respect to the compound mCBP used in Comparative Example 1 (Table 1). In addition, unless otherwise specified, the singlet energy (S ₁ ) and the triplet energy (T ₁ ) are the first excitation singlet energy and the first excitation triplet energy. Additionally, ΔE _ST is the difference between singlet energy and triplet energy.

<Example 2>

A single component vapor deposition film was produced in the same manner as in Example 1 except that compound (10P-gq-101-J11) was changed to compound (10P-g-101), and each spectrum was measured. Additionally, the ionization potential (Ip) and the like were obtained from each spectrum, and are shown in Table 1 as the difference with respect to Comparative Example 1.

<Comparative Example 1>

A single-component deposition film was prepared in the same manner as in Example 1, except that the compound (10P-gq-101-J11) was changed to the compound mCBP (3,3'-di(9H-carbazolyl-9-yl)biphenyl). Fabricated and measured each spectrum. Additionally, ionization potential (Ip), etc. were obtained from each spectrum and are shown in Table 1. Comparative Example 1 is a reference to Example 1, Example 2, and Comparative Example 2.

<Comparative Example 2>

A single component vapor deposition film was produced in the same manner as in Example 1 except that the compound (10P-gq-101-J11) was changed to the compound CBP, and each spectrum was measured. Additionally, the ionization potential (Ip) and the like were obtained from each spectrum, and are shown in Table 1 as the difference with respect to Comparative Example 1.

[Table 1]

As mentioned above, the basic physical properties of some of the compounds according to the present invention were evaluated, and it was shown that they had a high triplet excitation energy (T ₁ ) and a negative (-) large ΔE _ST , etc., but other compounds that were not evaluated also had the same properties. These compounds have a basic skeleton and a similar structure as a whole, and those skilled in the art can understand that they have equally excellent properties.

<Manufacture and characteristic evaluation of organic EL devices>

For example, the organic EL devices according to Examples 3, 4, and Comparative Example 3 can be manufactured with the layer configuration shown in Table 2.

[Table 2]

In Table 2, "HAT-CN" is 1,4,5,8,9,12-hexaazatriphenylenehexacarbonitrile, and "TBB" is N ⁴ , N ⁴ , N ^{4 '} , N ^4' - tetra([1,1'-biphenyl]-4-yl)-[1,1'-biphenyl]-4,4'-diamine, "TcTa" is tris(4-carbazolyl-9-ylphenyl )amine, "CBP" is 4,4'-di(9H-carbazolyl-9-yl)-1,1'-biphenyl, and "Ir(PPy) ₃ " is tris(2-phenylpyridine)iridium ( III), “TPBi” is 1,3,5-tris(1-phenyl-1H-benzo[d]imidazol-2-yl)benzene. The chemical structure is shown below.

<Example 3>

<Device using compound (10P-g-101) as the host material of the light-emitting layer>

A 26 mm x 28 mm x 0.7 mm glass substrate (Ophto Science Co., Ltd.) made by polishing the ITO film formed by sputtering to 50 nm was used as a transparent support substrate. This transparent support substrate was fixed to the substrate holder of a commercially available vapor deposition equipment (Choshu Sangyo Co., Ltd.), and HAT-CN, TBB, TcTa, compound (10P-g-101), Ir(PPy) ₃ , A tantalum deposition crucible containing TPBi and LiF, and an aluminum nitride deposition crucible containing aluminum are installed.

The following layers are sequentially formed on the ITO film of the transparent support substrate. The vacuum chamber was depressurized to ^2.0 By depositing to a thickness of 10 nm, a three-layer hole injection layer and hole transport layer are formed. Next, compound (10P-g-101) and Ir(PPy) ₃ are simultaneously heated and deposited to a film thickness of 30 nm to form a light emitting layer. The deposition rate is adjusted so that the weight ratio of compound (10P-g-101) and Ir(PPy) ₃ is about 95:5. Next, TPBi is heated and deposited to a film thickness of 50 nm to form an electron transport layer. The deposition rate of each layer so far is 0.01 to 1 nm/sec. Afterwards, LiF is heated and deposited at a deposition rate of 0.01 to 0.1 nm/sec to achieve a film thickness of 1 nm, and then aluminum is heated and deposited at a deposition rate of 0.1 to 2 nm/sec to achieve a film thickness of 100 nm to form a cathode. , an organic EL device is obtained.

Green light emission is obtained by applying a direct current voltage using the ITO electrode as the anode and the LiF/aluminum electrode as the cathode.

<Example 4>

<Device using compound (10P-gq-101-J11) as the host material of the light-emitting layer>

An organic EL device was obtained in the same manner as in Example 3, except that compound (10P-g-101), which was the host material of the light emitting layer, was changed to compound (10P-gq-101-J11). Additionally, light emission is obtained by applying a direct current voltage in the same manner.

<Comparative Example 3>

<Device using compound CBP as the host material of the light-emitting layer>

An organic EL device was obtained in the same manner as in Example 3, except that the compound (10P-g-101), which was the host material of the light emitting layer, was changed to the compound CBP.

Additionally, for example, organic EL devices according to Examples 5 and 6 can be manufactured with the layer configuration shown in Table 3.

[Table 3]

<Example 5>

<Device using compound (10P-g-101) as an electron transport layer>

A 26 mm x 28 mm x 0.7 mm glass substrate (Ophto Science Co., Ltd.) made by polishing the ITO film formed by sputtering to 50 nm was used as a transparent support substrate. This transparent support substrate was fixed to the substrate holder of a commercially available vapor deposition equipment (Choshu Sangyo Co., Ltd.), and HAT-CN, TBB, TcTa, CBP, Ir(PPy) ₃ , compound (10P-g-101), and LiF A crucible for deposition made of tantalum containing each of the following and a crucible for deposition made of aluminum nitride containing aluminum are installed.

The following layers are sequentially formed on the ITO film of the transparent support substrate. The vacuum chamber was depressurized to ^2.0 By depositing to a thickness of 10 nm, a three-layer hole injection layer and hole transport layer are formed. Next, CBP and Ir(PPy) ₃ are simultaneously heated and deposited to a film thickness of 30 nm to form a light emitting layer. The deposition rate is adjusted so that the weight ratio of CBP and Ir(PPy) ₃ is about 95:5. Next, compound (10P-g-101) is heated and deposited to a film thickness of 50 nm to form an electron transport layer. The deposition rate of each layer so far is 0.01 to 1 nm/sec. Afterwards, LiF is heated and deposited at a deposition rate of 0.01 to 0.1 nm/sec to achieve a film thickness of 1 nm, and then aluminum is heated and deposited at a deposition rate of 0.1 to 2 nm/sec to achieve a film thickness of 100 nm to form a cathode. , an organic EL device is obtained.

Green light emission is obtained by applying a direct current voltage using the ITO electrode as the anode and the LiF/aluminum electrode as the cathode.

<Example 6>

<Device using compound (10P-gq-101-J11) as an electron transport layer>

An organic EL device was obtained in the same manner as in Example 5, except that the compound (10P-g-101) in the electron transport layer was changed to compound (10P-gq-101-J11). Additionally, light emission is obtained by applying a direct current voltage in the same manner.

Additionally, for example, organic EL devices according to Examples 7, 8, and Comparative Example 4 can be manufactured with the layer configurations expected in Table 4.

[Table 4]

In Table 4, “Firpic” is bis[2-(4,6-difluorophenyl)pyridinato-N,C2](picorinato)iridium(III). The chemical structure is shown below.

<Example 7>

<Device using compound (10P-g-101) as the host material of the light-emitting layer>

A 26 mm x 28 mm x 0.7 mm glass substrate (Ophto Science Co., Ltd.) made by polishing the ITO film formed by sputtering to 50 nm was used as a transparent support substrate. This transparent support substrate was fixed to the substrate holder of a commercially available vapor deposition equipment (Choshu Sangyo Co., Ltd.), and each of HAT-CN, TBB, TcTa, compound (10P-g-101), Firpic, TPBi, and LiF was added thereto. A crucible for deposition made of tantalum and a crucible for deposition made of aluminum nitride containing aluminum are installed.

The following layers are sequentially formed on the ITO film of the transparent support substrate. The vacuum chamber was depressurized to ^2.0 By depositing to a thickness of 10 nm, a three-layer hole injection layer and hole transport layer are formed. Next, the compound (10P-g-101) and Firpic are simultaneously heated and deposited to a film thickness of 30 nm to form a light emitting layer. The deposition rate is adjusted so that the weight ratio of compound (10P-g-101) and Firpic is about 95:5. Next, TPBi is heated and deposited to a film thickness of 50 nm to form an electron transport layer. The deposition rate of each layer is 0.01 to 1 nm/sec. Afterwards, LiF is heated and deposited at a deposition rate of 0.01 to 0.1 nm/sec to achieve a film thickness of 1 nm, and then aluminum is heated and deposited at a deposition rate of 0.1 to 2 nm/sec to achieve a film thickness of 100 nm to form a cathode. , an organic EL device is obtained.

When a direct current voltage is applied using the ITO electrode as the anode and the LiF/aluminum electrode as the cathode, blue light emission is obtained.

<Example 8>

<Device using compound (10P-gq-101-J11) as the host material of the light-emitting layer>

An organic EL device was obtained in the same manner as in Example 7, except that compound (10P-g-101), which was the host material of the light emitting layer, was changed to compound (10P-gq-101-J11). When direct current voltage is applied to both electrodes, blue light emission is obtained.

<Comparative Example 4>

<Device using the compound mCBP as the host material of the light-emitting layer>

An organic EL device was obtained in the same manner as in Example 7, except that the compound (10P-g-101), which was the host material of the light emitting layer, was changed to the compound mCBP. When direct current voltage is applied to both electrodes, blue light emission is obtained.

Next, organic EL devices according to Examples 9 to 16 and Comparative Examples 5 to 8 were produced with the layer configuration shown in Table 5.

[Table 5]

In Table 5, "NPD" is N,N'-bis(naphthylen-1-yl)-N,N'-bis(phenyl)benzene, and "mCP" is 1,3-bis(carbazolyl-9 -yl)benzene, “DABNA2” is 9-([1,1'-biphenyl]-3-yl-N,N,5,11-tetraphenyl-5,9-dihydro-5,9-diaza -13b-boranaphtho[3,2,1-de]anthracen-3-amine, “DABNA3” is N,N,5,9-tetraphenyl-5,9-dihydro-5,9-diaza- “4CzIPN”, a dimer sharing one benzene ring with 13b-boranaphtho[3,2,1-de]anthracene-7-amine, is 2,4,5,6-tetra(9H-carbazole) -9-yl) Isophthalonitrile, "CzBPCN" is 4,4',6,6'-tetra(9H-carbazol-9-yl)-[1,1'-biphenyl]-3,3'- Dicarbonitrile, “TSPO1”, is diphenyl-4-triphenylsilylphenylphosphine oxide. The chemical structure is shown below.

<Example 9>

<Device using compound (10P-g-101) as the host and DABNA2 as the dopant>

A 26 mm x 28 mm x 0.7 mm glass substrate (Ophto Science Co., Ltd.) in which the ITO film formed by sputtering was polished to 50 nm was used as a transparent support substrate. This transparent support substrate was fixed to the substrate holder of a commercially available evaporation device (Choshu Sangyo Co., Ltd.), and a tantalum product containing each of NPD, TcTa, mCP, compound (10P-g-101), DABNA2, TSPO1, and LiF was added. A crucible for vapor deposition and a crucible for vapor deposition made of aluminum nitride filled with aluminum were installed.

The following layers were sequentially formed on the ITO film of the transparent support substrate. The vacuum chamber was depressurized to ^2.0 By depositing as much as possible, a three-layer hole injection layer and hole transport layer were formed. Next, the compound (10P-g-101) and DABNA2 were heated simultaneously and deposited to a film thickness of 20 nm to form a light emitting layer. The deposition rate was adjusted so that the weight ratio of compound (10P-g-101) and DABNA2 was about 98:2. Next, TSPO1 was heated and deposited to a film thickness of 40 nm to form an electron transport layer. The deposition rate of each layer was 0.01 to 1 nm/sec. Afterwards, LiF is heated and deposited at a deposition rate of 0.01 to 0.1 nm/sec to achieve a film thickness of 1 nm, and then aluminum is heated and deposited at a deposition rate of 0.1 to 2 nm/sec to achieve a film thickness of 100 nm to form a cathode. , an organic EL device was obtained.

When a direct current voltage was applied using the ITO electrode as the anode and the LiF/aluminum electrode as the cathode, blue light emission with a peak at about 466 nm was obtained. At a driving voltage of 4.10 V and a current density of 0.05 mA/cm ² , the luminance was 10 cd/m ² and the external quantum efficiency at this time was 18.2%.

<Example 10>

<Device using compound (10P-gq-101-J1) as the host and DABNA2 as the dopant>

An organic EL device was obtained in the same manner as in Example 9, except that compound (10P-g-101), which was the host material of the light emitting layer, was changed to compound (10P-gq-101-J11). When direct current voltage was applied to both electrodes, blue light emission was obtained. At a driving voltage of 3.82 V and a current density of 0.04 mA/cm ² , the luminance was 10 cd/m ² and the external quantum efficiency at this time was 22.6%. At a driving voltage of 4.70 V and a current density of 0.66 mA/cm ² , the luminance was 100 cd/m ² and the external quantum efficiency at this time was 15.3%. For Comparative Example 5, the external quantum efficiencies at 10 cd/m ² and 100 cd/m ² were both excellent.

<Comparative Example 5>

<Device using the compound mCBP as the host and DABNA2 as the dopant>

An organic EL device was obtained in the same manner as in Example 5, except that the compound (10P-g-101), which was the host material of the light emitting layer, was changed to the compound mCBP. When a direct current voltage was applied to both electrodes, blue light emission with a peak top at approximately 467 nm was obtained. At a driving voltage of 3.65 V and a current density of 0.06 mA/cm ² , the luminance was 10 cd/m ² and the external quantum efficiency at this time was 18.2%. At a driving voltage of 5.13 V and a current density of 0.92 mA/cm ² , the luminance was 100 cd/m ² and the external quantum efficiency at this time was 11.4%.

<Example 11>

<Device using compound (10P-g-101) as the host and DABNA3 as the dopant>

An organic EL device was obtained in the same manner as in Example 9, except that the compound DABNA2, which was the dopant material of the light emitting layer, was changed to the compound DABNA3. When direct current voltage is applied to both electrodes, blue light emission is obtained.

<Example 12>

<Device using compound (10P-gq-101-J11) as the host and DABNA3 as the dopant>

Organic EL was produced in the same manner as in Example 9, except that the host material of the emitting layer, compound (10P-g-101), was changed to compound (10P-gq-101-J11), and the dopant material, compound DABNA2, was changed to compound DABNA3. A device is obtained. When direct current voltage is applied to both electrodes, blue light emission is obtained.

<Comparative Example 6>

<Device using the compound mCBP as the host and DABNA3 as the dopant>

An organic EL device was obtained in the same manner as in Example 9, except that the compound (10P-g-101), the host material of the light emitting layer, was changed to the compound mCBP, and the dopant material, compound DABNA2, was changed to the compound DABNA3. When direct current voltage is applied to both electrodes, blue light emission is obtained.

<Example 13>

<Device using compound (10P-g-101) as the host and 4CzIPN as the dopant>

An organic EL device was obtained in the same manner as in Example 9, except that the compound DABNA2, which was the dopant material of the light emitting layer, was changed to the compound 4CzIPN. When direct current voltage is applied to both electrodes, green light emission is obtained.

<Example 14>

<Device using compound (10P-gq-101-J11) as the host and 4CzIPN as the dopant>

Organic EL was produced in the same manner as in Example 9, except that the host material of the emitting layer, compound (10P-g-101), was changed to compound (10P-gq-101-J11), and the dopant material, compound DABNA2, was changed to compound 4CzIPN. A device is obtained. When direct current voltage is applied to both electrodes, green light emission is obtained.

<Comparative Example 7>

<Device using the compound mCBP as the host and 4CzIPN as the dopant>

An organic EL device was obtained in the same manner as in Example 9, except that the compound (10P-g-101), which was the host material of the light emitting layer, was changed to the compound mCBP, and the compound DABNA2, which was the dopant material, was changed to the compound 4CzIPN. When direct current voltage is applied to both electrodes, green light emission is obtained.

<Example 15>

<Device using compound (10P-g-101) as the host and CzBPCN as the dopant>

An organic EL device was obtained in the same manner as in Example 9, except that the compound DABNA2, which was the dopant material of the light emitting layer, was changed to the compound CzBPCN. When direct current voltage is applied to both electrodes, blue light emission is obtained.

<Example 16>

<Device using compound (10P-gq-101-J11) as the host and CzBPCN as the dopant>

Organic EL was produced in the same manner as in Example 9, except that the host material of the light emitting layer (10P-g-101) was changed to compound (10P-gq-101-J11), and the dopant material, compound DABNA2, was changed to compound CzBPCN. A device is obtained. When direct current voltage is applied to both electrodes, blue light emission is obtained.

<Comparative Example 8>

<Device using the compound mCBP as the host and CzBPCN as the dopant>

An organic EL device was obtained in the same manner as in Example 9, except that the compound (10P-g-101), which was the host material of the light emitting layer, was changed to the compound mCBP, and the compound DABNA2, which was the dopant material, was changed to the compound CzBPCN. When direct current voltage is applied to both electrodes, blue light emission is obtained.

Next, an organic EL device according to Example 17 was manufactured with the layer composition shown in Table 6.

[Table 6]

<Example 17>

<Device using compound (10P-gq-100-J11) as the host and DABNA2 as the dopant>

A 26 mm x 28 mm x 0.7 mm glass substrate (Ophto Science Co., Ltd.) in which the ITO film formed by sputtering was polished to 50 nm was used as a transparent support substrate. This transparent support substrate was fixed to the substrate holder of a commercially available vapor deposition equipment (Choshu Sangyo Co., Ltd.), and each of NPD, TcTa, mCP, compound (10P-gq-100-J11), DABNA2, TSPO1, and LiF was added thereto. A crucible for vapor deposition made of tantalum and a crucible for vapor deposition made of aluminum nitride containing aluminum were installed.

The following layers were sequentially formed on the ITO film of the transparent support substrate. The vacuum chamber was depressurized to ^2.0 By depositing as much as possible, a three-layer hole injection layer and hole transport layer were formed. Next, the compound (10P-gq-100-J11) and DABNA2 were heated simultaneously and deposited to a film thickness of 20 nm to form a light-emitting layer. The deposition rate was adjusted so that the weight ratio of compound (10P-gq-100-J11) and DABNA2 was about 98:2. Next, TSPO1 was heated and deposited to a film thickness of 40 nm to form an electron transport layer. The deposition rate of each layer was 0.01 to 1 nm/sec. Afterwards, LiF is heated and deposited at a deposition rate of 0.01 to 0.1 nm/sec to achieve a film thickness of 1 nm, and then aluminum is heated and deposited at a deposition rate of 0.1 to 2 nm/sec to achieve a film thickness of 100 nm to form a cathode. , an organic EL device was obtained.

When a direct current voltage was applied using the ITO electrode as the anode and the LiF/aluminum electrode as the cathode, blue light emission peaking at about 469 nm was obtained. At a driving voltage of 4.00 V and a current density of 0.04 mA/cm ² , the luminance was 10 cd/m ² and the external quantum efficiency at this time was 25.0%. At a driving voltage of 4.84 V and a current density of 0.48 mA/cm ² , the luminance was 100 cd/m ² and the external quantum efficiency at this time was 21.0%.

Next, organic EL devices according to Examples 18 and 19 and Comparative Examples 9 and 10 were produced with the layer composition shown in Table 7.

[Table 7]

<Example 18>

<Device using compound (10P-gq-100-J11) as the host and DABNA2 as the dopant>

A 26 mm x 28 mm x 0.7 mm glass substrate (Ophto Science Co., Ltd.) in which the ITO film formed by sputtering was polished to 50 nm was used as a transparent support substrate. This transparent support substrate was fixed to the substrate holder of a commercially available vapor deposition equipment (Choshu Sangyo Co., Ltd.), and each of NPD, TcTa, mCP, compound (10P-gq-100-J11), DABNA2, TSPO1, and LiF was added thereto. A crucible for vapor deposition made of tantalum and a crucible for vapor deposition made of aluminum nitride containing aluminum were installed.

The following layers were sequentially formed on the ITO film of the transparent support substrate. The vacuum chamber was depressurized to ^2.0 By depositing as much as possible, a three-layer hole injection layer and hole transport layer were formed. Next, the compound (10P-gq-100-J11) and DABNA2 were heated simultaneously and deposited to a film thickness of 20 nm to form a light-emitting layer. The deposition rate was adjusted so that the weight ratio of compound (10P-gq-100-J11) and DABNA2 was about 98:2. Next, TSPO1 was heated and deposited to a film thickness of 30 nm to form an electron transport layer. The deposition rate of each layer was 0.01 to 1 nm/sec. Afterwards, LiF is heated and deposited at a deposition rate of 0.01 to 0.1 nm/sec to achieve a film thickness of 1 nm, and then aluminum is heated and deposited at a deposition rate of 0.1 to 2 nm/sec to achieve a film thickness of 100 nm to form a cathode. , an organic EL device was obtained.

When a direct current voltage was applied using the ITO electrode as the anode and the LiF/aluminum electrode as the cathode, blue light emission with a peak top at approximately 469 nm was obtained. At a driving voltage of 3.98 V and a current density of 0.04 mA/cm ² , the luminance was 10 cd/m ² and the external quantum efficiency at this time was 25.0%. At a driving voltage of 4.66 V and a current density of 0.48 mA/cm ² , the luminance was 100 cd/m ² and the external quantum efficiency at this time was 19.8%. For Comparative Example 9 below, the external quantum efficiencies at 10 cd/m ² and 100 cd/m ² were both excellent.

<Comparative Example 9>

<Device using the compound mCBP as the host and DABNA2 as the dopant>

An organic EL device was obtained in the same manner as in Example 18, except that the compound (10P-gq-100-J11), which was the host material of the light emitting layer, was changed to the compound mCBP. When a direct current voltage was applied to both electrodes, blue light emission with a peak top at approximately 467 nm was obtained. At a driving voltage of 4.50 V and a current density of 0.06 mA/cm ² , the luminance was 10 cd/m ² and the external quantum efficiency at this time was 17.6%. At a driving voltage of 5.38 V and a current density of 0.83 mA/cm ² , the luminance was 100 cd/m ² and the external quantum efficiency at this time was 12.4%.

<Example 19>

<Device using compound (10P-gq-100-J11) as the host and DABNA3 as the dopant>

An organic EL device was obtained in the same manner as in Example 18, except that the dopant material of the light emitting layer was changed to DABNA3. When a direct current voltage was applied to both electrodes, blue light emission with a peak top at approximately 472 nm was obtained. At a driving voltage of 4.00 V and a current density of 0.03 mA/cm ² , the luminance was 10 cd/m ² and the external quantum efficiency at this time was 34.5%. At a driving voltage of 5.38 V and a current density of 0.34 mA/cm ² , the luminance was 100 cd/m ² and the external quantum efficiency at this time was 32.7%. For Comparative Example 10 below, the external quantum efficiencies at 10 cd/m ² and 100 cd/m ² were both excellent.

<Comparative Example 10>

<Device using the compound mCBP as the host and DABNA3 as the dopant>

An organic EL device was obtained in the same manner as in Example 18, except that the compound (10P-gq-100-J11), the host material of the light-emitting layer, was changed to the compound mCBP, and the dopant material of the light-emitting layer was changed to DABNA3. When a direct current voltage was applied to both electrodes, blue light emission with a peak top at approximately 471 nm was obtained. At a driving voltage of 4.43 V and a current density of 0.05 mA/cm ² , the luminance was 10 cd/m ² and the external quantum efficiency at this time was 22.5%. At a driving voltage of 5.20 V and a current density of 0.63 mA/cm ² , the luminance was 100 cd/m ² and the external quantum efficiency at this time was 18.7%.

<Evaluation as a TADF compound>

Next, the structure of the TADF-active light-emitting material was designed using DFT calculations. After optimizing the structure of the ground state using the PBE0/6-31G(d) method, the vertical excitation energy from the ground state was calculated using the time-dependent DFT method, and ΔE _ST and oscillator strength were estimated. All calculations were performed using the quantum chemical calculation program Firefly (AA Granovsky, Firefly version 8).

<Calculation Comparative Example 1>

The S ₁ excitation energy, oscillator intensity, and ΔE _ST of the following comparative compound (TADF-EM1) were estimated to be 2.37 eV (522 nm in wavelength conversion), 0.0003, and ΔE _ST of 0.008 eV, respectively.

According to a presentation by Professor Yasuda of Kyushu University and others (Chem. Commun., 2017, 53, 8723-8726), S ₁ was calculated using PBE0/6-31G(d) as the calculation method in the paper. The energy, oscillator intensity, and ΔE _ST were estimated to be 2.34 eV (530 nm in terms of wavelength), 0.0057, and 0.008 eV, respectively. Additionally, the actual measured values of the emission wavelength, PLQY, and ΔE _ST were 504 nm, 97%, and 0.06 eV, respectively.

In this comparative calculation example, the S ₁ excitation energy calculated using the PBE0/6-31G(d) method was 18 nm shorter than the emission wavelength determined by actual measurement, and ΔE _ST was about 10 times smaller. In addition, although the calculated value of the oscillator strength was very small, the actual measured PLQY was very high.

If it is a molecule having a boron-containing sospiro structure of the present invention, it was determined whether the compound was a TADF-active fluorescent material or not, under the assumption that the calculated and measured values tended to be the same as those in Comparative Example 1. Specifically, the actual emission wavelength may be shorter than the calculation result of the S ₁ excitation energy, and the actual ΔE _ST is likely to be larger than the calculation result, and for PLQY, there is also a possibility that it is greater than the calculation result of the oscillator strength. It was assumed that there was. Accordingly, those with a ΔE _ST of the calculation result of less than 0.20 eV can be used as TADF fluorescent materials, and those with ΔE ST of less than 0.02 eV can be used more effectively as TADF fluorescent materials. In addition, when the oscillator strength is 0.0002 or more, high PLQY is obtained, and when it is less than 0.0002, low PLQY is obtained. In addition, although the actual emission wavelength is close to the calculation result of S ₁ excitation energy, there is a possibility that it may shift somewhat.

<Calculation Example 1>

The S ₁ excitation energy, oscillator intensity, and ΔE _ST of compound (10P-g-295) were estimated to be 3.08 eV (403 nm in terms of wavelength), 0.0138, and ΔE _ST of 0.135 eV, respectively. From the calculation results, the compound (10P-g-295) was expected to produce very deep blue emission, be usable as a TADF fluorescent material, and have a high PLQY.

<Calculation Example 2>

The S ₁ excitation energy, oscillator intensity, and ΔE _ST of the compound (10P-g-2011) were estimated to be 2.76 eV (449 nm in terms of wavelength), 0.0000, and ΔE _ST of 0.003 eV, respectively. From the calculation results, it was predicted that the compound (10P-g-2011) emits blue light, can be used more effectively as a TADF fluorescent material, and has a low PLQY.

<Calculation Example 3>

The S ₁ excitation energy, oscillator intensity, and ΔE _ST of the compound (10P-g-2021) were estimated to be 2.40 eV (517 nm when converted to wavelength), 0.0000, and ΔE _ST of 0.003 eV, respectively. From the calculation results, it was expected that the compound (10P-g-2021) emits green light, can be used more effectively as a TADF fluorescent material, and has a low PLQY.

<Calculation Example 4>

The S ₁ excitation energy, oscillator intensity, and ΔE _ST of compound (10P-g-2031) were estimated to be 2.90 eV (427 nm in wavelength conversion), 0.0000, and ΔE _ST of 0.004 eV, respectively. From the calculation results, it was predicted that the compound (10P-g-2031) emits blue light, can be used more effectively as a TADF fluorescent material, and has a low PLQY.

<Calculation Example 5>

The S ₁ excitation energy, oscillator intensity, and ΔE _ST of compound (10P-g-2041) were estimated to be 2.77 eV (447 nm in wavelength conversion), 0.0000, and ΔE _ST of 0.003 eV, respectively. From the calculation results, it was expected that the compound (10P-g-2041) emits blue light, can be used more effectively as a TADF fluorescent material, and has a low PLQY.

<Calculation Example 6>

The S ₁ excitation energy, oscillator intensity, and ΔE _ST of compound (10P-gq-2011-J11) were estimated to be 2.88 eV (430 nm in terms of wavelength), 0.0020, and ΔE _ST of 0.038 eV, respectively. From the calculation results, the compound (10P-gq-2011-J11) was expected to produce deep blue emission, be usable as a TADF fluorescent material, and have a high PLQY.

<Calculation Example 7>

The S ₁ excitation energy, oscillator intensity, and ΔE _ST of the compound (10P-gq-2021-J11) were estimated to be 2.54 eV (488 nm when converted to wavelength), 0.0042, and ΔE _ST of 0.014 eV, respectively. From the calculation results, the compound (10P-gq-2021-J11) was expected to emit blue to green light, be more effectively used as a TADF fluorescent material, and have a high PLQY.

<Calculation Example 8>

The S ₁ excitation energy, oscillator intensity, and ΔE _ST of compound (10P-gq-2031-J11) were estimated to be 3.05 eV (406 nm in terms of wavelength), 0.0016, and ΔE _ST of 0.147 eV, respectively. From the calculation results, the compound (10P-gq-2031-J11) was expected to emit deep blue light, be usable as a TADF fluorescent material, and have a high PLQY.

<Calculation Example 9>

The S ₁ excitation energy, oscillator intensity, and ΔE _ST of compound (10P-gq-2041-J11) were estimated to be 4.62 eV (474 nm in terms of wavelength), 0.0006, and ΔE _ST of 0.006 eV, respectively. From the calculation results, it was predicted that compound (10P-gq-2041-J11) emits blue to green light, can be used more effectively as a TADF fluorescent material, and has a high PLQY.

As mentioned above, some of the compounds according to the present invention were evaluated as materials for organic EL devices, and were shown to be excellent materials for organic devices. However, other compounds that were not evaluated also have the same basic skeleton and have similar structures as a whole. It is a compound having a , and those skilled in the art can understand that it is an equally excellent material for organic devices.

[Industrial applicability]

In the present invention, the selection of materials for organic devices such as organic EL elements can be increased by providing a novel compound using boron as a spiro atom. Additionally, by using a novel compound containing boron as a spiro atom as a material for an organic EL device, an excellent organic EL device, a display device equipped with the same, a lighting device equipped with the same, etc. can be provided.

100: Organic electroluminescent device
101: substrate
102: anode
103: Hole injection layer
104: Hole transport layer
105: light emitting layer
106: Electron transport layer
107: Electron injection layer
108: cathode

Claims (27)

delete delete delete Compounds represented by the following general formula (2):

(In equation (2) above,
Z ¹ and Z ² are each independently a single bond, -O-, -S-, -Se-, or -NR-, where R is aryl having 6 to 16 carbon atoms, and at least one of R Hydrogen may be substituted with alkyl having 1 to 6 carbon atoms, provided that Z ¹ and Z ² do not form a single bond at the same time,
R ¹ to R ⁸ and R ¹³ to R ¹⁶ are each independently hydrogen, aryl having 6 to 16 carbon atoms, or alkyl having 1 to 6 carbon atoms,
R ⁹ to R ¹² are each independently hydrogen, aryl having 6 to 16 carbon atoms, alkyl having 1 to 6 carbon atoms, or the following partial structural formula (TSG100), formula (TSG110), formula (TSG111), formula (TSG112), It is a group represented by the formula (TSG113), formula (TSG120), or formula (TSG121),

At least one hydrogen in the compound represented by formula (2) may be substituted with cyano, halogen, or deuterium. delete delete delete Compounds represented by the following chemical structures:

. delete delete delete delete Compounds represented by the following chemical structures:

. delete delete Compounds represented by the following chemical structures:

. According to clause 4,
Compounds satisfying the formula:
ΔE _ST ≤ 0.20eV. A material for an organic device containing the compound according to any one of claims 4, 8, 13, 16, and 17. According to clause 18,
A material for an organic device, wherein the material for an organic device is a material for an organic electroluminescent element, a material for an organic field effect transistor, or a material for an organic thin film solar cell. An organic electroluminescent device comprising a pair of electrodes consisting of an anode and a cathode, and an organic layer disposed between the pair of electrodes and containing the material for an organic electroluminescent device according to claim 19. According to clause 20,
It further has an electron transport layer and/or an electron injection layer, wherein at least one of the electron transport layer and the electron injection layer is selected from the group consisting of a quinolinol-based metal complex, a pyridine derivative, a phenanthroline derivative, a borane derivative, and a benzimidazole derivative. An organic electroluminescent element containing at least one selected element. According to clause 21,
The electron transport layer and/or the electron injection layer is an alkali metal, an alkaline earth metal, a rare earth metal, an oxide of an alkali metal, a halide of an alkali metal, an oxide of an alkaline earth metal, a halide of an alkaline earth metal, an oxide of a rare earth metal, An organic electroluminescent element further containing at least one selected from the group consisting of a halide of a rare earth metal, an organic complex of an alkali metal, an organic complex of an alkaline earth metal, and an organic complex of a rare earth metal. An organic electroluminescent device having a light-emitting layer, wherein the light-emitting layer includes:
As a first component, at least one host compound,
As a second component, it includes at least one heat-activated delayed phosphor,
An organic electroluminescent element comprising the compound according to any one of claims 4, 8, 13, and 16 as the first or second component. An organic electroluminescent device having a light-emitting layer, wherein the light-emitting layer includes:
As a first component, at least one host compound,
As a second component, it includes at least one heat-activated delayed phosphor,
An organic electroluminescent device comprising, as the first component, the compound according to any one of claims 4, 8, 13, and 16. An organic electroluminescent device having a light-emitting layer, wherein the light-emitting layer includes:
As a first component, at least one host compound,
As a second component, it includes at least one heat-activated delayed phosphor,
An organic electroluminescent device comprising, as the second component, the compound according to any one of claims 4, 8, 13, and 16. A display device comprising the organic electroluminescent element according to claim 20. A lighting device comprising the organic electroluminescent element according to claim 20.

Images