JP7398711B2 - Fluorine-substituted polycyclic aromatic compounds - Google Patents

Description

Application of Article 30, Paragraph 2 of the Patent Act (1) Publication date: November 9, 2017 (2) Publication: J. Am. Chem. Soc. , 2018, 140 (4), pp 1195-1198 (3) Publisher: Kohei Matsui, Susumu Oda, Kazuki Yoshiura, Kiichi Nakajima, Nobuhiro Yasuda, and Takuji Hatakeyama (4) Contents of the disclosed invention: Kohei Matsui, Susumu Oda, Kazuki Yoshiura, Kiichi Nakajima, Nobuhiro Yasuda, and Takuji Hatakeyama, in JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2018, 140 (4), pp 1195-1198, describe the polycyclic aromatic compound invented by Takuji Hatakeyama. The synthesis method was disclosed.

The present invention relates to a fluorine-substituted polycyclic aromatic compound, an organic electroluminescent device, an organic field effect transistor, an organic thin film solar cell, a display device, and a lighting device using the same. Note that in this specification, an "organic electroluminescent device" may be referred to as an "organic EL device" or simply "device."

Conventionally, display devices using light-emitting elements that emit electroluminescence have been studied in various ways because they can be made with low power consumption and thinner.Furthermore, organic electroluminescent elements made of organic materials can be easily made lighter and larger. As a result, it has been actively considered. In particular, we are developing organic materials that emit light such as blue, which is one of the three primary colors of light, and organic materials that have charge transport capabilities such as holes and electrons (which have the potential to become semiconductors and superconductors). Regarding development, research has been active so far, regardless of whether it is a high-molecular compound or a low-molecular compound.

An organic EL element has a structure consisting of a pair of electrodes consisting of an anode and a cathode, and one or more layers containing an organic compound and disposed between the pair of electrodes. 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, and various organic materials suitable for these layers have been developed.

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

Furthermore, in recent years, materials improved from triphenylamine derivatives have been reported as materials for use in organic EL elements and organic thin film solar cells (International Publication No. 2012/118164). This material was created based on N,N'-diphenyl-N,N'-bis(3-methylphenyl)-1,1'-biphenyl-4,4'-diamine (TPD), which had already been put into practical use. This material is characterized by having enhanced planarity by connecting the aromatic rings that make up triphenylamine. In this document, for example, the charge transport properties of an NO-linked compound (compound 1 on page 63) are evaluated, but there is no description of the method for producing materials other than the NO-linked compound, and there is no description of the method for producing materials other than the NO-linked compound. Since different compounds have different electronic states as a whole, the properties that can be obtained from materials other than NO-linked compounds are still unknown. Other examples of such compounds can be found (WO 2011/107186). For example, a compound having a conjugated structure with a large triplet exciton energy (T1) can emit phosphorescence with a shorter wavelength and is therefore useful as a material for a blue light-emitting layer. Furthermore, compounds having a novel conjugated structure with a large T1 are required as electron transport materials and hole transport materials that sandwich a light emitting layer.

Host materials for organic EL devices are generally molecules in which a plurality of existing aromatic rings, such as benzene and carbazole, are connected by single bonds, phosphorus atoms, and silicon atoms. This is because a large HOMO-LUMO gap (band gap Eg in a thin film) required for the host material is ensured by connecting a large number of relatively small conjugated aromatic rings. Furthermore, host materials for organic EL devices using phosphorescent materials or thermally activated delayed fluorescent materials require high triplet excitation energy ( _E By connecting SOMO1 and SOMO2 in the triplet excited state (T1), it is possible to improve the triplet excitation energy (E _T ) by reducing the exchange interaction between both orbitals. becomes. However, small aromatic rings in conjugated systems do not have sufficient redox stability, and devices using molecules that connect existing aromatic rings as host materials do not have sufficient lifespans. On the other hand, polycyclic aromatic compounds with extended π-conjugated systems generally have excellent redox stability, but their HOMO-LUMO gap (band gap Eg in thin films) and triplet excitation energy (E _T ) are low. It has been considered unsuitable as a host material.

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

As mentioned above, various materials have been developed for use in organic EL devices, but in order to increase the choice of materials for organic EL devices, it is desired to develop materials made of compounds different from conventional ones. There is. In particular, organic EL properties obtained from materials other than the NO-linked compounds reported in Patent Documents 1 to 4 and methods for producing the same are not yet known.

In addition, Patent Document 6 reports a polycyclic aromatic compound containing boron and an organic EL device using the same. There is a need for layer materials, especially dopant materials.

As a result of intensive studies to solve the above problems, the present inventors have found that by configuring, for example, an organic EL device by arranging a layer containing a polycyclic aromatic compound into which fluorine atoms are introduced between a pair of electrodes, It was discovered that an excellent organic EL device could be obtained, and the present invention was completed. That is, the present invention relates to the following fluorine-substituted polycyclic aromatic compounds or multimers thereof, and furthermore to the following fluorine-substituted polycyclic aromatic compounds or multimers thereof, for use in organic devices such as organic EL element materials. Provide materials.

Note that in this specification, chemical structures and substituents are sometimes expressed by the number of carbon atoms, but when a chemical structure is substituted with a substituent, or when a substituent is further substituted with a substituent, the number of carbon atoms is the same as the number of carbon atoms in the chemical structure. It means the number of carbon atoms of each substituent or substituent, and does not mean the total number of carbon atoms of the chemical structure and substituent, or the total number of carbon atoms of the substituent and substituent. For example, "substituent B having a carbon number Y substituted with a substituent A having a carbon number X" means that "substituent B having a carbon number Y" is substituted with "substituent A having a carbon number X". However, the carbon number Y is not the total carbon number of substituent A and substituent B. For example, "substituent B having carbon number Y and substituted by substituent A" means that "substituent B having carbon number Y" is substituted with "substituent A (of which the number of carbon atoms is not limited)". However, the carbon number Y is not the total carbon number of substituent A and substituent B.

（上記式（１）中、
Ａ環、Ｂ環およびＣ環は、それぞれ独立して、アリール環またはヘテロアリール環であり、これらの環における少なくとも１つの水素は置換されていてもよく、
Ｙ^１は、Ｂ、Ｐ、Ｐ＝Ｏ、Ｐ＝Ｓ、Ａｌ、Ｇａ、Ａｓ、Ｓｉ－ＲまたはＧｅ－Ｒであり、前記Ｓｉ－ＲおよびＧｅ－ＲのＲは、アリール、アルキルまたはシクロアルキルであり、
Ｘ^１およびＸ^２は、それぞれ独立して、Ｏ、Ｎ－Ｒ、ＳまたはＳｅであり、前記Ｎ－ＲのＲは、置換されていてもよいアリール、置換されていてもよいヘテロアリール、置換されていてもよいアルキルまたは置換されていてもよいシクロアルキルであり、また、前記Ｎ－ＲのＲは連結基または単結合により前記Ａ環、Ｂ環および／またはＣ環と結合していてもよく、
式（１）で表される化合物または構造における少なくとも１つの水素はシアノ、塩素、臭素、ヨウ素または重水素で置換されていてもよく、そして、
式（１）で表される化合物または構造における少なくとも１つの水素はフッ素で置換されている。）Item 1.
A polycyclic aromatic compound represented by the following general formula (1), or a multimer of a polycyclic aromatic compound having a plurality of structures represented by the following general formula (1).

(In the above formula (1),
Ring A, Ring B and Ring C are each independently an aryl ring or a heteroaryl ring, and at least one hydrogen in these rings may be substituted,
Y ¹ is B, P, P=O, P=S, Al, Ga, As, Si-R, or Ge-R, and R in the Si-R and Ge-R is aryl, alkyl, or cycloalkyl. and
X ¹ and X ² are each independently O, NR, S or Se, and R in NR is an optionally substituted aryl, an optionally substituted heteroaryl, a substituted an optionally substituted alkyl or an optionally substituted cycloalkyl, and R in the NR may be bonded to the A ring, B ring and/or C ring through a linking group or a single bond. often,
At least one hydrogen in the compound or structure represented by formula (1) may be substituted with cyano, chlorine, bromine, iodine or deuterium, and
At least one hydrogen in the compound or structure represented by formula (1) is substituted with fluorine. )

Item 2.
Ring A, Ring B, and Ring C are each independently an aryl ring or a heteroaryl ring, and at least one hydrogen in these rings is substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted diarylamino, substituted or unsubstituted diheteroarylamino, substituted or unsubstituted arylheteroarylamino, substituted or unsubstituted diarylboryl (two aryls are bonded via a single bond or a linking group) ), substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkoxy, or substituted or unsubstituted aryloxy, and these rings are Y ¹ , has a 5-membered ring or a 6-membered ring that shares a bond with the fused 2-ring structure at the center of the above formula consisting of X ¹ and X ² ,
Y ¹ is B, P, P=O, P=S, Al, Ga, As, Si-R, or Ge-R, and R in the Si-R and Ge-R is aryl, alkyl, or cycloalkyl. and
X ¹ and X ² are each independently O, NR, S or Se, and R in NR is aryl, alkyl or cycloalkyl which may be substituted with alkyl or cycloalkyl. It is optionally substituted heteroaryl, alkyl or cycloalkyl, and R in the above NR is -O-, -S-, -C(-R) ₂ - or a single bond to form the ring A, B It may be bonded to a ring and/or a C ring, and R in the -C(-R) ₂ - is hydrogen, alkyl or cycloalkyl,
At least one hydrogen in the compound or structure represented by formula (1) may be substituted with cyano, chlorine, bromine, iodine or deuterium,
In the case of a multimer, it is a di- or trimer having two or three structures represented by the general formula (1), and
At least one hydrogen in the compound or structure represented by formula (1) is substituted with fluorine,
Item 1. The polycyclic aromatic compound or multimer thereof.

（上記式（２）中、
Ｒ^１～Ｒ^１１は、それぞれ独立して、水素、アリール、ヘテロアリール、ジアリールアミノ、ジヘテロアリールアミノ、アリールヘテロアリールアミノ、ジアリールボリル（２つのアリールは単結合または連結基を介して結合していてもよい）、アルキル、シクロアルキル、アルコキシまたはアリールオキシであり、これらにおける少なくとも１つの水素は、アリール、ヘテロアリール、アルキルまたはシクロアルキルで置換されていてもよく、また、Ｒ^１～Ｒ^１１のうちの隣接する基同士が結合してａ環、ｂ環またはｃ環と共にアリール環またはヘテロアリール環を形成していてもよく、形成された環における少なくとも１つの水素は、アリール、ヘテロアリール、ジアリールアミノ、ジヘテロアリールアミノ、アリールヘテロアリールアミノ、ジアリールボリル（２つのアリールは単結合または連結基を介して結合していてもよい）、アルキル、シクロアルキル、アルコキシまたはアリールオキシで置換されていてもよく、これらにおける少なくとも１つの水素は、アリール、ヘテロアリール、アルキルまたはシクロアルキルで置換されていてもよく、
Ｙ^１は、Ｂ、Ｐ、Ｐ＝Ｏ、Ｐ＝Ｓ、Ａｌ、Ｇａ、Ａｓ、Ｓｉ－ＲまたはＧｅ－Ｒであり、前記Ｓｉ－ＲおよびＧｅ－ＲのＲは、炭素数６～１２のアリール、炭素数１～６のアルキルまたは炭素数３～１４のシクロアルキルであり、
Ｘ^１およびＸ^２は、それぞれ独立して、Ｏ、Ｎ－Ｒ、ＳまたはＳｅであり、前記Ｎ－ＲのＲは、炭素数６～１２のアリール、炭素数２～１５のヘテロアリール、炭素数１～６のアルキルまたは炭素数３～１４のシクロアルキルであり、また、前記Ｎ－ＲのＲは－Ｏ－、－Ｓ－、－Ｃ（－Ｒ）_２－または単結合により前記ａ環、ｂ環および／またはｃ環と結合していてもよく、前記－Ｃ（－Ｒ）_２－のＲは炭素数１～６のアルキルまたは炭素数３～１４のシクロアルキルであり、
式（２）で表される化合物における少なくとも１つの水素はシアノ、塩素、臭素、ヨウ素または重水素で置換されていてもよく、そして、
式（２）で表される化合物における少なくとも１つの水素はフッ素で置換されている。）Item 3.
The polycyclic aromatic compound or polymer thereof described in Item 1, represented by the following general formula (2).

(In the above formula (2),
R ¹ to R ¹¹ are each independently hydrogen, aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, diarylboryl (two aryls are bonded via a single bond or a linking group); ), alkyl, cycloalkyl, alkoxy or aryloxy, in which at least one hydrogen may be substituted with aryl, heteroaryl, alkyl or cycloalkyl, and R ¹ to R ¹¹ Adjacent groups of these groups may be combined with each other to form an aryl ring or a heteroaryl ring with the a-ring, b-ring, or c-ring, and at least one hydrogen in the formed ring is aryl, heteroaryl, diaryl. Even if substituted with amino, diheteroarylamino, arylheteroarylamino, diarylboryl (two aryls may be bonded via a single bond or a linking group), alkyl, cycloalkyl, alkoxy or aryloxy Often at least one hydrogen in these may be substituted with aryl, heteroaryl, alkyl or cycloalkyl,
Y ¹ is B, P, P=O, P=S, Al, Ga, As, Si-R or Ge-R, and R in the Si-R and Ge-R has 6 to 12 carbon atoms. Aryl, alkyl having 1 to 6 carbon atoms or cycloalkyl having 3 to 14 carbon atoms,
X ¹ and X ² are each independently O, NR, S or Se, and R in NR is an aryl having 6 to 12 carbon atoms, a heteroaryl having 2 to 15 carbon atoms, or It is an alkyl group having 1 to 6 carbon atoms or a cycloalkyl group having 3 to ₁₄ carbon atoms; , may be bonded to ring b and/or ring c, and R in the -C(-R) ₂ - is alkyl having 1 to 6 carbon atoms or cycloalkyl having 3 to 14 carbon atoms,
At least one hydrogen in the compound represented by formula (2) may be substituted with cyano, chlorine, bromine, iodine or deuterium, and
At least one hydrogen in the compound represented by formula (2) is substituted with fluorine. )

Item 4.
R ¹ to R ¹¹ are each independently hydrogen, aryl having 6 to 30 carbon atoms, heteroaryl having 2 to 30 carbon atoms, diarylamino (aryl is aryl having 6 to 12 carbon atoms), diarylboryl (however, Aryl is an aryl having 6 to 12 carbon atoms, two aryls may be bonded via a single bond or a linking group), an alkyl having 1 to 24 carbon atoms, or a cycloalkyl having 3 to 24 carbon atoms. , and adjacent groups among R ¹ to R ¹¹ are bonded together to form an aryl ring having 9 to 16 carbon atoms or a heteroaryl ring having 6 to 15 carbon atoms together with ring a, ring b, or ring c. and at least one hydrogen in the formed ring may be substituted with aryl having 6 to 10 carbon atoms, alkyl having 1 to 12 carbon atoms, or cycloalkyl having 3 to 16 carbon atoms,
Y ¹ is B, P, P═O, P═S, or Si—R, and R in the Si—R is aryl having 6 to 10 carbon atoms, alkyl having 1 to 4 carbon atoms, or alkyl having 5 to 4 carbon atoms. 10 cycloalkyl,
X ¹ and X ² are each independently O, NR, or S, and R in NR is aryl having 6 to 10 carbon atoms, alkyl having 1 to 4 carbon atoms, or C5 to 10 cycloalkyl,
At least one hydrogen in the compound represented by formula (2) may be substituted with cyano, chlorine, bromine, iodine or deuterium, and
At least one hydrogen in the compound represented by formula (2) is substituted with fluorine,
Item 3. The polycyclic aromatic compound or multimer thereof.

Item 5.
R ¹ to R ¹¹ are each independently hydrogen, aryl having 6 to 16 carbon atoms, heteroaryl having 2 to 20 carbon atoms, diarylamino (aryl is aryl having 6 to 10 carbon atoms), diarylboryl (however, Aryl is an aryl having 6 to 10 carbon atoms, two aryls may be bonded via a single bond or a linking group), an alkyl having 1 to 12 carbon atoms, or a cycloalkyl having 3 to 16 carbon atoms. ,
Y ¹ is B, P, P=O or P=S,
X ¹ and X ² are each independently O or NR, and R in NR is aryl having 6 to 10 carbon atoms, alkyl having 1 to 4 carbon atoms, or cycloalkyl, and
At least one hydrogen in the compound represented by formula (2) is substituted with fluorine,
Item 3. The polycyclic aromatic compound or multimer thereof.

Item 6.
R ¹ to R ¹¹ are each independently hydrogen, aryl having 6 to 16 carbon atoms, diarylamino (aryl is aryl having 6 to 10 carbon atoms), diarylboryl (aryl is aryl having 6 to 10 carbon atoms) and two aryls may be bonded via a single bond or a linking group), alkyl having 1 to 12 carbon atoms, or cycloalkyl having 3 to 16 carbon atoms,
Y ¹ is B,
X ¹ and X ² are both NR, or X ¹ is NR and X ² is O, and R in NR is aryl having 6 to 10 carbon atoms, or is an alkyl having 1 to 4 carbon atoms or a cycloalkyl having 5 to 10 carbon atoms, and
At least one hydrogen in the compound represented by formula (2) is substituted with fluorine,
Item 3. The polycyclic aromatic compound or multimer thereof.

Section 7.
Item 7. The polycyclic aromatic compound or multimer thereof according to any one of Items 1 to 6, wherein R in the NR is a fluorine-substituted aryl or heteroaryl.

Section 8.
Item 7. The polycyclic aromatic compound or multimer thereof according to Item 7, wherein R in NR is fluorine-substituted phenyl.

Item 9.
Fluorine-substituted alkyl group or cycloalkyl group, fluorine-substituted alkoxy group, fluorine-substituted diarylamino group, fluorine-substituted diarylboryl group (two aryls are bonded via a single bond or a linking group) The polycyclic aromatic compound or multimer thereof according to any one of Items 1 to 8, which is substituted with a fluorine-substituted carbazolyl group or a fluorine-substituted benzocarbazolyl group.

Item 10.
Item 9. The polycyclic aromatic compound or multimer thereof, which is substituted with a fluorine-substituted diarylamino group.

Item 11.
Item 11. The polycyclic aromatic compound or multimer thereof described in item 10, which is substituted with a fluorine-substituted diphenylamino group.

（上記各構造式中の「ｔＢｕ」はｔ－ブチル基を示す。）Item 12.
The polycyclic aromatic compound described in Item 1, which is represented by any of the following structural formulas.

(“tBu” in each of the above structural formulas represents a t-butyl group.)

（上記各構造式中の「Ｍｅ」はメチル基を示す。）Item 13.
The polycyclic aromatic compound described in Item 1, which is represented by any of the following structural formulas.

(“Me” in each of the above structural formulas represents a methyl group.)

Section 14.
Item 14. An organic device material containing the polycyclic aromatic compound or multimer thereof according to any one of Items 1 to 13.

Item 15.
Item 15. The organic device material according to Item 14, wherein the organic device material is an organic electroluminescent element material, an organic field effect transistor material, or an organic thin film solar cell material.

Section 16.
Item 15. The organic electroluminescent device material described in item 15, which is a material for a light emitting layer.

Section 17.
An organic electroluminescent device comprising a pair of electrodes consisting of an anode and a cathode, and a light-emitting layer disposed between the pair of electrodes and containing the material for a light-emitting layer described in Item 16.

Section 18.
Item 18. The organic electroluminescent device according to Item 17, wherein the light emitting layer includes a host and the light emitting layer material as a dopant.

Item 19.
Item 19. The organic electroluminescent device according to Item 18, wherein the host is an anthracene compound, a fluorene compound, or a dibenzochrycene compound.

Section 20.
It has an electron transport layer and/or an electron injection layer disposed between the cathode and the light emitting layer, and at least one of the electron transport layer and the electron injection layer is made of a borane derivative, a pyridine derivative, a fluoranthene derivative, a BO Item 17, containing at least one selected from the group consisting of anthracene derivatives, anthracene derivatives, benzofluorene derivatives, phosphine oxide derivatives, pyrimidine derivatives, carbazole derivatives, triazine derivatives, benzimidazole derivatives, phenanthroline derivatives, and quinolinol metal complexes. 20. The organic electroluminescent device according to any one of 19 to 19.

Section 21.
The electron transport layer and/or the electron injection layer further comprises an alkali metal, an alkaline earth metal, a rare earth metal, an alkali metal oxide, an alkali metal halide, an alkaline earth metal oxide, an alkaline earth metal oxide, and an alkaline earth metal oxide. Item 20, containing at least one selected from the group consisting of halides, rare earth metal oxides, rare earth metal halides, alkali metal organic complexes, alkaline earth metal organic complexes, and rare earth metal organic complexes. The organic electroluminescent device described in .

Section 22.
A display device or a lighting device comprising the organic electroluminescent device according to any one of Items 17 to 21.

According to a preferred embodiment of the present invention, it is possible to provide a novel fluorine-substituted polycyclic aromatic compound that can be used as a material for organic devices such as a material for organic EL elements, and the fluorine-substituted polycyclic aromatic compound By using the compound, excellent organic devices such as organic EL elements can be provided.

Specifically, the present inventors discovered that a polycyclic aromatic compound (basic skeleton) in which aromatic rings are connected with hetero elements such as boron, phosphorous, oxygen, nitrogen, and sulfur has a large HOMO-LUMO gap (in thin films). It was found that it has a band gap Eg) and a high triplet excitation energy (E _T ). This is because the 6-membered ring containing the hetero element has low aromaticity, which suppresses the decrease in the HOMO-LUMO gap accompanying expansion of the conjugated system, and the electronic perturbation of the hetero element causes the triplet excited state (T1 ) is thought to be caused by the localization of SOMO1 and SOMO2. In addition, in the polycyclic aromatic compound (basic skeleton part) containing a hetero element according to the present invention, the exchange interaction between both orbitals is reduced due to the localization of SOMO1 and SOMO2 in the triplet excited state (T1). Therefore, the energy difference between the triplet excited state (T1) and the singlet excited state (S1) is small, and it exhibits thermally activated delayed fluorescence, so it is also useful as a fluorescent material for organic EL devices. Further, a material having a high triplet excitation energy ( _ET ) is useful as an electron transport layer or a hole transport layer of a phosphorescent organic EL device or an organic EL device using thermally activated delayed fluorescence. Furthermore, these polycyclic aromatic compounds (basic skeleton parts) can arbitrarily move the HOMO and LUMO energies by introducing substituents, so the ionization potential and electron affinity can be optimized according to the surrounding materials. Is possible.

In addition to these characteristics of the basic skeleton, the compound of the present invention can be expected to have a lower sublimation temperature due to lower molecular polarity by introducing a fluorine atom. This means that in sublimation purification, which is almost essential as a purification method for materials for organic devices such as organic EL elements that require high purity, thermal decomposition of the material can be avoided because purification can be performed at a relatively low temperature. means. This also applies to the vacuum evaporation process, which is an effective means for producing organic devices such as organic EL elements.The process can be carried out at relatively low temperatures, which avoids thermal decomposition of the material, resulting in As a result, high performance organic devices can be obtained.

In addition to fluorine, halogens include chlorine, bromine, and iodine, but when chlorine, bromine, and iodine are substituted, the carbon bond is active, so it is chemically or electrochemically unstable, and organic devices When used as a material, drive deterioration may occur. On the other hand, carbon-fluorine bonds are inert and chemically and electrochemically stable, making them suitable as organic device materials.

In addition, since many polycyclic aromatic compound polymers have high sublimation temperatures due to their high molecular weights and high planarity, lowering the sublimation temperature by introducing fluorine atoms becomes more effective.

In addition, the emission wavelength can be shortened by introducing electron-accepting fluorine atoms. This is particularly important in display applications where blue light emission with high color purity is required.

FIG. 1 is a schematic cross-sectional view showing an organic EL element according to the present embodiment.

1. Fluorine-substituted polycyclic aromatic compound and its polymer A multimer of aromatic compounds, preferably a polycyclic aromatic compound represented by the following general formula (2), or a large amount of a polycyclic aromatic compound having a plurality of structures represented by the following general formula (2). and at least one hydrogen in these compounds or structures is replaced with fluorine. In formula (1), "A" and "C" as well as "B" in the ring are symbols indicating the ring structure represented by the ring, and the other symbols are the same as defined above.

Ring A, ring B, and ring C in general formula (1) are each independently an aryl ring or a heteroaryl ring, and at least one hydrogen in these rings may be substituted with a substituent. The substituents include substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted diarylamino, substituted or unsubstituted diheteroarylamino, substituted or unsubstituted arylheteroarylamino (aryl and (amino group with heteroaryl), substituted or unsubstituted diarylboryl (two aryls may be bonded via a single bond or a linking group), substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl , substituted or unsubstituted alkoxy, or substituted or unsubstituted aryloxy. When these groups have a substituent, examples of the substituent include aryl, heteroaryl, alkyl, and cycloalkyl. Further, the above aryl ring or heteroaryl ring may have a 5-membered ring or a 6-membered ring that shares a bond with the central condensed 2-ring structure of general formula (1) composed of Y ¹ , X ¹ and X ² . preferable.

Here, the term "fused two-ring structure" means a structure in which two saturated hydrocarbon rings containing Y ¹ , X ¹ and X ² shown in the center of general formula (1) are fused. . In addition, "a 6-membered ring that shares a bond with a fused 2-ring structure" refers to, for example, a ring a (benzene ring (6-membered ring)) fused to the fused 2-ring structure, as shown in the above general formula (2). means. In addition, "the aryl ring or heteroaryl ring (which is Ring A) has this 6-membered ring" means that Ring A is formed only with this 6-membered ring, or that it contains this 6-membered ring. This means that the A ring is formed by condensing another ring with this 6-membered ring. In other words, the term "aryl ring or heteroaryl ring having a 6-membered ring (which is Ring A)" as used herein means that the 6-membered ring constituting all or part of Ring A is fused to the fused two-ring structure. It means doing. The same explanation applies to "B ring (b ring)", "C ring (c ring)", and "5-membered ring".

Ring A (or ring B, ring C) in general formula (1) is ring a and its substituents R ¹ to R ³ in general formula (2) (or ring b and its substituents R ⁸ to R ¹¹ , c It corresponds to the ring and its substituents R ⁴ to R ⁷ ). That is, general formula (2) corresponds to a structure in which "A to C ring having a 6-membered ring" is selected as A to C rings in general formula (1). In this sense, each ring in the general formula (2) is represented by a lowercase letter a to c.

In the general formula (2), adjacent groups among the substituents R ¹ to R ¹¹ of rings a, b, and c combine to form an aryl ring or a heteroaryl ring together with rings a, b, or c. At least one hydrogen in the formed ring may be aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, diarylboryl (two aryls are connected via a single bond or a linking group). ), alkyl, cycloalkyl, alkoxy or aryloxy, and at least one hydrogen in these may be substituted with aryl, heteroaryl, alkyl or cycloalkyl. . Therefore, the polycyclic aromatic compound represented by the general formula (2) has the following formula (2-1) and the formula (2-2) depending on the mutual bonding form of the substituents in the a-ring, b-ring and c-ring. As shown in , the ring structure constituting the compound changes. Ring A', ring B' and ring C' in each formula correspond to ring A, ring B and ring C in general formula (1), respectively. Further, the definitions of R ¹ to R ¹¹ , a, b, c, Y ¹ , X ¹ and X ² in each formula are the same as those in general formula (2).

In the formula (2-1) and formula (2-2) above, the A' ring, B' ring and C' ring are adjacent to each other among the substituents R ¹ to R ¹¹ as explained in the general formula (2). This refers to an aryl ring or a heteroaryl ring formed by combining two groups together to form a-ring, b-ring, and c-ring (a fused ring formed by fusing another ring structure to a-ring, b-ring, or c-ring). ). Although not shown in the formula, there are also compounds in which all of ring a, ring b, and ring c are changed to ring A', ring B', and ring C'. Further, as can be seen from the above formulas (2-1) and (2-2), for example, R ⁸ of ring b and R ⁷ of ring c, R ¹¹ of ring b and R ¹ of ring a, R ⁴ and R ³ of ring a do not correspond to "adjacent groups" and do not bond together. That is, "adjacent groups" means groups that are adjacent on the same ring.

The compound represented by the above formula (2-1) or formula (2-2) has a benzene ring, an indole ring, a pyrrole ring, a benzofuran ring, for example, a benzene ring as a ring (or a ring b or a ring c). Or, it is a compound having an A' ring (or B' ring or C' ring) formed by condensing benzothiophene rings, and the resulting fused ring A' (or fused ring B' or fused ring C' ) are a naphthalene ring, a carbazole ring, an indole ring, a dibenzofuran ring or a dibenzothiophene ring, respectively.

Y ¹ in general formula (1) is B, P, P=O, P=S, Al, Ga, As, Si-R or Ge-R, and R of the Si-R and Ge-R is: Aryl, alkyl or cycloalkyl. In the case of P=O, P=S, Si-R or Ge-R, the atom bonded to ring A, ring B or ring C is P, Si or Ge. Y ¹ is preferably B, P, P=O, P=S or Si-R, and B is particularly preferable. This explanation is the same for ^Y1 in general formula (2).

In general formula (1), X ¹ and X ² are each independently O, NR, S or Se, and R of NR is optionally substituted aryl, substituted optionally substituted heteroaryl, optionally substituted alkyl, or optionally substituted cycloalkyl, and R in the NR is bonded to the B ring and/or the C ring through a linking group or a single bond. The linking group is preferably -O-, -S- or -C(-R) ₂ -. Note that R in the above "-C(-R) _2- " is hydrogen, alkyl, or cycloalkyl. This explanation is the same for X ¹ and X ² in general formula (2).

Here, the provision that "R of the NR is bonded to the A ring, B ring and/or C ring through a linking group or a single bond" in the general formula (1) corresponds to the general formula (2). According to the stipulation that "R in the above N-R is bonded to the a-ring, b-ring and/or c-ring through -O-, -S-, -C(-R) ₂ - or a single bond". handle.

This regulation can be expressed by a compound having a ring structure represented by the following formula (2-3-1) in which X ¹ and X ² are incorporated into fused ring B' and fused ring C'. That is, for example, a B' ^ring ( ^or C' ring). The resulting fused ring B' (or fused ring C') is, for example, a phenoxazine ring, a phenothiazine ring or an acridine ring.

In addition, the above provisions apply to compounds having a ring structure in which X ¹ and/ ^or But I can express it. That is, for example, it is a compound having an A' ring formed by condensing another ring so as to incorporate X ¹ (and/or X ² ) to the benzene ring that is the a ring in general formula (2). . The resulting fused ring A' is, for example, a phenoxazine ring, a phenothiazine ring or an acridine ring.

Examples of the "aryl ring" which is ring A, ring B, and ring C in general formula (1) include aryl rings having 6 to 30 carbon atoms, preferably aryl rings having 6 to 16 carbon atoms, and Aryl rings having 6 to 12 carbon atoms are more preferred, and aryl rings having 6 to 10 carbon atoms are particularly preferred. Note that this "aryl ring" is "an aryl ring formed by adjacent groups among R ¹ to R ¹¹ bonding together with ring a, ring b, or ring c" defined in general formula (2). Also, since ring a (or ring b, ring c) is already composed of a benzene ring with 6 carbon atoms, the total number of carbon atoms in the condensed ring with which a 5-membered ring is fused is 9, which is the lower limit of carbon atoms. It becomes a number.

Specific "aryl rings" include a monocyclic benzene ring, a biphenyl ring, a fused bicyclic naphthalene ring, and a tricyclic terphenyl ring (m-terphenyl, o -terphenyl, p-terphenyl), fused tricyclic ring systems such as acenaphthylene ring, fluorene ring, phenalene ring, phenanthrene ring, fused tetracyclic ring system such as triphenylene ring, pyrene ring, naphthacene ring, and fused pentacyclic ring system. Examples include perylene ring and pentacene ring.

Examples of the "heteroaryl ring" which is ring A, ring B, and ring C in general formula (1) include a heteroaryl ring having 2 to 30 carbon atoms, and preferably a heteroaryl ring having 2 to 25 carbon atoms. , a heteroaryl ring having 2 to 20 carbon atoms is more preferred, a heteroaryl ring having 2 to 15 carbon atoms is even more preferred, and a heteroaryl ring having 2 to 10 carbon atoms is particularly preferred. Examples of the "heteroaryl ring" include, for example, a heterocycle containing, in addition to carbon, 1 to 5 heteroatoms selected from oxygen, sulfur, and nitrogen as ring constituent atoms. In addition, this "heteroaryl ring" is a "heteroaryl formed by bonding adjacent groups among R ¹ to R ¹¹ together with ring a, ring b, or ring c," defined in general formula (2). In addition, since ring a (or ring b, ring c) is already composed of a benzene ring with 6 carbon atoms, the lower limit is 6 in total in the condensed ring with a 5-membered ring. The number of carbons is .

Specific "heteroaryl rings" include, for example, pyrrole ring, oxazole ring, isoxazole ring, thiazole ring, isothiazole ring, imidazole ring, 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, phenoxathiine ring, phenoxazine ring, phenothiazine ring, phenazine ring, indolizine ring, furan ring, Examples include benzofuran ring, isobenzofuran ring, dibenzofuran ring, thiophene ring, benzothiophene ring, dibenzothiophene ring, furazane ring, oxadiazole ring, and thianthrene ring.

At least one hydrogen in the above "aryl ring" or "heteroaryl ring" is the first substituent, substituted or unsubstituted "aryl", substituted or unsubstituted "heteroaryl", substituted or unsubstituted "aryl", substituted or unsubstituted "heteroaryl", "diarylamino", substituted or unsubstituted "diheteroarylamino", substituted or unsubstituted "arylheteroarylamino", substituted or unsubstituted "diarylboryl (two aryls are connected via a single bond or a linking group) substituted or unsubstituted "alkyl", substituted or unsubstituted "cycloalkyl", substituted or unsubstituted "alkoxy", or substituted or unsubstituted "aryloxy" However, as this first substituent, "aryl", "heteroaryl", aryl of "diarylamino", heteroaryl of "diheteroarylamino", aryl of "arylheteroarylamino" Examples of the heteroaryl, the aryl of "diarylboryl", and the aryl of "aryloxy" include the above-mentioned monovalent groups of the "aryl ring" or "heteroaryl ring".

Further, the "alkyl" as the first substituent may be either straight chain or branched chain, and includes, for example, straight chain alkyl having 1 to 24 carbon atoms or branched chain alkyl having 3 to 24 carbon atoms. Alkyl having 1 to 18 carbon atoms (branched alkyl having 3 to 18 carbon atoms) is preferable, alkyl having 1 to 12 carbon atoms (branched alkyl having 3 to 12 carbon atoms) is more preferable, and alkyl having 1 to 6 carbon atoms is preferable. (branched alkyl having 3 to 6 carbon atoms) is more preferred, and alkyl having 1 to 4 carbon atoms (branched alkyl having 3 to 4 carbon atoms) is particularly preferred.

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

In addition, "cycloalkyl" as the first substituent includes cycloalkyl having 3 to 24 carbon atoms, cycloalkyl having 3 to 20 carbon atoms, cycloalkyl having 3 to 16 carbon atoms, and cycloalkyl having 3 to 14 carbon atoms. , cycloalkyl having 5 to 10 carbon atoms, cycloalkyl having 5 to 8 carbon atoms, cycloalkyl having 5 to 6 carbon atoms, cycloalkyl having 5 carbon atoms, and the like.

Specific examples of cycloalkyl include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, and alkyl (particularly methyl) substituted products of these having 1 to 4 carbon atoms, norbornenyl, 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 .1.2]heptyl, bicyclo[2.2.2]octyl, adamantyl, diamantyl, decahydronaphthalenyl, decahydroazulenyl, and the like.

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

Specific examples of alkoxy include methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, s-butoxy, t-butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, and the like.

Further, as for "aryl" in "diarylboryl" as the first substituent, the above explanation of aryl can be cited. Further, these two aryls may be bonded via a single bond or a linking group (eg, >C(-R) ₂ , >O, >S or >NR). Here, R in >C(-R) ₂ and >N-R is aryl, heteroaryl, diarylamino, alkyl, cycloalkyl, alkoxy, or aryloxy (the above is a first substituent), and the first The substituent may be further substituted with aryl, heteroaryl, alkyl, or cycloalkyl (hereinafter referred to as the second substituent), and specific examples of these groups include the aryl, heteroaryl, and heteroaryl as the first substituent described above. References may be made to aryl, diarylamino, alkyl, cycloalkyl, alkoxy or aryloxy.

Specifically, the emission wavelength can be adjusted by the steric hindrance, electron donating and electron withdrawing properties of the structure of the first substituent, and preferably the following structural formulas (S-1) to (S-94) A group represented by any of the following, more preferably formula (S-1), formula (S-2), formula (S-5), formula (S-9) to formula (S-19), A group represented by any one of formula (S-24) to formula (S-50) and formula (S-51) to formula (S-94), more preferably a group represented by formula (S-1) or formula (S-94). (S-2), Formula (S-5), Formula (S-9), Formula (S-10), Formula (S-15), Formula (S-16), Formula (S-24), Formula ( S-30), Formula (S-46), Formula (S-48), Formula (S-50), Formula (S-51), Formula (S-56) to Formula (S-58), Formula (S -70), Formula (S-71), Formula (S-73), Formula (S-74), Formula (S-76), Formula (S-79), Formula (S-80), Formula (S- 83) and formula (S-84).

In the structural formula below, "Me" represents methyl and "tBu" represents t-butyl.

The first substituent is substituted or unsubstituted "aryl", substituted or unsubstituted "heteroaryl", substituted or unsubstituted "diarylamino", substituted or unsubstituted "diheteroarylamino", substituted or unsubstituted "arylheteroarylamino", substituted or unsubstituted "diarylboryl (two aryls may be bonded via a single bond or a linking group)", substituted or unsubstituted "alkyl", Substituted or unsubstituted "cycloalkyl," substituted or unsubstituted "alkoxy," or substituted or unsubstituted "aryloxy" is defined as substituted or unsubstituted, and at least one hydrogen thereof is It may be substituted with a second substituent. Examples of this second substituent include aryl, heteroaryl, alkyl, or cycloalkyl, and specific examples of these substituents include monovalent groups of the above-mentioned "aryl ring" or "heteroaryl ring". , reference may also be made to the explanation of "alkyl" or "cycloalkyl" as the first substituent. Further, in the aryl and heteroaryl as the second substituent, at least one hydrogen thereof is an aryl such as phenyl (specific examples are the groups mentioned above), an alkyl such as methyl (specific examples are the groups mentioned above), or A group substituted with cycloalkyl such as cyclohexyl (specific examples are the groups mentioned above) is also included in the aryl and heteroaryl as the second substituent. For example, when the second substituent is a carbazolyl group, a carbazolyl group in which at least one hydrogen at the 9-position is substituted with an aryl such as phenyl, an alkyl such as methyl, or a cycloalkyl such as cyclohexyl may also be used. It is included in heteroaryl as a substituent of 2.

Aryl, heteroaryl, aryl of diarylamino, heteroaryl of diheteroarylamino, aryl and heteroaryl of arylheteroarylamino, aryl of diarylboryl, or aryl of aryloxy in R ¹ to R ¹¹ of general formula (2) Examples include the monovalent group of the "aryl ring" or "heteroaryl ring" explained in general formula (1). For alkyl, cycloalkyl, or alkoxy in R ¹ to R ¹¹ , see the explanation of "alkyl,""cycloalkyl," or "alkoxy" as the first substituent in the explanation of general formula (1) above. can do. Furthermore, the same applies to aryl, heteroaryl, alkyl or cycloalkyl as a substituent to these groups. In addition, when adjacent groups among R ¹ to R ¹¹ are bonded together to form an aryl ring or a heteroaryl ring with ring a, ring b, or ring c, heteroaryl which is a substituent to these rings , diarylamino, diheteroarylamino, arylheteroarylamino, diarylboryl, alkyl, cycloalkyl, alkoxy or aryloxy, and the further substituents aryl, heteroaryl, alkyl or cycloalkyl.

R of Si-R and Ge-R in Y ¹ of general formula (1) is aryl, alkyl or cycloalkyl, and examples of the aryl, alkyl or cycloalkyl include the groups mentioned above. Particularly preferred are aryl having 6 to 10 carbon atoms (eg, phenyl, naphthyl, etc.), alkyl having 1 to 4 carbon atoms (eg, methyl, ethyl, etc.), or cycloalkyl having 5 to 10 carbon atoms (preferably cyclohexyl and adamantyl). This explanation is the same for ^Y1 in general formula (2).

R ⁱⁿ NR in X ¹ and At least one hydrogen may be substituted, for example by alkyl or cycloalkyl. Examples of the aryl, heteroaryl, alkyl and cycloalkyl include the groups mentioned above. In particular, aryl having 6 to 10 carbon atoms (e.g. phenyl, naphthyl, etc.), heteroaryl having 2 to 15 carbon atoms (e.g. carbazolyl, etc.), alkyl having 1 to 4 carbon atoms (e.g. methyl, ethyl, etc.) or 5 to 10 carbon atoms. cycloalkyl (preferably cyclohexyl or adamantyl) is preferred. This explanation is the same for X ¹ and X ² in general formula (2).

R in "-C(-R) ₂ --" which is a linking group in general formula (1) is hydrogen, alkyl or cycloalkyl, and examples of the alkyl and cycloalkyl include the groups mentioned above. In particular, alkyl having 1 to 4 carbon atoms (eg, methyl, ethyl, etc.) or cycloalkyl having 5 to 10 carbon atoms (preferably cyclohexyl or adamantyl) is preferred. This explanation also applies to "--C(--R) ₂ --" which is a linking group in general formula (2).

The present invention also provides a multimer of a polycyclic aromatic compound having a plurality of unit structures represented by the general formula (1), preferably a polycyclic aromatic compound having a plurality of unit structures represented by the general formula (2). It is a multimer of compounds. The multimer is preferably a dimer to hexamer, more preferably a dimer to trimer, and particularly preferably a dimer. The multimer may have a plurality of the above unit structures in one compound. For example, the above unit structure may be a single bond, a linking group such as an alkylene group having 1 to 3 carbon atoms, a phenylene group, or a naphthylene group. In addition to the form with multiple bonds (linked multimer), any ring (A ring, B ring or C ring, a ring, b ring or c ring) contained in the above unit structure is shared by multiple unit structures. In addition, any rings (A ring, B ring, C ring, a ring, b ring, or c ring) included in the above unit structure may be bonded together in this way (ring covalent multimer). may be in a form in which they are bonded together in a condensed manner (ring-fused type multimer), but ring-covalent type multimers and ring-fused type multimers are preferred, and ring-covalent type multimers are more preferred.

Examples of such multimers include the following formula (2-4), formula (2-4-1), formula (2-4-2), formula (2-5-1) to formula (2-5). -4) or a multimeric compound represented by formula (2-6). The multimer compound represented by the following formula (2-4) is represented by a plurality of general formulas (2) such that they share a benzene ring which is the a ring. It is a multimer compound (ring-covalent multimer) that has a unit structure in one compound. In addition, if the multimer compound represented by the following formula (2-4-1) is explained using the general formula (2), the two general formulas (2) share a benzene ring which is the a ring. It is a multimer compound (ring-covalent multimer) that has a unit structure represented by the following in one compound. In addition, if the multimer compound represented by the following formula (2-4-2) is explained using the general formula (2), the three general formulas (2) share a benzene ring which is the a ring. It is a multimer compound (ring-covalent multimer) that has a unit structure represented by the following in one compound. In addition, the multimer compounds represented by the following formulas (2-5-1) to (2-5-4) are benzene rings that are ring b (or ring c) when explained in general formula (2). It is a multimer compound (ring-covalent multimer) that has a plurality of unit structures represented by general formula (2) in one compound so that they share the same structure. Further, the multimer compound represented by the following formula (2-6) can be explained using the general formula (2), for example, a benzene ring which is the b ring (or a ring, c ring) of a certain unit structure and a certain unit A multimer compound having a plurality of unit structures represented by the general formula (2) in one compound (ring condensed type multimer).

The multimer compound has a multimerized form represented by formula (2-4), formula (2-4-1) or formula (2-4-2), and a multimerized form represented by formula (2-5-1) to formula (2-2). -5-4) or a multimerized form expressed by formula (2-6), the multimer may be a combination of any one of formula (2-5-1) to formula (2-5- 4) may be a combination of the multimerization form expressed by formula (2-6) and the multimerization form expressed by formula (2-4), formula (2-4), and formula (2-6). -4-1) or the multimerization form expressed by formula (2-4-2) and the multimerization form expressed by any of formulas (2-5-1) to (2-5-4). It may also be a multimer in which the multimerization form expressed by formula (2-6) is combined.

In addition, all or part of hydrogen in the chemical structure of the polycyclic aromatic compound represented by general formula (1) or (2) and its polymer may be cyano, chlorine, bromine, iodine, or deuterium. It's okay. For example, in formula (1), ring A, ring B, ring C (rings A to C are aryl rings or heteroaryl rings), substituents to rings A to C, and Y ¹ is Si-R or Ge-R. R (=alkyl, ^{cycloalkyl ,} aryl) when Alternatively, hydrogen may be substituted with deuterium, and examples include embodiments in which all or part of hydrogen in aryl or heteroaryl is substituted with cyano, chlorine, bromine, iodine, or deuterium. Among chlorine, bromine or iodine, chlorine or bromine is preferred, and chlorine is more preferred.

Moreover, the polycyclic aromatic compound and polymer thereof according to the present invention can be used as a material for organic devices. Examples of the organic device include an organic electroluminescent element, an organic field effect transistor, and an organic thin film solar cell. In particular, in organic electroluminescent devices, compounds in which Y ¹ is B, X ¹ and X ² are NR, Y ¹ is B, X ¹ is O, and X ² is NR A compound in which Y ¹ is B, X ¹ and X ² are O is preferable, and a compound in which Y ¹ is B, ^{X 1} is O, and A compound in which ¹ is ^B , ^{X 1} and X ² are O is preferred, and as an electron transport material, a compound in ^{which Y 1 is} B, X ^{1 and} Compounds in which is O are preferably used.

In addition, at least one hydrogen in the chemical structure of the polycyclic aromatic compound represented by general formula (1) or (2) and its polymer is substituted with fluorine, and all or part of the hydrogen is fluorine. It may be.

As the form of fluorine substitution, in addition to the form in which fluorine is directly substituted in the A to C rings of formula (1) and the form in which hydrogen selected as R ¹ to R ¹¹ in formula (2) is substituted with fluorine, The first substituent mentioned above is aryl, heteroaryl (especially carbazolyl group or benzocarbazolyl group), diarylamino, diheteroarylamino, arylheteroarylamino, diarylboryl (two aryls are a single bond or a linkage) at least one hydrogen of an alkyl, cycloalkyl, alkoxy or aryloxy (which may be bonded via a group), a hydrogen of an aryl, heteroaryl, alkyl or cycloalkyl which is the second substituent mentioned above At least one of them may be substituted with fluorine. Furthermore, at least one of the hydrogens in aryl, heteroaryl, alkyl, or cycloalkyl (first substituent) as R of NR, or a substituent thereto (second substituent) is fluorine. It may also be in a substituted form. Other examples include pentafluorosulfanyl group (-SF ₅ ).

Other forms of fluorine substitution include polycyclic aromatic compounds represented by general formula (1) or (2) and polymers thereof, such as fluorine-substituted aryl groups, fluorine-substituted alkyl groups, or cyclo Alkyl group, fluorine-substituted alkoxy group, fluorine-substituted diarylamino group, fluorine-substituted diarylboryl group (two aryls may be bonded via a single bond or a linking group), fluorine-substituted Examples include substitution with a carbazolyl group or a fluorine-substituted benzocarbazolyl group. Examples of the "aryl group", "alkyl group", "cycloalkyl group", "alkoxy group", "diarylamino group" and "diarylboryl group" include the groups explained as the "first substituent" above. Examples of the substitution form of fluorine on the diarylamino group, diarylboryl group, carbazolyl group and benzocarbazolyl group include examples in which some or all of the hydrogens in the aryl ring or benzene ring in these groups are substituted with fluorine. It will be done. In general formula ( ¹ ) or (2), X ¹ and The aryl of the diarylamino group as the substituent or the second substituent is preferably a fluorine-substituted aryl (especially fluorine-substituted phenyl), X ¹ and X ² are NR, and the It is more preferable that R is fluorine-substituted aryl (especially fluorine-substituted phenyl).

Examples of "aryl" substituted with fluorine include groups in which at least one hydrogen of the aryl is substituted with fluorine, but specifically, any of the following structural formulas (S-100) to (S-110) Examples include groups represented by Among these, groups represented by any of formulas (S-100) to (S-107) are preferred, and groups represented by formula (S-100), formula (S-103), and formula (S-107) are more preferred. -104) and formula (S-105). This explanation also applies when the aryl site of "diarylamino", "arylheteroarylamino", "diarylboryl" or "aryloxy" is substituted with fluorine.

Examples of "alkyl" substituted with fluorine include groups in which at least one hydrogen of the alkyl is substituted with fluorine, and specific examples include trifluoromethyl, difluoromethyl, monofluoromethyl, or pentafluoroethyl. trifluoromethyl is preferred. This explanation also applies when the alkyl moiety of "alkoxy (alkyloxy)" is substituted with fluorine. Examples of the "cycloalkyl" substituted with fluorine include a group in which at least one hydrogen of the cycloalkyl is substituted with fluorine.

Further, as a more specific example, in the polycyclic aromatic compound represented by the general formula (2) and its polymer, R ² is a fluorine-substituted diarylamino group, a fluorine-substituted diarylboryl group (2 The two aryls may be bonded via a single bond or a linking group) or a fluorine-substituted carbazolyl group.

An example of this is a polycyclic aromatic compound represented by the following general formula (2-A) or a polymer of a polycyclic aromatic compound having multiple structures represented by the following general formula (2-A). . The definition of each symbol in the structural formula is the same as the definition of each symbol in general formula (2).

Further, as specific examples of the fluorine-substituted polycyclic aromatic compounds and polymers thereof of the present invention, at least one hydrogen in one or more aromatic rings in the compound has one or more fluorine atoms. For example, compounds substituted with 1 to 2 fluorines are mentioned.

Specifically, compounds represented by the following structural formulas can be mentioned. In the following structural formula, each n is independently 0 to 2, preferably 1. In addition, "F" in the following structural formula represents fluorine, "OPh" represents a phenoxy group, and "Me" represents a methyl group.

More specific examples of the fluorine-substituted polycyclic aromatic compound of the present invention include compounds represented by the following structural formula. In the structural formula below, "F" represents fluorine, "D" represents deuterium, "Me" represents methyl group, "Et" represents ethyl group, and "tBu" represents t-butyl group.

2. Method for producing fluorine-substituted polycyclic aromatic compounds and multimers thereof Basically, the polycyclic aromatic compounds and multimers thereof represented by general formulas (1) and (2) are produced by first obtaining a ring A (a Ring), B ring (b ring) and C ring (c ring) are bonded together using a bonding group (group containing X ¹ or X ² ) to produce an intermediate (first reaction), and then A The final product can be produced by bonding a ring (a ring), a B ring (b ring), and a C ring (c ring) with a bonding group (a group containing ^Y1 ) (second reaction). For the first reaction, for example, a general reaction such as a nucleophilic substitution reaction or an Ullmann reaction can be used for an etherification reaction, and a general reaction such as a Buchwald-Hartwig reaction can be used for an amination reaction. Further, in the second reaction, a tandem hetero Friedel-Crafts reaction (continuous aromatic electrophilic substitution reaction, the same applies hereinafter) can be used. Furthermore, the compounds of the present invention can be fluorinated at desired positions by using a fluorinated raw material or adding a step of fluorination or introduction of a fluorine-containing substituent somewhere in these reaction steps. can be manufactured.

The second reaction is a reaction in which Y ¹ is introduced to bond ring A (ring a), ring B (ring b), and ring C (ring c), as shown in schemes (1) and (2) below. As an example, the case where Y ¹ is a boron atom and X ¹ and X ² are oxygen atoms is shown below. First, the hydrogen atom between X ¹ and X ² is orthometalized with n-butyllithium, sec-butyllithium, t-butyllithium, or the like. Next, boron trichloride, boron tribromide, etc. are added to perform a lithium-boron metal exchange, and a Brønsted base such as N,N-diisopropylethylamine is added to cause a tandem Bora-Friedel-Crafts reaction. can get things. In the second reaction, a Lewis acid such as aluminum trichloride may be added to accelerate the reaction. Note that the definitions of the symbols in each of the structural formulas in the following schemes (1) and (2) and in subsequent schemes (3) to (28) are the same as the above definitions.

Note that the above schemes (1) and (2) mainly show methods for producing polycyclic aromatic compounds represented by general formulas (1) and (2), but for the multimers, multiple It can be produced by using an intermediate having an A ring (a ring), a B ring (b ring) and a C ring (c ring). Details will be explained in the following schemes (3) to (5). In this case, the desired product can be obtained by doubling or tripling the amount of the reagent such as butyllithium used.

In the above scheme, lithium was introduced to the desired position by orthometalation, but it is also possible to introduce bromine atoms etc. to the desired position to introduce lithium and perform halogen-metal exchange as shown in schemes (6) and (7) below. Lithium can be introduced into desired positions.

Furthermore, regarding the method for producing the multimer explained in Scheme (3), a halogen such as a bromine atom or a chlorine atom is introduced into the position where lithium is desired to be introduced as shown in Schemes (6) and (7) above, and the halogen-metal Lithium can also be introduced into a desired position by exchange (schemes (8), (9), and (10) below).

According to this method, the desired product can be synthesized even in cases where ortho-metalation is not possible due to the influence of substituents and is useful.

By appropriately selecting the above-mentioned synthesis method and appropriately selecting the raw materials used, the desired position is fluorinated, the desired position has a substituent, Y ¹ is a boron atom, X ¹ and X ² are oxygen Polycyclic aromatic compounds that are atoms and their multimers can be synthesized.

Next, as an example, the case where Y ¹ is a boron atom and X ¹ and X ² are nitrogen atoms is shown in the following schemes (11) and (12). As in the case where X ¹ and X ² are oxygen atoms, first the hydrogen atom between X ¹ and X ² is orthometalated with n-butyllithium or the like. Next, boron tribromide or the like is added to perform lithium-boron metal exchange, and then a Brønsted base such as N,N-diisopropylethylamine is added to cause a tandem Bora-Friedel-Crafts reaction to obtain the desired product. I can do it. Here, a Lewis acid such as aluminum trichloride may be added to accelerate the reaction. Furthermore, as shown in Scheme (12') below, if the reaction is carried out at a high temperature of about 200°C, the desired product can be obtained using only boron tribromide. Furthermore, the compounds of the present invention can be fluorinated at desired positions by using a fluorinated raw material or adding a step of fluorination or introduction of a fluorine-containing substituent somewhere in these reaction steps. can be manufactured.

Also ^, for multimers in which Y ¹ is a boron atom and X ¹ and Lithium can also be introduced into a desired position by halogen-metal exchange (schemes (13), (14), and (15) below). Furthermore, as shown in the following scheme (13'), using boron triiodide and triphenylborane, even without using halogen-metal exchange, when Y ¹ is a boron atom and X ¹ and X ² are nitrogen atoms, Multimers can also be synthesized.

Next, as an example, cases where Y ¹ is phosphorus sulfide, phosphorus oxide, or a phosphorus atom, and X ¹ and X ² are oxygen atoms are shown in the following schemes (16) to (19). As before, first, the hydrogen atom between X ¹ and X ² is orthometalized with n-butyllithium or the like. Next, phosphorus trichloride and sulfur are added in this order, and finally a Lewis acid such as aluminum trichloride and a Brønsted base such as N,N-diisopropylethylamine are added to cause a tandem phosphatide Friedel-Crafts reaction, and ^Y1 is converted to phosphorus. Compounds that are sulfides can be obtained. Furthermore, by treating the obtained phosphorus sulfide compound with m-chloroperbenzoic acid (m-CPBA), a compound in which Y ¹ is phosphorus oxide can be obtained, and by treating with triethylphosphine, Y ¹ is phosphorus oxide. It is possible to obtain compounds that are atoms. Furthermore, the compounds of the present invention can be fluorinated at desired positions by using a fluorinated raw material or adding a step of fluorination or introduction of a fluorine-containing substituent somewhere in these reaction steps. can be manufactured.

Also ^, for multimers in which Y ¹ is phosphorus sulfide and X ¹ and Lithium can also be introduced into a desired position by halogen-metal exchange (Schemes (20), (21) and (22) below). Furthermore, the multimer formed in this manner in which Y ¹ is phosphorus sulfide and X ¹ and X ² are oxygen atoms can also be prepared using m-chloroperbenzoic acid ( By treatment with m-CPBA), a compound in which Y ¹ is phosphorus oxide can be obtained, and by treatment with triethylphosphine, a compound in which Y ¹ is a phosphorus atom can be obtained.

Here, an example has been described in which Y ¹ is B, P, P=O or P=S, and X ¹ and X ² are O or NR, but by appropriately changing the raw materials, Y ¹ can be Compounds in which Al, Ga, As, Si-R or Ge-R or in which X ¹ and X ² are S can also be synthesized.

In the above scheme, examples of using halogen-metal exchange and coupling reaction are given as examples of steps for producing the target product. Fluorine atoms are also included in halogens, but carbon-fluorine bonds are generally very inert, so when fluorine is used as a halogen, halogen-metal exchange and coupling reactions are generally not possible. It won't happen. Therefore, in most cases, even if fluorine atoms coexist, the reaction proceeds selectively at chlorine, bromine, or iodine positions, so even if raw materials containing fluorine atoms are used, the progress of the above-mentioned reactions will not be inhibited. Instead, compounds of the invention can be prepared that are fluorinated at desired positions.

In addition, raw materials substituted not only with fluorine atoms but also with fluorine-substituted alkyl groups, fluorine-substituted aryl groups, fluorine-substituted heteroaryl groups, fluorine-substituted aryloxy groups, or pentafluorosulfanyl groups (-SF ₅ ), etc. A compound of the present invention in which a desired position is fluorinated can be produced by using or adding a step of introducing these functional groups.

Specific examples of the solvent used in the above reaction include t-butylbenzene and xylene.

Furthermore, in the general formula (2), adjacent groups among the substituents R ¹ to R ¹¹ of rings a, b, and c are bonded together to form an aryl ring or a heteroaryl ring together with rings a, b, or c. A ring may be formed, and at least one hydrogen in the formed ring may be substituted with aryl or heteroaryl. Therefore, the polycyclic aromatic compound represented by the general formula (2) has the formula (2- As shown in 1) and formula (2-2), the ring structure constituting the compound changes. These compounds can be synthesized by applying the synthetic methods shown in schemes (1) to (19) above to the intermediates shown in schemes (23) and (24) below. Furthermore, the compounds of the present invention can be fluorinated at desired positions by using a fluorinated raw material or adding a step of fluorination or introduction of a fluorine-containing substituent somewhere in these reaction steps. can be manufactured.

In the A' ring, B' ring, and C' ring in the above formulas (2-1) and (2-2), adjacent groups among the substituents R ¹ to R ¹¹ are bonded to each other, and a It shows an aryl ring or a heteroaryl ring formed together with the ring, b ring, and c ring (it can also be said to be a fused ring formed by fusing another ring structure to the a ring, b ring, or c ring). Although not shown in the formula, there are also compounds in which all of ring a, ring b, and ring c are changed to ring A', ring B', and ring C'.

In general formula (2), "R of NR is bonded to the a-ring, b-ring and/or c-ring through -O-, -S-, -C(-R) ₂ - or a single bond. The stipulation "is present" refers to a compound having a ring structure in which X ^{1 or} Alternatively, it can be expressed by a compound having a ring structure in which X ¹ or X ² is incorporated into a condensed ring A′, as represented by formula (2-3-2) or formula (2-3-3). These compounds can be synthesized by applying the synthetic methods shown in schemes (1) to (19) above to the intermediate shown in scheme (25) below. Furthermore, the compounds of the present invention can be fluorinated at desired positions by using a fluorinated raw material or adding a step of fluorination or introduction of a fluorine-containing substituent somewhere in these reaction steps. can be manufactured.

In addition, in the synthesis methods of schemes (1) to (17) and (20) to (25) above, before adding boron trichloride, boron tribromide, etc., the hydrogen atom between X ¹ and X ² (or An example was shown in which a tandem hetero Friedel-Crafts reaction was carried out by orthometallating a halogen atom) with butyllithium, etc. However, without orthometallation using butyllithium, boron trichloride or tribromide The reaction can also be progressed by adding boron or the like.

In addition, when Y ¹ is phosphorus-based, as shown in the following schemes (26) and (27), the hydrogen atom between X ¹ and X ² (O in the following formula) is replaced with n-butyllithium, sec- By orthometallating with butyllithium or t-butyllithium, etc., then adding bisdiethylaminochlorophosphine to perform lithium-phosphorus metal exchange, and adding a Lewis acid such as aluminum trichloride, tandem phosphatide Friedel-Crafts The desired product can be obtained by reaction. This reaction method is also described in WO 2010/104047 (for example, page 27). Furthermore, the compounds of the present invention can be fluorinated at desired positions by using a fluorinated raw material or adding a step of fluorination or introduction of a fluorine-containing substituent somewhere in these reaction steps. can be manufactured.

In addition, in the above schemes (26) and (27), multimeric compounds are synthesized by using an orthometalation reagent such as butyllithium in a molar amount twice or three times the molar amount of intermediate 1. can do. Further, a halogen such as a bromine atom or a chlorine atom is introduced in advance at a position where a metal such as lithium is desired to be introduced, and the metal can be introduced into the desired position by performing halogen-metal exchange.

In addition, for polycyclic aromatic compounds represented by general formula (2-A), a desired position can be obtained by synthesizing a fluorinated intermediate and cyclizing it as shown in scheme (28) below. It is possible to synthesize polycyclic aromatic compounds in which is substituted with a fluorine atom. In scheme (28), X represents halogen or hydrogen, and the definitions of other symbols are the same as those in general formula (2).

The intermediate before cyclization in Scheme (28) can also be synthesized by the method shown in Scheme (1) and the like. That is, an intermediate having a desired substituent can be synthesized by appropriately combining Buchwald-Hartwig reaction, Suzuki coupling reaction, etherification reaction by nucleophilic substitution reaction, Ullmann reaction, etc. In these reactions, commercially available raw materials can be used as fluorinated precursors.

The compound of general formula (2-A) having a fluorinated diphenylamino group can also be synthesized, for example, by the following method. That is, after introducing a fluorinated diphenylamino group into commercially available bromopentafluorophenylbenzene and trihalogenated aniline by an amination reaction such as Buchwald-Hartwig reaction, X ¹ and X ² are NR. If X ^{1 and} Tandem bolar freeing is achieved by transmetallation with a metalation reagent such as butyl lithium, followed by a boron halide such as boron tribromide, and then a Brønsted base such as diethylisopropylamine. A compound of general formula (2-A) can be synthesized by Del-Crafts reaction. These reactions can also be applied to other fluorinated compounds.

The orthometalation reagents used in the above schemes (1) to (28) include alkyllithiums such as methyllithium, n-butyllithium, sec-butyllithium, and t-butyllithium, lithium diisopropylamide, and lithium tetramethyl. Examples include organic alkali compounds such as piperidide, lithium hexamethyldisilazide, and potassium hexamethyldisilazide.

The metal exchange reagents for metal- ^{Y 1} used in the above schemes (1) to (28) include trifluoride for Y ¹ , trichloride for Y ¹ , tribromide for Y ¹ , and triiodide for Y ¹ . Examples include halides of Y ¹ such as compounds, aminated halides of Y ¹ such as CIPN(NEt ₂ ) ₂ , alkoxides of Y ¹ , and aryl oxides of Y ¹ .

The Brønsted bases used in the above schemes (1) to (28) include N,N-diisopropylethylamine, triethylamine, 2,2,6,6-tetramethylpiperidine, 1,2,2,6,6 -Pentamethylpiperidine, N,N-dimethylaniline, N,N-dimethyltoluidine, 2,6-lutidine, sodium tetraphenylborate, potassium tetraphenylborate, triphenylborane, tetraphenylsilane, Ar ₄ BNa, Ar ₄ BK, Ar ₃ B, Ar ₄ Si (Ar is aryl such as phenyl), and the like.

The Lewis acids used in the above schemes (1) to (28) include AlCl ₃ , AlBr ₃ , AlF ₃ , BF ₃ .OEt ₂ , BCl ₃ , BBr 3 , GaCl ₃ , GaBr _{3 ,} InCl ₃ , InBr ₃ , IN (OTF) ₃ , SNCL ₄ , Snbr ₄ , Agotf, SCCL ₃ , SC (OTF), SC (OTF) _, ZNCL ₂ , ZNBR ₂ , ZN (OTF) ₂ , MGCL ₂ , MGBR ₂ , MGBR 2, MG (OTF) ₂ , LIOTF, NAOTF, NAOTF, NAOTF. , KOTf, _Me3SiOTf , Cu(OTf) ₂ , CuCl2 _{, YCl3} , Y(OTf) ₃ , _TiCl4 , _TiBr4 , _ZrCl4 , _ZrBr4 , FeCl3, _FeBr3 , _{CoCl3 ,} CoBr3 _, etc. can give.

In schemes (1) to (28) above, a Brønsted base or a Lewis acid may be used to promote the tandem hetero Friedel-Crafts reaction. However, when using a halide of Y 1 such as Y ¹ trifluoride, Y ¹ trichloride, Y ¹ tribromide, ^{Y 1} triiodide, etc., as the aromatic electrophilic substitution reaction progresses. Since acids such as , hydrogen fluoride, hydrogen chloride, hydrogen bromide, and hydrogen iodide are produced, it is effective to use a Brønsted base to scavenge the acids. On the other hand, when an aminated halide of Y ¹ or an alkoxylated compound of Y ¹ is used, a Brønsted base is often used because amines and alcohols are generated as the aromatic electrophilic substitution reaction progresses. Although not necessary, since the ability to eliminate amino groups and alkoxy groups is low, it is effective to use a Lewis acid that promotes their elimination.

In addition, the polycyclic aromatic compounds and polymers thereof of the present invention include structures in which at least some of the hydrogen atoms are substituted with cyano, structures in which they are substituted with halogens such as chlorine, bromine, and iodine, and structures in which at least some hydrogen atoms are substituted with halogens such as chlorine, bromine, and iodine, and structures in which at least some hydrogen atoms are substituted with cyano. Substituted structures are also included, but such compounds can be synthesized in the same manner as above by using raw materials that are cyanated, chlorinated, brominated, iodinated, or deuterated at the desired position. I can do it.

3. Organic Device The fluorine-substituted polycyclic aromatic compound according to the present invention can be used as a material for organic devices. Examples of the organic device include an organic electroluminescent element, an organic field effect transistor, and an organic thin film solar cell.

3-1. Organic EL device The organic EL device according to this embodiment will be described in detail below based on the drawings. FIG. 1 is a schematic cross-sectional view showing an organic EL element according to this embodiment.

<Structure of organic electroluminescent device>
The organic EL element 100 shown in FIG. 1 includes a substrate 101, an anode 102 provided on the substrate 101, a hole injection layer 103 provided on the anode 102, and a A hole transport layer 104 provided, 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 a light emitting layer 105 provided on the electron transport layer 106. It has an electron injection layer 107 and a cathode 108 provided on the electron injection layer 107.

Note that the organic EL element 100 can be manufactured in the reverse order, for example, by forming a substrate 101, a cathode 108 provided on the substrate 101, an electron injection layer 107 provided on the cathode 108, and an electron injection layer 107. an electron transport layer 106 provided on the electron transport layer 106; a light emitting layer 105 provided on the electron transport layer 106; a hole transport layer 104 provided on the light emitting layer 105; It is also possible to have a configuration including a hole injection layer 103 provided on the hole injection layer 103 and an anode 102 provided on the hole injection layer 103.

All of the above layers are not indispensable, and the minimum structural unit is the anode 102, the light emitting layer 105, and the cathode 108. Layer 107 is an optional layer. Moreover, each of the above layers may be composed of a single layer or a plurality of layers.

In addition to the above-mentioned configuration of "substrate/anode/hole injection layer/hole transport layer/light emitting layer/electron transport layer/electron injection layer/cathode", examples of the layers constituting the organic EL element include " "Substrate/Anode/Hole transport layer/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/Emissive layer/Electron transport layer/Electron injecting layer/Cathode", "Substrate/Anode/Hole transport layer/Emissive layer/Electron injecting layer/Cathode", "Substrate/Anode/Hole transport layer/Emissive 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" or "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 EL element 100, and is usually made of quartz, glass, metal, plastic, or the like. The substrate 101 is formed into a plate shape, a film shape, or a sheet shape depending on the purpose. For example, a glass plate, a metal plate, a metal foil, a plastic film, a plastic sheet, etc. are used. Among these, glass plates and plates made of transparent synthetic resins such as polyester, polymethacrylate, polycarbonate, and polysulfone are preferred. If it is a glass substrate, soda lime glass or non-alkali glass may be used, and the thickness may be sufficient to maintain mechanical strength, for example, 0.2 mm or more. The upper limit of the thickness is, for example, 2 mm or less, preferably 1 mm or less. Regarding the material of the glass, alkali-free glass is preferable because fewer ions elute from the glass, but soda lime glass coated with a barrier coating such as SiO ₂ is also commercially available, so it is recommended to use this. can. In addition, the substrate 101 may be provided with a gas barrier film such as a dense silicon oxide film on at least one side of the substrate 101 in order to improve gas barrier properties. In particular, a synthetic resin plate, film, or sheet with low gas barrier properties may be used as the substrate 101. When used, it is preferable to provide a gas barrier film.

<Anode in organic electroluminescent device>
The anode 102 plays the role of injecting holes into the light emitting layer 105. Note that 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. Examples of inorganic compounds include metals (aluminum, gold, silver, nickel, palladium, chromium, etc.), metal oxides (indium oxide, tin oxide, indium-tin oxide (ITO), indium-zinc oxide, etc.). (IZO, etc.), metal halides (copper iodide, etc.), copper sulfide, carbon black, ITO glass, Nesa glass, etc. Examples of the organic compound include polythiophenes such as poly(3-methylthiophene), conductive polymers such as polypyrrole, and polyaniline. In addition, materials that are used as anodes for organic EL devices may be selected as appropriate.

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 from the viewpoint of power consumption of the light emitting element, it is desirable that the resistance be low. For example, an ITO substrate with a resistance of 300 Ω/□ or less can function as an element electrode, but since it is now possible to supply substrates with a resistance of about 10 Ω/□, for example, 100 to 5 Ω/□, preferably 50 to 5 Ω. It is particularly desirable to use a low resistance product with /□. The thickness of ITO can be arbitrarily selected according to the resistance value, but it is usually used between 50 and 300 nm.

<Hole injection layer and hole transport layer in organic electroluminescent device>
The hole injection layer 103 plays a role of efficiently injecting holes moving from the anode 102 into the light emitting layer 105 or the hole transport layer 104. The hole transport layer 104 plays a role of efficiently transporting holes injected from the anode 102 or holes injected from the anode 102 via 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 and mixing one or more hole injection/transport materials, or by a mixture of a hole injection/transport material and a polymer binder. be done. Alternatively, the layer may 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 positive electrode between the electrodes where an electric field is applied, and the material has high hole injection efficiency and efficiently transports the injected holes. It is desirable to do so. For this purpose, it is preferable to use a substance that has a low ionization potential, high hole mobility, excellent stability, and does not easily generate trapping impurities during production and use.

Materials for forming the hole injection layer 103 and the hole transport layer 104 include compounds conventionally used as hole charge transport materials in photoconductive materials, p-type semiconductors, and hole injection layers of organic EL devices. Any compound can be selected and used from among the known compounds used in the hole transport layer. Specific examples thereof include carbazole derivatives (N-phenylcarbazole, polyvinylcarbazole, etc.), biscarbazole derivatives such as bis(N-arylcarbazole) or bis(N-alkylcarbazole), triarylamine derivatives (aromatic tertiary Polymer with amino in main chain or side chain, 1,1-bis(4-di-p-tolylaminophenyl)cyclohexane, N,N'-diphenyl-N,N'-di(3-methylphenyl)-4 ,4'-diaminobiphenyl, N,N'-diphenyl-N,N'-dinaphthyl-4,4'-diaminobiphenyl, 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-9H-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'-diamine, 4,4',4''-tris(3-methylphenyl(phenyl) triphenylamine derivatives (such as amino) triphenylamine, starburst amine derivatives, etc.), stilbene derivatives, phthalocyanine derivatives (metal-free, copper phthalocyanine, etc.), pyrazoline derivatives, hydrazone compounds, benzofuran derivatives and thiophene derivatives, oxadiazole derivatives , quinoxaline derivatives (for example, 1,4,5,8,9,12-hexaazatriphenylene-2,3,6,7,10,11-hexacarbonitrile, etc.), heterocyclic compounds such as porphyrin derivatives, polysilane, etc. As for polymer systems, polycarbonate, styrene derivatives, polyvinylcarbazole, polysilane, etc., which have the above-mentioned monomer in the side chain, are preferable, but they can form a thin film necessary for producing a light emitting device, and holes can be injected from the anode. Further, the compound is not particularly limited as long as it can transport holes.

It is also known that the conductivity of organic semiconductors is strongly influenced by their 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 with electron donating substances, strong electron acceptors such as tetracyanoquinone dimethane (TCNQ) or 2,3,5,6-tetrafluorotetracyano-1,4-benzoquinone dimethane (F4TCNQ) are known. (For example, the literature "M. Pfeiffer, A. Beyer, T. Fritz, K. Leo, Appl. Phys. Lett., 73(22), 3202-3204 (1998)" and the literature "J. Blochwitz, M. Pheiffer, T. Fritz, K. Leo, Appl. Phys. Lett., 73 (6), 729-731 (1998)). These generate so-called holes by electron transfer processes in electron-donating base materials (hole-transporting materials). Depending on the number and mobility of holes, the conductivity of the base material varies considerably. As matrix materials having hole transport properties, for example benzidine derivatives (TPD etc.) or starburst amine derivatives (TDATA etc.) or certain metal phthalocyanines (in particular zinc phthalocyanine (ZnPc) etc.) are known ( (Japanese Patent Application Publication No. 2005-167175).

<Light-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 the electrodes to which an electric field is applied. The material for forming the light-emitting layer 105 may be any compound (luminescent compound) that emits light when excited by recombination of holes and electrons, can form a stable thin film shape, and is in a solid state. It is preferable that the compound is a compound that exhibits strong luminescence (fluorescence) efficiency. In the present invention, as materials for the light-emitting layer, a host material and, for example, a polycyclic aromatic compound represented by the above general formula (1) as a dopant material can be used.

The light-emitting layer may be a single layer or composed of multiple layers, and each is formed from a material for the light-emitting layer (host material, dopant material). The host material and the dopant material may each be one type or a combination of a plurality of types. The dopant material may be contained entirely or partially in the host material. As a doping method, it can be formed by a co-evaporation method with a host material, but it may also be mixed with the host material in advance and then vapor-deposited at the same time.

The amount of host material used varies depending on the type of host material, and may be determined depending on the characteristics of the host material. The amount of the host material to be used is preferably 50 to 99.999% by weight, more preferably 80 to 99.95% by weight, and even more preferably 90 to 99.9% by weight of the entire material for the light emitting layer. It is.

The amount of dopant material to be used varies depending on the type of dopant material, and may be determined according to the characteristics of the dopant material. The amount of the dopant to be used is preferably 0.001 to 50% by weight, more preferably 0.05 to 20% by weight, and even more preferably 0.1 to 10% by weight based on the entire material for the light emitting layer. be. The above range is preferable in that, for example, concentration quenching phenomenon can be prevented.

Examples of host materials include fused ring derivatives such as anthracene, pyrene, dibenzochrysene, or fluorene, which have long been known as light emitters, bisstyryl derivatives such as bisstyrylanthracene derivatives and distyrylbenzene derivatives, tetraphenylbutadiene derivatives, and cyclopentadiene derivatives. etc. Particularly preferred are anthracene compounds, fluorene compounds, and dibenzochrysene compounds.

<Anthracene compound>
The anthracene compound as a host is, for example, a compound represented by the following general formula (3).

In general formula (3), each X is independently a group represented by the above formula (3-X1), formula (3-X2) or formula (3-X3), and The group represented by (3-X2) or formula (3-X3) is bonded to the anthracene ring of formula (3) at *. Preferably, two Xs do not simultaneously become groups represented by formula (3-X3). More preferably, two Xs do not simultaneously become groups represented by formula (3-X2).

Further, a multimer (preferably a dimer) may be formed using the structure represented by formula (3) as a unit structure. In this case, examples include a form in which the unit structures represented by formula (3) are bonded to each other via Groups having a divalent bond such as a dibenzofuran ring, a dibenzothiophene ring, a carbazole ring, a benzocarbazole ring, and a phenyl-substituted carbazole ring can be mentioned.

The naphthylene moiety in formula (3-X1) and formula (3-X2) may be fused with one benzene ring. The structure condensed in this way is as follows.

Ar ¹ and Ar ² are each independently hydrogen, phenyl, biphenylyl, terphenylyl, quaterphenylyl, naphthyl, phenanthryl, fluorenyl, benzofluorenyl, chrysenyl, triphenylenyl, pyrenylyl, or the above formula (A); The represented groups (including carbazolyl groups, benzocarbazolyl groups, and phenyl-substituted carbazolyl groups). In addition, when Ar ¹ or Ar ² is a group represented by formula (A), the group represented by formula (A) is a group represented by formula (3-X1) or formula (3-X2) in its *. Combines with naphthalene ring.

Ar ³ is phenyl, biphenylyl, terphenylyl, quaterphenylyl, naphthyl, phenanthryl, fluorenyl, benzofluorenyl, chrysenyl, triphenylenyl, pyrenylyl, or a group represented by the above formula (A) (carbazolyl group, benzocarba (also includes zolyl groups and phenyl-substituted carbazolyl groups). In addition, when Ar ³ is a group represented by formula (A), the group represented by formula (A) is bonded to the single bond represented by the straight line in formula (3-X3) at its *. . That is, the anthracene ring of formula (3) and the group represented by formula (A) are directly bonded.

Further, Ar ³ may have a substituent, and at least one hydrogen in Ar ³ may further include alkyl having 1 to 4 carbon atoms, cycloalkyl having 5 to 10 carbon atoms, phenyl, biphenylyl, terphenylyl, naphthyl, phenanthryl. , fluorenyl, chrysenyl, triphenylenyl, pyrenylyl, or a group represented by the above formula (A) (including a carbazolyl group and a phenyl-substituted carbazolyl group). Note that when the substituent that Ar ³ has is a group represented by formula (A), the group represented by formula (A) is bonded to Ar ³ in formula (3-X3) at its *.

Ar ⁴ is each independently substituted with hydrogen, phenyl, biphenylyl, terphenylyl, naphthyl, or alkyl having 1 to 4 carbon atoms (methyl, ethyl, t-butyl, etc.) and/or cycloalkyl having 5 to 10 carbon atoms This is Cyril.

Examples of alkyl having 1 to 4 carbon atoms to substitute for silyl include methyl, ethyl, propyl, i-propyl, butyl, sec-butyl, t-butyl, cyclobutyl, etc., and the three hydrogens in silyl are each independently , substituted with these alkyls.

Specific examples of "silyl substituted with alkyl having 1 to 4 carbon atoms" include trimethylsilyl, triethylsilyl, tripropylsilyl, tri-i-propylsilyl, tributylsilyl, trisec-butylsilyl, trit-butylsilyl, ethyl Dimethylsilyl, propyldimethylsilyl, i-propyldimethylsilyl, butyldimethylsilyl, sec-butyldimethylsilyl, t-butyldimethylsilyl, methyldiethylsilyl, propyldiethylsilyl, i-propyldiethylsilyl, butyldiethylsilyl, sec-butyl Diethylsilyl, t-butyldiethylsilyl, methyldipropylsilyl, ethyldipropylsilyl, butyldipropylsilyl, sec-butyldipropylsilyl, t-butyldipropylsilyl, methyldi-i-propylsilyl, ethyldi-i-propylsilyl, Examples include butyldi-i-propylsilyl, sec-butyldi-i-propylsilyl, t-butyldi-i-propylsilyl, and the like.

Cycloalkyl having 5 to 10 carbon atoms substituted for silyl is cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, norbornenyl, bicyclo[1.1.1]pentyl, bicyclo[2.0.1]pentyl, Bicyclo[1.2.1]hexyl, bicyclo[3.0.1]hexyl, bicyclo[2.1.2]heptyl, bicyclo[2.2.2]octyl, adamantyl, decahydronaphthalenyl, decahydro Examples include azulenyl, in which three hydrogens in silyl are each independently substituted with these cycloalkyl groups.

Specific examples of "silyl substituted with cycloalkyl having 5 to 10 carbon atoms" include tricyclopentylsilyl, tricyclohexylsilyl, and the like.

Substituted silyl also includes dialkylcycloalkylsilyl substituted with two alkyls and one cycloalkyl, and alkyldicycloalkylsilyl substituted with one alkyl and two cycloalkyls. Specific examples include the groups mentioned above.

Furthermore, hydrogen in the chemical structure of the anthracene compound represented by general formula (3) may be substituted with a group represented by formula (A) above. When substituted with a group represented by formula (A), the group represented by formula (A) replaces at least one hydrogen in the compound represented by formula (3) in its *.

The group represented by formula (A) is one of the substituents that the anthracene compound represented by formula (3) may have.

In the above formula (A), Y is -O-, -S- or >N-R ²⁹ , and R ²¹ to R ²⁸ are each independently hydrogen, optionally substituted alkyl, or optionally substituted cycloalkyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted alkoxy, optionally substituted aryloxy, optionally substituted arylthio, trialkylsilyl, Tricycloalkylsilyl, dialkylcycloalkylsilyl, alkyldicycloalkylsilyl, optionally substituted amino, halogen, hydroxy, or cyano, and adjacent groups among R ²¹ to R ²⁸ are bonded to each other to form a hydrocarbon ring. , may form an aryl ring or a heteroaryl ring, and R ²⁹ is hydrogen or an optionally substituted aryl.

The "alkyl" in "optionally substituted alkyl" in R ²¹ to R ²⁸ may be either straight chain or branched, for example, straight chain alkyl having 1 to 24 carbon atoms or straight chain alkyl having 3 to 24 carbon atoms. Examples include branched chain alkyl. Alkyl having 1 to 18 carbon atoms (branched alkyl having 3 to 18 carbon atoms) is preferable, alkyl having 1 to 12 carbon atoms (branched alkyl having 3 to 12 carbon atoms) is more preferable, and alkyl having 1 to 6 carbon atoms is preferable. (branched alkyl having 3 to 6 carbon atoms) is more preferred, and alkyl having 1 to 4 carbon atoms (branched alkyl having 3 to 4 carbon atoms) is particularly preferred.

Specific examples of "alkyl" include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, n-pentyl, isopentyl, neopentyl, t-pentyl, n-hexyl, 1 -Methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, n-heptyl, 1-methylhexyl, n-octyl, t-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-dodecyl, Examples include n-tridecyl, 1-hexylheptyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-eicosyl, and the like.

The "cycloalkyl" of "optionally substituted cycloalkyl" in R ²¹ to R ²⁸ includes cycloalkyl having 3 to 24 carbon atoms, cycloalkyl having 3 to 20 carbon atoms, and cycloalkyl having 3 to 16 carbon atoms. , cycloalkyl having 3 to 14 carbon atoms, cycloalkyl having 5 to 10 carbon atoms, cycloalkyl having 5 to 8 carbon atoms, cycloalkyl having 5 to 6 carbon atoms, cycloalkyl having 5 carbon atoms, and the like.

Specific examples of "cycloalkyl" include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, and alkyl (especially methyl) substituted products of these having 1 to 4 carbon atoms, norbornenyl, 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 [2.1.2]heptyl, bicyclo[2.2.2]octyl, adamantyl, diamantyl, decahydronaphthalenyl, decahydroazulenyl and the like.

The "aryl" of "optionally substituted aryl" in R ²¹ to R ²⁸ includes, for example, aryl having 6 to 30 carbon atoms, preferably aryl having 6 to 16 carbon atoms, and preferably aryl having 6 to 12 carbon atoms. aryl having 6 to 10 carbon atoms is more preferred, and aryl having 6 to 10 carbon atoms is particularly preferred.

Specific examples of "aryl" include phenyl, which is a monocyclic system, biphenylyl, which is a bicyclic system, naphthyl, which is a fused bicyclic system, and terphenylyl, which is a tricyclic system (m-terphenylyl, o-terphenylyl, p-terphenylyl). , fused tricyclic ring systems such as acenaphthylenyl, fluorenyl, phenalenyl, and phenanthrenyl; fused tetracyclic ring systems such as triphenylenyl, pyrenyl, and naphthacenyl; and fused pentacyclic ring systems such as perylenyl and pentacenyl.

Examples of the "heteroaryl" of "optionally substituted heteroaryl" in R ²¹ to R ²⁸ include heteroaryl having 2 to 30 carbon atoms, preferably heteroaryl having 2 to 25 carbon atoms, and Heteroaryl having 2 to 20 carbon atoms is more preferred, heteroaryl having 2 to 15 carbon atoms is even more preferred, and heteroaryl having 2 to 10 carbon atoms is particularly preferred. Examples of the heteroaryl include, for example, a heterocycle containing 1 to 5 heteroatoms selected from oxygen, sulfur, and nitrogen in addition to carbon as ring constituent atoms.

Specific examples of "heteroaryl" include pyrrolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, imidazolyl, oxadiazolyl, thiadiazolyl, triazolyl, tetrazolyl, pyrazolyl, pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl, triazinyl, indolyl, isoindolyl, 1H- indazolyl, benzimidazolyl, benzoxazolyl, benzothiazolyl, 1H-benzotriazolyl, quinolyl, isoquinolyl, cinnolyl, quinazolyl, quinoxalinyl, phthalazinyl, napthyridinyl, purinyl, pteridinyl, carbazolyl, acridinyl, phenoxathiinyl, phenoxazinyl, phenothiazinyl, Examples include phenazinyl, indolizinyl, furyl, benzofuranyl, isobenzofuranyl, dibenzofuranyl, thienyl, benzo[b]thienyl, dibenzothienyl, furazanyl, oxadiazolyl, thianthrenyl, naphthobenzofuranyl, and naphthobenzothienyl.

Examples of the "alkoxy" in "optionally substituted alkoxy" in R ²¹ to R ²⁸ include straight chain alkoxy having 1 to 24 carbon atoms or branched chain alkoxy having 3 to 24 carbon atoms. Alkoxy having 1 to 18 carbon atoms (branched alkoxy having 3 to 18 carbon atoms) is preferable, alkoxy having 1 to 12 carbon atoms (branched alkoxy having 3 to 12 carbon atoms) is more preferable, and alkoxy having 1 to 6 carbon atoms is preferable. Alkoxy (branched alkoxy having 3 to 6 carbon atoms) is more preferred, and alkoxy having 1 to 4 carbon atoms (branched alkoxy having 3 to 4 carbon atoms) is particularly preferred.

Specific examples of "alkoxy" include methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, s-butoxy, t-butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, and the like.

The "aryloxy" in the "optionally substituted aryloxy" in R ²¹ to R ²⁸ is a group in which the hydrogen of the -OH group is substituted with an aryl, and this aryl is the one in R ²¹ to R ²⁸ described above. Reference may be made to groups described as "aryl".

The "arylthio" in "optionally substituted arylthio" in R ²¹ to R ²⁸ is a group in which the hydrogen of the -SH group is substituted with aryl, and this aryl is the "arylthio" in "optionally substituted arylthio" in R ²¹ to R ²⁸ described above ” can be cited.

The "trialkylsilyl" in R ²¹ to R ²⁸ includes a group in which each of the three hydrogen atoms in the silyl group is independently substituted with alkyl, and this alkyl is the same as the "alkyl" in R ²¹ to R ²⁸ described above. The groups described may be cited. Preferred alkyls for substitution are those having 1 to 4 carbon atoms, and specific examples include methyl, ethyl, propyl, i-propyl, butyl, sec-butyl, t-butyl, and cyclobutyl.

Specific examples of "trialkylsilyl" include trimethylsilyl, triethylsilyl, tripropylsilyl, tri-i-propylsilyl, tributylsilyl, tri-sec-butylsilyl, tri-t-butylsilyl, ethyldimethylsilyl, propyldimethylsilyl, and i-propyl. Dimethylsilyl, butyldimethylsilyl, sec-butyldimethylsilyl, t-butyldimethylsilyl, methyldiethylsilyl, propyldiethylsilyl, i-propyldiethylsilyl, butyldiethylsilyl, sec-butyldiethylsilyl, t-butyldiethylsilyl, methyl Dipropylsilyl, ethyldipropylsilyl, butyldipropylsilyl, sec-butyldipropylsilyl, t-butyldipropylsilyl, methyldi-i-propylsilyl, ethyldi-i-propylsilyl, butyldi-i-propylsilyl, sec-butyldi-i -propylsilyl, t-butyldi-i-propylsilyl, and the like.

The "tricycloalkylsilyl" in R ²¹ to R ²⁸ includes a group in which three hydrogens in a silyl group are each independently substituted with cycloalkyl, and this cycloalkyl is the "tricycloalkylsilyl" in R ²¹ to R ²⁸ described above. Reference may be made to the groups explained as "cycloalkyl". Preferred cycloalkyl for substitution is cycloalkyl having 5 to 10 carbon atoms, specifically cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, bicyclo[1.1.1]pentyl, bicyclo[ 2.0.1] pentyl, bicyclo[1.2.1]hexyl, bicyclo[3.0.1]hexyl, bicyclo[2.1.2]heptyl, bicyclo[2.2.2]octyl, adamantyl, Examples include decahydronaphthalenyl and decahydroazulenyl.

Specific examples of "tricycloalkylsilyl" include tricyclopentylsilyl, tricyclohexylsilyl, and the like.

Specific examples of dialkylcycloalkylsilyl substituted with two alkyl and one cycloalkyl and alkyldicycloalkylsilyl substituted with one alkyl and two cycloalkyl are selected from the above-mentioned specific alkyl and cycloalkyl. Examples include silyl substituted with a group.

Examples of the "substituted amino" of the "optionally substituted amino" in R ²¹ to R ²⁸ include an amino group in which two hydrogen atoms are substituted with aryl or heteroaryl. An amino in which two hydrogens are substituted with aryl is diaryl-substituted amino, an amino in which two hydrogens are substituted with heteroaryl is diheteroaryl-substituted amino, and an amino in which two hydrogens are substituted with aryl and heteroaryl. is an arylheteroaryl substituted amino. As the aryl and heteroaryl, the groups explained as "aryl" and "heteroaryl" in R ²¹ to R ²⁸ above can be cited.

Specific examples of the "substituted amino" include diphenylamino, dinaphthylamino, phenylnaphthylamino, dipyridylamino, phenylpyridylamino, naphthylpyridylamino, and the like.

Examples of the "halogen" for R ²¹ to R ²⁸ include fluorine, chlorine, bromine, and iodine.

Some of the groups described as R ²¹ to R ²⁸ may be substituted as described above, and the substituents in this case include alkyl, cycloalkyl, aryl, or heteroaryl. As the alkyl, cycloalkyl, aryl or heteroaryl, the groups explained as "alkyl", "cycloalkyl", "aryl" or "heteroaryl" in R ²¹ to R ²⁸ above can be cited.

R ²⁹ in “>NR ²⁹ ” as Y is hydrogen or an optionally substituted aryl, and as this aryl, the groups explained as “aryl” in R ²¹ to R ²⁸ above can be cited. As the substituent, the groups explained as substituents for R ²¹ to R ²⁸ can be cited.

Adjacent groups among R ²¹ to R ²⁸ may be bonded to each other to form a hydrocarbon ring, an aryl ring, or a heteroaryl ring. A group that does not form a ring is a group represented by the following formula (A-1), and examples that form a ring include groups represented by the following formulas (A-2) to (A-14). It will be done. Note that at least one hydrogen in the group represented by any of formulas (A-1) to (A-14) is alkyl, cycloalkyl, aryl, heteroaryl, alkoxy, aryloxy, arylthio, trialkylsilyl, Optionally substituted with tricycloalkylsilyl, dialkylcycloalkylsilyl, alkyldicycloalkylsilyl, diaryl-substituted amino, diheteroaryl-substituted amino, arylheteroaryl-substituted amino, halogen, hydroxy or cyano.

Examples of the ring formed by bonding adjacent groups to each other include a cyclohexane ring in the case of a hydrocarbon ring, and examples of the aryl ring and heteroaryl ring include the above-mentioned "aryl" and "heteroaryl" in R ²¹ to R ²⁸ . These rings are formed so as to be fused with one or two benzene rings in the above formula (A-1).

Examples of the group represented by formula (A) include groups represented by any of the above formulas (A-1) to (A-14); -5) and groups represented by any of formulas (A-12) to (A-14) are preferred, and groups represented by any of formulas (A-1) to (A-4) above are preferred. is more preferable, a group represented by any one of the above formula (A-1), formula (A-3) and formula (A-4) is even more preferable, and a group represented by the above formula (A-1) is more preferably Particularly preferred.

The group represented by formula (A) is a naphthalene ring in formula (3-X1) or formula (3-X2), a single bond in formula (3-X3), or a group represented by * in formula (A). As mentioned above, it bonds with Ar ³ in (3-X3) and replaces at least one hydrogen in the compound represented by formula (3), but among these bonding forms, formula (3-X1) Alternatively, a form bonded to a naphthalene ring in formula (3-X2), a single bond in formula (3-X3), and/or Ar ³ in formula (3-X3) is preferable.

In addition, in the structure of the group represented by formula (A), a naphthalene ring in formula (3-X1) or formula (3-X2), a single bond in formula (3-X3), a single bond in formula (3-X3), ) in the structure of the group represented by formula (A), and the position substituted with at least one hydrogen in the compound represented by formula ( ³ ) is For example, either of the two benzene rings in the structure of formula (A) or an adjacent group among R ²¹ to R ²⁸ in the structure of formula (A) may be located at any position in the structure of formula (A). They can be bonded at any ring formed by bonding with each other or at any position in R ²⁹ in ">NR ²⁹ " as Y in the structure of formula (A).

Examples of the group represented by formula (A) include the following groups. Y and * in the formula have the same definitions as above.

Furthermore, all or part of hydrogen in the chemical structure of the anthracene compound represented by general formula (3) may be deuterium.

Specific examples of anthracene compounds include compounds represented by the following formulas (3-1) to (3-72). In the structural formula below, "Me" represents a methyl group, "D" represents deuterium, and "tBu" represents a t-butyl group.

The anthracene compound represented by formula (3) includes a compound having a reactive group at a desired position of the anthracene skeleton, and a compound having a reactive group in a partial structure such as X, Ar ⁴ and the structure of formula (A). can be produced by applying Suzuki coupling, Negishi coupling, and other known coupling reactions using as a starting material. Examples of the reactive group of these reactive compounds include halogen and boronic acid. As a specific manufacturing method, for example, the synthesis method in paragraphs [0089] to [0175] of International Publication No. 2014/141725 can be referred to.

<Fluorene compounds>
The compound represented by general formula (4) basically functions as a host.

In the above formula (4),
R ¹ to R ¹⁰ are each independently hydrogen, aryl, heteroaryl (the heteroaryl may be bonded to the fluorene skeleton in the above formula (4) via a linking group), diarylamino, dihetero arylamino, arylheteroarylamino, alkyl, cycloalkyl, alkenyl, alkoxy or aryloxy, in which at least one hydrogen may be substituted with aryl, heteroaryl, alkyl or cycloalkyl;
Furthermore, R ¹ and R ² , R ² and R ³ , R ³ and R ⁴ , R ⁵ and R ⁶ , R ⁶ and R ⁷ , R ⁷ and R ⁸ or R ⁹ and R ¹⁰ are each independently bonded. may form a condensed ring or a spiro ring, and at least one hydrogen in the formed ring may be an aryl or a heteroaryl (the heteroaryl may be bonded to the formed ring via a linking group). ), diarylamino, diheteroarylamino, arylheteroarylamino, alkyl, cycloalkyl, alkenyl, alkoxy or aryloxy, in which at least one hydrogen is aryl, heteroaryl, alkyl or cycloalkyl. may be replaced with, and
At least one hydrogen in the compound represented by formula (4) may be substituted with halogen, cyano, or deuterium.

For details of each group in the definition of the above formula (4), the explanation regarding the polycyclic aromatic compound of the formula (1) described above can be cited.

Examples of the alkenyl in R ¹ to R ¹⁰ include alkenyl having 2 to 30 carbon atoms, preferably alkenyl having 2 to 20 carbon atoms, more preferably alkenyl having 2 to 10 carbon atoms, and alkenyl having 2 to 6 carbon atoms. Alkenyl is more preferred, and alkenyl having 2 to 4 carbon atoms is particularly preferred. Preferred alkenyls are vinyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, or 5-hexenyl.

式（４－Ａｒ１）から式（４－Ａｒ５）中、Ｙ^１は、それぞれ独立して、Ｏ、ＳまたはＮ－Ｒであり、Ｒはフェニル、ビフェニリル、ナフチル、アントラセニルまたは水素であり、
上記式（４－Ａｒ１）から式（４－Ａｒ５）の構造における少なくとも１つの水素はフェニル、ビフェニリル、ナフチル、アントラセニル、フェナントレニル、メチル、エチル、プロピル、または、ブチルで置換されていてもよい。In addition, as a specific example of heteroaryl, any one from the following formula (4-Ar1), formula (4-Ar2), formula (4-Ar3), formula (4-Ar4) or formula (4-Ar5) Also included are monovalent groups represented by excluding one hydrogen atom.

In formulas (4-Ar1) to (4-Ar5), Y ¹ is each independently O, S or NR, R is phenyl, biphenylyl, naphthyl, anthracenyl or hydrogen,
At least one hydrogen in the structures of formulas (4-Ar1) to (4-Ar5) above may be substituted with phenyl, biphenylyl, naphthyl, anthracenyl, phenanthrenyl, methyl, ethyl, propyl, or butyl.

These heteroaryls may be bonded to the fluorene skeleton in formula (4) above via a linking group. That is, the fluorene skeleton in formula (4) and the above-mentioned heteroaryl may not only be directly bonded, but also be bonded through a linking group between them. Examples of the linking group include phenylene, biphenylene, naphthylene, anthracenylene, methylene, ethylene, -OCH ₂ CH ₂ -, -CH ₂ CH ₂ O-, or -OCH ₂ CH ₂ O-.

Furthermore, R ¹ and R ² , R ² and R ³ , R ³ and R ⁴ , R ⁵ and R ⁶ , R ⁶ and R ⁷ , or R ⁷ and R ⁸ in formula (4) are each independently bonded. R ⁹ and R ¹⁰ may combine to form a spiro ring. The condensed ring formed by R ¹ to R ⁸ is a ring condensed to the benzene ring in formula (4), and is an aliphatic ring or an aromatic ring. Preferably, it is an aromatic ring, and examples of the structure including a benzene ring in formula (4) include a naphthalene ring and a phenanthrene ring. The spiro ring formed by R ⁹ and R ¹⁰ is a ring spiro-bonded to the 5-membered ring in formula (4), and is an aliphatic ring or an aromatic ring. Preferably it is an aromatic ring, such as a fluorene ring.

The compound represented by the general formula (4) is preferably a compound represented by the following formula (4-1), formula (4-2) or formula (4-3), and each of the compounds represented by the general formula (4-1), ), a compound in which the benzene ring formed by combining R ¹ and R ² is fused, a compound in which the benzene ring formed by combining R ³ and R ⁴ in general formula (4) is fused, a compound in which the benzene ring formed by combining R 3 and R 4 in general formula (4) is fused, ) in which none of R ¹ to R ⁸ are bonded.

The definitions of R ¹ to R 10 in formula (4-1), formula (4-2), and formula ( ^4-3 ) are the same as the corresponding R ¹ to R ¹⁰ in formula (4), and The definitions of R ¹¹ to R ¹⁴ in 1) and formula (4-2) are also the same as R ¹ to R ¹⁰ in formula (4).

The compound represented by the general formula (4) is more preferably a compound represented by the following formula (4-1A), formula (4-2A) or formula (4-3A), each of which is represented by the formula (4-1A), formula (4-2A) or formula (4-3A), respectively. -1), a compound in which R ⁹ and R ¹⁰ are combined to form a spiro-fluorene ring in formula (4-1) or formula (4-3).

The definitions of R ² to R ⁷ in formula (4-1A), formula (4-2A) and formula (4-3A) are as follows in formula (4-1), formula (4-2) and formula (4-3). The definitions of R 11 to R 14 in formula (4-1A) and formula (4-2A) are the same as the corresponding R ² to R ⁷ , and the definitions of R ¹¹ to R ¹⁴ in formula (4-1) and formula (4-2) are also the same as R ¹¹ in formula (4-1) and formula (4-2). to R is the same as ¹⁴ .

Furthermore, all or part of hydrogen in the compound represented by formula (4) may be substituted with halogen, cyano, or deuterium.

<Dibenzochrysene compounds>
The dibenzochrysene compound as a host is, for example, a compound represented by the following general formula (5).

In the above formula (5),
R ¹ to R ¹⁶ each independently represent hydrogen, aryl, heteroaryl (the heteroaryl may be bonded to the dibenzochrysene skeleton in the above formula (5) via a linking group), diarylamino, diaryl, heteroarylamino, arylheteroarylamino, alkyl, cycloalkyl, alkenyl, alkoxy or aryloxy, in which at least one hydrogen may be substituted with aryl, heteroaryl, alkyl or cycloalkyl;
Further, adjacent groups among R ¹ to R ¹⁶ may be bonded to each other to form a condensed ring, and at least one hydrogen in the formed ring is an aryl or a heteroaryl (the heteroaryl is connected via a linking group). may be substituted with diarylamino, diheteroarylamino, arylheteroarylamino, alkyl, cycloalkyl, alkenyl, alkoxy or aryloxy, in which at least One hydrogen may be substituted with aryl, heteroaryl, alkyl or cycloalkyl, and
At least one hydrogen in the compound represented by formula (5) may be substituted with halogen, cyano, or deuterium.

For details of each group in the definition of the above formula (5), the explanation regarding the polycyclic aromatic compound of the formula (1) described above can be cited.

Examples of alkenyl in the definition of formula (5) above include alkenyl having 2 to 30 carbon atoms, preferably alkenyl having 2 to 20 carbon atoms, more preferably alkenyl having 2 to 10 carbon atoms, and alkenyl having 2 to 30 carbon atoms. Alkenyl having 6 carbon atoms is more preferred, and alkenyl having 2 to 4 carbon atoms is particularly preferred. Preferred alkenyls are vinyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, or 5-hexenyl.

式（５－Ａｒ１）から式（５－Ａｒ５）中、Ｙ^１は、それぞれ独立して、Ｏ、ＳまたはＮ－Ｒであり、Ｒはフェニル、ビフェニリル、ナフチル、アントラセニルまたは水素であり、
上記式（５－Ａｒ１）から式（５－Ａｒ５）の構造における少なくとも１つの水素はフェニル、ビフェニリル、ナフチル、アントラセニル、フェナントレニル、メチル、エチル、プロピル、または、ブチルで置換されていてもよい。Specific examples of heteroaryl include any one of the compounds of the following formula (5-Ar1), formula (5-Ar2), formula (5-Ar3), formula (5-Ar4), or formula (5-Ar5). Also included are monovalent groups represented by excluding one hydrogen atom.

In formulas (5-Ar1) to (5-Ar5), Y ¹ is each independently O, S or NR, R is phenyl, biphenylyl, naphthyl, anthracenyl or hydrogen,
At least one hydrogen in the structures of formulas (5-Ar1) to (5-Ar5) above may be substituted with phenyl, biphenylyl, naphthyl, anthracenyl, phenanthrenyl, methyl, ethyl, propyl, or butyl.

These heteroaryls may be bonded to the dibenzochrysene skeleton in formula (5) above via a linking group. That is, the dibenzochrysene skeleton in formula (5) and the above-mentioned heteroaryl may not only be directly bonded, but also may be bonded through a linking group between them. Examples of the linking group include phenylene, biphenylene, naphthylene, anthracenylene, methylene, ethylene, -OCH ₂ CH ₂ -, -CH ₂ CH ₂ O-, or -OCH ₂ CH ₂ O-.

In the compound represented by general formula (5), R ¹ , R ⁴ , R ⁵ , R ⁸ , R ⁹ , R ¹² , R ¹³ and R ¹⁶ are preferably hydrogen. In this case, R ² , R ³ , R ⁶ , R ⁷ , R ¹⁰ , R ¹¹ , R ¹⁴ and R ¹⁵ in formula (5) are each independently hydrogen, phenyl, biphenylyl, naphthyl, anthracenyl, phenanthrenyl. , a monovalent group having the structure of the above formula (5-Ar1), formula (5-Ar2), formula (5-Ar3), formula (5-Ar4) or formula (5-Ar5) (1 having the structure The valent group is phenylene, biphenylene, naphthylene, anthracenylene, methylene, ethylene, -OCH ₂ CH ₂ -, -CH ₂ CH ₂ O-, or -OCH ₂ CH ₂ O- via the above formula (5). ), methyl, ethyl, propyl, or butyl is preferable.

The compound represented by general formula (5) is more preferably R ¹ , R ² , R ⁴ , R ⁵ , R ⁷ , R 8 , R ⁹ , R ¹⁰ , R ¹² , R ¹³ , R ¹⁵ and ^{R 16} is hydrogen. In this case, at least one (preferably one or two, more preferably one) of R ³ , R ⁶ , R ¹¹ and R ¹⁴ in formula (5) is a single bond, phenylene, biphenylene, naphthylene, Anthracenylene, methylene, ethylene, -OCH ₂ CH ₂ -, -CH ₂ CH ₂ O-, or -OCH ₂ CH ₂ O-, the above formula (5-Ar1), formula (5-Ar2), formula (5-Ar3), a monovalent group having the structure of formula (5-Ar4) or formula (5-Ar5),
The positions other than at least one of the above (that is, positions other than those substituted by the monovalent group having the above structure) are hydrogen, phenyl, biphenylyl, naphthyl, anthracenyl, methyl, ethyl, propyl, or butyl, and at least one of these Hydrogen may be substituted with phenyl, biphenylyl, naphthyl, anthracenyl, methyl, ethyl, propyl, or butyl.

Furthermore, R ² , R ³ , R ⁶ , R ⁷ , R ¹⁰ , R ¹¹ , R ¹⁴ and R ¹⁵ in formula (5) are represented by the above formulas (5-Ar1) to (5-Ar5). When a monovalent group having a structure is selected, at least one hydrogen in the structure may bond with any of R ¹ to R ¹⁶ in formula (5) to form a single bond. .

<Electron injection layer and electron transport layer in organic electroluminescent device>
The electron injection layer 107 plays a role of efficiently injecting electrons moving from the cathode 108 into the light emitting layer 105 or the electron transport layer 106. The electron transport layer 106 plays a role of efficiently transporting electrons injected from the cathode 108 or electrons injected from the cathode 108 via the electron injection layer 107 to the light emitting layer 105. The electron transport layer 106 and the electron injection layer 107 are each formed by laminating and mixing one or more electron transport/injection materials, or by a mixture of an electron transport/injection material and a polymer binder.

The electron injection/transport layer is a layer that is in charge of injecting electrons from the cathode and further transporting electrons, and it is desirable that the electron injection efficiency is high and that the injected electrons are efficiently transported. For this purpose, it is preferable that the material has high electron affinity, high electron mobility, excellent stability, and does not easily generate trapping impurities during production and use. However, when considering the transport balance of holes and electrons, if the role is to efficiently prevent holes from the anode from flowing to the cathode side without recombining, the electron transport capacity is not so great. Even if it is not high, it has the same effect of improving luminous efficiency as a material with high electron transport ability. Therefore, the electron injection/transport layer in this embodiment may also include the function of a layer that can efficiently block the movement of holes.

The material (electron transport material) forming the electron transport layer 106 or the electron injection layer 107 may be a compound conventionally used as an electron transport compound in photoconductive materials, or a compound used in the electron injection layer and electron transport layer of an organic EL device. Any known compound may be selected and used.

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

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, diphenylquinone derivatives, perylene derivatives, and oxadiazoles. derivatives (1,3-bis[(4-t-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 oxine derivatives, quinolinol metal complexes, quinoxaline derivatives, polymers of quinoxaline derivatives, benzazole compounds, gallium complexes, pyrazole derivatives, perfluorinated phenylene derivatives, triazine derivatives, pyrazine derivatives, benzoquinolines derivatives (2,2'-bis(benzo[h]quinolin-2-yl)-9,9'-spirobifluorene, etc.), imidazopyridine derivatives, borane derivatives, benzimidazole derivatives (tris(N-phenylbenzimidazole- (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, phosphorus oxide derivatives , bisstyryl derivatives, etc.

Further, metal complexes having electron-accepting nitrogen can also be used, such as hydroxyazole complexes such as quinolinol metal complexes and hydroxyphenyloxazole complexes, azomethine complexes, tropolone metal complexes, flavonol metal complexes, and benzoquinoline metal complexes. can give.

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

Among the materials mentioned above, borane derivatives, pyridine derivatives, fluoranthene derivatives, BO derivatives, anthracene derivatives, benzofluorene derivatives, phosphine oxide derivatives, pyrimidine derivatives, carbazole derivatives, triazine derivatives, benzimidazole derivatives, phenanthroline derivatives, and quinolinol metals. Complexes are preferred.

上記式（ＥＴＭ－１）中、Ｒ^１１およびＲ^１２は、それぞれ独立して、水素、アルキル、シクロアルキル、置換されていてもよいアリール、置換されているシリル、置換されていてもよい窒素含有複素環、またはシアノの少なくとも１つであり、Ｒ^１３～Ｒ^１６は、それぞれ独立して、置換されていてもよいアルキル、置換されていてもよいシクロアルキルまたは置換されていてもよいアリールであり、Ｘは、置換されていてもよいアリーレンであり、Ｙは、置換されていてもよい炭素数１６以下のアリール、置換されているボリル、または置換されていてもよいカルバゾリルであり、そして、ｎはそれぞれ独立して０～３の整数である。また、「置換されていてもよい」または「置換されている」場合の置換基としては、アリール、ヘテロアリール、アルキルまたはシクロアルキルなどがあげられる。<Borane derivative>
The borane derivative is, for example, a compound represented by the following general formula (ETM-1), and is disclosed in detail in JP-A No. 2007-27587.

In the above formula (ETM-1), R ¹¹ and R ¹² are each independently hydrogen, alkyl, cycloalkyl, optionally substituted aryl, substituted silyl, optionally substituted nitrogen-containing is at least one of a heterocycle or cyano, and R ¹³ to R ¹⁶ are each independently an optionally substituted alkyl, an optionally substituted cycloalkyl, or an optionally substituted aryl; , X is an optionally substituted arylene, Y is an optionally substituted aryl having 16 or less carbon atoms, a substituted boryl, or an optionally substituted carbazolyl, and n are each independently an integer from 0 to 3. Further, examples of the substituent in the case of "optionally substituted" or "substituted" include aryl, heteroaryl, alkyl, and cycloalkyl.

式（ＥＴＭ－１－１）中、Ｒ^１１およびＲ^１２は、それぞれ独立して、水素、アルキル、シクロアルキル、置換されていてもよいアリール、置換されているシリル、置換されていてもよい窒素含有複素環、またはシアノの少なくとも１つであり、Ｒ^１３～Ｒ^１６は、それぞれ独立して、置換されていてもよいアルキル、置換されていてもよいシクロアルキルまたは置換されていてもよいアリールであり、Ｒ^２１およびＲ^２２は、それぞれ独立して、水素、アルキル、シクロアルキル、置換されていてもよいアリール、置換されているシリル、置換されていてもよい窒素含有複素環、またはシアノの少なくとも１つであり、Ｘ^１は、置換されていてもよい炭素数２０以下のアリーレンであり、ｎはそれぞれ独立して０～３の整数であり、そして、ｍはそれぞれ独立して０～４の整数である。また、「置換されていてもよい」または「置換されている」場合の置換基としては、アリール、ヘテロアリール、アルキルまたはシクロアルキルなどがあげられる。

式（ＥＴＭ－１－２）中、Ｒ^１１およびＲ^１２は、それぞれ独立して、水素、アルキル、シクロアルキル、置換されていてもよいアリール、置換されているシリル、置換されていてもよい窒素含有複素環、またはシアノの少なくとも１つであり、Ｒ^１３～Ｒ^１６は、それぞれ独立して、置換されていてもよいアルキル、置換されていてもよいシクロアルキルまたは置換されていてもよいアリールであり、Ｘ^１は、置換されていてもよい炭素数２０以下のアリーレンであり、そして、ｎはそれぞれ独立して０～３の整数である。また、「置換されていてもよい」または「置換されている」場合の置換基としては、アリール、ヘテロアリール、アルキルまたはシクロアルキルなどがあげられる。Among the compounds represented by the above general formula (ETM-1), compounds represented by the following general formula (ETM-1-1) and compounds represented by the following general formula (ETM-1-2) are preferred.

In formula (ETM-1-1), R ¹¹ and R ¹² are each independently hydrogen, alkyl, cycloalkyl, optionally substituted aryl, substituted silyl, optionally substituted nitrogen at least one of a containing heterocycle or cyano, and R ¹³ to R ¹⁶ are each independently an optionally substituted alkyl, an optionally substituted cycloalkyl, or an optionally substituted aryl. and R ²¹ and R ²² each independently represent at least one of hydrogen, alkyl, cycloalkyl, optionally substituted aryl, substituted silyl, optionally substituted nitrogen-containing heterocycle, or cyano. X ¹ is an optionally substituted arylene having 20 or less carbon atoms, n is each independently an integer of 0 to 3, and m is each independently an integer of 0 to 4. is an integer. Further, examples of the substituent in the case of "optionally substituted" or "substituted" include aryl, heteroaryl, alkyl, and cycloalkyl.

In formula (ETM-1-2), R ¹¹ and R ¹² are each independently hydrogen, alkyl, cycloalkyl, optionally substituted aryl, substituted silyl, optionally substituted nitrogen at least one of a containing heterocycle or cyano, and R ¹³ to R ¹⁶ are each independently an optionally substituted alkyl, an optionally substituted cycloalkyl, or an optionally substituted aryl. , X ¹ is an optionally substituted arylene having 20 or less carbon atoms, and n is each independently an integer of 0 to 3. Furthermore, examples of the substituent in the case of "optionally substituted" or "substituted" include aryl, heteroaryl, alkyl, and cycloalkyl.

（各式中、Ｒ^ａは、それぞれ独立してアルキル基、シクロアルキル基または置換されていてもよいフェニル基である。）Specific examples of X ¹ include divalent groups represented by any of the following formulas (X-1) to (X-9).

(In each formula, R ^a is each independently an alkyl group, a cycloalkyl group, or an optionally substituted phenyl group.)

Specific examples of this borane derivative include the following compounds.

This borane derivative can be produced using known raw materials and known synthesis methods.

<Pyridine derivative>
The pyridine derivative is, for example, a compound represented by the following formula (ETM-2), preferably a compound represented by the formula (ETM-2-1) or formula (ETM-2-2).

φ is an n-valent aryl ring (preferably an n-valent benzene ring, naphthalene ring, anthracene ring, fluorene ring, benzofluorene ring, phenalene ring, phenanthrene ring or triphenylene ring), and n is an integer of 1 to 4; be.

In the above formula (ETM-2-1), R ¹¹ to R ¹⁸ are each independently hydrogen, alkyl (preferably alkyl having 1 to 24 carbon atoms), and cycloalkyl (preferably cycloalkyl having 3 to 12 carbon atoms). alkyl) or aryl (preferably aryl having 6 to 30 carbon atoms).

In the above formula (ETM-2-2), R ¹¹ and R ¹² are each independently hydrogen, alkyl (preferably alkyl having 1 to 24 carbon atoms), and cycloalkyl (preferably cycloalkyl having 3 to 12 carbon atoms). alkyl) or aryl (preferably aryl having 6 to 30 carbon atoms), and R ¹¹ and R ¹² may be combined to form a ring.

In each formula, the "pyridine substituent" is one of the following formulas (Py-1) to (Py-15), and each pyridine substituent is independently an alkyl having 1 to 4 carbon atoms or a carbon It may be substituted with 5 to 10 cycloalkyl groups. Further, the pyridine substituent may be bonded to φ, anthracene ring or fluorene ring in each formula via a phenylene group or naphthylene group.

The pyridine substituent is any of the above formulas (Py-1) to (Py-15), and among these, any of the following formulas (Py-21) to (Py-44) It is preferable.

At least one hydrogen in each pyridine derivative may be substituted with deuterium, and among the two "pyridine substituents" in the above formulas (ETM-2-1) and (ETM-2-2), may be replaced with an aryl.

The "alkyl" in R ¹¹ to R ¹⁸ may be either straight chain or branched, and includes, for example, straight chain alkyl having 1 to 24 carbon atoms or branched alkyl having 3 to 24 carbon atoms. Preferred "alkyl" is alkyl having 1 to 18 carbon atoms (branched alkyl having 3 to 18 carbon atoms). More preferred "alkyl" is alkyl having 1 to 12 carbon atoms (branched alkyl having 3 to 12 carbon atoms). More preferred "alkyl" is alkyl having 1 to 6 carbon atoms (branched alkyl having 3 to 6 carbon atoms). Particularly preferred "alkyl" is alkyl having 1 to 4 carbon atoms (branched alkyl having 3 to 4 carbon atoms).

Specific examples of "alkyl" include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, n-pentyl, isopentyl, neopentyl, t-pentyl, n-hexyl, 1 -Methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, n-heptyl, 1-methylhexyl, n-octyl, t-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-dodecyl, Examples include n-tridecyl, 1-hexylheptyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-eicosyl, and the like.

As for the alkyl having 1 to 4 carbon atoms to be substituted with the pyridine substituent, the above description of alkyl can be cited.

Examples of the "cycloalkyl" in R ¹¹ to R ¹⁸ include cycloalkyl having 3 to 12 carbon atoms. Preferred "cycloalkyl" is cycloalkyl having 3 to 10 carbon atoms. More preferred "cycloalkyl" is cycloalkyl having 3 to 8 carbon atoms. More preferred "cycloalkyl" is cycloalkyl having 3 to 6 carbon atoms.
Specific examples of "cycloalkyl" include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methylcyclopentyl, cycloheptyl, methylcyclohexyl, cyclooctyl, and dimethylcyclohexyl.

As for the cycloalkyl having 5 to 10 carbon atoms to be substituted with the pyridine substituent, the above description of cycloalkyl can be cited.

As for "aryl" in R ¹¹ to R ¹⁸ , a preferable aryl is an aryl having 6 to 30 carbon atoms, a more preferable aryl is an aryl having 6 to 18 carbon atoms, and even more preferably an aryl having 6 to 14 carbon atoms. Especially preferred is aryl having 6 to 12 carbon atoms.

Specific examples of "aryl having 6 to 30 carbon atoms" include phenyl, which is a monocyclic aryl, (1-,2-)naphthyl, which is a fused bicyclic aryl, and acenaphthylene-(, which is a fused tricyclic aryl). 1-,3-,4-,5-)yl, fluorene-(1-,2-,3-,4-,9-)yl, phenalen-(1-,2-)yl, (1-,2-)yl -,3-,4-,9-)phenanthryl, fused tetracyclic aryl triphenylen-(1-,2-)yl, pyrene-(1-,2-,4-)yl, naphthacen-(1- ,2-,5-)yl, fused pentacyclic aryl perylene-(1-,2-,3-)yl, pentacen-(1-,2-,5-,6-)yl, etc. .

Preferred examples of "aryl having 6 to 30 carbon atoms" include phenyl, naphthyl, phenanthryl, chrysenyl, and triphenylenyl, more preferred are phenyl, 1-naphthyl, 2-naphthyl, and phenanthryl, and particularly preferred are phenyl, 1-naphthyl, and phenanthryl. -Naphthyl or 2-naphthyl.

R ¹¹ and R ¹² in the above formula (ETM-2-2) may be combined to form a ring, and as a result, the five-membered ring of the fluorene skeleton includes cyclobutane, cyclopentane, cyclopentene, cyclopentadiene, Cyclohexane, fluorene or indene may also be spiro-bonded.

Specific examples of this pyridine derivative include the following compounds.

This pyridine derivative can be produced using known raw materials and known synthesis methods.

<Fluoranthene derivative>
The fluoranthene derivative is, for example, a compound represented by the following general formula (ETM-3), and is disclosed in detail in International Publication No. 2010/134352.

In the above formula (ETM-3), X ¹² to X ²¹ are hydrogen, halogen, linear, branched or cyclic alkyl, linear, branched or cyclic alkoxy, substituted or unsubstituted aryl, or substituted or unsubstituted Represents a heteroaryl. Here, examples of the substituent when substituted include aryl, heteroaryl, alkyl, and cycloalkyl.

Specific examples of this fluoranthene derivative include the following compounds.

<BO derivative>
The BO derivative is, for example, a polycyclic aromatic compound represented by the following formula (ETM-4) or a multimer of a polycyclic aromatic compound having a plurality of structures represented by the following formula (ETM-4).

R ¹ to R ¹¹ are each independently hydrogen, aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, diarylboryl (two aryls are bonded via a single bond or a linking group); alkyl, cycloalkyl, alkoxy or aryloxy, in which at least one hydrogen may be substituted with aryl, heteroaryl, alkyl or cycloalkyl.

Further, adjacent groups among R ¹ to R ¹¹ may be bonded to each other to form an aryl ring or a heteroaryl ring together with ring a, ring b, or ring c, and at least one hydrogen in the formed ring is aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, diarylboryl (two aryls may be bonded via a single bond or a linking group), alkyl, cycloalkyl, alkoxy or aryl They may be substituted with oxy, and at least one hydrogen thereof may be substituted with aryl, heteroaryl, alkyl or cycloalkyl.

Furthermore, at least one hydrogen in the compound or structure represented by formula (ETM-4) may be substituted with halogen or deuterium.

For explanations of the substituents in formula (ETM-4), the form of ring formation, and the multimer formed by combining multiple structures of formula (ETM-4), The description of polycyclic aromatic compounds and multimers thereof can be cited.

Specific examples of this BO derivative include the following compounds.

This BO derivative can be produced using known raw materials and known synthesis methods.

<Anthracene derivative>
One of the anthracene derivatives is, for example, a compound represented by the following formula (ETM-5-1).

Ar is each independently divalent benzene or naphthalene, and R ¹ to R ⁴ are each independently hydrogen, alkyl having 1 to 6 carbon atoms, cycloalkyl having 3 to 6 carbon atoms, or It has 6 to 20 aryls.

Ar can be appropriately selected independently from divalent benzene or naphthalene, and the two Ars may be different or the same, but from the viewpoint of ease of synthesis of the anthracene derivative, they are the same. It is preferable that Ar combines with pyridine to form a "site consisting of Ar and pyridine", and this site can be used, for example, as an anthracene group as a group represented by any of the following formulas (Py-1) to (Py-12). is combined with

Among these groups, groups represented by any of the above formulas (Py-1) to (Py-9) are preferred, and groups represented by any of the above formulas (Py-1) to (Py-6) are preferred. More preferred are groups such as The two "sites consisting of Ar and pyridine" that bind to anthracene may have the same or different structures, but preferably have the same structure from the viewpoint of ease of synthesizing the anthracene derivative. However, from the viewpoint of device characteristics, it is preferable that the structures of the two "sites consisting of Ar and pyridine" be the same or different.

The alkyl having 1 to 6 carbon atoms in R ¹ to R ⁴ may be either straight chain or branched chain. That is, it is a straight chain alkyl having 1 to 6 carbon atoms or a branched alkyl having 3 to 6 carbon atoms. More preferred is alkyl having 1 to 4 carbon atoms (branched alkyl having 3 to 4 carbon atoms). Specific examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, n-pentyl, isopentyl, neopentyl, t-pentyl, n-hexyl, 1-methylpentyl, Examples include 4-methyl-2-pentyl, 3,3-dimethylbutyl, or 2-ethylbutyl, with methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, or t-butyl being preferred. , methyl, ethyl or t-butyl are more preferred.

Specific examples of cycloalkyl having 3 to 6 carbon atoms in R ¹ to R ⁴ include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methylcyclopentyl, cycloheptyl, methylcyclohexyl, cyclooctyl, and dimethylcyclohexyl.

The aryl having 6 to 20 carbon atoms in R ¹ to R ⁴ is preferably an aryl having 6 to 16 carbon atoms, more preferably an aryl having 6 to 12 carbon atoms, and particularly preferably an aryl having 6 to 10 carbon atoms.

Specific examples of "aryl having 6 to 20 carbon atoms" include monocyclic aryl such as phenyl, (o-,m-,p-)tolyl, (2,3-,2,4-,2,5- ,2,6-,3,4-,3,5-)xylyl, mesityl (2,4,6-trimethylphenyl), (o-,m-,p-)cumenyl, bicyclic aryl (2 -,3-,4-)biphenylyl, (1-,2-)naphthyl which is a fused bicyclic aryl, and terphenylyl (m-terphenyl-2'-yl, m-terphenyl-4) which is a tricyclic aryl. '-yl, m-terphenyl-5'-yl, o-terphenyl-3'-yl, o-terphenyl-4'-yl, p-terphenyl-2'-yl, m-terphenyl-2 -yl, m-terphenyl-3-yl, m-terphenyl-4-yl, o-terphenyl-2-yl, o-terphenyl-3-yl, o-terphenyl-4-yl, p- terphenyl-2-yl, p-terphenyl-3-yl, p-terphenyl-4-yl), fused tricyclic aryl, anthracen-(1-,2-,9-)yl, acenaphthylene- (1-,3-,4-,5-)yl, fluoren-(1-,2-,3-,4-,9-)yl, phenalen-(1-,2-)yl, (1-, 2-,3-,4-,9-)phenanthryl, fused tetracyclic aryl triphenylen-(1-,2-)yl, pyren-(1-,2-,4-)yl, tetracen-(1 -,2-,5-)yl, perylene-(1-,2-,3-)yl, which is a fused pentacyclic aryl, and the like.

Preferred "aryl having 6 to 20 carbon atoms" is phenyl, biphenylyl, terphenylyl or naphthyl, more preferably phenyl, biphenylyl, 1-naphthyl, 2-naphthyl or m-terphenyl-5'-yl, More preferably phenyl, biphenylyl, 1-naphthyl or 2-naphthyl, most preferably phenyl.

One of the anthracene derivatives is, for example, a compound represented by the following formula (ETM-5-2).

Each Ar ¹ is independently a single bond, divalent benzene, naphthalene, anthracene, fluorene, or phenalene.

Ar ² is each independently an aryl having 6 to 20 carbon atoms, and the same explanation as "aryl having 6 to 20 carbon atoms" in the above formula (ETM-5-1) can be cited. Aryl having 6 to 16 carbon atoms is preferred, aryl having 6 to 12 carbon atoms is more preferred, and aryl having 6 to 10 carbon atoms is particularly preferred. Specific examples include phenyl, biphenylyl, naphthyl, terphenylyl, anthracenyl, acenaphthylenyl, fluorenyl, phenalenyl, phenanthryl, triphenylenyl, pyrenyl, tetracenyl, perylenyl, and the like.

R ¹ to R ⁴ are each independently hydrogen, alkyl having 1 to 6 carbon atoms, cycloalkyl having 3 to 6 carbon atoms, or aryl having 6 to 20 carbon atoms, and the above formula (ETM-5-1) You can cite the explanation in .

Specific examples of these anthracene derivatives include the following compounds.

These anthracene derivatives can be produced using known raw materials and known synthesis methods.

<Benzofluorene derivative>
The benzofluorene derivative is, for example, a compound represented by the following formula (ETM-6).

Ar ¹ is each independently an aryl having 6 to 20 carbon atoms, and the same explanation as "aryl having 6 to 20 carbon atoms" in the above formula (ETM-5-1) can be cited. Aryl having 6 to 16 carbon atoms is preferred, aryl having 6 to 12 carbon atoms is more preferred, and aryl having 6 to 10 carbon atoms is particularly preferred. Specific examples include phenyl, biphenylyl, naphthyl, terphenylyl, anthracenyl, acenaphthylenyl, fluorenyl, phenalenyl, phenanthryl, triphenylenyl, pyrenyl, tetracenyl, perylenyl, and the like.

Ar ² is each independently hydrogen, alkyl (preferably alkyl having 1 to 24 carbon atoms), cycloalkyl (preferably cycloalkyl having 3 to 12 carbon atoms), or aryl (preferably aryl having 6 to 30 carbon atoms). ), and two Ar ² may be bonded to form a ring.

The "alkyl" in Ar ² may be either straight chain or branched, and includes, for example, straight chain alkyl having 1 to 24 carbon atoms or branched chain alkyl having 3 to 24 carbon atoms. Preferred "alkyl" is alkyl having 1 to 18 carbon atoms (branched alkyl having 3 to 18 carbon atoms). More preferred "alkyl" is alkyl having 1 to 12 carbon atoms (branched alkyl having 3 to 12 carbon atoms). More preferred "alkyl" is alkyl having 1 to 6 carbon atoms (branched alkyl having 3 to 6 carbon atoms). Particularly preferred "alkyl" is alkyl having 1 to 4 carbon atoms (branched alkyl having 3 to 4 carbon atoms). Specific examples of "alkyl" include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, n-pentyl, isopentyl, neopentyl, t-pentyl, n-hexyl, 1 -Methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, n-heptyl, 1-methylhexyl and the like.

Examples of the "cycloalkyl" in Ar ² include cycloalkyl having 3 to 12 carbon atoms. Preferred "cycloalkyl" is cycloalkyl having 3 to 10 carbon atoms. More preferred "cycloalkyl" is cycloalkyl having 3 to 8 carbon atoms. More preferred "cycloalkyl" is cycloalkyl having 3 to 6 carbon atoms. Specific examples of "cycloalkyl" include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methylcyclopentyl, cycloheptyl, methylcyclohexyl, cyclooctyl, and dimethylcyclohexyl.

As for "aryl" in Ar ² , preferable aryl is aryl having 6 to 30 carbon atoms, more preferable aryl is aryl having 6 to 18 carbon atoms, still more preferably aryl having 6 to 14 carbon atoms, and especially Aryl having 6 to 12 carbon atoms is preferred.

Specific examples of "aryl having 6 to 30 carbon atoms" include phenyl, naphthyl, acenaphthylenyl, fluorenyl, phenalenyl, phenanthryl, triphenylenyl, pyrenyl, naphthacenyl, perylenyl, and pentacenyl.

Two Ar ² may be combined to form a ring, and as a result, cyclobutane, cyclopentane, cyclopentene, cyclopentadiene, cyclohexane, fluorene, indene, etc. are spiro-bonded to the 5-membered ring of the fluorene skeleton. You can.

Specific examples of this benzofluorene derivative include the following compounds.

This benzofluorene derivative can be produced using known raw materials and known synthesis methods.

Ｒ^５は、置換または無置換の、炭素数１～２０のアルキル、炭素数３～２０のシクロアルキル、炭素数６～２０のアリールまたは炭素数５～２０のヘテロアリールであり、
Ｒ^６は、ＣＮ、置換または無置換の、炭素数１～２０のアルキル、炭素数３～２０のシクロアルキル、炭素数１～２０のヘテロアルキル、炭素数６～２０のアリール、炭素数５～２０のヘテロアリール、炭素数１～２０のアルコキシまたは炭素数６～２０のアリールオキシであり、
Ｒ^７およびＲ^８は、それぞれ独立して、置換または無置換の、炭素数６～２０のアリールまたは炭素数５～２０のヘテロアリールであり、
Ｒ^９は酸素または硫黄であり、
ｊは０または１であり、ｋは０または１であり、ｒは０～４の整数であり、ｑは１～３の整数である。
ここで、置換されている場合の置換基としては、アリール、ヘテロアリール、アルキルまたはシクロアルキルなどがあげられる。<Phosphine oxide derivative>
The phosphine oxide derivative is, for example, a compound represented by the following formula (ETM-7-1). Details are also described in International Publication No. 2013/079217.

R ⁵ is substituted or unsubstituted alkyl having 1 to 20 carbon atoms, cycloalkyl having 3 to 20 carbon atoms, aryl having 6 to 20 carbon atoms, or heteroaryl having 5 to 20 carbon atoms;
R ⁶ is CN, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, cycloalkyl having 3 to 20 carbon atoms, heteroalkyl having 1 to 20 carbon atoms, aryl having 6 to 20 carbon atoms, or 5 to 20 carbon atoms; 20 heteroaryl, alkoxy having 1 to 20 carbon atoms, or aryloxy having 6 to 20 carbon atoms,
R ⁷ and R ⁸ are each independently substituted or unsubstituted aryl having 6 to 20 carbon atoms or heteroaryl having 5 to 20 carbon atoms,
^R9 is oxygen or sulfur;
j is 0 or 1, k is 0 or 1, r is an integer from 0 to 4, and q is an integer from 1 to 3.
Here, examples of the substituent when substituted include aryl, heteroaryl, alkyl, and cycloalkyl.

The phosphine oxide derivative may be, for example, a compound represented by the following formula (ETM-7-2).

R ¹ to R ³ may be the same or different, and are hydrogen, an alkyl group, a cycloalkyl group, an aralkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, an alkoxy group, an alkylthio group, a cycloalkylthio group, an aryl ether group , an arylthioether group, an aryl group, a heterocyclic group, a halogen, a cyano group, an aldehyde group, a carbonyl group, a carboxyl group, an amino group, a nitro group, a silyl group, and in the condensed ring formed between adjacent substituents. selected from.

Ar ¹ may be the same or different and is an arylene group or a heteroarylene group. Ar ² may be the same or different and are an aryl group or a heteroaryl group. However, at least one of Ar ¹ and Ar ² has a substituent, or forms a condensed ring with an adjacent substituent. n is an integer from 0 to 3; when n is 0, no unsaturated structural moiety exists; when n is 3, R ¹ does not exist.

Among these substituents, the alkyl group refers to a saturated aliphatic hydrocarbon group such as a methyl group, an ethyl group, a propyl group, a butyl group, and may be unsubstituted or substituted. When substituted, there are no particular limitations on the substituent, and examples thereof include an alkyl group, an aryl group, a heterocyclic group, and the like, and this point is also common to the following description. Further, the number of carbon atoms in the alkyl group is not particularly limited, but is usually in the range of 1 to 20 from the viewpoint of availability and cost.

Further, the cycloalkyl group refers to, for example, a saturated alicyclic hydrocarbon group such as cyclopropyl, cyclohexyl, norbornyl, and adamantyl, which may be unsubstituted or substituted. The number of carbon atoms in the alkyl group moiety is not particularly limited, but is usually in the range of 3 to 20.

Furthermore, an aralkyl group refers to an aromatic hydrocarbon group via an aliphatic hydrocarbon such as a benzyl group or a phenylethyl group, and both aliphatic hydrocarbons and aromatic hydrocarbons may be unsubstituted or substituted. It doesn't matter. The number of carbon atoms in the aliphatic moiety is not particularly limited, but is usually in the range of 1 to 20.

Further, the alkenyl group refers to an unsaturated aliphatic hydrocarbon group containing a double bond, such as a vinyl group, an allyl group, a butadienyl group, etc., and it may be unsubstituted or substituted. The number of carbon atoms in the alkenyl group is not particularly limited, but is usually in the range of 2 to 20.

Furthermore, a cycloalkenyl group refers to an unsaturated alicyclic hydrocarbon group containing a double bond, such as a cyclopentenyl group, a cyclopentadienyl group, or a cyclohexene group, and may be unsubstituted or substituted. I don't mind.

Further, the alkynyl group refers to, for example, an unsaturated aliphatic hydrocarbon group containing a triple bond such as an acetylenyl group, which may be unsubstituted or substituted. The number of carbon atoms in the alkynyl group is not particularly limited, but is usually in the range of 2 to 20.

Further, the alkoxy group refers to, for example, an aliphatic hydrocarbon group such as a methoxy group via an ether bond, and the aliphatic hydrocarbon group may be unsubstituted or substituted. The number of carbon atoms in the alkoxy group is not particularly limited, but is usually in the range of 1 to 20.

Moreover, an alkylthio group is a group in which the oxygen atom of the ether bond of an alkoxy group is substituted with a sulfur atom.

Moreover, a cycloalkylthio group is a group in which the oxygen atom of the ether bond of a cycloalkoxy group is substituted with a sulfur atom.

Further, the aryl ether group refers to an aromatic hydrocarbon group such as a phenoxy group via an ether bond, and the aromatic hydrocarbon group may be unsubstituted or substituted. The number of carbon atoms in the aryl ether group is not particularly limited, but is usually in the range of 6 to 40.

Further, the arylthioether group is a group in which the oxygen atom of the ether bond of the aryl ether group is substituted with a sulfur atom.

Further, the aryl group refers to an aromatic hydrocarbon group such as a phenyl group, a naphthyl group, a biphenyl group, a phenanthryl group, a terphenyl group, and a pyrenyl group. The aryl group may be unsubstituted or substituted. The number of carbon atoms in the aryl group is not particularly limited, but is usually in the range of 6 to 40.

In addition, a heterocyclic group refers to a cyclic structural group having an atom other than carbon, such as a furanyl group, a thiophenyl group, an oxazolyl group, a pyridyl group, a quinolinyl group, and a carbazolyl group, which may be unsubstituted or substituted. I don't mind. The number of carbon atoms in the heterocyclic group is not particularly limited, but is usually in the range of 2 to 30.

Halogen refers to fluorine, chlorine, bromine, and iodine.

The aldehyde group, carbonyl group, and amino group can also include groups substituted with aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, heterocycles, and the like.

Furthermore, aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, and heterocycles may be unsubstituted or substituted.

The silyl group refers to a silicon compound group such as a trimethylsilyl group, which may be unsubstituted or substituted. The number of carbon atoms in the silyl group is not particularly limited, but is usually in the range of 3 to 20. Further, the silicon number is usually 1 to 6.

The condensed rings formed between adjacent substituents include, for example, Ar ¹ and R ² , Ar ¹ and R ³ , Ar 2 and R ² , Ar ² and R ³ , R ² and R ³ , Ar ^{1 and} It is a conjugated or non-conjugated condensed ring formed between Ar ² and the like. Here, when n is 1, two R ¹ may form a conjugated or non-conjugated condensed ring. These fused rings may contain nitrogen, oxygen, or sulfur atoms in the ring structure, or may be fused with another ring.

Specific examples of this phosphine oxide derivative include the following compounds.

This phosphine oxide derivative can be produced using known raw materials and known synthesis methods.

<Pyrimidine derivative>
The pyrimidine derivative is, for example, a compound represented by the following formula (ETM-8), preferably a compound represented by the following formula (ETM-8-1). Details are also described in International Publication No. 2011/021689.

Each Ar is independently an optionally substituted aryl or an optionally substituted heteroaryl. n is an integer of 1 to 4, preferably an integer of 1 to 3, more preferably 2 or 3.

Examples of "aryl" in "optionally substituted aryl" include aryl having 6 to 30 carbon atoms, preferably aryl having 6 to 24 carbon atoms, more preferably aryl having 6 to 20 carbon atoms, More preferably, it is an aryl having 6 to 12 carbon atoms.

Specific examples of "aryl" include phenyl, which is a monocyclic aryl, (2-,3-,4-)biphenylyl, which is a bicyclic aryl, and (1-,2-)naphthyl, which is a fused bicyclic aryl. , tricyclic aryl terphenylyl (m-terphenyl-2'-yl, m-terphenyl-4'-yl, m-terphenyl-5'-yl, o-terphenyl-3'-yl, o -terphenyl-4'-yl, p-terphenyl-2'-yl, m-terphenyl-2-yl, m-terphenyl-3-yl, m-terphenyl-4-yl, o-terphenyl -2-yl, o-terphenyl-3-yl, o-terphenyl-4-yl, p-terphenyl-2-yl, p-terphenyl-3-yl, p-terphenyl-4-yl) , fused tricyclic aryl, acenaphthylene-(1-,3-,4-,5-)yl, fluoren-(1-,2-,3-,4-,9-)yl, phenalene-(1 -,2-)yl, (1-,2-,3-,4-,9-)phenanthryl, tetracyclic aryl quaterphenylyl (5'-phenyl-m-terphenyl-2-yl), 5'-phenyl-m-terphenyl-3-yl, 5'-phenyl-m-terphenyl-4-yl, m-quaterphenylyl), fused tetracyclic aryl triphenylene-(1-,2 -)yl, pyrene-(1-,2-,4-)yl, naphthacen-(1-,2-,5-)yl, perylene-(1-,2-,3-) which is a fused pentacyclic aryl )yl, pentacen-(1-,2-,5-,6-)yl, etc.

Examples of "heteroaryl" in "optionally substituted heteroaryl" include heteroaryl having 2 to 30 carbon atoms, preferably heteroaryl having 2 to 25 carbon atoms, and heteroaryl having 2 to 20 carbon atoms. Aryl is more preferred, heteroaryl having 2 to 15 carbon atoms is even more preferred, and heteroaryl having 2 to 10 carbon atoms is particularly preferred. Examples of the heteroaryl include, for example, a heterocycle containing 1 to 5 heteroatoms selected from oxygen, sulfur, and nitrogen in addition to carbon as ring constituent atoms.

Specific heteroaryls include, for example, furyl, thienyl, pyrrolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, imidazolyl, pyrazolyl, oxadiazolyl, furazanyl, thiadiazolyl, triazolyl, tetrazolyl, pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl, triazinyl, benzofuranyl, Isobenzofuranyl, benzo[b]thienyl, indolyl, isoindolyl, 1H-indazolyl, benzimidazolyl, benzoxazolyl, benzothiazolyl, 1H-benzotriazolyl, quinolyl, isoquinolyl, cinnolyl, quinazolyl, quinoxalinyl, phthalazinyl, naphthyridinyl, purinyl , pteridinyl, carbazolyl, acridinyl, phenoxazinyl, phenothiazinyl, phenazinyl, phenoxathiinyl, thianthrenyl, indolizinyl, and the like.

Further, the above aryl and heteroaryl may be substituted, for example, each may be substituted with the above aryl or heteroaryl.

Specific examples of this pyrimidine derivative include the following compounds.

This pyrimidine derivative can be produced using known raw materials and known synthesis methods.

<Carbazole derivative>
The carbazole derivative is, for example, a compound represented by the following formula (ETM-9), or a multimer of a plurality of compounds bonded together through a single bond or the like. Details are described in US Publication No. 2014/0197386.

Each Ar is independently an optionally substituted aryl or an optionally substituted heteroaryl. n is an integer of 0 to 4, preferably an integer of 0 to 3, and more preferably 0 or 1.

Examples of "aryl" in "optionally substituted aryl" include aryl having 6 to 30 carbon atoms, preferably aryl having 6 to 24 carbon atoms, more preferably aryl having 6 to 20 carbon atoms, More preferably, it is an aryl having 6 to 12 carbon atoms.

Specific examples of "aryl" include phenyl, which is a monocyclic aryl, (2-,3-,4-)biphenylyl, which is a bicyclic aryl, and (1-,2-)naphthyl, which is a fused bicyclic aryl. , tricyclic aryl terphenylyl (m-terphenyl-2'-yl, m-terphenyl-4'-yl, m-terphenyl-5'-yl, o-terphenyl-3'-yl, o -terphenyl-4'-yl, p-terphenyl-2'-yl, m-terphenyl-2-yl, m-terphenyl-3-yl, m-terphenyl-4-yl, o-terphenyl -2-yl, o-terphenyl-3-yl, o-terphenyl-4-yl, p-terphenyl-2-yl, p-terphenyl-3-yl, p-terphenyl-4-yl) , fused tricyclic aryl, acenaphthylene-(1-,3-,4-,5-)yl, fluoren-(1-,2-,3-,4-,9-)yl, phenalene-(1 -,2-)yl, (1-,2-,3-,4-,9-)phenanthryl, tetracyclic aryl quaterphenylyl (5'-phenyl-m-terphenyl-2-yl), 5'-phenyl-m-terphenyl-3-yl, 5'-phenyl-m-terphenyl-4-yl, m-quaterphenylyl), fused tetracyclic aryl triphenylene-(1-,2 -)yl, pyrene-(1-,2-,4-)yl, naphthacen-(1-,2-,5-)yl, perylene-(1-,2-,3-) which is a fused pentacyclic aryl )yl, pentacen-(1-,2-,5-,6-)yl, etc.

Examples of "heteroaryl" in "optionally substituted heteroaryl" include heteroaryl having 2 to 30 carbon atoms, preferably heteroaryl having 2 to 25 carbon atoms, and heteroaryl having 2 to 20 carbon atoms. Aryl is more preferred, heteroaryl having 2 to 15 carbon atoms is even more preferred, and heteroaryl having 2 to 10 carbon atoms is particularly preferred. Examples of the heteroaryl include, for example, a heterocycle containing 1 to 5 heteroatoms selected from oxygen, sulfur, and nitrogen in addition to carbon as ring constituent atoms.

Specific heteroaryls include, for example, furyl, thienyl, pyrrolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, imidazolyl, pyrazolyl, oxadiazolyl, furazanyl, thiadiazolyl, triazolyl, tetrazolyl, pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl, triazinyl, benzofuranyl, Isobenzofuranyl, benzo[b]thienyl, indolyl, isoindolyl, 1H-indazolyl, benzimidazolyl, benzoxazolyl, benzothiazolyl, 1H-benzotriazolyl, quinolyl, isoquinolyl, cinnolyl, quinazolyl, quinoxalinyl, phthalazinyl, napthyridinyl, purinyl , pteridinyl, carbazolyl, acridinyl, phenoxazinyl, phenothiazinyl, phenazinyl, phenoxathiinyl, thianthrenyl, indolizinyl, and the like.

Further, the above aryl and heteroaryl may be substituted, for example, each may be substituted with the above aryl or heteroaryl.

The carbazole derivative may be a multimer in which a plurality of compounds represented by the above formula (ETM-9) are bonded through a single bond or the like. In this case, in addition to a single bond, they may be bonded through an aryl ring (preferably a polyvalent benzene ring, naphthalene ring, anthracene ring, fluorene ring, benzofluorene ring, phenalene ring, phenanthrene ring, or triphenylene ring).

Specific examples of this carbazole derivative include the following compounds.

This carbazole derivative can be produced using known raw materials and known synthesis methods.

<Triazine derivative>
The triazine derivative is, for example, a compound represented by the following formula (ETM-10), preferably a compound represented by the following formula (ETM-10-1). Details are described in US Publication No. 2011/0156013.

Each Ar is independently an optionally substituted aryl or an optionally substituted heteroaryl. n is an integer from 1 to 3, preferably 2 or 3.

Examples of "aryl" in "optionally substituted aryl" include aryl having 6 to 30 carbon atoms, preferably aryl having 6 to 24 carbon atoms, more preferably aryl having 6 to 20 carbon atoms, More preferably, it is an aryl having 6 to 12 carbon atoms.

Specific examples of "aryl" include phenyl, which is a monocyclic aryl, (2-,3-,4-)biphenylyl, which is a bicyclic aryl, and (1-,2-)naphthyl, which is a fused bicyclic aryl. , tricyclic aryl terphenylyl (m-terphenyl-2'-yl, m-terphenyl-4'-yl, m-terphenyl-5'-yl, o-terphenyl-3'-yl, o -terphenyl-4'-yl, p-terphenyl-2'-yl, m-terphenyl-2-yl, m-terphenyl-3-yl, m-terphenyl-4-yl, o-terphenyl -2-yl, o-terphenyl-3-yl, o-terphenyl-4-yl, p-terphenyl-2-yl, p-terphenyl-3-yl, p-terphenyl-4-yl) , fused tricyclic aryl, acenaphthylene-(1-,3-,4-,5-)yl, fluoren-(1-,2-,3-,4-,9-)yl, phenalene-(1 -,2-)yl, (1-,2-,3-,4-,9-)phenanthryl, tetracyclic aryl quaterphenylyl (5'-phenyl-m-terphenyl-2-yl), 5'-phenyl-m-terphenyl-3-yl, 5'-phenyl-m-terphenyl-4-yl, m-quaterphenylyl), fused tetracyclic aryl triphenylene-(1-,2 -)yl, pyrene-(1-,2-,4-)yl, naphthacen-(1-,2-,5-)yl, perylene-(1-,2-,3-) which is a fused pentacyclic aryl )yl, pentacen-(1-,2-,5-,6-)yl, etc.

Examples of "heteroaryl" in "optionally substituted heteroaryl" include heteroaryl having 2 to 30 carbon atoms, preferably heteroaryl having 2 to 25 carbon atoms, and heteroaryl having 2 to 20 carbon atoms. Aryl is more preferred, heteroaryl having 2 to 15 carbon atoms is even more preferred, and heteroaryl having 2 to 10 carbon atoms is particularly preferred. Examples of the heteroaryl include, for example, a heterocycle containing 1 to 5 heteroatoms selected from oxygen, sulfur, and nitrogen in addition to carbon as ring constituent atoms.

Specific heteroaryls include, for example, furyl, thienyl, pyrrolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, imidazolyl, pyrazolyl, oxadiazolyl, furazanyl, thiadiazolyl, triazolyl, tetrazolyl, pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl, triazinyl, benzofuranyl, Isobenzofuranyl, benzo[b]thienyl, indolyl, isoindolyl, 1H-indazolyl, benzimidazolyl, benzoxazolyl, benzothiazolyl, 1H-benzotriazolyl, quinolyl, isoquinolyl, cinnolyl, quinazolyl, quinoxalinyl, phthalazinyl, naphthyridinyl, purinyl , pteridinyl, carbazolyl, acridinyl, phenoxazinyl, phenothiazinyl, phenazinyl, phenoxathiinyl, thianthrenyl, indolizinyl, and the like.

Further, the above aryl and heteroaryl may be substituted, for example, each may be substituted with the above aryl or heteroaryl.

Specific examples of this triazine derivative include the following compounds.

This triazine derivative can be produced using known raw materials and known synthesis methods.

<Benzimidazole derivative>
The benzimidazole derivative is, for example, a compound represented by the following formula (ETM-11).

φ is an n-valent aryl ring (preferably an n-valent benzene ring, naphthalene ring, anthracene ring, fluorene ring, benzofluorene ring, phenalene ring, phenanthrene ring or triphenylene ring), and n is an integer of 1 to 4. "benzimidazole substituent" means that the pyridyl group in the "pyridine substituent" in the above formula (ETM-2), formula (ETM-2-1) and formula (ETM-2-2) is It is a substituent substituted for an imidazole group, and at least one hydrogen in the benzimidazole derivative may be substituted with deuterium.

R ¹¹ in the above benzimidazole group is hydrogen, alkyl having 1 to 24 carbon atoms, cycloalkyl having 3 to 12 carbon atoms, or aryl having 6 to 30 carbon atoms, and the above formula (ETM-2-1) and the formula ( The explanation of R ¹¹ in ETM-2-2) can be cited.

Further, φ is preferably an anthracene ring or a fluorene ring, and the structure in this case can be cited from the explanation for the above formula (ETM-2-1) or formula (ETM-2-2), and each For R ¹¹ to R ¹⁸ in the formula, the explanation for the above formula (ETM-2-1) or formula (ETM-2-2) can be cited. In addition, although the above formula (ETM-2-1) or formula (ETM-2-2) is explained in a form in which two pyridine-based substituents are bonded, when replacing these with benzimidazole-based substituents, both The pyridine substituent may be replaced with a benzimidazole substituent (i.e. n = 2), or one pyridine substituent may be replaced with a benzimidazole substituent and the other pyridine substituent may be replaced with R ¹¹ ~R ¹⁸ (ie n=1). Furthermore, for example, at least one of R ¹¹ to R ¹⁸ in the above formula (ETM-2-1) may be replaced with a benzimidazole substituent, and the "pyridine substituent" may be replaced with R ¹¹ to R ¹⁸ .

Specific examples of this benzimidazole derivative include 1-phenyl-2-(4-(10-phenylanthracen-9-yl)phenyl)-1H-benzo[d]imidazole, 2-(4-(10-( naphthalen-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(naphthalen-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- Examples include phenyl-1H-benzo[d]imidazole, 5-(9,10-di(naphthalen-2-yl)anthracen-2-yl)-1,2-diphenyl-1H-benzo[d]imidazole, and the like.

This benzimidazole derivative can be produced using known raw materials and known synthesis methods.

<Phenanthroline derivative>
The phenanthroline derivative is, for example, a compound represented by the following formula (ETM-12) or formula (ETM-12-1). Details are described in International Publication No. 2006/021982.

φ is an n-valent aryl ring (preferably an n-valent benzene ring, naphthalene ring, anthracene ring, fluorene ring, benzofluorene ring, phenalene ring, phenanthrene ring or triphenylene ring), and n is an integer of 1 to 4; be.

R ¹¹ to R ¹⁸ in each formula are each independently hydrogen, alkyl (preferably alkyl having 1 to 24 carbon atoms), cycloalkyl (preferably cycloalkyl having 3 to 12 carbon atoms), or aryl (preferably carbon aryl number 6 to 30). Further, in the above formula (ETM-12-1), any one of R ¹¹ to R ¹⁸ is bonded to φ, which is an aryl ring.

At least one hydrogen in each phenanthroline derivative may be replaced with deuterium.

As for the alkyl, cycloalkyl and aryl in R ¹¹ to R ¹⁸ , the explanation of R ¹¹ to R ¹⁸ in the above formula (ETM-2) can be cited. Further, in addition to the above-mentioned examples, φ may have the following structural formula, for example. In addition, R in the following structural formula is each independently hydrogen, methyl, ethyl, isopropyl, cyclohexyl, phenyl, 1-naphthyl, 2-naphthyl, biphenylyl, or terphenylyl.

Specific examples of this phenanthroline derivative include 4,7-diphenyl-1,10-phenanthroline, 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline, 9,10-di(1,10- phenanthrolin-2-yl)anthracene, 2,6-di(1,10-phenanthrolin-5-yl)pyridine, 1,3,5-tri(1,10-phenanthrolin-5-yl)benzene, 9,9' -difluoro-bi(1,10-phenanthrolin-5-yl), bathocuproine, 1,3-bis(2-phenyl-1,10-phenanthrolin-9-yl)benzene and compounds represented by the following structural formula, etc. can give.

This phenanthroline derivative can be produced using known raw materials and known synthesis methods.

式中、Ｒ^１～Ｒ^６は、それぞれ独立して、水素、フッ素、アルキル、シクロアルキル、アラルキル、アルケニル、シアノ、アルコキシまたはアリールであり、ＭはＬｉ、Ａｌ、Ｇａ、ＢｅまたはＺｎであり、ｎは１～３の整数である。<Quinolinol metal complex>
The quinolinol metal complex is, for example, a compound represented by the following general formula (ETM-13).

where R ¹ to R ⁶ are each independently hydrogen, fluorine, alkyl, cycloalkyl, aralkyl, alkenyl, cyano, alkoxy or aryl, and M is Li, Al, Ga, Be or Zn; n is an integer from 1 to 3.

Specific examples of quinolinol metal complexes include lithium 8-quinolinol, tris(8-quinolinolate)aluminum, tris(4-methyl-8-quinolinolate)aluminum, 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-quinolinolate)(4-phenylphenolate)aluminum, bis(2-methyl-8-quinolinolate)(2,3-dimethylphenolate)aluminum, bis(2-methyl-8-quinolinolate)( 2,6-dimethylphenolate)aluminum, bis(2-methyl-8-quinolinolate)(3,4-dimethylphenolate)aluminum, bis(2-methyl-8-quinolinolate)(3,5-dimethylphenolate) Aluminum, bis(2-methyl-8-quinolinolate)(3,5-di-t-butylphenolate)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-quinolinolate)(1-naphthlate)aluminum, bis(2-methyl-8-quinolinolate)(2 -naphthorate)aluminum, bis(2,4-dimethyl-8-quinolinolate)(2-phenylphenolate)aluminum, bis(2,4-dimethyl-8-quinolinolate)(3-phenylphenolate)aluminum, bis(2-dimethyl-8-quinolinolate)(3-phenylphenolate)aluminum, ,4-dimethyl-8-quinolinolate)(4-phenylphenolate)aluminum, bis(2,4-dimethyl-8-quinolinolate)(3,5-dimethylphenolate)aluminum, bis(2,4-dimethyl-8 -quinolinolate)(3,5-di-t-butylphenolate)aluminum, bis(2-methyl-8-quinolinolate)aluminum-μ-oxo-bis(2-methyl-8-quinolinolate)aluminum, bis(2, 4-dimethyl-8-quinolinolate)aluminum-μ-oxo-bis(2,4-dimethyl-8-quinolinolate)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-quinolinolate) aluminum-μ-oxo-bis(2-methyl-4-methoxy-8-quinolinolate) aluminum, Bis(2-methyl-5-cyano-8-quinolinolate)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, and the like.

This quinolinol metal complex can be produced using known raw materials and known synthesis methods.

ベンゾチアゾール誘導体は、例えば下記式（ＥＴＭ－１４－２）で表される化合物である。

<Thiazole derivatives and benzothiazole derivatives>
The thiazole derivative is, for example, a compound represented by the following formula (ETM-14-1).

The benzothiazole derivative is, for example, a compound represented by the following formula (ETM-14-2).

In each formula, φ is an n-valent aryl ring (preferably an n-valent benzene ring, naphthalene ring, anthracene ring, fluorene ring, benzofluorene ring, phenalene ring, phenanthrene ring, or triphenylene ring), and n is 1 to 4. is an integer of "thiazole-based substituent" and "benzothiazole-based substituent" in the above formula (ETM-2), formula (ETM-2-1) and formula (ETM-2-2). The pyridyl group in "Substituent" is a substituent substituted for the following thiazole group or benzothiazole group, and at least one hydrogen in the thiazole derivative and benzothiazole derivative may be substituted with deuterium.

Further, φ is preferably an anthracene ring or a fluorene ring, and the structure in this case can be cited from the explanation for the above formula (ETM-2-1) or formula (ETM-2-2), and each For R ¹¹ to R ¹⁸ in the formula, the explanation for the above formula (ETM-2-1) or formula (ETM-2-2) can be cited. In addition, although the above formula (ETM-2-1) or formula (ETM-2-2) is explained in a form in which two pyridine-based substituents are bonded, these are replaced by a thiazole-based substituent (or benzothiazole-based substituent). group), both pyridine-based substituents may be replaced with a thiazole-based substituent (or benzothiazole-based substituent) (i.e., n = 2), or any one pyridine-based substituent may be replaced with a thiazole-based substituent. (or benzothiazole-based substituent) and the other pyridine-based substituent may be replaced with R ¹¹ to R ¹⁸ (ie, n=1). Further, for example, by replacing at least one of R ¹¹ to R ¹⁸ in the above formula (ETM-2-1) with a thiazole substituent (or benzothiazole substituent), the "pyridine substituent" can be replaced with R ¹¹ to R ¹⁸ You can also replace it with

These thiazole derivatives or benzothiazole derivatives can be produced using known raw materials and known synthesis methods.

The electron transport layer or the electron injection layer may further contain a substance that can reduce the material forming the electron transport layer or the electron injection layer. A variety of substances can be used as this reducing substance as long as it has a certain reducing property, such as alkali metals, alkaline earth metals, rare earth metals, alkali metal oxides, alkali metal halides, and alkali metals. From the group consisting of earth metal oxides, alkaline earth metal halides, rare earth metal oxides, rare earth metal halides, alkali metal organic complexes, alkaline earth metal organic complexes, and rare earth metal organic complexes At least one selected can be suitably 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), and Ca (work function: 2.3 eV). Examples include alkaline earth metals such as Sr (2.0 to 2.5 eV), Sr (2.0 to 2.5 eV), and Ba (2.52 eV), and substances with a work function of 2.9 eV or less are particularly preferred. Among these, more preferable reducing substances are alkali metals such as K, Rb, or Cs, still more preferably Rb or Cs, and most preferable is Cs. These alkali metals have particularly high reducing ability, and by adding a relatively small amount to the material forming the electron transport layer or the electron injection layer, the luminance of the organic EL element can be improved and the life of the organic EL element can be extended. Further, as a reducing substance with a work function of 2.9 eV or less, a combination of two or more of these alkali metals is also preferable, and in particular, a combination containing Cs, such as Cs and Na, Cs and K, Cs and Rb, or A combination of Cs, Na and K is preferred. By including Cs, the reducing ability can be efficiently exhibited, and by adding it to the material forming the electron transport layer or the electron injection layer, the luminance of light emission and the longevity of the organic EL element can be improved.

<Cathode in organic electroluminescent device>
The cathode 108 serves to inject electrons into the light emitting layer 105 via 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 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 their alloys (magnesium-silver alloy, magnesium - indium alloys, aluminum-lithium alloys such as lithium fluoride/aluminum), etc.) are preferred. In order to increase electron injection efficiency and improve device characteristics, 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 the atmosphere. In order to improve this point, a method is known in which, for example, the organic layer is doped with a trace amount of lithium, cesium, or magnesium to use a highly stable electrode. Other dopants that can also be used are inorganic salts such as lithium fluoride, cesium fluoride, lithium oxide, and cesium oxide. However, it is not limited to these.

Additionally, metals such as platinum, gold, silver, copper, iron, tin, aluminum and indium, or alloys of these metals, as well as inorganic materials such as silica, titania and silicon nitride, polyvinyl alcohol, and vinyl chloride, are used to protect the electrodes. A preferred example is to laminate a hydrocarbon polymer compound or the like. The method for producing these electrodes is not particularly limited as long as conduction can be achieved, such as resistance heating, electron beam evaporation, sputtering, ion plating, and coating.

<Binders that may be used in each layer>
The above materials used for the hole injection layer, hole transport layer, light emitting layer, electron transport layer and electron injection layer can be used alone to form each layer, but polyvinyl chloride, polycarbonate, Polystyrene, poly(N-vinylcarbazole), polymethyl methacrylate, polybutyl methacrylate, polyester, polysulfone, polyphenylene oxide, polybutadiene, hydrocarbon resin, ketone resin, phenoxy resin, polyamide, ethyl cellulose, vinyl acetate resin, ABS resin, polyurethane resin It can also be used by dispersing it in solvent-soluble resins such as phenol resins, xylene resins, petroleum resins, urea resins, melamine resins, unsaturated polyester resins, alkyd resins, epoxy resins, and curable resins such as silicone resins. be.

<Method for manufacturing organic electroluminescent device>
Each layer constituting an organic EL element is formed into a thin film using a method such as evaporation, resistance heating evaporation, electron beam evaporation, sputtering, molecular lamination, printing, spin coating, casting, or coating. By doing so, it can be formed. The 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. When forming a thin film using an evaporation method, the evaporation conditions vary depending on the type of material, the intended crystal structure and association structure of the film, and so on. Generally, the deposition conditions are: boat heating temperature +50 to +400°C, vacuum degree 10 ^-6 to 10 ^-3 Pa, deposition rate 0.01 to 50 nm/sec, substrate temperature -150 to +300°C, and film thickness 2 nm to 5 μm. It is preferable to set it appropriately within a range.

Next, as an example of a method for producing an organic EL device, an organic EL device consisting of an anode/hole injection layer/hole transport layer/light emitting layer made of a host material and dopant material/electron transport layer/electron injection layer/cathode will be described. The manufacturing method will be explained. After a thin film of an anode material is formed on a suitable substrate by vapor deposition or the like to produce an anode, thin films of a hole injection layer and a hole transport layer are formed on this anode. On top of this, a host material and a dopant material are co-deposited to form a thin film 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 of a cathode material is further formed by vapor deposition or the like. By forming it and using it as a cathode, the desired organic EL element can be obtained. In addition, in the production of the above-mentioned organic EL element, it is also possible to reverse the production order and produce the cathode, electron injection layer, electron transport layer, light emitting layer, hole transport layer, hole injection layer, and anode in this order. It is.

When applying a direct current voltage to the organic EL element obtained in this way, it is sufficient to apply it with the anode as + polarity and the cathode as - polarity. Luminescence can be observed from the sides (anode or cathode, or both). This organic EL element also emits light when pulsed current or alternating current is applied. Note that the waveform of the applied alternating current may be arbitrary.

<Application examples of organic electroluminescent devices>
Further, the present invention can be applied to a display device equipped with an organic EL element or a lighting device equipped with an organic EL element.
A display device or a lighting device equipped with an organic EL element can be manufactured by a known method such as connecting the organic EL element according to this embodiment with a known drive device, and can be manufactured by a known method such as direct current drive, pulse drive, alternating current drive, etc. It can be driven using a known driving method as appropriate.

Examples of display devices include panel displays such as color flat panel displays, flexible displays such as flexible color organic electroluminescent (EL) displays, etc. (Refer to the official gazette, Japanese Patent Application Laid-open No. 2004-281086, etc.). In addition, examples of display methods include matrix and/or segment methods. Note that matrix display and segment display may coexist in the same panel.

In a matrix, display pixels are arranged two-dimensionally in a grid or mosaic pattern, and characters or images are displayed as a collection of pixels. The shape and size of pixels are determined by the application. For example, rectangular pixels with sides of 300 μm or less are usually used to display images and characters on computers, monitors, and televisions, and in the case of large displays such as display panels, pixels with sides of mm order are used. become. In the case of monochrome display, pixels of the same color may be arranged, but in the case of color display, red, green, and blue pixels are displayed side by side. In this case, there are typically delta types and striped types. As a driving method for this matrix, either a line sequential driving method or an active matrix driving method may be used. Line sequential driving has the advantage of a simpler structure, but when considering operating characteristics, active matrix driving may be superior in some cases, so it is necessary to use it properly depending on the application.

In the segment method (type), a pattern is formed to display predetermined information, and a predetermined area is caused to emit light. Examples include time and temperature displays on digital clocks and thermometers, operating status displays on audio equipment and electromagnetic cookers, and panel displays on automobiles.

Examples of lighting devices include lighting devices for indoor lighting, backlights for liquid crystal display devices, etc. etc.). Backlights are mainly used for the purpose of improving the visibility of display devices that do not emit light by themselves, and are used in liquid crystal display devices, watches, audio devices, automobile panels, display boards, signs, and the like. In particular, considering that it is difficult to reduce the thickness of liquid crystal display devices, especially backlights for personal computers where thinning is an issue, since conventional systems consist of fluorescent lamps and light guide plates, this embodiment A backlight using a light emitting element according to the above is characterized by being thin and lightweight.

3-2. Other Organic Devices The polycyclic aromatic compound according to the present invention can be used in the production of organic field effect transistors, organic thin film solar cells, etc. 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 a source electrode and a drain electrode. When a voltage is applied to the gate electrode, an electric field is generated, and the flow of electrons (or holes) flowing between the source and drain electrodes can be arbitrarily blocked and the current can be controlled. Field-effect transistors are easier to miniaturize than simple transistors (bipolar transistors), and are often used as elements constituting integrated circuits and the like.

The structure of an organic field effect transistor is usually such that a source electrode and a drain electrode are provided in contact with an organic semiconductor active layer formed using the polycyclic aromatic compound according to the present invention, and a source electrode and a drain electrode are further provided in contact with the organic semiconductor active layer. A gate electrode may be provided with an insulating layer (dielectric layer) sandwiched therebetween. 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 is It can be applied as a pixel drive switching element for active matrix drive type liquid crystal displays and organic electroluminescent displays.

An organic thin film solar cell has 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 laminated 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 polycyclic aromatic compound according to the present invention 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 polycyclic aromatic compound according to the present invention can function as a hole transport material or an electron transport material in an organic thin film solar cell. The organic thin film solar cell may appropriately include 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 the organic thin film solar cell, known materials used for organic thin film solar cells can be appropriately selected and used in combination.

EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited thereto. First, a synthesis example of a polycyclic aromatic compound will be explained below.

Synthesis example (1)
Synthesis of compound (1-1)

Under a nitrogen atmosphere, 1,2,3-trichloro-5-trifluoromethylbenzene (10.0 g), bis(4-(t-butyl)phenyl)amine (24.8 g), bis(dibenzylideneacetone)palladium ( 0) (Pd(dba) ₂ , 0.46 g), 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl (SPhos, 0.82 g), sodium-t-butoxide (NaOtBu, 9.6 g) and xylene (130 ml) was heated and stirred at 110° C. for 1 hour. After the reaction solution was cooled to room temperature, water and ethyl acetate were added to separate the layers. After washing the organic layer with water, the solvent was distilled off under reduced pressure. Thereafter, it was purified using a silica gel short column (eluent: toluene) and reprecipitated with heptane to obtain Intermediate A (17.1 g).

To a flask containing Intermediate A (17.0 g) and t-butylbenzene (120 ml) was added t-butyllithium/pentane solution (1.62 M, 28.4 ml) under a nitrogen atmosphere while cooling in an ice bath. added. After the dropwise addition was completed, the temperature was raised to 60°C and stirred for 1 hour, and components with a boiling point lower than t-butylbenzene were distilled off under reduced pressure. The mixture was cooled to −50° C., boron tribromide (11.5 g) was added, and the mixture was heated to room temperature and stirred for 0.5 hour. Thereafter, the mixture was cooled again in an ice bath and N,N-diisopropylethylamine (5.9 g) was added. The mixture was stirred at room temperature until the heat generation subsided, then heated to 100° C. and stirred for 1 hour. The reaction solution was cooled to room temperature, an aqueous sodium acetate solution cooled in an ice bath, and then ethyl acetate were added to separate the layers, and the solvent was distilled off under reduced pressure and washed with heptane. Next, it was purified with a silica gel short column (eluent: toluene), further precipitated with heptane, and finally purified by sublimation to obtain the compound of formula (1-1) (3.2 g).

The structure of the obtained compound was confirmed by NMR measurement.
¹ H-NMR (400 MHz, CDCl ₃ ): δ = 1.5 (s, 18H), 1.5 (s, 18H), 6.4 (s, 2H), 7.8 (d, 2H), 7 .3 (m, 4H), 7.6 (dd, 2H), 7.7 (m, 4H), 9.0 (d, 2H).

Synthesis example (2)
Synthesis of compound (1-82)

Under a nitrogen atmosphere, 1,3,5-tribromobenzene (1.57 g), 4,4'-difluorodiphenylamine (3.28 g), tris(dibenzylideneacetone)dipalladium(0) (Pd ₂ (dba) ₃ , 0.229 g), tri-t-butylphosphine (0.101 g), calcium-t-butoxide (KOtBu, 2.24 g), and toluene (40 ml) were heated and stirred at 100° C. for 20 hours. After the reaction solution was cooled to room temperature, it was filtered through a Florisil (registered trademark) pad, and dichloromethane was further passed through it. After concentrating the filtrate, the crude product obtained by concentration was washed with methanol to obtain Intermediate B (2.84 g).

Boron tribromide (19.0 μl, 0.20 mmol) was added to Intermediate B (0.137 g, 0.20 mmol) and 2,4-dichlorobenzene (2.0 ml) at room temperature under a nitrogen atmosphere, and the mixture was heated at 200°C. Stirred for 20 hours. Thereafter, the mixture was cooled to room temperature, N,N-diisopropylethylamine (0.10 ml, 0.6 mmol) was added, and the solvent was distilled off under reduced pressure. The crude product was washed with acetonitrile to obtain the compound of formula (1-82) as a yellow solid (0.128 g, yield 92%).

The structure of the obtained compound was confirmed by NMR measurement and mass spectrometry.
¹ H NMR (δppm in CDCl ₃ ); 5.44 (s, 2H), 6.67 (dd, 2H), 6.82-6.93 (m, 8H), 7.12 (ddd, 2H), 7.16-7.23 (m, 8H), 8.42 (dd, 2H).
^13C NMR (δppm in CDCl ₃ ); 96.9 (2C), 116.0 (4C), 118.0 (4C), 118.4-118.8 (7C), 125.2 (2C), 127 .7 (4C), 132.0 (4C), 138.0 (2C), 142.2 (2C), 144.2 (2C), 148.2 (2C), 151.9 (1C), 157. 2 (2C), 159.7 (2C), 162.3 (2C).
HRMS (DART) m/z [M+H] ⁺ calcd for C ₄₂ H ₂₄ BF ₆ N ₃ 696.2046, observed 696.2097.

Synthesis example (3)
Synthesis of compound (1-701)

Intermediate B (0.138 g, 0.20 mmol), 1,2-dichlorobenzene (5 ml) were added with boron triiodide (0.391 g, 0.10 mmol) and triphenylborane (96.7 mg) at room temperature under nitrogen atmosphere. , 0.40 mmol) and stirred at 200°C for 20 hours. Thereafter, the mixture was cooled to room temperature, N,N-diisopropylethylamine (0.52 ml, 3 mmol) was added, and the solvent was distilled off under reduced pressure. The crude product was washed with acetonitrile to obtain the compound of formula (1-701) as a yellow solid (81.9 mg, yield 58%).

The structure of the obtained compound was confirmed by NMR measurement and mass spectrometry.
¹ H NMR (500 MHz, (CDCl ₂ ) ₂ ) δ=5.10 (s, 1 H, a), 6.87 (dd, J=4.5, 9.0 Hz, 2 H), 7.14-7. 35 (m, 12H), 8.23 (dd, J = 4.5, 9.5Hz, 2H), 8.38 (dd, J = 3.0, 9.0Hz, 2H), 8.46 (dd , J=3.0, 9.0Hz, 2H).
^13C NMR (101MHz, (CDCl ₂ ) ₂ ) δ = 92.6 (2C), 93.2 (1C), 93.7 (2C), 99.5 (1C), 110.4 (2C), 116 .3-119.2 (m, 6C), 124.6 (2C), 125.7 (dd, J _CF =7.2, 20.4Hz, 2C), 131.2 (2C), 131. 7 (2C), 132.1 (2C), 137.4 (2C), 142.9 (2C), 143.7 (2C), 146.8 (2C), 149.9 (4C), 157.5 (d, J _C-F =242.3Hz, 2C), 158.9 (d, J _C-F =245.9Hz, 2C), 162.4 (d, J _C-F =254.3Hz, 2C) ．．
¹¹ B NMR (128 MHz, (CDCl ₂ ) ₂ ) δ=37.2.
^19F NMR (376 MHz, (CDCl ₂ ) ₂ ) δ=-123.0, -119.0, -112.3.
HRMS (DART) m/z [M+H] ⁺ calcd for C ₄₂ H ₂₁ B ₂ F ₆ N ₃ 704.1888; observed 704.1918.

Synthesis example (4)
Compound (1-883): 5,9-bis(2,6-difluorophenyl)-2,7,12-tris(2,6-dimethylphenyl)-5,9-dihydro-5,9-diaza Synthesis of -13b-boranaphtho[3,2,1-de]anthracene

Under a nitrogen atmosphere, 1-bromo-4-iodobenzene (14.2 g, 50.0 mmol), 2,6-dimethylphenylboronic acid (7.50 g, 50.0 mmol), tetrakis(triphenylphosphine)palladium (Pd( A flask containing PPh ₃ ) ₄ , 1.16 g, 1.00 mmol), potassium carbonate (20.7 g, 150 mmol), toluene (175 ml), and methanol (75.0 ml) was heated to 80° C. and stirred for 36 hours. did. After the reaction solution was cooled to room temperature, it was poured into water, and the aqueous layer was extracted with toluene. The obtained organic layer was washed with water and dried over anhydrous magnesium sulfate. This solution was concentrated under reduced pressure, and the residue was purified with a silica gel column (eluent: hexane) to obtain 4'-bromo-2,6-dimethyl-1,1'-biphenyl as a white solid ( 9.71 g, yield 74%).

The structure of the obtained compound was confirmed by NMR measurement.
¹ H-NMR (500 MHz, CDCl ₃ ): δ = 2.02 (s, 6H), 7.00-7.04 (m, 2H), 7.10 (d, J = 7.5Hz, 2H), 7.17 (t, J=8.0Hz, 1H), 7.53-7.56 (m, 2H).

Under a nitrogen atmosphere, 4'-bromo-2,6-dimethyl-1,1'-biphenyl (9.14 g, 35.0 mmol), 2,6-difluoroaniline (5.31 ml, 52.5 mmol), Pd ₂ ( dba) ₃ (0.481 g, 0.525 mmol), 2,2'-bis(diphenylphosphino)-1,1'-binaphthyl (BINAP, 0.654 g, 1.05 mmol), NaOtBu (5.05 g, 52 .5 mmol) and toluene (175 ml) was heated to 110° C. and stirred for 12 hours. After the reaction solution was cooled to room temperature, it was poured into water, and the aqueous layer was extracted with toluene. The obtained organic layer was washed with water and dried over anhydrous magnesium sulfate. This solution was concentrated under reduced pressure, and the residue was purified using a silica gel short pass column (eluent: hexane/toluene = 3/1 (volume ratio)), and further washed with hexane to obtain N-(2,6- Difluorophenyl)-2',6'-dimethyl-[1,1'-biphenyl]-4-amine was obtained as a white solid (9.93 g, yield 92%).

The structure of the obtained compound was confirmed by NMR measurement.
¹ H-NMR (500 MHz, CDCl ₃ ): δ = 2.06 (s, 6H), 5.53 (s, 1H), 6.87 (d, J = 8.6Hz, 2H), 6.94- 7.06 (m, 5H), 7.07-7.17 (m, 3H).

Under nitrogen atmosphere, 1-bromo-3,5-dichlorobenzene (11.3 g, 50.0 mmol), 2,6-dimethylphenylboronic acid (9.00 g, 60.0 mmol), Pd(PPh ₃ ) ₄ (1 A flask containing potassium carbonate (20.7 g, 150 mmol), toluene (175 ml), and methanol (75.0 ml) was heated to 65° C. and stirred for 16 hours. After the reaction solution was cooled to room temperature, it was poured into water, and the aqueous layer was extracted with toluene. The obtained organic layer was washed with water and dried over anhydrous magnesium sulfate. This solution was concentrated under reduced pressure, and the residue was purified using a silica gel column (eluent: hexane) to obtain 3',5'-dichloro-2,6-dimethyl-1,1'-biphenyl as a colorless liquid. (11.8 g, yield 94%).

The structure of the obtained compound was confirmed by NMR measurement.
^1H -NMR (500MHz, CDCl ₃ ): δ = 2.03 (s, 6H), 7.05 (d, J = 1.7Hz, 2H), 7.09 (d, J = 7.5Hz, 2H ), 7.17 (t, J=7.5Hz, 1H), 7.35 (t, J=1.7Hz, 1H).

Under nitrogen atmosphere, 3',5'-dichloro-2,6-dimethyl-1,1'-biphenyl (3.01 g, 12.0 mmol), N-(2,6-difluorophenyl)-2',6'-dimethyl-[1,1'-biphenyl]-4-amine (8.17 g, 26.4 mmol), Pd ₂ (dba) ₃ (0.275 g, 0.300 mmol), SPhos (0.246 g, 0.600 mmol) ), NaOtBu (2.54 g, 26.4 mmol), and toluene (60.0 ml) were heated to 110° C. and stirred for 16 hours. After the reaction solution was cooled to room temperature, it was poured into water, and the aqueous layer was extracted with toluene. The obtained organic layer was washed with water and dried over anhydrous magnesium sulfate. This solution was concentrated under reduced pressure, and the residue was purified using a silica gel short pass column (eluent: hexane/toluene = 3/1 (volume ratio)), and further washed with methanol and hexane sequentially to remove N ³ , N ⁵ -Bis(2,6-difluorophenyl)-N ³ ,N ⁵ -bis(2',6'-dimethyl-[1,1'-biphenyl]-4-yl)-2',6'-dimethyl- [1,1'-biphenyl]-3,5-diamine was obtained as a white solid (8.08 g, yield 85%).

The structure of the obtained compound was confirmed by NMR measurement.
¹ H-NMR (500 MHz, CDCl ₃ ): δ = 2.01 (s, 12H), 2.10 (s, 6H), 6.46 (d, J = 2.0Hz, 2H), 6.83 ( t, J=2.4Hz, 1H), 6.89-6.98 (m, 8H), 7.03-7.17 (m, 15H).

Under nitrogen atmosphere, N ³ ,N ⁵ -bis(2,6-difluorophenyl)-N ³ ,N ⁵ -bis(2',6'-dimethyl-[1,1'-biphenyl]-4-yl)- 2',6'-dimethyl-[1,1'-biphenyl]-3,5-diamine (1.59 g, 2.00 mmol), boron triiodide (6.26 g, 16.0 mmol), and 1,2 A flask containing ,4-trichlorobenzene (20.0 ml) was heated to 150° C. and stirred for 12 hours. After the reaction solution was cooled to room temperature, hydrogen iodide in the reaction solution was distilled off under reduced pressure. After diluting the reaction solution by adding dichloromethane (150 ml), a phosphate buffer solution (pH=7,200 ml) was added at 0°C, and the aqueous layer was extracted with dichloromethane. The obtained organic layer was washed with water and dried over anhydrous magnesium sulfate. This solution was concentrated under reduced pressure, and the obtained solid was dissolved in toluene (35.0 ml), acetic acid (7.00 ml, 122 mmol) was added, and the mixture was heated and stirred at 80° C. for 12 hours. The reaction solution was cooled to room temperature, a saturated aqueous solution of sodium hydrogen carbonate (100 ml) was added at room temperature, and the aqueous layer was extracted with toluene. The obtained organic layer was washed with water and dried over anhydrous magnesium sulfate. This solution was concentrated under reduced pressure, and the residue was purified using a silica gel column (eluent: hexane/dichloromethane = 2/1 (volume ratio)), and heated and washed at 80°C using acetonitrile. The compound (883) was obtained as a yellow solid (1.09 g, yield 68%).

The structure of the obtained compound was confirmed by NMR measurement.
¹ H-NMR (500 MHz, CDCl ₃ ): δ = 1.99 (s, 6H), 2.11 (s, 12H), 6.18 (s, 2H), 6.83 (d, J = 8. 6Hz, 2H), 7.04 (d, J=7.5Hz, 2H), 7.09-7.18 (m, 7H), 7.18-7.31 (m, 6H), 7.50- 7.58 (m, 2H), 8.60 (d, J=1.4Hz, 2H).
^13C -NMR (126MHz, _CDCl3 ): 20.8 (2C), 21.3 (4C), 105.6 (2C), 113.5 (d, _JCF = 22.8Hz, 4C), 115.2 (2C), 116.3 (1C), 118.6 (t, J _CF =18.0Hz, 2C), 124.4 (2C), 127.0 (2C), 127.2 ( 1C), 127.4 (2C), 127.6 (4C), 130.9 (t, J _CF =9.6Hz, 2C), 133.2 (2C), 133.5 (2C), 135 .8 (2C), 136.3 (2C), 136.7 (4C), 141.6 (2C), 142.5 (1C), 145.3 (2C), 145.9 (2C), 146. 1 (1C), 160.6 (dd, J _CF =3.7, 250.7Hz, 4C).

Synthesis example (5)
Compound (1-1674): N ⁷ ,N ¹³ ,5,15-tetrakis(2,6-difluorophenyl)-N ⁷ ,N ¹³ ,9,11-tetraphenyl-5,9,11,15-tetrahydro- Synthesis of 5,9,11,15-tetraaza-19b,20b-diborazinaphtho[3,2,1-de:1',2',3'-jk]pentacene-7,13-diamine

Under nitrogen atmosphere, bromobenzene (5.25 ml, 50.0 mmol), 2,6-difluoroaniline (7.59 ml, 75.0 mmol), Pd ₂ (dba) ₃ (0.687 mg, 0.750 mmol), BINAP ( A flask containing NaOtBu (7.21 g, 75.0 mmol), and toluene (150 ml) was heated to 110° C. and stirred for 4 hours. After the reaction solution was cooled to room temperature, it was poured into water, and the aqueous layer was extracted with toluene. The obtained organic layer was washed with water and dried over anhydrous magnesium sulfate. This solution was concentrated under reduced pressure, and the residue was purified using a silica gel short pass column (eluent: hexane/toluene = 5/1 (volume ratio)) to convert 2,6-difluoro-N-phenylaniline into a colorless liquid. (10.1 g, yield 98%).

The structure of the obtained compound was confirmed by NMR measurement.
^1H -NMR (500MHz, CDCl ₃ ): δ = 5.48 (s, 1H), 6.81 (dd, J = 1.2, 7.5Hz, 2H), 6.89-7.06 (m , 4H), 7.21-7.27 (m, 2H).

Under a nitrogen atmosphere, 1,3-dibromo-5-chlorobenzene (4.87 g, 18.0 mmol), 2,6-difluoro-N-phenylaniline (7.39 g, 36.0 mmol), Pd ₂ (dba) ₃ ( A flask containing 0.330 g, 0.360 mmol), SPhos (0.296 g, 0.720 mmol), NaOtBu (5.19 g, 54.0 mmol), and toluene (90.0 ml) was heated to 100 °C, Stir for hours. After the reaction solution was cooled to room temperature, it was poured into water, and the aqueous layer was extracted with toluene. The obtained organic layer was washed with water and dried over anhydrous magnesium sulfate. This solution was concentrated under reduced pressure, and the residue was purified with a silica gel column (eluent: hexane/toluene = 3/1 (volume ratio)), and further washed with methanol to obtain 5-chloro-N ¹ , N ³ -Bis(2,6-difluorophenyl)-N ¹ ,N ³ -diphenylbenzene-1,3-diamine was obtained as a white solid (7.17 g, yield 77%).

The structure of the obtained compound was confirmed by NMR measurement.
¹ H-NMR (500 MHz, CDCl ₃ ): δ = 6.40 (t, J = 1.7 Hz, 1H), 6.45 (d, J = 1.7 Hz, 2H), 6.89-6.96 (m, 4H), 6.98-7.07 (m, 6H), 7.14-7.25 (m, 6H).

N ¹ ,N ³ -diphenylbenzene-1,3-diamine (0.521 g, 2.00 mmol), 5-chloro-N ¹ synthesized according to the method described in International Publication No. 2018/212169 under a nitrogen atmosphere , N ³ -bis(2,6-difluorophenyl)-N ¹ ,N ³ -diphenylbenzene-1,3-diamine (2.28 g, 4.40 mmol), Pd ₂ (dba) ₃ (0.0916 g , 0.100 mmol), SPhos (0.0821 g, 0.200 mmol), NaOtBu (0.577 g, 6.00 mmol), and toluene (10.0 ml) were heated to 110 °C and stirred for 8 hours. . After the reaction solution was cooled to room temperature, it was poured into water, and the aqueous layer was extracted with toluene. The obtained organic layer was washed with water and dried over anhydrous magnesium sulfate. This solution was concentrated under reduced pressure, and the residue was purified with a silica gel column (eluent: hexane/ethyl acetate = 3/1 (volume ratio)), and further washed with hexane, allowing N ¹ , N ¹ '-( 1,3-phenylene)bis(N ³ ,N ⁵ -bis(2,6-difluorophenyl)-N ¹ ,N ³ ,N ⁵ -triphenylbenzene-1,3,5-triamine) was obtained as a white solid. (1.96 g, yield 80%).

The structure of the obtained compound was confirmed by NMR measurement.
^1H -NMR (500MHz, CDCl ₃ ): δ = 6.28-6.31 (m, 6H), 6.60 (dd, J = 2.3, 8.0Hz, 2H), 6.74 (t , J=2.2Hz, 1H), 6.79-6.98 (m, 27H), 7.02-7.14 (m, 16H).

Under nitrogen atmosphere, N ¹ ,N ¹ '-(1,3-phenylene)bis(N ³ ,N ⁵ -bis(2,6-difluorophenyl)-N ¹ ,N ³ ,N ⁵ -triphenylbenzene-1 , 3,5-triamine) (1.59 g, 1.30 mmol) and 1,2,4-trichlorobenzene (19.5 ml) was charged with boron tribromide (0.990 ml, 10.4 mmol). The mixture was added at room temperature and stirred at 180°C for 20 hours. After the reaction solution was cooled to room temperature, the remaining boron tribromide and hydrogen bromide in the reaction solution were distilled off under reduced pressure. After diluting the reaction solution by adding dichloromethane (150 ml), a phosphate buffer solution (pH=7,300 ml) was added at 0°C, and the aqueous layer was extracted with dichloromethane. The obtained organic layer was washed with water and dried over anhydrous magnesium sulfate. This solution was concentrated under reduced pressure, and the resulting solid was heated and washed with acetonitrile at 80° C. to obtain the compound of formula (1-1674) as a yellow solid (0.886 g, yield 55%).

The structure of the obtained compound was confirmed by NMR measurement.
¹ H-NMR (500 MHz, CDCl ₃ ): δ = 5.49 (d, J = 2.3 Hz, 2H), 5.59 (s, 2H), 5.73 (s, 1H), 6.70- 6.82 (m, 6H), 6.91-7.00 (m, 6H), 7.00-7.14 (m, 16H), 7.14-7.19 (m, 4H), 7. 32-7.40 (m, 4H), 7.46-7.51 (m, 2H), 9.22 (dd, J = 1.7, 7.5Hz, 2H), 10.5 (s, 1H ).
^13C -NMR (126MHz, _CDCl3 ): 93.7 (2C), 96.6 (2C), 103.4 (1C), 112.1 (d, _JCF = 24.0Hz, 4C), 112.4 (2C), 112.9 (d, J _CF = 22.8Hz, 4C), 115.1 (2C), 118.4 (2C), 118.7 (t, J _CF = 17.3Hz, 2C), 120.9 (2C), 122.1 (t, J _C-F = 14.5Hz, 2C), 124.0 (2C), 124.1 (4C), 125.1 ( 2C), 127.3 (t, J = 11.1Hz, 2C), 127.5 (2C), 128.8 (4C), 129.8 (4C), 130.1 (4C + 2C), 131.1 ( 2C), 135.7 (2C), 141.8 (2C), 143.7 (1C), 144.6 (2C), 146.6 (2C), 146.8 (2C), 148.5 (2C) ), 150.0 (2C), 150.4 (2C), 160.4 (dd, J _CF =4.2,254.7Hz, 4C), 160.5 (dd, J _CF =4 .2,253.6Hz, 4C).

Synthesis example (6)
Compound (1-1668): 9,11-bis(2,4-difluorophenyl)-N ⁷ ,N ⁷ ,N ¹³ ,N ¹³ ,5,15-hexaphenyl-5,9,11,15-tetrahydro- Synthesis of 5,9,11,15-tetraaza-19b,20b-diborazinaphtho[3,2,1-de:1',2',3'-jk]pentacene-7,13-diamine

Under nitrogen atmosphere, 1,3-dibromobenzene (1.22 ml, 10.0 mmol), 2,4-difluoroaniline (2.54 ml, 25.0 mmol), Pd ₂ (dba) ₃ (0.183 g, 0.200 mmol) ), SPhos (0.164 g, 0.400 mmol), NaOtBu (2.88 g, 30.0 mmol), and toluene (100 ml) were heated to 40° C. and stirred for 6 hours. After the reaction solution was cooled to room temperature, it was poured into water, and the aqueous layer was extracted with toluene. The obtained organic layer was washed with water and dried over anhydrous magnesium sulfate. This solution was concentrated under reduced pressure, and the residue was purified with a silica gel short pass column (eluent: toluene) and further washed with hexane to obtain N ¹ ,N ³ -bis(2,4-difluorophenyl). Benzene-1,3-diamine was obtained as a white solid (1.94 g, yield 58%).

The structure of the obtained compound was confirmed by NMR measurement.
¹ H-NMR (500 MHz, CDCl ₃ ): δ = 5.54 (s, 2H), 6.55-6.62 (m, 3H), 6.76-6.83 (m, 2H), 6. 86 (ddd, J=2.9, 8.6, 10.9Hz, 2H), 7.15 (t, J=8.0Hz, 1H), 7.26 (ddd, J=5.7, 9. 2,9.2Hz).

Under nitrogen atmosphere, N ¹ , N ³ -bis(2,4-difluorophenyl)benzene-1,3-diamine (0.997 mg, 3.00 mmol), described in International Publication No. 2018/212169 5-chloro- ^{N 1} ,N ¹ ,N ³ ,N ³ -tetraphenylbenzene-1,3-diamine (2.95 g, 6.60 mmol), Pd ₂ (dba) ₃ (0.137 g, A flask containing SPhos (0.123 g, 0.300 mmol), NaOtBu (0.865 g, 9.00 mmol), and toluene (15.0 ml) was heated to 110° C. and stirred for 24 hours. After the reaction solution was cooled to room temperature, it was poured into water, and the aqueous layer was extracted with toluene. The obtained organic layer was washed with water and dried over anhydrous magnesium sulfate. This solution was concentrated under reduced pressure, and the residue was purified with a silica gel column (eluent: hexane/dichloromethane = 3/2 (volume ratio)), and further washed with ethyl acetate to obtain N ¹ , N ¹ '-( 1,3-phenylene)bis(N ¹ -(2,4-difluorophenyl)-N ³ ,N ³ ,N ⁵ ,N ⁵ -tetraphenylbenzene-1,3,5-triamine) was obtained as a white solid. (2.76 g, yield 80%).

The structure of the obtained compound was confirmed by NMR measurement.
¹ H-NMR (500 MHz, CDCl ₃ ): δ = 6.25 (d, J = 2.3 Hz, 4H), 6.38 (t, J = 2.3 Hz, 2H), 6.41-6.46 (m, 3H), 6.65-6.74 (m, 4H), 6.85-7.02 (m, 27H), 7.09-7.16 (m, 16H).

Under nitrogen atmosphere, N ¹ ,N ¹ '-(1,3-phenylene)bis(N ¹ -(2,4-difluorophenyl)-N ³ ,N ³ ,N ⁵ ,N ⁵ -tetraphenylbenzene-1, Boron tribromide (0.114 ml, 1.20 mmol) was added to a flask containing 3,5-triamine) (0.173 g, 0.150 mmol) and 1,2,4-trichlorobenzene (3.00 ml) at room temperature. and stirred at 180°C for 20 hours. After the reaction solution was cooled to room temperature, the remaining boron tribromide and hydrogen bromide in the reaction solution were distilled off under reduced pressure. After diluting the reaction solution by adding dichloromethane (30.0 ml), a phosphate buffer solution (pH=7,100 ml) was added at 0°C, and the aqueous layer was extracted with dichloromethane. The obtained organic layer was washed with water and dried over anhydrous magnesium sulfate. This solution was concentrated under reduced pressure, and the resulting solid was heated and washed with acetonitrile at 80°C. Subsequently, by heating and washing with toluene at 110° C., the compound of formula (1-1668) was obtained as a yellow solid (0.121 g, yield 69%).

The structure of the obtained compound was confirmed by NMR measurement.
¹ H-NMR (500 MHz, (CDCl ₂ ) ₂ ): δ=5.61 (d, J=5.7 Hz, 1H), 5.66 (s, 2H), 5.66 (d, J=1. 7Hz, 2H), 6.71-6.83 (m, 6H), 6.90-6.99 (m, 12H), 7.02-7.13 (m, 10H), 7.21-7. 26 (m, 4H), 7.29-7.38 (m, 4H), 7.38-7.49 (m, 6H), 9.20 (dd, J = 1.7, 8.0Hz, 2H ), 10.5 (s, 1H).
^13C -NMR (126MHz, _CDCl3 ): 93.7 (2C), 96.6 (2C), 103.4 (1C), 112.1 (d, _JCF = 24.0Hz, 4C), 112.4 (2C), 112.9 (d, J _CF = 22.8Hz, 4C), 115.1 (2C), 118.4 (2C), 118.7 (t, J _CF = 17.3Hz, 2C), 120.9 (2C), 122.1 (t, J _C-F = 14.5Hz, 2C), 124.0 (2C), 124.1 (4C), 125.1 ( 2C), 127.3 (t, J = 11.1Hz, 2C), 127.5 (2C), 128.8 (4C), 129.8 (4C), 130.1 (4C + 2C), 131.1 ( 2C), 135.7 (2C), 141.8 (2C), 143.7 (1C), 144.6 (2C), 146.6 (2C), 146.8 (2C), 148.5 (2C) ), 150.0 (2C), 150.4 (2C), 160.4 (dd, J _CF =4.2,254.7Hz, 4C), 160.5 (dd, J _CF =4 .2,253.6Hz, 4C).

Synthesis example (7)
Compound (1-1666): 9,11-bis(2,6-difluorophenyl)-N ⁷ ,N ⁷ ,N ¹³ ,N ¹³ ,5,15-hexaphenyl-5,9,11,15-tetrahydro- Synthesis of 5,9,11,15-tetraaza-19b,20b-diborazinaphtho[3,2,1-de:1',2',3'-jk]pentacene-7,13-diamine

Under nitrogen atmosphere, 1,3-dibromobenzene (1.22 ml, 10.0 mmol), 2,6-difluoroaniline (3.04 ml, 30.0 mmol), Pd ₂ (dba) ₃ (0.183 g, 0.200 mmol) ), SPhos (0.164 g, 0.400 mmol), NaOtBu (2.88 g, 30.0 mmol), and toluene (50.0 ml) were heated to 60° C. and stirred for 2 hours. After the reaction solution was cooled to room temperature, it was poured into water, and the aqueous layer was extracted with toluene. The obtained organic layer was washed with water and dried over anhydrous magnesium sulfate. This solution was concentrated under reduced pressure, and the residue was purified using a silica gel short pass column (eluent: toluene) and further washed with hexane to obtain N ¹ ,N ³ -bis(2,6-difluorophenyl). Benzene-1,3-diamine was obtained as a white solid (3.20 g, yield 96%).

The structure of the obtained compound was confirmed by NMR measurement.
¹ H-NMR (500 MHz, CDCl ₃ ): δ = 5.43 (s, 2H), 6.26 (s, 1H), 6.36 (d, J = 8.0Hz, 2H), 6.90- 6.98 (m, 4H), 6.98-7.05 (m, 2H), 7.09 (t, J=8.0Hz, 1H).

Under nitrogen atmosphere, N ¹ , N ³ -bis(2,6-difluorophenyl)benzene-1,3-diamine (1.16 g, 3.50 mmol), described in International Publication No. 2018/212169 5-chloro- ^{N 1} ,N ¹ ,N ³ ,N ³ -tetraphenylbenzene-1,3-diamine (3.44 g, 7.70 mmol), Pd ₂ (dba) ₃ (0.160 g, A flask containing 0.180 mmol), SPhos (0.144 g, 0.350 mmol), NaOtBu (1.01 g, 10.5 mmol), and toluene (17.5 ml) was heated to 110° C. and stirred for 40 hours. After the reaction solution was cooled to room temperature, it was poured into water, and the aqueous layer was extracted with toluene. The obtained organic layer was washed with water and dried over anhydrous magnesium sulfate. This solution was concentrated under reduced pressure, and the residue was purified using a silica gel column (eluent: hexane/ethyl acetate = 5/1 (volume ratio)), and further washed with ethyl acetate to obtain N ¹ , N ¹ '- (1,3-phenylene)bis(N ¹ -(2,6-difluorophenyl)-N ³ ,N ³ ,N ⁵ ,N ⁵ -tetraphenylbenzene-1,3,5-triamine) was obtained as a white solid. (3.03 g, yield 75%).

The structure of the obtained compound was confirmed by NMR measurement.
¹ H-NMR (500 MHz, CDCl ₃ ): δ = 6.29 (d, J = 1.7 Hz, 4H), 6.38 (t, J = 2.3 Hz, 2H), 6.41 (t, J =2.3Hz, 1H), 6.51 (dd, J=2.3, 8.0Hz, 2H), 6.73-6.80 (m, 4H), 6.85-6.91 (m, 9H), 6.96-7.03 (m, 18H), 7.09-7.16 (m, 16H).

Under nitrogen atmosphere, N ¹ ,N ¹ '-(1,3-phenylene)bis(N ¹ -(2,6-difluorophenyl)-N ³ ,N ³ ,N ⁵ ,N ⁵ -tetraphenylbenzene-1, Boron tribromide (1.75 ml, 18.4 mmol) was added to a flask containing 3,5-triamine) (2.65 g, 2.30 mmol) and 1,2,4-trichlorobenzene (50.0 ml) at room temperature. and stirred at 200°C for 20 hours. After the reaction solution was cooled to room temperature, the remaining boron tribromide and hydrogen bromide in the reaction solution were distilled off under reduced pressure. After diluting the reaction solution by adding dichloromethane (500 ml), a phosphate buffer solution (pH=7,400 ml) was added at 0°C, and the aqueous layer was extracted with dichloromethane. The obtained organic layer was washed with water and dried over anhydrous magnesium sulfate. This solution was concentrated under reduced pressure, and the resulting solid was heated and washed with acetonitrile at 80°C. Subsequently, the compound of formula (1-1666) was obtained as a yellow solid by heating and washing with toluene at 110°C, purifying with a silica gel short pass column (eluent: toluene), and further heating and washing with toluene at 110°C. (1.617 g, yield 60%).

The structure of the obtained compound was confirmed by NMR measurement.
¹ H-NMR (500 MHz, (CDCl ₂ ) ₂ ): δ = 5.80 (s, 4H), 5.91 (s, 1H), 6.81-6.88 (m, 6H), 6.99 (t, J=7.5Hz, 4H), 7.03 (d, J=8.0Hz, 8H), 7.15 (t, J=8.0Hz, 8H), 7.18-7.26 ( m, 2H), 7.33 (d, J = 8.0Hz, 4H), 7.37-7.45 (m, 4H), 7.45-7.50 (m, 2H), 7.53 ( t, J=8.0Hz, 4H), 9.30 (d, J=7.5Hz, 2H), 10.5 (s, 1H).
^13C -NMR (126MHz, _CDCl3 ): 93.7 (2C), 96.6 (2C), 103.4 (1C), 112.1 (d, _JCF = 24.0Hz, 4C), 112.4 (2C), 112.9 (d, J _CF = 22.8Hz, 4C), 115.1 (2C), 118.4 (2C), 118.7 (t, J _CF = 17.3Hz, 2C), 120.9 (2C), 122.1 (t, J _C-F = 14.5Hz, 2C), 124.0 (2C), 124.1 (4C), 125.1 ( 2C), 127.3 (t, J = 11.1Hz, 2C), 127.5 (2C), 128.8 (4C), 129.8 (4C), 130.1 (4C + 2C), 131.1 ( 2C), 135.7 (2C), 141.8 (2C), 143.7 (1C), 144.6 (2C), 146.6 (2C), 146.8 (2C), 148.5 (2C) ), 150.0 (2C), 150.4 (2C), 160.4 (dd, J _CF =4.2,254.7Hz, 4C), 160.5 (dd, J _CF =4 .2,253.6Hz, 4C).

Comparative synthesis example (1)
Compound (C-1): Synthesis of N,N,5,9-tetraphenyl-5,9-dihydro-5,9-diaza-13b-boranaphtho[3,2,1-de]anthracen-7-amine

N ¹ ,N ¹ ,N ³ ,N ³ ,N ⁵ ,N ⁵ -hexaphenyl-1,3,5-benzenetriamine (11.6 g, 20 mmol) and orthodichlorobenzene (ODCB, 120 ml) were added under a nitrogen atmosphere. After adding boron tribromide (3.78 ml, 40 mmol) at room temperature, the mixture was heated and stirred at 170° C. for 48 hours. Thereafter, the reaction solution was distilled off under reduced pressure at 60°C. The mixture was filtered through a Florisil short-pass column, and the solvent was distilled off under reduced pressure to obtain a crude product. By washing the crude product with hexane, the compound of formula (C-1) was obtained as a yellow solid (11.0 g, yield 94%).

The structure of the obtained compound was confirmed by NMR measurement.
¹ H-NMR (400 MHz, CDCl ₃ ): δ = 5.62 (brs, 2H), 6.71 (d, 2H), 6.90-6.93 (m, 6H), 7.05-7. 09 (m, 4H), 7.20-7.27 (m, 6H), 7.33-7.38 (m, 4H), 7.44-7.48 (m, 4H), 8.90 ( dd, 2H).
¹³ C-NMR (101 MHz, CDCl ₃ ): δ = 98.4 (2C), 116.8 (2C), 119.7 (2C), 123.5 (2C), 125.6 (4C), 128. 1 (2C), 128.8 (4C), 130.2 (4C), 130.4 (2C), 130.7 (4C), 134.8 (2C), 142.1 (2C), 146.6 (2C), 147.7 (2C), 147.8 (2C), 151.1 (4H).

Comparative synthesis example (2)
Compound (C-2): N ⁷ , N ⁷ , N ¹³ , N ¹³ ,5,9,11,15-octaphenyl-5,9,11,15-tetrahydro-5,9,11,15-tetraaza- Synthesis of 19b,20b-diborazinaphtho[3,2,1-de:1',2',3'-jk]pentacene-7,13-diamine

Under nitrogen atmosphere, 1,3-dibromobenzene (25.0 g, 106 mmol), aniline (20.3 ml, 223 mmol), Pd ₂ (dba) ₃ (971 mg, 1.06 mmol), BINAP (1.98 g, 3.18 mmol) ), NaOtBu (25.5 g, 265 mmol) and toluene (400 ml) were heated to 110° C. and stirred for 18 hours. The reaction solution was cooled to room temperature, filtered using silica gel (eluent: toluene), and the solvent was distilled off under reduced pressure to obtain a crude product. After dissolving the obtained crude product in toluene, an appropriate amount was distilled off under reduced pressure, and hexane was added and reprecipitated to obtain N ¹ , N ³ -diphenylbenzene-1,3-diamine as a white solid. (16.5 g, yield 60%).

The structure of the obtained compound was confirmed by NMR spectrum.
¹ H-NMR (400 MHz, CDCl ₃ ): δ = 5.63 (s, 2H), 6.60 (dd, 2H), 6.74 (t, 1H), 6.90 (t, 2H), 7 .06 (d, 4H), 7.12 (t, 1H), 7.24 (dt, 4H).

Under nitrogen atmosphere, 1,3-dibromo-5-chlorobenzene (8.11 g, 30 mmol), diphenylamine (10.1 g, 60 mmol), Pd ₂ (dba) ₃ (550 mg, 0.6 mmol), SPhos (0.493 g, A flask containing NaOtBu (8.60 g, 90 mmol) and toluene (300 ml) was heated to 80° C. and stirred for 15 hours. The reaction solution was cooled to room temperature, filtered through silica gel (eluent: toluene), and the solvent was distilled off under reduced pressure to obtain a crude product. After dissolving the obtained crude product in toluene, evaporation under reduced pressure prepares a saturated solution, and by adding hexane and reprecipitating, 5-chloro- ^{N 1} , N ¹ , N ³ , N ³ -Tetraphenylbenzene-1,3-diamine was obtained as a white solid (5.66 g, yield 43%).

The structure of the obtained compound was confirmed by NMR spectrum.
¹ H-NMR (400 MHz, CDCl ₃ ): δ = 6.56 (d, 2H), 6.64 (t, 1H), 7.00 (t, 4H), 7.05 (d, 8H), 7 .21 (dd, 8H).

Under nitrogen atmosphere, N ¹ ,N ³ -diphenylbenzene-1,3-diamine (1.34 g, 5.1 mmol), 5-chloro- ^{N 1} ,N ¹ ,N ³ ,N ³ -tetraphenylbenzene-1, 3-diamine (4.80 g, 11 mmol), Pd ₂ (dba) ₃ (0.140 g, 0.15 mmol), tri-tert-butylphosphine (60.7 mg, 0.30 mmol), NaOtBu (1.47 g, 15 mmol) ) and toluene (200 ml) was heated to 110°C and stirred for 8 hours. The reaction solution was cooled to room temperature, filtered using silica gel (eluent: toluene), and the solvent was distilled off under reduced pressure to obtain a crude product. By washing the obtained crude product with hexane and methanol in that order, N ¹ ,N ¹ '-(1,3-phenylene)bis(N ¹ ,N ³ ,N ³ ,N ⁵ ,N ⁵ -pentaphenyl Benzene-1,3,5-triamine) was obtained as a white solid (4.80 g, yield 87%).

The structure of the obtained compound was confirmed by NMR spectrum.
¹ H-NMR (400 MHz, CDCl ₃ ): δ = 6.38 (d, 4H), 6.41 (t, 2H), 6.58 (dd, 2H), 6.70 (t, 1H), 6 .88-6.90 (m, 14H), 6.85 (t, 1H), 6.99 (d, 16H), 7.08-7.15 (m, 20H).

N ¹ ,N ¹ '-(1,3-phenylene)bis(N ¹ ,N ³ ,N ³ ,N ⁵ ,N ⁵ -pentaphenylbenzene-1,3,5-triamine) (3.24 g, 3. Boron tribromide (1.13 ml, 12 mmol) was added to a flask containing 0 mmol) and orthodichlorobenzene (400 ml) at room temperature under a nitrogen atmosphere. After the dropwise addition was completed, the temperature was raised to 180°C and stirred for 20 hours. Thereafter, the mixture was cooled to room temperature again, N-diisopropylethylamine (7.70 ml, 45 mmol) was added, and the mixture was stirred until the heat generation subsided. Thereafter, the reaction solution was distilled off at 60° C. under reduced pressure to obtain a crude product. The obtained crude product was washed with acetonitrile, methanol, and toluene in this order, and purified with a silica gel column (eluent: toluene). The crude product was recrystallized twice with o-dichlorobenzene, and then 1×10 ^-4 The compound of formula (C-2) was obtained by sublimation purification at 440° C. under reduced pressure of mmHg (1.17 g).

The structure of the obtained compound was confirmed by NMR spectrum.
¹ H-NMR (400 MHz, CDCl ₃ ): δ = 5.72 (s, 2H), 5.74 (s, 2H), 5.86 (s, 1H), 6.83 (d, 2H), 6 .88-6.93 (m, 12H), 7.05 (t, 8H), 7.12-7.19 (m, 6H), 7.24-7.26 (m, 4H), 7.05 (d, 4H), 7.12 (dd, 8H), 7.12-7.19 (m, 6H), 7.32 (d, 4H), 7.38 (dd, 2H), 7.42 ( t, 2H), 7.46 (dd, 2H), 7.47 (dd, 4H), 9.30 (d, 2H), 10.5 (s, 1H).
^13C -NMR (101MHz, CDCl ₃ ): 99.5 (2C + 2C), 103.4 (1C), 116.8 (2C), 120.0 (2C), 123.1 (4C), 125.3 ( 8C), 127.1 (2C), 127.6 (2C), 128.5 (8C), 129.6 (4C), 129.8 (4C), 130.2 (4C + 2C), 130.3 (4C ), 135.0 (2C), 142.1 (2C), 142.5 (2C), 143.3 (1C), 146.8 (4C), 147.9 (2C + 2C), 148.0 (2C) , 150.1 (2C), 151.1 (2C).

By appropriately changing the raw material compounds, other polycyclic aromatic compounds of the present invention can be synthesized by a method similar to the above-mentioned synthesis example.

Next, in order to explain the present invention in more detail, examples of organic EL devices using the compounds of the present invention will be shown, but the present invention is not limited thereto.

<Evaluation of organic EL elements>
The organic EL device according to Example ¹ was manufactured, and the voltage (V), emission wavelength (nm), and external quantum efficiency (%), which are characteristics when emitting light at 1000 cd/m2, were measured, and then at 10 mA/ ^cm2. The time required to maintain a brightness of 98% or more of the initial brightness when driving at a constant current density was measured.

There are two types of quantum efficiency for light-emitting devices: internal quantum efficiency and external quantum efficiency.Internal quantum efficiency is when external energy injected as electrons (or holes) into the light-emitting layer of a light-emitting device is converted purely into photons. It shows the percentage of On the other hand, external quantum efficiency is calculated based on the amount of photons emitted to the outside of the light-emitting element, and some of the photons generated in the light-emitting layer are absorbed or continue to be reflected inside the light-emitting element. Since the light is not emitted to the outside of the light emitting device, the external quantum efficiency is lower than the internal quantum efficiency.

The method for measuring external quantum efficiency is as follows. Using a voltage/current generator R6144 manufactured by Advantest, a voltage such that the luminance of the device was 1000 cd/m ² was applied to cause the device to emit light. Spectral radiance in the visible light region was measured in the direction perpendicular to the light emitting surface using a spectral radiance meter SR-3AR manufactured by TOPCON. Assuming that the light emitting surface is a completely diffusing surface, the number of photons at each wavelength is obtained by dividing the value of the measured spectral radiance of each wavelength component by the wavelength energy and multiplying by π. Next, the number of photons was integrated over the entire observed wavelength range to obtain the total number of photons emitted from the element. The value obtained by dividing the applied current value by the elementary charge is the number of carriers injected into the device, and the value obtained by dividing the total number of photons emitted from the device by the number of carriers injected into the device is the external quantum efficiency.

The material composition of each layer and EL characteristic data in the manufactured organic EL device according to Example 1 are shown in Tables 1A and 1B below.

In Table 1A, "HI" is N ⁴ ,N ^4' -diphenyl-N ⁴ ,N ^4' -bis(9-phenyl-9H-carbazol-3-yl)-[1,1'-biphenyl]-4, 4'-diamine, "HAT-CN" is 1,4,5,8,9,12-hexaazatriphenylenehexacarbonitrile, and "HT-1" is N-([1,1'-biphenyl ]-4-yl)-9,9-dimethyl-N-(4-(9-phenyl-9H-carbazol-3-yl)phenyl)-9H-fluoren-2-amine, and "HT-2" is N,N-bis(4-(dibenzo[b,d]furan-4-yl)phenyl)-[1,1':4',1"-terphenyl]-4-amine, "BH-1 ” is 2-(10-phenylanthracen-9-yl)naphtho[2,3-b]benzofuran, and “ET-1” is 4,6,8,10-tetraphenyl[1,4]benzoxaboly nino[2,3,4-kl]phenoxaborinine, and "ET-2" is 3,3'-((2-phenylanthracene-9,10-diyl)bis(4,1-phenylene))bis (4-methylpyridine). The chemical structure is shown below together with "Liq".

<Example 1>
A 26 mm x 28 mm x 0.7 mm glass substrate (manufactured by Optoscience Co., Ltd.), in which ITO was formed into a 180 nm thick film by sputtering and polished to 150 nm, was used as a transparent support substrate. This transparent support substrate was fixed to a substrate holder of a commercially available vapor deposition apparatus (manufactured by Showa Shinku Co., Ltd.), and HI, HAT-CN, HT-1, HT-2, BH-1, compound (1-1), ET A molybdenum vapor deposition boat containing ET-1 and ET-2, and an aluminum nitride vapor deposition boat containing Liq, LiF, and aluminum, respectively, were installed.

The following layers were sequentially formed on the ITO film of the transparent support substrate. The pressure in the vacuum chamber was reduced to 5 × 10 ^-4 Pa, first, HI was heated and deposited to a film thickness of 40 nm, then HAT-CN was heated and deposited to a film thickness of 5 nm, Next, HT-1 is heated and deposited to a thickness of 45 nm, and then HT-2 is heated and deposited to a thickness of 10 nm to form a hole layer consisting of four layers. did. Next, BH-1 and compound (1-1) were simultaneously heated and deposited to a thickness of 25 nm to form a light-emitting layer. The deposition rate was adjusted so that the weight ratio of BH-1 and compound (1-1) was approximately 98:2. Furthermore, ET-1 was heated and deposited to a thickness of 5 nm, and then ET-2 and Liq were simultaneously heated and deposited to a thickness of 25 nm to form a two-layer electronic layer. Formed. The deposition rate was adjusted so that the weight ratio of ET-2 to Liq was approximately 50:50. The deposition rate of each layer was 0.01-1 nm/sec. Thereafter, LiF is heated and deposited to a thickness of 1 nm at a deposition rate of 0.01 to 0.1 nm/sec, and then aluminum is heated and deposited to a thickness of 100 nm to form a cathode. An organic EL device was obtained.

When we applied a DC voltage using the ITO electrode as the anode and the LiF/aluminum electrode as the cathode and measured the characteristics when emitting light at 1000 cd/ ^m2 , blue light emission with a wavelength of 458 nm was obtained, the driving voltage was 3.90 V, and the external quantum efficiency was was 7.89%.

The material composition of each layer and EL characteristic data of the organic EL devices according to Examples 2 to 8 and Comparative Examples 1 to 2 produced are shown in Table 2A and Table 2B below.

In Table 2A, "BH-2" is 2-(10-phenylanthracen-9-yl)dibenzo[b,d]furan. The chemical structures of Compound (C-1) and Compound (C-2) are shown below.

<Example 2>
A 26 mm x 28 mm x 0.7 mm glass substrate (manufactured by Optoscience Co., Ltd.), in which ITO was formed into a 180 nm thick film by sputtering and polished to 150 nm, was used as a transparent support substrate. This transparent support substrate was fixed to a substrate holder of a commercially available vapor deposition apparatus (manufactured by Showa Shinku Co., Ltd.), and HI, HAT-CN, HT-1, HT-2, BH-2, compound (1-1), ET A molybdenum vapor deposition boat containing ET-1 and ET-2, and an aluminum nitride vapor deposition boat containing Liq, LiF, and aluminum, respectively, were installed.

The following layers were sequentially formed on the ITO film of the transparent support substrate. The pressure in the vacuum chamber was reduced to 5 × 10 ^-4 Pa, first, HI was heated and deposited to a film thickness of 40 nm, then HAT-CN was heated and deposited to a film thickness of 5 nm, Next, HT-1 is heated and deposited to a thickness of 45 nm, and then HT-2 is heated and deposited to a thickness of 10 nm to form a hole layer consisting of four layers. did. Next, BH-2 and compound (1-1) were simultaneously heated and deposited to a thickness of 25 nm to form a light-emitting layer. The deposition rate was adjusted so that the weight ratio of BH-2 and compound (1-1) was approximately 98:2. Furthermore, ET-1 was heated and deposited to a thickness of 5 nm, and then ET-2 and Liq were simultaneously heated and deposited to a thickness of 25 nm to form a two-layer electronic layer. Formed. The deposition rate was adjusted so that the weight ratio of ET-2 to Liq was approximately 50:50. The deposition rate of each layer was 0.01-1 nm/sec. Thereafter, LiF is heated and deposited to a thickness of 1 nm at a deposition rate of 0.01 to 0.1 nm/sec, and then aluminum is heated and deposited to a thickness of 100 nm to form a cathode. An organic EL device was obtained.

A DC voltage was applied using the ITO electrode as an anode and the LiF/aluminum electrode as a cathode, and the characteristics at 1000 cd/m ² emission were measured. The driving voltage was 3.80 V and the external quantum efficiency was 7.50%. Further, the time required to maintain a brightness of 98% or more of the initial brightness when driven at a constant current at a current density of 10 mA/cm ² was measured and found to be 53 hours.

<Examples 3 to 8 and Comparative Examples 1 to 2>
An organic EL device was produced in a manner similar to Example 2 (Table 2A), and its EL characteristics were measured (Table 2B).

<Example 9>
Next, in the compound represented by formula (1), the effect of shortening the emission wavelength by introducing an electron-accepting fluorine atom was verified by measuring the fluorescence spectrum.

To measure the fluorescence spectrum, prepare a measurement solution by dissolving the compound of formula (1-1666), formula (1-1674) or formula (1-1668) in toluene at a concentration of 2 × 10 ^-5 M, and then This was placed in a quartz optical cell, excited at an excitation wavelength of 380 nm, and the fluorescence spectrum was measured. The results are shown in Table 3A below.

In addition, a measurement solution was prepared by dissolving the compound of formula (C-2), which is a comparison compound, in toluene at a concentration of 2×10 ⁻⁵ M, and then the solution was placed in a quartz optical cell and the excitation wavelength was set at 380 nm. was excited and the fluorescence spectrum was measured. The results are shown in Table 3B below.

From the above results, the effect of shortening the wavelength of the fluorescence spectrum by introducing fluorine atoms was confirmed. This result shows that blue light emission with a shorter wavelength can be obtained by introducing fluorine atoms into the molecule.

In the present invention, by providing a novel fluorine-substituted polycyclic aromatic compound, it is possible to increase the selection of materials for organic devices such as materials for organic EL elements. In addition, by using the new fluorine-substituted polycyclic aromatic compound as a material for organic EL devices, we can produce, for example, organic EL devices with excellent luminous efficiency and long device life, display devices equipped with the same, and lighting devices equipped with the same. 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 (22)

A polycyclic aromatic compound represented by the following general formula (1).
(In the above formula (1),
Ring A, Ring B, and Ring C are each independently an aryl ring having 6 to 30 carbon atoms or a heteroaryl ring having 2 to 30 carbon atoms , and at least one hydrogen in these rings has 6 to 30 carbon atoms. ~30 aryl, heteroaryl with 2 to 30 carbon atoms, diarylamino (aryl is aryl with 6 to 12 carbon atoms), diarylboryl (aryl is aryl with 6 to 12 carbon atoms), or 1 to 24 carbon atoms may be substituted with an alkyl group, and at least one hydrogen in these groups is substituted with an aryl having 6 to 12 carbon atoms, a heteroaryl having 2 to 15 carbon atoms, or an alkyl having 1 to 6 carbon atoms. Good too,
^Y1 is B ,
X ¹ and X ² are each independently O, NR, S, or Se, and R in NR is an aryl having 6 to 30 carbon atoms , a heteroaryl having 2 to 30 carbon atoms , or alkyl having 1 to 24 carbon atoms , and at least one hydrogen in these groups is substituted with aryl having 6 to 12 carbon atoms, heteroaryl having 2 to 15 carbon atoms, or alkyl having 1 to 6 carbon atoms. Also , R in the NR may be bonded to the A ring, B ring and/or C ring through -O-, -S-, -C(-R) ₂ -, or a single bond. R in the -C(-R) ₂ - is hydrogen or alkyl having 1 to 6 carbon atoms,
At least one hydrogen in the compound represented by formula (1) may be substituted with cyano, chlorine, bromine, iodine, or deuterium, and
At least one hydrogen in the compound represented by formula (1) is substituted with fluorine. ) Ring A, Ring B, and Ring C are each independently an aryl ring having 6 to 16 carbon atoms or a heteroaryl ring having 2 to 20 carbon atoms , and at least one hydrogen in these rings has 6 to 16 carbon atoms. ~16 aryl, heteroaryl with 2 to 20 carbon atoms , diarylamino (aryl is aryl with 6 to 12 carbon atoms) , diarylboryl ( aryl is aryl with 6 to 12 carbon atoms ), or 1 to 18 carbon atoms may be substituted with an alkyl group, and at least one hydrogen in these groups is substituted with an aryl having 6 to 12 carbon atoms, a heteroaryl having 2 to 15 carbon atoms, or an alkyl having 1 to 6 carbon atoms. Also, the A ring, B ring, and C ring may be a 5-membered ring or a 6-membered ring that shares a bond with the fused 2-ring structure at the center of the above formula consisting of Y ¹ , ^{X 1 ,} and X 2 . has
^Y1 is B ,
X ¹ and X ² are each independently O, NR, S, or Se, and R in NR has 6 carbon atoms, which may be substituted with alkyl having 1 to 6 carbon atoms. -16 aryl, C2-20 heteroaryl optionally substituted with C1-6 alkyl, or C1-6 alkyl, and R in N-R is - It may be bonded to the A ring, B ring and/or C ring through O-, -S-, -C(-R) ₂ -, or a single bond, and the -C(-R) ₂ - R is hydrogen or alkyl having 1 to 6 carbon atoms ,
At least one hydrogen in the compound represented by formula (1) may be substituted with cyano, chlorine, bromine, iodine, or deuterium , and
At least one hydrogen in the compound represented by formula (1) is substituted with fluorine,
The polycyclic aromatic compound according to claim 1. The polycyclic aromatic compound according to claim 1, which is represented by the following general formula (2).
(In the above formula (2),
R ¹ to R ¹¹ are each independently hydrogen, aryl having 6 to 16 carbon atoms, heteroaryl having 2 to 20 carbon atoms , diarylamino (aryl is aryl having 6 to 12 carbon atoms) , diarylboryl ( however , Aryl is aryl having 6 to 12 carbon atoms ) or alkyl having 1 to 18 carbon atoms, and at least one hydrogen in these groups is aryl having 6 to 12 carbon atoms, heteroaryl having 2 to 15 carbon atoms, or It may be substituted with alkyl having 1 to 6 carbon atoms, or adjacent groups among R ¹ to R ¹¹ may be bonded to each other to form an aryl having 9 to 16 carbon atoms together with ring a, ring b, or ring c. It may form a ring or a heteroaryl ring having 6 to 20 carbon atoms , and at least one hydrogen in the formed ring is an aryl having 6 to 16 carbon atoms, a heteroaryl having 2 to 20 carbon atoms , a diarylamino ( However, aryl may be substituted with aryl having 6 to 12 carbon atoms), diarylboryl ( aryl having 6 to 12 carbon atoms ), or alkyl having 1 to 18 carbon atoms, and at least one of these groups Hydrogen may be substituted with an aryl having 6 to 12 carbon atoms, a heteroaryl having 2 to 15 carbon atoms, or an alkyl having 1 to 6 carbon atoms,
^Y1 is B ,
X ¹ and X ² are each independently O, NR, S, or Se, and R in NR is an aryl having 6 to 12 carbon atoms, a heteroaryl having 2 to 15 carbon atoms, or alkyl having 1 to 6 carbon atoms, and R in the NR is -O-, -S-, -C(-R) ₂ -, or a single bond that connects the a-ring, b-ring and/or or may be bonded to the c ring, R in the -C(-R) ₂ - is an alkyl having 1 to 6 carbon atoms,
At least one hydrogen in the compound represented by formula (2) may be substituted with cyano, chlorine, bromine, iodine, or deuterium, and
At least one hydrogen in the compound represented by formula (2) is substituted with fluorine. ) R ¹ to R ¹¹ are each independently hydrogen, aryl having 6 to 16 carbon atoms, heteroaryl having 2 to 20 carbon atoms, diarylamino (aryl is aryl having 6 to 12 carbon atoms), diarylboryl (however, Aryl is aryl having 6 to 12 carbon atoms) or alkyl having 1 to 18 carbon atoms, and adjacent groups among R ¹ to R ¹¹ are bonded to each other to form a ring with ring a, ring b, or ring c. It may form an aryl ring having 9 to 16 carbon atoms or a heteroaryl ring having 6 to 15 carbon atoms, and at least one hydrogen in the formed ring is an aryl ring having 6 to 10 carbon atoms, or an aryl ring having 1 to 15 carbon atoms. may be substituted with 12 alkyl,
^Y1 is B ,
X ¹ and X ² are each independently O, NR, or S, and R in NR is aryl having 6 to 10 carbon atoms or alkyl having 1 to 4 carbon atoms,
At least one hydrogen in the compound represented by formula (2) may be substituted with cyano, chlorine, bromine, iodine, or deuterium, and
At least one hydrogen in the compound represented by formula (2) is substituted with fluorine,
The polycyclic aromatic compound according to claim 3. R ¹ to R ¹¹ are each independently hydrogen, aryl having 6 to 16 carbon atoms, heteroaryl having 2 to 20 carbon atoms, diarylamino (aryl is aryl having 6 to 10 carbon atoms), diarylboryl (however, Aryl is aryl having 6 to 10 carbon atoms) or alkyl having 1 to 12 carbon atoms,
^Y1 is B ,
X ¹ and X ² are each independently O or NR, R in NR is aryl having 6 to 10 carbon atoms, or alkyl having 1 to 4 carbon atoms, and
At least one hydrogen in the compound represented by formula (2) is substituted with fluorine,
The polycyclic aromatic compound according to claim 3. R ¹ to R ¹¹ are each independently hydrogen, aryl having 6 to 16 carbon atoms, diarylamino (aryl is aryl having 6 to 10 carbon atoms), diarylboryl (aryl is aryl having 6 to 10 carbon atoms) ), or alkyl having 1 to 12 carbon atoms,
Y ¹ is B,
X ¹ and X ² are both NR, or X ¹ is NR and X ² is O, and R in NR is aryl having 6 to 10 carbon atoms, or carbon is an alkyl of numbers 1 to 4, and
At least one hydrogen in the compound represented by formula (2) is substituted with fluorine,
The polycyclic aromatic compound according to claim 3. The polycyclic aromatic compound according to any one of claims 1 to 6, wherein R in the NR is a fluorine-substituted aryl or heteroaryl. The polycyclic aromatic compound according to claim 7, wherein R in the NR is fluorine-substituted phenyl. Claims 1 to 3 are substituted with a fluorine-substituted alkyl group , a fluorine-substituted diarylamino group, a fluorine-substituted diarylboryl group , a fluorine-substituted carbazolyl group, or a fluorine-substituted benzocarbazolyl group. 8. The polycyclic aromatic compound described in any one of 8. The polycyclic aromatic compound according to claim 9, which is substituted with a fluorine-substituted diarylamino group. The polycyclic aromatic compound according to claim 10, which is substituted with a fluorine-substituted diphenylamino group. A polycyclic aromatic compound represented by any of the following structural formulas.
(“tBu” in each of the above structural formulas represents a t-butyl group.) A polycyclic aromatic compound represented by the following structural formula.
(“Me” in each of the above structural formulas represents a methyl group.) An organic device material containing the polycyclic aromatic compound according to any one of claims 1 to 13. The organic device material according to claim 14, wherein the organic device material is an organic electroluminescent element material, an organic field effect transistor material, or an organic thin film solar cell material. The material for an organic electroluminescent device according to claim 15, which is a material for a light emitting layer. An organic electroluminescent device comprising a pair of electrodes consisting of an anode and a cathode, and a luminescent layer disposed between the pair of electrodes and containing the luminescent layer material according to claim 16. 18. The organic electroluminescent device according to claim 17, wherein the light emitting layer includes a host and the material for the light emitting layer as a dopant. The organic electroluminescent device according to claim 18, wherein the host is an anthracene-based compound, a fluorene-based compound, or a dibenzochrysene-based compound. It has an electron transport layer and/or an electron injection layer disposed between the cathode and the light emitting layer, and at least one of the electron transport layer and the electron injection layer is made of a borane derivative, a pyridine derivative, a fluoranthene derivative, a BO A claim containing at least one selected from the group consisting of anthracene derivatives, anthracene derivatives, benzofluorene derivatives, phosphine oxide derivatives, pyrimidine derivatives, carbazole derivatives, triazine derivatives, benzimidazole derivatives, phenanthroline derivatives, and quinolinol metal complexes. 20. The organic electroluminescent device according to any one of 17 to 19. The electron transport layer and/or the electron injection layer further comprises an alkali metal, an alkaline earth metal, a rare earth metal, an alkali metal oxide, an alkali metal halide, an alkaline earth metal oxide, an alkaline earth metal oxide, and an alkaline earth metal oxide. A claim containing at least one selected from the group consisting of halides, rare earth metal oxides, rare earth metal halides, alkali metal organic complexes, alkaline earth metal organic complexes, and rare earth metal organic complexes. 21. The organic electroluminescent device according to 20. A display device or a lighting device comprising the organic electroluminescent element according to any one of claims 17 to 21.

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