Fluorine-substituted polycyclic aromatic compound

Abstract

To provide a material for organic EL elements.SOLUTION: The present invention provides a compound obtained by introducing a fluorine atom into a novel polycyclic aromatic compound which comprises a plurality of aromatic rings connected by, for example, a boron atom and an oxygen atom. For example, following compounds are illustrated. (In the structural formulae, "tBu" represents a t-butyl group).SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a fluorine-substituted polycyclic aromatic compound, an organic electroluminescent device, an organic field effect transistor, and an organic thin film solar cell using the same, as well as a display device and an illumination device. In the present specification, the "organic electroluminescent device" may be referred to as an "organic EL device" or simply an "element".

Background Art

[0002] Conventionally, display devices using light-emitting elements that emit light by an electric field have been variously studied because they can be made smaller in power consumption and thinner. Further, organic electroluminescent devices made of organic materials have been actively studied because they can be easily made lighter and larger. In particular, the development of organic materials having light-emitting characteristics such as blue, which is one of the three primary colors of light, and the development of organic materials having charge transport capabilities (capable of becoming semiconductors or superconductors) such as holes and electrons have been actively studied so far regardless of whether they are high molecular compounds or low molecular compounds.

[0003] An organic EL device has a structure including a pair of electrodes composed of an anode and a cathode, and one or more layers containing an organic compound disposed between the pair of electrodes. The layer containing an organic compound includes a light-emitting layer, a charge transport / injection layer that transports or injects charges such as holes and electrons, and various suitable organic materials have been developed for these layers.

[0004] As materials for the light-emitting layer, for example, benzofluorene-based compounds have been developed (International Publication No. 2004 / 061047). Further, as hole transport materials, for example, triphenylamine-based compounds have been developed (Japanese Patent Application Laid-Open No. 2001-172232). Further, as electron transport materials, for example, anthracene-based compounds have been developed (Japanese Patent Application Laid-Open No. 2005-170911).

[0005] In recent years, materials obtained by improving triphenylamine derivatives have also been reported as materials for use in organic EL elements and organic thin-film solar cells (International Publication No. WO 2012 / 118164). This material is characterized in that the planarity thereof is enhanced by connecting aromatic rings constituting triphenylamine to each other with reference to N,N'-diphenyl-N,N'-bis(3-methylphenyl)-1,1'-biphenyl-4,4'-diamine (TPD) which has already been put into practical use. In this document, for example, the charge transport characteristics of an NO linking system compound (Compound 1 on page 63) are evaluated, but the manufacturing method of materials other than the NO linking system compound is not described. Further, since the electronic state of the entire compound differs if the connecting element is different, the characteristics obtained from materials other than the NO linking system compound are not yet known. Examples of such compounds can also be found in other documents (International Publication No. 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 thus is useful as a material for a blue light-emitting layer. Further, there is a demand for a compound having a novel conjugated structure with a large T1 as an electron transport material or a hole transport material sandwiching the light-emitting layer.

[0006] The host material of an organic EL element is generally a molecule in which a plurality of existing aromatic rings such as benzene and carbazole are connected by single bonds or phosphorus atoms or 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 aromatic rings having a relatively small conjugated system. Further, the host material of an organic EL element using a phosphorescent material or a thermally activated delayed fluorescent material requires a high triplet excitation energy (E T ) as well. However, by connecting a donor or acceptor-type aromatic ring or substituent to the molecule, SOMO1 and SOMO2 in the triplet excited state (T1) are localized, and the exchange interaction between both orbits is reduced, thereby reducing the triplet excitation energy (E TIt becomes possible to improve. However, small aromatic rings with a conjugated system do not have sufficient redox stability, and devices using molecules formed by connecting existing aromatic rings as host materials do not have sufficient lifetimes. On the other hand, polycyclic aromatic compounds having an extended π-conjugated system generally have excellent redox stability, but the HOMO-LUMO gap (band gap Eg in the thin film) and triplet excitation energy (E T ) are low, so they have been considered unsuitable as host materials.

Prior Art Documents

Patent Documents

[0007]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Patent Document 5

Patent Document 6

Summary of the Invention

Problems to be Solved by the Invention

[0008] As described above, various materials have been developed as materials used in organic EL devices. However, in order to increase the options for materials for organic EL devices, the development of materials composed of compounds different from the conventional ones is desired. In particular, the organic EL characteristics obtained from materials other than the NO-linkage compounds reported in Patent Documents 1 to 4 and their manufacturing methods are not yet known.

[0009] In Patent Document 6, a polycyclic aromatic compound containing boron and an organic EL device using the same are reported. However, in order to further improve the device characteristics, there is a demand for a material for a light-emitting layer, particularly a dopant material, that can improve the light-emitting efficiency and device lifetime.

Means for Solving the Problems

[0010] As a result of intensive studies to solve the above problems, the present inventors have found that by disposing a layer containing a polycyclic aromatic compound having a fluorine atom introduced therein between a pair of electrodes to form, for example, an organic EL device, an excellent organic EL device can be obtained, and thus completed the present invention. That is, the present invention provides an organic device material such as a fluorine-substituted polycyclic aromatic compound or a multimer thereof as described below, and further an organic EL device material containing a fluorine-substituted polycyclic aromatic compound or a multimer thereof as described below.

[0011] In this specification, the chemical structure and substituents may be represented by the number of carbon atoms. However, the number of carbon atoms in the case where a substituent is substituted on the chemical structure, or the case where a further substituent is substituted on the substituent, means the number of carbon atoms of each of the chemical structure and the substituent, and does not mean the total number of carbon atoms of the chemical structure and the substituent, or the total number of carbon atoms of the substituent and the substituent. For example, "substituent B having Y carbon atoms substituted with substituent A having X carbon atoms" means that "substituent A having X carbon atoms" is substituted on "substituent B having Y carbon atoms", and Y is not the total number of carbon atoms of substituent A and substituent B. Further, for example, "substituent B having Y carbon atoms substituted with substituent A" means that "(substituent A without carbon number limitation)" is substituted on "substituent B having Y carbon atoms", and Y is not the total number of carbon atoms of substituent A and substituent B.

[0012] 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).

Chemical Formula

[0013] 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 may be substituted with substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted diarylamino, substituted or unsubstituted diheteroarylamino, substituted or unsubstituted arylheteroarylamino, substituted or unsubstituted diarylboryl (the 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, and further, these rings have a 5-membered ring or a 6-membered ring that shares a bond with the central fused 2-ring structure of the above formula composed of Y 1 , X 1 and X 2 and have a 5-membered ring or a 6-membered ring that shares a bond with the central fused 2-ring structure of the above formula. Y 1is B, P, P=O, P=S, Al, Ga, As, Si-R or Ge-R, where R in the Si-R and Ge-R is aryl, alkyl or cycloalkyl, X 1 and X 2 are each independently O, N-R, S or Se, where R in the N-R is aryl which may be substituted with alkyl or cycloalkyl, heteroaryl which may be substituted with alkyl or cycloalkyl, alkyl or cycloalkyl, and R in the N-R may be bonded to the A ring, B ring and / or C ring by -O-, -S-, -C(-R)2- or a single bond, 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 dimer or trimer having two or three structures represented by general formula (1), and At least one hydrogen in the compound or structure represented by formula (1) is substituted with fluorine, The polycyclic aromatic compound or its multimer according to item 1.

[0014] Item 3. The polycyclic aromatic compound or its multimer according to item 1, represented by the following general formula (2).

Chemical formula

[0015] Item 4. R 1 ~R 11is, independently of each other, hydrogen, aryl having 6 to 30 carbon atoms, heteroaryl having 2 to 30 carbon atoms, diarylamino (wherein aryl is aryl having 6 to 12 carbon atoms), diarylboryl (wherein aryl is aryl having 6 to 12 carbon atoms, and the two aryls may be bonded via a single bond or a linking group), alkyl having 1 to 24 carbon atoms or cycloalkyl having 3 to 24 carbon atoms, and R 1 ~R 11 adjacent groups among them may be bonded to each other to form an aryl ring having 9 to 16 carbon atoms or a heteroaryl ring having 6 to 15 carbon atoms together with the a-ring, b-ring or c-ring, 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 of the Si-R is aryl having 6 to 10 carbon atoms, alkyl having 1 to 4 carbon atoms or cycloalkyl having 5 to 10 carbon atoms, X 1 and X 2 are, independently of each other, O, N-R or S, and R of the N-R is aryl having 6 to 10 carbon atoms, alkyl having 1 to 4 carbon atoms or cycloalkyl having 5 to 10 carbon atoms, At least one hydrogen in the compound represented by the formula (2) may be substituted with cyano, chlorine, bromine, iodine or deuterium, and At least one hydrogen in the compound represented by the formula (2) is substituted with fluorine, The polycyclic aromatic compound or its multimer according to item 3.

[0016] Item 5. R 1 ~R 11is, independently of one another, hydrogen, aryl having 6 to 16 carbon atoms, heteroaryl having 2 to 20 carbon atoms, diarylamino (wherein aryl is aryl having 6 to 10 carbon atoms), diarylboryl (wherein aryl is aryl having 6 to 10 carbon atoms and the 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, P, P=O or P=S, X 1 and X 2 are, independently of one another, O or N-R, where R in said N-R is aryl having 6 to 10 carbon atoms, alkyl having 1 to 4 carbon atoms or cycloalkyl having 5 to 10 carbon atoms, and at least one hydrogen in the compound represented by formula (2) is substituted with fluorine, The polycyclic aromatic compound according to item 3 or a multimer thereof.

[0017] Item 6. R 1 ~R 11 are, independently of one another, hydrogen, aryl having 6 to 16 carbon atoms, diarylamino (wherein aryl is aryl having 6 to 10 carbon atoms), diarylboryl (wherein aryl is aryl having 6 to 10 carbon atoms and the 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 N-R, or X 1 is N-R and X 2 is O, where R in said N-R is aryl having 6 to 10 carbon atoms, alkyl having 1 to 4 carbon atoms or cycloalkyl having 5 to 10 carbon atoms, and at least one hydrogen in the compound represented by formula (2) is substituted with fluorine, The polycyclic aromatic compound according to item 3 or a multimer thereof.

[0018] Item 7. The polycyclic aromatic compound or its multimer according to any one of items 1 to 6, wherein R in N-R is a fluorine-substituted aryl or heteroaryl.

[0019] Item 8. The polycyclic aromatic compound or its multimer according to item 7, wherein R in N-R is a fluorine-substituted phenyl.

[0020] Item 9. The polycyclic aromatic compound or its multimer according to any one of items 1 to 8, which is substituted with a fluorine-substituted alkyl group or cycloalkyl group, a fluorine-substituted alkoxy group, a fluorine-substituted diarylamino group, a fluorine-substituted diarylboronyl group (the two aryls may be bonded via a single bond or a linking group), a fluorine-substituted carbazolyl group or a fluorine-substituted benzocarbazolyl group.

[0021] Item 10. The polycyclic aromatic compound or its multimer according to item 9, which is substituted with a fluorine-substituted diarylamino group.

[0022] Item 11. The polycyclic aromatic compound or its multimer according to item 10, which is substituted with a fluorine-substituted diphenylamino group.

[0023] Item 12. The polycyclic aromatic compound according to item 1, which is represented by any of the following structural formulas.

Chemical formula

[0024] Item 13. The polycyclic aromatic compound according to item 1, which is represented by any of the following structural formulas.

Chemical formula

[0025] Item 14. A material for an organic device, containing a polycyclic aromatic compound or a multimer thereof described in any one of Items 1 to 13.

[0026] Item 15. The material for an organic device according to Item 14, wherein the material for an organic device is a material for an organic electroluminescent element, a material for an organic field effect transistor, or a material for an organic thin film solar cell.

[0027] Item 16. The material for an organic electroluminescent element according to Item 15, which is a material for a light emitting layer.

[0028] Item 17. An organic electroluminescent element having a pair of electrodes composed 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.

[0029] Item 18. The organic electroluminescent element according to Item 17, wherein the light emitting layer includes a host and the material for a light emitting layer as a dopant.

[0030] Item 19. The organic electroluminescent element according to Item 18, wherein the host is an anthracene-based compound, a fluorene-based compound, or a dibenzocrisene-based compound.

[0031] Item 20. The organic electroluminescent element according to any one of Items 17 to 19, having 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 contains at least one selected from the group consisting of a borane derivative, a pyridine derivative, a fluoranthene derivative, a BO-based derivative, an anthracene derivative, a benzofluorene derivative, a phosphine oxide derivative, a pyrimidine derivative, a carbazole derivative, a triazine derivative, a benzimidazole derivative, a phenanthroline derivative, and a quinolinol-based metal complex.

[0032] Item 21. The organic electroluminescent device according to Item 20, wherein the electron transport layer and / or the electron injection layer further contains at least one selected from the group consisting of an alkali metal, an alkaline earth metal, a rare earth metal, an oxide of an alkali metal, a halide of an alkali metal, an oxide of an alkaline earth metal, a halide of an alkaline earth metal, an oxide of a rare earth metal, a halide of a rare earth metal, an organic complex of an alkali metal, an organic complex of an alkaline earth metal, and an organic complex of a rare earth metal.

[0033] Item 22. A display device or a lighting device including the organic electroluminescent device according to any one of Items 17 to 21.

Advantages of the Invention

[0034] According to a preferred embodiment of the present invention, a novel fluorine-substituted polycyclic aromatic compound that can be used as a material for an organic device such as a material for an organic EL device can be provided, and an excellent organic device such as an organic EL device can be provided by using this fluorine-substituted polycyclic aromatic compound.

[0035] Specifically, the present inventors have found that a polycyclic aromatic compound (basic skeleton part) in which aromatic rings are connected by hetero elements such as boron, phosphorus, oxygen, nitrogen, and sulfur has a large HOMO-LUMO gap (band gap Eg in a thin film) and high triplet excitation energy (E T) was found to have. This is because the 6-membered ring containing heteroatoms has low aromaticity, so the decrease in the HOMO-LUMO gap associated with the extension of the conjugated system is suppressed. It is considered that this is due to the localization of SOMO1 and SOMO2 in the triplet excited state (T1) by the electronic perturbation of the heteroatoms. In addition, the polycyclic aromatic compound (basic skeleton part) containing heteroatoms according to the present invention has a small exchange interaction between the two orbitals 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 elements. Also, a material having a high triplet excitation energy (E T ) is also useful as an electron transport layer or a hole transport layer of a phosphorescent organic EL element or an organic EL element using thermally activated delayed fluorescence. Furthermore, these polycyclic aromatic compounds (basic skeleton parts) can arbitrarily move the energies of HOMO and LUMO by introducing substituents, so it is possible to optimize the ionization potential and electron affinity according to the surrounding materials.

[0036] In addition to the characteristics of such a basic skeleton part, the compound of the present invention can be expected to have a lower sublimation temperature due to the decrease in the polarity of the molecule 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, it can be purified at a relatively low temperature, so thermal decomposition of the material can be avoided. The same applies to the vacuum deposition process, which is a powerful means for manufacturing organic devices such as organic EL elements. Since the process can be carried out at a relatively low temperature, thermal decomposition of the material can be avoided, and as a result, a high-performance material for organic devices can be obtained.

[0037] As halogens, in addition to fluorine, there are chlorine, bromine, and iodine. However, when chlorine, bromine, or iodine substitutes, the carbon bonds are active, making them somewhat unstable chemically or electrochemically, and there may be driving degradation when used as an organic device material. On the other hand, the carbon-fluorine bond is inert and stable both chemically and electrochemically, so it is suitable as an organic device material.

[0038] In addition, many polymers of polycyclic aromatic compounds have high sublimation temperatures due to factors such as high molecular weight and planarity. Therefore, the reduction in sublimation temperature by introducing fluorine atoms is more effective.

[0039] In addition, by introducing electron-withdrawing fluorine atoms, the emission wavelength can be shortened. This is particularly important in display applications where high color purity blue emission is required.

Brief Description of the Drawings

[0040]

Figure 1

Modes for Carrying Out the Invention

[0041] 1. Fluorine-substituted polycyclic aromatic compounds and their multimers The invention of the present application is a polycyclic aromatic compound represented by the following general formula (1), or a polymer of a polycyclic aromatic compound having a plurality of structures represented by the following general formula (1). Preferably, it is a polycyclic aromatic compound represented by the following general formula (2), or a polymer of a polycyclic aromatic compound having a plurality of structures represented by the following general formula (2). At least one hydrogen in these compounds or structures is substituted with fluorine. In formula (1), "B" in the ring together with "A" and "C" are symbols indicating ring structures represented by rings, and the other symbols are the same as the definitions described above.

Chemical Formula

[0042] In general 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 with a substituent. This substituent is preferably a substituted or unsubstituted aryl, a substituted or unsubstituted heteroaryl, a substituted or unsubstituted diarylamino, a substituted or unsubstituted diheteroarylamino, a substituted or unsubstituted arylheteroarylamino (an amino group having an aryl and a heteroaryl), a substituted or unsubstituted diarylboril (two aryls may be bonded via a single bond or a linking group), a substituted or unsubstituted alkyl, a substituted or unsubstituted cycloalkyl, a substituted or unsubstituted alkoxy, or a substituted or unsubstituted aryloxy. Examples of the substituent when these groups have a substituent include aryl, heteroaryl, alkyl, or cycloalkyl. Further, the above aryl ring or heteroaryl ring is Y 1 , X 1 and X 2 Preferably has a 5-membered ring or a 6-membered ring that shares a bond with the central fused 2-ring structure of general formula (1) composed of

[0043] Here, the "fused 2-ring structure" means a structure in which two saturated hydrocarbon rings composed of Y 1 , X 1 and X 2 shown in the center of general formula (1) are fused. Further, the "6-membered ring that shares a bond with the fused 2-ring structure" means, 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). Further, "(the aryl ring or heteroaryl ring that is ring A) has this 6-membered ring" means that ring A is formed only by this 6-membered ring, or ring A is formed by further fusing other rings or the like to this 6-membered ring so as to include this 6-membered ring. In other words, the "aryl ring or heteroaryl ring (ring A) having a 6-membered ring" referred to here means that the 6-membered ring constituting all or part of ring A is fused to the fused 2-ring structure. The same explanation applies to "ring B (ring b)", "ring C (ring c)", and "5-membered ring".

[0044] The A ring (or B ring, C ring) in general formula (1) corresponds to the a ring in general formula (2) and its substituents R 1 ~R 3 (or the b ring and its substituents R 8 ~R 11 , the c ring and its substituents R 4 ~R 7 ). That is, general formula (2) corresponds to a structure in which "A - C rings having a 6 - membered ring" are selected as the A - C rings of general formula (1). In that sense, each ring in general formula (2) is represented by lowercase a - c.

[0045] In general formula (2), adjacent groups among the substituents R 1 ~R 11 may combine with each other to form an aryl ring or a heteroaryl ring together with the a ring, b ring or c ring, and at least one hydrogen in the formed ring may be substituted with aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, diarylboril (the two aryls may be bonded 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, depending on the mutual bonding form of the substituents in the a ring, b ring and c ring, the polycyclic aromatic compound represented by general formula (2) has a ring structure change as shown in the following formulas (2 - 1) and (2 - 2). The A' ring, B' ring and C' ring in each formula correspond to the A ring, B ring and C ring in general formula (1) respectively. Also, the definitions of R 1 ~R 11 , a, b, c, Y 1 , X 1 and X 2 are the same as the definitions in general formula (2).

[0046]

Chemical formula

[0047] In the A' ring, B' ring, and C' ring in the above formulas (2-1) and (2-2), when explained by the general formula (2), the substituent R 1 ~R 11 represents an aryl ring or a heteroaryl ring formed by the bonding of adjacent groups among them together with the a ring, b ring, and c ring respectively (it can also be said to be a condensed ring formed by the condensation of 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 the a ring, b ring, and c ring have changed to the A' ring, B' ring, and C' ring. Also, as can be seen from the above formulas (2-1) and (2-2), for example, R 8 of the b ring and R 7 of the c ring, R 11 of the b ring and R 1 of the a ring, R 4 of the c ring and R 3 of the a ring, etc. do not fall under "adjacent groups", and they do not bond. That is, "adjacent groups" means groups adjacent on the same ring.

[0048] The compounds represented by the above formulas (2-1) and (2-2) are, for example, compounds having an A' ring (or B' ring or C' ring) formed by the condensation of a benzene ring, an indole ring, a pyrrole ring, a benzofuran ring, or a benzothiophene ring to the benzene ring which is the a ring (or b ring or c ring), and the formed condensed ring A' (or condensed ring B' or condensed ring C') is a naphthalene ring, a carbazole ring, an indole ring, a dibenzofuran ring, or a dibenzothiophene ring respectively.

[0049] Y 1 in the general formula (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. In the case of P=O, P=S, Si-R, or Ge-R, the atom bonding to the A ring, B ring, or C ring is P, Si, or Ge. Y 1 is preferably B, P, P=O, P=S, or Si-R, and B is particularly preferred. This explanation is the same for Y 1 in the general formula (2).

[0050] X in General Formula (1) 1 and X 2 are each independently O, N-R, S or Se, where R in N-R is optionally substituted aryl, optionally substituted heteroaryl, optionally substituted alkyl or optionally substituted cycloalkyl, and R in N-R may be bonded to the B ring and / or C ring by a linking group or a single bond. As the linking group, -O-, -S- or -C(-R)2- is preferred. Here, R in "-C(-R)2-" is hydrogen, alkyl or cycloalkyl. This description also applies to X 1 and X 2 in General Formula (2).

[0051] Here, the provision in General Formula (1) that "R in N-R is bonded to the A ring, B ring and / or C ring by a linking group or a single bond" corresponds to the provision in General Formula (2) that "R in N-R is bonded to the a ring, b ring and / or c ring by -O-, -S-, -C(-R)2- or a single bond".

[0052] This provision can be represented by a compound having a ring structure in which X 1 and X 2 are incorporated into the condensed ring B' and condensed ring C'. That is, for example, with respect to the benzene ring which is the b ring (or c ring) in General Formula (2), a compound having a B' ring (or C' ring) formed by condensing another ring so as to incorporate X 1 (or X 2 ). The formed condensed ring B' (or condensed ring C') is, for example, a phenoxazine ring, a phenothiazine ring or an acridine ring.

[0053] Also, the above provision can also be represented by a compound having a ring structure in which X 1 and / or X 2 is incorporated into the condensed ring A'. That is, for example, with respect to the benzene ring which is the a ring in General Formula (2), X 1 (and / or X2 ) is a compound having an A' ring formed by the condensation of other rings so as to incorporate

[0054]

Chemical formula

[0055] Examples of the "aryl ring" which is the A ring, B ring and C ring of the general formula (1) include aryl rings having 6 to 30 carbon atoms, preferably aryl rings having 6 to 16 carbon atoms, more preferably aryl rings having 6 to 12 carbon atoms, and particularly preferably aryl rings having 6 to 10 carbon atoms. This "aryl ring" corresponds to the "aryl ring" formed by the bonding of adjacent groups among 1 ~R 11 together with the a ring, b ring or c ring. Also, since the a ring (or b ring, c ring) is already composed of a benzene ring having 6 carbon atoms, the total number of carbon atoms in the condensed ring formed by the condensation of a 5-membered ring with this is 9, which is the lower limit of the number of carbon atoms.

[0056] Specific examples of the "aryl ring" include a benzene ring which is a monocyclic system, a biphenyl ring which is a bicyclic system, a naphthalene ring which is a condensed bicyclic system, a terphenyl ring which is a tricyclic system (m-terphenyl, o-terphenyl, p-terphenyl), an acenaphthylene ring, a fluorene ring, a phenalene ring, a phenanthrene ring which are condensed tricyclic systems, a triphenylene ring, a pyrene ring, a naphthacene ring which are condensed tetracyclic systems, a perylene ring, a pentacene ring which are condensed pentacyclic systems, etc.

[0057] Examples of the "heteroaryl ring" which is Ring A, Ring B and Ring C of the general formula (1) include heteroaryl rings having 2 to 30 carbon atoms, preferably heteroaryl rings having 2 to 25 carbon atoms, more preferably heteroaryl rings having 2 to 20 carbon atoms, still more preferably heteroaryl rings having 2 to 15 carbon atoms, and particularly preferably heteroaryl rings having 2 to 10 carbon atoms. Further, examples of the "heteroaryl ring" include heterocyclic rings containing 1 to 5 heteroatoms selected from oxygen, sulfur and nitrogen in addition to carbon as ring-constituting atoms. Note that this "heteroaryl ring" corresponds to the "heteroaryl ring" formed by bonding adjacent groups among "R 1 ~R 11 " together with Ring a, Ring b or Ring c. Also, since Ring a (or Ring b, Ring c) is already composed of a benzene ring having 6 carbon atoms, the total number of carbon atoms in the condensed ring formed by condensing a 5-membered ring with this is 6, which is the lower limit of the number of carbon atoms.

[0058] Specific examples of the "heteroaryl ring" 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, phenoxathiin ring, phenoxazine ring, phenothiazine ring, phenazine ring, indolizine ring, furan ring, benzofuran ring, isobenzofuran ring, dibenzofuran ring, thiophene ring, benzothiophene ring, dibenzothiophene ring, furazan ring, oxadiazole ring, thianthrene ring and the like.

[0059] At least one hydrogen in the above-mentioned "aryl ring" or "heteroaryl ring" may be substituted with a first substituent, which is a substituted or unsubstituted "aryl", a substituted or unsubstituted "heteroaryl", a substituted or unsubstituted "diaryl amino", a substituted or unsubstituted "diheteroaryl amino", a substituted or unsubstituted "aryl heteroaryl amino", a substituted or unsubstituted "diaryl boryl (the two aryls may be bonded via a single bond or a linking group)", a substituted or unsubstituted "alkyl", a substituted or unsubstituted "cycloalkyl", a substituted or unsubstituted "alkoxy", or a substituted or unsubstituted "aryloxy. However, as the first substituent, the "aryl", "heteroaryl", the aryl of "diaryl amino", the heteroaryl of "diheteroaryl amino", the aryl and heteroaryl of "aryl heteroaryl amino", the aryl of "diaryl boryl", and the aryl of "aryloxy" include the monovalent groups of the above-mentioned "aryl ring" or "heteroaryl ring".

[0060] Moreover, as the "alkyl" as the first substituent, it may be either linear or branched, for example, a linear alkyl having 1 to 24 carbon atoms or a branched alkyl having 3 to 24 carbon atoms. An alkyl having 1 to 18 carbon atoms (a branched alkyl having 3 to 18 carbon atoms) is preferred, an alkyl having 1 to 12 carbon atoms (a branched alkyl having 3 to 12 carbon atoms) is more preferred, an alkyl having 1 to 6 carbon atoms (a branched alkyl having 3 to 6 carbon atoms) is even more preferred, and an alkyl having 1 to 4 carbon atoms (a branched alkyl having 3 to 4 carbon atoms) is particularly preferred.

[0061] Specific alkyl groups 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, n-tridecyl, 1-hexylheptyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-eicosyl, and the like.

[0062] Also, as the "cycloalkyl" as the first substituent, cycloalkyl having 3 to 24 carbon atoms, cycloalkyl having 3 to 20 carbon atoms, 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 can be mentioned.

[0063] Specific cycloalkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, and their alkyl (especially methyl) substituents 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.

[0064] Examples of the "alkoxy" as the first substituent include linear alkoxy groups having 1 to 24 carbon atoms or branched alkoxy groups having 3 to 24 carbon atoms. Alkoxy groups having 1 to 18 carbon atoms (branched alkoxy groups having 3 to 18 carbon atoms) are preferred, alkoxy groups having 1 to 12 carbon atoms (branched alkoxy groups having 3 to 12 carbon atoms) are more preferred, alkoxy groups having 1 to 6 carbon atoms (branched alkoxy groups having 3 to 6 carbon atoms) are even more preferred, and alkoxy groups having 1 to 4 carbon atoms (branched alkoxy groups having 3 to 4 carbon atoms) are particularly preferred.

[0065] Specific examples of alkoxy include methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, s-butoxy, t-butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, and the like.

[0066] In addition, for the "aryl" in the "diarylboronyl" as the first substituent, the description of aryl mentioned above can be cited. Further, these two aryl groups may be bonded via a single bond or a linking group (for example, >C(-R)2, >O, >S, or >N-R). Here, R in >C(-R)2 and >N-R is aryl, heteroaryl, diarylamino, alkyl, cycloalkyl, alkoxy, or aryloxy (the above are the first substituents), and the first substituent may be further substituted with aryl, heteroaryl, alkyl, or cycloalkyl (the above are the second substituents). Specific examples of these groups can cite the description of aryl, heteroaryl, diarylamino, alkyl, cycloalkyl, alkoxy, or aryloxy as the first substituent mentioned above.

[0067] Specifically, the emission wavelength can be adjusted by the steric hindrance, electron-donating property, and electron-withdrawing property of the structure of the first substituent, and it is preferably a group represented by any of the following structural formulas (S-1) to (S-94), more preferably a group represented by any of formula (S-1), formula (S-2), formula (S-5), formula (S-9) to formula (S-19), formula (S-24) to formula (S-50), and formula (S-51) to formula (S-94), and even more preferably a group represented by any of formula (S-1), formula (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).

[0068] In the following structural formulas, "Me" represents methyl and "tBu" represents t-butyl.

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

[0069] The first substituent, a substituted or unsubstituted "aryl", a substituted or unsubstituted "heteroaryl", a substituted or unsubstituted "diaryl amino", a substituted or unsubstituted "diheteroaryl amino", a substituted or unsubstituted "aryl heteroaryl amino", a substituted or unsubstituted "diaryl boryl (the two aryls may be bonded via a single bond or a linking group)", a substituted or unsubstituted "alkyl", a substituted or unsubstituted "cycloalkyl", a substituted or unsubstituted "alkoxy", or a substituted or unsubstituted "aryloxy", as described as substituted or unsubstituted, at least one hydrogen in them may be substituted with a second substituent. Examples of this second substituent include aryl, heteroaryl, alkyl, or cycloalkyl, and specific substituents thereof can refer to the monovalent groups of the "aryl ring" or "heteroaryl ring" described above, or the descriptions of "alkyl" or "cycloalkyl" as the first substituent. Also, for aryl and heteroaryl as the second substituent, groups in which at least one hydrogen in them is substituted with an aryl such as phenyl (specific examples are the groups described above), an alkyl such as methyl (specific examples are the groups described above), or a cycloalkyl such as cyclohexyl (specific examples are the groups described above) are also included in aryl and heteroaryl as the second substituent. As an 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 is also included in heteroaryl as the second substituent.

[0070] R in general formula (2) 1 ~R 11 Examples of aryl, heteroaryl, aryl of diaryl amino, heteroaryl of diheteroaryl amino, aryl and heteroaryl of aryl heteroaryl amino, aryl of diaryl boryl, or aryl of aryloxy in ~R 1 ~R 11As the alkyl, cycloalkyl or alkoxy in [general formula (1)], reference can be made to the descriptions of "alkyl", "cycloalkyl" or "alkoxy" as the first substituent in the description of the above general formula (1). Further, aryl, heteroaryl, alkyl or cycloalkyl as substituents for these groups are the same. Also, R 1 ~R 11 When adjacent groups among them are bonded to form an aryl ring or a heteroaryl ring together with ring a, ring b or ring c, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, diarylboril, alkyl, cycloalkyl, alkoxy or aryloxy as substituents for these rings, and further aryl, heteroaryl, alkyl or cycloalkyl as additional substituents are the same.

[0071] Y in general formula (1) 1 In Si-R and Ge-R in [general formula (1)], R is aryl, alkyl or cycloalkyl, and examples of this aryl, alkyl or cycloalkyl include the groups described above. Particularly, aryl having 6 to 10 carbon atoms (for example, phenyl, naphthyl, etc.), alkyl having 1 to 4 carbon atoms (for example, methyl, ethyl, etc.) or cycloalkyl having 5 to 10 carbon atoms (preferably cyclohexyl or adamantyl) are preferred. This description is the same for Y in general formula (2) 1 as well.

[0072] X in general formula (1) 1 and X 2R in N-R in the above formula may be substituted with the above-described second substituent, and is aryl, heteroaryl, alkyl or cycloalkyl. At least one hydrogen in aryl or heteroaryl may be substituted with, for example, alkyl or cycloalkyl. Examples of this aryl, heteroaryl, alkyl and cycloalkyl include the groups described above. Particularly preferred are aryl having 6 to 10 carbon atoms (for example, phenyl, naphthyl, etc.), heteroaryl having 2 to 15 carbon atoms (for example, carbazolyl, etc.), alkyl having 1 to 4 carbon atoms (for example, methyl, ethyl, etc.) or cycloalkyl having 5 to 10 carbon atoms (preferably cyclohexyl or adamantyl). This description also applies to X in general formula (2). 1 and X 2 is the same.

[0073] R in the linking group “-C(-R)2-” in general formula (1) is hydrogen, alkyl or cycloalkyl. Examples of this alkyl and cycloalkyl include the groups described above. Particularly preferred are alkyl having 1 to 4 carbon atoms (for example, methyl, ethyl, etc.) or cycloalkyl having 5 to 10 carbon atoms (preferably cyclohexyl or adamantyl). This description also applies to the linking group “-C(-R)2-” in general formula (2).

[0074] The present invention also relates to a multimer of a polycyclic aromatic compound having a plurality of unit structures represented by the general formula (1), preferably a multimer of a polycyclic aromatic compound having a plurality of unit structures represented by the general formula (2). The multimer is preferably a dimer to hexamer, more preferably a dimer to trimer, and particularly preferably a dimer. The multimer may be in a form having a plurality of the above unit structures in one compound. For example, in addition to a form in which the above unit structures are bonded by a plurality of linking groups such as a single bond, an alkylene group having 1 to 3 carbon atoms, a phenylene group, and a naphthylene group (linked multimer), any ring (ring A, ring B or ring C, ring a, ring b or ring c) contained in the above unit structure may be bonded so as to be shared by a plurality of unit structures (ring-sharing multimer), or a form in which any rings (ring A, ring B or ring C, ring a, ring b or ring c) contained in the above unit structure are condensed and bonded (ring-condensed multimer). However, a ring-sharing multimer and a ring-condensed multimer are preferred, and a ring-sharing multimer is more preferred.

[0075] Examples of such multimers include multimer compounds represented by the following formula (2-4), formula (2-4-1), formula (2-4-2), formula (2-5-1) to formula (2-5-4), or formula (2-6). The multimer compound represented by the following formula (2-4) is a multimer compound (ring-sharing type multimer) having a plurality of unit structures represented by the general formula (2) in one compound such that the benzene ring which is the a ring is shared. Further, the multimer compound represented by the following formula (2-4-1) is a multimer compound (ring-sharing type multimer) having two unit structures represented by the general formula (2) in one compound such that the benzene ring which is the a ring is shared. Further, the multimer compound represented by the following formula (2-4-2) is a multimer compound (ring-sharing type multimer) having three unit structures represented by the general formula (2) in one compound such that the benzene ring which is the a ring is shared. Further, the multimer compounds represented by the following formula (2-5-1) to formula (2-5-4) are multimer compounds (ring-sharing type multimer) having a plurality of unit structures represented by the general formula (2) in one compound such that the benzene ring which is the b ring (or c ring) is shared. Further, the multimer compound represented by the following formula (2-6) is a multimer compound (ring-condensed type multimer) having a plurality of unit structures represented by the general formula (2) in one compound such that, for example, the benzene ring which is the b ring (or a ring, c ring) of a certain unit structure and the benzene ring which is the b ring (or a ring, c ring) of a certain unit structure are condensed.

[0076]

Chemical formula

[0077] The multimer compound may be a multimer in which the multimerization form represented by formula (2-4), formula (2-4-1) or formula (2-4-2) is combined with the multimerization form represented by any one of formulas (2-5-1) to (2-5-4) or formula (2-6), or may be a multimer in which the multimerization form represented by any one of formulas (2-5-1) to (2-5-4) is combined with the multimerization form represented by formula (2-6), or may be a multimer in which the multimerization form represented by formula (2-4), formula (2-4-1) or formula (2-4-2) is combined with the multimerization form represented by any one of formulas (2-5-1) to (2-5-4) and the multimerization form represented by formula (2-6).

[0078] In addition, all or part of the hydrogens in the chemical structures of the polycyclic aromatic compounds represented by general formula (1) or (2) and their multimers may be cyano, chlorine, bromine, iodine or deuterium. For example, in formula (1), ring A, ring B, ring C (rings A to C are aryl rings or heteroaryl rings), substituents on rings A to C, Y 1 when it is Si-R or Ge-R, R (= alkyl, cycloalkyl, aryl), and X 1 and X 2 when it is N-R, the hydrogen in R (= alkyl, cycloalkyl, aryl) may be substituted with cyano, chlorine, bromine, iodine or deuterium, and among these, there is an aspect in which all or part of the hydrogens in aryl or heteroaryl are substituted with cyano, chlorine, bromine, iodine or deuterium. Among chlorine, bromine or iodine, chlorine or bromine is preferable, and chlorine is more preferable.

[0079] In addition, the polycyclic aromatic compounds and their multimers according to the present invention can be used as materials for organic devices. Examples of the organic device include an organic electroluminescent element, an organic field effect transistor, or an organic thin film solar cell. In particular, in an organic electroluminescent element, as a dopant material for the light emitting layer, Y 1 is B, X 1 and X 2 is a compound in which it is N-R, Y 1 is B, X 1is O, X 2 a compound where it is N-R, Y 1 is B, X 1 and X 2 a compound where it is O is preferred, as a host material for the light-emitting layer, Y 1 is B, X 1 is O, X 2 a compound where it is N-R, Y 1 is B, X 1 and X 2 a compound where it is O is preferred, as an electron transport material, Y 1 is B, X 1 and X 2 a compound where it is O, Y 1 is P=O, X 1 and X 2 a compound where it is O is preferably used.

[0080] Also, at least one hydrogen in the chemical structure of the polycyclic aromatic compound represented by the general formula (1) or (2) and its multimer is fluorine-substituted, and all hydrogens or some hydrogens may be fluorine.

[0081] As the form of fluorine substitution, a form in which fluorine is directly substituted on the A to C rings of the formula (1), or R of the formula (2) 1 ~R 11In addition to the form in which the hydrogen selected as such is replaced by fluorine, at least one of the hydrogens of aryl, heteroaryl (especially a carbazolyl group or a benzocarbazolyl group), diarylamino, diheteroarylamino, arylheteroarylamino, diarylboril (the two aryls may be bonded via a single bond or a linking group), alkyl, cycloalkyl, alkoxy or aryloxy, which are the above-described first substituents, and at least one of the hydrogens of aryl, heteroaryl, alkyl or cycloalkyl, which are the above-described second substituents, may be replaced by fluorine. Further, at least one of the hydrogens in aryl, heteroaryl, alkyl or cycloalkyl (the above are the first substituents) or the substituents (the second substituents) thereof as R in N-R may be replaced by fluorine. In addition, a pentafluorosulfanyl group (-SF5) etc. can be mentioned.

[0082] As other forms of fluorine substitution, examples include polycyclic aromatic compounds represented by the general formula (1) or (2) and their multimers being substituted with, for example, a fluorine-substituted aryl group, a fluorine-substituted alkyl group or cycloalkyl group, a fluorine-substituted alkoxy group, a fluorine-substituted diarylamino group, a fluorine-substituted diarylboril group (the two aryls may be bonded via a single bond or a linking group), a fluorine-substituted carbazolyl group or a fluorine-substituted benzocarbazolyl group. For the "aryl group", "alkyl group", "cycloalkyl group", "alkoxy group", "diarylamino group" and "diarylboril group", the groups described as the above "first substituents" can be mentioned. As the form of fluorine substitution on the diarylamino group, diarylboril group, carbazolyl group and benzocarbazolyl group, examples include those in which some or all of the hydrogens of the aryl ring or benzene ring in these groups are replaced by fluorine. X in the general formula (1) or (2) 1 and X 2is N-R, where R is preferably a fluorine-substituted aryl (particularly fluorine-substituted phenyl), and the aryl of the diarylamino group as the first substituent or the second substituent is preferably a fluorine-substituted aryl (particularly fluorine-substituted phenyl), X 1 and X 2 is more preferably N-R, where R is a fluorine-substituted aryl (particularly fluorine-substituted phenyl).

[0083] Examples of the "aryl" substituted with fluorine include groups in which at least one hydrogen of the aryl is substituted with fluorine, and specifically include groups represented by any of the following structural formulas (S-100) to (S-110). Among these, groups represented by any of formulas (S-100) to (S-107) are preferred, and groups represented by any of formulas (S-100), (S-103), (S-104), and (S-105) are more preferred. This explanation also applies when fluorine is substituted at the aryl moiety of "diarylamino", "arylheteroarylamino", "diarylborol", or "aryloxy". [Chemical formula]

[0084] Examples of the "alkyl" substituted with fluorine include groups in which at least one hydrogen of the alkyl is substituted with fluorine, and specifically include trifluoromethyl, difluoromethyl, monofluoromethyl, pentafluoroethyl, etc., with trifluoromethyl being preferred. This explanation also applies when fluorine is substituted at the alkyl moiety of "alkoxy (alkyloxy)". Also, examples of the "cycloalkyl" substituted with fluorine include groups in which at least one hydrogen of the cycloalkyl is substituted with fluorine.

[0085] Furthermore, as more specific examples, R in the polycyclic aromatic compound represented by the general formula (2) and its multimer 2Examples include a fluorine-substituted diarylamino group, a fluorine-substituted diarylboryl group (the two aryl groups may be bonded via a single bond or a linking group), or a fluorine-substituted carbazolyl group.

[0086] As an example of this, there can be mentioned a polycyclic aromatic compound represented by the following general formula (2-A), or a multimer of a polycyclic aromatic compound having a plurality of structures represented by the following general formula (2-A). The definitions of the respective symbols in the structural formula are the same as those of the respective symbols in general formula (2).

Chemical formula

[0087] In addition, specific examples of the fluorine-substituted polycyclic aromatic compound and its multimer of the present invention include compounds in which at least one hydrogen in one or more aromatic rings in the compound is substituted with one or more fluorines, for example, compounds substituted with 1 to 2 fluorines.

[0088] Specifically, compounds represented by the following structural formulas can be mentioned. In the following structural formulas, n is independently 0 to 2, preferably 1. In the following structural formulas, "F" represents fluorine, "OPh" represents a phenoxy group, and "Me" represents a methyl group.

[0089]

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[0090]

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[0098] More specific examples of the fluorine-substituted polycyclic aromatic compounds of the present invention include compounds represented by the following structural formulas. In the following structural formulas, "F" represents fluorine, "D" represents deuterium, "Me" represents a methyl group, "Et" represents an ethyl group, and "tBu" represents a t-butyl group.

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[0287] 2. Method for producing fluorine-substituted polycyclic aromatic compounds and their multimers The polycyclic aromatic compounds represented by the general formula (1) or (2) and their multimers are basically first combined with the A ring (a ring), the B ring (b ring), and the C ring (c ring) by a linking group (X 1 or X 2 -containing group) to produce an intermediate (first reaction), and then the A ring (a ring), the B ring (b ring), and the C ring (c ring) are combined with a linking group (Y 1 -containing group) to produce the final product (second reaction). In the first reaction, for example, in the case of an etherification reaction, general reactions such as a nucleophilic substitution reaction and a Ullmann reaction can be used, and in the case of an amination reaction, a general reaction such as a Buchwald-Hartwig reaction can be used. In the second reaction, a tandem hetero Friedel-Crafts reaction (a continuous aromatic electrophilic substitution reaction, the same applies hereinafter) can be used. Further, in any of these reaction steps, by using a fluorinated raw material or adding a step of fluorination or introduction of a fluorine-containing substituent, the compound of the present invention in which the desired position is fluorinated can be produced.

[0288] The second reaction is a reaction for introducing Y 1 that binds the A ring (a ring), the B ring (b ring), and the C ring (c ring), as shown in the following scheme (1) or (2). As an example, Y 1 is a boron atom, X 1 and X2 The case where X is an oxygen atom is shown below. First, the hydrogen atom between X 1 and X 2 is orthometalated with n-butyllithium, sec-butyllithium, t-butyllithium or the like. Next, boron trichloride, boron tribromide or the like is added, and after performing lithium-boron metal exchange, a Brønsted base such as N,N-diisopropylethylamine is added to cause a tandem borofriedel-crafts reaction to obtain the target product. In the second reaction, a Lewis acid such as aluminum trichloride may be added to accelerate the reaction. In the following schemes (1) and (2), and further in each structural formula in the subsequent schemes (3) to (28), the definitions of the symbols are the same as those described above.

[0289]

Chemical formula

Chemical formula

[0290] Note that the above schemes (1) and (2) mainly show the production methods of polycyclic aromatic compounds represented by the general formulas (1) and (2). For their multimers, they can be produced by using intermediates having a plurality of A rings (a rings), B rings (b rings) and C rings (c rings). Details will be described in the following schemes (3) to (5). In this case, the target product can be obtained by doubling or tripling the amount of reagents such as butyllithium used.

[0291]

Chemical formula

Chemical formula

Chemical formula

[0292] In the above scheme, lithium was introduced to the desired position by orthometalation. However, as in the following schemes (6) and (7), a bromine atom or the like is introduced at the position where lithium is to be introduced, and lithium can also be introduced to the desired position by halogen-metal exchange.

[0293]

Chemical formula

Chemical formula

[0294] Also, regarding the method for producing the multimer described in Scheme (3), a halogen such as a bromine atom or a chlorine atom is introduced at the position where lithium is to be introduced as in the above Schemes (6) and (7), and lithium can also be introduced to the desired position by halogen-metal exchange (the following Schemes (8), (9) and (10)).

[0295]

Chemical formula

Chemical formula

Chemical formula

[0296] According to this method, the target product can be synthesized even in cases where orthometalation cannot be carried out due to the influence of substituents, which is useful.

[0297] By appropriately selecting the above synthetic methods and also appropriately selecting the raw materials to be used, the desired position can be fluorinated, having a substituent at the desired position, and a polycyclic aromatic compound and its multimer in which Y 1 is a boron atom, X 1 and X 2 are oxygen atoms can be synthesized.

[0298] Next, as an example, Y 1 is a boron atom, X1 and X 2 When is a nitrogen atom, it is shown in the following schemes (11) and (12). X 1 and X 2 Similar to the case where is an oxygen atom, first, the hydrogen atom between X 1 and X 2 is orthometalated with n-butyllithium or the like. Then, boron tribromide or the like is added, and after performing metal exchange of lithium-boron, a Brønsted base such as N,N-diisopropylethylamine is added to cause a tandem borofriedel-crafts reaction to obtain the target product. Here, a Lewis acid such as aluminum trichloride may be added to promote the reaction. Furthermore, as shown in the following scheme (12’), if the reaction is carried out at a high temperature of about 200 °C, the target product can also be obtained only with boron tribromide. Also, at some point in these reaction steps, a fluorinated raw material can be used, or a step of fluorination or introduction of a fluorine-containing substituent can be added to produce the compound of the present invention in which the desired position is fluorinated.

[0299]

Chemical formula

Chemical formula

Chemical formula

[0300] Also, when Y 1 is a boron atom, X 1 and X[[ID=3B]] 2 Regarding the multimer in the case where is a nitrogen atom, a halogen such as a bromine atom or a chlorine atom is introduced at the position where lithium is to be introduced as in the above schemes (6) and (7), and lithium can also be introduced to the desired position by halogen-metal exchange (the following schemes (13), (14) and (15)). 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, X 1 and X 2It is also possible to synthesize multimers when Y is a nitrogen atom.

[0301]

Chem.

Chem.

Chem.

Chem.

[0302] Next, as an example, when Y 1 is a phosphorothioate, phosphoxide or phosphorus atom, and X 1 and X 2 are oxygen atoms, the cases are shown in the following schemes (16) to (19). Similar to before, first, the hydrogen atom between X 1 and X 2 is orthometalated 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 Bronsted base such as N,N-diisopropylethylamine are added to cause a tandem phospha-Friedel-Crafts reaction to obtain a compound in which Y 1 is a phosphorothioate. Further, by treating the obtained phosphorothioate compound with m-chloroperbenzoic acid (m-CPBA), a compound in which Y 1 is a phosphoxide can be obtained, and by treating with triethylphosphine, a compound in which Y 1 [[ID=4,3]]is a phosphorus atom can be obtained. Further, at some point in these reaction steps, by using a fluorinated raw material or adding a step of fluorination or introduction of a fluorine-containing substituent, the compound of the present invention in which a desired position is fluorinated can be produced.

[0303]

Chem.

Chem.

[0304] Also, when Y 1 is a thionophosphide, X 1 and X 2 are oxygen atoms, for the multimer, halogen such as a bromine atom or a chlorine atom is introduced at the position where lithium is to be introduced as in the above schemes (6) and (7), and lithium can also be introduced at the desired position by halogen-metal exchange (the following schemes (20), (21) and (22)). Also, for the multimer in which Y 1 is a thionophosphide, X 1 and X 2 are oxygen atoms, the multimer can also be treated with m-chloroperbenzoic acid (m-CPBA) as in the above schemes (18) and (19) to obtain a compound in which Y 1 is a phosphine oxide, and treated with triethylphosphine to obtain a compound in which Y 1 is a phosphorus atom.

[0305] [Chemistry] [Chemistry] [Chemistry]

[0306] Here, examples where Y 1 is B, P, P=O or P=S, and X 1 and X 2 are O or NR have been described. However, by appropriately changing the raw materials, Y 1 can be Al, Ga, As, Si-R or Ge-R, or X 1 and X 2Compounds where it is S can also be synthesized.

[0307] In the above scheme, examples of steps for producing the target product include using halogen-metal exchange and coupling reactions. Although fluorine atoms are included among the halogens, generally, since the carbon-fluorine bond is very inert, when fluorine is used as the halogen, halogen-metal exchange and coupling reactions generally do not occur. Therefore, in most cases, even when fluorine atoms coexist, the reaction proceeds selectively at the positions of chlorine, bromine, or iodine, so using a raw material containing a fluorine atom does not inhibit the progress of the above-described reaction, and the compound of the present invention in which the desired position is fluorinated can be produced.

[0308] Also, not only fluorine atom substitution, but also using a raw material substituted with a fluorine-substituted alkyl group, a fluorine-substituted aryl group, a fluorine-substituted heteroaryl group, a fluorine-substituted aryloxy group, or a pentafluorosulfanyl group (-SF5), or adding a step of introducing these functional groups, the compound of the present invention in which the desired position is fluorinated can be produced.

[0309] Specific examples of the solvent used in the above reaction are t-butylbenzene, xylene, and the like.

[0310] Also, in the general formula (2), the substituents R of the a-ring, b-ring, and c-ring 1 ~R 11Among them, adjacent groups may combine with each other to form an aryl ring or a heteroaryl ring together with the a-ring, b-ring or c-ring, and at least one hydrogen in the formed ring may be substituted with an aryl or heteroaryl. Therefore, depending on the mutual bonding forms of the substituents in the a-ring, b-ring and c-ring, the polycyclic aromatic compound represented by the general formula (2) has a ring structure constituting the compound changed as shown in the formulas (2-1) and (2-2) of the following schemes (23) and (24). These compounds can be synthesized by applying the synthesis methods shown in the above schemes (1) to (19) to the intermediates shown in the following schemes (23) and (24). Also, at some point in these reaction steps, by using a fluorinated raw material or adding a step of fluorination or introduction of a fluorine-containing substituent, the compound of the present invention in which a desired position is fluorinated can be produced.

[0311] [Chemical formula] [Chemical formula]

[0312] The A'-ring, B'-ring and C'-ring in the above formulas (2-1) and (2-2) are such that adjacent groups among the substituents R 1 ~R 11 combine with each other to represent an aryl ring or a heteroaryl ring formed together with the a-ring, b-ring and c-ring respectively (which can also be said to be a condensed ring formed by condensing another ring structure with the a-ring, b-ring or c-ring). Although not shown in the formula, there are also compounds in which all of the a-ring, b-ring and c-ring have changed to the A'-ring, B'-ring and C'-ring.

[0313] Also, the provision in the general formula (2) that "R in N-R is bonded to the a-ring, b-ring and / or c-ring by -O-, -S-, -C(-R)2- or a single bond" is represented by the formula (2-3-1) in the following scheme (25), X 1 or X 2Compounds having a ring structure incorporated into the condensed ring B' and the condensed ring C', or X represented by the formula (2-3-2) or the formula (2-3-3) 1 or X 2 can be represented by a compound having a ring structure incorporated into the condensed ring A'. These compounds can be synthesized by applying the synthesis methods shown in the above schemes (1) to (19) to the intermediates shown in the following scheme (25). Further, at some point in these reaction steps, by using a fluorinated raw material or adding a step of fluorination or introduction of a fluorine-containing substituent, the compound of the present invention in which the desired position is fluorinated can be produced.

[0314]

Chemical formula

[0315] Also, in the synthesis methods of the above schemes (1) to (17) and (20) to (25), before adding boron trichloride, boron tribromide, etc., the hydrogen atom (or halogen atom) between X 1 and X 2 is ortho-metalated with butyllithium or the like to show an example of a tandem hetero Friedel-Crafts reaction, but the reaction can also proceed by adding boron trichloride, boron tribromide, etc. without performing ortho-metalation using butyllithium or the like.

[0316] Also, when Y 1 is a phosphorus-based compound, as shown in the following schemes (26) and (27), X 1 and X 2In the following formula, the hydrogen atom between O's is orthometalated with n-butyllithium, sec-butyllithium, t-butyllithium or the like, then bisdiethylaminophosphine chloride is added, and after metal exchange of lithium-phosphorus, a Lewis acid such as aluminum trichloride is added to carry out a tandem phospha-Friedel-Crafts reaction to obtain the target product. This reaction method is also described in International Publication No. WO2010 / 104047 (for example, page 27). Further, at some point in these reaction steps, a fluorinated raw material can be used or a step of fluorination or introduction of a fluorine-containing substituent can be added to produce the compound of the present invention in which the desired position is fluorinated.

[0317] [Chemical formula] [Chemical formula]

[0318] In addition, also in the above schemes (26) and (27), a multimeric compound can be synthesized by using an orthometalation reagent such as butyllithium in a molar amount 2 times or 3 times the molar amount of intermediate 1. Further, a halogen such as a bromine atom or a chlorine atom is introduced in advance at the position where a metal such as lithium is to be introduced, and the metal can be introduced at the desired position by halogen-metal exchange.

[0319] In addition, for the polycyclic aromatic compound represented by the general formula (2-A), as shown in the following scheme (28), a fluorinated intermediate is synthesized and cyclized to synthesize a polycyclic aromatic compound in which the desired position is substituted with a fluorine atom. In scheme (28), X represents a halogen or hydrogen, and the definitions of the other symbols are the same as the definitions of the symbols in the general formula (2).

[0320] [Chemical formula]

[0321] The intermediate before cyclization in Scheme (28) can also be synthesized by the methods shown in Scheme (1) and the like. That is, by appropriately combining reactions such as the Buchwald-Hartwig reaction, the Suzuki coupling reaction, or etherification reactions such as nucleophilic substitution reactions and Ullmann reactions, an intermediate having a desired substituent can be synthesized. In these reactions, commercially available raw materials can be used as precursors for fluorination.

[0322] 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 the Buchwald-Hartwig reaction, X 1 、X 2 When is N-R, by an amination reaction such as the Buchwald-Hartwig reaction, X 1 、X 2 When is O, it is derived into intermediate (M-3) by etherification using phenol, and then, for example, after acting a metalation reagent such as butyllithium for transmetalation, after acting a boron halide such as boron tribromide, the compound of general formula (2-A) can be synthesized by a tandem bora Friedel-Crafts reaction by acting a Brønsted base such as diethylisopropylamine. These reactions can also be applied to other fluorinated compounds.

[0323] Examples of the orthometalation reagent used in the above Schemes (1) to (28) include alkyllithiums such as methyllithium, n-butyllithium, sec-butyllithium, and t-butyllithium, and organic alkali compounds such as lithium diisopropylamide, lithium tetramethylpiperidide, lithium hexamethyldisilazide, and potassium hexamethyldisilazide.

[0324] In addition, the metal-Y used in the above Schemes (1) to (28) 1As the metal exchange reagent, Y 1 trifluoride, Y 1 trichloride, Y 1 tribromide, Y 1 triiodide, etc. of Y 1 halide, Y such as CIPN(NEt2)2 1 amino halide of Y 1 alkoxide of Y 1 aryloxide of Y, etc. can be mentioned.

[0325] In addition, as the Bronsted base used in the above schemes (1) to (28), 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, Ar4BNa, Ar4BK, Ar3B, Ar4Si (where Ar is an aryl such as phenyl), etc. can be mentioned.

[0326] As the Lewis acid used in the above schemes (1) to (28), AlCl3, AlBr3, AlF3, BF3·OEt2, BCl3, BBr3, GaCl3, GaBr3, InCl3, InBr3, In(OTf)3, SnCl4, SnBr4, AgOTf, ScCl3, Sc(OTf)3, ZnCl2, ZnBr2, Zn(OTf)2, MgCl2, MgBr2, Mg(OTf)2, LiOTf, NaOTf, KOTf, Me3SiOTf, Cu(OTf)2, CuCl2, YCl3, Y(OTf)3, TiCl4, TiBr4, ZrCl4, ZrBr4, FeCl3, FeBr3, CoCl3, CoBr3, etc. can be mentioned.

[0327] In the above schemes (1) to (28), a Bronsted base or a Lewis acid may be used to promote the tandem hetero - Friedel - Crafts reaction. However, Y 1 trifluoride, Y 1 trichloride, Y 1 tribromide, Y 1Y such as triiodide 1 When using a halide of 1 , as the aromatic electrophilic substitution reaction proceeds, acids such as hydrogen fluoride, hydrogen chloride, hydrogen bromide, and hydrogen iodide are generated. Therefore, the use of a Bronsted base that captures the acid is effective. On the other hand, Y 1 amino halide of 1 , Y 1 When using an alkoxide of 1 , as the aromatic electrophilic substitution reaction proceeds, amines and alcohols are generated. Therefore, in many cases, it is not necessary to use a Bronsted base. However, since the leaving ability of the amino group and the alkoxy group is low, the use of a Lewis acid that promotes the elimination is effective.

[0328] In addition, the polycyclic aromatic compounds and their multimers of the present invention also include structures in which at least some hydrogen atoms are substituted with cyano, structures substituted with halogens such as chlorine, bromine, and iodine, and structures substituted with deuterium. Such compounds can be synthesized in the same manner as described above by using raw materials in which the desired positions are cyanated, chlorinated, brominated, iodinated, or deuterated.

[0329] 3. Organic devices The fluorine-substituted polycyclic aromatic compound according to the present invention can be used as a material for an organic device. Examples of the organic device include an organic electroluminescent element, an organic field effect transistor, or an organic thin film solar cell.

[0330] 3-1. Organic electroluminescent devices Hereinafter, the organic EL element according to the present embodiment will be described in detail with reference to the drawings. FIG. 1 is a schematic cross-sectional view showing the organic EL element according to the present embodiment.

[0331] <Structure of Organic Electroluminescent Element> 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, a hole transport layer 104 provided on the hole injection layer 103, a light-emitting layer 105 provided on the hole transport layer 104, an electron transport layer 106 provided on the light-emitting layer 105, an electron injection layer 107 provided on the electron transport layer 106, and a cathode 108 provided on the electron injection layer 107.

[0332] Note that the organic EL element 100 may be configured such that the manufacturing order is reversed. For example, it may include a substrate 101, a cathode 108 provided on the substrate 101, an electron injection layer 107 provided on the cathode 108, an electron transport layer 106 provided on the electron injection layer 107, a light-emitting layer 105 provided on the electron transport layer 106, a hole transport layer 104 provided on the light-emitting layer 105, a hole injection layer 103 provided on the hole transport layer 104, and an anode 102 provided on the hole injection layer 103.

[0333] Not all of the above layers are essential. With a minimum structural unit consisting of an anode 102, a light-emitting layer 105, and a cathode 108, the hole injection layer 103, the hole transport layer 104, the electron transport layer 106, and the electron injection layer 107 are layers that can be optionally provided. Also, each of the above layers may consist of a single layer or a plurality of layers.

[0334] As aspects of the layers constituting the organic EL element, in addition to the above-described configuration aspect of "substrate / anode / hole injection layer / hole transport layer / emission layer / electron transport layer / electron injection layer / cathode", "substrate / anode / hole transport layer / emission layer / electron transport layer / electron injection layer / cathode", "substrate / anode / hole injection layer / emission layer / electron transport layer / electron injection layer / cathode", "substrate / anode / hole injection layer / hole transport layer / emission layer / electron injection layer / cathode", "substrate / anode / hole injection layer / hole transport layer / emission layer / electron transport layer / cathode", "substrate / anode / emission layer / electron transport layer / electron injection layer / cathode", "substrate / anode / hole transport layer / emission layer / electron injection layer / cathode", "substrate / anode / hole transport layer / emission layer / electron transport layer / cathode", "substrate / anode / hole injection layer / emission layer / electron injection layer / cathode", "substrate / anode / hole injection layer / emission layer / electron transport layer / cathode", "substrate / anode / emission layer / electron transport layer / cathode", "substrate / anode / emission layer / electron injection layer / cathode" may also be the configuration aspects.

[0335] <Substrate in the organic electroluminescent element> The substrate 101 is a support of the organic EL element 100, and usually, quartz, glass, metal, plastic, etc. are used. The substrate 101 is formed in a plate shape, a film shape, or a sheet shape according to the purpose, and for example, a glass plate, a metal plate, a metal foil, a plastic film, a plastic sheet, etc. are used. Among them, a glass plate and a plate made of a transparent synthetic resin such as polyester, polymethacrylate, polycarbonate, and polysulfone are preferable. In the case of a glass substrate, soda lime glass, alkali-free glass, etc. are used, and the thickness only needs to be sufficient to maintain mechanical strength. For example, a thickness of 0.2 mm or more is sufficient. As the upper limit value of the thickness, for example, it is 2 mm or less, preferably 1 mm or less. Regarding the material of the glass, since it is better that there are fewer eluted ions from the glass, alkali-free glass is preferable, but soda lime glass with a barrier coat such as SiO2 is also commercially available, so this can be used. Further, in order to enhance the gas barrier property, a gas barrier film such as a dense silicon oxide film may be provided on at least one side of the substrate 101. In particular, when a plate, film, or sheet made of a synthetic resin with low gas barrier property is used as the substrate 101, it is preferable to provide a gas barrier film.

[0336] <Anode in an organic electroluminescent device> The anode 102 serves to inject holes into the light-emitting layer 105. When a hole injection layer 103 and / or a 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 layers.

[0337] Examples of materials for forming the anode 102 include inorganic compounds and organic compounds. Examples of inorganic compounds include metals (such as aluminum, gold, silver, nickel, palladium, chromium, etc.), metal oxides (such as indium oxide, tin oxide, indium-tin oxide (ITO), indium-zinc oxide (IZO), etc.), metal halides (such as copper iodide, etc.), copper sulfide, carbon black, ITO glass, Nesa glass, etc. Examples of organic compounds include polythiophenes such as poly(3-methylthiophene), and conductive polymers such as polypyrrole and polyaniline. In addition, it can be appropriately selected and used from among substances used as anodes of organic EL devices.

[0338] The resistance of the transparent electrode is not limited as long as a current sufficient for the light emission of the light-emitting device can be supplied, but it is desirable to have a low resistance from the viewpoint of the power consumption of the light-emitting device. For example, an ITO substrate with a resistance of 300 Ω / square or less can function as an element electrode, but currently substrates with a resistance of about 10 Ω / square can also be supplied. Therefore, it is particularly desirable to use low-resistance products with a resistance of, for example, 100 to 5 Ω / square, preferably 50 to 5 Ω / square. The thickness of the ITO can be arbitrarily selected according to the resistance value, but it is usually used in the range of 50 to 300 nm.

[0339] <Hole injection layer and hole transport layer in an organic electroluminescent device> The positive hole injection layer 103 serves to efficiently inject the positive holes moving from the anode 102 into the light-emitting layer 105 or the positive hole transport layer 104. The positive hole transport layer 104 serves to efficiently transport the positive holes injected from the anode 102 or the positive holes injected from the anode 102 through the positive hole injection layer 103 to the light-emitting layer 105. The positive hole injection layer 103 and the positive hole transport layer 104 are each formed by laminating or mixing one or more of the positive hole injection / transport materials, or by a mixture of a positive hole injection / transport material and a polymer binder. Also, an inorganic salt such as iron(III) chloride may be added to the positive hole injection / transport material to form a layer.

[0340] As the positive hole injection / transport material, it is necessary to efficiently inject and transport the positive holes from the positive electrode between the electrodes to which an electric field is applied, and it is desirable that the positive hole injection efficiency is high and the injected positive holes are efficiently transported. For this purpose, it is preferably a material having a small ionization potential, a large positive hole mobility, excellent stability, and few impurities that can act as traps during production and use.

[0341] As the materials for forming the positive hole injection layer 103 and the positive hole transport layer 104, in the photoconductive material, any compound can be selected and used from the compounds conventionally used as the positive hole charge transport material, p-type semiconductors, and known compounds used for the positive hole injection layer and the positive hole transport layer of the organic EL element. Specific examples thereof include carbazole derivatives (N-phenylcarbazole, polyvinylcarbazole, etc.), biscarbazole derivatives such as bis(N-arylcarbazole) or bis(N-alkylcarbazole), triarylamine derivatives (polymers having an aromatic tertiary amino group in the 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, N4 , 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)amino)triphenylamine and other triphenylamine derivatives, starburst amine derivatives, etc.), stilbene derivatives, phthalocyanine derivatives (metal-free, copper phthalocyanine, etc.), pyrazoline derivatives, hydrazone-based 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. In the polymer system, polycarbonate, styrene derivatives, polyvinylcarbazole, and polysilane having the above monomer in the side chain are preferable, but it is not particularly limited as long as it can form a thin film necessary for manufacturing a light-emitting element, can inject holes from the anode, and can further transport holes.

[0342] Also, it is known that the conductivity of organic semiconductors is strongly affected by their doping. Such organic semiconductor matrix materials are composed of compounds with good electron-donating properties or compounds with good electron-accepting properties. For the doping of electron-donating substances, strong electron acceptors such as tetracyanoquinodimethane (TCNQ) or 2,3,5,6-tetrafluorotetracyano-1,4-benzoquinodimethane (F4TCNQ) are known (for example, see 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 the electron transfer process in electron-donating base materials (hole-transporting materials). The conductivity of the base material changes significantly depending on the number and mobility of the holes. As matrix materials having hole-transporting properties, for example, benzidine derivatives (such as TPD) or starburst amine derivatives (such as TDATA), or specific metal phthalocyanines (especially zinc phthalocyanine (ZnPc), etc.) are known (Japanese Patent Laid-Open No. 2005-167175).

[0343] <Light-emitting layer in the organic electroluminescent device> The light-emitting layer 105 is a layer that emits light by recombining holes injected from the anode 102 and electrons injected from the cathode 108 between electrodes to which an electric field is applied. As the material for forming the light-emitting layer 105, any compound (light-emitting compound) that is excited by the recombination of holes and electrons to emit light may be used, and it is preferable that the compound can form a stable thin film shape and exhibits high light emission (fluorescence) efficiency in the solid state. In the present invention, as the material 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.

[0344] The light-emitting layer may be either a single layer or composed of multiple layers, and each is formed by a light-emitting layer material (host material, dopant material). The host material and the dopant material may each be of one type or a combination of multiple types. The dopant material may be contained in the whole host material or partially contained, either is acceptable. As a doping method, it can be formed by co-evaporation with the host material, but it may also be co-evaporated after mixing with the host material in advance.

[0345] The amount of the host material used varies depending on the type of the host material and may be determined according to the characteristics of the host material. The guideline for the amount of the host material used is preferably 50 to 99.999% by weight of the total light-emitting layer material, more preferably 80 to 99.95% by weight, and still more preferably 90 to 99.9% by weight.

[0346] The amount of the dopant material used varies depending on the type of the dopant material and may be determined according to the characteristics of the dopant material. The guideline for the amount of the dopant used is preferably 0.001 to 50% by weight of the total light-emitting layer material, more preferably 0.05 to 20% by weight, and still more preferably 0.1 to 10% by weight. If it is within the above range, for example, it is preferable in that the concentration quenching phenomenon can be prevented.

[0347] Examples of the host material include condensed ring derivatives such as anthracene, pyrene, dibenzocrisene, or fluorene, which have been known as light emitters, bisstyryl derivatives such as bisstyrylanthracene derivatives and distyrylbenzene derivatives, tetraphenylbutadiene derivatives, and cyclopentadiene derivatives. In particular, anthracene-based compounds, fluorene-based compounds, or dibenzocrisene-based compounds are preferred.

[0348] <Anthracene-based compound> The anthracene-based compound as the host is, for example, a compound represented by the following general formula (3).

Chemical formula

[0349] 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 groups represented by formula (3-X1), formula (3-X2) or formula (3-X3) are bonded to the anthracene ring of formula (3) at *. Preferably, two Xs do not simultaneously become the group represented by formula (3-X3). More preferably, two Xs do not simultaneously become the group represented by formula (3-X2).

[0350] Also, a multimer (preferably a dimer) may be formed using the structure represented by formula (3) as a unit structure. In this case, for example, a form in which the unit structures represented by formula (3) are bonded to each other via X can be mentioned, and examples of this X include a single bond, arylene (such as phenylene, biphenylene and naphthylene), and heteroarylene (a group having a divalent valence such as a pyridine ring, a dibenzofuran ring, a dibenzothiophene ring, a carbazole ring, a benzocarbazole ring and a phenyl-substituted carbazole ring).

[0351] The naphthylene moiety in formula (3-X1) and formula (3-X2) may be condensed with one benzene ring. The structure condensed in this way is as follows.[[ID=I3]]

Chemical formula

[0352] Ar 1 and Ar 2 are each independently hydrogen, phenyl, biphenylyl, terphenylyl, quaterphenylyl, naphthyl, phenanthryl, fluorenyl, benzofluorenyl, chrysenyl, triphenylenyl, pyrenylyl, or a group represented by the above formula (A) (including a carbazolyl group, a benzocarbazolyl group and a phenyl-substituted carbazolyl group). When Ar 1 or Ar 2 is a group represented by formula (A), the group represented by formula (A) is bonded to the naphthalene ring in formula (3-X1) or formula (3-X2) at its *.

[0353] Ar 3 is phenyl, biphenylyl, terphenylyl, quarterphenylyl, naphthyl, phenanthryl, fluorenyl, benzofluorenyl, chrysenyl, triphenylenyl, pyrenylyl, or a group represented by the above formula (A) (including a carbazolyl group, a benzocarbazolyl group, and a phenyl-substituted carbazolyl group). When Ar 3 is a group represented by the formula (A), the group represented by the formula (A) is bonded to the single bond represented by the straight line in the formula (3-X3) at its *. That is, the anthracene ring of the formula (3) is directly bonded to the group represented by the formula (A).

[0354] Also, Ar 3 may have a substituent, and at least one hydrogen in Ar 3 may be further substituted with an alkyl having 1 to 4 carbon atoms, a 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). When the substituent that Ar 3 has is a group represented by the formula (A), the group represented by the formula (A) is bonded to Ar 3 in the formula (3-X3) at its *.

[0355] Ar 4 is each independently hydrogen, phenyl, biphenylyl, terphenylyl, naphthyl, or a silyl substituted with an alkyl having 1 to 4 carbon atoms (such as methyl, ethyl, t-butyl, etc.) and / or a cycloalkyl having 5 to 10 carbon atoms.

[0356] Examples of the alkyl having 1 to 4 carbon atoms that substitutes 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.

[0357] Specific examples of "silyl substituted with an alkyl having 1 to 4 carbon atoms" include trimethylsilyl, triethylsilyl, tripropylsilyl, tri-i-propylsilyl, tributylsilyl, tri-sec-butylsilyl, tri-t-butylsilyl, ethyldimethylsilyl, propyldimethylsilyl, i-propyldimethylsilyl, butyldimethylsilyl, sec-butyldimethylsilyl, t-butyldimethylsilyl, methyldiethylsilyl, propyldiethylsilyl, i-propyldiethylsilyl, butyldiethylsilyl, sec-butyldiethylsilyl, t-butyldiethylsilyl, methyldipropylsilyl, 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.

[0358] Examples of the cycloalkyl having 5 to 10 carbon atoms for substituting the silyl include 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, decahydroazulenyl, and the like, and three hydrogens in the silyl are each independently substituted with these cycloalkyls.

[0359] Specific examples of "silyl substituted with a cycloalkyl having 5 to 10 carbon atoms" include tricyclopentylsilyl, tricyclohexylsilyl, and the like.

[0360] Examples of the substituted silyl also include dialkylcycloalkylsilyl substituted with two alkyls and one cycloalkyl, and alkyldicycloalkylsilyl substituted with one alkyl and two cycloalkyls. Specific examples of the alkyl and cycloalkyl for substitution are the groups described above.

[0361] In addition, the hydrogen in the chemical structure of the anthracene-based compound represented by the general formula (3) may be substituted with a group represented by the above formula (A). When substituted with a group represented by the formula (A), the group represented by the formula (A) substitutes at least one hydrogen in the compound represented by the formula (3) therein.

[0362] The group represented by the formula (A) is one of the substituents that the anthracene-based compound represented by the formula (3) may have.

Chemical formula

[0363] In the above formula (A), Y is -O-, -S- or >N-R 29 and R 21 ~R 28 are each independently hydrogen, optionally substituted alkyl, 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 among R 21 ~R 28 adjacent groups may be bonded to each other to form a hydrocarbon ring, an aryl ring or a heteroaryl ring, and R 29 is hydrogen or optionally substituted aryl.

[0364] R 21 ~R 28In the case of "alkyl which may be substituted" in , the "alkyl" may be either linear or branched, and examples thereof include linear alkyl having 1 to 24 carbon atoms or branched alkyl having 3 to 24 carbon atoms. Alkyl having 1 to 18 carbon atoms (branched alkyl having 3 to 18 carbon atoms) is preferred, alkyl having 1 to 12 carbon atoms (branched alkyl having 3 to 12 carbon atoms) is more preferred, alkyl having 1 to 6 carbon atoms (branched alkyl having 3 to 6 carbon atoms) is even more preferred, and alkyl having 1 to 4 carbon atoms (branched alkyl having 3 to 4 carbon atoms) is particularly preferred.

[0365] Specific examples of the "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, n-tridecyl, 1-hexylheptyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-eicosyl, and the like.

[0366] R 21 ~R 28 In the case of "cycloalkyl which may be substituted" in , the "cycloalkyl" includes cycloalkyl having 3 to 24 carbon atoms, cycloalkyl having 3 to 20 carbon atoms, 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.

[0367] Specific examples of the "cycloalkyl" include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, and their C1-C4 alkyl (especially methyl) substituted derivatives, 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.

[0368] R 21 ~R 28 Examples of the "aryl" in the "optionally substituted aryl" for R~R include aryl having 6 to 30 carbon atoms, preferably aryl having 6 to 16 carbon atoms, more preferably aryl having 6 to 12 carbon atoms, and particularly preferably aryl having 6 to 10 carbon atoms.

[0369] Specific examples of the "aryl" include phenyl which is a monocyclic system, biphenylyl which is a bicyclic system, naphthyl which is a condensed bicyclic system, terphenyl (m-terphenyl, o-terphenyl, p-terphenyl) which is a tricyclic system, acenaphthylenyl, fluorenyl, phenalenyl, phenanthrenyl which are condensed tricyclic systems, triphenylenyl, pyrenyl, naphthacenyl which are condensed tetracyclic systems, perylenyl, pentacenyl which are condensed pentacyclic systems, and the like.

[0370] R 21 ~R 28 Examples of the "heteroaryl" in the "optionally substituted heteroaryl" for R~R include heteroaryl having 2 to 30 carbon atoms, preferably heteroaryl having 2 to 25 carbon atoms, more preferably heteroaryl having 2 to 20 carbon atoms, still more preferably heteroaryl having 2 to 15 carbon atoms, and particularly preferably heteroaryl having 2 to 10 carbon atoms. Further, examples of the heteroaryl include heterocycles containing 1 to 5 heteroatoms selected from oxygen, sulfur, and nitrogen in addition to carbon as ring-constituting atoms.

[0371] Specific "heteroaryl" includes, for example, 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, quinazolinyl, quinoxalinyl, phthalazinyl, naphthyridinyl, purinyl, pteridinyl, carbazolyl, acridinyl, phenoxathiinyl, phenoxazinyl, phenothiazinyl, phenazinyl, indolizinyl, furyl, benzofuranyl, isobenzofuranyl, dibenzofuranyl, thienyl, benzo[b]thienyl, dibenzothienyl, furazanyl, oxadiazolyl, thianthrenyl, naphthobenzofuranyl, naphthobenzothienyl and the like.

[0372] R 21 ~R 28 The "alkoxy" in the "optionally substituted alkoxy" in R~R includes, for example, a straight-chain alkoxy having 1 to 24 carbon atoms or a branched-chain alkoxy having 3 to 24 carbon atoms. An alkoxy having 1 to 18 carbon atoms (a branched-chain alkoxy having 3 to 18 carbon atoms) is preferred, an alkoxy having 1 to 12 carbon atoms (a branched-chain alkoxy having 3 to 12 carbon atoms) is more preferred, an alkoxy having 1 to 6 carbon atoms (a branched-chain alkoxy having 3 to 6 carbon atoms) is still more preferred, and an alkoxy having 1 to 4 carbon atoms (a branched-chain alkoxy having 3 to 4 carbon atoms) is particularly preferred.

[0373] Specific "alkoxy" includes methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, s - butoxy, t - butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy and the like.

[0374] R 21 ~R 28The "aryloxy" in "optionally substituted aryloxy" is a group in which the hydrogen of the -OH group is substituted by aryl, and this aryl is the group described as R 21 ~R 28 as described for "aryl" in. The group described for "aryl" can be cited.

[0375] R 21 ~R 28 The "arylthio" in "optionally substituted arylthio" is a group in which the hydrogen of the -SH group is substituted by aryl, and this aryl is the group described as R 21 ~R 28 as described for "aryl" in. The group described for "aryl" can be cited.

[0376] R 21 ~R 28 The "trialkylsilyl" in is a group in which the three hydrogens in the silyl group are each independently substituted by alkyl, and this alkyl is the group described as R 21 ~R 28 as described for "alkyl" in. Preferred alkyls for substitution are alkyls having 1 to 4 carbon atoms, specifically methyl, ethyl, propyl, i-propyl, butyl, sec-butyl, t-butyl, cyclobutyl, etc.

[0377] Specific "trialkylsilyl" groups include trimethylsilyl, triethylsilyl, tripropylsilyl, tri-i-propylsilyl, tributylsilyl, tri-sec-butylsilyl, tri-t-butylsilyl, ethyldimethylsilyl, propyldimethylsilyl, i-propyldimethylsilyl, butyldimethylsilyl, sec-butyldimethylsilyl, t-butyldimethylsilyl, methyldiethylsilyl, propyldiethylsilyl, i-propyldiethylsilyl, butyldiethylsilyl, sec-butyldiethylsilyl, t-butyldiethylsilyl, methyldipropylsilyl, 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.

[0378] R 21 ~R 28 The "tricycloalkylsilyl" in ~R 21 ~R 28 refers to a group in which the three hydrogens in the silyl group are each independently substituted with a cycloalkyl group, and this cycloalkyl group can be the group described as "cycloalkyl" in ~R

[0379] Specific "tricycloalkylsilyl" groups include tricyclopentylsilyl, tricyclohexylsilyl, and the like.

[0380] Specific examples of dialkylcycloalkylsilyl substituted with two alkyls and one cycloalkyl, and alkyldicycloalkylsilyl substituted with one alkyl and two cycloalkyls include silyl substituted with a group selected from the specific alkyls and cycloalkyls described above.

[0381] R 21 ~R 28 Examples of the "substituted amino" of the "optionally substituted amino" in R 21 ~R 28 include, for example, an amino group in which two hydrogens are substituted with aryl or heteroaryl. An amino in which two hydrogens are substituted with aryl is a diaryl-substituted amino, an amino in which two hydrogens are substituted with heteroaryl is a diheteroaryl-substituted amino, and an amino in which two hydrogens are substituted with aryl and heteroaryl is an arylheteroaryl-substituted amino. This aryl or heteroaryl can cite the groups described as "aryl" or "heteroaryl" in R

[0382] Specific examples of the "substituted amino" include diphenylamino, dinaphthylamino, phenylnaphthylamino, dipyridylamino, phenylpyridylamino, naphthylpyridylamino, and the like.

[0383] R 21 ~R 28 Examples of the "halogen" in R

[0384] R 21 ~R 28 Among the groups described as R 21 ~R 28 some may be optionally substituted as described above, and examples of the substituent in this case include alkyl, cycloalkyl, aryl, or heteroaryl. This alkyl, cycloalkyl, aryl, or heteroaryl can cite the groups described as "alkyl", "cycloalkyl", "aryl", or "heteroaryl" in R

[0385] " >N-R as Y 29 " R in 29 is hydrogen or aryl which may be substituted, and as this aryl, the groups described as "aryl" in R 21 ~R 28 can be cited, and as its substituents, the groups described as substituents for R 21 ~R 28 can be cited.

[0386] R 21 ~R 28 Among them, adjacent groups may combine with each other to form a hydrocarbon ring, an aryl ring or a heteroaryl ring. The case where no ring is formed is a group represented by the following formula (A-1), and examples of the case where a ring is formed include groups represented by the following formulas (A-2) to (A-14). In addition, at least one hydrogen in the group represented by any of the formulas (A-1) to (A-14) may be substituted with alkyl, cycloalkyl, aryl, heteroaryl, alkoxy, aryloxy, arylthio, trialkylsilyl, tricycloalkylsilyl, dialkylcycloalkylsilyl, alkyldicycloalkylsilyl, diaryl-substituted amino, diheteroaryl-substituted amino, arylheteroaryl-substituted amino, halogen, hydroxy or cyano.

Chemical formula

[0387] Examples of the ring formed by adjacent groups combining with each other include a cyclohexane ring in the case of a hydrocarbon ring, and the ring structures described as "aryl" and "heteroaryl" in R 21 ~R 28 can be cited, and these rings are formed so as to be condensed with one or two benzene rings in the above formula (A-1).

[0388] Examples of the group represented by formula (A) include groups represented by any of the above formulas (A-1) to (A-14), with groups represented by any of the above formulas (A-1) to (A-5) and formulas (A-12) to (A-14) being preferred, groups represented by any of the above formulas (A-1) to (A-4) being more preferred, groups represented by any of the above formulas (A-1), (A-3), and (A-4) being even more preferred, and the group represented by the above formula (A-1) being particularly preferred.

[0389] The group represented by formula (A) binds to the naphthalene ring in formula (3-X1) or formula (3-X2), the single bond in formula (3-X3), or Ar in formula (3-X3) at the *, in formula (A), and substitutes for at least one hydrogen in the compound represented by formula (3), as described above. Among these bonding forms, however, the bonding forms with the naphthalene ring in formula (3-X1) or formula (3-X2), the single bond in formula (3-X3), and / or Ar in formula (3-X3) are preferred. 3 Also, as described above, although the group represented by formula (A) binds to the naphthalene ring in formula (3-X1) or formula (3-X2), the single bond in formula (3-X3), or Ar in formula (3-X3) at the *, in formula (A), and substitutes for at least one hydrogen in the compound represented by formula (3), among these bonding forms, the bonding forms with the naphthalene ring in formula (3-X1) or formula (3-X2), the single bond in formula (3-X3), and / or Ar in formula (3-X3) are preferred. 3 is preferred.

[0390] In addition, in the structure of the group represented by formula (A), the position where the naphthalene ring in formula (3-X1) or formula (3-X2), the single bond in formula (3-X3), or Ar in formula (3-X3) binds, and the position where it substitutes for at least one hydrogen in the compound represented by formula (3) in the structure of the group represented by formula (A) can be any position in the structure of formula (A). For example, it can bind to either of the two benzene rings in the structure of formula (A), or to any of the rings formed by adjacent groups among R 3 ~R 21 binding to each other, or to any position in R 28 in ">N-R 29 " as Y in the structure of formula (A). 29 can bind at any position.

[0391] Examples of the group represented by formula (A) include the following groups. Y and * in the formula have the same definitions as above.

Chemical formula

[0392] In addition, all or part of the hydrogen in the chemical structure of the anthracene-based compound represented by the general formula (3) may be deuterium.

[0393] Specific examples of the anthracene-based compound include, for example, compounds represented by the following formulas (3-1) to (3-72). In the following structural formulas, "Me" represents a methyl group, "D" represents deuterium, and "tBu" represents a t-butyl group.

[0394]

Chemical formula

[0395]

Chemical formula

[0396]

Chemical formula

[0397]

Chemical formula

[0398] The anthracene-based compound represented by the formula (3) can be produced by applying Suzuki coupling, Negishi coupling, and other known coupling reactions using 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 the formula (A) as starting materials. Examples of the reactive groups of these reactive compounds include halogen and boronic acid. As a specific production method, for example, the synthesis methods in paragraphs

[0089] to

[0175] of WO 2014 / 141725 can be referred to.

[0399] <Fluorene-based compound> The compound represented by the general formula (4) basically functions as a host.

Chemical formula

[0400] 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, diheteroarylamino, arylheteroarylamino, alkyl, cycloalkyl, alkenyl, alkoxy or aryloxy, and at least one hydrogen in these may be substituted with aryl, heteroaryl, alkyl or cycloalkyl. Also, 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 may each independently combine to form a condensed ring or a spiro ring, and at least one hydrogen in the formed ring may be substituted with aryl, heteroaryl (the heteroaryl may be bonded to the formed ring via a linking group), diarylamino, diheteroarylamino, arylheteroarylamino, alkyl, cycloalkyl, alkenyl, alkoxy or aryloxy, and at least one hydrogen in these may be substituted with aryl, heteroaryl, alkyl or cycloalkyl. And At least one hydrogen in the compound represented by the formula (4) may be substituted with halogen, cyano or deuterium.

[0401] Details of each group in the definition of the above formula (4) can cite the description of the polycyclic aromatic compound of formula (1) described above.

[0402] R 1 to R 10 Examples of the alkenyl from R

[0403] In addition, as specific examples of heteroaryl, monovalent groups represented by removing any one hydrogen atom from the compounds of the following formula (4-Ar1), formula (4-Ar2), formula (4-Ar3), formula (4-Ar4) or formula (4-Ar5) can also be mentioned.

Chemical formula

[0404] These heteroaryls may be bonded to the fluorene skeleton in the above formula (4) via a linking group. That is, not only can the fluorene skeleton in formula (4) and the above heteroaryl be directly bonded, but they may also be bonded via a linking group therebetween. Examples of this linking group include phenylene, biphenylene, naphthylene, anthracenylene, methylene, ethylene, -OCH2CH2-, -CH2CH2O-, or -OCH2CH2O-.

[0405] Also, R in formula (4) 1 and R 2 , R 2 and R 3 , R 3 and R 4 , R 5 and R 6 , R 6 and R 7 Also, R 7 and R 8 may each independently be bonded to form a condensed ring, and R 9 and R 10 may be bonded 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 the 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, and examples include a fluorene ring.

[0406] The compound represented by general formula (4) is preferably a compound represented by the following formula (4-1), formula (4-2), or formula (4-3), which are, respectively, compounds in which the benzene ring formed by the bonding of R 1 and R 2 in general formula (4) is condensed, compounds in which the benzene ring formed by the bonding of R 3 and R 4 in general formula (4) is condensed, and compounds in which the benzene ring formed by the bonding of R in general formula (4)1 from R 8 is a compound in which none of them are bonded. [Chemical formula]

[0407] R in formula (4-1), formula (4-2) and formula (4-3) 1 from R 10 is defined as the corresponding R in formula (4) 1 from R 10 and is the same as R from R in formula (4-1) and formula (4-2). The definition of R from R in formula (4-1) and formula (4-2) 11 from R 14 is also the same as R from R in formula (4). 1 from R 10 and is the same as R from R in formula (4).

[0408] The compound represented by general formula (4) is more preferably a compound represented by the following formula (4-1A), formula (4-2A) or formula (4-3A), and in formula (4-1), formula (4-1) or formula (4-3), respectively, R 9 and R 10 are bonded to form a spiro-fluorene ring. [Chemical formula]

[0409] R in formula (4-1A), formula (4-2A) and formula (4-3A) 2 from R 7 is defined as the corresponding R in formula (4-1), formula (4-2) and formula (4-3) 2 from R 7 and is the same as R from R in formula (4-1) and formula (4-2). The definition of R from R in formula (4-1A) and formula (4-2A) 11 from R 14 is also the same as R from R in formula (4-1) and formula (4-2). 11 from R 14 and is the same as R from R in formula (4-1) and formula (4-2).

[0410] Also, all or part of the hydrogen in the compound represented by formula (4) may be substituted with halogen, cyano or deuterium.

[0411] <Dibenzochrysene-based compound> The dibenzochrysene-based compound as a host is, for example, a compound represented by the following general formula (5). [Chemical formula]

[0412] In the above formula (5), R 1 to R 16 are each independently hydrogen, aryl, heteroaryl (the heteroaryl may be bonded to the dibenzochrysene skeleton in the above formula (5) via a linking group), diarylamino, diheteroarylamino, arylheteroarylamino, alkyl, cycloalkyl, alkenyl, alkoxy or aryloxy, and at least one hydrogen in these may be substituted with aryl, heteroaryl, alkyl or cycloalkyl, also, among R 1 to R 16 adjacent groups may be bonded to each other to form a condensed ring, and at least one hydrogen in the formed ring may be substituted with aryl, heteroaryl (the heteroaryl may be bonded to the formed ring via a linking group), diarylamino, diheteroarylamino, arylheteroarylamino, alkyl, cycloalkyl, alkenyl, alkoxy or aryloxy, and at least one hydrogen in these 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.

[0413] Details of each group in the definition of the above formula (5) can cite the description in the polycyclic aromatic compound of formula (1) described above.

[0414] Examples of the alkenyl in the definition of the above formula (5) include alkenyls having 2 to 30 carbon atoms, preferably alkenyls having 2 to 20 carbon atoms, more preferably alkenyls having 2 to 10 carbon atoms, still more preferably alkenyls having 2 to 6 carbon atoms, and particularly preferably alkenyls having 2 to 4 carbon atoms. 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.

[0415] Specific examples of the heteroaryl also include monovalent groups represented by removing any one hydrogen atom from the compounds of the following formula (5-Ar1), formula (5-Ar2), formula (5-Ar3), formula (5-Ar4), or formula (5-Ar5).

Chemical formula

[0416] These heteroaryls may be bonded to the dibenzocrisene skeleton in the above formula (5) via a linking group. That is, not only can the dibenzocrisene skeleton in formula (5) and the above heteroaryl be directly bonded, but they may also be bonded via a linking group therebetween. Examples of this linking group include phenylene, biphenylene, naphthylene, anthracenylene, methylene, ethylene, -OCH2CH2-, -CH2CH2O-, or -OCH2CH2O-.

[0417] The compound represented by the general formula (5) preferably has R 1, R 4 , R 5 , R 8 , R 9 , R 12 , R 13 and R 16 is hydrogen. In this case, R 2 , R 3 , R 6 , R 7 , R 10 , R 11 , R 14 and R 15 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) (the monovalent group having the structure may be bonded to the dibenzocrisene skeleton in the above formula (5) via phenylene, biphenylene, naphthylene, anthracenylene, methylene, ethylene, -OCH2CH2-, -CH2CH2O-, or -OCH2CH2O-), methyl, ethyl, propyl, or butyl.

[0418] The compound represented by the 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, R 3 , R 6 , R 11 and R 14At least one (preferably one or two, more preferably one) of them is 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) via a single bond, phenylene, biphenylene, naphthylene, anthracenylene, methylene, ethylene, -OCH2CH2-, -CH2CH2O-, or -OCH2CH2O-. Except for the at least one (i.e., other than the position substituted with the monovalent group having the structure), it is hydrogen, phenyl, biphenylyl, naphthyl, anthracenyl, methyl, ethyl, propyl, or butyl, and at least one hydrogen in these may be substituted with phenyl, biphenylyl, naphthyl, anthracenyl, methyl, ethyl, propyl, or butyl.

[0419] Also, R in formula (5) 2 , R 3 , R 6 , R 7 , R 10 , R 11 , R 14 And R 15 When a monovalent group having the structure represented by the above formula (5-Ar1) to formula (5-Ar5) is selected as, at least one hydrogen in the structure may be combined with any one of R 1 to R 16 in formula (5) to form a single bond.

[0420] <Electron injection layer and electron transport layer in an organic electroluminescent element> The electron injection layer 107 serves to efficiently inject electrons moving from the cathode 108 into the light-emitting layer 105 or the electron transport layer 106. The electron transport layer 106 serves to efficiently transport electrons injected from the cathode 108 or electrons injected from the cathode 108 through the electron injection layer 107 to the light-emitting layer 105. The electron transport layer 106 and the electron injection layer 107 are each formed by laminating or mixing one or more of electron transport / injection materials, or by a mixture of an electron transport / injection material and a polymer binder.

[0421] The electron injection / transport layer is a layer that controls the injection of electrons from the cathode and further transports the electrons. It is desirable that the electron injection efficiency is high and the injected electrons can be transported efficiently. For this purpose, it is preferable that the material has a large electron affinity, a large electron mobility, excellent stability, and is less likely to generate trap impurities during manufacturing and use. However, when considering the transport balance of holes and electrons, if it mainly plays a role in efficiently preventing holes from the anode from flowing to the cathode without recombination, even if the electron transport ability is not so high, the effect of improving the light emission efficiency is equivalent to that of a material with a high electron transport ability. Therefore, the electron injection / transport layer in this embodiment may also include the function of a layer that can efficiently prevent the movement of holes.

[0422] As the material (electron transport material) for forming the electron transport layer 106 or the electron injection layer 107, it can be arbitrarily selected and used from compounds that have been conventionally used as electron transfer compounds in photoconductive materials and known compounds used in the electron injection layer and electron transport layer of organic EL elements.

[0423] As the material used for the electron transport layer or the electron injection layer, it is preferable to contain at least one selected from compounds composed of aromatic rings or heteroaromatic rings composed of one or more atoms selected from carbon, hydrogen, oxygen, sulfur, silicon, and phosphorus, pyrrole derivatives and their condensed ring derivatives, and metal complexes having electron-accepting nitrogen. Specifically, condensed ring aromatic ring derivatives such as naphthalene and anthracene, styryl aromatic ring derivatives typified by 4,4'-bis(diphenylethenyl)biphenyl, perinone derivatives, coumarin derivatives, naphthalimide derivatives, quinone derivatives such as anthraquinone and diphenoquinone, phosphorus oxide derivatives, carbazole derivatives, and indole derivatives can be mentioned. Examples of the metal complex 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.

[0424] In addition, 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, oxadiazole derivatives (such as 1,3-bis[(4-t-butylphenyl)1,3,4-oxadiazolyl]phenylene), thiophene derivatives, triazole derivatives (such as N-naphthyl-2,5-diphenyl-1,3,4-triazole), thiadiazole derivatives, metal complexes of oxine derivatives, quinolinol-based metal complexes, quinoxaline derivatives, polymers of quinoxaline derivatives, benzazole compounds, gallium complexes, pyrazole derivatives, perfluorinated phenylene derivatives, triazine derivatives, pyrazine derivatives, benzoquinoline derivatives (such as 2,2’-bis(benzo[h]quinolin-2-yl)-9,9’-spirobifluorene), imidazopyridine derivatives, borane derivatives, benzimidazole derivatives (such as tris(N-phenylbenzimidazol-2-yl)benzene), benzoxazole derivatives, benzothiazole derivatives, quinoline derivatives, oligopyridine derivatives such as terpyridine, bipyridine derivatives, terpyridine derivatives (such as 1,3-bis(4’-(2,2’:6’2”-terpyridinyl))benzene), naphthyridine derivatives (such as bis(1-naphthyl)-4-(1,8-naphthyridin-2-yl)phenylphosphine oxide), aldazine derivatives, carbazole derivatives, indole derivatives, phosphine oxide derivatives, bisstyryl derivatives, and the like.

[0425] Moreover, metal complexes having electron-accepting nitrogen can also be used. For example, hydroxyazole complexes such as quinolinol-based metal complexes and hydroxyphenyloxazole complexes, azomethine complexes, tropolone metal complexes, flavonol metal complexes, and benzoquinoline metal complexes can be mentioned.

[0426] The materials described above can be used alone or may be used in admixture with different materials.

[0427] Among the above-described materials, borane derivatives, pyridine derivatives, fluoranthene derivatives, BO-based derivatives, anthracene derivatives, benzofluorene derivatives, phosphine oxide derivatives, pyrimidine derivatives, carbazole derivatives, triazine derivatives, benzimidazole derivatives, phenanthroline derivatives, and quinolinol-based metal complexes are preferable.

[0428] <Borane derivative> The borane derivative is, for example, a compound represented by the following general formula (ETM-1), and specifically, it is disclosed in JP-A-2007-27587. [Chemical formula] In the above formula (ETM-1), R 11 and R 12 are each independently at least one of hydrogen, alkyl, cycloalkyl, optionally substituted aryl, substituted silyl, optionally substituted nitrogen-containing heterocyclic ring, or cyano, and R 13 ~R 16 are each independently optionally substituted alkyl, optionally substituted cycloalkyl or optionally substituted aryl, X is optionally substituted arylene, Y is optionally substituted aryl having 16 or less carbon atoms, substituted boryl, or optionally substituted carbazolyl, and n is each independently an integer of 0 to 3. Further, examples of the substituent in the case of "optionally substituted" or "substituted" include aryl, heteroaryl, alkyl or cycloalkyl.

[0429] 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 preferable. [Chemical formula] In formula (ETM-1-1), R 11 and R 12is, independently of each other, at least one of hydrogen, alkyl, cycloalkyl, optionally substituted aryl, substituted silyl, optionally substituted nitrogen-containing heterocycle, or cyano, and R 13 ~R 16 is, independently of each other, optionally substituted alkyl, optionally substituted cycloalkyl or optionally substituted aryl, and R 21 and R 22 is, independently of each other, at least one of hydrogen, alkyl, cycloalkyl, optionally substituted aryl, substituted silyl, optionally substituted nitrogen-containing heterocycle, or cyano, and X 1 is optionally substituted arylene having 20 or less carbon atoms, n is an integer of 0 to 3 independently of each other, and m is an integer of 0 to 4 independently of each other. Further, examples of the substituent in the case of "optionally substituted" or "substituted" include aryl, heteroaryl, alkyl or cycloalkyl.

Chemical formula

[0430] X 1 Specific examples of include divalent groups represented by any of the following formulas (X-1) to (X-9). [Chemical formula] (In each formula, R a is independently an alkyl group, a cycloalkyl group, or a phenyl group which may be substituted.)

[0431] Specific examples of this borane derivative include, for example, the following compounds. [Chemical formula]

[0432] This borane derivative can be produced using known raw materials and known synthesis methods.

[0433] <Pyridine derivative> The pyridine derivative is, for example, a compound represented by the following formula (ETM-2), and preferably a compound represented by formula (ETM-2-1) or formula (ETM-2-2). [Chemical formula]

[0434] 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 from 1 to 4.

[0435] In the above formula (ETM-2-1), R 11 ~R 18 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 aryl having 6 to 30 carbon atoms).

[0436] In the above formula (ETM-2-2), R 11 and R 12is, independently of each other, 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 R 11 and R 12 may combine to form a ring.

[0437] In each formula, the "pyridine-based substituent" is any one of the following formulas (Py-1) to (Py-15), and the pyridine-based substituents may each independently be substituted with alkyl having 1 to 4 carbon atoms or cycloalkyl having 5 to 10 carbon atoms. Further, the pyridine-based substituent may be bonded to φ, an anthracene ring or a fluorene ring in each formula via a phenylene group or a naphthylene group.

[0438]

Chemical formula

[0439] The pyridine-based substituent is any one of the above formulas (Py-1) to (Py-15), and among these, it is preferably any one of the following formulas (Py-21) to (Py-44).

Chemical formula

[0440] At least one hydrogen in each pyridine derivative may be substituted with deuterium, and one of the two "pyridine-based substituents" in the above formulas (ETM-2-1) and (ETM-2-2) may be replaced with aryl.

[0441] R 11 ~R 18The "alkyl" herein may be either straight-chain or branched-chain, and examples thereof include 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-chain alkyl having 3 to 18 carbon atoms). More preferred "alkyl" is alkyl having 1 to 12 carbon atoms (branched-chain alkyl having 3 to 12 carbon atoms). Even more preferred "alkyl" is alkyl having 1 to 6 carbon atoms (branched-chain alkyl having 3 to 6 carbon atoms). Particularly preferred "alkyl" is alkyl having 1 to 4 carbon atoms (branched-chain alkyl having 3 to 4 carbon atoms).

[0442] 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, n-tridecyl, 1-hexylheptyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-eicosyl, and the like.

[0443] As for the alkyl having 1 to 4 carbon atoms substituting the pyridine-based substituent, the description of the above alkyl can be cited.

[0444] R 11 ~R 18 The "cycloalkyl" in R Specific examples of "cycloalkyl" include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methylcyclopentyl, cycloheptyl, methylcyclohexyl, cyclooctyl, dimethylcyclohexyl, and the like.

[0445] Regarding the cycloalkyl having 5 to 10 carbon atoms that substitutes the pyridine-based substituent, the description of the above cycloalkyl can be cited.

[0446] R 11 ~R 18 In R

[0447] ~R

[0448] the preferable "aryl" has 6 to 30 carbon atoms, more preferably 6 to 18 carbon atoms, still more preferably 6 to 14 carbon atoms, and particularly preferably 6 to 12 carbon atoms.

[0449] Specific examples of "aryl having 6 to 30 carbon atoms" include phenyl which is a monocyclic aryl, (1-,2-)naphthyl which is a condensed bicyclic aryl, acenaphthylen-(1-,3-,4-,5-)yl, fluorene-(1-,2-,3-,4-,9-)yl, phenalen-(1-,2-)yl, (1-,2-,3-,4-,9-)phenanthryl which are condensed tricyclic aryls, triphenylene-(1-,2-)yl, pyrene-(1-,2-,4-)yl, naphthacene-(1-,2-,5-)yl which are condensed tetracyclic aryls, perylene-(1-,2-,3-)yl, pentacene-(1-,2-,5-,6-)yl which are condensed pentacyclic aryls, and the like.

[0448] Preferable "aryl having 6 to 30 carbon atoms" includes phenyl, naphthyl, phenanthryl, chrysenyl, triphenylenyl, and the like, more preferably phenyl, 1-naphthyl, 2-naphthyl, or phenanthryl, and particularly preferably phenyl, 1-naphthyl, or 2-naphthyl.

[0449] In the above formula (ETM-2-2), R 11 and R 12They may combine to form a ring. As a result, a cyclobutane, cyclopentane, cyclopentene, cyclopentadiene, cyclohexane, fluorene, indene, or the like may be spiro-bonded to the 5-membered ring of the fluorene skeleton.

[0450] Specific examples of this pyridine derivative include, for example, the following compounds.

Chemical formula

[0451] This pyridine derivative can be produced using known raw materials and known synthesis methods.

[0452] <Fluoranthene derivative> The fluoranthene derivative is, for example, a compound represented by the following general formula (ETM-3), and specifically, it is disclosed in International Publication No. 2010 / 134352.

Chemical formula

[0453] In the above formula (ETM-3), X 12 ~X 21 represent hydrogen, halogen, linear, branched or cyclic alkyl, linear, branched or cyclic alkoxy, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl. Here, examples of the substituent when it is substituted include aryl, heteroaryl, alkyl, or cycloalkyl.

[0454] Specific examples of this fluoranthene derivative include, for example, the following compounds.

Chemical formula

[0455] <BO-based derivative> The BO-based 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). [Chemical formula]

[0456] R 1 ~R 11 are each independently hydrogen, aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, diarylboril (the two aryls may be bonded 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.

[0457] Also, adjacent groups among R 1 ~R 11 may combine with each other to form an aryl ring or a heteroaryl ring together with the a-ring, b-ring or c-ring, and at least one hydrogen in the formed ring may be substituted with aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, diarylboril (the two aryls may be bonded 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.

[0458] Also, at least one hydrogen in the compound or structure represented by the formula (ETM-4) may be substituted with halogen or deuterium.

[0459] Regarding the description of the substituents, ring-forming forms in the formula (ETM-4), and the multimer formed by combining a plurality of structures of the formula (ETM-4), the description of the polycyclic aromatic compound represented by the above general formula (1) or formula (2) and its multimer can be cited.

[0460] Specific examples of this BO-based derivative include, for example, the following compounds. [Chemical formula]

[0461] This BO-based derivative can be produced using known raw materials and known synthesis methods.

[0462] <Anthracene derivative> One of the anthracene derivatives is, for example, a compound represented by the following formula (ETM-5-1). [Chemical formula]

[0463] Ar is, independently of each other, divalent benzene or naphthalene, and R 1 ~R 4 are, independently of each other, hydrogen, alkyl having 1 to 6 carbon atoms, cycloalkyl having 3 to 6 carbon atoms, or aryl having 6 to 20 carbon atoms.

[0464] Ar can be appropriately selected independently of each other from divalent benzene or naphthalene, and the two Ars may be different or the same, but it is preferably the same from the viewpoint of the ease of synthesis of the anthracene derivative. Ar is bonded to pyridine to form a "site consisting of Ar and pyridine", and this site is bonded to anthracene as a group represented by, for example, any of the following formulas (Py-1) to (Py-12).

[0465] [Chemical formula]

[0466] Among these groups, a group represented by any one of the above formulas (Py-1) to (Py-9) is preferable, and a group represented by any one of the above formulas (Py-1) to (Py-6) is more preferable. The two "sites composed of Ar and pyridine" bonded to anthracene may have the same or different structures, but from the viewpoint of ease of synthesis of the anthracene derivative, it is preferable that they have the same structure. However, from the viewpoint of device characteristics, it is preferable that the structures of the two "sites composed of Ar and pyridine" are the same or different.

[0467] R 1 ~R 4 For the alkyl having 1 to 6 carbon atoms in R~R, either a straight-chain or a branched-chain may be used. That is, it is a straight-chain alkyl having 1 to 6 carbon atoms or a branched-chain alkyl having 3 to 6 carbon atoms. More preferably, it is an alkyl having 1 to 4 carbon atoms (a branched-chain 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, 4-methyl-2-pentyl, 3,3-dimethylbutyl, or 2-ethylbutyl, etc. Methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, or t-butyl is preferable, and methyl, ethyl, or t-butyl is more preferable.

[0468] R 1 ~R 4 Specific examples of the cycloalkyl having 3 to 6 carbon atoms in R~R include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methylcyclopentyl, cycloheptyl, methylcyclohexyl, cyclooctyl, or dimethylcyclohexyl, etc.

[0469] R 1 ~R 4 For the aryl having 6 to 20 carbon atoms in R~R, an aryl having 6 to 16 carbon atoms is preferable, an aryl having 6 to 12 carbon atoms is more preferable, and an aryl having 6 to 10 carbon atoms is particularly preferable.

[0470] Specific examples of "aryl having 6 to 20 carbon atoms" include phenyl, which is a monocyclic aryl, (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, (2-, 3-, 4-) biphenylyl which is a bicyclic aryl, (1-, 2-) naphthyl which is a condensed bicyclic 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) which is a tricyclic aryl, anthracene-(1-, 2-, 9-) yl, acenaphthylene-(1-, 3-, 4-, 5-) yl, fluorene-(1-, 2-, 3-, 4-, 9-) yl, phenalene-(1-, 2-) yl, (1-, 2-, 3-, 4-, 9-) phenanthryl which are condensed tricyclic aryls, triphenylene-(1-, 2-) yl, pyrene-(1-, 2-, 4-) yl, tetracene-(1-, 2-, 5-) yl which are condensed tetracyclic aryls, perylene-(1-, 2-, 3-) yl which is a condensed pentacyclic aryl, and the like.

[0471] 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, still more preferably phenyl, biphenylyl, 1-naphthyl or 2-naphthyl, and most preferably phenyl.

[0472] One of the anthracene derivatives is, for example, a compound represented by the following formula (ETM-5-2).

Chemical formula

[0473] Ar 1 is, independently of one another, a single bond, divalent benzene, naphthalene, anthracene, fluorene, or phenalene.

[0474] Ar 2 is, independently of one another, aryl having 6 to 20 carbon atoms, and the same description 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, etc.

[0475] R 1 ~R 4 is, independently of one another, 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 description in the above formula (ETM-5-1) can be cited.

[0476] Specific examples of these anthracene derivatives include, for example, the following compounds.

Chemical formula

[0477] These anthracene derivatives can be produced using known raw materials and known synthetic methods.

[0478] <Benzofluorene derivative> The benzofluorene derivative is, for example, a compound represented by the following formula (ETM-6).

Chemical formula

[0479] Ar1 is, independently of each other, aryl having 6 to 20 carbon atoms, and the same description 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.

[0480] Ar 2 is, independently of each other, 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 Ars 2 may be bonded to form a ring.

[0481] Ar 2 The "alkyl" in Ar may be either linear or branched, and examples thereof include linear 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). Even 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 "alkyl" includes 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.

[0482] Ar 2Examples of the "cycloalkyl" in [compound name] include cycloalkyls 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. Even more preferred "cycloalkyl" is cycloalkyl having 3 to 6 carbon atoms. Specific examples of "cycloalkyl" include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methylcyclopentyl, cycloheptyl, methylcyclohexyl, cyclooctyl, dimethylcyclohexyl, and the like.

[0483] Ar 2 Examples of the "aryl" in [compound name], preferred aryl is aryl having 6 to 30 carbon atoms, more preferred aryl is aryl having 6 to 18 carbon atoms, even more preferably aryl having 6 to 14 carbon atoms, and particularly preferably aryl having 6 to 12 carbon atoms.

[0484] Specific examples of the "aryl having 6 to 30 carbon atoms" include phenyl, naphthyl, acenaphthylenyl, fluorenyl, phenalenyl, phenanthryl, triphenylenyl, pyrenyl, naphthacenyl, perylenyl, pentacenyl, and the like.

[0485] Two Ar 2 may be bonded to form a ring. As a result, cyclobutane, cyclopentane, cyclopentene, cyclopentadiene, cyclohexane, fluorene, indene, or the like may be spiro-bonded to the 5-membered ring of the fluorene skeleton.

[0486] Specific examples of this benzofluorene derivative include, for example, the following compounds.

Chemical formula

[0487] This benzofluorene derivative can be produced using known raw materials and known synthesis methods.

[0488] <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. WO2013 / 079217. [Chemical formula] R 5 is a 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, a 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, heteroaryl having 5 to 20 carbon atoms, alkoxy having 1 to 20 carbon atoms, or aryloxy having 6 to 20 carbon atoms, R 7 and R 8 are each independently a substituted or unsubstituted aryl having 6 to 20 carbon atoms or heteroaryl having 5 to 20 carbon atoms, R 9 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 in the case of being substituted include aryl, heteroaryl, alkyl, cycloalkyl, and the like.

[0489] The phosphine oxide derivative may also be, for example, a compound represented by the following formula (ETM-7-2). [Chemical formula]

[0490] R 1 ~R 3may be the same or different and is selected from 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 a condensed ring formed between adjacent substituents.

[0491] 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 is an aryl group or a heteroaryl group. However, Ar 1 and Ar 2 at least one of which has a substituent or forms a condensed ring with an adjacent substituent. n is an integer from 0 to 3. When n is 0, there is no unsaturated structure moiety. When n is 3, R 1 does not exist.

[0492] Among these substituents, the alkyl group refers to, for example, a saturated aliphatic hydrocarbon group such as a methyl group, an ethyl group, a propyl group, or a butyl group, which may be unsubstituted or substituted. There are no particular restrictions on the substituents when it is substituted. For example, an alkyl group, an aryl group, a heterocyclic group, etc. can be mentioned. This point is also common to the following descriptions. Also, the number of carbon atoms of the alkyl group is not particularly limited, but usually ranges from 1 to 20 from the viewpoints of availability and cost.

[0493] Also, the cycloalkyl group refers to, for example, a saturated alicyclic hydrocarbon group such as cyclopropyl, cyclohexyl, norbornyl, or adamantyl, which may be unsubstituted or substituted. The number of carbon atoms in the alkyl group part is not particularly limited, but usually ranges from 3 to 20.

[0494] An aralkyl group refers to, for example, an aromatic hydrocarbon group via an aliphatic hydrocarbon such as a benzyl group or a phenylethyl group. Both the aliphatic hydrocarbon and the aromatic hydrocarbon may be unsubstituted or substituted. The number of carbon atoms in the aliphatic moiety is not particularly limited, but is usually in the range of 1 to 20.

[0495] An alkenyl group refers to, for example, an unsaturated aliphatic hydrocarbon group containing a double bond such as a vinyl group, an allyl group, or a butadienyl group, which 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.

[0496] A cycloalkenyl group refers to, for example, an unsaturated alicyclic hydrocarbon group containing a double bond such as a cyclopentenyl group, a cyclopentadienyl group, or a cyclohexenyl group, which may be unsubstituted or substituted.

[0497] An alkynyl group refers to, for example, an unsaturated aliphatic hydrocarbon group containing a triple bond such as an ethynyl 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.

[0498] An alkoxy group refers to, for example, an aliphatic hydrocarbon group via an ether bond such as a methoxy group. 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.

[0499] An alkylthio group is a group in which the oxygen atom of the ether bond of an alkoxy group is replaced by a sulfur atom.

[0500] A cycloalkylthio group is a group in which the oxygen atom of the ether bond of a cycloalkoxy group is replaced by a sulfur atom.

[0501] The aryl ether group refers to, for example, an aromatic hydrocarbon group linked through an ether bond such as a phenoxy group, 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.

[0502] The aryl thioether group is a group in which the oxygen atom of the ether bond of the aryl ether group is substituted with a sulfur atom.

[0503] The aryl group refers to, for example, aromatic hydrocarbon groups 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.

[0504] The heterocyclic group refers to, for example, 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, and this may be unsubstituted or substituted. The number of carbon atoms in the heterocyclic group is not particularly limited, but is usually in the range of 2 to 30.

[0505] Halogen refers to fluorine, chlorine, bromine, and iodine.

[0506] The aldehyde group, carbonyl group, and amino group may also include groups substituted with an aliphatic hydrocarbon, an alicyclic hydrocarbon, an aromatic hydrocarbon, a heterocycle, or the like.

[0507] Also, the aliphatic hydrocarbon, alicyclic hydrocarbon, aromatic hydrocarbon, and heterocycle may be unsubstituted or substituted.

[0508] The silyl group refers to, for example, a silicon compound group such as a trimethylsilyl group, and this 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. Also, the number of silicon atoms is usually 1 to 6.

[0509] The condensed ring formed between adjacent substituents is, 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 Ar 2 etc. It is a conjugated or non-conjugated condensed ring formed between them. Here, when n is 1, two R 1 may form a conjugated or non-conjugated condensed ring with each other. These condensed rings may contain nitrogen, oxygen, or sulfur atoms in the ring structure, and may further condense with another ring.

[0510] Specific examples of this phosphine oxide derivative include, for example, the following compounds.

Chemical formula

[0511] This phosphine oxide derivative can be produced using known raw materials and known synthesis methods.

[0512] <Pyrimidine derivative> The pyrimidine derivative is, for example, a compound represented by the following formula (ETM-8), and preferably a compound represented by the following formula (ETM-8-1). Details are also described in International Publication No. 2011 / 021689.

Chemical formula

[0513] Ar is each independently optionally substituted aryl or optionally substituted heteroaryl. n is an integer from 1 to 4, preferably an integer from 1 to 3, and more preferably 2 or 3.

[0514] Examples of the "aryl" in "aryl which may be substituted" 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, and even more preferably aryl having 6 to 12 carbon atoms.

[0515] Specific examples of the "aryl" include phenyl which is a monocyclic aryl, (2-, 3-, 4-) biphenylyl which is a bicyclic aryl, (1-, 2-) naphthyl which is a condensed bicyclic aryl, terphenyl (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) which is a tricyclic aryl, acenaphthylene-(1-, 3-, 4-, 5-)yl, fluorene-(1-, 2-, 3-, 4-, 9-)yl, phenalene-(1-, 2-)yl, (1-, 2-, 3-, 4-, 9-)phenanthryl which are condensed tricyclic aryls, quarterphenyl (5'-phenyl-m-terphenyl-2-yl, 5'-phenyl-m-terphenyl-3-yl, 5'-phenyl-m-terphenyl-4-yl, m-quarterphenyl) which is a tetracyclic aryl, triphenylene-(1-, 2-)yl, pyrene-(1-, 2-, 4-)yl, naphthacene-(1-, 2-, 5-)yl which are condensed tetracyclic aryls, perylene-(1-, 2-, 3-)yl, pentacene-(1-, 2-, 5-, 6-)yl which are condensed pentacyclic aryls, and the like.

[0516] Examples of the "heteroaryl" in the "optionally substituted heteroaryl" include heteroaryls having 2 to 30 carbon atoms, preferably heteroaryls having 2 to 25 carbon atoms, more preferably heteroaryls having 2 to 20 carbon atoms, still more preferably heteroaryls having 2 to 15 carbon atoms, and particularly preferably heteroaryls having 2 to 10 carbon atoms. Further examples of the heteroaryl include heterocycles containing 1 to 5 heteroatoms selected from oxygen, sulfur, and nitrogen in addition to carbon as ring-constituting atoms.

[0517] Specific examples of the heteroaryl 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, quinazolinyl, quinoxalinyl, phthalazinyl, naphthyridinyl, purinyl, pteridinyl, carbazolyl, acridinyl, phenoxazinyl, phenothiazinyl, phenazinyl, phenoxathiinyl, thianthrenyl, indolizinyl, and the like.

[0518] Also, the above aryl and heteroaryl may be substituted, and may be substituted, for example, with the above aryl or heteroaryl, respectively.

[0519] Specific examples of this pyrimidine derivative include, for example, the following compounds.

Chemical formula

[0520] This pyrimidine derivative can be produced using known raw materials and known synthesis methods.

[0521] <Carbazole derivative> The carbazole derivative is, for example, a compound represented by the following formula (ETM-9), or a multimer in which a plurality of them are bonded by a single bond or the like. Details are described in US Patent Publication No. 2014 / 0197386.

Chemical formula

[0522] Ar is, independently of each other, an aryl which may be substituted or a heteroaryl which may be substituted. n is an integer of 0 to 4, preferably an integer of 0 to 3, more preferably 0 or 1.

[0523] Examples of the "aryl" in the "aryl which may be substituted" include aryls having 6 to 30 carbon atoms, preferably aryls having 6 to 24 carbon atoms, more preferably aryls having 6 to 20 carbon atoms, and still more preferably aryls having 6 to 12 carbon atoms.

[0524] Specific examples of the "aryl" include phenyl which is a monocyclic aryl, (2-, 3-, 4-) biphenylyl which is a bicyclic aryl, (1-, 2-) naphthyl which is a condensed bicyclic aryl, terphenylyl which is a tricyclic aryl (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), acenaphthylen-(1-, 3-, 4-, 5-) yl, fluorene-(1-, 2-, 3-, 4-, 9-) yl, phenalen-(1-, 2-) yl, (1-, 2-, 3-, 4-, 9-) phenanthryl which are condensed tricyclic aryls, quaterphenylyl which is a tetracyclic aryl (5'-phenyl-m-terphenyl-2-yl, 5'-phenyl-m-terphenyl-3-yl, 5'-phenyl-m-terphenyl-4-yl, m-quaterphenylyl), triphenylene-(1-, 2-) yl, pyrene-(1-, 2-, 4-) yl, naphthacene-(1-, 2-, 5-) yl which are condensed tetracyclic aryls, perylene-(1-, 2-, 3-) yl, pentacene-(1-, 2-, 5-, 6-) yl which are condensed pentacyclic aryls, and the like.

[0525] Examples of the "heteroaryl" in the "optionally substituted heteroaryl" include heteroaryls having 2 to 30 carbon atoms, preferably heteroaryls having 2 to 25 carbon atoms, more preferably heteroaryls having 2 to 20 carbon atoms, still more preferably heteroaryls having 2 to 15 carbon atoms, and particularly preferably heteroaryls having 2 to 10 carbon atoms. Further examples of the heteroaryl include heterocycles containing 1 to 5 heteroatoms selected from oxygen, sulfur, and nitrogen in addition to carbon as ring-constituting atoms.

[0526] 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, quinazolinyl, quinoxalinyl, phthalazinyl, naphthyridinyl, purinyl, pteridinyl, carbazolyl, acridinyl, phenoxazinyl, phenothiazinyl, phenazinyl, phenoxathiinyl, thianthrenyl, indolizinyl, etc.

[0527] Also, the above aryl and heteroaryl may be substituted, and may be substituted with, for example, the above aryl or heteroaryl, respectively.

[0528] The carbazole derivative may be a multimer in which the compound represented by the above formula (ETM-9) is bonded by a plurality of single bonds or the like. In this case, in addition to the single bond, it may be bonded by an aryl ring (preferably a polyvalent benzene ring, naphthalene ring, anthracene ring, fluorene ring, benzofluorene ring, phenalene ring, phenanthrene ring or triphenylene ring).

[0529] Specific examples of this carbazole derivative include, for example, the following compounds.

Chemical formula

[0530] This carbazole derivative can be produced using known raw materials and known synthesis methods.

[0531] <Triazine derivative> The triazine derivative is a compound represented by, for example, the following formula (ETM-10), preferably a compound represented by the following formula (ETM-10-1). Details are described in U.S. Patent Publication No. 2011 / 0156013. [Chemical formula]

[0532] Each Ar is independently optionally substituted aryl or optionally substituted heteroaryl. n is an integer from 1 to 3, preferably 2 or 3.

[0533] Examples of the "aryl" in the "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, and still more preferably aryl having 6 to 12 carbon atoms.

[0534] Specific "aryl" includes phenyl which is a monocyclic aryl, (2-, 3-, 4-) biphenylyl which is a bicyclic aryl, (1-, 2-) naphthyl which is a condensed bicyclic aryl, terphenylyl which is a tricyclic aryl (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), acenaphthylene-(1-, 3-, 4-, 5-)yl, fluorene-(1-, 2-, 3-, 4-, 9-)yl, phenalene-(1-, 2-)yl, (1-, 2-, 3-, 4-, 9-)phenanthryl which are condensed tricyclic aryls, quarterphenyl (5'-phenyl-m-terphenyl-2-yl, 5'-phenyl-m-terphenyl-3-yl, 5'-phenyl-m-terphenyl-4-yl, m-quarterphenyl) which is a tetracyclic aryl, triphenylene-(1-, 2-)yl, pyrene-(1-, 2-, 4-)yl, naphthacene-(1-, 2-, 5-)yl which are condensed tetracyclic aryls, perylene-(1-, 2-, 3-)yl, pentacene-(1-, 2-, 5-, 6-)yl which are condensed pentacyclic aryls, etc.

[0535] Examples of the "heteroaryl" in "optionally substituted heteroaryl" include heteroaryl having 2 to 30 carbon atoms, preferably heteroaryl having 2 to 25 carbon atoms, more preferably heteroaryl having 2 to 20 carbon atoms, still more preferably heteroaryl having 2 to 15 carbon atoms, and particularly preferably heteroaryl having 2 to 10 carbon atoms. Further, examples of the heteroaryl include heterocycles containing 1 to 5 heteroatoms selected from oxygen, sulfur and nitrogen in addition to carbon as ring-constituting atoms.

[0536] Specific heteroaryl groups 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, quinazolinyl, quinoxalinyl, phthalazinyl, naphthyridinyl, purinyl, pteridinyl, carbazolyl, acridinyl, phenoxazinyl, phenothiazinyl, phenazinyl, phenoxathiinyl, thianthrenyl, indolizinyl, and the like.

[0537] In addition, the above aryl and heteroaryl groups may be substituted, and may be substituted, for example, with the above aryl or heteroaryl groups, respectively.

[0538] Specific examples of this triazine derivative include, for example, the following compounds.

Chemical formula

[0539] This triazine derivative can be produced using known raw materials and known synthetic methods.

[0540] <Benzimidazole derivative> The benzimidazole derivative is, for example, a compound represented by the following formula (ETM-11).

Chemical formula

[0541] 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), n is an integer from 1 to 4, and the "benzimidazole-based substituent" is a substituent in which the pyridyl group in the "pyridine-based substituent" in the above formula (ETM-2), formula (ETM-2-1) and formula (ETM-2-2) is replaced by a benzimidazole group. At least one hydrogen in the benzimidazole derivative may be replaced by deuterium.

Chemical formula

[0542] R in the above benzimidazole group 11 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 description of R 11 in the above formula (ETM-2-1) and formula (ETM-2-2) can be cited.

[0543] φ is preferably further an anthracene ring or a fluorene ring. In this case, the structure can cite the description in the above formula (ETM-2-1) or formula (ETM-2-2), and R 11 ~R 18 in each formula can cite the description in the above formula (ETM-2-1) or formula (ETM-2-2). Also, in the above formula (ETM-2-1) or formula (ETM-2-2), the two pyridine-based substituents are described in the form of being bonded. When replacing these with benzimidazole-based substituents, both pyridine-based substituents may be replaced by benzimidazole-based substituents (i.e., n = 2), or either one of the pyridine-based substituents may be replaced by a benzimidazole-based substituent and the other pyridine-based substituent may be replaced by R 11 ~R 18 (i.e., n = 1). Further, for example, R 11 ~R 18Replace at least one of them with a benzimidazole-based substituent to obtain a "pyridine-based substituent" R 11 ~R 18 It may be replaced.

[0544] Specific examples of this benzimidazole derivative include, for example, 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-phenyl-1H-benzo[d]imidazole, and 5-(9,10-di(naphthalen-2-yl)anthracen-2-yl)-1,2-diphenyl-1H-benzo[d]imidazole.

Chemical formula

[0545] This benzimidazole derivative can be produced using known raw materials and known synthesis methods.

[0546] <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.

Chemical formula

[0547] 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 from 1 to 4.

[0548] R in each formula 11 ~R 18 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 aryl having 6 to 30 carbon atoms). Further, in the above formula (ETM-12-1), one of R 11 ~R 18 is bonded to φ which is an aryl ring.

[0549] At least one hydrogen in each phenanthroline derivative may be substituted with deuterium.

[0550] R 11 ~R 18 For the alkyl, cycloalkyl and aryl in R 11 ~R 18 in the above formula (ETM-2), the description can be cited. Further, in addition to the above examples, φ can be, for example, the following structural formulas. In the following structural formulas, each R is independently hydrogen, methyl, ethyl, isopropyl, cyclohexyl, phenyl, 1-naphthyl, 2-naphthyl, biphenylyl or terphenyl.

Chemical formula

[0551] Specific examples of this phenanthroline derivative include, for example, 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-bis(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. [Chemical formula]

[0552] This phenanthroline derivative can be produced using known raw materials and known synthesis methods.

[0553] <Quinolinol-based metal complex> The quinolinol-based metal complex is, for example, a compound represented by the following general formula (ETM-13). [Chemical formula] In the formula, R 1 ~R 6 are each independently hydrogen, fluorine, alkyl, cycloalkyl, aralkyl, alkenyl, cyano, alkoxy or aryl, M is Li, Al, Ga, Be or Zn, and n is an integer from 1 to 3.

[0554] Specific examples of the quinolinol-based metal complex include lithium 8-quinolinolate, tris(8-quinolinolato)aluminum, tris(4-methyl-8-quinolinolato)aluminum, tris(5-methyl-8-quinolinolato)aluminum, tris(3,4-dimethyl-8-quinolinolato)aluminum, tris(4,5-dimethyl-8-quinolinolato)aluminum, tris(4,6-dimethyl-8-quinolinolato)aluminum, bis(2-methyl-8-quinolinolato)(phenolato)aluminum, bis(2-methyl-8-quinolinolato)(2-methylphenolato)aluminum, bis(2-methyl-8-quinolinolato)(3-methylphenolato)aluminum, bis(2-methyl-8-quinolinolato)(4-methylphenolato)aluminum, bis(2-methyl-8-quinolinolato)(2-phenylphenolato)aluminum, bis(2-methyl-8-quinolinolato)(3-phenylphenolato)aluminum, bis(2-methyl-8-quinolinolato)(4-phenylphenolato)aluminum, bis(2-methyl-8-quinolinolato)(2,3-dimethylphenolato)aluminum, bis(2-methyl-8-quinolinolato)(2,6-dimethylphenolato)aluminum, bis(2-methyl-8-quinolinolato)(3,4-dimethylphenolato)aluminum, bis(2-methyl-8-quinolinolato)(3,5-dimethylphenolato)aluminum, bis(2-methyl-8-quinolinolato)(3,5-di-t-butylphenolato)aluminum, bis(2-methyl-8-quinolinolato)(2,6-diphenylphenolato)aluminum, bis(2-methyl-8-quinolinolato)(2,4,6-triphenylphenolato)aluminum, bis(2-methyl-8-quinolinolato)(2,4,6-trimethylphenolato)aluminum, bis(2-methyl-8-quinolinolato)(2,4,5,6-tetramethylphenolato)aluminum, bis(2-methyl-8-quinolinolato)(1-naphtholato)aluminum, bis(2-methyl-8-quinolinolato)(2-naphtholato)aluminum, bis(2,4-dimethyl-8-quinolinolato)(2-phenylphenolato)aluminum, bis(2,Aluminum (4-dimethyl-8-quinolinolate)(3-phenylphenolate), Aluminum bis(2,4-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)-μ-oxo-bis(2-methyl-8-quinolinolate)aluminum, Aluminum bis(2,4-dimethyl-8-quinolinolate)-μ-oxo-bis(2,4-dimethyl-8-quinolinolate)aluminum, Aluminum bis(2-methyl-4-ethyl-8-quinolinolate)-μ-oxo-bis(2-methyl-4-ethyl-8-quinolinolate)aluminum, Aluminum bis(2-methyl-4-methoxy-8-quinolinolate)-μ-oxo-bis(2-methyl-4-methoxy-8-quinolinolate)aluminum, Aluminum bis(2-methyl-5-cyano-8-quinolinolate)-μ-oxo-bis(2-methyl-5-cyano-8-quinolinolate)aluminum, Aluminum bis(2-methyl-5-trifluoromethyl-8-quinolinolate)-μ-oxo-bis(2-methyl-5-trifluoromethyl-8-quinolinolate)aluminum, Beryllium bis(10-hydroxybenzo[h]quinoline), etc. can be mentioned.,

[0555] This quinolinol-based metal complex can be produced using known raw materials and known synthesis methods.

[0556] <Thiazole derivatives and benzothiazole derivatives> The thiazole derivative is, for example, a compound represented by the following formula (ETM-14-1).

Chemical formula

Chemical formula

[0557] Each 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), n is an integer from 1 to 4, and the "thiazole-based substituent" and "benzothiazole-based substituent" are substituents in which the pyridyl group among the "pyridine-based substituents" in the above formula (ETM-2), formula (ETM-2-1) and formula (ETM-2-2) is replaced by the following thiazole group or benzothiazole group, and at least one hydrogen in the thiazole derivative and benzothiazole derivative may be replaced by deuterium.

Chemical formula

[0558] φ is further preferably an anthracene ring or a fluorene ring. In this case, the structure can cite the description in the above formula (ETM-2-1) or formula (ETM-2-2), and R 11 ~R 18 in each formula can cite the description in the above formula (ETM-2-1) or formula (ETM-2-2). Also, although the above formula (ETM-2-1) or formula (ETM-2-2) is described in the form of two pyridine-based substituents being bonded, when replacing these with thiazole-based substituents (or benzothiazole-based substituents), both pyridine-based substituents may be replaced with thiazole-based substituents (or benzothiazole-based substituents) (that is, n = 2), or either one of the pyridine-based substituents may be replaced with a thiazole-based substituent (or benzothiazole-based substituent) and the other pyridine-based substituent may be replaced with R 11 ~R 18 (that is, n = 1). Further, for example, at least one of R 11 ~R 18 in the above formula (ETM-2-1) is replaced with a thiazole-based substituent (or benzothiazole-based substituent) to replace the "pyridine-based substituent" with R 11 ~R 18 may also be possible.

[0559] These thiazole derivatives or benzothiazole derivatives can be produced using known raw materials and known synthesis methods.

[0560] The electron transport layer or the electron injection layer may further contain a substance capable of reducing the material forming the electron transport layer or the electron injection layer. As long as this reducing substance has a certain reducing property, various substances can be used. For example, at least one selected from the group consisting of alkali metals, alkaline earth metals, rare earth metals, oxides of alkali metals, halides of alkali metals, oxides of alkaline earth metals, halides of alkaline earth metals, oxides of rare earth metals, halides of rare earth metals, organic complexes of alkali metals, organic complexes of alkaline earth metals, and organic complexes of rare earth metals can be preferably used.

[0561] Preferred reducing substances include alkali metals such as Na (work function 2.36 eV), K (2.28 eV), Rb (2.16 eV), or Cs (1.95 eV), and alkaline earth metals such as Ca (2.9 eV), Sr (2.0 - 2.5 eV), or Ba (2.52 eV). Substances with a work function of 2.9 eV or less are particularly preferred. Among these, more preferred reducing substances are alkali metals of K, Rb, or Cs, even more preferably Rb or Cs, and most preferably 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, an improvement in the emission luminance and an extension of the lifetime in the organic EL element can be achieved. Also, as reducing substances with a work function of 2.9 eV or less, combinations of two or more of these alkali metals are also preferred, particularly combinations containing Cs, such as combinations of Cs and Na, Cs and K, Cs and Rb, or Cs and Na and K. By containing Cs, the reducing ability can be efficiently exerted, and by adding it to the material forming the electron transport layer or the electron injection layer, an improvement in the emission luminance and an extension of the lifetime in the organic EL element can be achieved.

[0562] <Cathode in the 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.

[0563] The material for forming the cathode 108 is not particularly limited as long as it can efficiently inject electrons into the organic layer, and the same materials as those used for 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 (such as magnesium-silver alloy, magnesium-indium alloy, aluminum-lithium alloy such as lithium fluoride / aluminum, etc.) are preferred. In order to improve the device characteristics by increasing the electron injection efficiency, lithium, sodium, potassium, cesium, calcium, magnesium, or alloys containing these low work function metals are effective. However, these low work function metals are generally often unstable in the atmosphere. To improve this point, for example, a method of doping a trace amount of lithium, cesium, or magnesium into the organic layer and using a highly stable electrode is known. Other dopants such as inorganic salts such as lithium fluoride, cesium fluoride, lithium oxide, and cesium oxide can also be used. However, it is not limited to these.

[0564] Furthermore, for electrode protection, it is preferable to laminate metals such as platinum, gold, silver, copper, iron, tin, aluminum, and indium, or alloys using these metals, and inorganic substances such as silica, titania, and silicon nitride, polyvinyl alcohol, vinyl chloride, hydrocarbon-based polymer compounds, etc. The manufacturing methods of these electrodes are not particularly limited as long as conduction can be achieved, such as resistance heating, electron beam evaporation, sputtering, ion plating, and coating.

[0565] <Binder that may be used in each layer> The materials used for the above hole injection layer, hole transport layer, light-emitting layer, electron transport layer, and electron injection layer can form each layer independently. However, they can also be used by being dispersed in solvent-soluble resins such as 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, etc., or curable resins such as phenol resin, xylene resin, petroleum resin, urea resin, melamine resin, unsaturated polyester resin, alkyd resin, epoxy resin, silicone resin, etc.

[0566] <Method for manufacturing organic electroluminescent device> Each layer constituting the organic EL device can be formed by forming a thin film of the material to be used for each layer by methods such as evaporation method, resistance heating evaporation, electron beam evaporation, sputtering, molecular lamination method, printing method, spin coating method, casting method, coating method, etc. There is no particular limitation on the film thickness of each layer formed in this way, and it can be appropriately set according to the properties of the material, but it is usually in the range of 2 nm to 5000 nm. The film thickness can usually be measured with a crystal oscillator type film thickness measuring device, etc. When thinning by the evaporation method, the evaporation conditions vary depending on the type of material, the intended crystal structure and association structure of the film, etc. The evaporation conditions are generally preferably set appropriately in the range of boat heating temperature +50 to +400 °C, vacuum degree 10 -6 ~10 -3 Pa, evaporation rate 0.01 to 50 nm / second, substrate temperature -150 to +300 °C, and film thickness 2 nm to 5 μm.

[0567] Next, as an example of a method for manufacturing an organic EL element, a method for manufacturing an organic EL element composed of an anode / hole injection layer / hole transport layer / light-emitting layer composed of a host material and a dopant material / electron transport layer / electron injection layer / cathode will be described. After forming a thin film of an anode material on a suitable substrate by a vapor deposition method or the like to fabricate an anode, thin films of a hole injection layer and a hole transport layer are formed on this anode. A host material and a dopant material are co-evaporated thereon to form a thin film as a light-emitting layer, an electron transport layer and an electron injection layer are formed on this light-emitting layer, and further a thin film composed of a cathode material is formed by a vapor deposition method or the like to form a cathode, whereby the target organic EL element can be obtained. In addition, in the fabrication of the above-described organic EL element, it is also possible to fabricate in the reverse order of fabrication, that is, in the order of cathode, electron injection layer, electron transport layer, light-emitting layer, hole transport layer, hole injection layer, and anode.

[0568] When a DC voltage is applied to the organic EL element thus obtained, it may be applied with the anode as the + polarity and the cathode as the - polarity. When a voltage of about 2 to 40 V is applied, light emission can be observed from the transparent or semi-transparent electrode side (anode or cathode, and both). In addition, this organic EL element also emits light when a pulse current or an alternating current is applied. The waveform of the applied alternating current may be arbitrary.

[0569] <Application Examples of Organic Electroluminescent Elements> In addition, the present invention can also be applied to a display device including an organic EL element or a lighting device including an organic EL element. A display device or a lighting device including an organic EL element can be manufactured by a known method such as connecting the organic EL element according to this embodiment and a known driving device, and can be driven by appropriately using a known driving method such as DC driving, pulse driving, or AC driving.

[0570] Examples of the display device include panel displays such as color flat panel displays, and flexible displays such as flexible color organic electroluminescence (EL) displays (see, for example, Japanese Patent Application Laid-Open Nos. 10-335066, 2003-321546, 2004-281086, etc.). Examples of the display method of the display include, for example, matrix and / or segment methods. Note that matrix display and segment display may coexist in the same panel.

[0571] In a matrix, pixels for display are arranged two-dimensionally in a grid or mosaic pattern, and characters and images are displayed by a set of pixels. The shape and size of the pixels are determined by the application. For example, for image and character display of a personal computer, monitor, or television, square pixels with a side length of usually 300 μm or less are used. In the case of a large display such as a display panel, pixels with a side length on the order of mm are used. In the case of monochrome display, pixels of the same color may be arranged. In the case of color display, red, green, and blue pixels are arranged for display. In this case, typically, there are delta type and stripe type. As for the driving method of this matrix, either a line sequential driving method or an active matrix may be used. The line sequential driving has the advantage of a simple structure, but considering the operating characteristics, the active matrix may be superior in some cases, so it is also necessary to use them appropriately depending on the application.

[0572] In the segment method (type), a pattern is formed to display predetermined information, and a predetermined area is made to emit light. For example, time and temperature display in a digital clock or thermometer, operation state display of audio equipment or electromagnetic cooker, and panel display of an automobile, etc. can be mentioned.

[0573] Examples of lighting devices include lighting devices such as indoor lighting, and backlights for liquid crystal display devices (see, for example, Japanese Patent Application Laid-Open Nos. 2003-257621, 2003-277741, 2004-119211, etc.). Backlights are mainly used for the purpose of improving the visibility of display devices that do not emit light spontaneously, and are used in liquid crystal display devices, watches, audio devices, automotive panels, display boards, and signs. In particular, as a backlight for a personal computer application where thinning is an issue, especially for a liquid crystal display device, considering that it is difficult to thin the conventional method because it consists of a fluorescent lamp and a light guide plate, the backlight using the light-emitting element according to this embodiment is characterized by being thin and lightweight.

[0574] 3-2. Other organic devices In addition to the organic electroluminescent element described above, the polycyclic aromatic compound according to the present invention can be used for the production of an organic field effect transistor or an organic thin film solar cell.

[0575] An organic field effect transistor is a transistor that controls current by an electric field generated by a voltage input, and a gate electrode is provided 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 it is a transistor that can arbitrarily block the flow of electrons (or holes) flowing between the source electrode and the drain electrode to control the current. The field effect transistor is easier to miniaturize than a simple transistor (bipolar transistor), and is often used as an element constituting an integrated circuit or the like.

[0576] The structure of the organic field effect transistor usually has a source electrode and a drain electrode provided in contact with an organic semiconductor active layer formed using the polycyclic aromatic compound according to the present invention, and a gate electrode may be provided with an insulating layer (dielectric layer) in contact with the organic semiconductor active layer interposed therebetween. Examples of the element structure include the following structures. (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 and drain electrode (3) Substrate / Organic semiconductor active layer / Source electrode and drain electrode / Insulator layer / Gate electrode (4) Substrate / Source electrode and drain electrode / Organic semiconductor active layer / Insulator layer / Gate electrode The organic field effect transistor configured as described above can be applied as a pixel drive switching element for a liquid crystal display or an organic electroluminescence display using an active matrix drive method, etc.

[0577] The 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 the hole transport layer, p-type semiconductor layer, n-type semiconductor layer, and electron transport layer according to 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. In addition to the above, 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. Known materials used for organic thin film solar cells can be appropriately selected and combined for use in the organic thin film solar cell.

Example

[0578] Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited thereto. First, a synthesis example of the polycyclic aromatic compound will be described below.

[0579] Synthesis example (1) Synthesis of compound (1-1)

Chemical formula

[0580] Under a nitrogen atmosphere, a flask containing 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 and separated by liquid separation. After the organic layer was washed with water, the solvent was distilled off under reduced pressure. Then, it was purified by a silica gel short column (eluent: toluene) and reprecipitated with heptane to obtain Intermediate A (17.1 g).

Chemical formula

[0581] To a flask containing Intermediate A (17.0 g) and t-butylbenzene (120 ml), under a nitrogen atmosphere, while cooling in an ice bath, a t-butyllithium / pentane solution (1.62 M, 28.4 ml) was added. After the addition was completed, the temperature was raised to 60 °C and stirred for 1 hour, and the components with a lower boiling point than t-butylbenzene were distilled off under reduced pressure. It was cooled to -50 °C, boron tribromide (11.5 g) was added, the temperature was raised to room temperature and stirred for 0.5 hour. Then, it was cooled again in an ice bath and N,N-diisopropylethylamine (5.9 g) was added. After stirring at room temperature until the exothermic reaction subsided, the temperature was raised to 100 °C and heated and stirred for 1 hour. The reaction solution was cooled to room temperature, an aqueous sodium acetate solution cooled in an ice bath was added, then ethyl acetate was added for liquid separation, and then the solvent was distilled off under reduced pressure and washed with heptane. Then, it was purified by a silica gel short column (eluent: toluene), further reprecipitated with heptane, and finally sublimated and purified to obtain the compound of formula (1-1) (3.2 g).

Chemical formula

[0582] The structure of the compound obtained by NMR measurement was confirmed. 11H-NMR (400 MHz, CDCl3): 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).

[0583] Synthesis Example (2) Synthesis of Compound (1-82) [Chemical formula]

[0584] Under a nitrogen atmosphere, a flask containing 1,3,5-tribromobenzene (1.57 g), 4,4'-difluorodiphenylamine (3.28 g), tris(dibenzylideneacetone)dipalladium(0) (Pd2(dba)3, 0.229 g), tri-t-butylphosphine (0.101 g), calcium t-butoxide (KOtBu, 2.24 g) and toluene (40 ml) was heated and stirred at 100 °C for 20 hours. After cooling the reaction solution to room temperature, it was filtered through a Florisil® pad and further rinsed with dichloromethane. After concentrating the filtrate, the crude product obtained by concentration was washed with methanol to obtain Intermediate B (2.84 g). [Chemical formula]

[0585] To Intermediate B (0.137 g, 0.20 mmol) in 2,4-dichlorobenzene (2.0 ml) under a nitrogen atmosphere, boron tribromide (19.0 μl, 0.20 mmol) was added at room temperature, and the mixture was stirred at 200 °C for 20 hours. Then, it 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%). [Chemical formula]

[0586] The structure of the compound obtained by NMR measurement and mass spectrometry was confirmed. 1 1H NMR (δ ppm in CDCl3); 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). 13 13C NMR (δ ppm in CDCl3); 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 BF6N3 696.2046, observed 696.2097.

[0587] Synthesis Example (3) Synthesis of Compound (1 - 701)

Chemical formula

[0588] To intermediate B (0.138 g, 0.20 mmol) in 1,2 - dichlorobenzene (5 ml) under a nitrogen atmosphere at room temperature, boron triiodide (0.391 g, 0.10 mmol) and triphenylborane (96.7 mg, 0.40 mmol) were added, and the mixture was stirred at 200 °C for 20 hours. Then, it 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%).

Chemical formula

[0589] The structure of the compound obtained by NMR measurement and mass spectrometry was confirmed. 1 1H NMR (500 MHz, (CDCl2)2) δ = 5.10 (s, 1H, a), 6.87 (dd, J = 4.5, 9.0 Hz, 2H), 7.14 - 7.35 (m, 12H), 8.23 (dd, J = 4.5, 9.5 Hz, 2H), 8.38 (dd, J = 3.0, 9.0 Hz, 2H), 8.46 (dd, J = 3.0, 9.0 Hz, 2H). 13 13C NMR (101 MHz, (CDCl2)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 C-F = 7.2, 20.4 Hz, 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 = 242.3 Hz, 2C), 158.9 (d, J C-F = 245.9 Hz, 2C), 162.4 (d, J C-F = 254.3 Hz, 2C). 11 11B NMR (128 MHz, (CDCl2)2) δ = 37.2. 19 19F NMR (376 MHz, (CDCl2)2) δ = -123.0, -119.0, -112.3. HRMS (DART) m / z [M + H] + calcd for C 42 H 21 B2F6N3 704.1888; observed 704.1918.

[0590] Synthesis Example (4) Synthesis of Compound (1 - 883): 5,9 - Bis(2,6 - difluorophenyl)-2,7,12 - tris(2,6 - dimethylphenyl)-5,9 - dihydro - 5,9 - diaza - 13b - borananaphtho[3,2,1 - de]anthracene

Chemical Structure

[0591] Under a nitrogen atmosphere, a flask containing 1-bromo-4-iodobenzene (14.2 g, 50.0 mmol), 2,6-dimethylphenylboronic acid (7.50 g, 50.0 mmol), tetrakis(triphenylphosphine)palladium (Pd(PPh3)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. 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 by silica gel column (eluent: hexane) to obtain 4'-bromo-2,6-dimethyl-1,1'-biphenyl as a white solid (9.71 g, yield 74%).

Chemical formula

[0592] The structure of the compound obtained by NMR measurement was confirmed. 1 1H-NMR (500 MHz, CDCl3): δ = 2.02 (s, 6H), 7.00 - 7.04 (m, 2H), 7.10 (d, J = 7.5 Hz, 2H), 7.17 (t, J = 8.0 Hz, 1H), 7.53 - 7.56 (m, 2H).

[0593] Under a nitrogen atmosphere, a flask containing 4'-bromo-2,6-dimethyl-1,1'-biphenyl (9.14 g, 35.0 mmol), 2,6-difluoroaniline (5.31 ml, 52.5 mmol), Pd2(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 by a silica gel short path 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 as a white solid (9.93 g, yield 92%). [Chemical formula]

[0594] The structure of the obtained compound was confirmed by NMR measurement. 1 1H-NMR (500 MHz, CDCl3): δ = 2.06 (s, 6H), 5.53 (s, 1H), 6.87 (d, J = 8.6 Hz, 2H), 6.94 - 7.06 (m, 5H), 7.07 - 7.17 (m, 3H).

[0595] Under a nitrogen atmosphere, a flask containing 1-bromo-3,5-dichlorobenzene (11.3 g, 50.0 mmol), 2,6-dimethylphenylboronic acid (9.00 g, 60.0 mmol), Pd(PPh3)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 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 by 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%).

Chemical formula

[0596] The structure of the compound obtained by NMR measurement was confirmed. 1 1H-NMR (500 MHz, CDCl3): δ = 2.03 (s, 6H), 7.05 (d, J = 1.7 Hz, 2H), 7.09 (d, J = 7.5 Hz, 2H), 7.17 (t, J = 7.5 Hz, 1H), 7.35 (t, J = 1.7 Hz, 1H).

[0597] Under a nitrogen atmosphere, a flask containing 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), Pd2(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) was 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 by a silica gel short-path column (eluent: hexane / toluene = 3 / 1 (volume ratio)), and further washed successively with methanol and hexane to obtain 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 as a white solid (8.08 g, yield 85%).

Chemical formula

[0598] The structure of the compound obtained by NMR measurement was confirmed. 1 1H-NMR (500 MHz, CDCl3): δ = 2.01 (s, 12H), 2.10 (s, 6H), 6.46 (d, J = 2.0 Hz, 2H), 6.83 (t, J = 2.4 Hz, 1H), 6.89 - 6.98 (m, 8H), 7.03 - 7.17 (m, 15H).

[0599] Under a 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 1,2,4-trichlorobenzene (20.0 ml) were placed in a flask and 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. Dichloromethane (150 ml) was added to dilute the reaction solution, and then 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 by silica gel column (eluent: hexane / dichloromethane = 2 / 1 (volume ratio)), and heated and washed at 80 °C using acetonitrile to obtain the compound of formula (1-883) as a yellow solid (1.09 g, yield: 68%).

Chemical formula

[0600] The structure of the compound obtained by NMR measurement was confirmed. 1 1H-NMR (500 MHz, CDCl3): δ = 1.99 (s, 6H), 2.11 (s, 12H), 6.18 (s, 2H), 6.83 (d, J = 8.6 Hz, 2H), 7.04 (d, J = 7.5 Hz, 2H), 7.09 - 7.18 (m, 7H), 7.18 - 7.31 (m, 6H), 7.50 - 7.58 (m, 2H), 8.60 (d, J = 1.4 Hz, 2H). 13 13C-NMR (126 MHz, CDCl3): 20.8 (2C), 21.3 (4C), 105.6 (2C), 113.5 (d, J C-F= 22.8 Hz, 4C), 115.2 (2C), 116.3 (1C), 118.6 (t, J C-F = 18.0 Hz, 2C), 124.4 (2C), 127.0 (2C), 127.2 (1C), 127.4 (2C), 127.6 (4C), 130.9 (t, J C-F = 9.6 Hz, 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 C-F = 3.7, 250.7 Hz, 4C).

[0601] 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-5,9,11,15-tetraaza-19b,20b-diboranaphtho[3,2,1-de:1’,2’,3’-jk]pentacene-7,13-diamine synthesis

Chemical Structure

[0602] Under a nitrogen atmosphere, a flask containing bromobenzene (5.25 ml, 50.0 mmol), 2,6-difluoroaniline (7.59 ml, 75.0 mmol), Pd2(dba)3 (0.687 mg, 0.750 mmol), BINAP (0.934 g, 1.50 mmol), NaOtBu (7.21 g, 75.0 mmol), and toluene (150 ml) was heated to 110 °C and stirred for 4 hours. After cooling the reaction solution 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 by a silica gel short-path column (eluent: hexane / toluene = 5 / 1 (volume ratio)) to obtain 2,6-difluoro-N-phenylaniline as a colorless liquid (10.1 g, yield 98%). [Chemical formula]

[0603] The structure of the compound obtained by NMR measurement was confirmed. 1 1H-NMR (500 MHz, CDCl3): δ = 5.48 (s, 1H), 6.81 (dd, J = 1.2, 7.5 Hz, 2H), 6.89 - 7.06 (m, 4H), 7.21 - 7.27 (m, 2H).

[0604] Under a nitrogen atmosphere, a flask containing 1,3-dibromo-5-chlorobenzene (4.87 g, 18.0 mmol), 2,6-difluoro-N-phenylaniline (7.39 g, 36.0 mmol), Pd2(dba)3 (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 and stirred for 3 hours. After cooling the reaction solution 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 by 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, 77% yield).

Chemical formula

[0605] The structure of the compound obtained by NMR measurement was confirmed. 1 1H-NMR (500 MHz, CDCl3): 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).

[0606] Under a nitrogen atmosphere, N synthesized according to the method described in International Publication No. 2018 / 212169 1 ,N 3 -Diphenylbenzene-1,3-diamine (0.521 g, 2.00 mmol), 5-chloro-N 1 ,N 3 -Bis(2,6-difluorophenyl)-N 1 ,N 3 -Diphenylbenzene-1,3-diamine (2.28 g, 4.40 mmol), Pd2(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 placed in a flask and heated to 110 °C and stirred for 8 hours. After cooling the reaction solution 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 by silica gel column (eluent: hexane / ethyl acetate = 3 / 1 (volume ratio)) and further washed with hexane to obtain N 1 ,N 1 ’-(1,3-phenylene)bis(N 3 ,N 5 -Bis(2,6-difluorophenyl)-N 1 ,N 3 ,N5 -Triphenylbenzene-1,3,5-triamine) was obtained as a white solid (1.96 g, yield 80%).

Chemical formula

[0607] The structure of the compound obtained by NMR measurement was confirmed. 1 1H-NMR (500 MHz, CDCl3): δ = 6.28 - 6.31 (m, 6H), 6.60 (dd, J = 2.3, 8.0 Hz, 2H), 6.74 (t, J = 2.2 Hz, 1H), 6.79 - 6.98 (m, 27H), 7.02 - 7.14 (m, 16H).

[0608] Under a nitrogen atmosphere, N 1 ,N 1 ’-(1,3-phenylene)bis(N 3 ,N 5 -bis(2,6-difluorophenyl)-N 1 ,N 3 ,N 5 To a flask containing -triphenylbenzene-1,3,5-triamine (1.59 g, 1.30 mmol) and 1,2,4-trichlorobenzene (19.5 ml), boron tribromide (0.990 ml, 10.4 mmol) was added at room temperature, and the mixture was stirred at 180 °C for 20 hours. After the reaction solution was cooled to room temperature, the residual boron tribromide and hydrogen bromide in the reaction solution were distilled off under reduced pressure. Dichloromethane (150 ml) was added to dilute the reaction solution, and then 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 obtained 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%).

Chemical formula

[0609] The structure of the compound obtained by NMR measurement was confirmed. 1 1H-NMR (500 MHz, CDCl3): 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, 7.5 Hz, 2H), 10.5 (s, 1H). 13 13C-NMR (126 MHz, CDCl3): 93.7 (2C), 96.6 (2C), 103.4 (1C), 112.1 (d, J C-F = 24.0 Hz, 4C), 112.4 (2C), 112.9 (d, J C-F = 22.8 Hz, 4C), 115.1 (2C), 118.4 (2C), 118.7 (t, J C-F = 17.3 Hz, 2C), 120.9 (2C), 122.1 (t, J C-F = 14.5 Hz, 2C), 124.0 (2C), 124.1 (4C), 125.1 (2C), 127.3 (t, J = 11.1 Hz, 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 C-F = 4.2, 254.7 Hz, 4C), 160.5 (dd, J C-F = 4.2, 253.6 Hz, 4C).

[0610] Synthesis Example (6) Compound (1 - 1668): Synthesis of 9,11-bis(2,4-difluorophenyl)-N 7 ,N 7 ,N 13 ,N 13 ,5,15-hexaphenyl-5,9,11,15-tetrahydro-5,9,11,15-tetraaza-19b,20b-diborazinaphtho[3,2,1-de:1’,2’,3’-jk]pentacene-7,13-diamine [Chem.]

[0611] Under a nitrogen atmosphere, a flask containing 1,3-dibromobenzene (1.22 ml, 10.0 mmol), 2,4-difluoroaniline (2.54 ml, 25.0 mmol), Pd2(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) was 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 by a silica gel short path column (eluent: toluene) and further washed with hexane to obtain N 1 ,N 3 -bis(2,4-difluorophenyl)benzene-1,3-diamine as a white solid (1.94 g, yield 58%). [Chem.]

[0612] The structure of the compound obtained by NMR measurement was confirmed. 1 1H-NMR (500 MHz, CDCl3): 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, 10.9 Hz, 2H), 7.15 (t, J = 8.0 Hz, 1H), 7.26 (ddd, J = 5.7, 9.2, 9.2 Hz).

[0613] Under a nitrogen atmosphere, N 1 ,N 3 -bis(2,4-difluorophenyl)benzene-1,3-diamine (0.997 mg, 3.00 mmol), 5-chloro-N synthesized according to the method described in International Publication No. WO 2018 / 212169 1 ,N 1 ,N3 , N 3 -Tetraphenylbenzene-1,3-diamine (2.95 g, 6.60 mmol), Pd2(dba)3 (0.137 g, 0.150 mmol), SPhos (0.123 g, 0.300 mmol), NaOtBu (0.865 g, 9.00 mmol), and toluene (15.0 ml) were placed in a flask and 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 by silica gel column (eluent: hexane / dichloromethane = 3 / 2 (volume ratio)) and further washed with ethyl acetate to obtain 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) as a white solid (2.76 g, yield 80%).

Chemical formula

[0614] The structure of the obtained compound was confirmed by NMR measurement. 1 1H-NMR (500 MHz, CDCl3): 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).

[0615] Under a nitrogen atmosphere, N 1 , N 1 ’-(1,3-Phenylene)bis(N 1 -(2,4-difluorophenyl)-N 3 , N 3 , N 5 , N 5To a flask containing (0.173 g, 0.150 mmol) of 1,3,5-triaminotetraphenylbenzene and 3.00 ml of 1,2,4-trichlorobenzene, boron tribromide (0.114 ml, 1.20 mmol) was added at room temperature, and the mixture was stirred at 180 °C for 20 hours. After the reaction solution was cooled to room temperature, the residual boron tribromide and hydrogen bromide in the reaction solution were distilled off under reduced pressure. Dichloromethane (30.0 ml) was added to dilute the reaction solution, and then 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 obtained 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%).

Chemical formula

[0616] The structure of the compound obtained by NMR measurement was confirmed. 1 H-NMR (500 MHz, (CDCl2)2): δ = 5.61 (d, J = 5.7 Hz, 1H), 5.66 (s, 2H), 5.66 (d, J = 1.7 Hz, 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, 8.0 Hz, 2H), 10.5 (s, 1H). 13 C-NMR (126 MHz, CDCl3): 93.7 (2C), 96.6 (2C), 103.4 (1C), 112.1 (d, J C-F = 24.0 Hz, 4C), 112.4 (2C), 112.9 (d, J C-F = 22.8 Hz, 4C), 115.1 (2C), 118.4 (2C), 118.7 (t, J C-F = 17.3 Hz, 2C), 120.9 (2C), 122.1 (t, J C-F= 14.5 Hz, 2C), 124.0 (2C), 124.1 (4C), 125.1 (2C), 127.3 (t, J = 11.1 Hz, 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 C-F = 4.2, 254.7 Hz, 4C), 160.5 (dd, J C-F = 4.2, 253.6 Hz, 4C).

[0617] Synthesis Example (7) Compound (1-1666): Synthesis of 9,11-bis(2,6-difluorophenyl)-N 7 ,N 7 ,N 13 ,N 13 ,5,15-hexaphenyl-5,9,11,15-tetrahydro-5,9,11,15-tetraaza-19b,20b-diboradina naphtho[3,2,1-de:1’,2’,3’-jk]pentacene-7,13-diamine [Chemical Structure

[0618] Under a nitrogen atmosphere, a flask containing 1,3-dibromobenzene (1.22 ml, 10.0 mmol), 2,6-difluoroaniline (3.04 ml, 30.0 mmol), Pd2(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) was heated to 60 °C and stirred for 2 hours. After cooling the reaction solution 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 by a silica gel short path 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%). [Chemical formula]

[0619] The structure of the compound obtained by NMR measurement was confirmed. 1 1H-NMR (500 MHz, CDCl3): δ = 5.43 (s, 2H), 6.26 (s, 1H), 6.36 (d, J = 8.0 Hz, 2H), 6.90 - 6.98 (m, 4H), 6.98 - 7.05 (m, 2H), 7.09 (t, J = 8.0 Hz, 1H).

[0620] Under a nitrogen atmosphere, N 1 ,N 3 -Bis(2,6-difluorophenyl)benzene-1,3-diamine (1.16 g, 3.50 mmol), 5-chloro-N 1 ,N 1 ,N 3 ,N 3 ,N -Tetraphenylbenzene-1,3-diamine (3.44 g, 7.70 mmol), Pd2(dba)3 (0.160 g, 0.180 mmol), SPhos (0.144 g, 0.350 mmol), NaOtBu (1.01 g, 10.5 mmol), and a flask containing toluene (17.5 ml) were heated to 110 °C and stirred for 40 hours. After cooling the reaction solution 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 by 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%).

Chemical formula

[0621] The structure of the compound obtained by NMR measurement was confirmed. 1 1H-NMR (500 MHz, CDCl3): δ = 6.29 (d, J = 1.7 Hz, 4H), 6.38 (t, J = 2.3 Hz, 2H), 6.41 (t, J = 2.3 Hz, 1H), 6.51 (dd, J = 2.3, 8.0 Hz, 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).

[0622] Under a nitrogen atmosphere, N 1 ,N 1 ’-(1,3-phenylene)bis(N 1 -(2,6-difluorophenyl)-N 3 ,N 3 ,N 5 ,N 5 -Tetraphenylbenzene-1,3,5-triamine) (2.65 g, 2.30 mmol) and boron tribromide (1.75 ml, 18.4 mmol) were added to a flask containing 1,2,4-trichlorobenzene (50.0 ml) at room temperature, and the mixture was stirred at 200 °C for 20 hours. After cooling the reaction solution to room temperature, the residual boron tribromide and hydrogen bromide in the reaction solution were distilled off under reduced pressure. Dichloromethane (500 ml) was added to dilute the reaction solution, and then a phosphate buffer solution (pH = 7, 400 ml) was added at 0 °C. 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 washed by heating with acetonitrile at 80 °C. Subsequently, it was washed by heating with toluene at 110 °C, purified by a silica gel short-path column (eluent: toluene), and further washed by heating with toluene at 110 °C to obtain the compound of formula (1-1666) as a yellow solid (1.617 g, yield 60%). [Chemical formula]

[0623] The structure of the compound obtained by NMR measurement was confirmed. 1 H-NMR(500 MHz, (CDCl2)2): δ = 5.80 (s, 4H), 5.91 (s, 1H), 6.81 - 6.88 (m, 6H), 6.99 (t, J = 7.5 Hz, 4H), 7.03 (d, J = 8.0 Hz, 8H), 7.15 (t, J = 8.0 Hz, 8H), 7.18 - 7.26 (m, 2H), 7.33 (d, J = 8.0 Hz, 4H), 7.37 - 7.45 (m, 4H), 7.45 - 7.50 (m, 2H), 7.53 (t, J = 8.0 Hz, 4H), 9.30 (d, J = 7.5 Hz, 2H), 10.5 (s, 1H). 13 C-NMR(126 MHz, CDCl3): 93.7 (2C), 96.6 (2C), 103.4 (1C), 112.1 (d, J C-F = 24.0 Hz, 4C), 112.4 (2C), 112.9 (d, J C-F = 22.8 Hz, 4C), 115.1 (2C), 118.4 (2C), 118.7 (t, J C-F = 17.3 Hz, 2C), 120.9 (2C), 122.1 (t, J C-F = 14.5 Hz, 2C), 124.0 (2C), 124.1 (4C), 125.1 (2C), 127.3 (t, J = 11.1 Hz, 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 C-F = 4.2, 254.7 Hz, 4C), 160.5 (dd, J C-F = 4.2, 253.6 Hz, 4C).

[0624] Comparative Synthesis Example (1) Synthesis of Compound (C-1): N,N,5,9-Tetraphenyl-5,9-dihydro-5,9-diaza-13b-boranaphtho[3,2,1-de]anthracen-7-amine

Chem.

[0625] N 1 ,N 1 ,N 3 ,N 3 ,N 5 ,N 5 To - hexaphenyl-1,3,5-benzenetriamine (11.6 g, 20 mmol) and ortho-dichlorobenzene (ODCB, 120 ml) under a nitrogen atmosphere at room temperature, boron tribromide (3.78 ml, 40 mmol) was added, and then the mixture was heated with stirring at 170 °C for 48 h. Thereafter, the reaction solution was distilled off under reduced pressure at 60 °C. Filtration was carried out through a florisil short-path 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%).

Chem.

[0626] The structure of the obtained compound was confirmed by NMR measurement. 1 1H-NMR (400 MHz, CDCl3): 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). 1313C-NMR (101 MHz, CDCl3): 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).

[0627] 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-19b,20b-diboranaphtho[3,2,1-de:1’,2’,3’-jk]pentacene-7,13-diamine Synthesis

Chemical Structure

[0628] Under a nitrogen atmosphere, a flask containing 1,3-dibromobenzene (25.0 g, 106 mmol), aniline (20.3 ml, 223 mmol), Pd2(dba)3 (971 mg, 1.06 mmol), BINAP (1.98 g, 3.18 mmol), NaOtBu (25.5 g, 265 mmol) and toluene (400 ml) was 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 for reprecipitation to obtain N 1 , N 3 -diphenylbenzene-1,3-diamine as a white solid (16.5 g, yield 60%).

Chemical Structure

[0629] The structure of the compound obtained was confirmed by NMR spectrum. 1 H-NMR (400 MHz, CDCl3): 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).

[0630] Under a nitrogen atmosphere, a flask containing 1,3-dibromo-5-chlorobenzene (8.11 g, 30 mmol), diphenylamine (10.1 g, 60 mmol), Pd2(dba)3 (550 mg, 0.6 mmol), SPhos (0.493 g, 1.2 mmol), 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, a saturated solution was prepared by distilling off the solvent under reduced pressure, and hexane was added for reprecipitation to obtain 5-chloro-N 1 ,N 1 ,N 3 ,N 3 -tetraphenylbenzene-1,3-diamine as a white solid (5.66 g, yield 43%).

Chemical Structure

[0631] The structure of the compound obtained was confirmed by NMR spectrum. 1 H-NMR (400 MHz, CDCl3): δ = 6.56 (d, 2H), 6.64 (t, 1H), 7.00 (t, 4H), 7.05 (d, 8H), 7.21 (dd, 8H).

[0632] Under a 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), Pd2(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) were placed in a flask and heated to 110 °C and stirred for 8 hours. The reaction mixture 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. The obtained crude product was washed successively with hexane and methanol to obtain N 1 ,N 1 ’-(1,3-phenylene)bis(N 1 ,N 3 ,N 3 ,N 5 ,N 5 -pentaphenylbenzene-1,3,5-triamine) as a white solid (4.80 g, yield 87%).

Chemical formula

[0633] The structure of the compound obtained was confirmed by NMR spectrum. 1 1H-NMR (400 MHz, CDCl3): 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).

[0634] N 1 ,N 1 ’-(1,3-phenylene)bis(N 1 ,N 3 ,N 3 ,N 5 ,N 5To a flask containing (3.24 g, 3.0 mmol) of 1,3,5-triaminopentaphenylbenzene and 400 ml of orthodichlorobenzene, boron tribromide (1.13 ml, 12 mmol) was added at room temperature under a nitrogen atmosphere. After the addition was complete, the temperature was raised to 180 °C and the mixture was stirred for 20 hours. Then, it was cooled again to room temperature, N,N-diisopropylethylamine (7.70 ml, 45 mmol) was added, and the mixture was stirred until the exothermic reaction subsided. Then, the reaction solution was distilled off under reduced pressure at 60 °C to obtain a crude product. The obtained crude product was washed successively with acetonitrile, methanol, and toluene, purified by a silica gel column (eluent: toluene), and the crude solid was recrystallized twice from o-dichlorobenzene. Then, it was sublimated and purified at 440 °C under a reduced pressure of 1×10 -4 mmHg to obtain the compound of formula (C-2) (1.17 g). [Chemical formula]

[0635] The structure of the obtained compound was confirmed by NMR spectrum. 1 1H-NMR (400 MHz, CDCl3): 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). 1313C-NMR (101 MHz, CDCl3): 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).

[0636] By appropriately changing the starting compound, other polycyclic aromatic compounds of the present invention can be synthesized by a method according to the above-described synthesis examples.

[0637] Next, in order to explain the present invention in more detail, examples of organic EL elements using the compounds of the present invention are shown, but the present invention is not limited thereto.

[0638] <Evaluation of Organic EL Element> An organic EL element according to Example 1 was fabricated, and the voltage (V), emission wavelength (nm), and external quantum efficiency (%) which are characteristics during emission were measured. Next, the time for maintaining a luminance of 98% or more of the initial luminance when driven at a constant current with a current density of 10 mA / cm² was measured. 2 2

[0639] Regarding the quantum efficiency of a light-emitting element, there are an internal quantum efficiency and an external quantum efficiency. The internal quantum efficiency indicates the ratio at which external energy injected as electrons (or holes) into the light-emitting layer of the light-emitting element is purely converted into photons. On the other hand, the external quantum efficiency is calculated based on the amount of photons emitted to the outside of the light-emitting element. Since some of the photons generated in the light-emitting layer are absorbed or continuously reflected inside the light-emitting element and are not emitted to the outside of the light-emitting element, the external quantum efficiency is lower than the internal quantum efficiency.

[0640] ​​The method for measuring the external quantum efficiency is as follows. Using an Advantest voltage / current generator R6144, a voltage at which the luminance of the device becomes 1000 cd / m 2 was applied to cause the device to emit light. Using a TOPCON spectro-radiance meter SR-3AR, the spectro-radiance in the visible light region was measured from the direction perpendicular to the light-emitting surface. Assuming that the light-emitting surface is a perfect diffuser, the value obtained by dividing the measured spectro-radiance value of each wavelength component by the wavelength energy and multiplying by π is the number of photons at each wavelength. Next, the number of photons was integrated over the entire observed wavelength region to obtain the total number of photons emitted from the device. Using the value obtained by dividing the applied current value by the elementary charge as the number of carriers injected into the device, 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.

[0641] The material compositions of the respective layers and the EL characteristic data in the fabricated organic EL device according to Example 1 are shown in Tables 1A and 1B below.

Table 1A

Table 1B

[0642] 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, where "HAT-CN" is 1,4,5,8,9,12-hexaazatriphenylene hexacarbonitrile, "HT-1" is N-([1,1'-biphenyl]-4-yl)-9,9-dimethyl-N-(4-(9-phenyl-9H-carbazol-3-yl)phenyl)-9H-fluorene-2-amine, "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, "ET-1" is 4,6,8,10-tetraphenyl[1,4]benzoxaborinin[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".

[0643] [Chemical Structure]

[0644] [Example 1] A 26 mm × 28 mm × 0.7 mm glass substrate (manufactured by OptoSciences Co., Ltd.) with ITO film formed by sputtering and polished to a thickness of 180 nm to 150 nm was used as the transparent support substrate. This transparent support substrate was fixed to the substrate holder of a commercially available vapor deposition apparatus (manufactured by Showa Vacuum Co., Ltd.), and molybdenum vapor deposition boats containing HI, HAT-CN, HT-1, HT-2, BH-1, Compound (1-1), ET-1, and ET-2 respectively, and aluminum nitride vapor deposition boats containing Liq, LiF, and aluminum were mounted.

[0645] The following layers were sequentially formed on the ITO film of the transparent support substrate. The vacuum chamber was 5×10 -4The pressure was reduced to Pa. First, HI was heated and vapor-deposited to a film thickness of 40 nm. Next, HAT-CN was heated and vapor-deposited to a film thickness of 5 nm. Then, HT-1 was heated and vapor-deposited to a film thickness of 45 nm. Next, HT-2 was heated and vapor-deposited to a film thickness of 10 nm to form a hole layer composed of four layers. Next, BH-1 and compound (1-1) were simultaneously heated and vapor-deposited to a film thickness of 25 nm to form a light-emitting layer. The deposition rate was adjusted so that the weight ratio of BH-1 to compound (1-1) was approximately 98 to 2. Further, ET-1 was heated and vapor-deposited to a film thickness of 5 nm. Then, ET-2 and Liq were simultaneously heated and vapor-deposited to a film thickness of 25 nm to form an electron layer composed of two layers. The deposition rate was adjusted so that the weight ratio of ET-2 to Liq was approximately 50 to 50. The deposition rate of each layer was 0.01 - 1 nm / second. Thereafter, LiF was heated and vapor-deposited at a deposition rate of 0.01 - 0.1 nm / second to a film thickness of 1 nm, and then aluminum was heated and vapor-deposited to a film thickness of 100 nm to form a cathode, thereby obtaining an organic EL element.

[0646] A DC voltage was applied with the ITO electrode as the anode and the LiF / aluminum electrode as the cathode, and 1000 cd / m 2 When the characteristics during light emission were measured, blue light emission with a wavelength of 458 nm was obtained, the driving voltage was 3.90 V, and the external quantum efficiency was 7.89%.

[0647] The material compositions of each layer and the EL characteristic data in the organic EL elements according to Examples 2 - 8 and Comparative Examples 1 - 2 prepared are shown in Tables 2A and 2B below. [[ID=,11]]

Table 2A

Table 2B

[0648] In Table 2A, "BH-2" is 2-(10-phenylanthracen-9-yl)dibenzofuran. The chemical structures are shown below together with compound (C-1) and compound (C-2).

[0649]

Chem.

[0650] <Example 2> A glass substrate (manufactured by Opto Science Co., Ltd.) with dimensions of 26 mm × 28 mm × 0.7 mm, on which ITO film formed by sputtering with a thickness of 180 nm was polished to 150 nm, was used as the transparent support substrate. This transparent support substrate was fixed to the substrate holder of a commercially available vapor deposition apparatus (manufactured by Showa Vacuum Co., Ltd.), and molybdenum vapor deposition boats filled with HI, HAT-CN, HT-1, HT-2, BH-2, Compound (1-1), ET-1, and ET-2 respectively, and aluminum nitride vapor deposition boats filled with Liq, LiF, and aluminum respectively were mounted.

[0651] The following layers were sequentially formed on the ITO film of the transparent support substrate. The vacuum chamber was evacuated to 5×10 -4 Pa, and first, HI was heated and vapor-deposited to a film thickness of 40 nm. Next, HAT-CN was heated and vapor-deposited to a film thickness of 5 nm. Then, HT-1 was heated and vapor-deposited to a film thickness of 45 nm. Next, HT-2 was heated and vapor-deposited to a film thickness of 10 nm to form a hole layer consisting of 4 layers. Next, BH-2 and Compound (1-1) were heated simultaneously and vapor-deposited to a film thickness of 25 nm to form a light-emitting layer. The deposition rate was adjusted so that the weight ratio of BH-2 to Compound (1-1) was approximately 98 to 2. Further, ET-1 was heated and vapor-deposited to a film thickness of 5 nm. Then, ET-2 and Liq were heated simultaneously and vapor-deposited to a film thickness of 25 nm to form an electron layer consisting of 2 layers. The deposition rate was adjusted so that the weight ratio of ET-2 to Liq was approximately 50 to 50. The deposition rate of each layer was 0.01 - 1 nm / second. After that, LiF was heated and vapor-deposited at a deposition rate of 0.01 - 0.1 nm / second to a film thickness of 1 nm, and then aluminum was heated and vapor-deposited to a film thickness of 100 nm to form the cathode, obtaining an organic EL element.

[0652] A DC voltage was applied with the ITO electrode as the anode and the LiF / aluminum electrode as the cathode, and 1000 cd / m 2When the characteristics during light emission were measured, the driving voltage was 3.80 V and the external quantum efficiency was 7.50%. Also, when the time for maintaining a luminance of 98% or more of the initial luminance during constant current driving at a current density of 10 mA / cm 2 was measured, it was 53 hours.

[0653] <Examples 3 to 8 and Comparative Examples 1 to 2> An organic EL element was fabricated by a method similar to that of Example 2 (Table 2A), and the EL characteristics were measured (Table 2B).

[0654] <Example 9> Next, regarding the short-wavelength shift effect of the emission wavelength by introducing an electron-accepting fluorine atom in the compound represented by formula (1), the fluorescence spectrum was measured and verified.

[0655] The fluorescence spectrum was measured 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 to prepare a measurement solution, then putting this into a quartz optical cell and exciting it at an excitation wavelength of 380 nm to measure the fluorescence spectrum. The results are shown in Table 3A below.

Table 3A

[0656] Also, the compound of formula (C-2) which is a comparative compound was dissolved in toluene at a concentration of 2×10 -5 M to prepare a measurement solution, then putting this into a quartz optical cell and exciting it at an excitation wavelength of 380 nm to measure the fluorescence spectrum. The results are shown in Table 3B below.

Table 3B

[0657] From the above results, the short-wavelength shift effect of the fluorescence spectrum by introducing a fluorine atom was confirmed. This result indicates that by introducing a fluorine atom into the molecule, blue light emission with a shorter wavelength can be obtained.

Industrial Applicability

[0658] In the present invention, by providing a novel fluorine-substituted polycyclic aromatic compound, it is possible to increase the options for materials for organic devices such as materials for organic EL elements. Further, by using a novel fluorine-substituted polycyclic aromatic compound as a material for an organic EL element, it is possible to provide, for example, an organic EL element excellent in light emission efficiency and element lifetime, a display device including the same, and a lighting device including the same.

Explanation of reference numerals

[0659] 100 Organic electroluminescent element 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

1. A dimer of a polycyclic aromatic compound having two unit structures represented by the following general formula (1), wherein the A ring, B ring, or C ring in the unit structure is bonded so as to be shared by two unit structures, a ring-sharing dimer. 【Chemical 1】 (In the above formula (1), the A ring, B ring, and C ring 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 is an aryl having 6 to 30 carbon atoms, a heteroaryl having 2 to 30 carbon atoms, diarylamino (wherein aryl is aryl having 6 to 12 carbon atoms), diarylboryl (wherein aryl is aryl having 6 to 12 carbon atoms), alkyl having 1 to 24 carbon atoms, or cycloalkyl having 3 to 24 carbon atoms, and at least one hydrogen in these groups may be substituted with aryl having 6 to 12 carbon atoms, heteroaryl having 2 to 15 carbon atoms, alkyl having 1 to 6 carbon atoms, or cycloalkyl having 3 to 14 carbon atoms, Y １ is B, X １ and X ２ is independently N-R, where R of the N-R is aryl having 6 to 30 carbon atoms, heteroaryl having 2 to 30 carbon atoms, alkyl having 1 to 24 carbon atoms, or cycloalkyl having 3 to 24 carbon atoms, and at least one hydrogen in these groups may be substituted with aryl having 6 to 12 carbon atoms, heteroaryl having 2 to 15 carbon atoms, alkyl having 1 to 6 carbon atoms, or cycloalkyl having 3 to 14 carbon atoms. Also, R of the N-R may be bonded to the A ring, B ring, and / or C ring by -O-, -S-, -C(-R) ２ -, or a single bond, and R of the -C(-R) ２ - is hydrogen, alkyl having 1 to 6 carbon atoms, or cycloalkyl having 3 to 14 carbon atoms, at least one hydrogen in the unit structure represented by formula (1) may be substituted with cyano, chlorine, bromine, iodine, or deuterium, and at least one hydrogen in the "diarylamino (wherein aryl is aryl having 6 to 12 carbon atoms)" which is a substituent on the A ring, B ring, and C ring and the "aryl having 6 to 30 carbon atoms" which is R of N-R is substituted with fluorine.)

2. 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 is an aryl having 6 to 16 carbon atoms, a heteroaryl having 2 to 20 carbon atoms, diarylamino (wherein aryl is aryl having 6 to 12 carbon atoms), diarylboril (wherein aryl is aryl having 6 to 12 carbon atoms), alkyl having 1 to 18 carbon atoms, or cycloalkyl having 3 to 20 carbon atoms, and at least one hydrogen in these groups may be substituted with an aryl having 6 to 12 carbon atoms, a heteroaryl having 2 to 15 carbon atoms, alkyl having 1 to 6 carbon atoms, or cycloalkyl having 3 to 14 carbon atoms. Further, Ring A, Ring B, and Ring C are Y １ , X １ , and X ２ and have a 5-membered or 6-membered ring that shares a bond with the central condensed bicyclic structure of the above formula composed of Y １ is B, X １ and X ２ are each independently N-R, where R of the N-R is aryl having 6 to 16 carbon atoms which may be substituted with alkyl having 1 to 6 carbon atoms or cycloalkyl having 3 to 14 carbon atoms, heteroaryl having 2 to 20 carbon atoms which may be substituted with alkyl having 1 to 6 carbon atoms or cycloalkyl having 3 to 14 carbon atoms, alkyl having 1 to 6 carbon atoms, or cycloalkyl having 3 to 14 carbon atoms, and R of the N-R is also bonded to the A ring, B ring and / or C ring by -O-, -S-, -C(-R) ２ -, or a single bond, and R of the -C(-R) ２ - is hydrogen, alkyl having 1 to 6 carbon atoms, or cycloalkyl having 3 to 14 carbon atoms, at least one hydrogen in the unit structure represented by formula (1) may be substituted with cyano, chlorine, bromine, iodine, or deuterium, and at least one hydrogen in the "diarylamino (wherein aryl is aryl having 6 to 12 carbon atoms)" which is a substituent on the A ring, B ring, and C ring and the "aryl having 6 to 16 carbon atoms" which is R of N-R is substituted with fluorine, The ring-sharing dimer according to Claim 1.

3. The ring-sharing dimer according to Claim 1, wherein the unit structure is represented by the following general formula (2). [Chemical 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 (wherein aryl is aryl having 6 to 12 carbon atoms), diarylboryl (wherein aryl is aryl having 6 to 12 carbon atoms), alkyl having 1 to 18 carbon atoms, or cycloalkyl having 3 to 20 carbon atoms, and at least one hydrogen in these groups may be substituted with aryl having 6 to 12 carbon atoms, heteroaryl having 2 to 15 carbon atoms, alkyl having 1 to 6 carbon atoms, or cycloalkyl having 3 to 14 carbon atoms. Also, R １ to R １１ adjacent groups among them may combine to form an aryl ring having 9 to 16 carbon atoms or a heteroaryl ring having 6 to 20 carbon atoms together with the a-ring, b-ring, or c-ring, and at least one hydrogen in the formed ring may be substituted with aryl having 6 to 16 carbon atoms, heteroaryl having 2 to 20 carbon atoms, diarylamino (wherein aryl is aryl having 6 to 12 carbon atoms), diarylboryl (wherein aryl is aryl having 6 to 12 carbon atoms), alkyl having 1 to 18 carbon atoms, or cycloalkyl having 3 to 20 carbon atoms, and at least one hydrogen in these groups may be substituted with aryl having 6 to 12 carbon atoms, heteroaryl having 2 to 15 carbon atoms, alkyl having 1 to 6 carbon atoms, or cycloalkyl having 3 to 14 carbon atoms. Y １ is B, X １ and X ２ is each independently N-R, where R of the N-R is aryl having 6 to 12 carbon atoms, heteroaryl having 2 to 15 carbon atoms, alkyl having 1 to 6 carbon atoms, or cycloalkyl having 3 to 14 carbon atoms, and R of the N-R may be bonded to the a-ring, b-ring and / or c-ring by -O-, -S-, -C(-R) ２ -, or a single bond, and R of 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 unit structure represented by formula (2) may be substituted with cyano, chlorine, bromine, iodine, or deuterium, and At least one hydrogen in the “diaryl amino (where aryl is an aryl having 6 to 12 carbon atoms)” among R1 to R11, the “diaryl amino (where aryl is an aryl having 6 to 12 carbon atoms)” which is a substituent on the formed ring, and the “aryl having 6 to 12 carbon atoms” which is R of N-R is substituted with fluorine.

4. R １ to R １１ each independently represents hydrogen, aryl having 6 to 16 carbon atoms, heteroaryl having 2 to 20 carbon atoms, diarylamino (wherein aryl is aryl having 6 to 12 carbon atoms), diarylboryl (wherein aryl is aryl having 6 to 12 carbon atoms), alkyl having 1 to 18 carbon atoms, or cycloalkyl having 3 to 20 carbon atoms, and further, R １ to R １１ adjacent groups among them may combine with each other to form an aryl ring having 9 to 16 carbon atoms or a heteroaryl ring having 6 to 15 carbon atoms together with the a ring, b ring, or c ring, and at least one hydrogen in the formed ring may be substituted with aryl having 6 to 10 carbon atoms, diarylamino (wherein aryl is aryl having 6 to 12 carbon atoms), 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 each independently N-R, where R of the N-R is aryl having 6 to 10 carbon atoms, alkyl having 1 to 4 carbon atoms, or cycloalkyl having 5 to 10 carbon atoms, At least one hydrogen in the unit structure represented by formula (2) may be substituted with cyano, chlorine, bromine, iodine, or deuterium, and At least one hydrogen in the “diaryl amino (where aryl is an aryl having 6 to 12 carbon atoms)” among R1 to R11, the “diaryl amino (where aryl is an aryl having 6 to 12 carbon atoms)” which is a substituent on the formed ring, and the “aryl having 6 to 10 carbon atoms” which is R of N-R is substituted with fluorine. The ring-sharing dimer according to claim 3.

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 (wherein aryl is aryl having 6 to 10 carbon atoms), diarylboryl (wherein aryl is 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, X １ and X ２ are each independently N-R, where R of the N-R is aryl having 6 to 10 carbon atoms, alkyl having 1 to 4 carbon atoms, or cycloalkyl having 5 to 10 carbon atoms, and At least one hydrogen in the “diaryl amino (where aryl is an aryl having 6 to 10 carbon atoms)” among R1 to R11 and the “aryl having 6 to 10 carbon atoms” which is R of N-R is substituted with fluorine. The ring-sharing dimer according to claim 3.

6. The ring-sharing dimer according to any one of claims 1 to 5, wherein R of N-R is phenyl substituted with fluorine.

7. The ring-sharing dimer according to any one of claims 1 to 6, which is substituted with a fluorine-substituted diaryl amino group.

8. The ring-sharing dimer according to claim 7, which is substituted with a fluorine-substituted diphenyl amino group.

9. A ring-sharing dimer represented by any of the following structural formulas. 【Chemical Formula 4】

10. A material for an organic device, containing the ring-sharing dimer according to any one of claims 1 to 9.

11. The material for an organic device according to claim 10, wherein the material for an organic device is a material for an organic electroluminescent element, a material for an organic field effect transistor, or a material for an organic thin film solar cell.

12. The material for an organic electroluminescent element according to claim 11, which is a material for a light-emitting layer.

13. An organic electroluminescent element having a pair of electrodes composed 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 according to claim 12.

14. The organic electroluminescent device according to claim 13, wherein the light-emitting layer includes a host and the material for the light-emitting layer as a dopant.

15. The organic electroluminescent device according to claim 14, wherein the host is an anthracene-based compound, a fluorene-based compound, or a dibenzocrisene-based compound.

16. The organic electroluminescent device according to any one of claims 13 to 15, having 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 contains at least one selected from the group consisting of a borane derivative, a pyridine derivative, a fluoranthene derivative, a BO-based derivative, an anthracene derivative, a benzofluorene derivative, a phosphine oxide derivative, a pyrimidine derivative, a carbazole derivative, a triazine derivative, a benzimidazole derivative, a phenanthroline derivative, and a quinolinol-based metal complex.

17. The organic electroluminescent device according to claim 16, wherein the electron transport layer and / or the electron injection layer further contains at least one selected from the group consisting of an alkali metal, an alkaline earth metal, a rare earth metal, an oxide of an alkali metal, a halide of an alkali metal, an oxide of an alkaline earth metal, a halide of an alkaline earth metal, an oxide of a rare earth metal, a halide of a rare earth metal, an organic complex of an alkali metal, an organic complex of an alkaline earth metal, and an organic complex of a rare earth metal.

18. A display device or a lighting device including the organic electroluminescent device according to any one of claims 13 to 17.

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