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JP-7856248-B2 - Polycyclic aromatic compounds

JP7856248B2JP 7856248 B2JP7856248 B2JP 7856248B2JP-7856248-B2

Inventors

  • 畠山 琢次
  • 清水 瑛治
  • 高村 大作
  • 田島 晶夫
  • 影山 明子
  • 菊池 貴夫
  • 大森 英史
  • 馬場 大輔

Assignees

  • 学校法人関西学院
  • エスケーマテリアルズジェイエヌシー株式会社

Dates

Publication Date
20260511
Application Date
20220719
Priority Date
20210917

Claims (9)

  1. A polycyclic aromatic compound represented by the following general formula (1). In the above formula (1), R1 to R11 are each independently hydrogen, diarylamino, diheteroarylamino, arylheteroarylamino, diarylboryl, alkyl, cycloalkyl, alkenyl, alkoxy, aryloxy, arylthio, triarylsilyl, trialkylsilyl, tricycloalkylsilyl, dialkylcycloalkylsilyl, or alkyldicycloalkylsilyl, wherein the two aryls of the diarylamino may be linked via a linking group, the two heteroaryls of the diheteroarylamino may be linked via a linking group, the aryl and heteroaryl of the arylheteroarylamino may be linked via a linking group, and the two aryls of the diarylboryl may be linked via a linking group. Adjacent groups among R1 to R11 may bond together to form a naphthalene ring, a phenanthrene ring, a dibenzothiophene ring, a dibenzofuran ring, or a carbazole ring together with at least one of the a, b, and c rings, and at least one hydrogen atom in the formed ring may be independently substituted with diarylamino, diheteroarylamino, arylheteroarylamino, diarylboryl, alkyl, cycloalkyl, alkenyl, alkoxy, aryloxy, arylthio, triarylsilyl, trialkylsilyl, tricycloalkylsilyl, dialkylcycloalkylsilyl, or alkyldicycloalkylsilyl, and the two aryls of the diarylamino may be bonded via a linking group, the two heteroaryls of the diheteroarylamino may be bonded via a linking group, the aryl and heteroaryl of the arylheteroarylamino may be bonded via a linking group, and the two aryls of the diarylboryl may be bonded via a linking group. However, at least one group represented by the above general formula (G) is bonded to the "a-ring" or "ring formed together with the a-ring," at least one group represented by the above general formula (G) is bonded to the "b-ring" or "ring formed together with the b-ring," and at least one group represented by the above general formula (G) is bonded to the "c-ring" or "ring formed together with the c-ring," and these groups represented by formula (G) may be the same or different. In the above formula (G), Cy 1 and Cy 2 are each independently a benzene ring, a naphthalene ring, a phenanthrene ring, a pyridine ring, a quinoline ring, a dibenzofuran ring, a dibenzothiophene ring, or a carbazole ring whose N position may be substituted with phenyl, and at least one hydrogen in these rings may each independently be substituted with diarylamino, diheteroarylamino, arylheteroarylamino, diarylboryl, alkyl, cycloalkyl, alkenyl, alkoxy, aryloxy, arylthio, triarylsilyl, trialkylsilyl, tricycloalkylsilyl, dialkylcycloalkylsilyl, alkyldicycloalkylsilyl, or cyano, and the two aryls of the diarylamino may be linked via a linking group, the two heteroaryls of the diheteroarylamino may be linked via a linking group, the aryl and heteroaryl of the arylheteroarylamino may be linked via a linking group, and the two aryls of the diarylboryl may be linked via a linking group, and * is the bond position to the a ring, b ring, c ring, and the ring formed together with these rings, and At least one hydrogen atom in the compound represented by formula (1) above may be substituted with deuterium, cyano, or halogen.
  2. In the above formula (1), R1 to R11 are, independently, hydrogen, diarylamino (where aryl is an aryl with 6 to 12 carbon atoms), diheteroarylamino (where heteroaryl is a heteroaryl with 2 to 15 carbon atoms), arylheteroarylamino (where aryl is an aryl with 6 to 12 carbon atoms, and heteroaryl is a heteroaryl with 2 to 15 carbon atoms), diarylboryl (where aryl is an aryl with 6 to 12 carbon atoms), alkyl with 1 to 24 carbon atoms, cycloalkyl with 3 to 24 carbon atoms, alkenyl with 1 to 24 carbon atoms, alkoxy with 1 to 24 carbon atoms, aryloxy with 6 to 30 carbon atoms, arylthio with 6 to 30 carbon atoms, triarylsilyl (where aryl is an aryl with 6 to 12 carbon atoms), trialkylsilyl (where alkyl is an alkyl with 1 to 12 carbon atoms), and tricycloal The compounds are cyclosilyl (where the cycloalkyl is a cycloalkyl having 3 to 12 carbon atoms), dialkylcycloalkylsilyl (where the alkyl is an alkyl having 1 to 12 carbon atoms, and the cycloalkyl is a cycloalkyl having 3 to 12 carbon atoms), or alkyldicycloalkylsilyl (where the alkyl is an alkyl having 1 to 12 carbon atoms, and the cycloalkyl is a cycloalkyl having 3 to 12 carbon atoms), and the two aryls of the diarylamino may be linked via a linking group, the two heteroaryls of the diheteroarylamino may be linked via a linking group, the aryl and heteroaryl of the arylheteroarylamino may be linked via a linking group, and the two aryls of the diarylboryl may be linked via a linking group, and the linking group is a single bond, -CH 2 - CH2 -,-CHR-CHR-,- CR2 - CR2 -,-CH=CH-,-CR=CR-,-C≡C-,-N(-R)-,-O-,-S-,-C(-R) 2 -,-Si(-R) 2- , or-Se-, where R is independently hydrogen, a C6-C12 aryl, a C2-C15 heteroaryl, a C1-C24 alkyl, a C1-C24 alkenyl, a C1-C24 alkynyl, or a C3-C24 cycloalkyl, and at least one hydrogen in R may be substituted with a C1-C24 alkyl or a C3-C24 cycloalkyl. Adjacent groups among R1 to R11 may bond together to form a naphthalene ring, a phenanthrene ring, a dibenzothiophene ring, a dibenzofuran ring, or a carbazole ring together with at least one of the a, b, and c rings, and at least one hydrogen in the formed ring may independently be a diarylamino (where aryl is a C6-C12 aryl), a diheteroarylamino (where heteroaryl is a C2-C15 heteroaryl), an arylheteroarylamino (where aryl is a C6-C12 aryl, and heteroaryl is a C2-C15 heteroaryl), a diarylboryl (where aryl is a C6-C12 aryl), a C1-C24 alkyl, a C3-C24 cycloalkyl, a C1-C24 alkenyl, a C1-C24 alkoxy, a C6-C30 aryloxy, a C6-C30 arylthio, or a triarylsilyl (where aryl is an aryl) The aryl in the diarylamino may be substituted with an aryl group having 6 to 12 carbon atoms, a trialkylsilyl group (where the alkyl group is an alkyl group having 1 to 12 carbon atoms), a tricycloalkylsilyl group (where the cycloalkyl group is a cycloalkyl group having 3 to 12 carbon atoms), a dialkylcycloalkylsilyl group (where the alkyl group is an alkyl group having 1 to 12 carbon atoms, and the cycloalkyl group is a cycloalkyl group having 3 to 12 carbon atoms), and the two aryls in the diarylamino may be linked via a linking group, the two heteroaryls in the diheteroarylamino may be linked via a linking group, the aryl and heteroaryl in the arylheteroarylamino may be linked via a linking group, and the two aryls in the diarylboryl may be linked via a linking group, and the linking group may be a single bond, -CH 2 - CH2 -,-CHR-CHR-,- CR2 - CR2 -,-CH=CH-,-CR=CR-,-C≡C-,-N(-R)-,-O-,-S-,-C(-R) 2 -,-Si(-R) 2- , or-Se-, where R is independently hydrogen, a C6-C12 aryl, a C2-C15 heteroaryl, a C1-C24 alkyl, a C1-C24 alkenyl, a C1-C24 alkynyl, or a C3-C24 cycloalkyl, and at least one hydrogen in R may be substituted with a C1-C24 alkyl or a C3-C24 cycloalkyl. However, at least one group represented by the above general formula (G) is bonded to the "a-ring" or "ring formed together with the a-ring," at least one group represented by the above general formula (G) is bonded to the "b-ring" or "ring formed together with the b-ring," and at least one group represented by the above general formula (G) is bonded to the "c-ring" or "ring formed together with the c-ring," and these groups represented by formula (G) may be the same or different. In the above formula (G), Cy1 and Cy2 are, independently, a benzene ring, a naphthalene ring, a phenanthrene ring, a pyridine ring, a quinoline ring, a dibenzofuran ring, a dibenzothiophene ring, or a carbazole ring whose N position may be substituted with phenyl, and at least one hydrogen in these rings is, independently, a diarylamino (where aryl is a C6-C12 aryl), a diheteroarylamino (where heteroaryl is a C2-C15 heteroaryl), an arylheteroarylamino (where aryl is a C6-C12 aryl and heteroaryl is a C2-C15 heteroaryl), a diarylboryl (where aryl is a C6-C12 aryl), an alkyl (C1-C24), a cycloalkyl (C3-C24), an alkenyl (C1-C24), an alkoxy (C1-C24), an aryloxy (C6-C30), an arylthio (C6-C30), or a triarylsilyl (where aryl is a C6 They may be substituted with aryls (up to 12), trialkylsilyls (where alkyl is an alkyl having 1 to 12 carbon atoms), tricycloalkylsilyls (where cycloalkyl is a cycloalkyl having 3 to 12 carbon atoms), dialkylcycloalkylsilyls (where alkyl is an alkyl having 1 to 12 carbon atoms, and cycloalkyl is a cycloalkyl having 3 to 12 carbon atoms), alkyldicycloalkylsilyls (where alkyl is an alkyl having 1 to 12 carbon atoms, and cycloalkyl is a cycloalkyl having 3 to 12 carbon atoms), or cyano, and the two aryls of the diarylamino may be linked via a linking group, the two heteroaryls of the diheteroarylamino may be linked via a linking group, the aryl and heteroaryl of the arylheteroarylamino may be linked via a linking group, and the two aryls of the diarylboryl may be linked via a linking group, and the linking group may be a single bond, -CH 2- CH2- , -CHR-CHR-, -CR2- CR2- , -CH=CH-, -CR=CR-, -C≡C-, -N(-R ) -, -O-, -S-, -C(-R) 2- , -Si(-R) 2- , or -Se-, where R is independently hydrogen, a C6-C12 aryl, a C2-C15 heteroaryl, a C1-C24 alkyl, a C1-C24 alkenyl, a C1-C24 alkynyl, or a C3-C24 cycloalkyl, and at least one hydrogen in R may be substituted with a C1-C24 alkyl or a C3-C24 cycloalkyl, where * is the bond position to the a-ring, b-ring, c-ring, and the ring formed together with those rings, and, In the compound represented by formula (1) above, at least one hydrogen atom may be substituted with deuterium, cyanopropyl alcohol, or halogen. The polycyclic aromatic compound according to claim 1.
  3. In the above formula (1), R1 to R11 are each independently hydrogen, diarylamino (where aryl has 6 to 12 carbon atoms), alkyl with 1 to 24 carbon atoms, cycloalkyl with 3 to 24 carbon atoms, alkoxy with 1 to 24 carbon atoms, aryloxy with 6 to 30 carbon atoms, or arylthio with 6 to 30 carbon atoms. The two aryls of the diarylamino may be linked via a linking group, which can be a single bond, -CH2- CH2- , -CHR-CHR-, -CR2- CR2- , -CH=CH-, -CR= CR- , -C≡C-, -N(-R)-, -O-, -S-, -C(-R) 2- , or -Si(-R) 2 R is - or -Se-, and each R is independently hydrogen, a C6-C12 aryl, a C1-C24 alkyl, or a C3-C24 cycloalkyl, and at least one hydrogen in R may be substituted with a C1-C24 alkyl or a C3-C24 cycloalkyl. Adjacent groups among R1 to R11 may bond together to form a naphthalene ring, a phenanthrene ring, a dibenzothiophene ring, a dibenzofuran ring, or a carbazole ring, together with at least one of the a, b, and c rings, and at least one hydrogen in the formed ring may be independently substituted with a diarylamino (where the aryl is a C6-C12 aryl), a C1-C24 alkyl, a C3-C24 cycloalkyl, a C1-C24 alkoxy, a C6-C30 aryloxy, or a C6-C30 arylthio, and the two aryls of the diarylamino may be bonded via a linking group, and the linking group may be a single bond, -CH2- CH2- , -CHR-CHR-, -CR2 - CR2 -, -CH=CH-, -CR=CR-, -C≡C-, -N(-R)-, -O-, -S-, -C(-R) ²- , -Si(-R) ²- , or -Se-, where R is independently hydrogen, a carbon-6 to carbon-12 aryl, a carbon-1 to carbon-24 alkyl, or a carbon-3 to carbon-24 cycloalkyl, and at least one hydrogen in R may be substituted with a carbon-1 to carbon-24 alkyl or a carbon-3 to carbon-24 cycloalkyl. However, at least one group represented by the above general formula (G) is bonded to the "a-ring" or "ring formed together with the a-ring," at least one group represented by the above general formula (G) is bonded to the "b-ring" or "ring formed together with the b-ring," and at least one group represented by the above general formula (G) is bonded to the "c-ring" or "ring formed together with the c-ring," and these groups represented by formula (G) may be the same or different. In the above formula (G), Cy1 and Cy2 are each independently a benzene ring, a naphthalene ring, a phenanthrene ring, a pyridine ring, a quinoline ring, a dibenzofuran ring, a dibenzothiophene ring, or a carbazole ring whose N position may be substituted with phenyl, and at least one hydrogen in each of these rings may be independently substituted with a diarylamino (where the aryl is a C6-C12 aryl), a C1-C24 alkyl, a C3-C24 cycloalkyl, a C1-C24 alkoxy, a C6-C30 aryloxy, a C6-C30 arylthio, or a cyano, and the two aryls of the diarylamino may be linked via a linking group, which may be a single bond, -CH2 - CH2- , -CHR-CHR-, -CR2 - CR2 -, -CH=CH-, -CR=CR-, -C≡C-, -N(-R)-, -O-, -S-, -C(-R) ²- , -Si(-R) ²- , or -Se-, where R is independently hydrogen, a C6-C12 aryl, a C1-C24 alkyl, or a C3-C24 cycloalkyl, and at least one hydrogen in R may be substituted with a C1-C24 alkyl or a C3-C24 cycloalkyl, where * is the bond position to the a ring, b ring, c ring, and the ring formed together with those rings, and, In the compound represented by formula (1) above, at least one hydrogen atom may be substituted with deuterium, cyanopropyl alcohol, or halogen. The polycyclic aromatic compound according to claim 1.
  4. In the above formula (1), R1 to R11 are each independently hydrogen, diarylamino (where aryl is an aryl with 6 to 12 carbon atoms), alkyl with 1 to 24 carbon atoms, or cycloalkyl with 3 to 24 carbon atoms. Adjacent groups among R1 to R11 may bond together to form a naphthalene ring, a phenanthrene ring, a dibenzothiophene ring, a dibenzofuran ring, or a carbazole ring together with at least one of the a, b, and c rings, and at least one hydrogen atom in the formed ring may be independently substituted with a diarylamino (where the aryl is an aryl having 6 to 12 carbon atoms), an alkyl having 1 to 24 carbon atoms, or a cycloalkyl having 3 to 24 carbon atoms. However, at least one group represented by the above general formula (G) is bonded to the "a-ring" or "ring formed together with the a-ring," at least one group represented by the above general formula (G) is bonded to the "b-ring" or "ring formed together with the b-ring," and at least one group represented by the above general formula (G) is bonded to the "c-ring" or "ring formed together with the c-ring," and these groups represented by formula (G) may be the same or different. In the above formula (G), Cy1 and Cy2 are, independently, a benzene ring, a naphthalene ring, a phenanthrene ring, a pyridine ring, a quinoline ring, a dibenzofuran ring, a dibenzothiophene ring, or a carbazole ring whose N position may be substituted with phenyl, and at least one hydrogen in these rings may independently be substituted with a diarylamino (where the aryl is a C6-C12 aryl), a C1-C24 alkyl, a C3-C24 cycloalkyl, or a cyano, and * is the bond position to the a ring, b ring, c ring, and the ring formed together with these rings, and, In the compound represented by formula (1) above, at least one hydrogen atom may be substituted with deuterium, cyanopropyl alcohol, or halogen. The polycyclic aromatic compound according to claim 1.
  5. In the above formula (1), R1 to R11 are each independently hydrogen or an alkyl group having 1 to 24 carbon atoms. However, at least one of R1 to R3 in ring a, at least one of R4 to R7 in ring b, and at least one of R8 to R11 in ring c are groups represented by the above general formula (G), and these groups represented by formula (G) may be the same or different. In the above formula (G), Cy1 and Cy2 are, independently, a benzene ring, a naphthalene ring, a phenanthrene ring, a pyridine ring, a quinoline ring, a dibenzofuran ring, a dibenzothiophene ring, or a carbazole ring whose N position may be substituted with phenyl, and at least one hydrogen in each of these rings may independently be substituted with an alkyl or cyano having 1 to 24 carbon atoms, and * indicates the bonding position to the a, b, and c rings, and, In the compound represented by formula (1) above, at least one hydrogen atom may be substituted with deuterium, cyanopropyl alcohol, or halogen. The polycyclic aromatic compound according to claim 1.
  6. A polycyclic aromatic compound as described in claim 1, represented by any of the following structural formulas.
  7. A polycyclic aromatic compound as described in claim 1, represented by any of the following structural formulas.
  8. An organic electroluminescent element comprising a pair of electrodes consisting of an anode and a cathode, a light-emitting layer disposed between the pair of electrodes, and at least one electron transport layer and electron injection layer disposed between the cathode and the light-emitting layer, containing a polycyclic aromatic compound as described in any one of claims 1 to 7.
  9. A display device or lighting device comprising an organic electroluminescent element as described in claim 8.

Description

This invention relates to polycyclic aromatic compounds, organic devices such as organic electroluminescent elements, organic field-effect transistors, organic thin-film solar cells, and wavelength conversion filters using the same, as well as display devices and lighting devices. In this specification, "organic electroluminescent element" may be referred to as "organic EL element" or simply "element." Conventionally, display devices using electroluminescent light-emitting elements have been extensively studied due to their potential for power saving and miniaturization. Furthermore, organic electroluminescent elements made from organic materials have been actively investigated due to their ease of weight reduction and scaling up. In particular, the development of organic materials with luminescence properties such as blue (one of the three primary colors of light), and organic materials possessing charge transport capabilities (potentially becoming semiconductors or superconductors), have been actively researched, regardless of whether they are polymer or low-molecular-weight compounds. Organic EL devices have a structure consisting of a pair of electrodes, an anode and a cathode, and one or more layers containing an organic compound, placed between the pair of electrodes. These layers containing the organic compound include light-emitting layers and charge transport/injection layers that transport or inject charges such as holes and electrons. Various organic materials suitable for these layers have been developed. For example, improved triphenylamine derivatives have been reported for use in organic EL devices and organic thin-film solar cells (International Publication No. 2012/118164). This material, based on the already commercialized N,N'-diphenyl-N,N'-bis(3-methylphenyl)-1,1'-biphenyl-4,4'-diamine (TPD), is characterized by its enhanced planarity while positioning nitrogen at the center of the ring structure by linking the aromatic rings that constitute triphenylamine. While this document evaluates the charge transport properties of NO-linked compounds (compound 1 on page 63), it does not describe manufacturing methods for materials other than NO-linked compounds. Furthermore, since the electronic state of the entire compound differs depending on the linked elements, the properties obtained from materials other than NO-linked compounds were also unknown. In this context, compounds in which multiple aromatic rings are fused around a central atom such as boron have recently been reported (International Publication No. 2015/102118). This document describes the evaluation of organic EL devices using such compounds as materials for light-emitting layers and charge transport layers, including electrons. Furthermore, examples of larger quantities of these compounds (International Publication No. 2018/212169) and examples of expanding the conjugated system via intramolecular linking groups have also been reported (Korean Patent Publication No. 10-2020-0121228, International Publication No. 2020/217229). International Publication No. 2012/118164International Publication No. 2015/102118International Publication No. 2018/212169Korean Published Patent No. 10-2020-0121228International Publication No. 2020/217229 This is a schematic cross-sectional view showing an organic EL element according to this embodiment. 1. Polycyclic aromatic compounds<Description of the overall structure of the compound> The present invention relates to a polycyclic aromatic compound represented by the following general formula (1), characterized by having a group represented by the following general formula (G). The definitions of the symbols in the following structural formulas are the same as those described above, and furthermore, the definitions of the symbols in all structural formulas shown in this paragraph and thereafter are the same as those described above. The compound of formula (1) has a structure in which an a-ring, a b-ring, and a c-ring are fused to a condensed biring structure. A condensed biring structure is a structure in which two six-membered saturated hydrocarbon rings are fused together, and in the above structural formula, it is a decahydronaphthalene-type structure composed of B (boron) and two O (oxygen) atoms. The group represented by formula (G) is a group formed by the bonding of Cy 1 and Cy 2 having a specific ring structure, where Cy 1 and Cy 2 are independently a benzene ring, a naphthalene ring, a phenanthrene ring, a pyridine ring, a quinoline ring, a dibenzofuran ring, a dibenzothiophene ring, or a carbazole ring whose N position may be substituted with phenyl. The group represented by formula (G) is bonded to the structure of formula (1) at *. The bonding configuration of the group represented by formula (G) will be described in detail later. <Explanation of substituents R1 to R11 on the a, b,andcrings> In formula (1), the a-ring, b-ring, and c-ring each have R1 to R3 , R4 to R7 , and R8 to R11 , res