CN116789687A - Polycyclic aromatic compound, material for organic device, organic electroluminescent element, display device, or lighting device - Google Patents

Polycyclic aromatic compound, material for organic device, organic electroluminescent element, display device, or lighting device Download PDF

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CN116789687A
CN116789687A CN202310274655.7A CN202310274655A CN116789687A CN 116789687 A CN116789687 A CN 116789687A CN 202310274655 A CN202310274655 A CN 202310274655A CN 116789687 A CN116789687 A CN 116789687A
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group
substituted
formula
ring
aryl
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畠山琢次
前田健永
石川泰嗣
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Kwansei Gakuin Educational Foundation
SK Materials JNC Co Ltd
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Kwansei Gakuin Educational Foundation
SK Materials JNC Co Ltd
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Abstract

The present invention provides a novel compound which is useful as a polycyclic aromatic compound, a material for an organic device, an organic electroluminescent element, a display device or a lighting device. A polycyclic aromatic compound having a structure comprising one or more structural units represented by the formula (1).

Description

Polycyclic aromatic compound, material for organic device, organic electroluminescent element, display device, or lighting device
Technical Field
The present invention relates to a polycyclic aromatic compound. In particular, the present invention relates to a polycyclic aromatic compound containing nitrogen and boron. The present invention also relates to a material for organic devices, an organic electroluminescent element, a display device, and a lighting device, each of which contains the polycyclic aromatic compound.
Background
In the past, various studies have been made on display devices using light emitting elements that perform electroluminescence, because power saving and thickness reduction have been possible, and further, organic electroluminescent elements including organic materials have been actively studied because weight reduction and size increase have been facilitated. In particular, development of organic materials having light-emitting characteristics such as blue, which is one of three primary colors of light, and development of organic materials having charge transporting ability (possibility of becoming a semiconductor or superconductor) such as holes, electrons, and the like have been actively studied, regardless of high molecular compounds or low molecular compounds.
The organic electroluminescent element has a structure including: a pair of electrodes including an anode and a cathode, and one or more layers disposed between the pair of electrodes and including an organic compound. The organic compound-containing layer includes a light-emitting layer, a charge transport/injection layer that transports or injects charges such as holes and electrons, and various organic materials suitable for these layers have been developed.
Among them, patent documents 1 to 4 disclose that a boron-containing polycyclic aromatic compound is effectively used as a material for an organic electroluminescent element or the like. And it is reported that the organic electroluminescent element containing the polycyclic aromatic compound has good external quantum efficiency. Patent document 2 and patent document 3 disclose structures obtained by condensing heterocyclic rings such as benzothiophene. Patent document 4 discloses a structure in which a heterocyclic ring such as a dibenzofuran ring is introduced into a substituent moiety.
[ Prior Art literature ]
[ patent literature ]
[ patent document 1] International publication No. 2015/102118
[ patent document 2] International publication No. 2020/111830
[ patent document 3] International publication No. 2020/251049
[ patent document 4] International publication No. 2019/132028
Disclosure of Invention
[ problem to be solved by the invention ]
As described above, various materials have been developed as materials for organic Electroluminescence (EL) elements, but in order to increase options for materials for organic EL elements, it is desired to develop materials containing compounds different from those in the past.
The present invention addresses the problem of providing a novel compound which is effectively used as a material for organic devices such as organic EL elements.
[ means of solving the problems ]
The present inventors have made an effort to solve the above-mentioned problems, and have succeeded in producing a polycyclic aromatic compound which is obtained by combining a specific condensed ring structure with a substituent in the structure of the compound described in patent documents 1 to 4, thereby imparting high luminous efficiency. Further, it has been found that an excellent organic EL element can be obtained by disposing a layer containing the polycyclic aromatic compound between a pair of electrodes to form an organic EL element, and the present invention has been completed. That is, the present invention provides a polycyclic aromatic compound as described below, a material for organic devices containing the polycyclic aromatic compound as described below, and the like.
Specifically, the present invention has the following structure.
< 0 > a polycyclic aromatic compound having a structure comprising one or more structural units represented by the formula (1);
[ chemical 1]
In the formula (1), the components are as follows,
the A ring and the B ring are each independently a substituted or unsubstituted aryl ring or a substituted or unsubstituted heteroaryl ring, the C ring is a ring represented by the formula (C),
in the formula (C), the components of the compound,
X c is > O, > N-R, > C (-R) 2 、＞Si(-R) 2 , > S, or > Se, said > N-R, said > C (-R) 2 The above-mentioned material is > Si (-R) 2 R of (C) is independently hydrogen, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted alkyl, or substituted or unsubstituted cycloalkyl, said > C (-R) 2 The above-mentioned material is > Si (-R) 2 Can be bonded to each other to form a ring,
either two Z in succession C One of which is with Y 1 Bonded carbon, the other being bonded to > N-G B Is selected from the group consisting of N-bonded carbons,
other Z C Each independently is N or C-R C ，
R C Each independently hydrogen or any substituent selected from substituent group ZB,
wherein two adjacent R's on the c2 ring C Can be bonded to each other and form together with the carbon to which they are bonded an aryl ring or a heteroaryl ring, the aryl ring formed and the heteroaryl ring formed being substituted by at least one substituent selected from the substituent group ZB,
Y 1 For B, P, P = O, P = S, al, ga, as, si-R, or Ge-R, R of the Si-R and the Ge-R are substituted or unsubstituted aryl, substituted or unsubstituted heteroarylA substituted or unsubstituted alkyl group, or a substituted or unsubstituted cycloalkyl group,
G A 、G B each independently represents a monovalent group represented by the formula (G),
in the formula (G), the amino acid sequence of the formula (G),
Z a each independently is N or C-R a ，
R a Each independently is hydrogen or any substituent selected from substituent group ZB, or R adjacent to a And together with the carbon to which they are bonded form an aryl or heteroaryl ring, which aryl ring and which heteroaryl ring may each be substituted by at least one substituent selected from the substituent group ZB,
a is > O, > N-R A 、＞Si(-R A ) 2 、＞C(-R A ) 2 S, or Se, R A Each independently is hydrogen, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted alkyl, or substituted or unsubstituted cycloalkyl, the > Si (-R) A ) 2 Is set at least two R A Can be bonded to each other to form a ring, and the above-mentioned groups > C (-R) A ) 2 Is set at least two R A Can be bonded to each other to form a ring,
wherein the monovalent group represented by the formula (G) is bonded to > N-G at any position A Or > N-G B Is bonded to the substrate via a N-bond,
at least one of the aryl or heteroaryl rings in the structure may be condensed by at least one cycloalkane, which may have a substituent, at least one of the cycloalkanes being-CH 2 The group may be substituted by-O-groups,
at least one hydrogen in the structure may be substituted with cyano, halogen, or deuterium.
< 1 > a polycyclic aromatic compound having a structure comprising one or more structural units represented by the formula (1);
[ chemical 2]
In the formula (1), the components are as follows,
the A ring and the B ring are each independently a substituted or unsubstituted aryl ring or a substituted or unsubstituted heteroaryl ring, the C ring is a ring represented by the formula (C),
in the formula (C), the components of the compound,
X c is > O, > N-R, > C (-R) 2 、＞Si(-R) 2 , > S, or > Se, said > N-R, said > C (-R) 2 The above-mentioned material is > Si (-R) 2 R of (C) is independently hydrogen, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted alkyl, or substituted or unsubstituted cycloalkyl, said > C (-R) 2 The above-mentioned material is > Si (-R) 2 Can be bonded to each other to form a ring,
either two Z in succession C One of which is with Y 1 Bonded carbon, the other being bonded to > N-G B Is selected from the group consisting of N-bonded carbons,
Other Z C Each independently is N or C-R C ，
R C Each independently hydrogen or any substituent selected from substituent group ZB,
two adjacent R's on the c2 ring C Can be bonded to each other and form together with the carbon to which they are bonded an aryl ring or a heteroaryl ring, the aryl ring formed and the heteroaryl ring formed being substituted by at least one substituent selected from the substituent group ZB,
Y 1 for B, P, P = O, P = S, al, ga, as, si-R, or Ge-R, R of the Si-R and the Ge-R being a substituted or unsubstituted aryl, a substituted or unsubstituted heteroaryl, a substituted or unsubstituted alkyl, or a substituted or unsubstituted cycloalkyl,
G A 、G B each independently represents a monovalent group represented by the formula (G),
in the formula (G), the amino acid sequence of the formula (G),
Z a each independently is N or C-R a ，
R a Each independently is hydrogen or any substituent selected from substituent group ZB, or R adjacent to a And together with the carbon to which they are bonded form an aryl or heteroaryl ring, which aryl ring and which heteroaryl ring may each be substituted by at least one substituent selected from the substituent group ZB,
a is > O, > N-R A 、＞Si(-R A ) 2 、＞C(-R A ) 2 S, or Se, R A Each independently is hydrogen, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted alkyl, or substituted or unsubstituted cycloalkyl, the > Si (-R) A ) 2 Is set at least two R A Can be bonded to each other to form a ring, and the above-mentioned groups > C (-R) A ) 2 Is set at least two R A Can be bonded to each other to form a ring,
wherein the monovalent group represented by the formula (G) is bonded to > N-G at any position A Or > N-G B Is bonded to the substrate via a N-bond,
at least one of the aryl or heteroaryl rings in the structure may be condensed by at least one cycloalkane, which may have a substituent, at least one of the cycloalkanes being-CH 2 The group may be substituted by-O-groups,
wherein,,
when X is c When S is > S, the B ring is a substituted or unsubstituted aryl ring, and the monocyclic ring directly bonded to nitrogen in the monovalent group represented by the formula (G) is not condensed by a cycloalkane,
when X is c At least one of the A ring, B ring, and C ring selected from the group consisting of aryl ring and heteroaryl ring having at least one substituent selected from the group consisting of substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted diarylamino, substituted or unsubstituted arylheteroarylamino, and substituted or unsubstituted cycloalkyl in > O, or at least one of the structures selected from the group consisting of aryl ring and heteroaryl ring being condensed by a cycloalkane, the cycloalkane may have A substituent, at least one of the cycloalkanes-CH 2 The group may be substituted by-O-groups,
at least one hydrogen in the structure may be substituted with cyano, halogen, or deuterium.
< 2 > the polycyclic aromatic compound according to < 1 > represented by the formula (1 a);
[ chemical 3]
In the formula (1 a), Z is N or C-R independently 11 ，
R 11 Each independently is hydrogen or any substituent selected from substituent group ZB, or R adjacent to 11 Bonded and forming together with the a-ring or the b-ring an aryl-ring or a heteroaryl-ring, which formed aryl-ring and which formed heteroaryl-ring may be substituted with at least one substituent selected from the substituent group ZB,
Y 1 、G A g, G B Respectively with Y in formula (1) 1 、G A G, G B X is the same meaning c Z is as follows c Respectively with X in the formula (C) c Z is as follows c Are the same meaning;
at least one of the aryl or heteroaryl rings in formula (1 a) may be condensed with at least one cycloalkane, which may have a substituent, at least one of the cycloalkanes-CH 2 -may be substituted by-O-;
at least one hydrogen in formula (1 a) may be substituted with cyano, halogen, or deuterium.
< 3 > polycyclic aromatic compounds according to < 1 > or < 2 >, wherein G A G (G) B Each independently is a group represented by the formula (G-1), the formula (G-4), or the formula (G-5), or a group in which one or two hydrogens in the structure represented by the formula (G-1), the formula (G-4), or the formula (G-5) are substituted with an alkyl group or a cycloalkyl group.
[ chemical 4]
< 4 > the polycyclic aromatic compound according to any one of < 1 > to < 3 >, wherein A is > O.
< 5 > the polycyclic aromatic compound according to < 1 > represented by any one of the formula (1 a-1), the formula (1 a-2), or the formula (1 a-3);
[ chemical 5]
In the formula (1 a-1),
R a1 、R a2 、R a3 、R b1 、R b2 、R b3 、R b4 、R c1 、R c2 、R c3 、R c4 、R g1 、R g2 、R g3 、R g4 、R g5 、R g6 、R g7 、R g8 、R g9 、R g10 、R g11 、R g12 、R g13 and R is g14 Each independently hydrogen or any substituent selected from substituent group ZB,
wherein R is b1 、R b2 、R b3 And R is b4 Can be bonded to each other and form together with the carbon to which they are bonded an aryl ring, which can be substituted with at least one substituent selected from the substituent group ZB,
at least one of the aryl or heteroaryl rings in formula (1 a-1) may be condensed with at least one cycloalkane, which may have a substituent, at least one of the cycloalkanes-CH 2 -may be substituted by-O-wherein the alkylene is not condensed in the g11 ring and the g13 ring;
in the formula (1 a-2),
R a1 、R a2 、R a3 、R b1 、R b2 、R b3 、R b4 、R c1 、R c2 、R c3 、R c4 、R g1 、R g2 、R g3 、R g4 、R g5 、R g6 、R g7 、R g8 、R g9 、R g10 、R g11 、R g12 、R g13 and R is g14 Each independently is hydrogen or any substituent selected from substituent group ZB, wherein R a1 、R a2 、R a3 、R b1 、R b2 、R b3 、R b4 、R c1 、R c2 、R c3 And R is c4 At least one of which is a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted diarylamino group, a substituted or unsubstituted arylheteroarylamino group, or a substituted or unsubstituted cycloalkyl group, or at least one selected from the group consisting of an aryl ring and a heteroaryl ring in formula (1 a-2) is condensed with a cycloalkane, which may have a substituent, at least one of the cycloalkanes being-CH 2 The group may be substituted by-O-groups,
R b1 、R b2 、R b3 、R b4 、R c1 、R c2 、R c3 and R is c4 Can be bonded to each other and form together with the carbon to which they are bonded an aryl or heteroaryl ring, which aryl ring formed can be substituted by at least one substituent selected from the substituent group ZB,
at least one of the aryl or heteroaryl rings in formula (1 a-2) may be condensed with at least one cycloalkane, which may have a substituent, at least one of the cycloalkanes-CH 2 -may be substituted by-O-;
in the formula (1 a-3),
R a1 、R a2 、R a3 、R b1 、R b2 、R b3 、R b4 、R c1 、R c2 、R c3 、R c4 、R g1 、R g2 、R g3 、R g4 、R g5 、R g6 、R g7 、R g8 、R g9 、R g10 、R g11 、R g12 、R g13 and R is g14 Each independently hydrogen or any substituent selected from substituent group ZB,
wherein R is b1 、R b2 、R b3 、R b4 、R c1 、R c2 、R c3 And R is c4 Can be bonded to each other and form together with the carbon to which they are bonded an aryl or heteroaryl ring, which aryl ring formed can be substituted by at least one substituent selected from the substituent group ZB,
at least one of the aryl or heteroaryl rings in formula (1 a-3) may be condensed with at least one cycloalkane, which may have a substituent, at least one of the cycloalkanes-CH 2 -may be substituted by-O-;
at least one hydrogen of the formulae (1 a-1), formula (1 a-2), and formula (1 a-3) may be substituted with cyano, halogen, or deuterium.
< 6 > the polycyclic aromatic compound according to < 3 >, represented by any one of the following formulas;
[ chemical 6]
[ chemical 7]
[ chemical 8]
In the formula, me is methyl, tBu is tertiary butyl, and D is deuterium.
< 7 > the polycyclic aromatic compound according to < 3 >, represented by any one of the following formulas;
[ chemical 9]
[ chemical 10]
In the formula, me is methyl, tBu is tertiary butyl, tAm is tertiary amyl, and D is deuterium.
< 8 > the polycyclic aromatic compound according to < 5 > is represented by the formula (1 a-3).
< 9 > the polycyclic aromatic compound according to < 8 >, represented by any one of the following formulas;
[ chemical 11]
[ chemical 12]
In the formula, me is methyl, and tBu is tert-butyl.
< 10 > a material for organic devices comprising the polycyclic aromatic compound according to any one of < 1 > to < 9 >.
< 11 > an organic electroluminescent element comprising: a pair of electrodes including an anode and a cathode; and a light-emitting layer disposed between the pair of electrodes, wherein the light-emitting layer contains the polycyclic aromatic compound according to any one of < 1 > to < 9 >.
< 12 > the organic electroluminescent element according to < 11 >, wherein the light-emitting layer comprises a host, and the polycyclic aromatic compound as a dopant.
< 13 > the organic electroluminescent element according to < 12 >, wherein the host is an anthracene compound, a fluorene compound, or a dibenzo A compound.
< 14 > a display device or an illumination device comprising the organic electroluminescent element according to any one of < 11 > to < 13 >.
[ Effect of the invention ]
The present invention can provide a novel polycyclic aromatic compound which is effectively used as a material for organic devices such as organic electroluminescent elements. The polycyclic aromatic compound of the present invention can be used for producing organic devices such as organic electroluminescent elements.
Drawings
Fig. 1 is a schematic cross-sectional view showing an example of an organic electroluminescent device.
Fig. 2 is an energy level diagram showing the energy relationship of a host, an auxiliary dopant, and an emission dopant of a TAF element using a general fluorescent dopant.
Fig. 3 is an energy level diagram showing an example of energy relationships among a host, an auxiliary dopant, and an emission dopant in an organic electroluminescent element according to an embodiment of the present invention.
Description of symbols
100: organic electroluminescent element
101: substrate board
102: anode
103: hole injection layer
104: hole transport layer
105: light-emitting layer
106: electron transport layer
107: electron injection layer
108: cathode electrode
Detailed Description
The present invention will be described in detail below. The following description of the structural elements is based on the representative embodiments or specific examples, but the present invention is not limited to such embodiments. In the present specification, the numerical range indicated by the term "to" means a range including numerical values described before and after the term "to" as a lower limit value and an upper limit value. In the description of the structural formula in the present specification, "hydrogen" means "hydrogen atom (H)", and "oxygen" means "oxygen atom (O)". Other elements are also described in the same manner.
In this specification, "Me" represents methyl, "Et" represents ethyl, "nBu" represents n-butyl (normal butyl), "tBu" represents tert-butyl (tert-butyl), "iBu" represents isobutyl, "secBu" represents sec-butyl (sec-butyl), "nPr" represents n-propyl (normal propyl), "iPr" represents isopropyl, "tAm" represents tert-pentyl, "2EH" represents 2-ethylhexyl, "tcoct" represents tert-octyl, "Ph" represents phenyl, "Mes" represents mesityl (2, 4, 6-trimethylphenyl), "Ad" represents 1-adamantyl, "Tf" represents trifluoromethylsulfonyl, "TMS" represents trimethylsilyl "and" D "represents deuterium.
In this specification, the organic electroluminescent element is sometimes referred to as an organic EL element.
In the present specification, the chemical structure or the substituent may be represented by the number of carbons, but the number of carbons in the case of a substituent substituted in the chemical structure or in the case of a substituent further substituted in the substituent refers to the number of carbons in the chemical structure or the substituent, and does not refer to the total number of carbons in the chemical structure and the substituent or the total number of carbons in the substituent and the substituent. For example, "substituent B having carbon number Y substituted with substituent a having carbon number X" means that "substituent a having carbon number X" is substituted with "substituent B having carbon number Y" which is not the total carbon number of substituent a and substituent B. For example, "substituent B having a carbon number Y substituted with substituent a" means that substituent a (not limited to the carbon number) is substituted on "substituent B having a carbon number Y, and that carbon number Y is not the total carbon number of substituent a and substituent B.
The chemical structural formula described in the present specification (including the general formula depicted by a markush (Markush) structural formula as in the following formula (1)) is a planar structural formula, and thus various isomer structures such as enantiomers (enantiomers), diastereomers, and rotamers may actually exist. In the present specification, unless otherwise specified, the compounds described may have any isomer structure considered from the plane structural formula thereof, and may be a mixture of any ratio of possible isomers. Among these isomers, those that do not isomerize at ordinary temperature can be easily separated by recrystallization, sublimation purification, or separation chromatography.
In the present specification, structural formulae of a plurality of aromatic compounds are described. The aromatic compound is described as a combination of double bonds and single bonds, but actually has pi electron resonance, and therefore, there is an equivalent resonance structure such as a plurality of double bonds and single bonds being alternately replaced for a single substance. In the present specification, only one resonance structural formula is described for one substance, but unless otherwise specified, other resonance structural formulas that are organic chemical equivalents are also included. The above-described case is referred to in the following description of "z=z", etc. That is, for example, "z=z" in the following formula (1), an example is as follows. The present invention is not limited to this, and is applicable to not only one of the described resonant structural formulas but also other equivalent resonant structural formulas.
[ chemical 13]
In the present specification, the term "may" and the term "not" are used, and the term "may" and the term "not" are used, respectively, but these terms have the same meaning.
In the present specification, when referred to as "adjacent group", it means two groups respectively bonded to two atoms adjacent in the structural formula (two atoms directly bonded through a covalent bond).
< 0. Description of Ring and substituent >
First, the ring and substituents used in the present specification will be described in detail below.
The "aryl ring" in the present specification includes, for example, an aryl ring having 6 to 30 carbon atoms, preferably an aryl ring having 6 to 16 carbon atoms, more preferably an aryl ring having 6 to 12 carbon atoms, and particularly preferably an aryl ring having 6 to 10 carbon atoms.
As concrete "Aryl ring ", can be cited: benzene ring as a monocyclic system, biphenyl ring as a bicyclic system, naphthalene ring and indene ring as condensed bicyclic system, terphenyl ring as a tricyclic system (m-terphenyl, o-terphenyl, p-terphenyl), acenaphthene ring, fluorene ring, phenalene ring, phenanthrene ring, anthracene ring as condensed tricyclic system, triphenylene ring, pyrene ring, tetracene ring as condensed tetracyclic system, A ring, a perylene ring, a pentacene ring, and the like as condensed pentacyclic systems. The fluorene ring, benzofluorene ring, and indene ring also include structures in which a fluorene ring, a benzofluorene ring, a cyclopentane ring, and the like are spiro-bonded, respectively. Further, two of two hydrogens including a methylene group in the fluorene ring, the benzofluorene ring, and the indene ring are substituted with an alkyl group such as a methyl group as a first substituent described later, respectively, to form a ring such as a dimethylfluorene ring, a dimethylbenzofluorene ring, and a dimethylindene ring. />
Examples of the "heteroaryl ring" include a heteroaryl ring having 2 to 30 carbon atoms, preferably a heteroaryl ring having 2 to 25 carbon atoms, more preferably a heteroaryl ring having 2 to 20 carbon atoms, still more preferably a heteroaryl ring having 2 to 15 carbon atoms, and particularly preferably a heteroaryl ring having 2 to 10 carbon atoms. Examples of the "heteroaryl ring" include a heterocyclic ring containing one to five heteroatoms selected from oxygen, sulfur and nitrogen as ring constituent atoms in addition to carbon.
Specific examples of the "heteroaryl ring" include: pyrrole rings, oxazole rings, isoxazole rings, thiazole rings, isothiazole rings, imidazole rings, oxadiazole rings, thiadiazole rings, triazole rings, tetrazole rings, pyrazole rings, pyridine rings, pyrimidine rings, pyridazine rings, pyrazine rings, triazine rings, indole rings, isoindole rings, 1H-indazole rings, benzimidazole rings, benzoxazole rings, benzothiazole rings, 1H-benzotriazole rings, quinoline rings, isoquinoline rings, cinnoline rings, quinazoline rings, quinoxaline rings, phthalazine rings, naphthyridine rings, purine rings, pteridine rings, carbazole rings, carboline rings, acridine rings, phenoxazine rings, phenothiazine rings, phenazine rings, benzothiophene rings, benzofurane rings, isobenzofuran rings, dibenzofuran rings, thiophene rings, benzothiophene rings, dibenzothiophene rings, furazane rings, thianthracene rings, indolo-benzoindolo rings, benzoindolo-carbazole rings, dibenzoindole rings, dibenzo-carbazole rings, naphthyridine rings, 2-naphthyridine rings, 3-naphthyridine rings, and the like. The dihydroacridine ring, the xanthene ring, and the thioxanthene ring are also preferably rings such as a dimethyldihydroacridine ring, a dimethylxanthene ring, and a dimethylthioxanthene ring, each of which is formed by substituting an alkyl group such as a methyl group as a first substituent described later. The bipyridine ring, phenylpyridine ring, pyridylphenyl ring, terpyridine ring, bipyridylphenyl ring, and pyridylbiphenyl ring as the tricyclic ring system may be mentioned as "heteroaryl ring". The "heteroaryl ring" is also defined as containing a pyran ring.
In the present specification, a substituent is sometimes further substituted with a substituent. (with respect to substituents, they are sometimes described as "substituted or unsubstituted"). This means that at least one hydrogen of a substituent ("first substituent" or "first substituent") is further substituted with a substituent ("second substituent" or "second substituent") or is unsubstituted. The first substituent (first substituent) and the second substituent (second substituent) are described in the specification.
In the present specification, substituent group ZB includes:
aryl which may be substituted with at least one group selected from the group consisting of aryl, heteroaryl, diarylamino, alkyl, cycloalkyl, and substituted silyl;
heteroaryl groups which may be substituted with at least one group selected from the group consisting of aryl, heteroaryl, diarylamino, alkyl, cycloalkyl, and substituted silyl groups;
diarylamino groups that may be substituted with at least one group selected from the group consisting of aryl groups, heteroaryl groups, diarylamino groups, alkyl groups, cycloalkyl groups, and substituted silyl groups (two aryl groups may be bonded to each other via a linking group);
di-heteroarylamino group which may be substituted with at least one group selected from the group consisting of aryl, heteroaryl, diarylamino, alkyl, cycloalkyl and substituted silyl (two heteroaryl groups may be bonded to each other via a linking group);
Arylheteroarylamino groups which may be substituted with at least one group selected from the group consisting of aryl, heteroaryl, diarylamino, alkyl, cycloalkyl and substituted silyl groups (aryl and heteroaryl may be bonded to each other via a linking group);
diaryl boron groups which may be substituted with at least one group selected from the group consisting of aryl, heteroaryl, diarylamino, alkyl, cycloalkyl, and substituted silyl groups (two aryl groups may be bonded via a single bond or a linking group);
alkyl groups which may be substituted with at least one group selected from the group consisting of aryl, heteroaryl, diarylamino, cycloalkyl, and substituted silyl groups;
cycloalkyl which may be substituted with at least one group selected from the group consisting of aryl, heteroaryl, diarylamino, alkyl, cycloalkyl, and substituted silyl;
alkoxy which may be substituted with at least one group selected from the group consisting of aryl, heteroaryl, diarylamino, cycloalkyl, and substituted silyl;
aryloxy which may be substituted with at least one group selected from the group consisting of aryl, heteroaryl, diarylamino, alkyl, cycloalkyl, and substituted silyl;
arylthio which may be substituted with at least one group selected from the group consisting of aryl, heteroaryl, diarylamino, alkyl, cycloalkyl, and substituted silyl; and
Substituted silyl groups.
The aryl group as the second substituent in each group of substituent group ZB may be further substituted with aryl, heteroaryl, alkyl, or cycloalkyl, and likewise, the heteroaryl group as the second substituent may be substituted with aryl, heteroaryl, alkyl, or cycloalkyl.
In the present specification, when referred to as a "substituent", any one group selected from the substituent group ZB may be used unless otherwise specified. For example, when a "substituted or unsubstituted" group is substituted, the group may be substituted with at least one group selected from the substituent group ZB.
In the present specification, the "aryl" is, for example, an aryl group having 6 to 30 carbon atoms, preferably an aryl group having 6 to 24 carbon atoms, more preferably an aryl group having 6 to 20 carbon atoms, still more preferably an aryl group having 6 to 16 carbon atoms, particularly preferably an aryl group having 6 to 12 carbon atoms, and most preferably an aryl group having 6 to 10 carbon atoms.
Specific "aryl" groups may be exemplified by monovalent radicals of the "aryl ring", such as: phenyl as a monocyclic system, biphenyl (2-biphenyl, 3-biphenyl, or 4-biphenyl) as a bicyclic system, naphthyl (1-naphthyl or 2-naphthyl) as a condensed bicyclic system, 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, or p-terphenyl-4-yl) as a tricyclic system, acenaphthenyl- (1-, 3-, 4-, or 5-) yl, fluorene- (1-, 2-, 3-, 4-, or 9-) yl, phenalene- (1-, 2-, 3-, 4-, 9-, or 4-, m-terphenyl-, 2-, 4-, or 4-, or 5' -biphenyl-5-, or tetra (m-phenyl) as a condensed tricyclic system, 5' -phenyl-m-terphenyl-4-yl, or m-tetralin), triphenylene- (1-or 2-) yl, pyrene- (1-, 2-, or 4-) yl, or naphthacene- (1-, 2-, or 5-) yl as a condensed tetracyclic system, perylene- (1-, 2-, or 3-) yl, or pentacene- (1-, 2-, 5-, or 6-) yl as a condensed pentacyclic system, and the like. In addition, monovalent groups of spirofluorene and the like are exemplified.
The aryl group as the second substituent may also include a structure in which the aryl group is substituted with at least one group selected from the group consisting of aryl groups such as phenyl groups (specifically, the groups described below), alkyl groups such as methyl groups (specifically, the groups described below), and cycloalkyl groups such as cyclohexyl groups or adamantyl groups (specifically, the groups described below).
Examples thereof include those wherein the 9-position of the fluorenyl group as the second substituent is substituted with an aryl group such as a phenyl group, an alkyl group such as a methyl group, or a cycloalkyl group such as a cyclohexyl group or an adamantyl group.
The "arylene group" is, for example, an arylene group having 6 to 30 carbon atoms, preferably an arylene group having 6 to 20 carbon atoms, an arylene group having 6 to 16 carbon atoms, an arylene group having 6 to 12 carbon atoms, an arylene group having 6 to 10 carbon atoms, or the like.
Specific examples of the "arylene group" include a divalent group obtained by removing one hydrogen from the "aryl group" (monovalent group).
Examples of the "heteroaryl group" include heteroaryl groups having 2 to 30 carbon atoms, preferably heteroaryl groups having 2 to 25 carbon atoms, more preferably heteroaryl groups having 2 to 20 carbon atoms, still more preferably heteroaryl groups having 2 to 15 carbon atoms, and particularly preferably heteroaryl groups having 2 to 10 carbon atoms. Examples of the "heteroaryl" include a heterocyclic ring containing one to five heteroatoms selected from oxygen, sulfur, nitrogen, and the like as ring constituent atoms in addition to carbon.
As specific "heteroaryl" there may be mentioned monovalent radicals of said "heteroaryl ring", 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, quinolinyl, isoquinolinyl, cinnolinyl, quinazolinyl, quinoxalinyl, phenanthrolinyl, phthalazinyl, naphthyridinyl, purinyl, pteridinyl, carbazolyl, acridinyl, phenoxazinyl, phenothiazinyl, phenazasilnyl, indolizinyl, furanyl, benzofuranyl, isobenzofuranyl, dibenzofuranyl, naphthyridinyl, thienyl, benzothienyl, dibenzothienyl, naphthyridinyl, naphthyridin, benzothienyl, monovalent benzophosphoryl, monovalent benzocyclopentadienyl, or monovalent benzocarbazolyl, or monovalent benzoindolyl, benzoxazolyl, or the like. In addition to this, there may be mentioned: monovalent radicals of spiro [ fluorene-9, 9' -xanthene ], monovalent radicals of spirodi [ silafluorene ], monovalent radicals of benzoselenophene.
The heteroaryl group as the second substituent may also include a structure in which the heteroaryl group is substituted with at least one group selected from the group consisting of an aryl group such as a phenyl group (specifically, the group described below), an alkyl group such as a methyl group (specifically, the group described below), and a cycloalkyl group such as a cyclohexyl group or an adamantyl group (specifically, the group described below).
As an example thereof, there may be mentioned: the 9-position of the carbazolyl group as the second substituent is substituted with an aryl group such as a phenyl group, an alkyl group such as a methyl group, or a cycloalkyl group such as a cyclohexyl group or an adamantyl group. In addition, a nitrogen-containing heteroaryl group such as a pyridyl group, a pyrimidinyl group, a triazinyl group, a carbazolyl group, or the like, which is further substituted with a phenyl group, a biphenyl group, or the like, is also included in the heteroaryl group as a second substituent.
"heteroarylene" is, for example, a heteroarylene group having 2 to 30 carbon atoms, preferably a heteroarylene group having 2 to 25 carbon atoms, a heteroarylene group having 2 to 20 carbon atoms, a heteroarylene group having 2 to 15 carbon atoms, a heteroarylene group having 2 to 10 carbon atoms, or the like. The "heteroarylene group" is, for example, a divalent group such as a heterocyclic ring containing one to five hetero atoms selected from oxygen, sulfur, nitrogen, and the like as ring constituent atoms in addition to carbon.
Specific examples of the "heteroarylene group" include a divalent group obtained by removing one hydrogen from the "heteroaryl group" (monovalent group).
"diarylamino" is an amino group in which two aryl groups have been substituted, and references to the details of the aryl groups are made to the description of the "aryl groups".
"Diheteroarylamino" is an amino group in which two heteroaryl groups have been substituted, and reference is made to the description of "heteroaryl" for details of said heteroaryl groups.
"arylheteroarylamino" is an amino group in which an aryl group and a heteroaryl group are substituted, and the details of the aryl group and the heteroaryl group are described by referring to the "aryl group" and the "heteroaryl group".
The two aryl groups in the diarylamino group as the first substituent may be bonded to each other via a linking group, the two heteroaryl groups in the diarylamino group as the first substituent may be bonded to each other via a linking group, and the aryl group and the heteroaryl group of the arylheteroarylamino group as the first substituent may be bonded to each other via a linking group. Here, the expression "bonded via a linking group" means that two phenyl groups representing, for example, a diphenylamino group are bonded via a linking group as described below. In addition, the description also applies to diheteroarylamino and arylheteroarylamino groups formed from aryl or heteroaryl groups.
[ chemical 14]
Specifically, examples of the linking group include: > O, > N-R X 、＞C(-R X ) 2 、-C(-R X )＝C(-R X )-、＞Si(-R X ) 2 、＞S、＞CO、＞CS、＞SO、＞SO 2 And > Se. R is R X Each independently is alkyl, cycloalkyl, aryl, or heteroaryl, which may be substituted with alkyl, cycloalkyl, aryl, or heteroaryl. In addition, > C (-R) X ) 2 、-C(-R X )＝C(-R X )-、＞Si(-R X ) 2 Each two R X Through single bonds or linking groups X Y Are bonded to each other to form a ring. As X Y Examples of the method include: > O, > N-R Y 、＞C(-R Y ) 2 、＞Si(-R Y ) 2 、＞S、＞CO、＞CS、＞SO、＞SO 2 And > Se, R Y Each independently is alkyl, cycloalkyl, aryl, or heteroaryl, which may be substituted with alkyl, cycloalkyl, aryl, or heteroaryl. Wherein, at X Y Is > C (-R) Y ) 2 > Si (-R) Y ) 2 In the case of (2), two R Y No bonding is performed to further form a ring. Further, as the linking group, an alkenylene group may be mentioned. By a means ofAny hydrogen of the alkenylene groups may be independently bound to R 2X Substituted, R 2X Each independently is alkyl, cycloalkyl, substituted silyl, aryl, and heteroaryl, which may be substituted with alkyl, cycloalkyl, substituted silyl, aryl. -C (-R) X )＝C(-R X ) Two R in X May be bonded to each other and form together with the c=c to which they are bonded an aryl (benzene ring, etc.) or heteroaryl ring. I.e., -C (-R) X )＝C(-R X ) Can be arylene (1, 2-phenylene, etc.) or heteroarylene.
In the case where "diarylamino", "diheteroarylamino" or "arylheteroarylamino" is simply described in the present specification, unless otherwise specified, the description is given of "two aryl groups of the diarylamino are not bonded to each other or are linked via a linking group", "two heteroaryl groups of the diheteroarylamino are not bonded to each other or are linked via a linking group", and "aryl groups and heteroaryl groups of the arylheteroarylamino are not bonded to each other or are linked via a linking group".
The "alkyl group" may be a straight-chain or branched alkyl group having 1 to 24 carbon atoms or a branched alkyl group having 3 to 24 carbon atoms. The alkyl group is preferably an alkyl group having 1 to 18 carbon atoms (branched alkyl group having 3 to 18 carbon atoms), more preferably an alkyl group having 1 to 12 carbon atoms (branched alkyl group having 3 to 12 carbon atoms), still more preferably an alkyl group having 1 to 8 carbon atoms (branched alkyl group having 3 to 8 carbon atoms), particularly preferably an alkyl group having 1 to 6 carbon atoms (branched alkyl group having 3 to 6 carbon atoms), and most preferably an alkyl group having 1 to 5 carbon atoms (branched alkyl group having 3 to 5 carbon atoms).
Specific examples of the alkyl group include: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl (t-pentyl) (t-amyl), n-hexyl, 1-methylpentyl, 4-methyl-2-pentyl, 3-dimethylbutyl, 2-ethylbutyl, n-heptyl, 1-methylhexyl, n-octyl, tert-octyl (1, 3-tetramethylbutyl), 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2-dimethylheptyl, 2, 6-dimethyl-4-heptyl, 3, 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. In addition, for example, there may be mentioned: 1-ethyl-1-methylpropyl, 1-diethylpropyl, 1-dimethylbutyl, 1-ethyl-1-methylbutyl, 1, 4-trimethylpentyl, 1, 2-trimethylpropyl 1, 1-dimethyloctyl, 1-dimethylpentyl, 1-dimethylheptyl, 1, 5-trimethylhexyl, 1-ethyl-1-methylhexyl, 1-ethyl-1, 3-dimethylbutyl 1, 2-tetramethylpropyl, 1-butyl-1-methylpentyl, 1-diethylbutyl, 1-ethyl-1-methylpentyl, 1, 3-trimethylbutyl 1-propyl-1-methylpentyl, 1, 2-trimethylpropyl, 1-ethyl-1, 2-trimethylpropyl, 1-propyl-1-methylbutyl, 1-dimethylhexyl and the like.
"alkylene" is a divalent group obtained by removing any hydrogen from "alkyl", and is, for example, methylene, ethylene, propylene.
Examples of "cycloalkyl" include: cycloalkyl group having 3 to 24 carbon atoms, cycloalkyl group having 3 to 20 carbon atoms, cycloalkyl group having 3 to 16 carbon atoms, cycloalkyl group having 3 to 14 carbon atoms, cycloalkyl group having 5 to 10 carbon atoms, cycloalkyl group having 5 to 8 carbon atoms, cycloalkyl group having 5 to 6 carbon atoms, cycloalkyl group having 5 carbon atoms, and the like. As the cyclohexyl group in the present specification, as will be described later, a polycyclic group such as an adamantyl group is included in addition to a monocyclic cyclohexyl group and the like.
Specific cycloalkyl groups include: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, bicyclo [1.1.0] butyl, bicyclo [1.1.1] pentyl, bicyclo [2.1.0] pentyl, bicyclo [2.1.1] hexyl, bicyclo [3.1.0] hexyl, bicyclo [2.2.1] heptyl (norbornyl), bicyclo [2.2.2] octyl, adamantyl, diamantanyl, decahydronaphthyl, decahydroazulenyl, alkyl (particularly methyl) substituents of these having 1 to 5 carbon atoms, and the like.
Examples of the "alkenyl group" include a straight-chain alkenyl group having 2 to 24 carbon atoms and a branched alkenyl group having 4 to 24 carbon atoms. The alkenyl group is preferably an alkenyl group having 2 to 18 carbon atoms, more preferably an alkenyl group having 2 to 12 carbon atoms, still more preferably an alkenyl group having 2 to 6 carbon atoms, and particularly preferably an alkenyl group having 2 to 4 carbon atoms. The "alkenyl" may be referred to as the description of the "alkyl" and includes a group in which a c—c single bond in the structure of the "alkyl" is replaced with a c=c double bond, and also includes a group in which not only one single bond but two or more single bonds are replaced with double bonds (also referred to as an alkadienyl group or an alkatrienyl group).
Specific examples of the "alkenyl group" include: vinyl, allyl, butadienyl, and the like.
"alkenylene" is a divalent group obtained by removing any hydrogen from "alkenyl", and examples thereof include vinylidene.
The term "alkynyl" refers to the description of the "alkyl" and includes a group in which a single bond of C-C in the structure of the "alkyl" is replaced with a triple bond of C.ident.C, and also includes a group in which not only one single bond but two or more single bonds are replaced with a triple bond (also referred to as an alkanediyne-yl group or an alkanetriyne-yl group).
Examples of the "alkoxy group" include straight-chain alkoxy groups having 1 to 24 carbon atoms and branched-chain alkoxy groups having 3 to 24 carbon atoms. The alkoxy group is preferably an alkoxy group having 1 to 18 carbon atoms (branched alkoxy group having 3 to 18 carbon atoms), more preferably an alkoxy group having 1 to 12 carbon atoms (branched alkoxy group having 3 to 12 carbon atoms), still more preferably an alkoxy group having 1 to 6 carbon atoms (branched alkoxy group having 3 to 6 carbon atoms), particularly preferably an alkoxy group having 1 to 5 carbon atoms (branched alkoxy group having 3 to 5 carbon atoms).
Specific examples of the alkoxy group include: methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-pentoxy, hexoxy, heptoxy, octoxy and the like.
As "aryloxy" is meant the hydrogen of the-OH group being substituted by aryl, said aryl and its preferred ranges may refer to the groups described.
As "arylthio" is mentioned an aryl-substituted radical of the hydrogen of the-SH group, said aryl and its preferred range being cited as the radicals indicated.
Examples of the "substituted silyl group" include a silyl group substituted with three substituents selected from the group consisting of an alkyl group, a cycloalkyl group, and an aryl group. Examples include: trialkylsilyl, tricycloalkylsilyl, dialkylcycloalkylsilyl, alkyldicycloalkylsilyl, triarylsilyl, dialkylarylsilyl, and alkyldiarylsilyl.
As the "trialkylsilyl group", three hydrogens in the silyl group are each independently substituted with an alkyl group, and the alkyl group and its preferred range may refer to the group described as the "alkyl group" in the first substituent. Preferred alkyl groups for substitution are alkyl groups having 1 to 5 carbon atoms, and specific examples thereof include: methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-pentyl, and the like.
Specific trialkylsilyl groups include: trimethylsilyl, triethylsilyl, tripropylsilyl, triisopropylsilyl, tributylsilyl, tri-sec-butylsilyl, tri-tert-pentylsilyl, ethyldimethylsilyl, propyldimethylsilyl, isopropyldimethylsilyl, butyldimethylsilyl, sec-butyldimethylsilyl, tert-pentyldimethylsilyl, methyldiethylsilyl, propyldiethylsilyl, isopropyldiethylsilyl, butyldiethylsilyl, sec-butyldiethylsilyl, tert-pentyldiethylsilyl, methyldipropylsilyl, ethyldipropylsilyl, butyldipropylsilyl, sec-butyldipropylsilyl, tert-pentyldipropylsilyl, methyldiisopropylsilyl, ethyldiisopropylsilyl, butyldiisopropylsilyl, sec-butyldiisopropylsilyl, tert-pentyldiisopropylsilyl, and the like.
As the "tricycloalkylsilane group", three hydrogens in the silane group may be cited as groups each independently substituted with a cycloalkyl group, and the cycloalkyl group and its preferred range may be cited as the group described as the "cycloalkyl group" in the first substituent. Preferred cycloalkyl groups for substitution are cycloalkyl groups having 5 to 10 carbon atoms, and specific examples thereof include: cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, bicyclo [1.1.1] pentyl, bicyclo [2.1.0] pentyl, bicyclo [2.1.1] hexyl, bicyclo [3.1.0] hexyl, bicyclo [2.2.1] heptyl, bicyclo [2.2.2] octyl, adamantyl, decalinyl, decahydroazulenyl, and the like.
Specific tricycloalkylsilane groups include tricyclopentylsilane groups and tricyclohexylsilane groups.
Specific examples of the dialkylcycloalkylsilyl group substituted with two alkyl groups and one cycloalkyl group, and the alkylbicycloalkylsilyl group substituted with one alkyl group and two cycloalkyl groups include silyl groups substituted with groups selected from the specific alkyl groups and cycloalkyl groups.
Specific examples of the dialkylarylsilane group substituted with two alkyl groups and one aryl group, the alkyldiarylsilane group substituted with one alkyl group and two aryl groups, and the triarylsilane group substituted with three aryl groups include silane groups substituted with groups selected from the specific alkyl groups and aryl groups. As a specific example of the triarylsilyl group, a triphenylsilyl group is particularly exemplified.
As the "aryl group" in the "diarylboro group" and the preferred ranges thereof, the description of the aryl group may be cited. In addition, the two aryl groups may be linked via a single bond or linking group (e.g., -ch=ch-, -cr=cr-, -c≡c-, > N-R, > O, > S, > C (-R) 2 、＞Si(-R) 2 Or > Se). Here, the-CR=CR-R, > N-R, > C (-R) 2 R of (C) and > Si (-R) is aryl, heteroaryl, diarylamino, alkyl, alkenyl, alkynyl, cycloalkyl, alkoxy, or aryloxy, at least one hydrogen in said R may be further substituted with aryl, heteroaryl, alkyl, alkenyl, alkynyl, or cycloalkyl. In addition, two adjacent R groups may bond to each other to form a ring, thereby forming cycloalkylene, arylene, and heteroarylene. The details of the substituents listed herein may be referred to individually as descriptions of the substituents. In the case where the "diarylboronyl" is simply described in the present specification, unless otherwise specified, the two aryl groups to which the "diarylboronyl" is added may be allowed to pass through each otherA single bond or a linking group.
In this specification, when two groups bonded to the same atom are bonded to each other to form a ring, the term "ring" means that the atom and the two groups form a ring. The two groups may be bonded by a single bond or a linking group (these are also collectively referred to as a linking group), and examples of the linking group include: -CH 2 -CH 2 -、-CHR-CHR-、-CR 2 -CR 2 -、-CH＝CH-、-CR＝CR-、-C≡C-、-N(-R)-、-O-、-S-、-C(-R) 2 -、-Si(-R) 2 Examples of-or-Se-, include the following structures. In addition, R, -CR of the-CHR-CHR-is 2 -CR 2 -R, -cr=cr-R, -N (-R) -R, -C (-R) 2 -R, and-Si (-R) 2 -R is each independently hydrogen, aryl which may be substituted by alkyl or cycloalkyl, heteroaryl which may be substituted by alkyl or cycloalkyl, alkyl which may be substituted by cycloalkyl, alkenyl which may be substituted by alkyl or cycloalkyl, alkynyl which may be substituted by alkyl or cycloalkyl, or cycloalkyl which may be substituted by alkyl or cycloalkyl. In addition, two adjacent R groups may bond to each other to form a ring, thereby forming a cycloalkylene group, an arylene group, or a heteroarylene group.
[ 15]
As a bonding group, a radical of a bond, preferably a single bond, -cr=cr-, -N (-R) -, -O-, -S-, -C (-R) as a linking group 2 -、-Si(-R) 2 -, a part of-Se-, more preferably a single bond, -CR=CR-, -N (-R) -, -O-, -S-, and-C (-R) as a linking group 2 -, further, it is preferably a single bond, -CR=CR-, -N (-R) -, -O-, and-S-, most preferably a single bond.
The position where two R groups are bonded through the bonding group is not particularly limited as long as it is a position capable of bonding, but bonding at the nearest position is preferable, for example, when two groups are phenyl groups, bonding is preferable between each other at the ortho position (2-position) based on the bonding position (1-position) of "C" or "Si" in the phenyl group (refer to the structural formula).
< 1. Polycyclic aromatic Compounds >
The polycyclic aromatic compound of the present invention is a polycyclic aromatic compound having one or more structures including a structural unit represented by formula (1), and preferably a polycyclic aromatic compound having one or more structures including a structural unit represented by formula (1 a). The polycyclic aromatic compound of the present invention has a narrow emission half-value width and excellent color purity, and can reduce the driving voltage of an organic EL element and improve the emission quantum yield (photoluminescence quantum yield, PLQY).
[ 16]
[ description of Ring Structure in Compounds ]
In the formula (1), the "a", "B" and "C" in the circles are symbols indicating the ring structures indicated by the respective circles. The structure represented by formula (1) has the following structure: the ring structure is further formed by connecting at least four aromatic rings, which are ring a, ring B, and ring c1 and ring c2, with boron, oxygen, sulfur, nitrogen, or other hetero elements. The ring structure formed is a condensed ring structure comprising at least six rings.
In formula (1), the A ring and the B ring are each independently a substituted or unsubstituted aryl ring or a substituted or unsubstituted heteroaryl ring. Wherein when X is c When S, the B ring is a substituted or unsubstituted aryl ring.
The a ring forms a trivalent radical having a bond with three atoms (preferably carbon) in succession on the ring of the aryl or heteroaryl ring in its structure. Of the three bond, ring A and Y 1 Two N bonds. The B ring forms a divalent radical having a bond between two consecutive atoms (preferably carbon) in the ring of the aryl or heteroaryl ring in its structure. In the two bonding bonds, the B ring and the Y 1 And N bonding.
Examples of the substituent for each of the aryl ring and the heteroaryl ring include those selected from the group consisting ofAny one substituent in substituent group ZB. For the preferred range of substituents, reference may be made to R described below 11 Is not limited to the preferred range of (2).
The aryl or heteroaryl ring in ring A is preferably a 5-or 6-membered ring with Y 1 Two N bonds. The aryl or heteroaryl ring in ring B is preferably a 5-or 6-membered ring with Y 1 And N bonding. By "bonded with a 5-or 6-membered ring" is meant that the ring is formed solely from the 5-or 6-membered ring, or that the other ring is further condensed to form a ring in a manner that includes the 5-or 6-membered ring. In other words, 5-or 6-membered rings and B, Y which constitute all or part of the ring 1 Two N, or Y 1 And N bonding. In the aryl or heteroaryl rings of rings A and B, two or three successive rings form an atom (carbon atom) with Y 1 Two N, or Y 1 The N is directly bonded.
Examples of the 6-membered ring in the a ring and the B ring include: benzene ring, pyridine ring, pyrazine ring, pyrimidine ring, etc. Examples of the condensation of the 6-membered ring with another ring include: naphthalene ring, quinoline ring, dibenzofuran ring, dibenzothiophene ring, carbazole ring, and the like. As examples of the 5-membered ring, there may be mentioned: furan ring, thiophene ring, pyrrole ring, thiazole ring, and the like. Examples of the condensation of the 5-membered ring with another ring include: benzofuran rings, benzothiophene rings, indole rings, and the like. As the aryl ring or heteroaryl ring in the A ring, a benzene ring is preferable. As the aryl ring or heteroaryl ring in the B ring, a benzene ring is preferable.
In the formula (1) and the formula (2), the C ring has a ring structure represented by the formula (C). In formula (C), two Z's in succession C One of which is with Y 1 The other is a carbon bonded to N. Namely Y 1 And N is contiguous on the C ring. As shown below, this means that two Z's can be consecutively located in the c1 ring C And Y is equal to 1 And N-bonding, and two Z's which may be consecutive in the c2 ring C And Y is equal to 1 And N bonding.
In the formula (C), X c Is > O, > N-R, > C (-R) 2 、＞Si(-R) 2 , > S, or > Se, said > N-R, said > C (-R) 2 The above-mentioned material is > Si (-R) 2 R of (C) is independently hydrogen, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, said > C (-R) 2 The above-mentioned material is > Si (-R) 2 Is bonded to each other to form a ring, or is not bonded to each other to form a ring. These groups are described as "substituted or unsubstituted", and as substituents, aryl, heteroaryl, diarylamino, alkyl, cycloalkyl, or substituted silyl groups are preferred. In addition, the aryl group of the diarylamino group is substituted with an alkyl group or a cycloalkyl group, or is unsubstituted. The first substituent and the second substituent, and the statements used herein and the preferred ranges thereof may be referred to the descriptions in the specification. X is X c Preferably > O, > C (-R) 2 Or > S, more preferably > S.
In the formula (C), Z C Each independently is N or C-R C ，R C Each independently is hydrogen or any substituent selected from substituent group ZB. In the formula (C), Z is N C Preferably zero to two, more preferably zero to one, particularly preferably zero. In the formula (C), R is preferably a substituent C Zero to one, other R C Is hydrogen.
In addition, two adjacent R's on the c2 ring C May be bonded to each other to form an aryl or heteroaryl ring. The aryl ring and heteroaryl ring formed may each be substituted with at least one substituent selected from substituent group ZB. The substituent selected from the substituent group ZB at this time is preferably a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted diarylamino group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, or a substituted silyl group. The aryl ring to be formed is preferably a benzene ring, naphthalene ring, indene ring, or cyclopentadiene ring, and the heteroaryl ring to be formed is preferably a thiophene ring, pyrrole ring, furan ring, benzothiophene ring, benzofuran ring, or indole ring, and most preferably a benzene ring.
The following shows a loop represented by formula (C)Examples of the bonding form of the structure with other partial structures of formula (2). Preferably, Z is represented by the formula (1 a), the formula (1 b), the formula (1 c), the formula (1 d), the formula (1 e), the formula (1 f), the formula (1 g) and the formula (1 h) c Each independently all being C-R C In the form of (2), and also preferably Z in the c2 ring in the formulae (1 c), (1 d), (1 e), (1 f), (1 g) and (1 h) c Each independently all being C-R c As will be described later, R is adjacent to R c Form bonds to each other to form an aryl ring (preferably a benzene ring). Among the formulae (1 a), (1 b), (1 c), (1 d), (1 e), (1 f), (1 g) and (1 h), the formulae (1 a), (1 b) and (1 b) are preferable, and the formula (1 a) is most preferable. For the description of each symbol and sentence, reference is made to the description of the present specification described later.
[ chemical 17]
Among the formulae (1 c), (1 d), (1 e), (1 f), (1 g) and (1 h), Z of the c2 ring is preferable C All independently of one another are N or C-R C And adjacent C-R C Forming a bond with each other to form an aryl ring, or a heteroaryl ring (preferably an aryl ring, more preferably a benzene ring). The following shows a preferred embodiment thereof. The definitions of the symbols of the formulae (1 c-2), (1 d-2), (1 e-2), (1 f-2), (1 g-2) and (1 h-2), and preferred ranges thereof can be described with reference to the formulae (1 c), (1 d), (1 e), (1 f), (1 g) and (1 h).
[ chemical 18]
[Y 1 Description of (2)]
In formula (1) and its preferred form, Y 1 Each independently B, P, P = O, P = S, al, ga, as, si-R, or Ge-R, preferably B or p=o, most preferably B. The R of the Si-R and the Ge-R is aryl with 6-12 carbon atoms, alkyl with 1-6 carbon atoms or over-3 carbon atoms 14. Y of formula (1) 1 R of Si-R and Ge-R is aryl, alkyl or cycloalkyl, and examples of the aryl, alkyl or cycloalkyl include the above groups. Particularly preferred are aryl groups having 6 to 10 carbon atoms (e.g., phenyl, naphthyl, etc.), alkyl groups having 1 to 5 carbon atoms (e.g., methyl, ethyl, etc.), and cycloalkyl groups having 5 to 10 carbon atoms (preferably cyclohexyl or adamantyl groups).
[G A G (G) B Description of (2)]
In formula (1) and its preferred form, G A G (G) B Each independently represents a monovalent group represented by the formula (G).
[ chemical 19]
In the formula (G), Z a Each independently is N or C-R a . In the formula (G), Z is N a Preferably zero to three, more preferably zero to two, still more preferably zero to one, and particularly preferably zero. R is R a Each independently is hydrogen or any substituent selected from substituent group ZB, or R adjacent to a Bonded to form an aryl or heteroaryl ring. The aryl ring and heteroaryl ring formed may each be substituted with at least one substituent selected from any one of substituent groups ZB. The substituent in this case is preferably a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted cycloalkyl group, which are selected from any one of the substituents in the substituent group ZB. R is R a Preferably hydrogen or one to three substituents each independently selected from substituent groups ZB, R a More preferably, each is hydrogen or one to two substituents each independently is any substituent selected from the substituent group ZB, R a Further, hydrogen is preferable.
In the formula (G), A is > O, > N-R A 、＞Si(-R A ) 2 、＞C(-R A ) 2 S, or Se, R A Each independently is hydrogen, substituted orUnsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, said > Si (-R) A ) 2 Is set at least two R A And said > C (-R) A ) 2 R of (2) A Are bonded to each other to form a ring, or are not bonded to each other to form a ring. As A, > O, > N-R are preferred A 、＞C(-R A ) 2 Or > S, more preferably > O, > N-R A Or > S, most preferably > O. In addition, regarding > N-R as A A R of (2) A Preferably a substituted or unsubstituted aryl or substituted or unsubstituted heteroaryl. As a substituent when referred to herein as "substituted or unsubstituted", it is preferable that aryl, heteroaryl, diarylamino, alkyl, cycloalkyl, or substituted silyl groups, and aryl groups of diarylamino groups may be substituted with alkyl or cycloalkyl groups.
The monovalent radical of formula (G) being in any position and > N-G A Or > N-G B N bond of (c). The position of the formula (G) bonded to N may be: as Z a C-H (corresponding to C-R) a R of (2) a In the case of H), C (carbon atom) as Z a C-R of (2) a R of (2) a Any C (carbon atom), adjacent C-R a Is set at least two R a C (carbon atom) on any one of the aryl or heteroaryl rings formed by bonding to each other, adjacent C-R a Is set at least two R a Substituents of aryl or heteroaryl rings bound to each other, i.e. R a Any C (carbon atom), any C (carbon atom) on a substituent of a monovalent group represented by the formula (G), any C (carbon atom) on R > N-R as A, and > Si (-R) as A 2 Any C (carbon atom) on R of (2), or > C (-R) as A 2 Any C (carbon atom) on R of (C) is preferably Z a C-H (corresponding to C-R) a R of (2) a In the case of H), or adjacent C-R a Is set at least two R a And C (carbon atom) on any one of the aryl ring or heteroaryl ring formed by bonding to each other.
As a specific form of the monovalent group represented by the formula (G), for exampleExamples of the monovalent group include monovalent groups represented by any one of the following formulas (G-1) to (G-52). The examples are not limited thereto. In the following formula, the symbols are represented by and > N-G A The bonding position of N in (c). In addition, the symbols in the formulae can be referred to the descriptions in the specification. The monovalent group represented by the formulas (G-1) to (G-52) may have any one group selected from the substituent group ZB as a substituent. The substituent is most preferably an alkyl group (particularly, tR described later) or a cycloalkyl group. The monovalent groups represented by the formulas (G-1) to (G-52) may be condensed with at least one cycloalkane as described later.
The monovalent groups represented by the formulas (G-1) to (G-52) are preferably unsubstituted or one or both hydrogens in the structure are substituted with an alkyl group (particularly, tR described later) or a cycloalkyl group.
[ chemical 20]
[ chemical 21]
Among them, the formula (G-1), the formula (G-4), the formula (G-5), the formula (G-7), the formula (G-10), the formula (G-11), the formula (G-25), the formula (G-34), or the formula (G-39) is preferable, the formula (G-1), the formula (G-4), the formula (G-5), the formula (G-7), the formula (G-10), or the formula (G-11) is more preferable, and the formula (G-1), the formula (G-4), or the formula (G-5) is most preferable.
G A G (G) B May be the same or different. G A G (G) B Preferably groups each represented by the formula (G-1), or G A Is a group represented by the formula (G-5), G B The groups represented by the formula (G-1) are more preferably groups each represented by the formula (G-1).
[ description of Z in formula (1 a) ]
[ chemical 22]
In the formula (1 a), Z is N or C-R independently 11 . In the formula (1 a), Z as N is preferably zero to three, more preferably zero to two, still more preferably zero to one, particularly preferably zero.
C-R 11 R of (2) 11 Each independently hydrogen or any substituent selected from substituent group ZB, two adjacent Rs 11 May be bonded to each other and form together with the a-or b-ring an aryl or heteroaryl ring. The aryl ring and heteroaryl ring formed may each be substituted with at least one substituent selected from substituent group ZB.
As R 11 Preferably hydrogen, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted diarylamino group, a substituted or unsubstituted arylheteroarylamino group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, or a substituted silyl group.
Z is preferably all, independently of one another, C-R 11 . In this case, it is further preferable that Y be formed on the benzene ring 1 R of para-position of (2) 11 Is hydrogen or a substituent other than hydrogen, R 11 Is hydrogen. In the B ring, more preferably Y on the benzene ring 1 R of para-position of (2) 11 Is a substituent other than hydrogen, R 11 Is hydrogen. Examples of the substituent in this case include: tertiary alkyl groups (tertiary butyl groups, tertiary amyl groups, etc.), cycloalkyl groups, diarylamino groups or arylheteroarylamino groups which may be substituted with tertiary alkyl groups or other alkyl groups represented by formula (tR), etc. In the A ring, more preferably Y on the benzene ring 1 R of para-position of (2) 11 Is hydrogen or alkyl (methyl or tert-butyl, etc.), other R 11 Is hydrogen.
In addition, when X c When > O, R 11 Has at least one substituent selected from the group consisting of a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted diarylamino group, a substituted or unsubstituted arylheteroarylamino group, and a substituted or unsubstituted cycloalkyl group, or At least one selected from the group consisting of an aryl ring and a heteroaryl ring in the formula (1 a) is condensed from a cycloalkane as described later.
Two adjacent R 11 May be bonded to each other and form an aryl or heteroaryl ring together with the carbon to which they are bonded. Wherein when X is c When S is > R in the b ring 11 Are not bonded to each other and form together with the carbon to which they are bonded a heteroaryl ring. The aryl ring and heteroaryl ring formed may be substituted with at least one substituent selected from substituent group ZB. The substituent in this case is preferably a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted diarylamino group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, or a substituted silyl group. The aryl group of the diarylamino group is preferably unsubstituted or substituted with an alkyl or cycloalkyl group. The aryl ring to be formed is preferably a benzene ring, naphthalene ring, indene ring, or cyclopentadiene ring, and the heteroaryl ring to be formed is preferably a thiophene ring, pyrrole ring, furan ring, benzothiophene ring, benzofuran ring, or indole ring.
[ formula (1 a-1), formula (1 a-2), and formula (1 a-3) ]
Further, as a more preferable embodiment of the formula (1 a), the following formulas (1 a-1), formula (1 a-2), and formula (1 a-3) are exemplified.
[ chemical 23]
In the formula (1 a-1), the formula (1 a-2) and the formula (1 a-3), R a1 ～R a3 、R b1 ～R b4 And R is c1 ～R c4 Each independently is hydrogen or any substituent selected from substituent group ZB, preferably hydrogen or any substituent selected from substituent group ZB-2 described below, more preferably hydrogen or any substituent selected from substituent group ZB-3 described below. Preferably R a1 ～R a3 Zero to one of R b1 ～R b4 Zero to one of them, R c1 ～R c4 Zero to one of the substituents are any substituent selected from substituent groups ZB, and the others are hydrogen. R is R a1 、R a3 、R b1 、R b4 And R is c1 Preferably all are hydrogen.
Substituent group ZB-2 comprises the following:
alkyl group,
Cycloalkyl (optionally substituted by alkyl),
Aryl (cycloalkyl which may be substituted by alkyl or alkyl),
Heteroaryl (which may be substituted by alkyl or cycloalkyl substituted by alkyl),
Diarylamino (cycloalkyl which may be substituted with alkyl or may be substituted with alkyl), and
arylheteroarylamino (cycloalkyl which may be substituted with alkyl or with alkyl).
Substituent group ZB-3 includes the following.
Methyl group,
Tertiary amyl radical,
Tertiary butyl group,
Adamantyl (optionally substituted by methyl),
Phenyl (which may be substituted by methyl, tert-amyl, tert-butyl, or adamantyl (which may be substituted by methyl)), a process for preparing the same,
Biphenyl (which may be substituted by methyl, tert-amyl, tert-butyl, or adamantyl (which may be substituted by methyl)), a,
Dibenzofuranyl (optionally substituted with methyl, t-amyl, t-butyl, or adamantyl (optionally substituted with methyl)), diarylamino (the aryl group of diarylamino is selected from the group consisting of phenyl, biphenyl, and naphthyl, and optionally substituted with alkyl, or optionally substituted with alkyl-substituted cycloalkyl), and
arylheteroarylamino (the aryl of arylheteroarylamino is selected from the group comprising phenyl, biphenyl, and naphthyl, the heteroaryl is selected from the group comprising dibenzofuranyl, dibenzothienyl, or N-phenylcarbazolyl, and the aryl, and the heteroaryl may be substituted with alkyl, or cycloalkyl which may be substituted with alkyl).
A compound of the formula (1 a-1),In the formula (1 a-2) and the formula (1 a-3), R a2 R is R b3 Also preferred are diarylamino groups, or arylheteroarylamino groups, each independently. Regarding possible substituents and preferred forms thereof, reference may be made to the descriptions regarding diarylamino groups and arylheteroarylamino groups in substituent group ZB-3.
In the formula (1 a-1), the formula (1 a-2) and the formula (1 a-3), R is g1 、R g2 、R g3 、R g4 、R g5 、R g6 、R g7 、R g8 、R g9 、R g10 、R g11 、R g12 、R g13 And R is g14 Reference is made to R in formula (G) a Is described in (2). Regarding the groups containing G11 ring and G12 ring and the groups containing G13 ring and G14 ring in the formula (1 a-1), the formula (1 a-2) and the formula (1 a-3) corresponding to the monovalent group represented by the formula (G), reference may be made to the description regarding the monovalent group represented by the formula (G), and for example, among the monovalent groups represented by any one of the formulas (G-1) to (G-52), a group in which a is > O may be exemplified. In addition, R g1 、R g6 、R g8 And R is g13 Preferably all hydrogen, is also preferably selected from the group consisting of R g2 、R g5 、R g9 、R g12 One to four of the groups formed are each independently a group selected from the substituent group ZB-2.
In the formula (1 a-1), R b1 ～R b4 Can be bonded to each other and together with the carbon to which they are bonded form an aryl ring, which can be substituted with at least one substituent selected from the substituent group ZB. The substituent is preferably any one group selected from the substituent group ZB-2.
At least one of the aryl ring or the heteroaryl ring in the structure in formula (1 a-1) may be condensed with at least one cycloalkane, which may have a substituent, as described later, at least one of the cycloalkanes-CH 2 -may be substituted by-O-. Wherein the alkylene groups in the g11 ring and the g13 ring are not condensed. Preferably, all of the g11 ring, the g12 ring, the g13 ring, and the g14 ring are not condensed with cycloalkanes.
In the formula (1 a-2), R a1 ～R a3 、R b1 ～R b4 And R is c1 ～R c4 Is a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted diarylamino group, a substituted or unsubstituted arylheteroarylamino group, or a substituted or unsubstituted cycloalkyl group, or at least one selected from the group consisting of an aryl ring and a heteroaryl ring in the formula (1 a-2) is condensed with a cycloalkane as described later.
When R is a1 ～R a3 、R b1 ～R b4 And R is c1 ～R c4 Comprises R when at least one of the substituents is the same a1 ～R a3 Is composed of R b1 ～R b4 Group of (C) and R c1 ～R c4 Preferably at least one group in each of at least two groups, more preferably at least one group in each of three groups, is a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted diarylamino group, a substituted or unsubstituted arylheteroarylamino group, or a substituted or unsubstituted cycloalkyl group. The preferable substituents and ranges of these substituents can be referred to as descriptions of diarylamino groups and arylheteroarylamino groups in the substituent group ZB-2.
In the formula (1 a-2), R b1 ～R b4 R is R c1 ～R c4 May be bonded to each other and form together with the carbon to which they are bonded an aryl or heteroaryl ring. The aryl ring formed may be substituted with at least one substituent selected from substituent group ZB. The substituent is preferably a group selected from ZB-2.
At least one of the aryl or heteroaryl ring in formula (1 a-2) may be condensed with at least one cycloalkane, which may have a substituent, at least one of the cycloalkanes-CH, as described later 2 -may be substituted by-O-.
In the formula (1 a-3), R a1 ～R a3 、R b1 ～R b4 、R c1 ～R c4 And R is g1 ～R g14 Each independently is hydrogen or any substituent selected from substituent group ZB. R is R b1 ～R b4 R is R c1 ～R c4 May be bonded to each other and form together with the carbon to which they are bonded an aryl or heteroaryl ring. The aryl and heteroaryl rings formed may be substituted with at least one substituent selected from substituent group ZB. The substituent is preferably a group selected from ZB-2.
At least one of the aryl or heteroaryl rings in the structure of formula (1 a-3) may be condensed with at least one cycloalkane, which may have a substituent, at least one of the cycloalkanes-CH, as described later 2 -may be substituted by-O-.
[ Structure of one or more than two comprising structural units ]
The polycyclic aromatic compound of the present invention is a polycyclic aromatic compound having one or more structures including structural units represented by formula (1) and preferred forms thereof. The polycyclic aromatic compound having a structure including one of the structural units includes a polycyclic aromatic compound represented by the above-described formula as a structural unit represented by the formula (1). Examples of the polycyclic aromatic compound having two or more structures including the structural unit represented by the formula (1) include a compound corresponding to a polymer of the polycyclic aromatic compound represented by the above-described formula as the structural unit represented by the formula (1). The polymer is preferably a dimer to hexamer, more preferably a dimer to trimer, and particularly preferably a dimer. The polymer may be in the form of having a plurality of the unit structures in one compound, and may be in the form of bonding so that any ring (a ring, B ring or C ring) included in the structural unit is shared among the plurality of unit structures, or may be in the form of bonding so that any rings (a ring, B ring or C ring) included in the unit structures are condensed with each other. The unit structure may be a plurality of units bonded via a single bond, a linking group such as an alkylene group having 1 to 3 carbon atoms, a phenylene group, or a naphthylene group. Among these, a form in which bonding is performed in a common ring is preferable.
[ Cycloalkane condensation ]
The polycyclic aromatic compound having one or two or more structures including the structural unit represented by the formula (1), and at least one selected from the group consisting of aryl rings and heteroaryl rings in a preferred form thereof are not condensed by at least one cycloalkane or are condensed by at least one cycloalkane.
The cycloalkane may be any cycloalkane having 3 to 24 carbon atoms. In this case, the cycloalkane may be substituted with an aryl group having 6 to 30 carbon atoms, a heteroaryl group having 2 to 30 carbon atoms, an alkyl group having 1 to 24 carbon atoms or a cycloalkyl group having 3 to 24 carbon atoms, and at least one of the cycloalkanes may be-CH 2 -may be substituted by-O-, preferably all-CH 2 -cycloalkanes.
In the case where one or more structures including the structural unit represented by the formula (1) are condensed with at least one cycloalkane, at least one cycloalkane is a cycloalkane having 3 to 20 carbon atoms, preferably a cycloalkane which may be substituted with an aryl group having 6 to 16 carbon atoms, a heteroaryl group having 2 to 22 carbon atoms, an alkyl group having 1 to 12 carbon atoms or a cycloalkyl group having 3 to 16 carbon atoms.
As the cycloalkane, cycloalkanes having 3 to 24 carbon atoms are preferable, and as a further preferable example, there are, in order: cycloalkanes having 3 to 20 carbon atoms, cycloalkanes having 3 to 16 carbon atoms, cycloalkanes having 3 to 14 carbon atoms, cycloalkanes having 5 to 10 carbon atoms, cycloalkanes having 5 to 8 carbon atoms, cycloalkanes having 5 to 6 carbon atoms, and cycloalkanes having 6 carbon atoms.
Specific cycloalkanes include: cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane, cyclodecane, bicyclo [1.1.0] butane, bicyclo [1.1.1] pentane, bicyclo [2.1.0] pentane, bicyclo [2.1.1] hexane, bicyclo [3.1.0] hexane, bicyclo [2.2.1] heptane (norbornane), bicyclo [2.2.2] octane, adamantane, diamantane, decalin and decahydro azulene, and alkyl (particularly methyl) substituents, halogen (particularly fluorine) substituents, deuterium substituents, and the like of these having 1 to 5 carbon atoms.
Among these, for example, a structure in which at least one hydrogen on the carbon in the α -position of a cycloalkane (carbon in the position adjacent to the carbon in the condensation site in the cycloalkane condensed in the aryl ring or heteroaryl ring, which corresponds to the benzyl position) is substituted, as shown in the following structural formula, more preferably a structure in which two hydrogens on the carbon in the α -position are substituted, and still more preferably a structure in which a total of four hydrogens on the two carbons in the α -position are substituted is preferable. This is to improve the durability of the compound in order to protect chemically active sites. As the substituent, there may be mentioned: alkyl (particularly methyl) substituents, halogen (particularly fluorine) substituents, deuterium substituents and the like having 1 to 5 carbon atoms. Particularly preferred is a structure in which a partial structure represented by the following formulas (Z-11) and (Z-12) is bonded to adjacent carbon atoms in the aryl ring or heteroaryl ring, and more preferred is a structure represented by the formula (Z-11).
[ chemical 24]
In the formula (Z-11) and the formula (Z-12), me represents methyl, and represents a bonding position.
The number of cycloalkanes condensed in one aryl ring or heteroaryl ring is preferably one to three, more preferably one or two, and further preferably one. Examples of condensed one or more cycloalkanes in one benzene ring (phenyl) are shown below, for example. * The bond position is represented, and the position may be any carbon constituting a benzene ring and not constituting a cycloalkane. Cycloalkanes condensed as in formula (Cy-1-4) and formula (Cy-2-4) may be condensed with each other. The same applies to the case where the condensed ring (group) is an aryl ring or heteroaryl ring other than a benzene ring (phenyl group), or the case where the cycloalkane to be condensed is cyclopentane or cycloalkane other than cyclohexane.
[ chemical 25]
At least one-CH in cycloalkane 2 -may be substituted by-O-. For example, one or more-CH's in cycloalkanes condensed in a benzene ring (phenyl) are shown below 2 -examples of substitution by-O-. The same applies to the case where the condensed ring (group) is an aromatic ring or a heteroaromatic ring other than a benzene ring (phenyl group), or the case where the cycloalkane to be condensed is cyclopentane or another cycloalkane other than cyclohexane.
[ chemical 26]
At least one hydrogen in the cycloalkane may be substituted, and as the substituent, for example, any one group selected from substituent groups ZB may be cited. Among these substituents, alkyl groups (for example, alkyl groups having 1 to 6 carbon atoms) and cycloalkyl groups (for example, cycloalkyl groups having 3 to 14 carbon atoms) are preferable. It is also preferable that any hydrogen is substituted with halogen (e.g., fluorine) or deuterium. In the case of substitution with a cycloalkyl group, the substitution pattern may be one that forms a spiro structure, and examples thereof are shown below.
[ chemical 27]
As a form of cycloalkane condensation, first, a form in which any one of the a ring, the B ring, and the C ring (C1 ring or C2 ring) in a polycyclic aromatic compound having one or two or more structures including the structural unit represented by the formula (1) is condensed with cycloalkane is exemplified.
As another form of cycloalkane condensation, there may be mentioned a polycyclic aromatic compound having one or more structures including a structural unit represented by the formula (1), and G in a preferred form thereof A Or G B In the form in which any one of the rings is condensed with a cycloalkane (wherein, when X c When S is > S, the monocyclic ring directly bonded to nitrogen in the monovalent group represented by the formula (G) is not condensed by cycloalkane), and the aromatic or heteroaromatic group in the formula (1), that is, diarylamino group condensed by cycloalkane (condensed to its aryl moiety), carbazolyl condensed by cycloalkane (condensed to its benzene ring moiety) or condensed by cycloalkane Examples of the benzocarbazolyl group (condensed to the benzene ring portion thereof), the aryl group as a substituent condensed by a cycloalkane, the heteroaryl group as a substituent condensed by a cycloalkane, the aryl group condensed by a cycloalkane as a partial structure of a substituent (for example, the aryl portion of an aryloxy group), and the heteroaryl group condensed by a cycloalkane as a partial structure of a substituent (for example, the heteroaryl portion of a diheteroarylamino group).
In the polycyclic aromatic compound having one or two or more structures including the structural unit represented by the formula (1), and a preferred form thereof, the cycloalkane condensation is preferably a form condensed in an aryl ring or heteroaryl ring in an a ring, a B ring, or a C ring, and more preferably a form condensed in an aryl ring or heteroaryl ring in a B ring or a C ring. It is also preferable that the compound has a condensed form in both the B ring and the C ring.
Further, by introducing a cycloalkane structure into the polycyclic aromatic compound of the present invention, a reduction in melting point or sublimation temperature can be expected. In this case, in sublimation purification, which is almost indispensable for a purification method of an organic material for an organic EL element or the like requiring high purity, purification can be performed at a relatively low temperature, and thus thermal decomposition or the like of the material is avoided. In addition, the same applies to the vacuum deposition process, which is a powerful means for producing organic devices such as organic EL elements, and the process can be performed at a relatively low temperature, so thermal decomposition of the material can be avoided, and as a result, high-performance organic devices can be obtained. Further, since the cycloalkane structure is introduced to improve the solubility in an organic solvent, the method can be applied to the production of devices by a coating process. The present invention is not limited to these principles. Therefore, in the polycyclic aromatic compound having one or more structures including the structural unit represented by the formula (1), and a preferred form thereof, it is preferable to introduce the cycloalkane condensation.
[ substitution with deuterium, cyano, or halogen ]
All or part of hydrogen in one or more structures comprising the structural unit represented by formula (1) and its preferred form may be substituted with deuterium, cyano, or halogen.
For example, in a structure comprising one or more of the structural units represented by the formula (1) and preferred forms thereof, the substituents on the A ring, B ring, C ring, A ring to C ring, Y 1 R (=alkyl, cycloalkyl, aryl) when Si-R or Ge-R, and G A Or G B The hydrogen in (a) may be substituted with deuterium, cyano or halogen, but all or part of the hydrogen in aryl or heteroaryl may be substituted with deuterium, cyano or halogen. Halogen is fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine, more preferably fluorine or chlorine, and still more preferably fluorine. In particular, the deuterium-substituted form of hydrogen is preferred because it increases the stability of the compound. Preferably one hydrogen is substituted with deuterium, more preferably a plurality of hydrogens are substituted with deuterium, further preferably all of the hydrogens of the aromatic moiety are substituted with deuterium, most preferably all of the hydrogens are substituted with deuterium.
[ preferred substituent ]
Among the polycyclic aromatic compounds used as the emission dopant (among other compounds used as the dopant), as a substituent containing an "alkyl group", a tertiary alkyl group represented by the following formula (tR) is one of substituents particularly preferred as a substituent for an aryl ring or a heteroaryl ring in the a ring, the B ring and the C ring. The reason for this is that the intermolecular distance is increased by such a bulky substituent, and thus the luminescence quantum yield (PLQY) is improved. In addition, a substituent in which the tertiary alkyl group represented by the formula (tR) is substituted with another substituent as the second substituent is also preferable. Specifically, a tertiary alkyl-substituted diarylamino group represented by (tR), a tertiary alkyl-substituted carbazolyl group represented by (tR) (preferably an N-carbazolyl group), or a tertiary alkyl-substituted benzocarbazolyl group represented by (tR) (preferably an N-benzocarbazolyl group) may be mentioned. Examples of the substitution pattern of the group of the formula (tR) for the diarylamino group, the carbazolyl group and the benzocarbazolyl group include substitution of part or all of hydrogen of the aryl ring or the benzene ring in these groups with the group of the formula (tR).
[ chemical 28]
In the formula (tR), R a 、R b And R is c Each independently represents an alkyl group having 1 to 24 carbon atoms, and any of the alkyl groups is-CH 2 -optionally-O-substituted, the group represented by formula (tR) being set as a bonding position.
As R a 、R b R is R c The "alkyl group having 1 to 24 carbon atoms" in (a) may be any of a straight chain and a branched chain, and examples thereof include: a linear alkyl group having 1 to 24 carbon atoms or a branched alkyl group having 3 to 24 carbon atoms, an alkyl group having 1 to 18 carbon atoms (branched alkyl group having 3 to 18 carbon atoms), an alkyl group having 1 to 12 carbon atoms (branched alkyl group having 3 to 12 carbon atoms), an alkyl group having 1 to 6 carbon atoms (branched alkyl group having 3 to 6 carbon atoms), an alkyl group having 1 to 4 carbon atoms (branched alkyl group having 3 to 4 carbon atoms).
R in formula (tR) of formula (1) a 、R b And R is c The total of carbon numbers of (2) is preferably 3 to 20 carbon numbers, and particularly preferably 3 to 10 carbon numbers.
As R a 、R b And R is c Specific alkyl groups in (a) may be mentioned: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, n-hexyl, 1-methylpentyl, 4-methyl-2-pentyl, 3-dimethylbutyl, 2-ethylbutyl, n-heptyl, 1-methylhexyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2-dimethylheptyl, 2, 6-dimethyl-4-heptyl, 3, 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.
Examples of the group represented by the formula (tR) include: tert-butyl, tert-amyl, 1-ethyl-1-methylpropyl, 1-diethylpropyl, 1-dimethylbutyl, 1-ethyl-1-methylbutyl, 1, 3-tetramethylbutyl, 1, 4-trimethylpentyl 1, 2-trimethylpropyl, 1-dimethyloctyl, 1-dimethylpentyl, 1-dimethylheptyl, 1, 5-trimethylhexyl, 1-ethyl-1-methylhexyl 1-ethyl-1, 3-dimethylbutyl, 1, 2-tetramethylpropyl, 1-butyl-1-methylpentyl, 1-diethylbutyl, 1-ethyl-1-methylpentyl, 1, 3-trimethylbutyl 1-propyl-1-methylpentyl, 1, 2-trimethylpropyl, 1-ethyl-1, 2-trimethylpropyl, 1-propyl-1-methylbutyl, 1-dimethylhexyl and the like. Among these, tert-butyl and tert-amyl are preferred.
The emission wavelength can be adjusted by steric hindrance, electron donating property, and electron withdrawing property of the structure of the substituent possessed by the compound serving as the dopant (auxiliary dopant or emission dopant). The group represented by the following structural formula is more preferable, and methyl group, tert-butyl group, tert-amyl group, tert-octyl group, neopentyl group, adamantyl group, dimethyladamantanyl group, phenyl group, o-tolyl group, p-tolyl group, 2, 4-xylyl group, 2, 5-xylyl group, 2, 6-xylyl group, 2,4, 6-mesityl group, diphenylamino group, di-p-tolylamino group, bis (p- (tert-butyl) phenyl) amino group, carbazolyl group, 3, 6-dimethylcarbazolyl group, 3, 6-di-tert-butylcarbazolyl group and phenoxy group are more preferable, and methyl group, tert-butyl group, tert-amyl group, tert-octyl group, neopentyl group, adamantyl group, phenyl group, o-tolyl group, 2, 6-xylyl group, 2,4, 6-mesityl group, diphenylamino-tolylamino group, bis (p- (tert-butyl) phenyl) amino group, carbazolyl group, 3, 6-dimethyl carbazolyl group, 3, 6-di-tert-butylcarbazolyl group and tribenzoazepine group are more preferable. From the viewpoint of ease of synthesis, a group having a large steric hindrance is preferable because of selective synthesis, and specifically, tertiary butyl, tertiary amyl, tertiary octyl, adamantyl, dimethyladamantanyl, o-tolyl, p-tolyl, 2, 4-xylyl, 2, 5-xylyl, 2, 6-xylyl, 2,4, 6-mesityl, di-p-tolylamino, bis (p- (tertiary butyl) phenyl) amino, 3, 6-dimethylcarbazolyl and 3, 6-di-t-butylcarbazolyl are preferable.
In the following structural formula, the bonding position is represented.
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/>
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The polycyclic aromatic compound having one or two or more structures including the structural unit represented by the formula (1) and its preferred form is preferably a structure including at least one tertiary alkyl group (tertiary butyl group, tertiary amyl group, etc.), neopentyl group, or adamantyl group represented by the formula (tR), and more preferably a structure including a tertiary alkyl group (tertiary butyl group, tertiary amyl group, etc.) represented by the formula (tR). The reason for this is that the intermolecular distance is increased by such a bulky substituent, and thus the luminescence quantum yield (PLQY) is improved. In addition, as a substituent, a diarylamino group (two aryl groups are not bonded to each other or may be bonded via a linking group) is also preferable. Further, a diarylamino group substituted with a group of formula (tR) (two aryl groups are not bonded to each other or may be bonded via a linking group), a carbazolyl group substituted with a group of formula (tR) (preferably an N-carbazolyl group), or a benzocarbazolyl group substituted with a group of formula (tR) (preferably an N-benzocarbazolyl group) is also preferable. Examples of the substitution pattern of the group of the formula (tR) for the diarylamino group in which two aryl groups of the diarylamino group are not bonded to each other or are bonded via a linking group, the carbazolyl group and the benzocarbazolyl group include substitution of part or all of hydrogen of an aryl ring or a benzene ring in these groups with the group of the formula (tR).
[ concrete examples of polycyclic aromatic Compounds ]
Further specific examples of the polycyclic aromatic compound represented by the formula (1) of the present invention include the following compounds. The following configuration is an example.
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Process for producing polycyclic aromatic compound
The polycyclic aromatic compound of the present invention having one or more structures comprising the structural unit represented by the formula (1) essentially first uses a bonding group (comprising N-G A Or N-G B (group) A ring (a ring) is bonded to B ring (B ring) and C ring (C ring), thereby producing an intermediate (first reaction), followed by using a bonding group (containing Y) 1 The group of (a) is bonded to the A ring (a ring), the B ring (B ring) and the C ring (C ring), whereby the final product (second reaction) can be produced. In the first Reaction, for example, general reactions such as nucleophilic substitution Reaction and Ullmann Reaction (Ullmann Reaction) can be used in the case of etherification Reaction, and general reactions such as Buchwald-Hartwig Reaction (Buchwald-Hartwig Reaction), nucleophilic substitution Reaction and goldberg amination (Goldberg Amination) can be used in the case of amination Reaction. In the second Reaction, a Tandem type heterofriedel-Crafts Reaction (continuous aromatic electrophilic substitution Reaction, the same applies hereinafter) can be used. The target compound can be produced by using a raw material having a desired condensed ring at a certain position in the reaction step, or by adding a step of condensing the ring.
< manufacturing method via intermediate 1 >)
The polycyclic aromatic compound of the present invention can be produced by a production method comprising the following steps. For each of the following steps, refer to the description of International publication No. 2015/102118.
The following describes the reaction comprising the following reaction steps: synthesis of intermediate 1 from halogenated precursor, N-G in intermediate 1 was synthesized using an organic base compound A With N-G B A reaction step in which a halogen atom (Hal) is metallized; using a compound selected from the group consisting of Y 1 Is a halide, Y 1 Amino halides, Y 1 Alkoxylates of (A) and Y 1 The metal is reacted with Y by an agent selected from the group consisting of aryloxy compounds of (C) 1 A reaction step of exchanging; and utilizing the Y by successive aromatic electrophilic substitution reactions using Bronsted base 1 A reaction step of bonding the B ring to the C ring. The halogen atom (Hal) in the formula may be any one of F, cl, br, I, and may be appropriately selected in consideration of the reactivity of the substrate.
[ 63]
As the metallizing agent used in the halogen-metal exchange reaction in the scheme described so far, there may be mentioned: lithium chloride complexes of alkyl lithium such as methyl lithium, n-butyl lithium, sec-butyl lithium, and tert-butyl lithium, isopropyl magnesium chloride, isopropyl magnesium bromide, phenyl magnesium chloride, phenyl magnesium bromide, and isopropyl magnesium chloride known as tabog reagent (Turbo Grignard Reagent).
The metallizing agent used in the ortho-metal exchange reaction in the scheme described so far may be exemplified by, in addition to the above-mentioned agents: lithium diisopropylamide, lithium tetramethylpiperidine, lithium hexamethyldisilazide, potassium hexamethyldisilazide, lithium tetramethylpiperidyl magnesium chloride-lithium chloride complex, lithium tri-n-butylmagnesium oxide and the like.
Further, examples of the additive for promoting the reaction when using lithium alkyl as the metallizing agent include: n, N, N ', N' -tetramethyl ethylenediamine, 1, 4-diazabicyclo [2.2.2] octane, N, N-dimethylpropyleneurea, and the like.
The lewis acid used in the schemes described so far may be: alCl 3 、AlBr 3 、AlF 3 、BF 3 -OEt 2 、BCl 3 、BBr 3 、BI 3 、GaCl 3 、GaBr 3 、InCl 3 、InBr 3 、In(OTf) 3 、SnCl 4 、SnBr 4 、AgOTf、ScCl 3 、Sc(OTf) 3 、ZnCl 2 、ZnBr 2 、Zn(OTf) 2 、MgCl 2 、MgBr 2 、Mg(OTf) 2 、LiOTf、NaOTf、KOTf、Me 3 SiOTf、Cu(OTf) 2 、CuCl 2 、YCl 3 、Y(OTf) 3 、TiCl 4 、TiBr 4 、ZrCl 4 、ZrBr 4 、FeCl 3 、FeBr 3 、CoCl 3 、CoBr 3 Etc. In addition, a solid supported lewis acid may be used in the same manner. In addition, in the present specification, "OTf" means "trifluoromethylsulfonyl", or "trifluoromethylsulfonate".
The bronsted acid used in the schemes described so far may be: p-toluenesulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid, fluorosulfonic acid, carborane acid, trifluoroacetic acid, (trifluoromethanesulfonyl) imide, tris (trifluoromethanesulfonyl) methane, hydrogen chloride, hydrogen bromide, hydrogen fluoride, and the like. Further, as the solid bronsted acid, there may be mentioned: ambarist (Amberlist) (trade name: dow Chemical), nafion (trade name: duPont), zeolite (Zeolite), di-solid (Taycacure) (trade name: di-Chemical (Tayca) Co., ltd.) and the like.
The amines that can be added in the schemes described so far include: diisopropylethylamine, triethylamine, tributylamine, 1, 4-diazabicyclo [2.2.2] octane, N-dimethyl-p-toluidine, N-dimethylaniline, pyridine, 2, 6-lutidine, 2, 6-di-t-butylamine and the like.
The solvents used in the flow paths described so far include: o-dichlorobenzene, chlorobenzene, toluene, benzene, methylene chloride, chloroform, dichloroethylene, benzotrifluoride, decalin, cyclohexane, hexane, heptane, 1,2, 4-trimethylbenzene, xylene, diphenyl ether, anisole, cyclopentylmethyl ether, tetrahydrofuran, dioxane, methyl-t-butyl ether, and the like.
Here, describe Y 1 In the case of B, Y can be synthesized by appropriately changing the raw materials 1 A compound which is P, P = O, P = S, al, ga, as, si-R or Ge-R.
In the scheme, bronsted bases or Lewis acids may be used to promote the tandem Heterofriedel-crafts reaction. Wherein, in using Y 1 Is a trifluoride of (C), Y 1 Trichlorides, Y 1 Tribromide, Y 1 Y of tri-iodide etc 1 In the case of the halide of (c), an acid such as hydrogen fluoride, hydrogen chloride, hydrogen bromide, or hydrogen iodide is generated with the progress of the aromatic electrophilic substitution reaction, and therefore, it is effective to use a bronsted base that captures the acid. On the other hand, in using Y 1 Amino halides, Y 1 In the case of the alkoxylate of (a), an amine or an alcohol is produced as the aromatic electrophilic substitution reaction proceeds, and therefore, a bronsted base is not required in many cases, but a lewis acid that promotes the dissociation of an amino group or an alkoxy group is effectively used because of the low dissociation ability of the amino group or the alkoxy group.
The polycyclic aromatic compound of the present invention may also include a compound in which at least a part of hydrogen atoms is substituted with deuterium or cyano groups, or a compound in which at least a part of hydrogen atoms is substituted with halogen such as fluorine or chlorine, and such a compound or the like can be synthesized in the same manner as described above by using a raw material in which a desired position is deuterated, cyanated, fluorinated or chlorinated.
< 2 > organic devices >
The polycyclic aromatic compound of the present invention is useful as a material for organic devices. Examples of the organic device include: organic electroluminescent elements, organic field effect transistors, organic thin film solar cells, and the like.
The polycyclic aromatic compound of the present invention is useful as a material for organic devices. Examples of the organic device include: an organic electroluminescent element, an organic field effect transistor, an organic thin film solar cell, or the like, but an organic electroluminescent element is preferable. The polycyclic aromatic compound of the present invention is preferably an organic electroluminescent element material, more preferably a material for a light-emitting layer (light-emitting material), and most preferably a dopant material for a light-emitting layer.
< 2-1. Organic electroluminescent device >
2-1-1 Structure of organic electroluminescent device
Fig. 1 is a schematic cross-sectional view showing an example of an organic EL element.
The organic EL element 100 shown in fig. 1 has: the light-emitting device comprises a substrate 101, an anode 102 arranged on the substrate 101, a hole injection layer 103 arranged on the anode 102, a hole transport layer 104 arranged on the hole injection layer 103, a light-emitting layer 105 arranged on the hole transport layer 104, an electron transport layer 106 arranged on the light-emitting layer 105, an electron injection layer 107 arranged on the electron transport layer 106, and a cathode 108 arranged on the electron injection layer 107.
The organic EL element 100 may be manufactured in the reverse order, for example, by a structure including: the light-emitting device comprises a substrate 101, a cathode 108 arranged on the substrate 101, an electron injection layer 107 arranged on the cathode 108, an electron transport layer 106 arranged on the electron injection layer 107, a light-emitting layer 105 arranged on the electron transport layer 106, a hole transport layer 104 arranged on the light-emitting layer 105, a hole injection layer 103 arranged on the hole transport layer 104 and an anode 102 arranged on the hole injection layer 103.
The minimum structural unit is a structure including the anode 102, the light-emitting layer 105, and the cathode 108, and the hole injection layer 103, the hole transport layer 104, the electron transport layer 106, and the electron injection layer 107 are arbitrarily provided. In addition, each layer may comprise a single layer or multiple layers.
As the form of the layers constituting the organic EL element, in addition to the structural form of the "substrate/anode/hole injection layer/hole transport layer/light emitting layer/electron transport layer/electron injection layer/cathode", the forms of the "substrate/anode/hole transport layer/light emitting layer/electron transport layer/cathode", "substrate/anode/hole injection layer/light emitting layer/electron injection layer/cathode", "substrate/anode/hole injection layer/hole transport layer/light emitting layer/electron transport layer/cathode", "substrate/anode/hole transport layer/light emitting layer/electron injection layer/electron transport layer/cathode", "substrate/anode/electron transport layer/light emitting layer/electron transport layer/cathode", "substrate/anode/electron injection layer/light emitting layer/electron transport layer/cathode" may be mentioned.
2-1-2. Light-emitting layer in organic electroluminescent element >)
The polycyclic aromatic compound of the present invention is preferably used as a material for forming an organic layer of at least one of the organic electroluminescent elements, and more preferably used as a material for forming a light-emitting layer. The light-emitting layer 105 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 a material for forming the light-emitting layer 105, a compound which emits light by excitation by recombination of holes and electrons (a light-emitting compound) is preferable, and a compound which can form a stable thin film shape and exhibits high light-emitting (fluorescence) efficiency in a solid state is preferable. The polycyclic aromatic compound of the present invention is useful as a material for a light-emitting layer, as a dopant material, or as a host material, but is preferably used as a material for a light-emitting layer, and more preferably used as a dopant material.
In addition, as the dopant, there is an example in which an auxiliary dopant and an emission dopant are used in combination, but in the present specification, the term "dopant" is simply described as "a light-emitting dopant" used alone.
The light-emitting layer may be a single layer or may include a plurality of layers, and each may be formed of a material (host material, dopant material) for the light-emitting layer. The host material and the dopant material may be one or a combination of two or more kinds, respectively. The dopant material may be included in the bulk of the host material or may be included in a portion of the host material, either of which may be included.
Dopant material
The doping method may be formed by co-evaporation with the host material, or may be performed by simultaneous evaporation after being mixed with the host material in advance. Specific examples of the dopant combined with the compound of the present invention when the dopant is made into a plurality of combinations are shown below.
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The amount of the dopant material to be used varies depending on the type of the dopant material, and is determined by matching the characteristics of the dopant material. The amount of the dopant to be used is preferably 0.001 to 50% by mass, more preferably 0.05 to 20% by mass, and still more preferably 0.1 to 10% by mass, based on the entire material for the light-emitting layer. If the concentration is within the above range, it is preferable in terms of preventing concentration quenching, for example.
< subject Material >)
As a host materialExamples thereof include anthracene, pyrene, and dibenzo which have been known as light emittersOr a condensed ring derivative of fluorene, a bisstyryl derivative such as a bisstyryl anthracene derivative or a distyryl benzene derivative, a tetraphenyl butadiene derivative, a cyclopentadiene derivative, a fluorene derivative, a benzofluorene derivative, or the like. />
As the host material, for example, a compound represented by any one of the following formulas (H1), (H2) and (H3) can be used.
[ chemical 68]
In the formula (H1), the formula (H2) and the formula (H3), L 1 The arylene group is an arylene group having 6 to 24 carbon atoms, a heteroarylene group having 2 to 24 carbon atoms, a heteroarylene group having 6 to 24 carbon atoms, or an arylene heteroarylene group having 6 to 24 carbon atoms, preferably an arylene group having 6 to 16 carbon atoms, more preferably an arylene group having 6 to 12 carbon atoms, particularly preferably an arylene group having 6 to 10 carbon atoms, and specifically, a divalent group such as a benzene ring, a biphenyl ring, a terphenyl ring, or a fluorene ring is exemplified. The heteroarylene group is preferably a heteroarylene group having 2 to 24 carbon atoms, more preferably a heteroarylene group having 2 to 20 carbon atoms, still more preferably a heteroarylene group having 2 to 15 carbon atoms, particularly preferably a heteroarylene group having 2 to 10 carbon atoms, and specifically, examples thereof include: 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, phenoxazine ring, phenothiazine ring, phenazine ring, indolizine ring, furan ring, benzofuran ring, isobenzofuran ring, dibenzofuran ring Divalent radicals such as thiophene ring, benzothiophene ring, dibenzothiophene ring, furazan ring, oxadiazole ring, and thianthrene ring. At least one hydrogen in the compounds represented by the formulas may be substituted with an alkyl group having 1 to 6 carbon atoms, a cyano group, a halogen or deuterium.
As preferable specific examples, compounds represented by any of the following structural formulas are cited. In the structural formulae shown below, at least one hydrogen may be substituted with halogen, cyano, alkyl group having 1 to 4 carbon atoms (for example, methyl group or tert-butyl group), phenyl group, naphthyl group, or the like.
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The amount of the host material to be used varies depending on the type of the host material, and may be determined by matching the characteristics of the host material. The amount of the host material to be used is preferably 50 to 99.999% by mass, more preferably 80 to 99.95% by mass, and still more preferably 90 to 99.9% by mass, based on the total amount of the light-emitting layer material.
< anthracene Compounds >)
Examples of the anthracene compound as the main body include a compound represented by the formula (3-H) and a compound represented by the formula (3-H2).
[ 73]
In the formula (3-H),
x and Ar 4 Each independently is hydrogen, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted diarylamino, substitutable diheteroarylamino, substituted or unsubstituted arylheteroarylamino, substituted or unsubstituted alkyl, substitutable cycloalkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkoxy, substituted or unsubstituted aryloxy, substituted or unsubstituted arylthio, or substituted silyl, all X and Ar 4 Not simultaneously hydrogen, the two aryl groups of the diarylamino group are not bonded to each other or are bonded via a linking group, the two heteroaryl groups of the diarylamino group are not bonded to each other or are bonded via a single bond or a linking group, and the aryl and heteroaryl groups of the arylheteroarylamino group are not bonded to each other or are bonded via a single bond or a linking group.
At least one hydrogen in the compound represented by the formula (3-H) is substituted with halogen, cyano, deuterium or a substitutable heteroaryl group, or is unsubstituted.
In addition, the structure represented by the formula (3-H) may be used as a unit structure to form a polymer (preferably a dimer). In this case, for example, the unit structures represented by the formula (3-H) are bonded to each other via X, and examples of X include a single bond, arylene (phenylene, biphenylene, naphthylene, etc.), heteroarylene (pyridine ring, dibenzofuran ring, dibenzothiophene ring, carbazole ring, benzocarbazole ring, phenyl-substituted carbazole ring, etc.), and the like.
The details of each group in the compound represented by the formula (3-H) can be described by referring to the description of the formula (1), and further described in the following column of preferred embodiments.
Preferred modes of the anthracene compound are described below. The definition of symbols in the following structures is the same as the definition described.
[ chemical 74]
In formula (3-H), X is independently a group represented by formula (3-X1), formula (3-X2) or formula (3-X3), and a group represented by formula (3-X1), formula (3-X2) or formula (3-X3) is bonded to the anthracycline of formula (3-H) at that position. Preferably, two X's do not simultaneously become the groups represented by the formula (3-X3). More preferably, both X's do not simultaneously become the groups represented by the formula (3-X2).
In addition, the structure represented by the formula (3-H) may be used as a unit structure to form a polymer (preferably a dimer). In this case, for example, the unit structures represented by the formula (3-H) are bonded to each other via X, and examples of X include a single bond, arylene (phenylene, biphenylene, naphthylene, etc.), heteroarylene (pyridine ring, dibenzofuran ring, dibenzothiophene ring, carbazole ring, benzocarbazole ring, phenyl-substituted carbazole ring, etc.), and the like.
The naphthylene moiety in the formula (3-X1) and the formula (3-X2) may be condensed by one benzene ring. The structure condensed in this manner is as follows.
[ 75]
Ar 1 Ar and Ar 2 Each independently is hydrogen, phenyl, biphenyl, terphenyl, tetrabiphenyl, naphthyl, phenanthryl, fluorenyl, benzofluorenyl, A group, a triphenylene group, a pyrenyl group, or a group represented by the formula (a) (including a carbazolyl group, a benzocarbazolyl group, and a phenyl-substituted carbazolyl group). In addition, in Ar 1 Or Ar 2 In the case of the group represented by formula (A), the group represented by formula (A) is the same as naphthalene in formula (3-X1) or formula (3-X2)And (3) ring bonding.
Ar 3 Is phenyl, biphenyl, terphenyl, tetrabiphenyl, naphthyl, phenanthryl, fluorenyl, benzofluorenyl,A group, a triphenylene group, a pyrenyl group, or a group represented by the formula (a) (including a carbazolyl group, a benzocarbazolyl group, and a phenyl-substituted carbazolyl group). In addition, in Ar 3 In the case of the group represented by formula (a), the group represented by formula (a) is bonded to a single bond represented by a straight line in formula (3-X3) at the point. That is, the anthracycline of formula (3-H) is directly bonded to the group represented by formula (A).
In addition, ar 3 May have a substituent, ar 3 At least one hydrogen of the catalyst may be further substituted by C1-C4 alkyl, C5-C10 cycloalkyl, phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, fluorenyl,A group, a triphenylene group, a pyrenyl group, or a group represented by the formula (a) (including carbazolyl groups and phenyl-substituted carbazolyl groups as well). In addition, in Ar 3 In the case where the substituent is a group represented by the formula (A), the group represented by the formula (A) is represented by the formula (3-X3) and Ar 3 And (5) bonding.
Ar 4 Each independently represents hydrogen, phenyl, biphenyl, terphenyl, naphthyl, or a silyl group substituted with an alkyl group having 1 to 4 carbon atoms (methyl, ethyl, t-butyl, etc.) and/or a cycloalkyl group having 5 to 10 carbon atoms.
Examples of the alkyl group having 1 to 4 carbon atoms substituted in the silyl group include: methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, cyclobutyl, etc., and three hydrogens in the silane groups are each independently substituted with these alkyl groups.
Specific examples of the "silyl group substituted with an alkyl group having 1 to 4 carbon atoms" include: trimethylsilyl, triethylsilyl, tripropylsilyl, triisopropylsilyl, tributylsilyl, tri-sec-butylsilyl, tri-tert-butylsilyl, ethyldimethylsilyl, propyldimethylsilyl, isopropyldimethylsilyl, butyldimethylsilyl, sec-butyldimethylsilyl, tert-butyldimethylsilyl, methyldiethylsilyl, propyldiethylsilyl, isopropyldiethylsilyl, butyldiethylsilyl, sec-butyldiethylsilyl, tert-butyldiethylsilyl, methyldipropylsilyl, ethyldipropylsilyl, butyldipropylsilyl, sec-butyldipropylsilyl, tert-butyldipropylsilyl, methyldiisopropylsilyl, ethyldiisopropylsilyl, butyldiisopropylsilyl, sec-butyldiisopropylsilyl, tert-butyldiisopropylsilyl, and the like.
Cycloalkyl groups having 5 to 10 carbon atoms substituted in the silyl group include: cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, bicyclo [1.1.1] pentyl, bicyclo [2.1.0] pentyl, bicyclo [2.1.1] hexyl, bicyclo [3.1.0] hexyl, bicyclo [2.2.1] heptyl (norbornyl), bicyclo [2.2.2] octyl, adamantyl, decalinyl, decahydroazulenyl, and the like, three hydrogens in the silane groups each being independently substituted with these cycloalkyl groups.
Specific examples of the "cycloalkyl-substituted silyl group having 5 to 10 carbon atoms" include a tricyclopentylsilyl group, a tricyclohexylsilyl group and the like.
Examples of the substituted silyl group include a dialkylcycloalkylsilyl group substituted with two alkyl groups and one cycloalkyl group, and an alkylbicycloalkylsilyl group substituted with one alkyl group and two cycloalkyl groups, and specific examples of the substituted alkyl group and cycloalkyl group include the above-mentioned groups.
In addition, hydrogen in the chemical structure of the anthracene compound represented by the formula (3-H) may be substituted with a group represented by the formula (a). In the case of substitution with a group represented by formula (a), the group represented by formula (a) is substituted at the point with at least one hydrogen in the compound represented by formula (3-H).
The group represented by the formula (A) is one of substituents which the anthracene compound represented by the formula (3-H) may have.
[ chemical 76]
In the formula (A), Y is-O-, -S-or > N-R 29 ，R 21 ～R 28 Each independently is 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, alkylbicycloalkylsilyl, optionally substituted amino, halogen, hydroxy or cyano, R 21 ～R 28 Wherein adjacent groups may be bonded to each other to form a hydrocarbon ring, an aryl ring or a heteroaryl ring, R 29 Is hydrogen or an aryl group which may be substituted.
Y in formula (A) is preferably-O-.
As R 21 ～R 28 The "alkyl group" of the "optionally substituted alkyl group" may be any of a straight chain and branched chain, and examples thereof include a straight chain alkyl group having 1 to 24 carbon atoms and a branched chain alkyl group having 3 to 24 carbon atoms. The alkyl group is preferably an alkyl group having 1 to 18 carbon atoms (branched alkyl group having 3 to 18 carbon atoms), more preferably an alkyl group having 1 to 12 carbon atoms (branched alkyl group having 3 to 12 carbon atoms), still more preferably an alkyl group having 1 to 6 carbon atoms (branched alkyl group having 3 to 6 carbon atoms), particularly preferably an alkyl group having 1 to 4 carbon atoms (branched alkyl group having 3 to 4 carbon atoms).
Specific "alkyl" groups include: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, n-hexyl, 1-methylpentyl, 4-methyl-2-pentyl, 3-dimethylbutyl, 2-ethylbutyl, n-heptyl, 1-methylhexyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2-dimethylheptyl, 2, 6-dimethyl-4-heptyl, 3, 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.
As R 21 ～R 28 "cycloalkyl" of the "cycloalkyl group which may be substituted" in (a) may be exemplified by: cycloalkyl group having 3 to 24 carbon atoms, cycloalkyl group having 3 to 20 carbon atoms, cycloalkyl group having 3 to 16 carbon atoms, cycloalkyl group having 3 to 14 carbon atoms, cycloalkyl group having 5 to 10 carbon atoms, cycloalkyl group having 5 to 8 carbon atoms, cycloalkyl group having 5 to 6 carbon atoms, cycloalkyl group having 5 carbon atoms, and the like.
Specific "cycloalkyl" groups include: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, alkyl (particularly methyl) substituents of 1 to 4 carbon atoms of these, or bicyclo [1.1.0] butyl, bicyclo [1.1.1] pentyl, bicyclo [2.1.0] pentyl, bicyclo [2.1.1] hexyl, bicyclo [3.1.0] hexyl, bicyclo [2.2.1] heptyl (norbornyl), bicyclo [2.2.2] octyl, adamantyl, diamantanyl, decahydronaphthyl, decahydroazulenyl, and the like.
As R 21 ～R 28 Examples of the "aryl group" of the "optionally substituted aryl group" include aryl groups having 6 to 30 carbon atoms, preferably aryl groups having 6 to 16 carbon atoms, more preferably aryl groups having 6 to 12 carbon atoms, and particularly preferably aryl groups having 6 to 10 carbon atoms.
Specific examples of the "aryl group" include: phenyl as a monocyclic system, biphenyl as a bicyclic system, naphthyl as a condensed bicyclic system, terphenyl (m-terphenyl, o-terphenyl, p-terphenyl) as a tricyclic system, acenaphthylenyl, fluorenyl, phenalkenyl, phenanthryl as a condensed tricyclic system, triphenylenyl, pyrenyl, tetracenyl as a condensed tetracyclic system, perylene as a condensed pentacyclic system, pentacenyl, and the like.
As R 21 ～R 28 Examples of the "heteroaryl group" of the "optionally substituted heteroaryl group" include heteroaryl groups having 2 to 30 carbon atoms, preferably heteroaryl groups having 2 to 25 carbon atoms, more preferably heteroaryl groups having 2 to 20 carbon atoms, still more preferably heteroaryl groups having 2 to 15 carbon atoms, and particularly preferably heteroaryl groups having 2 to 10 carbon atoms. Examples of the heteroaryl group include a heterocyclic ring containing one to five heteroatoms selected from oxygen, sulfur and nitrogen as ring constituting atoms in addition to carbon.
Specific "heteroaryl" groups include, 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-benzotriazole, quinolinyl, isoquinolinyl, cinnolinyl, quinazolinyl, quinoxalinyl, phthalazinyl, naphthyridinyl, purinyl, pteridinyl, carbazolyl, acridinyl, phenoxazinyl, phenothiazinyl, phenazinyl, indolizinyl, furanyl, benzofuranyl, isobenzofuranyl, dibenzofuranyl, thienyl, benzo [ b ] thienyl, dibenzothienyl, furazanyl, thianthrenyl, naphthobenzofuranyl, naphthobenzothienyl, and the like.
As R 21 ～R 28 Examples of the "alkoxy" of the "optionally substituted alkoxy" include straight-chain alkoxy having 1 to 24 carbon atoms and branched alkoxy having 3 to 24 carbon atoms. The alkoxy group is preferably an alkoxy group having 1 to 18 carbon atoms (branched alkoxy group having 3 to 18 carbon atoms), more preferably an alkoxy group having 1 to 12 carbon atoms (branched alkoxy group having 3 to 12 carbon atoms), still more preferably an alkoxy group having 1 to 6 carbon atoms (branched alkoxy group having 3 to 6 carbon atoms), particularly preferably an alkoxy group having 1 to 4 carbon atoms (branched alkoxy group having 3 to 4 carbon atoms).
Specific examples of the "alkoxy group" include: methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, pentoxy, hexoxy, heptoxy, octoxy and the like.
As R 21 ～R 28 "aryloxy" of the "optionally substituted aryloxy" is an aryl-substituted radical of the hydrogen of the-OH group, said aryl being referred to as R 21 ～R 28 The "aryl" of (3) is defined as the group.
As R 21 ～R 28 "arylthio" of the "optionally substituted arylthio" group is an aryl-substituted group for hydrogen of-SH group, and the aryl group may be cited as R 21 ～R 28 The "aryl" of (3) is defined as the group.
As R 21 ～R 28 As the "trialkylsilyl group" in (a), three hydrogens in the silyl group may be mentioned, each independently substituted with an alkyl group, which may be cited as R 21 ～R 28 The "alkyl" of (3) is described. Preferred alkyl groups for substitution are alkyl groups having 1 to 4 carbon atoms, and specific examples thereof include: methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, cyclobutyl and the like.
Specific examples of the "trialkylsilyl group" include: trimethylsilyl, triethylsilyl, tripropylsilyl, triisopropylsilyl, tributylsilyl, tri-sec-butylsilyl, tri-tert-butylsilyl, ethyldimethylsilyl, propyldimethylsilyl, isopropyldimethylsilyl, butyldimethylsilyl, sec-butyldimethylsilyl, tert-butyldimethylsilyl, methyldiethylsilyl, propyldiethylsilyl, isopropyldiethylsilyl, butyldiethylsilyl, sec-butyldiethylsilyl, tert-butyldiethylsilyl, methyldipropylsilyl, ethyldipropylsilyl, butyldipropylsilyl, sec-butyldipropylsilyl, tert-butyldipropylsilyl, methyldiisopropylsilyl, ethyldiisopropylsilyl, butyldiisopropylsilyl, sec-butyldiisopropylsilyl, tert-butyldiisopropylsilyl, and the like.
As R 21 ～R 28 As the "tricycloalkylsilane group" in (a) there may be mentioned three hydrogen groups in the silane groups each independently substituted with a cycloalkyl group which may be cited as R 21 ～R 28 The "cycloalkyl" of (3) is a radical as specified. Preferred cycloalkyl groups for substitution are cycloalkyl groups having 5 to 10 carbon atoms, and specific examples thereof include: cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl and bicyclo [1.1.1]Amyl, bicyclo [2.1.0 ]]Amyl, bicyclo [2.1.1]Hexyl, bicyclo [3.1.0]Hexyl, bicyclo [2.2.1]Heptyl, bicyclo [2.2.2]Octyl, adamantyl, decalinyl, decahydroazulenyl, and the like.
Specific examples of the "tricycloalkylsilane group" include tricyclopentylsilane group and tricyclohexylsilane group.
Specific examples of the dialkylcycloalkylsilyl group substituted with two alkyl groups and one cycloalkyl group, and the alkylbicycloalkylsilyl group substituted with one alkyl group and two cycloalkyl groups include silyl groups substituted with groups selected from the specific alkyl groups and cycloalkyl groups.
As R 21 ～R 28 Examples of the "substituted amino group" of the "amino group which may be substituted" include amino groups in which two hydrogens are substituted with an aryl group or a heteroaryl group. The two hydrogen aryl-substituted amino groups are diaryl (the two aryl groups are not bonded to each other or may be bonded via a linking group) substituted amino groups, the two hydrogen heteroaryl-substituted amino groups are diheteroaryl-substituted amino groups, and the two hydrogen aryl-and heteroaryl-substituted amino groups are arylheteroaryl-substituted amino groups. The aryl or heteroaryl groups may be referred to as R 21 ～R 28 The "aryl" or "heteroaryl" groups of (a) are described.
Specific "substituted amino group" includes: diphenylamino, dinaphthylamino, phenylnaphthylamino, bipyridylamino, phenylpyridylamino, naphthylpyridylamino and the like.
As R 21 ～R 28 The "halogen" in (a) may be exemplified by: fluorine, chlorine, bromine, iodine.
As R 21 ～R 28 In the above-described groups, a plurality of groups may be substituted as described above, and examples of the substituent in the above-described case include: alkyl, cycloalkyl, aryl or heteroaryl. The alkyl, cycloalkyl, aryl or heteroaryl groups may be referred to as R 21 ～R 28 The radicals indicated for "alkyl", "cycloalkyl", "aryl" or "heteroaryl".
"N-R as Y 29 R in 29 Is hydrogen or an optionally substituted aryl group, as the aryl group, the one mentioned as R 21 ～R 28 The radicals stated for "aryl" in (a) are, in addition, cited as radicals for R 21 ～R 28 A group as described above.
R 21 ～R 28 The adjacent groups of (a) may be bonded to 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 one of the formulas (a-1) to (a-14) may be substituted with an alkyl group, a cycloalkyl group, an aryl group, a heteroaryl group, an alkoxy group, an aryloxy group, an arylthio group, a trialkylsilyl group, a tricycloalkyl group, a dialkylcycloalkyl silyl group, an alkylbicycloalkyl group, a diaryl group (the two aryl groups may not be bonded to each other or may be bonded via a linking group) substituted amino group, a diheteroaryl substituted amino group, an arylheteroaryl substituted amino group, a halogen group, a hydroxyl group or a cyano group.
[ chemical 77]
The ring formed by bonding adjacent groups to each other may be a hydrocarbon ring, for example, a cyclohexane ring, and the aryl or heteroaryl ring may be R 21 ～R 28 The ring structure described in "aryl" or "heteroaryl" in (a-1) is formed by condensing with one or two benzene rings in the formula (a-1).
The group represented by formula (a) is a group obtained by removing one hydrogen at any position of formula (a), and represents the position. That is, the group represented by the formula (A) may have any one of the positions as a bonding position. For example, R in the structure of formula (A) may be any one of carbon atoms on two benzene rings in the structure of formula (A) 21 ～R 28 Wherein adjacent groups are bonded to each other to form an atom on any ring or "> N-R as Y in the structure of formula (A) 29 R in 29 Or "> N-R 29 N (R) in 29 A bond) is directly bonded. The same applies to any of the groups represented by the formulas (A-1) to (A-14).
Examples of the group represented by the formula (A) include groups represented by any of the formulas (A-1) to (A-14), preferably groups represented by any of the formulas (A-1) to (A-5) and (A-12) to (A-14), more preferably groups represented by any of the formulas (A-1) to (A-4), still more preferably groups represented by any of the formulas (A-1), formula (A-3) and formula (A-4), and particularly preferably groups represented by the formula (A-1).
Examples of the group represented by the formula (a) include the following groups. Wherein Y and x are as defined above.
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[ chemical 79]
In the compound represented by the formula (3-H), the group represented by the formula (A) is preferably a naphthalene ring in the formula (3-X1) or the formula (3-X2), a single bond in the formula (3-X3) and Ar in the formula (3-X3) 3 Any one of the bonding forms.
In addition, all or part of hydrogen in the chemical structure of the anthracene compound represented by the formula (3-H) may be deuterium.
The anthracene compound as a main body may be, for example, a compound represented by the following formula (3-H2).
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Ar in formula (3-H2) c Is an aryl group which may be substituted or a heteroaryl group which may be substituted, R c Is hydrogen, alkyl, or cycloalkyl, ar 11 、Ar 12 、Ar 13 、Ar 14 、Ar 15 、Ar 16 、Ar 17 Ar, ar 18 Each independently is hydrogen, an optionally substituted aryl, an optionally substituted heteroaryl, an optionally substituted diarylamino (the two aryl groups are not bonded to each other, or may be bonded via a linking group)) The compound represented by the formula (3-H2) may have at least one hydrogen substituted with halogen, cyano, or deuterium, or a compound represented by the formula (3-H2), a di-heteroarylamino group which may be substituted (two heteroaryl groups may not be bonded to each other, or may be bonded via a single bond or a linking group), an arylheteroarylamino group which may be substituted (aryl group and heteroaryl group may not be bonded to each other, or may be bonded via a single bond or a linking group), an alkyl group which may be substituted, a cycloalkyl group which may be substituted, an alkenyl group which may be substituted, an alkoxy group which may be substituted, an aryloxy group which may be substituted, an arylthio group which may be substituted, or a silyl group which may be substituted.
"substitutable aryl", "substitutable heteroaryl", "substitutable diarylamino (two aryl groups are not bonded to each other or may be bonded via a linking group)", "substitutable diarylamino (two heteroaryl groups are not bonded to each other or may be bonded via a single bond or a linking group)", "substitutable arylheteroarylamino (aryl and heteroaryl groups are not bonded to each other or may be bonded via a single bond or a linking group)", "substitutable alkyl", "substitutable cycloalkyl", "substitutable alkenyl", "substitutable alkoxy", "substitutable aryloxy", "substitutable arylthio", or "substitutable silane group" in formula (3-H) are the same as those defined in formula (1) above.
The "optionally substituted aryl" is also preferably a group represented by any one of the following formulas (3-H2-X1) to (3-H2-X8).
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In the formulae (3-H2-X1) to (3-H2-X8), the bonding position is represented. Ar in the formulae (3-H2-X1) to (3-H2-X3) 21 、Ar 22 Ar, ar 23 Each independently is hydrogen, phenyl, biphenyl, terphenyl, tetrabiphenyl, naphthyl, phenanthryl, fluorenyl, benzofluorenyl, A group, a triphenylene group, a pyrenyl group, an anthryl group, or a group represented by the formula (A). In the description of the formula (3-H2), the group represented by the formula (A) is the same as that described for the anthracene compound represented by the formula (3-H).
Ar in the formulae (3-H2-X4) to (3-H2-X8) 24 、Ar 25 、Ar 26 、Ar 27 、Ar 28 、Ar 29 Ar, ar 30 Are each independently hydrogen, phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, fluorenyl,A group, a triphenylene group, a pyrenyl group, or a group represented by the formula (A). In addition, any one or two or more hydrogens of the groups represented by the formulas (3-H2-X1) to (3-H2-X8) may be substituted with an alkyl group having 1 to 6 carbon atoms (preferably, a methyl group or a tert-butyl group).
Further, preferable examples of the "optionally substituted aryl" include those selected from the group consisting of phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, fluorenyl, and the like,A terphenyl group (particularly, m-terphenyl-5' -group) substituted with one or more substituents selected from the group consisting of a group represented by the formula (A), a triphenylene group, a pyrenyl group and a group represented by the formula (A).
As the "heteroaryl group which may be substituted", a group represented by the formula (A) may also be mentioned. In addition, specific examples of the "optionally substituted aryl" and the "optionally substituted heteroaryl" include: dibenzofuranyl, naphthobenzofuranyl, phenyl-substituted dibenzofuranyl, and the like.
At least one hydrogen in the compound represented by the formula (3-H2) may be substituted with halogen, cyano, or deuterium. As the "halogen" in this case, there may be mentioned: fluorine, chlorine, bromine, and iodine. Particularly preferred are deuterium-substituted compounds of all hydrogens in the compound represented by the formula (3-H2).
In the formula (3-H2), R c Hydrogen, alkyl, or cycloalkyl, preferably hydrogen, methyl, or tert-butylMore preferably hydrogen.
In the formula (3-H2), ar is preferable 11 ～Ar 18 Is an aryl group which may be substituted or a heteroaryl group which may be substituted. That is, the anthracene compound represented by the formula (3-H2) preferably has a structure in which at least three substituents selected from the group consisting of a substitutable aryl group and a substitutable heteroaryl group are bonded to an anthracycline.
The anthracene compound represented by the formula (3-H2) is more preferably Ar 11 ～Ar 18 Two of which are optionally substituted aryl or optionally substituted heteroaryl, and the other six are hydrogen, optionally substituted alkyl, optionally substituted cycloalkyl, optionally substituted alkenyl or optionally substituted alkoxy. That is, the anthracene compound represented by the formula (3-H2) more preferably has a structure in which three substituents selected from the group consisting of a substitutable aryl group and a substitutable heteroaryl group are bonded to an anthracycline.
The anthracene compound represented by the formula (3-H2) is more preferably Ar 11 ～Ar 18 Any two of which are optionally substituted aryl or optionally substituted heteroaryl, and the other six are hydrogen, methyl, or tert-butyl.
Further, R in the formula (3-H2) is preferable c Is hydrogen and Ar 11 ～Ar 18 Is hydrogen.
The anthracene compound represented by the formula (3-H2) is preferably an anthracene compound represented by the following formula (3-H2-A), formula (3-H2-B), formula (3-H2-C), formula (3-H2-D), or formula (3-H2-E).
[ chemical 82]
Ar in formula (3-H2-A), formula (3-H2-B), formula (3-H2-C), formula (3-H2-D) or formula (3-H2-E) c '、Ar 11 '、Ar 12 '、Ar 13 '、Ar 14 '、Ar 15 '、Ar 17 ', ar 18 ' are each independently phenyl, biphenyl, terphenyl, tetrabiphenyl, naphthyl, phenanthryl, fluorenyl, benzofluorenyl,A group, a triphenylene group, a pyrenyl group, or a group represented by the formula (A), at least one hydrogen of these groups being capable of being substituted with a phenyl group, a biphenyl group, a terphenyl group, a tetrabiphenyl group, a naphthyl group, a phenanthryl group, a fluorenyl group, a benzofluorenyl group, or a benzofluorenyl group>A group, a triphenylene group, a pyrenyl group, or a group represented by formula (A). Here, when the hydrogen of the methylene group in the fluorenyl group and the benzofluorenyl group is substituted with a phenyl group, these phenyl groups may be bonded to each other by a single bond. Not bonded Ar c '、Ar 11 '、Ar 12 '、Ar 13 '、Ar 14 '、Ar 15 '、Ar 17 ', ar 18 Instead of hydrogen, the carbon atom of the' anthracycline may have a methyl or tert-butyl group bonded thereto.
When Ar is c '、Ar 11 '、Ar 12 '、Ar 13 '、Ar 14 '、Ar 15 '、Ar 17 ', ar 18 When' is a substituted or unsubstituted phenyl group or a substituted or unsubstituted naphthyl group, it is preferably a group represented by any one of the above formulas (3-H2-X1) to (3-H2-X7).
Ar c '、Ar 11 '、Ar 12 '、Ar 13 '、Ar 14 '、Ar 15 '、Ar 17 ', ar 18 More preferably, each independently is a phenyl group, a biphenyl group (particularly biphenyl-2-yl or biphenyl-4-yl), a terphenyl group (particularly m-terphenyl-5' -yl), a naphthyl group, a phenanthryl group, a fluorenyl group, or a group represented by any of the formulas (A-1) to (A-4), in which case at least one hydrogen of these groups may be substituted with a phenyl group, a biphenyl group, a naphthyl group, a phenanthryl group, a fluorenyl group, or a group represented by any of the formulas (A-1) to (A-4).
In addition, at least one hydrogen in the compound represented by the formula (3-H2-A), the formula (3-H2-B), the formula (3-H2-C), the formula (3-H2-D), or the formula (3-H2-E) may be substituted with halogen, cyano, or deuterium. The form is preferably deuterated, and more preferably a form in which all of the anthracyclines are deuterated or a form in which all of the hydrogen atoms are deuterated.
As a particularly preferred anthracene compound represented by the formula (3-H2), an anthracene compound represented by the following formula (3-H2-Aa) is exemplified.
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Ar in formula (3-H2-Aa) c '、Ar 14 ', ar 15 ' are each independently phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, fluorenyl, benzofluorenyl, A group, a triphenylene group, a pyrenyl group, or a group represented by any one of the above-mentioned formulas (A-1) to (A-11), at least one hydrogen of these groups being capable of being substituted with a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, a phenanthryl group, a fluorenyl group, a benzofluorenyl group, or a combination thereof>A group, a triphenylene group, a pyrenyl group, or a group represented by any one of the formulae (A-1) to (A-11). Here, when the hydrogen of the methylene group in the fluorenyl group and the benzofluorenyl group is substituted with a phenyl group, these phenyl groups may be bonded to each other by a single bond. In addition, ar is not bonded c '、Ar 14 ', ar 15 The carbon atoms of the' anthracycline may be substituted with methyl or tert-butyl groups instead of hydrogen. At least one hydrogen in the compound represented by the formula (3-H2-Aa) may be substituted with halogen or cyano, and at least one hydrogen in the compound represented by the formula (3-H2-Aa) may be substituted with deuterium.
Ar in formula (3-H2-Aa) c '、Ar 14 ', ar 15 ' is preferably a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, a phenanthryl group, a fluorenyl group, or a group represented by any one of the above formulas (A-1) to (A-4), at least one hydrogen of which may be substituted with a phenyl group, a naphthyl group, a phenanthryl group, a fluorenyl group, or a group represented by any one of the formulas (A-1) to (A-4), independently of each other.
Represented by the formula (3-H2-Aa)Of the compounds, at least a carbon bonded to the 10-position of the anthracycline is preferred (Ar c The' bonded carbon is set to the 9-position) hydrogen is substituted with deuterium. That is, the compound represented by the formula (3-H2-Aa) is preferably a compound represented by the following formula (3-H2-Ab). In the formula (3-H2-Ab), D is deuterium, ar c '、Ar 14 ', ar 15 ' the definition is the same as in the formula (3-H2-Aa). D in the formula (3-H2-Ab) represents that at least the above-mentioned position is deuterium, and any one or more other hydrogens in the formula (3-H2-Ab) may be simultaneously deuterium, and it is preferable that all hydrogens in the formula (3-H2-Ab) are deuterium.
[ chemical 84]
Specific examples of the anthracene compound include compounds represented by the formulas (3-131-Y) to (3-182-Y), compounds represented by the formulas (3-183-N), formulas (3-184-Y) to (3-284-Y), and formulas (3-500) to (3-557), and formulas (3-600) to (3-605), and compounds represented by the formulas (3-606-Y) to (3-626-Y). The hydrogen atoms in these formulae may be partially or completely substituted with deuterium, but examples of particularly preferred forms of deuterium substitution are listed. Wherein Y can be-O-, -S-, > N-R 29 (R 29 Is as defined above) or > C (-R) 30 ) 2 (R 30 Is any one of attachable aryl or alkyl), R 29 For example phenyl, R 30 For example methyl. In the case of formula numbers, for example, in the case where Y is O, the formula (3-131-Y) is set to the formula (3-131-O), and in the case where Y is-S-or > N-R 29 In the case of (C), the formula (3-131-S) or the formula (3-131-N) is set, respectively.
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In the formula, D is deuterium.
Of these compounds, preferred are formula (3-131-Y) to formula (3-134-Y), formula (3-138-Y), formula (3-140-Y) to formula (3-143-Y), formula (3-150-Y), formula (3-153-Y) to formula (3-156-Y), formula (3-166-Y), formula (3-168-Y), formula (3-173-Y), formula (3-177-Y), formula (3-180-Y) to formula (3-183-N), formula (3-185-Y), formula (3-190-Y), formula (3-223-Y), formula (3-241-Y), formula (3-250-Y), formula (3-252-Y) to formula (3-254-Y), formula (3-270-Y) to formula (3-284-Y), formula (3-501), formula (3-507), formula (3-508), formula (3-509), formula (3-513), formula (3-514), formula (3-519), the compounds represented by the formula (3-538) to the formula (3-547) or the formula (3-600) to the formula (3-605) and the formula (3-606-Y) to the formula (3-626-Y). In addition, Y is preferably-O-or > N-R 29 More preferably-O-. In addition, deuterium substituted forms are also preferred.
The anthracene compound may be one having a reactive group at a desired position of an anthracene skeleton as a starting material, and is represented by the formula (3-H) at X, ar 4 And a compound having a reactive group on a part of the structure such as the structure of formula (A) as a starting material, and is produced by using bell wood coupling, root-bank coupling, and other known coupling reactions. Examples of the reactive group of the reactive compound include halogen and boric acid. As a specific manufacturing method, reference is made, for example, to paragraph [0089 ] of International publication No. 2014/141725]Paragraph [0175 ]]Is a synthesis method of the above.
< fluorene Compound >)
The compound represented by the formula (4-H) basically functions as a main body.
[ 105]
In the formula (4-H),
R 1 to R 10 Are each independently hydrogen, arylHeteroaryl (which may be bonded to the fluorene skeleton in formula (4-H) via a linking group), diarylamino (two aryl groups may not be bonded to each other or may be bonded via a linking group), diheteroarylamino (two heteroaryl groups may not be bonded to each other or may be bonded via a single bond or a linking group), arylheteroarylamino (aryl and heteroaryl groups may not be bonded to each other or may be bonded via a single bond or a linking group), alkyl, cycloalkyl, alkenyl, alkoxy or aryloxy groups, at least one hydrogen of which may be substituted with aryl, heteroaryl, alkyl or cycloalkyl groups, and R 1 And R is R 2 、R 2 And R is R 3 、R 3 And R is R 4 、R 5 And R is R 6 、R 6 And R is R 7 、R 7 And R is R 8 Or R is 9 And R is R 10 At least one hydrogen in the formed ring may be substituted with an aryl group, a heteroaryl group (the heteroaryl group may be bonded to the formed ring via a linking group), a diarylamino group (the two aryl groups may not be bonded to each other or may be bonded via a linking group), a diheteroarylamino group (the two heteroaryl groups may not be bonded to each other or may be bonded via a single bond or a linking group), an arylheteroarylamino group (the aryl group and the heteroaryl group may not be bonded to each other or may be bonded via a single bond or a linking group), an alkyl group, a cycloalkyl group, an alkenyl group, an alkoxy group, or an aryloxy group, at least one hydrogen in these may be substituted with an aryl group, a heteroaryl group, an alkyl group, or a cycloalkyl group, and at least one hydrogen in the compound represented by the formula (4-H) may be substituted with halogen, cyano group, or deuterium.
Details of each group in the definition of the formula (4-H) can be cited as descriptions in the polycyclic aromatic compound of the formula (1).
As R 1 To R 10 Examples of the alkenyl group in (a) include alkenyl groups having 2 to 30 carbon atoms, preferably alkenyl groups having 2 to 20 carbon atoms, more preferably alkenyl groups having 2 to 10 carbon atoms, still more preferably alkenyl groups having 2 to 6 carbon atoms, and particularly preferably alkenyl groups having 2 to 4 carbon atoms. Preferred alkenyl groups 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 Alkenyl, or 5-hexenyl.
Further, specific examples of the heteroaryl group include monovalent groups represented by removing any one hydrogen atom from the compounds of the following formulae (4-Ar 1), (4-Ar 2), (4-Ar 3), (4-Ar 4) and (4-Ar 5).
[ 106]
In the formulae (4-Ar 1) to (4-Ar 5), Y 1 Each independently O, S or N-R, R is phenyl, biphenyl, naphthyl, anthracenyl or hydrogen, at least one hydrogen in the structures of formulae (4-Ar 1) to (4-Ar 5) being optionally substituted by phenyl, biphenyl, naphthyl, anthracenyl, phenanthryl, methyl, ethyl, propyl or butyl.
These heteroaryl groups may be bonded to the fluorene skeleton in formula (4-H) via a linking group. That is, the fluorene skeleton in the formula (4-H) and the heteroaryl group may be bonded not only directly but also via a linking group. Examples of the linking group include: phenylene, biphenylene, naphthylene, anthracenylene, methylene, ethylene, -OCH 2 CH 2 -、-CH 2 CH 2 O-, or-OCH 2 CH 2 O-, and the like.
In addition, R in formula (4-H) 1 And R is R 2 、R 2 And R is R 3 、R 3 And R is R 4 、R 5 And R is R 6 、R 6 And R is R 7 Or R is 7 And R is R 8 Can be independently bonded to form condensed rings, R 9 And R is R 10 Can be bonded to form a spiro ring. From R 1 To R 8 The condensed ring formed is a ring condensed on the benzene ring in the formula (4-H), and is an aliphatic ring or an aromatic ring. Aromatic rings are preferable, and examples of the structure containing the benzene ring in the formula (4-H) include naphthalene rings and phenanthrene rings. From R 9 And R is R 10 The spiro ring formed is a ring in which a spiro bond is made to the 5-membered ring in the formula (4-H), and is an aliphatic ring or an aromatic ring. Aromatic rings are preferable, and fluorene rings and the like are exemplified.
(4-H) The compound represented by the following formula (4-H-1), formula (4-H-2) or formula (4-H-3) is preferably a compound represented by the formula (4-H), and R in the formula (4-H), respectively 1 And R is R 2 Compounds condensed with benzene rings formed by bonding, R in formula (4-H) 3 And R is R 4 Compounds condensed with benzene rings formed by bonding, R in formula (4-H) 1 To R 8 Any of which are not bonded.
[ chemical 107]
R in the formula (4-H-1), the formula (4-H-2) and the formula (4-H-3) 1 To R 10 Definition of (A) corresponds to R in the formula (4-H) 1 To R 10 Similarly, R in formula (4-H-1) and formula (4-H-2) 11 To R 14 Also defined as R in formula (4-H) 1 To R 10 The same applies.
The compound represented by the formula (4-H) is further preferably a compound represented by the following formula (4-H-1A), formula (4-H-2A) or formula (4-H-3A), and R in the formula (4-H-1), formula (4-H-2) or formula (4-H-3), respectively 9 And R is R 10 A compound bonded to form a spiro-fluorene ring.
[ chemical 108]
R in the formula (4-H-1A), the formula (4-H-2A) and the formula (4-H-3A) 2 To R 7 R is defined as corresponding to formula (4-1), formula (4-2) and formula (4-3) 2 To R 7 Similarly, R in formula (4-H-1A) and formula (4-H-2A) 11 To R 14 Is also defined as R in formula (4-1) and formula (4-2) 11 To R 14 The same applies.
In addition, all or part of hydrogen in the compound represented by the formula (4-H) may be substituted with halogen, cyano or deuterium.
More specific examples of the fluorene compound as the main body of the present invention include compounds represented by the following structural formulas. In addition, "Me" represents methyl.
[ 109]
< dibenzoCompound >
Dibenzo as hostThe compound is, for example, a compound represented by the following formula (5-H).
[ 110]
In the formula (5-H), R 1 To R 16 Each independently hydrogen, aryl, heteroaryl (the heteroaryl may be linked to the dibenzo of formula (5-H) via a linker)Skeleton bond), diarylamino (two aryl groups are not bonded to each other, or may be bonded via a linking group), diheteroarylamino (two heteroaryl groups are not bonded to each other, or may be bonded via a single bond or a linking group), arylheteroarylamino (aryl and heteroaryl groups are not bonded to each other, or may be bonded via a single bond or a linking group), alkyl, cycloalkyl, alkenyl, alkoxy, or aryloxy groups, at least one of which hydrogen may be substituted with aryl, heteroaryl, alkyl, or cycloalkyl groups, and, in addition, R 1 To R 16 Wherein adjacent groups may be bonded to each other to form a condensed ring, at least one hydrogen in the formed ring may be bonded to the formed ring via an aryl group, a heteroaryl group (which may be bonded to the formed ring via a linking group), a diarylamino group (the two aryl groups may not be bonded to each other, or may be bonded to each other via a linking group), a diheteroarylamino group (the two heteroaryl groups may not be bonded to each otherOr may be bonded via a single bond or a linking group), an arylheteroarylamino group (an aryl group, a heteroaryl group may not be bonded to each other, or may be bonded via a single bond or a linking group), an alkyl group, a cycloalkyl group, an alkenyl group, an alkoxy group, or an aryloxy group, at least one hydrogen of these may be substituted with an aryl group, a heteroaryl group, an alkyl group, or a cycloalkyl group, and at least one hydrogen in the compound represented by the formula (5-H) may be substituted with halogen, cyano group, or deuterium.
Details of each group in the definition of the formula (5-H) can be cited as descriptions in the polycyclic aromatic compound of the formula (1).
Examples of the alkenyl group in the definition of the formula (5-H) include alkenyl groups having 2 to 30 carbon atoms, preferably alkenyl groups having 2 to 20 carbon atoms, more preferably alkenyl groups having 2 to 10 carbon atoms, still more preferably alkenyl groups having 2 to 6 carbon atoms, and particularly preferably alkenyl groups having 2 to 4 carbon atoms. Preferred alkenyl groups 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.
Further, specific examples of the heteroaryl group include monovalent groups represented by removing any one hydrogen atom from the compounds of the following formulae (5-Ar 1), (5-Ar 2), (5-Ar 3), (5-Ar 4) and (5-Ar 5).
[ chemical 111]
In the formulae (5-Ar 1) to (5-Ar 5), Y 1 Each independently O, S or N-R, R is phenyl, biphenyl, naphthyl, anthracenyl or hydrogen, at least one hydrogen in the structures of formulae (5-Ar 1) to (5-Ar 5) being optionally substituted by phenyl, biphenyl, naphthyl, anthracenyl, phenanthryl, methyl, ethyl, propyl or butyl.
These heteroaryl groups may be bonded to the dibenzo of formula (5-H) via a linking groupAnd (5) skeleton bonding. Namely, two in the formula (5-H)Benzo->The backbone and the heteroaryl group may be bonded not only directly but also via a linking group between these. Examples of the linking group include: phenylene, biphenylene, naphthylene, anthracenylene, methylene, ethylene, -OCH 2 CH 2 -、-CH 2 CH 2 O-, or-OCH 2 CH 2 O-, and the like.
The compound represented by the formula (5-H) is preferably R 1 、R 4 、R 5 、R 8 、R 9 、R 12 、R 13 R is R 16 Is hydrogen. In said case, R in formula (5-H) 2 、R 3 、R 6 、R 7 、R 10 、R 11 、R 14 R is R 15 Preferably, each independently is hydrogen, phenyl, biphenyl, naphthyl, anthryl, phenanthryl, a monovalent group having a structure of formula (5-Ar 1), formula (5-Ar 2), formula (5-Ar 3), formula (5-Ar 4) or formula (5-Ar 5) (the monovalent group having the structure may be a monovalent group having a structure selected from the group consisting of phenylene, biphenylene, naphthylene, anthrylene, methylene, ethylene and-OCH) 2 CH 2 -、-CH 2 CH 2 O-, or-OCH 2 CH 2 O-with dibenzo of formula (5-H)Backbone linkages), methyl, ethyl, propyl, or butyl.
The compound represented by the formula (5-H) 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 R is R 16 Is hydrogen. In said case, R in formula (5-H) 3 、R 6 、R 11 R is R 14 At least one (preferably one or two, more preferably one) of (a) is a single bond, via phenylene, biphenylene, naphthylene, anthracenylene, methylene, ethylene, -OCH 2 CH 2 -、-CH 2 CH 2 O-, or-OCH 2 CH 2 The monovalent group of O-having the structure of formula (5-Ar 1), formula (5-Ar 2), formula (5-Ar 3), formula (5-Ar 4), or formula (5-Ar 5), at least one of which is other than (i.e., other than the position where the monovalent group having the structure is substituted) hydrogen, phenyl, biphenyl, naphthyl, anthracenyl, methyl, ethyl, propyl, or butyl, at least one of which hydrogen may be substituted with phenyl, biphenyl, naphthyl, anthracenyl, methyl, ethyl, propyl, or butyl.
In addition, R in formula (5-H) 2 、R 3 、R 6 、R 7 、R 10 、R 11 、R 14 R is R 15 In the case where a monovalent group having structures represented by the formulas (5-Ar 1) to (5-Ar 5) is selected, at least one hydrogen in the structures may be bonded to R in the formula (5-H) 1 To R 16 Is bonded to form a single bond.
With respect to dibenzo as the subject of the present invention More specific examples of the compound include compounds represented by the following structural formulae.
[ chemical 112]
[ 113]
The material for a light-emitting layer (host material and dopant material) may be used as a polymer compound obtained by polymerizing a reactive compound substituted with a reactive substituent in the material for a light-emitting layer (host material and dopant material) as a monomer, or as a polymer crosslinked body thereof, or as a polymer compound obtained by reacting a main chain polymer with the reactive compound. As the reactive substituent in this case, description in the polycyclic aromatic compound represented by the formula (1) can be cited.
< luminescent layer comprising auxiliary dopant and emissive dopant >)
The light-emitting layer in the organic electroluminescent element may include a host compound as a first component, an auxiliary dopant (compound) as a second component, and an emission dopant (compound) as a third component. The polycyclic aromatic compounds of the present invention are also preferably used as emissive dopants. As the auxiliary dopant (compound), a thermally active type delayed phosphor may be used.
In the following description, an organic electroluminescent element using a thermally active delayed fluorescent substance as an auxiliary dopant is sometimes referred to as a "TAF element" (thermally active delayed fluorescence (thermally activated delayed fluorescence, TADF) auxiliary fluorescence (Assisting Fluorescence) element). The "host compound" in the TAF element is a compound having a higher minimum excited singlet energy level obtained from a shoulder at the peak short wavelength side of the fluorescence spectrum than the thermally active type delayed fluorescent material as the second component and the emission dopant as the third component.
The term "thermally active delayed fluorescent material" refers to a compound capable of emitting delayed fluorescence by absorbing heat energy, causing intersystem crossing from a lowest excited triplet state to a lowest excited singlet state, and emitting and deactivating the lowest excited singlet state. Among them, the term "thermally active delayed fluorescence" also includes a case where a higher-order triplet state is passed through the excitation process from the lowest excited triplet state to the lowest excited singlet state. Examples thereof include papers (Nature communication (NATURE COMMUNICATIONS), 7:13680, digital object identifier (digital object identifier, DOI): 10.1038/ncoms 13680) published by Meng Keman (Monkman) et al of university Du Lun (Durham), papers (Housokai et al), papers (Science Advances, sci.Adv.) 2017, 3:e 1603282) published by Zygen et al of Kyoto university (Science report (Scientific Reports), papers (7:4810, DOI:10.1038/s 41598-017-05007-7) published by Zygen et al of Kyoto university (Japanese society of chemical society, no. 2I 4-15), and organic light emitting devices using diazanaphthyridine (diazaboronan) DABANAPBANADE as a light emitting mechanism in Kyoto university. In the present invention, regarding a sample containing a target compound, the target compound is determined to be a "thermally active delayed phosphor" based on the observation of a slow fluorescent component when the fluorescence lifetime is measured at 300K. Here, the slow fluorescence component means a component having a fluorescence lifetime of 0.1 μsec or more. The fluorescence lifetime can be measured, for example, using a fluorescence lifetime measuring device (C11367-01, manufactured by Binsonite photon (Hamamatsu Photonics)).
The polycyclic aromatic compound of the present invention can function as an emission dopant, and the "thermally active type delayed fluorescent material" can function as an auxiliary dopant for assisting the emission of the polycyclic aromatic compound of the present invention.
Fig. 2 shows an energy level diagram of a light-emitting layer of a TAF element using a general fluorescent dopant for an Emission Dopant (ED). In the figure, the energy level of the ground state of the main body is E (1, G), the lowest excited singlet energy level of the main body obtained from the shoulder peak on the short wavelength side of the fluorescence spectrum is E (1, S, sh), the lowest excited triplet energy level of the main body obtained from the shoulder peak on the short wavelength side of the phosphorescence spectrum is E (1, T, sh), the energy level of the ground state of the auxiliary dopant as the second component is E (2, G), the lowest excited singlet energy level of the auxiliary dopant as the second component obtained from the shoulder peak on the short wavelength side of the fluorescence spectrum is E (2, S, sh), the lowest excited singlet energy level of the auxiliary dopant as the second component obtained from the shoulder peak on the short wavelength side of the phosphorescence spectrum is E (2, T, sh), the energy level of the ground state of the emission dopant as the third component is E (3, G), the lowest excited singlet energy level of the auxiliary dopant as the short wavelength side of the fluorescence spectrum is E (3, S, sh), and the electron-transferred energy level of the auxiliary dopant as the third component is E (3, sh). In the TAF element, in the case where a general fluorescent dopant is used as the Emission Dopant (ED), the energy Up-converted (Up Conversion) from the auxiliary dopant is converted to the lowest excited singlet energy level E (3, s, sh) of the emission dopant and light emission is performed. However, a portion of the lowest excited triplet level E (2, t, sh) on the auxiliary dopant shifts to the lowest excited triplet level E (3, t, sh) of the emissive dopant, or intersystem crossing from the lowest excited singlet level E (3, s, sh) to the lowest excited triplet level E (3, t, sh) occurs on the emissive dopant, followed by thermal deactivation to the ground state E (3, g). Because of the path, a portion of the energy is not used to emit light, and a waste of energy occurs.
In contrast, in the organic electroluminescent element according to the present embodiment, the energy efficiency of the self-supporting dopant moving to the emissive dopant can be used to emit light well, and thus high light emission efficiency can be achieved. This is presumably caused by the following light emission mechanism.
Fig. 3 shows a preferable energy relationship in the organic electroluminescent element of the present embodiment. In the organic electroluminescent element of the present embodiment, the compound having a boron atom as an emission dopant has a high minimum excited triplet level E (3, t, sh). Therefore, in the case where the excited singlet energy up-converted by the auxiliary dopant is inter-spanned to the lowest excited triplet energy level E (3, t, sh), for example, by the emission dopant, the lowest excited triplet energy level E (2, t, sh) on the auxiliary dopant (thermally active type delayed phosphor) is up-converted or recovered also on the emission dopant. Therefore, the generated excitation energy can be used for light emission without waste. In addition, it is expected that by assigning the functions of up-conversion and luminescence to two molecules with each function highlighted, the retention time of high energy is reduced and the burden on the compound is reduced.
In this embodiment, as the host compound, a known compound may be used, and examples thereof include a compound having at least one of a carbazole ring and a furan ring, and among them, a compound having at least one of a furan group and a carbazole group and at least one of an arylene group and a heteroarylene group bonded thereto is preferably used. Specific examples include mCP and mCBP.
The lowest excited triplet level E (1, t, sh) of the host compound, which is obtained from the shoulder on the short wavelength side of the peak of the phosphorescence spectrum, is preferably higher than the lowest excited triplet levels E (2, t, sh), E (3, t, sh) of the emission dopant or auxiliary dopant having the highest lowest excited triplet level in the light-emitting layer, and specifically, the lowest excited triplet level E (1, t, sh) of the host compound is preferably 0.01eV or more, more preferably 0.03eV or more, and even more preferably 0.1eV or more, than E (2, t, sh), E (3, t, sh), from the viewpoint of promoting but not blocking the generation of TADF in the light-emitting layer. In addition, compounds having TADF activity may also be used as host compounds.
For example, the host compound may be a compound represented by any one of the above formulas (H1), (H2) and (H3).
< thermally active delayed phosphor (auxiliary dopant) >)
The thermally active type delayed phosphor (TADF compound) used in the TAF element is preferably a donor-acceptor type thermally active type delayed phosphor (D-a type TADF compound) as follows: it is designed to use electron-donating substituents called donors and electron-accepting substituents called acceptors to localize the highest occupied molecular orbital (Highest Occupied Molecular Orbital, HOMO) and the lowest unoccupied molecular orbital (Lowest Unoccupied Molecular Orbital, LUMO) within the molecule to produce an efficient reverse intersystem crossing (reverse intersystem crossing). In the present specification, the "electron donating substituent" (donor) means a substituent and a partial structure which are locally present in HOMO in the thermally active type delayed fluorescent substance molecule, and the "electron accepting substituent" (acceptor) means a substituent and a partial structure which are locally present in LUMO in the thermally active type delayed fluorescent substance molecule.
In general, thermally active delayed phosphors using donors or acceptors have large spin-orbit coupling (SOC: spin Orbit Coupling) and small exchange interactions of HOMO and LUMO, and small ΔE (ST), for structural reasons, thus achieving very fast reverse intersystem crossing speeds. On the other hand, a thermally active type delayed fluorescent material using a donor or an acceptor has a large structural relaxation in an excited state (a stable structure in a certain molecule is different between a ground state and an excited state, and therefore if a transition from the ground state to the excited state occurs by an external stimulus, the structure is changed to a stable structure in the excited state thereafter), and thus a broad emission spectrum is provided, and therefore when used as a light-emitting material, there is a possibility that color purity may be lowered.
As the thermally active delayed fluorescence material in the TAF element, for example, a compound in which a donor and an acceptor are bonded directly or via a spacer can be used. Examples of electron donating groups (donor structures) and electron accepting groups (acceptor structures) used in the thermally active delayed fluorescence of the present invention include those described in "materials chemistry (Chemistry of Materials)", 2017,29,1946-1963. Examples of the structure of the donor include: carbazole, dimethylcarbazole, di-tert-butylcarbazole, dimethoxycarbazole, tetramethylcarbazole, benzofluorocarbazole, benzothiophenocarbazole, phenylindoliocarbazole, phenylbicarbazole, bicarbazole, triphenylcarbazolylamine, tetraphenylcarbazolyldiamine, phenoxazine, dihydrophenazine, phenothiazine, dimethyldihydroacridine, diphenylamine, bis (tert-butylphenyl) amine, N1- (4- (diphenylamino) phenyl) -N4, N4-diphenyl benzene-1, 4-diamine, dimethyltetraphenyldihydroacridinediamine, tetramethyl-dihydro-indenyl acridine, diphenyl-dihydrodibenzoazepine, and the like. Examples of the acceptor structure include: sulfonyldiphenyl, benzophenone, phenylenedi (phenylketone), benzonitrile, isonicotinic nitrile, phthalonitrile, isophthalonitrile, p-phthalonitrile, benzonitrile, triazole, oxazole, thiadiazole, benzothiazole, benzobis (thiazole), benzoxazole, benzobis (oxazole), quinoline, benzimidazole, dibenzoquinoxaline, heptaazaphenalene, thioxanthone dioxide, dimethyl anthrone, anthracenedione, 5H-cyclopenta [1,2-b:5,4-b' ] bipyridines, fluorenedicarbonitriles, triphenyltriazines, pyrazinedicarbonitriles, pyrimidines, phenylpyrimidines, methylpyrimidines, pyridyldinitriles, dibenzoquinoxalinedicarbonitriles, bis (phenylsulfonyl) benzenes, dimethylthioxanthene dioxides, thianthrene tetraoxides, tris (dimethylphenyl) boranes and the like. In particular, the thermally active fluorescence-delaying compound in the TAF element is preferably a compound having at least one selected from carbazole, phenoxazine, acridine, triazine, pyrimidine, pyrazine, thioxanthene, benzonitrile, phthalonitrile, isophthalonitrile, diphenyl sulfone, triazole, oxadiazole, thiadiazole, and benzophenone as a partial structure.
The compound used as the second component of the light-emitting layer in the TAF element is a thermally active type delayed phosphor, and is preferably a compound whose light emission spectrum overlaps at least a part of the absorption peak of the emission dopant. Hereinafter, a compound that can be used as the second component (thermally active type delayed phosphor) of the light-emitting layer in the TAF element is exemplified. Among them, compounds useful as thermally active type delayed phosphors in TAF elements are not to be construed restrictively by the following exemplified compounds. In the following formula, wavy lines indicate bonding positions.
[ 114]
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[ 115]
[ 116]
[ chemical 117]
[ chemical 118]
Further, as the thermally active type delayed phosphor, a compound represented by any one of the following formulas (AD 1), (AD 2) and (AD 3) may be used.
[ 119]
In the formula (AD 1), the formula (AD 2) and the formula (AD 3), M is independently a single bond, -O-, > N-Ar or > CAr 2 From the viewpoints of the depth of HOMO of the partial structure formed and the heights of the lowest excited singlet energy level and the lowest excited triplet energy level, single bond, -O-, or > N-Ar is preferable. J is a spacer structure separating the donor partial structure from the acceptor partial structure, and is independently an arylene group having 6 to 18 carbon atoms, and is preferably an arylene group having 6 to 12 carbon atoms from the viewpoint of the size of the conjugation exuded from the donor partial structure and the acceptor partial structure. More specifically, it is possible to list: phenylene, methylparaben and dimethylparaben. Q is independently =c (-H) -or =n-, and is preferably =n-from the viewpoints of the shallowness of LUMO of the partial structure formed and the heights of the lowest excited singlet energy level and the lowest excited triplet energy level. Ar is independently hydrogen, an aryl group having 6 to 24 carbon atoms, a heteroaryl group having 2 to 24 carbon atoms, an alkyl group having 1 to 12 carbon atoms or a cycloalkyl group having 3 to 18 carbon atoms, and is preferably hydrogen, an aryl group having 6 to 12 carbon atoms, a heteroaryl group having 2 to 14 carbon atoms, an alkyl group having 1 to 4 carbon atoms or a cycloalkyl group having 6 to 10 carbon atoms, more preferably hydrogen, phenyl, tolyl, xylyl, mesityl, biphenyl, pyridyl, bipyridyl, triazinyl, carbazolyl, dimethylcarbazolyl, di-t-butylcarbazolyl, benzimidazolyl or phenylbenzimidazolyl, and further preferably hydrogen, phenyl or carbazolyl, from the viewpoints of the depth of the formed partial structure HOMO and the height of the lowest excited singlet energy level and the lowest excited triplet energy level. m is 1 or 2.n is an integer of (6-m) or less, in view of steric hindrance In terms of points, an integer of 4 to (6-m) is preferable. Further, at least one hydrogen in the compounds represented by the formulas may be substituted with halogen or deuterium.
More specifically, the compounds used as the second component of this form are preferably 4CzBN, 4CzBN-Ph, 5CzBN, 3Cz2DPhCzBN, 4CzIPN, 2PXZ-TAZ, cz-TRZ3, BDPCC-TPTA, MA-TA, PA-TA, FA-TA, PXZ-TRZ, DMAC-TRZ, BCzT, DCzTrz, DDCzTRz, spiro AC-TRZ, ac-HPM, ac-PPM, ac-MPM, TCzTrz, tmCzTrz and DCzmCzTrz.
The compound used as the second component of the present embodiment may be a donor-acceptor type TADF compound represented by D-a in which one donor D is bonded directly to one acceptor a or bonded via a linking group, and a compound having a structure represented by the following formula (DAD 1) in which a plurality of donors D are bonded directly to one acceptor a or bonded via a linking group is preferable because it is a compound having more excellent characteristics of an organic electroluminescent element.
(D 1 -L 1 )n-A 1 (DAD1)
The formula (DAD 1) includes a compound represented by the following formula (DAD 2).
D 2 -L 2 -A 2 -L 3 -D 3 (DAD2)
In the formula (DAD 1) and the formula (DAD 2), D 1 、D 2 D (D) 3 Each independently represents an donor group. As the Shi Tixing base, the donor-type structure can be used. A is that 1 A is a 2 Each independently represents a acceptor group. As the acceptor group, the acceptor structure can be used. L (L) 1 、L 2 L and L 3 Each independently represents a single bond or a conjugated linking group. The conjugated linking group is a spacer structure separating the donor group and the acceptor group, and is preferably an arylene group having 6 to 18 carbon atoms, more preferably an arylene group having 6 to 12 carbon atoms. L (L) 1 、L 2 L and L 3 Further, it is preferably independently phenylene, methylphenyl or dimethylphenylene. N in the formula (DAD 1) is 2 or more and represents A 1 An integer of not more than the maximum number of substitutions can be made. n can be selected, for example, in the range from 2 to 10, or in the range from 2 to 6. When n is 2, is of the formula (DAD 2)A compound represented by the formula (I). n numbers D 1 Can be the same or different, n L 1 May be the same or different. As preferable specific examples of the compounds represented by the formula (DAD 1) and the formula (DAD 2), 2PXZ-TAZ or the following compounds are given, and the second component employable in the invention is not limited to these compounds.
[ 120]
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In this embodiment, the light-emitting layer may be a single layer or may include a plurality of layers. The host compound, the thermally active delayed fluorescence and the polycyclic aromatic compound of the present invention may be contained in the same layer, or may contain at least one component in multiple layers. The host compound, the thermally active type delayed fluorescent material, and the polycyclic aromatic compound of the present invention included in the light-emitting layer may be one kind or a combination of plural kinds, respectively. The auxiliary dopant and the emission dopant may be included in the bulk compound as a host or may be included in a portion of the bulk compound as a host. The light emitting layer doped with the auxiliary dopant and the emission dopant may be formed by: a method of forming a film of a host compound, an auxiliary dopant, and an emissive dopant by a ternary co-evaporation process; a method of vapor deposition simultaneously after pre-mixing the host compound, the auxiliary dopant and the emission dopant; a wet film forming method of coating a composition (paint) for forming a light-emitting layer prepared by dissolving a host compound, an auxiliary dopant and an emission dopant in an organic solvent.
The amount of the host compound to be used varies depending on the type of the host compound, and is determined by blending the characteristics of the host compound. The amount of the host compound to be used is preferably 40 to 99.999% by mass, more preferably 50 to 99.99% by mass, and still more preferably 60 to 99.9% by mass, based on the total amount of the material for the light-emitting layer. If the range is within this range, efficient charge transport and efficient energy transfer to the dopant are preferable, for example.
The amount of the auxiliary dopant (thermally active type retarder phosphor) to be used varies depending on the type of the auxiliary dopant, and is determined by blending the characteristics of the auxiliary dopant. The amount of the auxiliary dopant to be used is preferably 1 to 60% by mass, more preferably 2 to 50% by mass, and still more preferably 5 to 30% by mass, based on the total amount of the material for the light-emitting layer. If the range is within this range, for example, it is preferable to move the energy efficiently to the emissive dopant.
The amount of the emission dopant (compound having boron atom) to be used varies depending on the kind of the emission dopant, and is determined by matching the characteristics of the emission dopant. The amount of the emission dopant to be used is preferably 0.001 to 30% by mass, more preferably 0.01 to 20% by mass, and still more preferably 0.1 to 10% by mass, based on the entire material for the light-emitting layer. If the concentration is within the above range, it is preferable in terms of preventing concentration quenching, for example.
In terms of preventing the concentration quenching phenomenon, it is preferable that the amount of the emission dopant used is a low concentration. In terms of efficiency of the thermally active delayed fluorescence mechanism, it is preferable that the auxiliary dopant is used in a high concentration. Further, in terms of efficiency of the thermally active delayed fluorescence mechanism of the auxiliary dopant, it is preferable that the amount of the emission dopant used is low in comparison with the amount of the auxiliary dopant used.
2-1-3 substrate in organic electroluminescent element
The substrate 101 is a support for the organic EL element 100, and quartz, glass, metal, plastic, or the like is generally 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 foil, a plastic film, a plastic sheet, or the like can be used. Among them, glass plates and transparent synthetic resin plates such as polyester, polymethacrylate, polycarbonate, polysulfone and the like are preferable. In the case of a glass substrate, soda lime glass, alkali-free glass, or the like may be used, and the thickness may be a thickness sufficient to maintain mechanical strength, and thus, for example, 0.2mm or more may be used. The upper limit of the thickness is, for example, 2mm or lessPreferably 1mm or less. As for the material of the glass, since the eluted ions from the glass are preferably small, alkali-free glass is preferable, and SiO is applied 2 Soda lime glass of the barrier coat (Barrier coat) and the like are also commercially available, and therefore the soda lime glass can be used. In order to improve the gas barrier properties, a gas barrier film such as a fine silicon oxide film may be provided on at least one surface of the substrate 101, and particularly, in the case of using a synthetic resin plate, film or sheet having low gas barrier properties as the substrate 101, it is preferable to provide a gas barrier film.
2-1-4 anode in organic electroluminescent element
The anode 102 plays a role of injecting holes into the light-emitting layer 105. In the case where any one of the hole injection layer 103 and the hole transport layer 104 is provided between the anode 102 and the light-emitting layer 105, holes are injected into the light-emitting layer 105 through these layers.
As a material for forming the anode 102, an inorganic compound and an organic compound can be cited. Examples of the inorganic compound include: metals (aluminum, gold, silver, nickel, palladium, chromium, etc.), metal oxides (Indium oxides, tin oxides, indium-Tin oxides (ITO), indium-zinc oxides (Indium Zinc Oxide, IZO), etc.), halogenated metals (copper iodide, etc.), copper sulfide, carbon black, ITO glass, or NESA (NESA) glass, etc. Examples of the organic compound include: and conductive polymers such as polythiophene such as poly (3-methylthiophene), polypyrrole, and polyaniline. Further, it can be suitably selected from materials used as an anode of an organic EL element.
The resistance of the transparent electrode is not limited as long as it can supply a sufficient current for light emission of the light emitting element, but is desirably low in terms of power consumption of the light emitting element. For example, an ITO substrate of 300 Ω/γ or less functions as an element electrode, but a substrate of about 10 Ω/γ can be supplied at present, and thus, it is particularly preferable to use a low-resistance product of, for example, 100 Ω/γ to 5 Ω/γ, preferably 50 Ω/γ to 5 Ω/γ. The thickness of ITO can be arbitrarily selected depending on the resistance value, but is usually used in a range of 50nm to 300 nm.
2-1-5 hole injection layer and hole transport layer in organic electroluminescent device
The hole injection layer 103 plays a role of efficiently injecting holes migrating from the anode 102 into the light-emitting layer 105 or the hole transport layer 104. The hole transport layer 104 functions to efficiently transport holes injected from the anode 102 or holes injected from the anode 102 via the hole injection layer 103 to the light-emitting layer 105. The hole injection layer 103 and the hole transport layer 104 are formed by stacking and mixing one or more of the hole injection/transport materials, or by mixing the hole injection/transport materials and the polymer binder. In addition, an inorganic salt such as iron (III) chloride may be added to the hole injection/transport material to form a layer.
As the hole injecting/transporting substance, it is necessary to efficiently inject/transport holes from the positive electrode between electrodes to which an electric field is applied, and it is desirable that the hole injecting efficiency is high and the injected holes are efficiently transported. Therefore, a substance having a small ionization potential, a large hole mobility, and excellent stability, and which is less likely to cause impurities that become traps during production and use, is preferable.
As a material for forming the hole injection layer 103 and the hole transport layer 104, any compound can be selected from among compounds conventionally used as a charge transport material for holes in photoconductive materials, p-type semiconductors, and known compounds used in hole injection layers and hole transport layers of organic EL elements. Specific examples of these compounds are carbazole derivatives (N-phenylcarbazole, polyvinylcarbazole, etc.), biscarbazole derivatives such as bis (N-arylcarbazole) or bis (N-alkylcarbazole), triarylamine derivatives (4, 4' -tris (N-carbazolyl) triphenylamine, polymers having aromatic tertiary amino groups in the main chain or side chains, 1-bis (4-di-p-tolylaminophenyl) cyclohexane, N, N ' -diphenyl-N, N ' -bis (3-methylphenyl) -4,4' -diaminobiphenyl, N ' -diphenyl-N, N ' -dinaphthyl-4, 4' -diaminobiphenyl, N ' -diphenyl-N, N ' -bis (3-methylphenyl) -4,4' -diphenyl-1, 1' -diamine, N ' -dinaphthyl-N, N ' -diphenyl-4, 4' -diphenyl-1, 1' -diamine, N 4 ,N 4 ' -diphenyl-N 4 ,N 4 '-bis (9-phenyl-9H-carbazol-3-yl) - [1,1' -biphenyl]-4,4' -diamine, N 4 ,N 4 ,N 4 ',N 4 '-tetra ([ 1,1' -biphenyl)]-4-yl) - [1,1' -biphenyl]Triphenylamine derivatives such as 4,4 '-diamine, 4' -tris (3-methylphenyl (phenyl) amino) triphenylamine, starburst amine derivatives, etc.), stilbene derivatives, phthalocyanine derivatives (metal-free, copper phthalocyanine, etc.), pyrazoline derivatives, hydrazone compounds, benzofuran derivatives or thiophene derivatives, oxadiazole derivatives, quinoxaline derivatives (e.g., 1,4,5,8,9, 12-hexaazatriphenylene-2, 3,6,7,10, 11-hexacarbonitrile, etc.), heterocyclic compounds such as porphyrin derivatives, polysilanes, etc. Among the polymer systems, polycarbonate, styrene derivative, polyvinylcarbazole, polysilane, and the like having the above-mentioned monomers in the side chain are preferable, but the compound is not particularly limited as long as it is a compound that can inject holes from the anode and further can transport holes in order to form a thin film necessary for the production of a light-emitting element.
In addition, it is known that the conductivity of an organic semiconductor is strongly affected by doping. Such an organic semiconductor matrix material contains a compound having good electron donating properties or a compound having good electron accepting properties. For doping electron donating substances, strong electron acceptors such as Tetracyanoquinodimethane (TCNQ) or 2,3,5,6-tetrafluorotetracyano-1, 4-benzoquinone dimethane (2, 3,5, 6-tetrafluoro-etracyano-1, 4-benzoquinodimethane, F4 TCNQ) are known (for example, refer to the literature "m.fyifole, a. Bayer, t.friez, k.lio (M.Pfeiffer, A.Beyer, T.Fritz, K.Leo)", application physics rapid report (applied. Letters), 73 (22), 3202-3204 (1998) ", literature" j. Bruch, m.fyifole, t.friez, k.lio (J.Blochwitz, M.Pfeiffer, T.Fritz, K.Leo) ", application physics rapid report (applied. Lett.), 73 (6), 729-731)". These generate so-called holes by an electron transfer process in the electron-donating base substance (hole-transporting substance). The conductivity of the base material varies considerably depending on the number of holes and mobility. As a matrix material having hole transporting properties, for example, benzidine derivatives (N, N ' -bis (3-methylphenyl) -N, N ' -bis (phenyl) benzidine (N, N ' -bis (3-methylphenyl) -N, N ' -bis (phenyl) benzodine, TPD) and the like) or starburst amine derivatives (4, 4',4"-tris (N, N-diphenylamino) triphenylamine, TDATA) and the like), or specific metal phthalocyanines (particularly zinc phthalocyanine (ZnPc) and the like) are known (japanese patent laid-open publication No. 2005-167175). The polycyclic aromatic compound of the present invention can be used as a hole injection layer forming material or a hole transport layer forming material.
2-1-6. Electron blocking layer in organic electroluminescent device >)
An electron blocking layer that prevents diffusion of electrons from the light emitting layer may also be provided between the hole injection/transport layer and the light emitting layer. The electron blocking layer may be formed using a compound represented by any one of the above formulas (H1), (H2) and (H3). The polycyclic aromatic compound of the present invention is useful as a material for forming an electron blocking layer.
2-1-7. Electron injection layer, electron transport layer in organic electroluminescent element ]
The electron injection layer 107 plays a role of efficiently injecting electrons migrating from the cathode 108 into the light emitting layer 105 or the electron transport layer 106. The electron transport layer 106 functions to efficiently transport electrons injected from the cathode 108 or electrons injected from the cathode 108 through the electron injection layer 107 to the light emitting layer 105. The electron transport layer 106 and the electron injection layer 107 are formed by stacking and mixing one or more of the electron transport/injection materials, or by mixing the electron transport/injection materials and the polymer binder.
The electron injection/transport layer is a layer that is responsible for injecting electrons from the cathode and transporting the electrons, and preferably has high electron injection efficiency and good efficiency in transporting the injected electrons. Therefore, a substance having a high electron affinity, a high electron mobility, and excellent stability, and which is less likely to cause impurities that become traps during production and use, is preferable. However, considering the balance of hole and electron transport, when an effect of blocking holes from the anode to the cathode side without recombination is mainly exerted, the effect of improving the light-emitting efficiency is equivalent to a material having a high electron transport ability even if the electron transport ability is not so high. Therefore, the electron injection/transport layer in this embodiment mode can also include a function of a layer that can efficiently block migration of holes.
The material (electron-transporting material) for forming the electron-transporting layer 106 or the electron-injecting layer 107 may be any one selected from among compounds conventionally used as electron-transporting compounds in photoconductive materials, known compounds used in electron-injecting layers and electron-transporting layers of organic EL elements, and the like.
As a material used in the electron transport layer or the electron injection layer, it is preferable to contain at least one compound selected from the following compounds: a compound containing an aromatic ring or a heteroaromatic ring containing at least one atom selected from the group consisting of carbon, hydrogen, oxygen, sulfur, silicon, and phosphorus; pyrrole derivatives and condensed ring derivatives thereof; a metal complex having an electron accepting nitrogen. Specifically, there may be mentioned: condensed ring aromatic ring derivatives such as naphthalene and anthracene, styryl aromatic ring derivatives typified by 4,4' -bis (diphenylvinyl) biphenyl, cyclic ketone derivatives, coumarin derivatives, naphthalimide derivatives, quinone derivatives such as anthraquinone and diphenoquinone, phosphine oxide derivatives, aryl nitrile derivatives, indole derivatives, and the like. Examples of the metal complex having an electron accepting nitrogen include: and hydroxyzole complexes such as hydroxyphenyloxazole complexes, azomethine complexes, tropolone metal complexes, flavonol metal complexes, and benzoquinoline metal complexes. These materials may be used alone or in combination with different materials.
Specific examples of the other electron transfer compound include: pyridine derivatives, naphthalene derivatives, fluoranthene derivatives, BO-series derivatives, anthracene derivatives, phenanthroline derivatives, cyclic ketone derivatives, coumarin derivatives, naphthalimide derivatives, anthraquinone derivatives, diphenoquinone derivatives, diphenylquinone derivatives, perylene derivatives, oxadiazole derivatives (1, 3-bis [ (4-t-butylphenyl) 1,3, 4-oxadiazolyl ] phenylene and the like), thiophene derivatives, triazole derivatives (N-naphthyl-2, 5-diphenyl-1, 3, 4-triazole and the like), thiadiazole derivatives, metal complexes of 8-hydroxyquinoline (oxaine) derivatives, metal complexes of hydroxyquinoline series, quinoxaline derivatives, polymers of quinoxaline derivatives, indole (benzozole) compounds, gallium complexes, pyrazole derivatives, perfluorinated phenylene derivatives, triazine derivatives, pyrazine derivatives, benzoquinoline derivatives (2, 2 '-bis (benzo [ h ] quinolin-2-yl) -9,9' -spirobi-and the like), imidazopyridine derivatives, borane derivatives, benzimidazole derivatives (tris (N-phenyl) benzoimidazole) derivatives, benzoquinoline (2-phenyl) benzoquinoline, benzoquinoline derivatives, benzoterpyridine derivatives (2 ', benzoterpyridine derivatives and the like), and the like, and derivatives (2, 4' -terpyridine derivatives and the like), naphthyridine derivatives (bis (1-naphthyl) -4- (1, 8-naphthyridin-2-yl) phenylphosphine oxide and the like), aldazine derivatives, pyrimidine derivatives, aryl nitrile derivatives, indole derivatives, phosphine oxide derivatives, bisstyryl derivatives, silole derivatives, oxazoline derivatives and the like.
In addition, metal complexes having electron accepting nitrogen may also be used, and examples thereof include: and hydroxyquinoline metal complexes, hydroxyoxazole complexes such as hydroxyphenyloxazole complexes, azomethine complexes, tropolone metal complexes, flavonol metal complexes, and benzoquinoline metal complexes.
The materials may be used alone or in combination with different materials.
Among the above materials, 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, an aryl nitrile derivative, a triazine derivative, a benzimidazole derivative, a phenanthroline derivative, a hydroxyquinoline metal complex, a thiazole derivative, a benzothiazole derivative, a silole derivative, and an oxazoline derivative are preferable.
The polycyclic aromatic compound of the present invention can be used as an electron injection layer forming material or an electron transport layer forming material.
The electron transport layer or the electron injection layer may contain a substance that reduces a material forming the electron transport layer or the electron injection layer. The reducing substance may be any substance having a certain reducing property, and 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 may be preferably used.
Preferable reducing substances include alkali metals such as Na (work function 2.36 eV), K (work function 2.28 eV), rb (work function 2.16 eV), cs (work function 1.95 eV), alkaline earth metals such as Ca (work function 2.9 eV), sr (work function 2.0eV to 2.5 eV), and Ba (work function 2.52 eV), and particularly preferably substances having a work function of 2.9eV or less. Of these, the more preferable reducing substance is K, rb or Cs, more preferable Rb or Cs, and most preferable Cs as an alkali metal. These alkali metals have particularly high reducing power, and by adding a relatively small amount of the alkali metal to a material forming the electron transport layer or the electron injection layer, an improvement in light-emitting luminance or a longer lifetime in the organic EL element can be achieved. The reducing substance having a work function of 2.9eV or less is preferably a combination of two or more of these alkali metals, and particularly preferably a combination containing Cs, for example, a combination of Cs and Na, cs and K, cs and Rb, or Cs and Na and K. The inclusion of Cs can effectively exhibit the reducing ability, and the addition of Cs to a material forming the electron transport layer or the electron injection layer can improve the light-emitting luminance and prolong the lifetime of the organic EL element.
2-1-8. Cathode in organic electroluminescent device >)
The cathode 108 plays a role of injecting electrons into the light-emitting layer 105 through the electron injection layer 107 and the electron transport layer 106.
The material forming the cathode 108 is not particularly limited as long as it is a material capable of injecting electrons into the organic layer with good efficiency, and the same material as that 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, alloys of these (magnesium-silver alloy, magnesium-indium alloy, aluminum-lithium alloy such as lithium fluoride/aluminum, and the like), and the like are preferable. In order to improve the electron injection efficiency to improve the element characteristics, lithium, sodium, potassium, cesium, calcium, magnesium, or an alloy containing these low work function metals is effective. However, in general, these low work function metals are mostly unstable in the atmosphere. In order to improve this, for example, a method of doping an organic layer with a small amount of lithium, cesium or magnesium and using an electrode having high stability is known. As the other dopant, an inorganic salt such as lithium fluoride, cesium fluoride, lithium oxide, and cesium oxide can be used. However, the present invention is not limited thereto.
Further, the following preferable examples are given: metals such as platinum, gold, silver, copper, iron, tin, aluminum, and indium, alloys of these metals, inorganic substances such as silica, titania, and silicon nitride, polyvinyl alcohol, vinyl chloride, and hydrocarbon polymer compounds are laminated to protect the electrodes. The method for producing these electrodes is not particularly limited as long as it is a method capable of achieving conduction, such as resistance heating, electron beam evaporation, sputtering, ion plating, and coating.
< 2-1-9. Binders that can be used in the layers >
The materials used for the hole injection layer, the hole transport layer, the light emitting layer, the electron transport layer, and the electron injection layer may be formed as separate layers, or may be dispersed in a curable resin 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, ethylcellulose, vinyl acetate resin, acrylonitrile-butadiene-styrene (acrylonitrile butadiene styrene, ABS) resin, polyurethane resin, phenol resin, xylene resin, petroleum resin, urea resin, melamine resin, unsaturated polyester resin, alkyd resin, epoxy resin, silicone resin, or the like as a polymer binder.
2-1-10. Method for manufacturing organic electroluminescent device
Each layer constituting the organic EL element can be formed by forming a thin film of a material to be formed into each layer by a method such as a vapor deposition method, a resistance heating vapor deposition method, an electron beam vapor deposition method, a sputtering method, a molecular lamination method, a printing method, an inkjet method, a spin coating method, a casting method, or a coating method. The film thickness of each layer formed in this manner is not particularly limited, and may be appropriately set according to the nature of the material, but is usually in the range of 2nm to 5000 nm. The film thickness can be measured by a crystal oscillation type film thickness measuring device or the like. In the case of thinning by the vapor deposition method, the vapor deposition conditions are different depending on the type of material, the target crystal structure and association structure of the film, and the like. The evaporation conditions are generally preferably a boat heating temperature of +50 to +400℃and a vacuum degree of 10 -6 Pa～10 -3 Pa, a vapor deposition rate of 0.01nm/sec to 50nm/sec, a substrate temperature of-150 ℃ to +300 ℃, and a film thickness of 2nm to 5 μm.
Next, as an example of a method for manufacturing an organic EL element, a method for manufacturing an organic EL element including an anode, a hole injection layer, a hole transport layer, a light emitting layer including a host material and a dopant material, an electron transport layer, an electron injection layer, and a cathode will be described. An anode is produced by forming a thin film of an anode material on an appropriate substrate by vapor deposition or the like, and then a thin film of a hole injection layer and a hole transport layer is formed on the anode. The target organic EL element is obtained by forming a thin film as a light-emitting layer by co-vapor deposition of a host material and a dopant material on the thin film, forming an electron transport layer and an electron injection layer on the light-emitting layer, and forming a thin film containing a substance for a cathode as a cathode by vapor deposition or the like. In the production of the organic EL element, the production order may be reversed, and the cathode, the electron injection layer, the electron transport layer, the light emitting layer, the hole transport layer, the hole injection layer, and the anode may be produced in this order.
In the case where a direct current voltage is applied to the organic EL element obtained in the above-described manner, the anode may be applied as a positive polarity and the cathode may be applied as a negative polarity, and when a voltage of about 2V to 40V is applied, light emission is observed from the transparent or semitransparent electrode side (anode or cathode, or both). The organic EL element emits light even when a pulse current or an alternating current is applied thereto. Further, the waveform of the applied alternating current may be arbitrary.
Application example of organic electroluminescent element 2-1-11
The organic EL element can also be applied to a display device, a lighting device, or the like.
The display device or the lighting device including the organic EL element can be manufactured by a known method such as connecting the organic EL element to a known driving device, and can be driven by a known driving method such as direct current driving, pulse driving, or alternating current driving.
Examples of the display device include: a panel display such as a color flat panel display, a flexible display such as a flexible color organic Electroluminescence (EL) display, and the like (for example, refer to japanese patent laid-open publication No. 10-335066, japanese patent laid-open publication No. 2003-321546, japanese patent laid-open publication No. 2004-281086, and the like). The display mode of the display may be, for example, any of a matrix mode and a segment mode. In addition, matrix display and segment display may coexist in the same panel.
In the matrix, pixels for display are two-dimensionally arranged in a grid shape, a mosaic shape, or the like, and characters or images are displayed by a set of pixels. The shape or size of the pixels is determined according to the application. For example, in the image and character display of a personal computer, a monitor, and a television, a square pixel having one side of 300 μm or less is generally used, and in the case of a large display such as a display screen, a pixel having one side of mm is used. In the case of monochrome display, pixels of the same color may be arranged, and in the case of color display, red, green, and blue pixels may be arranged in parallel to perform display. In this case, there are typically triangular and stripe types. Also, as a driving method of the matrix, either a line-sequential (line-sequential) driving method or an active matrix may be used. The line sequential driving has an advantage of simple structure, but in consideration of the operation characteristics, the active matrix is sometimes more excellent, and thus the driving method also needs to be used differently according to the purpose.
In the segmentation method (type), a pattern is formed so as to display information determined in advance, and the determined region is made to emit light. Examples include: time and temperature display in a digital clock or a thermometer, running state display of audio equipment, an induction cooker and the like, panel display of an automobile and the like.
Examples of the illumination device include an illumination device such as indoor illumination and a backlight of a liquid crystal display device (for example, refer to japanese patent application laid-open publication No. 2003-257621, japanese patent application laid-open publication No. 2003-277741, japanese patent application laid-open publication No. 2004-119211, and the like). Backlight is mainly used for improving visibility of a display device that does not emit light, and is used for a liquid crystal display device, a timepiece, an audio device, an automobile panel, a display panel, a sign, and the like. In particular, as a backlight for personal computers, which is a problem of thinning in a liquid crystal display device, a backlight using an organic EL element has a thin and lightweight characteristic in consideration of the difficulty in thinning due to the inclusion of a fluorescent lamp or a light guide plate in the conventional method.
< 2-2. Other organic devices >
The polycyclic aromatic compound of the present invention can be used for the production of organic field effect transistors, organic thin film solar cells, and the like, in addition to the organic electroluminescent elements.
The organic field effect transistor is a transistor that controls a current by an electric field generated by a voltage input, and is provided with a gate electrode in addition to an active electrode and a drain electrode. The organic field effect transistor is a transistor as follows: when a voltage is applied to the gate electrode, an electric field is generated, and electrons (or holes) flowing between the source electrode and the drain electrode can be arbitrarily blocked to control a current. Field effect transistors are easily miniaturized as compared with single transistors (bipolar transistors), and are often used as elements constituting integrated circuits and the like.
In general, the structure of an organic field effect transistor is such that a source electrode and a drain electrode are provided in contact with an organic semiconductor active layer formed using the polycyclic aromatic compound of the present invention, and a gate electrode is provided via an insulating layer (dielectric layer) in contact with the organic semiconductor active layer. The following structures are examples of the element 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/drain electrode
(3) Substrate/organic semiconductor active layer/source electrode/drain electrode/insulator layer/gate electrode
(4) Substrate/source electrode/drain electrode/organic semiconductor active layer/insulator layer/gate electrode
The organic field effect transistor configured in the above manner can be applied to a liquid crystal display of an active matrix driving method, a pixel driving switching element of an organic electroluminescent display, or the like.
The organic thin film solar cell has a structure in which an anode, a hole transport layer, a photoelectric conversion layer, an electron transport layer, and a cathode, such as ITO, 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 of the present invention can be used as a material for a hole transport layer, a p-type semiconductor layer, an n-type semiconductor layer, or an electron transport layer, depending on the physical properties thereof. In the organic thin film solar cell, the polycyclic aromatic compound of the present invention can function as a hole transporting material or an electron transporting material. The organic thin film solar cell may suitably include a hole blocking layer, an electron injection layer, a hole injection layer, a smoothing layer, and the like, in addition to the above. Among the organic thin film solar cells, known materials used in the organic thin film solar cells can be suitably selected for use in combination.
< 3 wavelength conversion Material >
The polycyclic aromatic compounds of the present invention are useful as wavelength conversion materials.
Currently, application of multicolor technology based on a color conversion scheme to a liquid crystal display or an organic EL display, illumination, or the like is actively studied. The color conversion means that the emission wavelength from the light emitting body is converted into light having a longer wavelength, and for example, means that ultraviolet light or blue light is converted into green light or red light. By forming the wavelength conversion material having the color conversion function into a film, for example, by combining the wavelength conversion material with a blue light source, three primary colors of blue, green, and red, that is, white light can be extracted from the blue light source. A full-color display (full color display) can be produced by combining a white light source, which is formed by combining a blue light source and a wavelength conversion film having a color conversion function, as a light source unit, with a liquid crystal driving portion and a color filter. Further, without the liquid crystal driving portion, the liquid crystal display device can be used as a white light source, for example, a white light source for light-emitting diode (LED) illumination or the like. In addition, a full-color organic EL display can be manufactured without using a metal mask by using a blue organic EL element as a light source in combination with a wavelength conversion film that converts blue light into green light and red light. Further, a full-color micro LED display at low cost can be manufactured by using a blue micro LED as a light source in combination with a wavelength conversion film that converts blue light into green light and red light.
The polycyclic aromatic compound of the present invention can be used as the wavelength conversion material. The wavelength conversion material containing the polycyclic aromatic compound of the present invention can be used to convert ultraviolet light or light from a light source or a light emitting element that generates blue light having a shorter wavelength into blue light or green light having a high color purity suitable for use in a display device (a display device using an organic EL element or a liquid crystal display device). The color to be converted can be adjusted by appropriately selecting a substituent of the polycyclic aromatic compound of the present invention, a binder resin used in a wavelength conversion composition to be described later, and the like. The wavelength conversion material is prepared as a wavelength conversion composition comprising the polycyclic aromatic compound of the present invention. The wavelength conversion film may be formed using the wavelength conversion composition.
The wavelength conversion composition may contain a binder resin, other additives, and a solvent in addition to the polycyclic aromatic compound of the present invention. As the binder resin, for example, the resins described in paragraphs 0173 to 0176 of International publication No. 2016/190283 can be used. As other additives, the compounds described in paragraphs 0177 to 0181 of International publication No. 2016/190283 can be used. As the solvent, the description of the solvent contained in the composition for forming a light-emitting layer can be referred to.
The wavelength conversion film includes a wavelength conversion layer formed by hardening a wavelength conversion composition. As a method for producing the wavelength conversion layer from the wavelength conversion composition, a known film formation method can be referred to. The wavelength conversion film may include only a wavelength conversion layer formed of a composition containing the polycyclic aromatic compound of the present invention, and may also include other wavelength conversion layers (e.g., a wavelength conversion layer that converts blue light into green light or red light, a wavelength conversion layer that converts blue light or green light into red light). Further, the wavelength conversion film may include a base layer or a barrier layer for preventing degradation of the color conversion layer due to oxygen, moisture, or heat.
Examples (example)
Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.
In an embodiment, "APCI-MS (air pressure chemical ionization-mass spectrometry)" refers to atmospheric pressure chemical ionization mass spectrometry.
Synthesis example (1):
synthesis of Compound (1-1)
[ chemical 121]
Intermediate (X-1) (138.7 g), 1-tert-butyl-3, 4, 5-trichlorobenzene (65.6 g), bis [ di-tert-butyl (4-dimethylaminophenyl) phosphino ] palladium (II) (Pd-132) (9.78 g), sodium t-butoxide (NaOtBu, 39.8 g) and toluene (500 ml) as palladium catalysts were placed in a flask under a nitrogen atmosphere, and heated at 120℃for 5 hours. After the completion of the reaction, water and ethyl acetate were added to the reaction solution and stirred, and then the organic layer was separated and washed with water. Thereafter, the crude product obtained by concentrating the organic layer was purified by a silica gel short-path column (eluent: heptane), whereby 116.5g of intermediate (X-2) was obtained.
[ chemical 122]
Intermediate (X-2) (116.5 g), intermediate (X-3) (70.5 g), pd-132 (5.86 g) as a palladium catalyst, naOtBu (23.86 g) and toluene (500 ml) were placed in a flask under a nitrogen atmosphere, and heated at 120℃for 3 hours. After the completion of the reaction, water and ethyl acetate were added to the reaction solution and stirred, and then the organic layer was separated and washed with water. Thereafter, the crude product obtained by concentrating the organic layer was purified by a silica gel short-path column (eluent: toluene/heptane=1/9 (capacity ratio)), whereby 97.7g of intermediate (X-4) was obtained.
[ 123]
Under nitrogen atmosphere at 0deg.C, to which intermediate (X-4) (10.3 g) and tert-butylbenzene were added t Bu-benzene (Benzene), 100 ml) in a flask was added 1.60M t-butyllithium pentane solution t BuLi,11.8 ml). After the completion of the dropwise addition, the temperature was raised to 70℃and stirred for 0.5 hour, and then the components having a boiling point lower than that of t-butylbenzene were distilled off under reduced pressure. Boron tribromide (4.72 g) was added to cool to-50 ℃, warmed to room temperature and stirred for 0.5 hours. Thereafter, N-diisopropylethylamine (EtN) was added thereto after cooling again to 0 ℃ i Pr 2 2.44 g) was stirred at room temperature until the heat generation ceased, and then heated to 100℃and stirred for 1 hour. The reaction solution was cooled to room temperature, and an aqueous sodium acetate solution cooled by an ice bath was added thereto, followed by addition of ethyl acetate to separate the solution. The organic layer was concentrated and purified by a short-path column of silica gel (eluent: chlorobenzene). The obtained crude product was recrystallized from toluene to obtain 3.01g of compound (1-1).
[ chemical 124]
The structure of the compound obtained by nuclear magnetic resonance (nuclear magnetic resonance, NMR) measurement was confirmed.
1 H-NMR(500MHz,CDCl 3 )：δ＝0.38(s,3H),0.79(s,9H),0.85(s,3H),1.26(s,3H),1.30(s,3H),1.44-1.62(m,4H),6.08-6.15(m,2H),6.36-6.42(m,2H),6.77-6.93(m,10H),6.99-7.02(m,1H),7.18-7.25(m,3H),7.33-7.51(m,6H),7.58(dt,2H),7.62-7.71(m,3H),7.84(s,1H),7.93-7.96(m,2H),8.03-8.08(m,1H),8.28-8.31(m,1H),8.64(dd,1H).
Synthesis example (2): synthesis of Compound (1-2)
Compound (1-2) was obtained in the same manner as in Synthesis example 1 except that compound (X-4) was changed to compound (X-4-2).
M/z (m+h) = 1066.46 was observed by APCI-MS, and the formation of compound (1-2) as the target was confirmed.
[ 125]
Synthesis example (3): synthesis of Compound (1-6)
Compounds (1-6) were obtained in the same manner as in Synthesis example 1 except that Compound (X-4) was changed to Compound (X-4-6).
M/z (m+h) = 990.43 was observed by APCI-MS, and the formation of compound (1-6) as the target was confirmed.
[ 126]
Synthesis example (4): synthesis of Compound (1-30)
Compounds (1-30) were obtained in the same manner as in Synthesis example 1 except that Compound (X-4) was changed to Compound (X-4-30).
M/z (m+h) = 936.38 was observed by APCI-MS, and the formation of compound (1-30) as the target was confirmed.
[ 127]
Synthesis example (5): synthesis of Compound (1-46)
Compounds (1-46) were obtained in the same manner as in Synthesis example 1 except that Compound (X-4) was changed to Compound (X-4-46).
M/z (m+h) = 1090.46 was observed by APCI-MS, and the formation of compound (1-46) as a target was confirmed.
[ 128]
Synthesis example (6): synthesis of Compound (1-48)
Compounds (1-48) were obtained in the same manner as in Synthesis example 1 except that Compound (X-4) was changed to Compound (X-4-48).
M/z (m+h) = 1118.49 was observed by APCI-MS, and the formation of the compound (1-48) as the target was confirmed.
[ 129]
Synthesis example (7): synthesis of Compound (1-49)
Compounds (1-49) were obtained in the same manner as in Synthesis example 1 except that Compound (X-4) was changed to Compound (X-4-49).
M/z (m+h) = 1118.49 was observed by APCI-MS, and the formation of compound (1-49) as a target was confirmed.
[ 130]
Synthesis example (8): synthesis of Compound (1-56)
Compounds (1-56) were obtained in the same manner as in Synthesis example 1 except that Compound (X-4) was changed to Compound (X-4-56).
M/z (m+h) = 1042.46 was observed by APCI-MS, and the formation of the target compound (1-56) was confirmed.
[ 131]
Synthesis example (9): synthesis of Compound (1-80)
Compounds (1-80) were obtained in the same manner as in Synthesis example 1 except that Compound (X-4) was changed to Compound (X-4-80).
M/z (m+h) = 1050.48 was observed by APCI-MS, and the formation of compound (1-80) as the target was confirmed.
[ chemical 132]
Synthesis example (10): synthesis of Compound (1-81)
Compounds (1-81) were obtained in the same manner as in Synthesis example 1 except that Compound (X-4) was changed to Compound (X-4-81).
M/z (m+h) = 1050.48 was observed by APCI-MS, and the formation of compound (1-81) as the target was confirmed.
[ chemical 133]
Synthesis example (11): synthesis of Compound (1-84)
Compounds (1-84) were obtained in the same manner as in Synthesis example 1 except that Compound (X-4) was changed to Compound (X-4-84).
M/z (m+h) = 996.44 was observed by APCI-MS, and the formation of compound (1-84) as a target was confirmed.
[ 134]
Synthesis example (12): synthesis of Compound (1-102)
Compounds (1-102) were obtained in the same manner as in Synthesis example 1 except that Compound (X-4) was changed to Compound (X-4-102).
M/z (m+h) = 1106.55 was observed by APCI-MS, and the formation of the compound (1-102) as the target was confirmed.
[ chemical 135]
Synthesis example (13): synthesis of Compound (1-113)
Compounds (1-113) were obtained in the same manner as in Synthesis example 1 except that Compound (X-4) was changed to Compound (X-4-113).
M/z (m+h) = 1100.67 was observed by APCI-MS, and the formation of compound (1-113) as the target was confirmed.
[ chemical 136]
Synthesis example (14): synthesis of Compound (1-117)
Compounds (1-117) were obtained in the same manner as in Synthesis example 1 except that Compound (X-4) was changed to Compound (X-4-117).
M/z (m+h) = 1138.74 was observed by APCI-MS, and the formation of compound (1-117) as the target was confirmed.
[ 137]
Synthesis example (15): synthesis of Compound (1-118)
Compounds (1-118) were obtained in the same manner as in Synthesis example 1 except that Compound (X-4) was changed to Compound (X-4-118).
M/z (m+h) = 955.45 was observed by APCI-MS, and the formation of the target compound (1-118) was confirmed.
[ 138]
Synthesis example (16): synthesis of Compound (1-123)
Compounds (1-123) were obtained in the same manner as in Synthesis example 1 except that Compound (X-4) was changed to Compound (X-4-123).
M/z (m+h) = 825.37 was observed by APCI-MS, and the formation of compound (1-123) as a target was confirmed.
[ chemical 139]
Synthesis example (17): synthesis of Compound (1-130)
Compounds (1-130) were obtained in the same manner as in Synthesis example 1, except that Compound (X-4) was changed to Compound (X-4-130).
M/z (m+h) = 1007.48 was observed by APCI-MS, and the formation of the compound (1-130) as the target was confirmed.
[ 140]
Synthesis example (18): synthesis of Compound (1-134)
Compounds (1-134) were obtained in the same manner as in Synthesis example 1 except that Compound (X-4) was changed to Compound (X-4-134).
M/z (m+h) = 889.40 was observed by APCI-MS, and the formation of the target compound (1-134) was confirmed.
[ 141]
Synthesis example (19): synthesis of Compound (1-139)
Compounds (1-139) were obtained in the same manner as in Synthesis example 1, except that Compound (X-4) was changed to Compound (X-4-139).
M/z (m+h) = 939.47 was observed by APCI-MS, and the formation of the compound (1-139) as the target was confirmed.
[ 142]
Synthesis example (20): synthesis of Compound (1-153)
Compounds (1-153) were obtained in the same manner as in Synthesis example 1 except that Compound (X-4) was changed to Compound (X-4-153).
M/z (m+h) = 991.50 was observed by APCI-MS, and the formation of compound (1-153) as the target was confirmed.
[ 143]
Synthesis example (21): synthesis of Compound (1-161)
Compounds (1-161) were obtained in the same manner as in Synthesis example 1, except that Compound (X-4) was changed to Compound (X-4-161).
M/z (m+h) = 980.61 was observed by APCI-MS, and the formation of compound (1-161) as a target was confirmed.
[ 144]
Synthesis example (22): synthesis of Compound (1-164)
Compounds (1-164) were obtained in the same manner as in Synthesis example 1 except that Compound (X-4) was changed to Compound (X-4-164).
M/z (m+h) = 1009.50 was observed by APCI-MS, and the formation of compound (1-164) as a target was confirmed.
[ chemical 145]
/>
Synthesis example (23): synthesis of Compound (1-173)
Compounds (1-173) were obtained in the same manner as in Synthesis example 1 except that Compound (X-4) was changed to Compound (X-4-173).
M/z (m+h) = 1061.53 was observed by APCI-MS, and the formation of the compound (1-173) as the target was confirmed.
[ 146]
Synthesis example (24): synthesis of Compound (1-174)
Compounds (1-174) were obtained in the same manner as in Synthesis example 1 except that Compound (X-4) was changed to Compound (X-4-174).
M/z (m+h) = 985.50 was observed by APCI-MS, and the formation of the compound (1-174) as the target was confirmed.
[ chemical 147]
Synthesis example (25): synthesis of Compound (1-186)
Compounds (1-186) were obtained in the same manner as in Synthesis example 1 except that Compound (X-4) was changed to Compound (X-4-186).
M/z (m+h) = 993.52 was observed by APCI-MS, and the formation of the target compound (1-186) was confirmed.
[ 148]
Synthesis example (26): synthesis of Compound (1-200)
Compounds (1-200) were obtained in the same manner as in Synthesis example 1 except that Compound (X-4) was changed to Compound (X-4-200).
M/z (m+h) = 883.41 was observed by APCI-MS, and the formation of compound (1-200) as the target was confirmed.
[ 149]
Synthesis example (27): synthesis of Compound (1-204)
Compounds (1-204) were obtained in the same manner as in Synthesis example 1 except that Compound (X-4) was changed to Compound (X-4-204).
M/z (m+h) = 939.47 was observed by APCI-MS, and the formation of the compound (1-204) as the target was confirmed.
[ 150]
Synthesis example (28): synthesis of Compound (1-205)
Compounds (1-205) were obtained in the same manner as in Synthesis example 1, except that Compound (X-4) was changed to Compound (X-4-205).
M/z (m+h) = 981.42 was observed by APCI-MS, and the formation of compound (1-205) as a target was confirmed.
[ 151]
Synthesis example (29): synthesis of Compound (1-207)
Compounds (1-207) were obtained in the same manner as in Synthesis example 1 except that Compound (X-4) was changed to Compound (X-4-207).
M/z (m+h) = 913.45 was observed by APCI-MS, and the formation of the target compound (1-207) was confirmed.
[ 152]
Synthesis example (30): synthesis of Compound (1-210)
Compounds (1-210) were obtained in the same manner as in Synthesis example 1 except that Compound (X-4) was changed to Compound (X-4-210).
M/z (m+h) = 1240.65 was observed by APCI-MS, and the formation of compound (1-210) as a target was confirmed.
[ chemical 153]
Synthesis example (31): synthesis of Compound (1-211)
Compounds (1-211) were obtained in the same manner as in Synthesis example 1 except that Compound (X-4) was changed to Compound (X-4-211).
M/z (m+h) = 1092.53 was observed by APCI-MS, and the formation of compound (1-211) as a target was confirmed.
[ 154]
Synthesis example (32): synthesis of Compound (1-214)
Compounds (1-214) were obtained in the same manner as in Synthesis example 1 except that Compound (X-4) was changed to Compound (X-4-214).
M/z (m+h) = 778.33 was observed by APCI-MS, and the formation of compound (1-214) as a target was confirmed.
[ chemical 155]
Synthesis example (33): synthesis of Compound (1-215)
Compounds (1-215) were obtained in the same manner as in Synthesis example 1 except that Compound (X-4) was changed to Compound (X-4-215).
M/z (m+h) = 1020.51 was observed by APCI-MS, and the formation of the compound (1-215) as the target was confirmed.
[ chemical 156]
Synthesis example (34): synthesis of Compound (1-216)
Compounds (1-216) were obtained in the same manner as in Synthesis example 1 except that Compound (X-4) was changed to Compound (X-4-216).
M/z (m+h) = 1240.65 was observed by APCI-MS, and the formation of the compound (1-216) as the target was confirmed.
[ 157]
Synthesis example (35): synthesis of Compound (1-219)
Compounds (1-219) were obtained in the same manner as in Synthesis example 1, except that Compound (X-4) was changed to Compound (X-4-219).
M/z (m+h) = 1168.56 was observed by APCI-MS, and the formation of compound (1-219) as the target was confirmed.
[ chemical 158]
Synthesis example (36): synthesis of Compound (1-220)
Compounds (1-220) were obtained in the same manner as in Synthesis example 1, except that Compound (X-4) was changed to Compound (X-4-220).
M/z (m+h) = 874.42 was observed by APCI-MS, and the formation of compound (1-220) as a target was confirmed.
[ 159]
Synthesis example (37): synthesis of Compound (1-225)
Compounds (1-225) were obtained in the same manner as in Synthesis example 1 except that Compound (X-4) was changed to Compound (X-4-225).
M/z (m+h) = 940.37 was observed by APCI-MS, and the formation of compound (1-225) as a target was confirmed.
[ 160]
Synthesis example (38): synthesis of Compound (1-227)
Compounds (1-227) were obtained in the same manner as in Synthesis example 1 except that Compound (X-4) was changed to Compound (X-4-227).
M/z (m+h) = 1276.75 was observed by APCI-MS, and the formation of compound (1-227) as a target was confirmed.
[ 161]
Synthesis example (39): synthesis of Compound (1-228)
Compounds (1-228) were obtained in the same manner as in Synthesis example 1 except that Compound (X-4) was changed to Compound (X-4-228).
M/z (m+h) = 1066.48 was observed by APCI-MS, and the formation of the compound (1-228) as the target was confirmed.
[ 162]
Synthesis example (40): synthesis of Compound (1-229)
Compounds (1-229) were obtained in the same manner as in Synthesis example 1 except that Compound (X-4) was changed to Compound (X-4-229).
M/z (m+h) = 793.27 was observed by APCI-MS, and the formation of the target compound (1-229) was confirmed.
[ 163]
Synthesis example (41): synthesis of Compound (1-232)
Compounds (1-232) were obtained in the same manner as in Synthesis example 1 except that Compound (X-4) was changed to Compound (X-4-232).
M/z (m+h) = 1072.46 was observed by APCI-MS, and the formation of compound (1-232) as a target was confirmed.
[ chemical 164]
Synthesis example (42): synthesis of Compound (1-236)
Compounds (1-236) were obtained in the same manner as in Synthesis example 1 except that Compound (X-4) was changed to Compound (X-4-236).
M/z (m+h) = 1166.62 was observed by APCI-MS, and the formation of the compound (1-236) as the target was confirmed.
[ 165]
Synthesis example (43): synthesis of Compound (1-238)
Compounds (1-238) were obtained in the same manner as in Synthesis example 1 except that Compound (X-4) was changed to Compound (X-4-238).
M/z (m+h) = 966.42 was observed by APCI-MS, and the formation of compound (1-238) as a target was confirmed.
[ 166]
Synthesis example (44): synthesis of Compound (1-239)
Compounds (1-239) were obtained in the same manner as in Synthesis example 1, except that Compound (X-4) was changed to Compound (X-4-239).
M/z (m+h) = 1154.78 was observed by APCI-MS, and the formation of the target compound (1-239) was confirmed.
[ 167]
Synthesis example (45): synthesis of Compound (1-241)
Compounds (1-241) were obtained in the same manner as in Synthesis example 1 except that Compound (X-4) was changed to Compound (X-4-241).
M/z (m+h) = 1023.60 was observed by APCI-MS, and the formation of compound (1-241) as a target was confirmed.
[ chemical 168]
Synthesis example (46): synthesis of Compound (1-243)
Compounds (1-243) were obtained in the same manner as in Synthesis example 1, except that Compound (X-4) was changed to Compound (X-4-243).
M/z (m+h) = 1154.58 was observed by APCI-MS, and the formation of compound (1-243) as the target was confirmed.
[ 169]
Synthesis example (47): synthesis of Compound (1-244)
Compounds (1-244) were obtained in the same manner as in Synthesis example 1 except that Compound (X-4) was changed to Compound (X-4-244).
M/z (m+h) = 1022.49 was observed by APCI-MS, and the formation of the compound (1-244) as the target was confirmed.
[ chemical 170]
Synthesis example (48): synthesis of Compound (1-249)
Compounds (1-249) were obtained in the same manner as in Synthesis example 1 except that Compound (X-4) was changed to Compound (X-4-249).
M/z (m+h) = 1042.45 was observed by APCI-MS, and the formation of the target compound (1-249) was confirmed.
[ chemical 171]
Synthesis example (49): synthesis of Compound (1-250)
Compounds (1-250) were obtained in the same manner as in Synthesis example 1, except that Compound (X-4) was changed to Compound (X-4-250).
M/z (m+h) = 1041.55 was observed by APCI-MS, and the formation of compound (1-250) as a target was confirmed.
[ chemical 172]
Synthesis example (50): synthesis of Compound (1-252)
Compounds (1-252) were obtained in the same manner as in Synthesis example 1 except that Compound (X-4) was changed to Compound (X-4-252).
M/z (m+h) = 1146.52 was observed by APCI-MS, and the formation of the compound (1-252) as the target was confirmed.
[ chemical 173]
Synthesis example (51): synthesis of Compound (1-254)
Compounds (1-254) were obtained in the same manner as in Synthesis example 1 except that Compound (X-4) was changed to Compound (X-4-254).
M/z (m+h) = 1050.42 was observed by APCI-MS, and the formation of the target compound (1-254) was confirmed.
[ 174]
Synthesis example (52): synthesis of Compound (1-256)
Compounds (1-256) were obtained in the same manner as in Synthesis example 1 except that Compound (X-4) was changed to Compound (X-4-256).
M/z (m+h) = 1027.54 was observed by APCI-MS, and the formation of compound (1-256) as the target was confirmed.
[ 175]
/>
Synthesis example (53): synthesis of Compound (1-258)
Compounds (1-258) were obtained in the same manner as in Synthesis example 1 except that Compound (X-4) was changed to Compound (X-4-258).
M/z (m+h) = 1148.53 was observed by APCI-MS, and the formation of the compound (1-258) as the target was confirmed.
[ chemical 176]
Synthesis example (54): synthesis of Compound (1-261)
Compounds (1-261) were obtained in the same manner as in Synthesis example 1 except that Compound (X-4) was changed to Compound (X-4-261).
M/z (m+h) = 1006.45 was observed by APCI-MS, and the formation of the compound (1-261) as the target was confirmed.
[ chemical 177]
Synthesis example (55): synthesis of Compound (1-263)
Compounds (1-263) were obtained in the same manner as in Synthesis example 1, except that compound (X-4) was changed to compound (X-4-263).
M/z (m+h) = 1128.56 was observed by APCI-MS, and the formation of the target compound (1-263) was confirmed.
[ chemical 178]
Synthesis example (56): synthesis of Compound (1-265)
Compounds (1-265) were obtained in the same manner as in Synthesis example 1 except that Compound (X-4) was changed to Compound (X-4-265).
M/z (m+h) = 1030.45 was observed by APCI-MS, and the formation of the target compound (1-265) was confirmed.
[ chemical 179]
Synthesis example (57): synthesis of Compound (1-268)
Compounds (1-268) were obtained in the same manner as in Synthesis example 1 except that Compound (X-4) was changed to Compound (X-4-268).
M/z (m+h) = 1042.45 was observed by APCI-MS, and the formation of the target compound (1-268) was confirmed.
[ 180]
Synthesis example (58): synthesis of Compound (1-269)
Compounds (1-269) were obtained in the same manner as in Synthesis example 1 except that Compound (X-4) was changed to Compound (X-4-269).
M/z (m+h) = 1128.56 was observed by APCI-MS, and the formation of the target compound (1-269) was confirmed.
[ 181]
Synthesis example (59): synthesis of Compound (1-270)
Compounds (1-270) were obtained in the same manner as in Synthesis example 1 except that Compound (X-4) was changed to Compound (X-4-270).
M/z (m+h) = 1184.63 was observed by APCI-MS, and the formation of compound (1-270) as a target was confirmed.
[ 182]
Synthesis example (60): synthesis of Compound (1-272)
Compounds (1-272) were obtained in the same manner as in Synthesis example 1 except that Compound (X-4) was changed to Compound (X-4-272).
M/z (m+h) = 1009.49 was observed by APCI-MS, and the formation of the target compound (1-272) was confirmed.
[ 183]
Synthesis example (61): synthesis of Compound (1-273)
Compounds (1-273) were obtained in the same manner as in Synthesis example 1 except that Compound (X-4) was changed to Compound (X-4-273).
M/z (m+h) = 1147.63 was observed by APCI-MS, and the formation of the target compound (1-273) was confirmed.
[ 184]
Synthesis example (62): synthesis of Compound (1-274)
Compounds (1-274) were obtained in the same manner as in Synthesis example 1 except that Compound (X-4) was changed to Compound (X-4-274).
M/z (m+h) = 1037.52 was observed by APCI-MS, and the formation of the target compound (1-274) was confirmed.
[ chemical 185]
The other compounds of the present invention can be synthesized by the method according to the synthesis example by appropriately changing the compounds used as the raw materials.
Method for evaluating basic Properties
Preparation of sample
In the case of evaluating the absorption characteristics and the luminescence characteristics (fluorescence and phosphorescence) of a compound to be evaluated, there are a case of dissolving the compound to be evaluated in a solvent and evaluating the compound in a solvent, and a case of evaluating the compound in a thin film state. Further, in the case of performing the evaluation in a thin film state, there are a case of performing the evaluation by thinning only the compound to be evaluated according to the use form of the organic EL element of the compound to be evaluated and a case of performing the evaluation by dispersing the compound to be evaluated in an appropriate matrix material and thinning the compound to be evaluated. Here, a film obtained by vapor deposition of only the compound to be evaluated is referred to as a "single film", and a film obtained by coating a coating liquid containing the compound to be evaluated and a matrix material and drying the coating liquid is referred to as a "coating film".
As the matrix material, commercially available polymethyl methacrylate (polymethyl methacrylate, PMMA) and the like can be used. In this example, a sample was prepared by dissolving PMMA and a compound to be evaluated in toluene, and then forming a thin film on a transparent support substrate (10 mm. Times.10 mm) made of quartz by spin coating.
In addition, a film sample in which the host compound was the matrix material was prepared as follows. A quartz transparent support substrate (10 mm. Times.10 mm. Times.1.0 mm) was fixed to a substrate holder of a commercially available vapor deposition apparatus (manufactured by Changzhou industries, ltd.) and a molybdenum vapor deposition boat containing a host compound was mounted thereon, and a doping material was placed thereonAfter the molybdenum evaporation boat for the agent material was used, the vacuum vessel was depressurized to 5×10 -4 Pa. Next, the evaporation boat in which the host compound is placed and the evaporation boat in which the dopant material is placed are heated simultaneously, and the host compound and the dopant material are co-evaporated to an appropriate film thickness, thereby forming a mixed thin film (sample) of the host compound and the dopant material. Here, the vapor deposition rate is controlled according to the set mass ratio of the host compound to the dopant material.
< evaluation of absorption Properties and luminescence Properties >
The absorption spectrum of the sample was measured by using an ultraviolet-visible near infrared spectrophotometer (Shimadzu corporation, inc., UV-2600). The fluorescence spectrum or phosphorescence spectrum of the sample was measured using a spectrofluorometer (manufactured by Hitachi High-Tech (Stry), F-7000).
For measurement of fluorescence spectrum, photoluminescence (photoluminescence) is measured by excitation at an appropriate excitation wavelength at room temperature. For the measurement of the phosphorescence spectrum, the measurement was performed in a state where the sample was immersed in liquid nitrogen (temperature 77K) using an attached cooling unit. For observation of the phosphorescence spectrum, a light-shielding device (optical chopper) was used to adjust the delay time from irradiation of the excitation light until the measurement was started. The photoluminescence of the sample was measured by excitation at an appropriate excitation wavelength.
In addition, the fluorescence quantum yield (PLQY) was measured using an absolute PL quantum yield measuring device (manufactured by Pinus maritima photon (Hamamatsu Photonics) (Strand), C9920-02G).
Next, basic physical properties of the polycyclic aromatic compound of the present invention are evaluated.
< evaluation of fluorescence lifetime (delayed fluorescence) >)
Fluorescence lifetime was measured at 300K using a fluorescence lifetime measuring device (manufactured by Binsonite photon (Hamamatsu Photonics) (Strand), C11367-01). Specifically, a light-emitting component having a fast fluorescence lifetime and a light-emitting component having a slow fluorescence lifetime in the maximum light-emitting wavelength measured at an appropriate excitation wavelength are observed. In the measurement of fluorescence lifetime at room temperature of a general organic EL material that emits fluorescence, a triplet component is deactivated by heat, and thus a slow light-emitting component in which a triplet component derived from phosphorescence participates is hardly observed. In the case where a slow light-emitting component is observed in a compound to be evaluated, triplet energy indicating a long excitation lifetime is shifted to singlet energy by thermal activation and is observed as delayed fluorescence.
< calculation of energy gap (Eg) >)
From the long wavelength end a (nm) of the absorption spectrum obtained by the method, it was calculated using eg=1240/a.
< measurement of ionization potential (Ip) >)
A transparent support substrate (28 mm. Times.26 mm. Times.0.7 mm) on which ITO (indium tin oxide) was deposited was fixed to a substrate holder of a commercially available deposition apparatus (manufactured by Changzhou industries, ltd.) to which a molybdenum deposition boat containing a target compound was attached, and then the vacuum vessel was depressurized to 5X 10 -4 Pa. Next, the evaporation boat is heated to evaporate the target compound, thereby forming an individual film (undoped) of the target compound.
The ionization potential of the object compound was measured using a photoelectric spectrometer (PYS-201, sumitomo heavy machinery industries, ltd.) using the obtained individual film as a sample.
< calculation of electron affinity (Ea) >)
The electron affinity can be estimated from the difference between the ionization potential measured by the method and the energy gap calculated by the method.
Determination of the minimum excited singlet level E (S, sh), the minimum excited triplet level E (T, sh)
For an individual film of a target compound formed on a glass substrate, a fluorescence spectrum was observed at 77K with the second absorption peak from the long wavelength side of the absorption spectrum as excitation light, and the lowest excitation singlet energy level E (S, sh) was obtained from the shoulder peak on the short wavelength side of the peak of the fluorescence spectrum. Further, the phosphorescence spectrum was observed at 77K with respect to the single film of the target compound formed on the glass substrate, with the second absorption peak from the long wavelength side of the absorption spectrum as excitation light, and the lowest excitation triplet level E (T, sh) was obtained from the shoulder peak on the peak short wavelength side of the phosphorescence spectrum.
< evaluation of organic EL element >
As described above, since the compound of the present invention has an appropriate energy gap (Eg), a high minimum excited triplet energy (E T ) And a small Δest, for example, can be expected to be applied to a light-emitting layer and a charge transport layer, and particularly, can be expected to be applied to a light-emitting layer.
Next, the production and evaluation of an organic EL element using the polycyclic aromatic compound of the present invention will be described.
Structure of organic EL element
The polycyclic aromatic compound of the present invention is used to produce an organic EL element.
[ element Structure A ]
The material structure of each layer in the organic EL element of example 1 is shown in table 1 below.
TABLE 1
The chemical structures of "HI", "HAT-CN", "HT-1", "HT-2", "BH", "ET-1", "ET-2", "Liq", the comparative compound (1) and the comparative compound (5) described in Korean patent application publication No. 2022/074408, the comparative compound (2) described in International publication No. 2022/103018, the comparative compound (3) described in U.S. patent application publication No. 2022/02091, and the comparative compound (4) described in International publication No. 2021/194216 in Table 1 and Table 2 are shown below.
[ 186]
Example 1
A glass substrate (manufactured by photo Science) of 26mm by 28mm by 0.7mm, which was formed by sputtering ITO having a thickness of 180nm and was polished to 150nm, was used as a transparent support substrate. The transparent support substrate was fixed to a substrate holder of a commercially available vapor deposition apparatus (manufactured by Showa vacuum (R)), and a molybdenum vapor deposition boat in which HI, HAT-CN, HT-1, HT-2, BH, compound (1-1), ET-1, and ET-2 were placed, and an aluminum nitride vapor deposition boat in which Liq, liF, and aluminum were placed, respectively, were mounted.
The following layers were formed in this order on the ITO film of the transparent support substrate. The vacuum vessel was depressurized to 5X 10 -4 Pa, first, HI was heated and vapor-deposited so that the film thickness became 40nm, next, HAT-CN was heated and vapor-deposited so that the film thickness became 5nm, next, HT-1 was heated and vapor-deposited so that the film thickness became 45nm, next, HT-2 was heated and vapor-deposited so that the film thickness became 10nm, and a hole layer including four layers was formed. Then, BH and the compound (1-1) are heated simultaneously and vapor deposited so that the film thickness becomes 25nm, thereby forming a light-emitting layer. The vapor deposition rate was adjusted so that the mass ratio of BH to the compound (1-1) became approximately 97 to 3. Then, ET-1 was heated and vapor deposited so that the film thickness became 5nm, and then ET-2 and Liq were heated simultaneously and vapor deposited so that the film thickness became 25nm, thereby forming an electron layer including two layers. The vapor deposition rate was adjusted so that the mass ratio of ET-2 to Liq became approximately 50 to 50. The vapor deposition rate of each layer is 0.01 nm/second to 1 nm/second. Then, liF was heated and vapor-deposited at a vapor deposition rate of 0.01 nm/sec to 0.1 nm/sec so that the film thickness became 1nm, and then aluminum was heated and vapor-deposited so that the film thickness became 100nm to form a cathode, thereby obtaining an organic EL element.
(examples 2 to 61, comparative examples 1 to 5)
Organic EL elements of examples 2 to 61 and comparative examples 1 to 5 were obtained in the same manner as in example 1 except that the materials described in table 2 were used instead of the compound (1-1).
< evaluation item and evaluation method >)
As evaluation items, there are a driving voltage (V), an emission wavelength (nm), and the International Commission on illumination (Com)mission Internationale de L' Eclairage, CIE) chromaticity (x, y), external quantum efficiency (%), maximum wavelength (nm) of the luminescence spectrum, half-value width (nm), and the like. For example, 1000cd/m can be used as these evaluation items 2 Value at the time of light emission.
The quantum efficiency of the light-emitting element includes an internal quantum efficiency and an external quantum efficiency, and the internal quantum efficiency represents a proportion of pure conversion of external energy injected as electrons (or holes) into the light-emitting layer of the light-emitting element into photons. On the other hand, the external quantum efficiency is calculated based on the amount of the photons released to the outside of the light emitting element, and a part of photons generated in the light emitting layer is absorbed or continuously reflected by the inside of the light emitting element without being released to the outside of the light emitting element, so the external quantum efficiency is lower than the internal quantum efficiency.
The method for measuring the spectral emission luminance (emission spectrum) and the external quantum efficiency is as follows. The brightness of the applied element was 1000cd/m using a voltage/current generator R6144 manufactured by Advantest (Advantest) 2 The element emits light. The spectral emission luminance in the visible light region was measured from a direction perpendicular to the light emitting surface using a spectroradiometer SR-3AR manufactured by Topcon (TOPCon). Assuming that the light emitting surface is a completely diffusing surface, the value obtained by dividing the measured spectral emission luminance value of each wavelength component by the wavelength energy and multiplying by pi is the number of photons at each wavelength. Then, the number of photons is accumulated over the full wavelength region observed, and set to the total number of photons released from the element. The value obtained by dividing the applied current value by the meta-charge (elementary charge) is set as the number of carriers (carriers) injected into the element, and the value obtained by dividing the total number of photons released from the element by the number of carriers injected into the element is the external quantum efficiency. The half width of the emission spectrum is obtained as the width between the upper and lower wavelengths having an intensity of 50% around the maximum emission wavelength.
The organic EL elements of examples 1 to 61 and comparative examples 1 to 5 were measured by applying a DC voltage to an ITO electrode as an anode and a LiF/aluminum electrode as a cathode, and 1000cd/m was measured 2 Characteristics at the time of light emission.
The results are shown in Table 2.
TABLE 2
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[ Industrial applicability ]
The polycyclic aromatic compound of the present invention is useful as a material for organic devices, particularly a material for light-emitting layers for forming light-emitting layers of organic electroluminescent elements. By using the polycyclic aromatic compound of the present invention as a dopant for a light-emitting layer, an organic electroluminescent element that emits light at a low voltage and high efficiency can be obtained.

Claims (14)

1. A polycyclic aromatic compound having a structure comprising one or more structural units represented by formula (1);
in the formula (1), the components are as follows,
the A and B rings are each independently a substituted or unsubstituted aryl ring or a substituted or unsubstituted heteroaryl ring,
the C ring is a ring represented by the formula (C),
in the formula (C), the components of the compound,
X c is > O, > N-R, > C (-R) 2 、＞Si(-R) 2 , > S, or > Se, said > N-R, said > C (-R) 2 The above-mentioned material is > Si (-R) 2 R of (C) is independently hydrogen, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted alkyl, or substituted or unsubstituted cycloalkyl, said > C (-R) 2 The above-mentioned material is > Si (-R) 2 Can be bonded to each other to form a ring,
either two Z in succession C One of which is with Y 1 Bonded carbon, the other being bonded to > N-G B Is selected from the group consisting of N-bonded carbons,
other Z C Each independently is N or C-R C ，
R C Each independently hydrogen or any substituent selected from substituent group ZB,
two adjacent R's on the c2 ring C Can be bonded to each other and form together with the carbon to which they are bonded an aryl ring or a heteroaryl ring, the aryl ring formed and the heteroaryl ring formed being substituted by at least one substituent selected from the substituent group ZB,
Y 1 for B, P, P = O, P = S, al, ga, as, si-R, or Ge-R, R of the Si-R and the Ge-R being a substituted or unsubstituted aryl, a substituted or unsubstituted heteroaryl, a substituted or unsubstituted alkyl, or a substituted or unsubstituted cycloalkyl,
G A 、G B each independently represents a monovalent group represented by the formula (G),
in the formula (G), the amino acid sequence of the formula (G),
Z a each independently is N or C-R a ，
R a Each independently is hydrogen or any substituent selected from substituent group ZB, or R adjacent to a And together with the carbon to which they are bonded form an aryl or heteroaryl ring, which aryl ring and which heteroaryl ring may each be substituted by at least one substituent selected from the substituent group ZB,
A is > O, > N-R A 、＞Si(-R A ) 2 、＞C(-R A ) 2 S, or Se, R A Each independently is hydrogen, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted alkyl, or substituted or unsubstituted cycloalkyl, the > Si (-R) A ) 2 Is set at least two R A Can be bonded to each other to form a ring, and the above-mentioned groups > C (-R) A ) 2 Is set at least two R A Can be bonded to each other to formThe ring is provided with a plurality of grooves,
wherein the monovalent group represented by the formula (G) is bonded to > N-G at any position A Or > N-G B Is bonded to the substrate via a N-bond,
at least one of the aryl or heteroaryl rings in the structure may be condensed by at least one cycloalkane, which may have a substituent, at least one of the cycloalkanes being-CH 2 The group may be substituted by-O-groups,
wherein,,
when X is c When S is > S, the B ring is a substituted or unsubstituted aryl ring, and the monocyclic ring directly bonded to nitrogen in the monovalent group represented by the formula (G) is not condensed by a cycloalkane,
when X is c At least one of the A ring, B ring, and C ring selected from the group consisting of aryl ring and heteroaryl ring having at least one substituent selected from the group consisting of substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted diarylamino, substituted or unsubstituted arylheteroarylamino, and substituted or unsubstituted cycloalkyl, or at least one of the structures selected from the group consisting of aryl ring and heteroaryl ring being condensed by a cycloalkane, which cycloalkane may have a substituent, at least one of the cycloalkanes being-CH 2 The group may be substituted by-O-groups,
at least one hydrogen in the structure may be substituted with cyano, halogen, or deuterium,
substituent group ZB comprises:
aryl which may be substituted with at least one group selected from the group consisting of aryl, heteroaryl, diarylamino, alkyl, cycloalkyl, and substituted silyl;
heteroaryl groups which may be substituted with at least one group selected from the group consisting of aryl, heteroaryl, diarylamino, alkyl, cycloalkyl, and substituted silyl groups;
a diarylamino group which may be substituted with at least one group selected from the group consisting of an aryl group, a heteroaryl group, a diarylamino group, an alkyl group, a cycloalkyl group, and a substituted silyl group, two aryl groups of the diarylamino group may be bonded to each other via a linking group;
a diheteroarylamino group which may be substituted with at least one group selected from the group consisting of aryl, heteroaryl, diarylamino, alkyl, cycloalkyl and substituted silyl groups, two heteroaryl groups of the diheteroarylamino group being bonded to each other via a linking group;
an arylheteroarylamino group which may be substituted with at least one group selected from the group consisting of an aryl group, a heteroaryl group, a diarylamino group, an alkyl group, a cycloalkyl group, and a substituted silyl group, and an aryl group and a heteroaryl group of the arylheteroarylamino group may be bonded to each other via a linking group;
A diarylboronyl group which may be substituted with at least one group selected from the group consisting of aryl, heteroaryl, diarylamino, alkyl, cycloalkyl, and substituted silyl groups, two aryl groups of the diarylboronyl group may be bonded via a single bond or a linking group;
alkyl groups which may be substituted with at least one group selected from the group consisting of aryl, heteroaryl, diarylamino, cycloalkyl, and substituted silyl groups;
cycloalkyl which may be substituted with at least one group selected from the group consisting of aryl, heteroaryl, diarylamino, alkyl, cycloalkyl, and substituted silyl;
alkoxy which may be substituted with at least one group selected from the group consisting of aryl, heteroaryl, diarylamino, cycloalkyl, and substituted silyl;
aryloxy which may be substituted with at least one group selected from the group consisting of aryl, heteroaryl, diarylamino, alkyl, cycloalkyl, and substituted silyl;
arylthio which may be substituted with at least one group selected from the group consisting of aryl, heteroaryl, diarylamino, alkyl, cycloalkyl, and substituted silyl; and substituted silyl groups.
2. The polycyclic aromatic compound according to claim 1, represented by formula (1 a);
In the formula (1 a), Z is N or C-R independently 11 ，
R 11 Each independently is hydrogen or any substituent selected from substituent group ZB, or R adjacent to 11 Bonded and forming together with the a-ring or the b-ring an aryl-ring or a heteroaryl-ring, which formed aryl-ring and which formed heteroaryl-ring may be substituted with at least one substituent selected from the substituent group ZB,
Y 1 、G A g, G B Respectively with Y in formula (1) 1 、G A G, G B X is the same meaning C Z is as follows C Respectively with X in the formula (C) C Z is as follows C Are the same meaning;
at least one of the aryl or heteroaryl rings in formula (1 a) may be condensed with at least one cycloalkane, which may have a substituent, at least one of the cycloalkanes-CH 2 -may be substituted by-O-;
at least one hydrogen in formula (1 a) may be substituted with cyano, halogen, or deuterium.
3. The polycyclic aromatic compound according to claim 1 or 2, wherein G A G (G) B Each independently is a group represented by the formula (G-1), the formula (G-4), or the formula (G-5), or a group in which one or two hydrogens in the structure represented by the formula (G-1), the formula (G-4), or the formula (G-5) are substituted with an alkyl group or a cycloalkyl group,
4. a polycyclic aromatic compound according to any one of claims 1 to 3, wherein a is > O.
5. The polycyclic aromatic compound according to claim 1, represented by any one of formula (1 a-1), formula (1 a-2), or formula (1 a-3);
in the formula (1 a-1),
R a1 、R a2 、R a3 、R b1 、R b2 、R b3 、R b4 、R c1 、R c2 、R c3 、R c4 、R g1 、R g2 、R g3 、R g4 、R g5 、R g6 、R g7 、R g8 、R g9 、R g10 、R g11 、R g12 、R g13 and R is g14 Each independently hydrogen or any substituent selected from substituent group ZB,
wherein R is b1 、R b2 、R b3 And R is b4 Can be bonded to each other and form together with the carbon to which they are bonded an aryl ring, which can be substituted with at least one substituent selected from the substituent group ZB,
at least one of the aryl or heteroaryl rings in formula (1 a-1) may be condensed with at least one cycloalkane, which may have a substituent, at least one of the cycloalkanes-CH 2 -may be substituted by-O-wherein the alkylene is not condensed in the g11 ring and the g13 ring;
in the formula (1 a-2),
R a1 、R a2 、R a3 、R b1 、R b2 、R b3 、R b4 、R c1 、R c2 、R c3 、R c4 、R g1 、R g2 、R g3 、R g4 、R g5 、R g6 、R g7 、R g8 、R g9 、R g10 、R g11 、R g12 、R g13 and R is g14 Each independently is hydrogen or any substituent selected from substituent group ZB, wherein R a1 、R a2 、R a3 、R b1 、R b2 、R b3 、R b4 、R c1 、R c2 、R c3 And R is c4 At least one of which is a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted diarylamino group, a substituted or unsubstituted arylheteroarylamino group, or a substituted or unsubstituted cycloalkyl group, or at least one selected from the group consisting of an aryl ring and a heteroaryl ring in formula (1 a-2) is condensed with a cycloalkane, which may have a substituent, at least one of the cycloalkanes being-CH 2 The group may be substituted by-O-groups,
R b1 、R b2 、R b3 、R b4 、R c1 、R c2 、R c3 and R is c4 Can be bonded to each other and form together with the carbon to which they are bonded an aryl or heteroaryl ring, which aryl ring formed can be substituted by at least one substituent selected from the substituent group ZB,
at least one of the aryl or heteroaryl rings in formula (1 a-2) may be condensed with at least one cycloalkane, which may have a substituent, at least one of the cycloalkanes-CH 2 -may be substituted by-O-;
in the formula (1 a-3),
R a1 、R a2 、R a3 、R b1 、R b2 、R b3 、R b4 、R c1 、R c2 、R c3 、R c4 、R g1 、R g2 、R g3 、R g4 、R g5 、R g6 、R g7 、R g8 、R g9 、R g10 、R g11 、R g12 、R g13 and R is g14 Each independently hydrogen or any substituent selected from substituent group ZB,
wherein R is b1 、R b2 、R b3 、R b4 、R c1 、R c2 、R c3 And R is c4 Two adjacent ones of which may be bonded to each other and form together with the carbon to which they are bonded an aryl or heteroaryl ring, the aryl ring formed may beSubstituted with at least one substituent selected from the substituent group ZB,
at least one of the aryl or heteroaryl rings in formula (1 a-3) may be condensed with at least one cycloalkane, which may have a substituent, at least one of the cycloalkanes-CH 2 -may be substituted by-O-;
at least one hydrogen of the formulae (1 a-1), formula (1 a-2), and formula (1 a-3) may be substituted with cyano, halogen, or deuterium.
6. The polycyclic aromatic compound according to claim 3, represented by any one of the following formulas;
In the formula, me is methyl, tBu is tertiary butyl, and D is deuterium.
7. The polycyclic aromatic compound according to claim 3, represented by any one of the following formulas;
in the formula, me is methyl, tBu is tertiary butyl, tAm is tertiary amyl, and D is deuterium.
8. The polycyclic aromatic compound according to claim 5, represented by formula (1 a-3).
9. The polycyclic aromatic compound according to claim 8, represented by any one of the following formulas;
in the formula, me is methyl, and tBu is tert-butyl.
10. A material for organic devices, comprising the polycyclic aromatic compound according to any one of claims 1 to 9.
11. An organic electroluminescent element comprising: a pair of electrodes including an anode and a cathode; and a light-emitting layer disposed between the pair of electrodes, the light-emitting layer containing the polycyclic aromatic compound according to any one of claims 1 to 9.
12. The organic electroluminescent element according to claim 11, wherein the light-emitting layer comprises a host, and the polycyclic aromatic compound as a dopant.
13. The organic electroluminescent element according to claim 12, wherein the host is an anthracene compound, a fluorene compound, or a dibenzo A compound.
14. A display device or a lighting device comprising the organic electroluminescent element according to any one of claims 11 to 13.
CN202310274655.7A 2022-03-22 2023-03-21 Polycyclic aromatic compound, material for organic device, organic electroluminescent element, display device, or lighting device Pending CN116789687A (en)

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