CN115746032A - Polycyclic aromatic compound, material for organic device, organic electroluminescent element, display device, and lighting device - Google Patents
Polycyclic aromatic compound, material for organic device, organic electroluminescent element, display device, and lighting device Download PDFInfo
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- CN115746032A CN115746032A CN202211090571.XA CN202211090571A CN115746032A CN 115746032 A CN115746032 A CN 115746032A CN 202211090571 A CN202211090571 A CN 202211090571A CN 115746032 A CN115746032 A CN 115746032A
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Abstract
The invention provides a polycyclic aromatic compound, a material for an organic device, an organic electroluminescent element, a display device, and a lighting device. The polycyclic aromatic compound has one or more structures containing a structural unit represented by formula (1); [ ring A and ring B are substituted or unsubstituted aryl rings orHeteroaryl ring, C ring being a ring of formula (C), Y 1 B, etc., X 1 And X 2 Is > N-R etc. (R is aryl etc.), two Z's optionally adjacent C Is with Y 1 And X 2 Directly bound carbon, other Z C Is C-R C Etc. two adjacent R C Can be bonded to each other to form a compound represented by R C2 A substituted aryl or heteroaryl ring, the ring represented by formula (C), as R C Or R C2 And comprises aryl or heteroaryl substituted by formula (D-1) or formula (D-2), and the other R C And R C2 Is H, etc., R D Is alkyl or the like, L is alkylene or arylene or the like, X c Is > S, etc]。
Description
Technical Field
The present invention relates to a polycyclic aromatic compound. The invention relates in particular 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 comprises the polycyclic aromatic compound.
Background
Conventionally, various studies have been made on display devices using light emitting elements that perform electroluminescence, in order to achieve power saving and reduction in thickness, and further, active studies have been made on organic electroluminescence elements including organic materials, in order to facilitate weight reduction and size increase. In particular, in the development of an organic material having light-emitting characteristics such as blue, which is one of the three primary colors of light, and in the development of an organic material having charge transport capabilities (having a possibility of becoming a semiconductor or a superconductor) including holes, electrons, and the like, both high molecular compounds and low molecular compounds have been actively studied so far.
The organic electroluminescent element has a structure including: a pair of electrodes including an anode and a cathode, and one or more layers which are disposed between the pair of electrodes and include an organic compound. The layer containing an organic compound includes a light-emitting layer, a charge transporting/injecting layer for transporting or injecting charges such as holes and electrons, and various organic materials suitable for the layers have been developed.
Among them, patent document 1 discloses that a polycyclic aromatic compound containing boron is effectively used as a material for an organic electroluminescent element or the like. It has been reported that the organic electroluminescent element containing the polycyclic aromatic compound has good external quantum efficiency. Patent documents 2 and 3 disclose polycyclic aromatic compounds containing boron to which a heterocyclic ring such as benzothiophene is condensed.
[ Prior art documents ]
[ patent document ]
[ patent document 1] International publication No. 2015/102118
[ patent document 2] International publication No. 2020/111830
[ patent document 3] International publication No. 2020/251049
Disclosure of Invention
[ problems to be solved by the invention ]
As described above, various materials have been developed as materials for organic Electroluminescence (EL) devices, but in order to increase the selection of materials for organic EL devices, it is desired to develop materials containing novel compounds.
The present invention addresses the problem of providing a novel compound which can be effectively used as a material for an organic device such as an organic EL element.
[ means for solving the problems ]
The present inventors have made extensive studies to solve the above-mentioned problems, and have succeeded in producing a novel polycyclic aromatic compound having more excellent light-emitting characteristics among polycyclic aromatic compounds having a structure similar to that of the compound described in patent document 1. Further, the present inventors have found that an excellent organic EL element can be obtained by configuring an organic EL element by disposing a layer containing the polycyclic aromatic compound between a pair of electrodes, and have completed the present invention. That is, the present invention provides the following polycyclic aromatic compound, and a material for an organic device and the like containing the following polycyclic aromatic compound.
The present invention specifically has the following structure.
< 1 > a polycyclic aromatic compound having one or more structures containing a structural unit represented by the following formula (1);
[ solution 1]
In the formula (1), the reaction mixture is,
the A ring and the B ring are respectively and independently substituted or unsubstituted aryl rings or substituted or unsubstituted heteroaryl rings;
ring C is a ring represented by the formula (C),
in the formula (C), the reaction mixture is,
X c is > O, > N-R, > C (-R) 2 、＞Si(-R) 2 S or Se, said > N-R, said > C (-R) 2 And said > Si (-R) 2 Each R of (A) is independently hydrogen, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted alkyl, or substituted or unsubstituted cycloalkyl, > C (-R) 2 And said > Si (-R) 2 Two R's may be bonded to each other to form a ring,
two Z's arbitrarily adjacent C Are each independently of Y 1 Or X 2 The carbon to which any one of them is directly bonded,
other Z C Are each independently N or C-R C ，R C Each independently is hydrogen, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted diarylamino, substituted or unsubstituted diheteroarylamino, substituted or unsubstituted arylheteroarylamino, substituted or unsubstituted diarylboron, substituted or unsubstituted arylboron, orUnsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkoxy, substituted or unsubstituted aryloxy, substituted or unsubstituted arylthio, or substituted silyl, the two aryl groups of the diarylamino group being able to be bonded to one another via a linking group, the two heteroaryl groups of the diheteroarylamino group being able to be bonded to one another via a linking group, the aryl and heteroaryl groups of the arylheteroarylamino group being able to be bonded to one another via a linking group, the two aryl groups of the diarylboron group being able to be bonded to one another via a single bond or a linking group,
two adjacent R C May be bonded to each other to form an aryl or heteroaryl ring, each of which is unsubstituted or substituted with at least one R C2 Substituted, R C2 And R C Are the same as each other, wherein R C2 Not being hydrogen, and two R being adjacent C2 Are not bonded to each other to form an aryl or heteroaryl ring,
in the ring represented by the formula (C), as R C Or R C2 And an aryl group substituted with at least a group represented by the formula (D-1) or the formula (D-2) or a heteroaryl group substituted with at least a group represented by the formula (D-1) or the formula (D-2);
the groups represented by the formulae (D-1) and (D-2) are bonded at two points to two adjacent rings in the aryl or heteroaryl ring,
in the formulae (D-1) and (D-2), R D Each independently is substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted alkyl, or substituted or unsubstituted cycloalkyl, each independently is substituted or unsubstituted alkylene, substituted or unsubstituted alkenylene, substituted or unsubstituted arylene, or substituted or unsubstituted heteroarylene;
Y 1 is B, P = O, P = S, al, ga, as, si-R, or Ge-R, said Si-R and R of said Ge-R being a substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted alkyl, or substituted or unsubstituted cycloalkyl;
X 1 and X 2 Independently of each other > O, > N-R, > C (-R) 2 、＞Si(-R) 2 R > N-R is hydrogen, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted alkyl, or substituted or unsubstituted cycloalkyl, > C (-R) 2 And said > Si (-R) 2 Each R of (A) is independently hydrogen, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted alkyl, or substituted or unsubstituted cycloalkyl, > C (-R) 2 And said > Si (-R) 2 May bond to each other to form a ring, and further, the R > N-R and/or the > C (-R) 2 R of (A) may be bonded to the A ring and/or the B ring, or the A ring and/or the C ring via a linking group or a single bond,
at least one hydrogen in the structure may be substituted with cyano, halogen, or deuterium.
< 2 > the polycyclic aromatic compound of < 1 > wherein R is C Or R C2 The aryl group substituted with at least a group represented by the formula (D-1) or the formula (D-2) or the heteroaryl group substituted with at least a group represented by the formula (D-1) or the formula (D-2) may further contain, as a partial structure, at least one ring selected from the group consisting of an aryl ring substituted with at least a group represented by the formula (D-1) or the formula (D-2) and a heteroaryl ring substituted with at least a group represented by the formula (D-1) or the formula (D-2).
< 3 > the polycyclic aromatic compound according to < 1 > or < 2 >, wherein the structural unit represented by the formula (1) is a structural unit represented by the formula (2);
[ solution 2]
In the formula (2), the reaction mixture is,
z is each independently N or C-R 11 Or Z = Z is each independently > O, > N-R, > C (-R) 2 、＞Si(-R) 2 S or Se, said > N-R, said > C (-R) 2 And said > Si (-R) 2 Each R of (A) is independently hydrogen, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted alkyl, or substituted or unsubstituted cycloalkyl, > C (-R) 2 And said > Si (-R) 2 Two R's may be bonded to each other to form a ring,
the C-R 11 R of (A) 11 Each independently hydrogen, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted diarylamino, substituted or unsubstituted diheteroarylamino, substituted or unsubstituted arylheteroarylamino, substituted or unsubstituted diarylboron, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkoxy, substituted or unsubstituted aryloxy, substituted or unsubstituted arylthio, or substituted silyl,
the two aryl groups of the diarylamino group may be bonded to each other via a linking group, the two heteroaryl groups of the diheteroarylamino group may be bonded to each other via a linking group, the aryl group and the heteroaryl group of the arylheteroarylamino group may be bonded to each other via a linking group, the two aryl groups of the diarylboron group may be bonded to each other via a single bond or a linking group,
two adjacent R 11 May be bonded to each other and together with the a-ring or the b-ring form an aryl ring or heteroaryl ring, each unsubstituted or substituted with at least one R 11b Substituted, R 11b And R 11 Are the same as each other, wherein R 11b Not being hydrogen, and two R being adjacent 11b Are not bonded to each other to form an aryl or heteroaryl ring,
the C ring is a ring represented by the formula (C);
Y 1 is B, P = O, P = S, al, ga, as, si-R, or Ge-R, said Si-R and R of said Ge-R being substituted or unsubstituted aryl, substituted or unsubstituted heteroarylSubstituted or unsubstituted alkyl, or substituted or unsubstituted cycloalkyl;
X 1 and X 2 Independently of each other > O, > N-R, > C (-R) 2 、＞Si(-R) 2 R > N-R is hydrogen, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted alkyl, or substituted or unsubstituted cycloalkyl, > C (-R) 2 And said > Si (-R) 2 Each R of (A) is independently hydrogen, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted alkyl, or substituted or unsubstituted cycloalkyl, > C (-R) 2 And said > Si (-R) 2 May bond to each other to form a ring, and further, the R > N-R and/or the > C (-R) 2 R of (A) may be bonded to the a ring and/or the b ring, or the a ring and/or the C ring, through a linking group or a single bond;
at least one hydrogen in the structure may be substituted with cyano, halogen, or deuterium.
< 4 > the polycyclic aromatic compound according to < 3 > wherein the structural unit represented by the formula (2) is a structural unit represented by the formula (2 a-1);
[ solution 3]
In the formula (2 a-1), Y 1 、X 1 、X 2 、X C And Y in formula (2) 1 、X 1 、X 2 、X C Are each the same as R 11b 、R C2 And R in the formula (2) 11b 、R C2 Are respectively defined as the same meaning as that of each other,
n1 is an integer of 1 to 4, n2 is an integer of 0 to 4, n3 is an integer of 0 to 3,
at least one hydrogen in the structure may be substituted with cyano, halogen, or deuterium.
< 5 > the polycyclic aromatic compound according to < 4 > represented by any one of the following formulae.
[ solution 4]
[ solution 5]
[ solution 6]
[ solution 7]
[ solution 8]
[ solution 9]
In the formula, me is methyl, tBu is tert-butyl, and D is deuterium.
< 6 > the polycyclic aromatic compound according to < 3 > wherein the structural unit represented by the formula (2) is a structural unit represented by the formula (2 a-2);
[ solution 10]
In the formula (2 a-2), Y 1 、X 1 、X 2 、X C And Y in formula (2) 1 、X 1 、X 2 、X C Are each the same as R 11b 、R C2 And R in the formula (2) 11b 、R C2 Are respectively the same as the above-mentioned definition,
X 3 and X 4 Each independently is a single bond, > O, > N-R, > C (-R) 2 Or > S, wherein X 3 And X 4 Is not a single bond at the same time,
n1 is an integer of 1 to 4, n2 is an integer of 0 to 4, n3 is an integer of 0 to 3, n4 is an integer of 0 to 2,
at least one hydrogen in the structure may be substituted with cyano, halogen, or deuterium.
< 7 > the polycyclic aromatic compound according to < 6 > represented by any one of the following formulae.
[ solution 11]
Wherein Me is methyl and tBu is tert-butyl.
< 8 > the polycyclic aromatic compound of < 3 > is represented by the following formula.
[ solution 12]
< 9 > a polycyclic aromatic compound having one or more structures containing a structural unit represented by the following formula (1');
[ solution 13]
In the formula (1'), in the presence of a catalyst,
the A ring and the B ring are respectively and independently substituted or unsubstituted aryl rings or substituted or unsubstituted heteroaryl rings;
ring C is a ring represented by the formula (C),
in the formula (C), the compound represented by the formula (A),
X c is > O, > N-R, > C (-R) 2 、＞Si(-R) 2 S or Se, said > N-R, said > C (-R) 2 And said > Si (-R) 2 Each R of (A) is independently hydrogen, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted alkyl, or substituted or unsubstituted cycloalkyl, > C (-R) 2 And said > Si (-R) 2 Two R's may be bonded to each other to form a ring,
two Z's arbitrarily adjacent C Are each independently of Y 1 Or X 2 The carbon to which any one of them is directly bonded,
other Z C Are each independently N or C-R C ，R C Each independently hydrogen, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted diarylamino, substituted or unsubstituted diheteroarylamino, substituted or unsubstituted arylheteroarylamino, substituted or unsubstituted diarylboron, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkoxy, substituted or unsubstituted aryloxy, substituted or unsubstituted arylthio, or substituted silyl, the two aryl groups of the diarylamino being bondable to one another via a linking group, the two heteroaryl groups of the diheteroarylamino being bondable to one another via a linking group, the aryl and heteroaryl groups of the arylheteroarylamino being bondable to one another via a linking group, the two aryl groups of the diarylboron being bondable to one another via a single bond or a linking group,
two adjacent R C Can be bonded to each other to form an aryl ring or heteroaryl ring, each of which is unsubstituted or substituted with at least one R C2 Substituted, R C2 And R C Are the same as each other, wherein R C2 Not being hydrogen, and two R being adjacent C2 Are not bonded to each other to form an aryl or heteroaryl ring,
Y 1 is B, P = O, P = S, al, ga, as, si-R, or Ge-R, said Si-R and R of said Ge-R being a substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted alkyl, or substituted or unsubstituted cycloalkyl;
X 1 and X 2 Independently of each other > O, > N-R, > C (-R) 2 、＞Si(-R) 2 R > N-R is hydrogen, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted alkyl, or substituted or unsubstituted cycloalkyl, > C (-R) 2 And said > Si (-R) 2 Each R of (A) is independently hydrogen, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted alkyl, or substituted or unsubstituted cycloalkyl, > C (-R) 2 And said > Si (-R) 2 May bond to each other to form a ring, and further, the R > N-R and/or the > C (-R) 2 R of (A) may be bonded to the A ring and/or the B ring, or the A ring and/or the C ring through a linking group or a single bond;
the structure comprising at least one selected from the group consisting of an aryl ring substituted with at least a group represented by the formula (D-1) and a heteroaryl ring substituted with at least a group represented by the formula (D-1) as a partial structure,
the group represented by the formula (D-1) is bonded at two points to two adjacent rings in any one of the aryl or heteroaryl rings in the structure, and R is represented by the formula (D-1) D Each independently is substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted alkyl, or substituted or unsubstituted cycloalkyl, each independently is substituted or unsubstituted alkylene, substituted or unsubstituted alkenylene, substituted or unsubstituted arylene, or substituted or unsubstituted heteroarylene;
at least one hydrogen in the structure may be substituted with cyano, halogen, or deuterium.
< 10 > the polycyclic aromatic compound of < 9 > wherein the group represented by the formula (D-1) is a group represented by the formula (D-1-1);
[ chemical 14]
R D Each independently is substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted alkyl, or substituted or unsubstituted cycloalkyl.
< 11 > the polycyclic aromatic compound of < 10 > is represented by any one of the following formulae.
[ solution 15]
[ solution 16]
< 12 > a material for organic devices, comprising the polycyclic aromatic compound according to any one of < 1 > to < 11 >.
< 13 > 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 < 11 >.
< 14 > the organic electroluminescent element according to < 13 >, wherein the light-emitting layer comprises a host and the polycyclic aromatic compound as a dopant.
< 15 > the organic electroluminescent element according to < 14 >, wherein the host is an anthracene compound, a fluorene compound, or a dibenzo
A compound is provided.
< 16 > a display device or a lighting device comprising the organic electroluminescent element according to any one of < 13 > to < 15 >.
[ Effect of the invention ]
The present invention provides a novel polycyclic aromatic compound which can be effectively used as a material for an organic device such as an organic electroluminescent element. The polycyclic aromatic compound of the present invention can be used for producing an organic device such as an organic electroluminescent device.
Drawings
Fig. 1 is a schematic cross-sectional view showing an example of an organic electroluminescent element.
Fig. 2 is an energy level diagram showing an energy relationship among a host, an auxiliary dopant, and an emissive dopant of a TAF element using a general fluorescent dopant.
Fig. 3 is a level diagram showing an example of the energy relationship among the host, the assist dopant, and the emitting dopant in the organic electroluminescent device according to one embodiment of the present invention.
Description of the reference numerals
100: organic electroluminescent element
101: substrate
102: anode
103: hole injection layer
104: hole transport layer
105: luminescent layer
106: electron transport layer
107: electron injection layer
108: cathode electrode
E (1, G): energy level of ground state of host
E (1, S, sh): lowest excited singlet level of the host
E (1, T, sh): lowest excited triplet level of the host
E (2, G): assisting energy level of ground state of dopant
E (2, S, sh): lowest excited singlet level of the auxiliary dopant
E (2, T, sh): lowest excited triplet energy level/a part of excited triplet energy level of auxiliary dopant
E (3, G): energy level of ground state of emitting dopant
E (3, S, sh): lowest excited singlet energy level of an emissive dopant
E (3, T, sh): lowest excited triplet energy level of emissive dopant
h + : cavities of the wafer
e - : electronic device
FRET: fluorescence resonance energy transfer
Detailed Description
The present invention will be described in detail below. The following description of the constituent elements may be based on typical embodiments or specific examples, but the present invention is not limited to such embodiments. In the present specification, the numerical range expressed by the term "to" means a range including the numerical values described before and after the term "to" as the lower limit value and the upper limit value. In the description of the structural formulae in the present specification, "hydrogen" means "hydrogen atom (H)" and "carbon" means "carbon atom (C)". In this specification, an organic electroluminescent element is sometimes referred to as an organic EL element.
In the present specification, the chemical structure or the substituent is sometimes represented by a carbon number, but the carbon number when the substituent is substituted in the chemical structure or when the substituent is further substituted on the substituent means the carbon number of each of the chemical structure or the substituent, and does not mean the total carbon number of the chemical structure and the substituent or the total carbon number of the substituent and the substituent. For example, the "substituent B having a carbon number Y substituted with the substituent a having a carbon number X" means that the "substituent a having a carbon number X" is substituted with the "substituent B having a carbon number Y, and the carbon number Y is not the total carbon number of the substituent a and the substituent B. For example, the "substituent B having a carbon number Y substituted by the substituent a" means that the substituent a "(not limited to a carbon number) is substituted on the" substituent B having a carbon number Y ", and the carbon number Y is not the total carbon number of the substituent a and the substituent B.
Since the chemical structural formula described in the present specification (including a general formula depicted by a markush (markush) structural formula as in formula (1) described later) is a planar structural formula, various isomeric structures such as an enantiomer (enantiomer), a diastereomer, or a rotamer may actually exist. In the present specification, unless otherwise specified, the compound described may have any isomeric structure that can be considered from the planar structural formula thereof, and may be a mixture of possible isomers in any ratio.
In the present specification, structural formulae of a plurality of aromatic compounds are described. An aromatic compound is described by combining a double bond and a single bond, but actually, since pi electrons resonate, there is an equivalent resonance structure in which a plurality of double bonds and single bonds are alternately replaced with each other for a single substance. In the present specification, only one resonance structural formula is described for one substance, but other resonance structural formulas that are equivalent in organic chemistry are also included unless otherwise specified. For this purpose, the following description of "Z = Z" and the like can be referred to. That is, for example, "Z = Z" in formula (2) described later is as follows as an example. However, the present invention is not limited to this, and is applicable to not only the one described above but also other conceivable equivalent resonance structural formulas.
[ solution 17]
In the present specification, the expression "may" is used in some cases, and this is the same meaning as "does not" or "does not mean" does.
In the present specification, "adjacent" is used with respect to two atoms directly bonded by a covalent bond in the structural formula, or two groups to which two atoms directly bonded by a covalent bond are respectively bonded.
In the present specification, a substituent is sometimes substituted with a further substituent. For example, reference to a particular substituent will sometimes be described as "substituted or unsubstituted". This means that at least one hydrogen of the specified substituent is substituted by a further substituent, or is unsubstituted. In the present specification, the specific substituent at this time is sometimes referred to as a "first substituent", and the further substituent is sometimes referred to as a "second substituent".
< 1. Polycyclic aromatic Compound >
The polycyclic aromatic compound of the present invention is a polycyclic aromatic compound having one or more structures containing the structural unit represented by formula (1). The present inventors have found that an organic electroluminescent element having a longer lifetime and higher luminous efficiency can be produced by preparing a compound having a group represented by the formula (D-1) or the formula (D-2).
[ formula 18]
In formula (1), ring A and ring B are each independently a substituted or unsubstituted aryl ring or a substituted or unsubstituted heteroaryl ring. As the substituent, in addition to the group represented by the formula (D-1) or the formula (D-2), a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted diarylamino group, a substituted or unsubstituted diheteroarylamino group, a substituted or unsubstituted arylheteroarylamino group, a substituted or unsubstituted diarylboron group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted arylthio group, or a substituted silane group may be mentioned. Here, the aryl group, the heteroaryl group, the diarylamino group, the diheteroarylamino group, the arylheteroarylamino group, the diarylboron group, the alkyl group, the cycloalkyl group, the alkenyl group, the alkoxy group, the aryloxy group, the arylthio group, the substituted silane group are first substituent groups. The substituent (second substituent) in the "substituted or unsubstituted" in the "substituted" is preferably an aryl group, a heteroaryl group, a diarylamino group, an alkyl group, a cycloalkyl group, or a substituted silane group. Further, as the substituent (second substituent) in the case of "substituted" in the "substituted or unsubstituted aryl group" or the "substituted or unsubstituted heteroaryl group", there may be mentioned a group represented by the formula (D-1) or the formula (D-2).
In the formula (1), the ring C is a ring structure represented by the formula (C). In the formula (C), two Z's are optionally adjacent C Is with Y 1 Or X 2 A bonded carbon. Specifically, two Z's arbitrarily adjacent to each other C With Y 1 To which one is bonded to X 2 Bonding. As shown in the following specific example, two adjacent Z's on the c1 ring C Can be any one of with Y 1 And X 2 Bonded carbon, in addition to two Z's adjacent to the c2 ring C Can be with Y 1 And X 2 A bound carbon.
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 And said > Si (-R) 2 Each R of (A) is independently hydrogen, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, > C (-R) 2 And said > Si (-R) 2 Two R's may be bonded to each other to form a ring. Here, as the substituent (second substituent) in the case of "substituted" in "substituted or unsubstituted", an aryl group, a heteroaryl group, a diarylamino group, an alkyl group, a cycloalkyl group, or a substituted silane group is preferable. In addition, two aryl groups of the diarylamino group may be bonded to each other. Further, as the substituent for the "substituted" in the "substituted or unsubstituted aryl" or "substituted or unsubstituted heteroaryl", there may be mentioned a group represented by the formula (D-1) or the formula (D-2).
In formula (C), except as with Y 1 Or X 2 Z of carbon to which any one of them is bonded C Z other than Z C Are each independently N or C-R C . Wherein, except as with Y 1 Or X 2 Z of carbon to which any one of them is bonded C Z other than Z C Not all will be N. R C Each independently is hydrogen, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted diarylamino, substituted or unsubstituted diheteroarylamino, substituted or unsubstituted arylheteroarylamino, substituted or unsubstituted diarylboron, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkoxy, substituted or unsubstituted aryloxy, substituted or unsubstituted arylthio, or substituted silyl.
Here, as the substituent (second substituent) in the case of "substituted" in "substituted or unsubstituted", an aryl group, a heteroaryl group, a diarylamino group, an alkyl group, a cycloalkyl group, or a substituted silane group is preferable. Further, as the substituent for the "substituted" in the "substituted or unsubstituted aryl" or "substituted or unsubstituted heteroaryl", there may be mentioned a group represented by the formula (D-1) or the formula (D-2).
In the formula (C), two adjacent R C May be bonded to each other (and to these R's) C The two carbons bonded together) to form an aryl or heteroaryl ring. The aryl and heteroaryl rings formed are each unsubstituted or substituted with at least one R C2 And (4) substitution. R is C2 And R C Are of the same meaning, wherein R C2 Not being hydrogen, and two R being adjacent C2 Are not bonded to each other to form an aryl or heteroaryl ring.
In the ring represented by the formula (C), as R C Or R C2 And an aryl group substituted with at least a group represented by the formula (D-1) or the formula (D-2) or a heteroaryl group substituted with at least a group represented by the formula (D-1) or the formula (D-2).
The group represented by the formula (D-1) and the group represented by the formula (D-2) are each bonded at two star points to two adjacent rings of the aryl ring or the heteroaryl ring. R is D Each independently is substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted alkyl, or substituted or unsubstituted cycloalkyl, L each independently is substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted alkyl, or substituted or unsubstituted cycloalkylSubstituted or unsubstituted alkylene, substituted or unsubstituted alkenylene, substituted or unsubstituted arylene, or substituted or unsubstituted heteroarylene. Here, the arylene group and the heteroarylene group in L preferably have an aryl ring and two adjacent ring constituent atoms of a heteroaryl ring as bonding positions, respectively.
[ formula 19]
The group represented by the formula (D-1) or (D-2) is substituted at two adjacent ring-constituting atoms in the aryl or heteroaryl ring to form a fused ring structure in which at least two rings are condensed. For example, a condensed ring in which a benzene ring is condensed with cyclohexane is formed by substituting a group represented by formula (D-2) in which L is ethylene on the benzene ring (phenyl group).
In the formulae (D-1) and (D-2), by R D The substituent other than hydrogen may stabilize the structure in which the group represented by the formula (D-1) or the group represented by the formula (D-2) is substituted on the aromatic ring. R D Each independently is preferably a substituted or unsubstituted aryl group, or a substituted or unsubstituted alkyl group, more preferably a phenyl group or an alkyl group, which alkyl group may be substituted. R D Most preferably both are methyl.
In the formula (D-1) and the formula (D-2), L is preferably a substituted or unsubstituted alkylene group or a substituted or unsubstituted arylene group, respectively, and more preferably a methylene group, an ethylene group, a phenylene group which may be substituted with an alkyl group (particularly, a1, 2-phenylene group).
Specific examples of the group represented by the formula (D-1) are shown below.
[ solution 20]
Specific examples of the group represented by the formula (D-2) are shown below.
[ solution 21]
In the formulae (D-1-1) to (D-1-6) and (D-2-1) to (D-2-2), R D The definitions and preferred ranges of (A) are the same as those of the formulae (D-1) and (D-2), respectively. At least one hydrogen in formulae (D-1-1) to (D-1-6) and (D-2-1) to (D-2-2) may be substituted with a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group (preferably an alkyl group (more preferably an unsubstituted methyl group) or a phenyl group in which at least one hydrogen may be substituted with a methyl group or a tert-butyl group).
Among the formulae (D-1-1) to (D-1-6) and the formulae (D-2-1) to (D-2-2), the formula (D-1-1) is particularly preferable. By using a polycyclic aromatic compound having an aryl ring or heteroaryl ring structure substituted with a group represented by the formula (D-1-1) in the formation of a light-emitting layer of an organic EL element, particularly in a dopant material, an organic EL element having higher light-emitting efficiency and a long lifetime can be obtained.
The polycyclic aromatic compound of the present invention is expected to have a reduced melting point or sublimation temperature by containing an aryl group substituted with at least a group represented by the formula (D-1) or the formula (D-2) or a heteroaryl group substituted with at least a group represented by the formula (D-1) or the formula (D-2). This means that in sublimation purification, which is almost indispensable as a purification method for materials for organic devices such as organic EL elements requiring high purity, since purification can be performed at a relatively low temperature, thermal decomposition of the materials and the like can be avoided. In addition, since the vacuum deposition process, which is a powerful means for fabricating organic devices such as organic EL elements, can be performed at a relatively low temperature, thermal decomposition of materials can be avoided, and as a result, high-performance organic devices can be obtained. Further, the introduction of the group represented by the formula (D-1) or (D-2) improves the solubility in an organic solvent, and thus the introduction can be applied to the production of a device by a coating process. However, the present invention is not particularly limited to these principles.
The polycyclic aromatic compound having one or more structures containing the structural unit represented by the formula (1) may be represented by R C Or R C2 The aryl group substituted with at least the group represented by the formula (D-1) or the formula (D-2) or the heteroaryl group substituted with at least the group represented by the formula (D-1) or the formula (D-2) may further contain, as a partial structure, at least one ring selected from the group consisting of an aryl ring substituted with at least the group represented by the formula (D-1) or the formula (D-2) and a heteroaryl ring substituted with at least the group represented by the formula (D-1) or the formula (D-2).
For example, there may be mentioned a form in which the aryl ring or heteroaryl ring in the A ring, B ring and C ring is substituted with a group represented by the formula (D-1) or (D-2). In particular, there can be mentioned a form in which the a ring, b ring, c1 ring, c2 ring (or c3 ring) in the polycyclic aromatic compound having one or two or more structures containing the structural unit represented by the formula (2) is substituted with a group represented by the formula (D-1) or the formula (D-2). Among these, preferred is a form in which the aryl ring or heteroaryl ring in the B ring is substituted with a group represented by the formula (D-1) or the formula (D-2) (particularly a form in which the aryl ring or heteroaryl ring in the B ring of the formula (2) is substituted with a group represented by the formula (D-1) or the formula (D-2)).
The polycyclic aromatic compound of the present invention preferably contains in its structure at least an aryl ring substituted with at least a group represented by the formula (D-1) or a heteroaryl ring substituted with at least a group represented by the formula (D-1) as at least one partial structure. When the compound contains a group represented by the formula (D-1), the compound is represented by the formula C Or R C2 The compound may contain a group represented by the formula (D-1) or the formula (D-2) or may not contain a group represented by the formula (D-1) or the formula (D-2). In the present specification, such a structure is represented by formula (1'). The polycyclic aromatic compound having a structure containing the structural unit represented by the formula (1') is more preferably a polycyclic aromatic compound having, as at least one partial structure, an aryl ring substituted with at least a group represented by the formula (D-1-1) or a heteroaryl ring substituted with at least a group represented by the formula (D-1-1) in its structure.
In the formula (C), X c Preferably > O, > N-R, or > S, more preferably > O or > S, and still more preferably > S. Z in relation to formula (C) C Reference is made to the preferred rangesThe following specific examples are described.
X in the formula (1) 1 And X 2 Independently of each other > O, > N-R, > Si (-R) 2 、＞C(-R) 2 S, or Se. Preferably X 1 And X 2 One is > N-R, the other is > N-R, > C (-R) 2 Or > O, more preferably X 1 And X 2 Are each independently > N-R.
In the formula (1), as X 1 Or X 2 R of (1) is hydrogen, an aryl group which may be substituted (wherein, as a substituent, an amino group is excluded), a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted alkyl group or a substituted or unsubstituted cycloalkyl group. As X 1 And X 2 Is > Si (-R) 2 Each R of (a) is independently hydrogen, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted alkyl, or substituted or unsubstituted cycloalkyl. Here, as the substituent (second substituent) in the "substituted or unsubstituted" in the "substituted" group, an aryl group, a heteroaryl group, a diarylamino group, an alkyl group, a cycloalkyl group, or a substituted silane group is preferable. Further, as the substituent for "substituted" in "substituted or unsubstituted aryl" or "substituted or unsubstituted heteroaryl", there may be mentioned a group represented by the formula (D-1) or the formula (D-2).
In the formula (1), as X 1 Or X 2 Is > Si (-R) 2 And > C (-R) 2 Each R of (A) is independently hydrogen, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted alkyl, or substituted or unsubstituted cycloalkyl, preferably both R are the same, and both R may be bonded to form a ring.
In formula (1), with respect to X 1 Or X 2 Is > N-R, > Si (-R) 2 Or > C (-R) 2 The aryl, heteroaryl, alkyl and cycloalkyl groups in R in (1) can be referred to the description of each group described later.
In the formula (1), as X 1 Or X 2 R > N-R is preferably substituted or unsubstitutedAryl, substituted or unsubstituted heteroaryl, or substituted or unsubstituted cycloalkyl, more preferably substituted or unsubstituted aryl or substituted or unsubstituted heteroaryl. Examples of the cycloalkyl group include those described later. The aryl group is preferably a phenyl group, a biphenyl group (particularly a 2-biphenyl group), or a terphenyl group (particularly a terphenyl-2' -yl group), and the heteroaryl group is preferably a benzothienyl group (such as a 2-benzothienyl group or a 6-benzothienyl group), a benzofuranyl group (such as a 2-benzofuranyl group or a 3-benzofuranyl group, or a 5-benzofuranyl group), a dibenzofuranyl group (such as a 2-dibenzofuranyl group, a 3-dibenzofuranyl group, a 4-dibenzofuranyl group, or a 5-dibenzofuranyl group), or the like. The substituent is preferably a tertiary alkyl group (particularly, a tertiary butyl group) represented by the following formula (tR) or a cycloalkyl group (particularly, an adamantyl group). The number of substituents in the aryl group and the heteroaryl group is preferably 0 to 2, more preferably 1 or 2, and still more preferably 1. The aryl group is also preferably a group substituted with a group represented by the formula (D-1) or the formula (D-2).
In the formula (1), as X 1 Or X 2 R > N-R is preferably a phenyl group, a naphthyl group, a biphenyl group, a terphenyl group, a quaterphenyl group, a dibenzofuranyl group, a dibenzothiophenyl group, a fluorenyl group, or a carbazolyl group, more preferably a phenyl group, a naphthyl group, a biphenyl group, a terphenyl group, a dibenzofuranyl group, or a carbazolyl group, and further preferably a phenyl group, a biphenyl group, or a dibenzofuranyl group. Further, at least one hydrogen of the phenyl group, the naphthyl group, the biphenyl group, the terphenyl group, the quaterphenyl group, the dibenzofuranyl group, the dibenzothiophenyl group, the fluorenyl group, and the carbazolyl group, respectively, independently, may be replaced with 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 diarylboron group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted arylthio group, orSubstituted silyl groups. In addition, two hydrogens bonded to adjacent carbons may be substituted with a group represented by formula (D-1) or formula (D-2). As the substituent, among the above, preferred is a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, or a group represented by the formula (D-1) or the formula (D-2), more preferred is a substituted or unsubstituted aryl group, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted cycloalkyl group, or a group represented by the formula (D-1) or the formula (D-2), and further preferred is a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, or a group represented by the formula (D-1) or the formula (D-2). The phenyl group, the biphenyl group, the terphenyl group, and the quaterphenyl group are preferably any of the following groups. In the following formula, X represents a group represented by 1 Or X 2 A bonding position of N > N-R.
[ solution 22]
As a part of preferable examples of the case where the phenyl group, the biphenyl group, the terphenyl group, or the quaterphenyl group has a substituent, a group represented by the following formula (X-4) can be mentioned.
[ chemical No. 23]
( tBu represents a tert-butyl group, and represents a bonding position to N; p and q are each independently an integer of 0 to 3 )
In the formula (1), as X 1 Or X 2 R of > N-R is also preferably an aryl group (which may be further substituted) substituted with a group represented by the formula (D-1) or the formula (D-2). As the aryl group substituted with the group represented by the formula (D-1) or the formula (D-2), the following is particularly preferable.
[ solution 24]
( Me represents a methyl group, tBu represents a tert-butyl group, and represents a bonding position with N; p and q are each independently an integer of 0 to 3 )
In the formula (1), X 1 Or X 2 It is preferred that each independently > N-R, and it is preferred that at least one R > N-R is a group represented by formula (D-X-3), formula (D-X-4), formula (D-X-5), or formula (X-4). In addition, X is also preferable 2 R of (2) is a group represented by the formula (D-X-3), the formula (D-X-4), the formula (D-X-5) or the formula (X-4).
In the formula (1), as X 1 Or X 2 Is > N-R, > Si (-R) 2 And > C (-R) 2 R in at least one of (a) and (B) may be bonded to any one of the rings a and B or any one of the rings a and C through a connecting group or a single bond. I.e. as X 1 Is > N-R, > Si (-R) 2 And > C (-R) 2 R in at least one of (a) and (B) may be bonded to any of the ring A and the ring B as X 2 Is > N-R, > Si (-R) 2 And > C (-R) 2 R in at least one of (a) and (b) may be bonded to any one of the a ring and the C ring through a linking group or a single bond. As a linking group, a group having a hydroxyl group, preferably-O-, -S-) or-C (-R) 13 ) 2 -。R 13 The alkyl group or cycloalkyl group refers to the description of each group described later. Particularly preferred is an alkyl group having 1 to 5 carbon atoms (for example, methyl group, ethyl group, etc.) or a cycloalkyl group having 5 to 10 carbon atoms (preferably, cyclohexyl group or adamantyl group).
Further, the regulation may be represented by a structure represented by the following formula (1-3-2) and having X > N-R 1 A ring structure introduced into the condensed ring A'. I.e. for example with other rings to introduce X 1 And X 2 Any of the above forms is condensed to an A' ring formed as an A ring of a benzene ring. The condensed ring A' formed is, for example, a carbazole ring, a phenoxazine ring, or a phenothiazine ring.
[ solution 25]
For example, R > N-R is preferably a substituted or unsubstituted cycloalkyl group and is bonded to the A, B, or C ring by a single bond. As the cycloalkyl group, a substituted or unsubstituted cyclopentyl group or a substituted or unsubstituted cyclohexyl group is preferable.
As a particularly preferable example of the condensed ring formed as described above, a structure represented by formula (a 11) can be mentioned. In the formula (A11),' As X 1 Or X 2 Is > N-R, > Si (-R) 2 And > C (-R) 2 The above-mentioned definition that R in at least one of (a) and (B) rings may be bonded to any one of the a ring and the B ring, or any one of the a ring and the C ring by a connecting group or a single bond "corresponds to a form in which R is bonded by a single bond. As described above, in this case, the two carbons substituted with the methyl group are asymmetric carbons, and as the compound represented by the formula (1), diastereoisomers and enantiomers may exist, and as the compound represented by the formula (1), any of these isomers may be contained, and in addition, the isomers may be mixed in an arbitrary ratio.
[ solution 26]
In formula (a 11), me is methyl, and is linked to X at the position of 1 Or X 2 One of the two rings to which it is bonded, at the position of which it is bonded to the other ring.
Similarly, the following examples are given as forms in which R > N-R is a phenyl group and is bonded to the A ring, the B ring, or the C ring by a single bond.
[ chemical No. 27]
In the formula (A12), X and X are at the positions 1 Or X 2 One of the two rings to which it is bonded, at the position of which it is bonded to the other ring.
By using > N-R having R in the preferred range as X 1 Or X 2 The compound of the present invention is used as a light-emitting material for manufacturing a device, and can further improve light-emitting efficiency or device lifetime.
X as formula (1) 1 Or X 2 Is > Si (-R) 2 R of (a) is hydrogen, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted alkyl, or substituted or unsubstituted cycloalkyl. The aryl, heteroaryl, alkyl or cycloalkyl groups are each as described below. Particularly preferred is an aryl group having 6 to 10 carbon atoms (e.g., phenyl group, naphthyl group, etc.), a heteroaryl group having 2 to 15 carbon atoms (e.g., carbazolyl group, etc.), an alkyl group having 1 to 5 carbon atoms (e.g., methyl group, ethyl group, etc.), or a cycloalkyl group having 5 to 10 carbon atoms (preferably cyclohexyl group or adamantyl group). As a substituent (second substituent) when "substituted or unsubstituted" is mentioned, an aryl group, a heteroaryl group, a diarylamino group, an alkyl group, a cycloalkyl group, or a substituted silane group is preferable. Further, as the substituent for the "substituted" in the "substituted or unsubstituted aryl" or "substituted or unsubstituted heteroaryl", there may be mentioned a group represented by the formula (D-1) or the formula (D-2).
X as formula (1) 1 Or X 2 Is greater than C (-R) 2 R of (a) is hydrogen, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted alkyl, or substituted or unsubstituted cycloalkyl. As the aryl group, heteroaryl group, alkyl group or cycloalkyl group, the following explanations of the groups can be referred to. Particularly preferred is an aryl group having 6 to 10 carbon atoms (for example, phenyl group, naphthyl group, etc.), a heteroaryl group having 2 to 15 carbon atoms (for example, carbazolyl group, etc.), an alkyl group having 1 to 5 carbon atoms (for example, methyl group, ethyl group, etc.), or a cycloalkyl group having 5 to 10 carbon atoms (preferably cyclohexyl group or adamantyl group). As the substituent (second substituent) when "substituted or unsubstituted" is mentioned, aryl, heteroaryl, diarylamino, alkyl, or the like is preferableCycloalkyl, or substituted silyl. Further, as the substituent for "substituted" in "substituted or unsubstituted aryl" or "substituted or unsubstituted heteroaryl", there may be mentioned a group represented by the formula (D-1) or the formula (D-2).
Preferred examples of the structural unit represented by formula (1) include structural units represented by the following formula (2).
[ solution 28]
In the formula (2), Z is N or C-R independently in the ring a and the ring b 11 Or Z = Z is each independently > O, > N-R, > C (-R) 2 、＞Si(-R) 2 S or Se, said > N-R, said > C (-R) 2 And said > Si (-R) 2 Each R of (A) is independently hydrogen, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, > C (-R) 2 And said > Si (-R) 2 Two R's may be bonded to each other to form a ring. Here, as a substituent (second substituent) when "substituted or unsubstituted" is mentioned, an aryl group, a heteroaryl group, a diarylamino group, an alkyl group, a cycloalkyl group, or a substituted silane group is preferable. Further, as the substituent for the "substituted" in the "substituted or unsubstituted aryl" or "substituted or unsubstituted heteroaryl", there may be mentioned a group represented by the formula (D-1) or the formula (D-2).
In the formula (2), C-R 11 R of (A) to (B) 11 Each independently is hydrogen, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted diarylamino, substituted or unsubstituted diheteroarylamino, substituted or unsubstituted arylheteroarylamino, substituted or unsubstituted diarylboron, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkoxy, or substituted or unsubstituted heteroarylboronA substituted or unsubstituted aryloxy group, a substituted or unsubstituted arylthio group, or a substituted silyl group. Here, as a substituent when "substituted or unsubstituted" is mentioned, an aryl group, a heteroaryl group, a diarylamino group, an alkyl group, a cycloalkyl group, or a substituted silane group is preferable. Further, as the substituent for the "substituted" in the "substituted or unsubstituted aryl" or "substituted or unsubstituted heteroaryl", there may be mentioned a group represented by the formula (D-1) or the formula (D-2).
As R 11 Preferably, it is hydrogen, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted diarylamino, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, or substituted silyl.
Next, for "Z = Z, each is independently > O, > N-R, > C (-R) 2 、＞Si(-R) 2 The description of "S" or "Se" is given. For example, in the b-ring in formula (2), the site as "Z = Z" is substituted by > O, > N-R, > C (-R) 2 、＞Si(-R) 2 Rings obtained by "S" or "Se" may be mentioned: cyclopentadiene rings, pyrrole rings, furan rings, thiophene rings, and the like. Shown below is that in the b-ring one Z = Z is > N-R, > O, > S, > C (-R) 2 And the remainder of Z are C-H, and one Z = Z being > N-R, > O, > S, > C (-R) 2 And the remaining Z are C-R 11 R's adjacent to each other as described later 11 Examples of benzene rings are formed. However, the form that the b-ring and the like can take is not limited to the following examples.
[ solution 29]
As described above, since the aromatic compound has a resonance structural formula which is completely equivalent in organic chemistry, any possible resonance structural formula can be used as a base. Further, the > N-R, the > C (-R) as Z = Z 2 And said > Si (-R) 2 R of (A) is each independently hydrogenSubstituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, > C (-R) 2 And said > Si (-R) 2 Two R's may be bonded to each other to form a ring. As the substituent (second substituent) when "substituted or unsubstituted" is mentioned, an aryl group, a heteroaryl group, a diarylamino group, an alkyl group, a cycloalkyl group, or a substituted silane group is preferable. Further, as the substituent for "substituted" in "substituted or unsubstituted aryl" or "substituted or unsubstituted heteroaryl", there may be mentioned a group represented by the formula (D-1) or the formula (D-2).
In the formula (2), Z is preferably all C-R independently 11 。
Two adjacent R 11 May be bonded to each other and together with the a-ring or b-ring form an aryl or heteroaryl ring. The aryl and heteroaryl rings formed are each unsubstituted or substituted with at least one R 11b And (4) substitution. R 11b And R 11 Are of the same meaning, wherein R 11b Not being hydrogen, and two R being adjacent 11b Are not bonded to each other to form an aryl or heteroaryl ring. As the aryl ring or heteroaryl ring herein, the following description of each ring can be referred to.
As the aryl ring formed together with the a ring or the b ring, a naphthalene ring, an anthracene ring, a fluorene ring, an indene ring, a 9, 10-dihydroanthracene ring (particularly, a 9, 10-tetramethyl-9, 10-dihydroanthracene ring), an acridine dihydroring, or a xanthene ring is preferable, and as the heteroaryl ring formed, a benzothiophene ring, an indole ring, a benzofuran ring, a dibenzothiophene ring, a dibenzofuran ring, or a carbazole ring is preferable.
Two adjacent R are shown below 11 Examples of aryl or heteroaryl rings are bonded to each other and together with the b ring. Furthermore, the benzene ring in the following structures may further have at least one R 11b As a substituent.
[ solution 30]
Further preferable examples of the formula (2) include the following formula (2 a), formula (2 b), formula (2 c), formula (2 d), formula (2 e), formula (2 f), formula (2 g) and formula (2 h).
[ solution 31]
Preferably, in the formulae (2 a), (2 b), (2 c), (2 d), (2 e), (2 f), (2 g) and (2 h), Z C Independently of each other are all C-R 11 In the formulae (2 a), (2 b), (2 c), (2 d), (2 e), (2 f), (2 g) and (2 h), Z in the c2 ring is C Independently of each other are all C-R C And R is adjacent as described later C The form in which the bond is formed with each other to form an aryl ring (preferably a benzene ring) is also preferable. Among formulae (2 a), (2 b), (2 c), (2 d), (2 e), (2 f), (2 g) and (2 h), formulae (2 a), (2 b) and (2 a) are preferable, and formula (2 a) is most preferable. Note that, for the description of each symbol and each phrase, the description of the present specification to be described later can be referred to.
In the formulae (2 c), (2 d), (2 e), (2 f), (2 g) and (2 h), Z of the c2 ring is preferred C Are all C-R C And two adjacent R C Are bonded to each other to form an aryl ring or heteroaryl ring (more preferably an aryl ring, and further preferably a benzene ring). This preferred mode is shown below. The definitions of the symbols of formula (2 c-2), formula (2 d-2), formula (2 e-2), formula (2 f-2), formula (2 g-2) and formula (2 h-2) and their preferred ranges can be referred to the description of formula (2).
[ solution 32]
Further, the structural unit represented by formula (2 a) is preferably a structural unit represented by the following formula (2 a-1) or formula (2 a-2).
[ solution 33]
In the formula (2 a-1) or the formula (2 a-2), Y 1 、X 1 、X 2 、X C And Y in the formula (1) 1 、X 1 、X 2 、X C Are each the same as R 11b 、R C2 And R in the formula (2) 11b 、R C2 Are respectively defined in the same meaning. X 3 And X 4 Each independently is a single bond, > O, > N-R, > C (-R) 2 Or > S, wherein X 3 And X 4 Not simultaneously a single bond. n1 is an integer of 1 to 4, n2 is an integer of 0 to 4, n3 is an integer of 0 to 3, and n4 is an integer of 0 to 2. At least one of the aryl ring or heteroaryl ring in the structure comprising one or two or more of the structural units represented by formula (2 a-1) or formula (2 a-2) may be substituted with at least one group represented by formula (D-1) or formula (D-2).
In the formulae (2 a-1) and (2 a-2), Y 1 、X 1 、X 2 And X C With Y in the formula (1) 1 、X 1 、X 2 And X C The preferred ranges of (a) and (b) are the same. In the formula (2 a-2), X is preferred 3 And X 4 One of them is > C (-R) 2 And the other is > O, > N-R, or > C (-R) 2 Or one of them is a single bond and the other is > O or > N-R. n1 is preferably 1 to 2, more preferably 1. n2 is preferably 0 to 2, more preferably 0 or 1. n3 is preferably 0 or 1. n4 is preferably 0.
The structural unit represented by the formula (2 a-1) or the formula (2 a-2) contains, as R, an aryl group substituted with at least a group represented by the formula (D-1) or the formula (D-2) or a heteroaryl group substituted with at least a group represented by the formula (D-1) or the formula (D-2) C2 . R in the structure of a compound represented by the formula (2 a-1) or the formula (2 a-2) C2 And at least one of the aryl ring and the heteroaryl ring at the other position may be substituted with a group represented by the formula (D-1) or the formula (D-2).
In the formula (1), and in the formula (2) and the like which are preferred embodiments thereof, Y 1 Each independently is B, P = O, P = S, al, ga, asSi-R, or Ge-R, preferably B, P = O or P = S, most preferably B. R of the Si-R and Ge-R is aryl with 6-12 carbon atoms, alkyl with 1-6 carbon atoms or cycloalkyl with 3-14 carbon atoms. Y of formula (1) 1 In the above-mentioned Si-R and Ge-R, R is an aryl group, an alkyl group or a cycloalkyl group, and the aryl group, the alkyl group or the cycloalkyl group may be the groups described later. Particularly preferred is an aryl group having 6 to 10 carbon atoms (e.g., phenyl group, naphthyl group, etc.), an alkyl group having 1 to 5 carbon atoms (e.g., methyl group, ethyl group, etc.), or a cycloalkyl group having 5 to 10 carbon atoms (preferably cyclohexyl group or adamantyl group).
The polycyclic aromatic compound of the present invention is a polycyclic aromatic compound having one or more structures including the structural unit represented by the formula (1) or the formula (2) or the like as a preferred embodiment thereof. Examples of the polycyclic aromatic compound having a structure including one of the structural units include polycyclic aromatic compounds represented by the formula (1) (or the formula (2) as a preferred embodiment thereof). Examples of the polycyclic aromatic compound having two or more structures including the structural unit represented by formula (1) include compounds corresponding to multimers of the polycyclic aromatic compound represented by the above-described formula as the structural unit represented by formula (1). The multimer is preferably a dimer to hexamer, more preferably a dimer to trimer, and particularly preferably a dimer. The multimer may be in a form having a plurality of unit structures in one compound, and may be in a form in which arbitrary rings (a ring), B ring (B ring), or C ring (C1 ring, C2 ring, C3 ring)) included in the unit structures are bonded in a common manner in the plurality of unit structures, or in a form in which arbitrary rings (a ring), B ring (B ring), or C ring (C1 ring, C2 ring, C3 ring)) included in the unit structures are bonded so as to be condensed with each other. The above unit structure may be a plurality of units bonded by a single bond, a linking group having 1 to 3 carbon atoms such as alkylene, phenylene, or naphthylene. Among these, the compound is preferably bonded so as to have a common ring.
All or part of hydrogen in one or two or more structures including the structural unit represented by the formula (1) and a preferred form thereof may be substituted by deuterium, cyano group, or halogen.
For example, in one or more structures including the structural unit represented by the formula (1) and preferred embodiments thereof, the substituent on the a ring (ring a), the B ring (ring B), the C ring (ring C1, ring C2 (, ring C3)), the a ring to the C ring, and Y 1 R (= alkyl, cycloalkyl, aryl) when Si-R or Ge-R is used, and X 1 And X 2 Hydrogen in R > N-R in one of the above may be substituted by deuterium, cyano or halogen, and among these, there may be mentioned forms in which all or a part of hydrogen in an aryl group or a heteroaryl group is substituted by deuterium, cyano or halogen. Halogen is fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine, more preferably fluorine or chlorine, and further preferably fluorine. In particular, the form in which hydrogen is substituted with deuterium is preferable because stability of the compound is improved. In the case where hydrogen is substituted by deuterium, as long as one hydrogen is substituted by deuterium, it is preferable that a plurality of hydrogens are substituted by deuterium, more preferably all hydrogens of the aromatic moiety are substituted by deuterium, and still more preferably all hydrogens are substituted by deuterium.
The details of the ring and the substituent used in the present specification are described below.
Examples of the "aryl ring" in the present specification include aryl rings having 6 to 30 carbon atoms, preferably aryl rings having 6 to 16 carbon atoms, more preferably aryl rings having 6 to 12 carbon atoms, and particularly preferably aryl rings having 6 to 10 carbon atoms.
Specific "aryl ring" may include: benzene ring as a monocyclic system, biphenyl ring as a bicyclic system, naphthalene ring and indene ring as a condensed bicyclic system, terphenyl ring (m-terphenyl, o-terphenyl, p-terphenyl) as a tricyclic system, acenaphthylene ring (acenaphthylene ring), fluorene ring (fluorene ring), phenalene ring (phenalene ring), phenanthrene ring (phenanthrene ring), anthracene ring, 9, 10-dihydroanthracene ring as a condensed tricyclic system, triphenylene ring, pyrene ring, tetracene ring, perylene ring, pentacene ring, etc,
Rings, perylene rings as condensed five-ring systems, pentacene rings, and the like. The fluorene ring, the benzfluorene ring, and the indene ring also include a structure in which a fluorene ring, a benzfluorene ring, a cyclopentane ring, and the like are spiro-bonded.The fluorene ring, the benzofluorene ring, and the indene ring also include rings such as a dimethylfluorene ring, a dimethylbenzene ring, and a dimethylindene ring, in which two hydrogens of a methylene group are substituted with an alkyl group such as a methyl group as a first substituent described later. The 9, 10-dihydroanthracene ring also includes rings such as a 9, 10-tetramethyl-9, 10-dihydroanthracene ring in which four hydrogens of two methylene groups are each substituted with an alkyl group such as a methyl group as a first substituent described later.
The "heteroaryl ring" in the present specification includes, for example, 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, further 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 heterocyclic rings containing 1 to 5 heteroatoms selected from oxygen, sulfur and nitrogen as ring-constituting atoms in addition to carbon.
Specific examples of the "heteroaryl ring" include: <xnotran> , , , , , , ( ), , , , , , , , , , , , 1H- , , , , 1H- , , , , , , , , , , , (carboline) , , , , , , (phenazasiline) , , , , , , , , , , , , , , , , , , (dibenzodioxin) . </xnotran> In addition, in the dihydroacridine ring, the xanthene ring, and the thioxanthene ring, it is also preferable that two of the two hydrogens of the methylene group are each substituted with an alkyl group such as a methyl group as a first substituent described later to form a ring such as a dimethyldihydroacridine ring, a dimethylxanthene ring, or a dimethylthioxanthene ring. In addition, a bipyridine ring, a phenylpyridine ring, a pyridylphenyl ring as a bicyclic system, a terpyridine (terpyridyl) ring, a bispyridylphenyl ring, and a pyridylbiphenyl ring as a tricyclic system may also be exemplified as the "heteroaryl ring". In addition, the "heteroaryl ring" also includes a pyran ring.
In addition, the following formula (BO) is also included in the heteroaryl ring.
[ chemical 34]
Further, the a ring, the B ring in formula (1) are each independently a substituted or unsubstituted aryl ring or a substituted or unsubstituted heteroaryl ring, where at least one of the "aryl ring" or the "heteroaryl ring" may be substituted with a substituted or unsubstituted "aryl", a substituted or unsubstituted "heteroaryl", a substituted or unsubstituted "diarylamino", a substituted or unsubstituted "diheteroarylamino", a substituted or unsubstituted "arylheteroarylamino", a substituted or unsubstituted "diarylboryl", a substituted or unsubstituted "alkyl", a substituted or unsubstituted "alkenyl", a substituted or unsubstituted "cycloalkyl", a substituted or unsubstituted "alkoxy", a substituted or unsubstituted "aryloxy", a substituted or unsubstituted "arylthio", or a "substituted silyl" as a first substituent.
The "aryl group" in the present specification is a monovalent group obtained by removing one hydrogen from the "aryl ring", and examples thereof include aryl groups having 6 to 30 carbon atoms, preferably aryl groups having 6 to 24 carbon atoms, more preferably aryl groups having 6 to 20 carbon atoms, still more preferably aryl groups having 6 to 16 carbon atoms, particularly preferably aryl groups having 6 to 12 carbon atoms, and most preferably aryl groups having 6 to 10 carbon atoms.
The "heteroaryl group" is a monovalent group obtained by removing one hydrogen from the "heteroaryl ring", and examples thereof include a heteroaryl group having 2 to 30 carbon atoms, preferably a heteroaryl group having 2 to 25 carbon atoms, more preferably a heteroaryl group having 2 to 20 carbon atoms, still more preferably a heteroaryl group having 2 to 15 carbon atoms, and particularly preferably a heteroaryl group having 2 to 10 carbon atoms. Examples of the heteroaryl group include a heterocyclic ring containing 1 to 5 heteroatoms selected from oxygen, sulfur and nitrogen as ring-constituting atoms in addition to carbon.
As the aryl or heteroaryl group in the "substituted or unsubstituted diarylamino group", "substituted or unsubstituted diheteroarylamino group", "substituted or unsubstituted arylheteroarylamino group" as the first substituent, the above-mentioned groups explained as "aryl" or "heteroaryl" may be cited along with their preferred ranges.
Two aryl groups of the diarylamino groups as the first substituent may be bonded to each other via a linking group, two heteroaryl groups of the diheteroarylamino groups as the first substituent may be bonded to each other via a linking group, and an aryl group and a heteroaryl group of the arylheteroarylamino groups as the first substituent may be bonded to each other via a linking group. The expression "bonded via a linking group" used herein means that, for example, two phenyl groups of a diphenylamino group form a bond via the linking group as shown below. In addition, the description is also applicable to diheteroarylamino and arylheteroarylamino groups formed from aryl or heteroaryl groups.
[ solution 35]
Specific 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 X Each independently is alkyl, cycloalkyl, aryl, or heteroaryl, which may be substituted with alkyl, cycloalkyl, aryl, or heteroaryl. Additionally, > C (-R) X ) 2 、-(C-R X )＝(C-R X )-、＞Si(-R X ) 2 Two of each R X Can also be via a single bond or a linking group X Y Are bonded to each other to form a ring. As X Y Examples are > O, > N-R Y 、＞C(-R Y ) 2 、＞Si(-R Y ) 2 、＞S、＞CO、＞CS、＞SO、＞SO 2 And > Se, R Y Each independently being an alkyl, cycloalkyl, aryl or heteroaryl group, which may be substituted by an alkyl, cycloalkyl, aryl or heteroaryl group. Wherein, in X Y Is > C (-R) Y ) 2 And > Si (-R) Y ) 2 In the case of (2), two R Y No further ring formation occurs. Further, as the linking group, an alkenylene group may be mentioned. Any hydrogen of the alkenylene group may be independently represented by R 2X Substituted, R 2X Independently from each other, alkyl, cycloalkyl, substituted silyl, aryl and heteroaryl, which may be substituted with alkyl, cycloalkyl, substituted silyl, aryl. - (C-R) X )＝(C-R X ) Two of (A-B-C) X May be bonded to each other and together with these bonded C = C form an aryl ring (benzene ring, etc.) or heteroaryl ring. I.e., - (C-R) X )＝(C-R X ) May be an arylene (1, 2-phenylene, etc.) or heteroarylene group.
In addition, in the case where only "diarylamino group", "diheteroarylamino group", or "arylheteroarylamino group" is described in the present specification, unless otherwise specified, it is considered that "two aryl groups to which diarylamino groups are added may be bonded to each other via a linking group", "two heteroaryl groups of the diarylamino groups may be bonded to each other via a linking group", and "aryl and heteroaryl groups of the arylheteroarylamino groups may be bonded to each other via a linking group", respectively.
The "alkyl group" as the first substituent may be either a straight chain or a 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. 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-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. Further, for example, there can be mentioned: <xnotran> 1- -1- ,1,1- ,1,1- ,1- -1- ,1,1,4- ,1,1,2- ,1,1- ,1,1- ,1,1- ,1,1,5- ,1- -1- ,1- -1,3- ,1,1,2,2- ,1- -1- ,1,1- ,1- -1- ,1,1,3- ,1- -1- ,1,1,2- ,1- -1,2,2- ,1- -1- ,1,1- . </xnotran>
As the substituent containing the "alkyl group", a tertiary alkyl group represented by the following formula (tR) is one of particularly preferable substituents 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 bulky substituents, and thus the luminescence quantum yield (PLQY) is improved. In addition, a tertiary alkyl group represented by the formula (tR) is also preferable as a substituent in which a second substituent is substituted with another substituent. 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. The "diarylamino group" includes the following groups described as the "first substituent". Examples of the substitution pattern of the group of formula (tR) for the diarylamino group, the carbazolyl group, and the benzocarbazolyl group include those in which some or all of the hydrogens of the aryl ring or the phenyl ring are substituted with the group of formula (tR).
[ solution 36]
In the formula (tR), R a 、R b And R c Each independently represents an alkyl group having 1 to 24 carbon atoms, wherein-CH is an optional group in the alkyl group 2 -may be substituted by-O-where the group represented by formula (tR) is substituted with at least one hydrogen in the structure comprising the structural unit represented by formula (1).
R a 、R b And R c The "alkyl group having 1 to 24 carbon atoms" may be either a straight chain or a branched chain, and examples thereof include: a linear alkyl group having 1 to 24 carbon atoms, a branched alkyl group having 3 to 24 carbon atoms, an alkyl group having 1 to 18 carbon atoms (a branched alkyl group having 3 to 18 carbon atoms), an alkyl group having 1 to 12 carbon atoms (a branched alkyl group having 3 to 12 carbon atoms), an alkyl group having 1 to 6 carbon atoms (a branched alkyl group having 3 to 6 carbon atoms), and an alkyl group having 1 to 4 carbon atoms (a branched alkyl group having 3 to 4 carbon atoms).
R in formula (tR) of formula (1) a 、R b And R c The total number of carbon atoms of (b) is preferably 3 to 20 carbon atoms, and particularly preferably 3 to 10 carbon atoms.
As R a 、R b And R c Specific examples of the alkyl group of (1) include: <xnotran> , , , , , , , , , , , , ,1- ,4- -2- ,3,3- ,2- , ,1- , , ,1- ,2- ,2- , ,2,2- ,2,6- -4- ,3,5,5- , , ,1- </xnotran>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 formula (tR) include: <xnotran> , ,1- -1- ,1,1- ,1,1- ,1- -1- ,1,1,3,3- ,1,1,4- ,1,1,2- ,1,1- ,1,1- ,1,1- ,1,1,5- ,1- -1- ,1- -1,3- ,1,1,2,2- ,1- -1- ,1,1- ,1- -1- ,1,1,3- ,1- -1- ,1,1,2- ,1- -1,2,2- ,1- -1- ,1,1- . </xnotran> Of these, preferred are tert-butyl and tert-amyl.
Examples of the "cycloalkyl group" as the first substituent include a cycloalkyl group having 3 to 24 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, a cycloalkyl group having 3 to 16 carbon atoms, a cycloalkyl group having 3 to 14 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, a cycloalkyl group having 5 to 6 carbon atoms, and a cycloalkyl group having 5 carbon atoms. The cycloalkyl group in the present specification includes, as exemplified below, in addition to a monocyclic cycloalkyl group and the like, a polycyclic cycloalkyl group such as an adamantyl group and the like.
As specific cycloalkyl groups, there may be mentioned: 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, decahydronaphthyl, decahydroazulenyl, and alkyl (particularly methyl) substituents having 1 to 5 carbon atoms of these groups.
Examples of the "alkenyl group" as the first substituent include a linear 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.
Specific "alkenyl" may include: vinyl, allyl, butadienyl, and the like.
Examples of the "alkoxy" as the first substituent include a linear alkoxy group having 1 to 24 carbon atoms and a branched alkoxy group having 3 to 24 carbon atoms. An alkoxy group having 1 to 18 carbon atoms (a branched alkoxy group having 3 to 18 carbon atoms) is preferable, an alkoxy group having 1 to 12 carbon atoms (a branched alkoxy group having 3 to 12 carbon atoms) is more preferable, an alkoxy group having 1 to 6 carbon atoms (a branched alkoxy group having 3 to 6 carbon atoms) is still more preferable, and an alkoxy group having 1 to 5 carbon atoms (a branched alkoxy group having 3 to 5 carbon atoms) is particularly preferable.
Specific examples of the alkoxy group include: methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-pentyloxy, hexyloxy, heptyloxy, octyloxy, and the like.
The "aryloxy" as the first substituent is a group in which hydrogen of the-OH group is substituted with an aryl group, and the aryl group and preferred ranges thereof can refer to the groups described above.
The "arylthio" as the first substituent is a group in which the hydrogen of the-SH group is substituted with an aryl group, and the aryl group and preferred ranges thereof may refer to the groups described above.
Examples of the "substituted silyl group" as the first substituent 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 thereof include: trialkylsilyl, tricycloalkylsilyl, dialkylcycloalkylsilyl, alkylbicycloalkylsilyl, triarylsilyl, dialkylarylsilyl, and alkyldiarylsilyl groups.
As the "trialkylsilyl group", there may be mentioned a group in which three hydrogens of the silyl group are each independently substituted with an alkyl group, and the alkyl group and the preferable range thereof may refer to the group described as the "alkyl group" in the first substituent. The alkyl group which is preferred for substitution is an alkyl group 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, methyldiisopropylsilane, ethyldiisopropylsilane, butyldiisopropylsilane, sec-butyldiisopropylsilane, tert-pentyldiisopropylsilane, etc.
As the "tricycloalkylsilyl group", there can be cited a group in which three hydrogens in the silyl group are each independently substituted with a cycloalkyl group, and the cycloalkyl group and preferred ranges thereof can be cited as the group explained as the "cycloalkyl group" in the first substituent. The cycloalkyl group preferable for substitution is a cycloalkyl group having 5 to 10 carbon atoms, and specifically, there may be mentioned: 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, decahydronaphthyl, decahydroazulenyl and the like.
Specific examples of the tricycloalkylsilyl group include tricyclopentylsilyl group and tricyclohexylsilyl 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 a group selected from the specific alkyl groups and cycloalkyl groups.
Specific examples of the dialkylarylsilyl group substituted with two alkyl groups and one aryl group, the alkyldiarylsilyl group substituted with one alkyl group and two aryl groups, and the triarylsilyl group substituted with three aryl groups include a silyl group substituted with a group selected from the specific alkyl groups and aryl groups. Specific examples of the triarylsilyl group include triphenylsilyl groups.
In addition, "aryl" in "diarylboron group" as the first substituent and its preferred range can refer to the description of the aryl. In addition, the two aryl groups may be linked via a single bond or a linking group (e.g., > C (-R) 2 A > O, > S, or > N-R) bond. Here, > C (-R) 2 And R > N-R is aryl, heteroaryl, diarylamino (two aryl groups may be bonded to each other via a linking group), alkyl, cycloalkyl, alkoxy, or aryloxy (the above is a first substituent), which may be further substituted with aryl, heteroaryl, alkyl, or cycloalkyl (the above is a second substituent), and as specific examples of these groups, the above description of aryl, heteroaryl, diarylamino (two aryl groups may be bonded to each other via a linking group), alkyl, cycloalkyl, alkoxy, or aryloxy as the first substituent may be cited. In addition, in the case where only "diarylboron group" is described in the present specification, unless otherwise specified, it is considered that "two aryl groups to which the diarylboron group is added may be bonded to each other via a single bond or a linking group".
When "aryl", "heteroaryl", "diarylamino", "diheteroarylamino", "arylheteroarylamino", "diarylboryl", "alkyl", "cycloalkyl", "alkenyl", "alkoxy", "aryloxy", "arylthio" as a first substituent is specified as substituted or unsubstituted, at least one of these may be substituted with a second substituent. The second substituent is preferably, unless otherwise specified, as follows: specific examples of the aryl group, heteroaryl group, diarylamino group, alkyl group, cycloalkyl group, or substituted silane group can be described with reference to "aryl group", "heteroaryl group", "diarylamino group", "alkyl group", "cycloalkyl group", or "substituted silane group" as the first substituent. The aryl group or heteroaryl group as the second substituent also includes a group in which at least one hydrogen of these groups is substituted with an aryl group such as a phenyl group (specifically, the above-mentioned group), an alkyl group such as a methyl group or a tert-butyl group (specifically, the above-mentioned group), or a cycloalkyl group such as a cyclohexyl group (specifically, the above-mentioned group). Examples thereof include a group in which 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. The cycloalkyl group as the second substituent also includes a group in which at least one hydrogen of these groups is substituted with an alkyl group such as a methyl group or a tert-butyl group. The description may also be applied to the description of the other first substituent and second substituent in the present specification. In addition, when two or more hydrogens of the first substituent are respectively substituted with a second substituent, the two or more second substituents may be the same as or different from each other.
The emission wavelength can be adjusted by steric hindrance, electron donating property, and electron withdrawing property of the structure of the substituent. Preferred are groups represented by the following structural formulae, more preferred are methyl group, t-butyl group, t-amyl group, t-octyl group, neopentyl group, adamantyl group, dimethyladamantyl 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- (t-butyl) phenyl) amino group, carbazolyl group, 3, 6-dimethylcarbazolyl group, 3, 6-di-t-butylcarbazolyl group and phenoxy group, and further preferred are methyl group, t-butyl group, t-amyl group, t-octyl group, neopentyl group, adamantyl group, dimethyladamantyl group, phenyl group, o-tolyl group, 2, 6-xylyl group, 2,4, 6-mesityl group, diphenylamino group, di-p-tolylamino group, bis (p- (t-butyl) phenyl) amino group, carbazolyl group, 3, 6-dimethylcarbazolyl group and 3, 6-di-t-butylcarbazolyl group. From the viewpoint of ease of synthesis, a group having a large steric hindrance is preferred for selective synthesis, and specifically, a tert-butyl group, a tert-amyl group, a tert-octyl group, an adamantyl group, a dimethyladamantyl group, an o-tolyl group, a p-tolyl group, a 2, 4-xylyl group, a 2, 5-xylyl group, a 2, 6-xylyl group, a 2,4, 6-mesityl group, a di-p-tolylamino group, a bis (p- (tert-butyl) phenyl) amino group, a 3, 6-dimethylcarbazolyl group, and a 3, 6-di-tert-butylcarbazolyl group are preferred.
In the following structural formulae, "Me" represents a methyl group, "tBu" represents a tert-butyl group, "tAm" represents a tert-pentyl group, "thoct" represents a tert-octyl group, and "-" represents a bonding position.
[ solution 37]
*-Me *-tBu *-tAm *-tOct
[ solution 38]
[ solution 39]
[ solution 40]
[ solution 41]
[ solution 42]
[ solution 43]
[ solution 44]
[ solution 45]
[ chemical formula 46]
[ solution 47]
[ solution 48]
[ solution 49]
[ solution 50]
As the substituent when two or three hydrogens bonded to consecutive (adjacent) carbon atoms are substituted, in addition to the group represented by the above formula (D-1) or formula (D-2), any of the following groups may be used.
[ solution 51]
In each formula, me is methyl. In each formula, the bond may be bonded to two or three atoms continuously (adjacently) bonded to the aryl ring or heteroaryl ring in any of the a, B, and C rings.
The polycyclic aromatic compound having one or two or more structures containing the structural unit represented by the formula (1) and the preferred form thereof is preferably a polycyclic aromatic compound having a structure containing at least one tertiary alkyl group (such as a tertiary butyl group or a tertiary pentyl group) represented by the formula (tR), a neopentyl group, or an adamantyl group, and more preferably a polycyclic aromatic compound having a structure containing a tertiary alkyl group (such as a tertiary butyl group or a tertiary pentyl group) represented by the formula (tR). The reason for this is that the intermolecular distance is increased by such bulky substituents, and thus the luminescence quantum yield (PLQY) is improved. In addition, as a substituent, a diarylamino group (two aryl groups may be bonded to each other via a linking group) is also preferable. Furthermore, a diarylamino group substituted with a group of the formula (tR) (two aryl groups may be bonded to each other via a linking group), a carbazolyl group substituted with a group of the formula (tR) (preferably, an N-carbazolyl group), or a benzocarbazolyl group substituted with a group of the formula (tR) (preferably, an N-benzocarbazolyl group) is also preferable. Examples of substitution patterns of the group of formula (tR) for a diarylamino group (wherein two aryl groups of the diarylamino group may be bonded to each other via a linking group), a carbazolyl group, and a benzocarbazolyl group include substitution patterns in which some or all of the hydrogens of the aryl ring or benzene ring in these groups are substituted by the group of formula (tR).
As further specific examples of the polycyclic aromatic compound represented by the formula (1) of the present invention, the following compounds can be mentioned. In the following structural formula, "Me" represents a methyl group, "tBu" represents a tert-butyl group, and "D" represents deuterium. The following configuration is an example.
[ solution 52]
[ chemical formula 53]
[ solution 54]
[ solution 55]
[ solution 56]
[ solution 57]
[ solution 58]
[ chemical 59]
The polycyclic aromatic compound of the present invention can be produced by the following procedure.
< method for producing polycyclic aromatic Compound >
Basically, the polycyclic aromatic compound having one or more structures including the structural unit represented by the formula (1) or (2) first utilizes a bonding group (including X) 1 Or X 2 A ring (a ring) is bonded to a ring (B ring) and a ring (a condensed ring including a C1 ring and a C2 ring) to produce an intermediate (first reaction), and then, a bonding group (including Y) is used 1 A group of (A) a ring, (B) a ring and (C) a ringRing) to produce a final product (second reaction). In the first Reaction, for example, in the case of etherification, a typical Reaction such as nucleophilic substitution Reaction or Ullmann Reaction (Ullmann Reaction) can be used, and in the case of amination, a typical Reaction such as Buchwald-Hartwig Reaction (Buchwald-Hartwig Reaction) can be used. In the second Reaction, a Tandem Hetero Friedel-Crafts Reaction (consecutive aromatic electrophilic substitution Reaction, the same applies hereinafter) can be used. The compound can be produced by using a raw material having a desired condensed ring at a certain part of the reaction step or by adding a step of condensing a ring, and by using a condensed ring in which at least one ring selected from the group consisting of a ring a, a ring B and a ring C is composed of two or more rings selected from the group consisting of a monocyclic aryl ring, a monocyclic heteroaryl ring and a cyclopentadiene ring.
< method for producing intermediate 1 >
The polycyclic aromatic compound of the present invention can be produced by a production method including the following steps. For the following steps, reference is made to the description of International publication No. 2015/102118.
The following expression includes the reaction of the following reaction sequence: the use of an organic base compound for X in the following intermediate 1 1 And X 2 Metallization of the halogen atoms (Hal) in between; using a compound selected from the group consisting of Y 1 Halide of (2), Y 1 Of an aminated halide of, Y 1 Alkoxylates of (D) and Y 1 With a reagent of the group consisting of aryloxides of (A) and (B) to react the metal with Y 1 Exchanging the data; and using said Y through successive aromatic electrophilic substitution reactions using a Bronsted base 1 To bond the B-ring to the C-ring.
[ solution 60]
Examples of the metalating agent used in the halogen-metal exchange reaction in the above-described process include alkyllithium such as methyllithium, n-butyllithium, sec-butyllithium and tert-butyllithium, isopropylmagnesium chloride, isopropylmagnesium bromide, phenylmagnesium chloride and phenylmagnesium bromide, and lithium chloride complexes of isopropylmagnesium chloride known as a Tabo Grignard reagent (Turbo Grignard reagent).
In addition, examples of the metallation reagent used in the ortho-position metal exchange reaction in the above-described flow chart include: organic basic compounds such as lithium diisopropylamide, lithium tetramethylpiperidide, lithium hexamethyldisilazide, potassium hexamethyldisilazide, lithium tetramethylpiperidyl magnesium chloride-lithium chloride complex, tri-n-butyllithium magnesium chloride, and the like.
Further, examples of the additive for promoting the reaction when an alkyllithium is used as a metallizing agent include N, N, N ', N' -tetramethylethylenediamine, 1, 4-diazabicyclo [2.2.2] octane, N, N-dimethylpropyleneurea and the like.
In addition, as the lewis acid used in the flow chart described so far, alCl can be cited 3 、AlBr 3 、AlF 3 、BF 3 ·OEt 2 、BCl 3 、BBr 3 、GaCl 3 、GaBr 3 、InCl 3 、InBr 3 、In(OTf) 3 、SnCl 4 、SnBr 4 、AgOTf、ScCl 3 、Sc(OTf) 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 And the like. In addition, those having these lewis acids supported on a solid can be used in the same manner.
Examples of the bronsted acid used in the above-described process include p-toluenesulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid, fluorosulfonic acid, carboxylic acid, trifluoroacetic acid, (trifluoromethanesulfonyl) imide, tris (trifluoromethanesulfonyl) methane, hydrogen chloride, hydrogen bromide, and hydrogen fluoride. Examples of the solid bronsted acid include amberlyst (Amberlist) (trade name: dow Chemical (Dow Chemical)), nafion (Nafion) (trade name: dupont (Dupont)), zeolite (zeolite), and etidocin (Taycacure) (trade name: etidocin (Tayca) gmbh).
Examples of the amine that can be added in the above-described process include diisopropylethylamine, triethylamine, tributylamine, 1, 4-diazabicyclo [2.2.2] octane, N-dimethyl-p-toluidine, N-dimethylaniline, pyridine, 2, 6-lutidine, and 2, 6-di-tert-butylamine.
Examples of the solvent used in the above-described flow include o-dichlorobenzene, chlorobenzene, toluene, benzene, dichloromethane, chloroform, dichloroethylene, benzotrifluoride (benzotrifluoride), decahydronaphthalene, cyclohexane, hexane, heptane, 1,2, 4-trimethylbenzene, xylene, diphenyl ether, anisole, cyclopentyl methyl ether, tetrahydrofuran, dioxane, methyl-t-butyl ether, and the like.
Here, Y is described 1 As an example of B, Y can also be synthesized by appropriately changing the raw materials 1 A compound that is P, P = O, P = S, al, ga, as, si-R, or Ge-R.
In the scheme, in order to promote the tandem heterolydrol-quart reaction, a bransted base or a lewis acid may also be used. Wherein in the use of Y 1 Of (b) a trifluoride, Y 1 Trichloride of (a) and Y 1 Tribromide of (3), Y 1 Y being triiodide or the like 1 In the case of the halide of (3), an acid such as hydrogen fluoride, hydrogen chloride, hydrogen bromide, or hydrogen iodide is generated as the aromatic electrophilic substitution reaction proceeds, and therefore, it is effective to use a Bronsted base which traps an acid. On the other hand, in the use of Y 1 Of an aminated halide of, Y 1 In the case of the alkoxylate (b), since an amine or an alcohol is produced as the aromatic electrophilic substitution reaction proceeds, it is not necessary to use a bronsted base in many cases, but since the ability to remove an amino group or an alkoxy group is low, it is effective to use a lewis acid for accelerating the removal thereof.
The polycyclic aromatic compound of the present invention also includes a compound in which at least a part of hydrogen atoms is substituted with deuterium or cyano group, or a compound substituted with halogen such as fluorine or chlorine, and such a compound 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 device >
The polycyclic aromatic compound of the present invention is useful as a material for organic devices. Examples of the organic device include: organic electroluminescent devices, 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. As the organic device, for example, there can be mentioned: an organic electroluminescent device, an organic field effect transistor, an organic thin film solar cell, or the like, but an organic electroluminescent device 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 element
< 2-1-1. Structure of organic electroluminescent element
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 includes: the light-emitting device includes a substrate 101, an anode 102 disposed on the substrate 101, a hole injection layer 103 disposed on the anode 102, a hole transport layer 104 disposed on the hole injection layer 103, a light-emitting layer 105 disposed on the hole transport layer 104, an electron transport layer 106 disposed on the light-emitting layer 105, an electron injection layer 107 disposed on the electron transport layer 106, and a cathode 108 disposed on the electron injection layer 107.
In addition, the organic EL element 100 may be formed by reversing the manufacturing order, for example, by a structure including: a substrate 101, a cathode 108 disposed on the substrate 101, an electron injection layer 107 disposed on the cathode 108, an electron transport layer 106 disposed on the electron injection layer 107, an emission layer 105 disposed on the electron transport layer 106, a hole transport layer 104 disposed on the emission layer 105, a hole injection layer 103 disposed on the hole transport layer 104, and an anode 102 disposed on the hole injection layer 103.
All of the layers are not indispensable, and the minimum structural unit is configured to include 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 layers that can be arbitrarily provided. In addition, each of the layers may include a single layer, or may include a plurality of layers.
As the form of the layers constituting the organic EL element, in addition to the structural form of the above-mentioned "substrate/anode/hole injection layer/hole transport layer/light-emitting layer/electron transport layer/electron injection layer/cathode", the structure may be "substrate/anode/hole transport layer/light-emitting layer/electron transport layer/electron injection layer/cathode", "substrate/anode/hole injection layer/hole transport layer/light-emitting layer/electron transport layer/cathode", "substrate/anode/light-emitting layer/electron injection layer/cathode", "substrate/anode/hole transport layer/light-emitting layer/electron injection layer/cathode", "substrate/anode/hole injection layer/light-emitting layer/electron transport layer/cathode", "substrate/anode/light-emitting layer/electron injection layer/cathode".
< 2-1-2. Luminescent layer in organic electroluminescent element
The polycyclic aromatic compound of the present invention is preferably used as a material for forming one or more organic layers in the organic electroluminescent element, and more preferably used as a material for forming a light-emitting layer. The light-emitting layer 105 emits light by recombination of holes injected from the anode 102 and electrons injected from the cathode 108 between electrodes to which an electric field is applied. The material for forming the light-emitting layer 105 may be a compound (light-emitting compound) which emits light by being excited by recombination of holes and electrons, and is preferably a compound which can be formed into a stable thin film shape and which exhibits strong light emission (fluorescence) efficiency in a solid state. The polycyclic aromatic compound of the present invention can be used as a material for a light-emitting layer, a dopant material, or 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, although an example in which an auxiliary dopant and an emission dopant are used in combination is given as a dopant, the light-emitting dopant used alone is referred to when only "dopant" is described in this specification.
The light-emitting layer may be a single layer or may include a plurality of layers, and each of the layers is formed of a material (host material or dopant material) for the light-emitting layer. The host material and the dopant material may be one kind or a combination of two or more kinds, respectively. The dopant material may be contained within the bulk of the host material, or may be contained within a portion of the host material, either. The doping method may be a co-evaporation method with the host material, or may be a method in which the host material is mixed in advance and then evaporated at the same time. Specific examples of dopants to be combined with the compound of the present invention when a plurality of dopants are combined are shown below. In the following structural formula, "Me" represents a methyl group, "tBu" represents a tert-butyl group, and "D" represents deuterium.
[ solution 61]
[ chemical formula 62]
[ solution 63]
[ chemical formula 64]
The amount of the host material to be used differs depending on the type of the host material, and may be determined in accordance with the characteristics of the host material. The amount of the host material used is preferably 50 to 99.999 mass%, more preferably 80 to 99.95 mass%, and still more preferably 90 to 99.9 mass%, based on the total mass of the materials for the light-emitting layer.
The amount of the dopant material used differs depending on the type of the dopant material, and may be determined by matching the characteristics of the dopant material. The amount of the dopant used is preferably 0.001 to 50 mass%, more preferably 0.05 to 20 mass%, and still more preferably 0.1 to 10 mass% based on the total mass of the material for the light-emitting layer. The above range is preferable, for example, in terms of preventing the concentration quenching phenomenon.
< host Material >
As the host material, anthracene, pyrene, dibenzo known as a light-emitting body from the past can be mentioned
Or fused ring derivatives such as fluorene, bisstyryl derivatives such as bisstyrylanthracene derivatives or distyrylbenzene derivatives, tetraphenylbutadiene derivatives, cyclopentadiene derivatives, fluorene derivatives, benzofluorene derivatives, and the like.
As the host material, for example, a compound represented by any one of the following formulae (H1), (H2), and (H3) can be used.
[ solution 65]
In the formulae (H1), (H2) and (H3), L 1 Is an arylene group having 6 to 24 carbon atoms, a heteroarylene group having 2 to 24 carbon atoms, a heteroarylene arylene group having 6 to 24 carbon atoms or an aryleneheteroarylene group having 6 to 24 carbon atoms, and is preferably an arylene-heteroarylene group having 6 to 24 carbon atomsThe arylene group has 6 to 16 carbon atoms, more preferably 6 to 12 carbon atoms, and particularly preferably 6 to 10 carbon atoms, and specific examples thereof include divalent groups such as a benzene ring, a biphenyl ring, a terphenyl ring, and a fluorene ring. 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, the heteroarylene group includes: a divalent group such as a pyrrole ring, an oxazole ring, an isoxazole ring, a thiazole ring, an isothiazole ring, an imidazole ring, an oxadiazole ring (furazan ring or the like), a thiadiazole ring, a triazole ring, a tetrazole ring, a pyrazole ring, a pyridine ring, a pyrimidine ring, a pyridazine ring, a pyrazine ring, a triazine ring, an indole ring, an isoindole ring, a 1H-indazole ring, a benzimidazole ring, a benzoxazole ring, a benzothiazole ring, a 1H-benzotriazole ring, a quinoline ring, an isoquinoline ring, a cinnoline ring, a quinazoline ring, a quinoxaline ring, a phthalazine ring, a naphthyridine ring, a purine ring, a pyridine ring, a carbazole ring, an acridine ring, a phenoxazine ring, a phenothiazine ring, an indolizine ring, a furan ring, a benzofuran ring, an isobenzofuran ring, a dibenzofuran ring, a thiophene ring, a dibenzothiophene ring, and a thiophene ring. At least one hydrogen in the compounds represented by the formulae may be substituted by an alkyl group having 1 to 6 carbon atoms, a cyano group, a halogen or deuterium.
Specific preferred examples thereof include compounds represented by any of the following structural formulae. In the structural formulae given below, at least one hydrogen may be substituted by a halogen, a cyano group, an alkyl group having 1 to 4 carbon atoms (for example, a methyl group or a tert-butyl group), a phenyl group, a naphthyl group, or the like.
[ solution 66]
[ solution 67]
[ solution 68]
[ solution 69]
< Anthracene Compound >
Examples of the anthracene compound as a host include a compound represented by the formula (3-H) and a compound represented by the formula (3-H2).
[ solution 70]
In the formula (3-H), the compound (A),
x and Ar 4 Each independently hydrogen, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted diarylamino, optionally substituted diheteroarylamino, optionally substituted arylheteroarylamino, optionally substituted alkyl, optionally substituted cycloalkyl, optionally substituted alkenyl, optionally substituted alkoxy, optionally substituted aryloxy, optionally substituted arylthio or substituted silyl, all X and Ar 4 The two aryl groups of the diarylamino group may be bonded to each other via a linking group, the two heteroaryl groups of the diheteroarylamino group may be bonded to each other via a linking group, and the aryl group and the heteroaryl group of the arylheteroarylamino group may be bonded to each other via a linking group, without being simultaneously hydrogen.
At least one hydrogen in the compound represented by formula (3-H) is substituted with halogen, cyano, deuterium, or a substitutable heteroaryl, or is unsubstituted.
In addition, the structure represented by formula (3-H) as a unit structure to form polymer (preferably two dimer). In this case, for example, the unit structures represented by the formula (3-H) are bonded to each other via X, and X may be a single bond, an arylene group (e.g., phenylene, biphenylene, and naphthylene), a heteroarylene group (e.g., a group having a divalent bonding valence such as a pyridine ring, a dibenzofuran ring, a dibenzothiophene ring, a carbazole ring, a benzocarbazole ring, and a phenyl-substituted carbazole ring), or the like.
The details of each group in the compound represented by the formula (3-H) can be described with reference to the formula (1), and further described in the following preferred embodiment column.
Preferred embodiments of the anthracene compound will be described below. The symbols in the following structures are defined as described above.
[ solution 71]
In the formula (3-H), X is a group represented by the formula (3-X1), the formula (3-X2) or the formula (3-X3), and the group represented by the formula (3-X1), the formula (3-X2) or the formula (3-X3) is bonded with the anthracene ring of the formula (3-H) at the position of X. Preferably, two xs do not simultaneously form a group represented by the formula (3-X3). More preferably, two X's are not simultaneously a group represented by the formula (3-X2).
In addition, the structure represented by formula (3-H) as a unit structure to form polymer (preferably two dimers). In this case, for example, the unit structures represented by the formula (3-H) are bonded to each other via X, and X may be a single bond, an arylene group (e.g., phenylene, biphenylene, and naphthylene), a heteroarylene group (e.g., a group having a divalent bonding valence such as a pyridine ring, a dibenzofuran ring, a dibenzothiophene ring, a carbazole ring, a benzocarbazole ring, and a phenyl-substituted carbazole ring), or the like.
The naphthylene moiety in the formulae (3-X1) and (3-X2) may be condensed with a benzene ring. The structure obtained by condensation in the above-described manner is as follows.
[ chemical 72]
Ar 1 And Ar 2 Each independently hydrogen, phenyl, biphenyl, terphenyl, quaterphenyl, naphthyl, phenanthryl, fluorenyl, benzofluorenyl,
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 the formula (A), the group represented by the formula (A) is bonded to the naphthalene ring in the formula (3-X1) or the formula (3-X2) at the position.
Ar 3 Is phenyl, biphenyl, terphenyl, quaterphenyl, naphthyl, phenanthryl, fluorenyl, benzofluorenyl, or the like,
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 position indicated by a letter X. That is, the anthracene ring of the formula (3-H) is directly bonded to the group represented by the formula (A).
In addition, ar 3 May have a substituent, ar 3 At least one hydrogen in (b) may further be an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, a phenanthryl group, a fluorenyl group,
A triphenylene group, a pyrenyl group, or a group represented by the formula (A) (including a carbazolyl group and a phenyl-substituted carbazolyl group). In addition, in Ar 3 When the substituent is a group represented by formula (A), the group represented by formula (A) is bonded to Ar in formula (3-X3) 3 And (4) bonding.
Ar 4 Each independently hydrogen, phenyl, biphenyl, terphenyl, naphthyl, or alkyl with 1-4 carbon atoms (methyl, ethyl, tert-butyl, etc.) and/or alkyl with 5-10 carbon atomsCycloalkyl-substituted silyl groups.
Examples of the alkyl group having 1 to 4 carbon atoms which is substituted with a silyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, a tert-butyl group, and a cyclobutyl group, and three hydrogens of the silyl group are 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.
Examples of the cycloalkyl group 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, decahydronaphthyl, decahydroazulenyl and the like, and three hydrogens in the silane group are each independently substituted by these cycloalkyl groups.
Specific examples of the "silyl group substituted with a cycloalkyl group having 5 to 10 carbon atoms" include tricyclopentylsilyl group and tricyclohexylsilyl group.
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.
In addition, the hydrogen in the chemical structure of the anthracene compound represented by the formula (3-H) may be substituted with the group represented by the formula (a). In the case of substitution by the group represented by formula (a), the group represented by formula (a) is substituted at said site 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 73]
In the formula (A), Y is-O-, -S-or > N-R 29 ，R 21 ～R 28 Each independently hydrogen, alkyl which may be substituted, cycloalkyl which may be substituted, aryl which may be substituted, heteroaryl which may be substituted, alkoxy which may be substituted, aryloxy which may be substituted, arylthio which may be substituted, trialkylsilyl, tricycloalkylsilyl, dialkylcycloalkylsilyl, alkylbicycloalkylsilyl, amino which may be substituted, 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 a substituted aryl group.
Y in the formula (A) is preferably-O-.
As R 21 ～R 28 The "alkyl group" of the "alkyl group which may be substituted" in (1) may be either a straight chain or a branched chain, and examples thereof include a straight chain alkyl group having 1 to 24 carbon atoms and a branched alkyl group having 3 to 24 carbon atoms. 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), and particularly preferably an alkyl group having 1 to 4 carbon atoms (branched alkyl group having 3 to 4 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, 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 The "cycloalkyl group" of the "cycloalkyl group which may be substituted" in (1) 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, and alkyl (particularly methyl) substituents having 1 to 4 carbon atoms of these groups, 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, decahydronaphthyl, decahydroazulenyl, and the like.
As R 21 ～R 28 The "aryl group" of the "aryl group which may be substituted" in (1) includes, for example, an aryl group having 6 to 30 carbon atoms, preferably an aryl group having 6 to 16 carbon atoms, more preferably an aryl group having 6 to 12 carbon atoms, and particularly preferably an aryl group having 6 to 10 carbon atoms.
Specific "aryl" groups 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, acenaphthyl, fluorenyl, phenaenyl, phenanthryl as a condensed tricyclic system, triphenylene, pyrenyl, tetracenyl as a condensed tetracyclic system, perylenyl, pentacenyl as a condensed pentacyclic system, and the like.
As R 21 ～R 28 The "heteroaryl group" of the "heteroaryl group which may be substituted" in (1) includes, for example, a heteroaryl group having 2 to 30 carbon atoms, preferably a heteroaryl group having 2 to 25 carbon atoms, more preferably a heteroaryl group having 2 to 20 carbon atoms, further preferably a heteroaryl group having 2 to 15 carbon atoms, and particularly preferably a heteroaryl group having 2 to 10 carbon atoms. Examples of the heteroaryl group include a heterocyclic ring containing 1 to 5 heteroatoms selected from oxygen, sulfur and nitrogen as ring-constituting atoms in addition to carbon.
Specific examples of the "heteroaryl group" include: pyrrolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, imidazolyl, oxadiazolyl, thiadiazolyl, triazolyl, tetrazolyl, pyrazolyl, pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl, triazinyl, indolyl, isoindolyl, 1H-indazolyl, benzimidazolyl, benzoxazolyl, benzothiazolyl, 1H-benzotriazolyl, quinolyl, isoquinolyl, cinnolinyl, quinazolinyl, quinoxalinyl, phthalazinyl, naphthyridinyl, purinyl, pteridinyl, carbazolyl, acridinyl, phenoxathiyl, phenoxazinyl, phenothiazinyl, phenazinyl, indolizinyl, furyl, benzofuryl, isobenzofuryl, dibenzofuryl, thienyl, benzo [ b ] thienyl, dibenzothienyl, furazanyl, thianthrenyl, naphthobenzofuryl, naphthobenzothienyl and the like.
As R 21 ～R 28 Examples of the "alkoxy group" of the "alkoxy group which may be substituted" in (1) include a linear alkoxy group having 1 to 24 carbon atoms and a branched alkoxy group having 3 to 24 carbon atoms. An alkoxy group having 1 to 18 carbon atoms (a branched alkoxy group having 3 to 18 carbon atoms) is preferable, an alkoxy group having 1 to 12 carbon atoms (a branched alkoxy group having 3 to 12 carbon atoms) is more preferable, an alkoxy group having 1 to 6 carbon atoms (a branched alkoxy group having 3 to 6 carbon atoms) is still more preferable, and an alkoxy group having 1 to 4 carbon atoms (a branched alkoxy group having 3 to 4 carbon atoms) is particularly preferable.
Specific "alkoxy" groups include: methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, and the like.
R 21 ～R 28 The "aryloxy group" of the "aryloxy group which may be substituted" in (1) is a group in which hydrogen of an-OH group is substituted by an aryl group which may be cited as the R 21 ～R 28 The "aryl" in (1).
R 21 ～R 28 The "arylthio group" of the "arylthio group which may be substituted" in (1) is a group in which hydrogen of the-SH group is substituted with an aryl group, which may be cited as the R 21 ～R 28 The "aryl group" in (1).
As R 21 ～R 28 As the "trialkylsilyl group" in (1), there can be mentioned groups in which three hydrogens in the silyl group are each independently substituted with an alkyl group, and the alkyl group can be cited as the R 21 ～R 28 The "alkyl" in (1) or (b). The alkyl group preferred for substitution is an alkyl group having 1 to 4 carbon atoms, and specifically, there may be mentioned: methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, cyclobutyl and the like.
Specific "trialkylsilyl group" includes: 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 "tricycloalkylsilyl group" in (1), there can be mentioned groups in which three hydrogens in the silyl group are each independently substituted with a cycloalkyl group, which can be cited as theR 21 ～R 28 The "cycloalkyl" in (1) above. The cycloalkyl group preferable for substitution is a cycloalkyl group having 5 to 10 carbon atoms, and specifically, there may be mentioned: cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, bicyclo [1.1.1]Pentyl, bicyclo [2.1.0]]Pentyl, bicyclo [2.1.1] s]Hexyl, bicyclo [3.1.0]Hexyl, bicyclo [2.2.1]Heptyl, bicyclo [2.2.2]Octyl, adamantyl, decahydronaphthyl, decahydroazulenyl, and the like.
Specific examples of the "tricycloalkylsilyl group" include tricyclopentylsilyl group and tricyclohexylsilyl 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 a group selected from the specific alkyl groups and cycloalkyl groups.
As R 21 ～R 28 The "substituted amino group" of the "amino group which may be substituted" in (1) includes, for example, an amino group in which two hydrogens are substituted with an aryl group or a heteroaryl group. Two hydrogens are substituted with aryl for a diaryl (two aryls may be bonded to each other via a linker) substituted amino, two hydrogens are substituted with heteroaryl for a diheteroaryl substituted amino, and two hydrogens are substituted with aryl and heteroaryl for an arylheteroaryl substituted amino. Said aryl or heteroaryl may be cited as said R 21 ～R 28 The "aryl" or "heteroaryl" in (1).
Specific "substituted amino group" includes: diphenylamino, dinaphthylamino, phenylnaphthylamino, bipyridylamino, phenylpyridylamino, naphthylpyridylamino and the like.
As R 21 ～R 28 Examples of the "halogen" in (1) include: fluorine, chlorine, bromine, iodine.
As R 21 ～R 28 Among the groups described above, some of the groups may be substituted as described above, and as the substituents in the above case, there may be mentioned: alkyl, cycloalkyl, aryl or heteroaryl. The alkyl, cycloalkyl, aryl or heteroaryl groups may be cited asIs the said R 21 ～R 28 The "alkyl", "cycloalkyl", "aryl" or "heteroaryl" in (1).
"> N-R as Y 29 R in ` 29 Is hydrogen or a substituted aryl group, as said aryl group, the R group can be cited 21 ～R 28 The substituent mentioned for the "aryl" in (1) may be cited as the substituent mentioned for R 21 ～R 28 The substituent(s) of (1).
R 21 ～R 28 Adjacent groups in (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 the case where a ring is formed is, for example, a group represented by the following formulae (A-2) to (A-14). Further, at least one hydrogen in the group represented by any one of the formulae (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 tricycloalkylsilyl group, a dialkylcycloalkylsilyl group, an alkylbicycloalkylsilyl group, a diaryl group (two aryl groups may be bonded to each other via a linking group), a substituted amino group, a diheteroaryl substituted amino group, an arylheteroaryl substituted amino group, a halogen, a hydroxyl group, or a cyano group.
[ chemical formula 74]
As the ring formed by bonding adjacent groups to each other, a hydrocarbon ring may be mentioned, for example, a cyclohexane ring, and as the aryl ring or heteroaryl ring, the above-mentioned R 21 ～R 28 The ring structure illustrated in the "aryl" or "heteroaryl" in (a), the ring being formed by condensation 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 an arbitrary position as a bonding position. For example, it may be a carbon atom bonded to either of the two benzene rings in the structure of formula (A)R in the structure of the 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 the formula (A) 29 "R of 29 In any position or "> N-R 29 "N (R) 29 A bond) directly bonded. The same applies to the group represented by any one of the formulae (A-1) to (A-14).
Examples of the group represented by formula (A) include a group represented by any one of formulae (A-1) to (A-14), preferably a group represented by any one of formulae (A-1) to (A-5) and formulae (A-12) to (A-14), more preferably a group represented by any one of formulae (A-1) to (A-4), still more preferably a group represented by any one of formulae (A-1), (A-3) and (A-4), and particularly preferably a group represented by formula (A-1).
Examples of the group represented by the formula (a) include the following groups. Y and x in the formula are as defined above.
[ solution 75]
[ 76]
In the compound represented by the formula (3-H), the group represented by the formula (A) is preferably a group bonded to the naphthalene ring in the formula (3-X1) or the formula (3-X2), the single bond in the formula (3-X3) or Ar in the formula (3-X3) 3 Any one of the above forms of bonds.
In addition, all or a part of hydrogen in the chemical structure of the anthracene compound represented by the formula (3-H) may be deuterium.
The anthracene compound serving as a host may be, for example, a compound represented by the following formula (3-H2).
[ solution 77]
In the formula (3-H2), ar c Is optionally substituted aryl or optionally substituted heteroaryl, R c Is hydrogen, alkyl, or cycloalkyl, ar 11 、Ar 12 、Ar 13 、Ar 14 、Ar 15 、A 16 、Ar 17 And Ar 18 Each independently hydrogen, an aryl group which may be substituted, a heteroaryl group which may be substituted, a diarylamino group which may be substituted (two aryl groups may be bonded to each other via a linking group), a diheteroarylamino group which may be substituted (two heteroaryl groups may be bonded to each other via a linking group), an arylheteroarylamino group which may be substituted (aryl group and heteroaryl group may be bonded to each other via 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, at least one hydrogen in the compound represented by formula (3-H2) may be substituted by halogen, cyano group, or deuterium.
The definition of "substituted aryl group", "substituted heteroaryl group", "substituted diarylamino group (two aryl groups may be bonded to each other via a linking group)", "substituted diheteroarylamino group (two heteroaryl groups may be bonded to each other via a linking group)", "substituted arylheteroarylamino group (aryl groups and heteroaryl groups may be bonded to each other via a linking group)", "substituted alkyl group", "substituted cycloalkyl group", "substituted alkenyl group", "substituted alkoxy group", "substituted aryloxy group", "substituted arylthio group", or "substituted silyl group" in the formula (3-H) is the same as that shown in the formula (3-H), and the description in the formula (3-H) can be cited.
The "optionally substituted aryl" is preferably a group represented by any one of the following formulae (3-H2-X1) to (3-H2-X8).
[ solution 78]
In the formulae (3-H2-X1) to (3-H2-X8), a bond site is represented. In the formulae (3-H2-X1) to (3-H2-X3), ar 21 、Ar 22 And Ar 23 Each independently hydrogen, phenyl, biphenyl, terphenyl, quaterphenyl, naphthyl, phenanthryl, fluorenyl, benzofluorenyl,
A phenyl group, a triphenylene group, a pyrenyl group, an anthracenyl 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 the group described for the anthracene compound represented by the formula (3-H).
In the formulae (3-H2-X4) to (3-H2-X8), ar 24 、Ar 25 、Ar 26 、Ar 27 、Ar 28 、Ar 29 And Ar 30 Each independently hydrogen, phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, fluorenyl,
A triphenylene group, a pyrenyl group, or a group represented by the formula (A). Further, one or two or more hydrogens of each of the groups represented by the formulae (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, as a preferable example of the "aryl group which may be substituted", examples thereof include compounds selected from the group consisting of phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, fluorenyl,
A terphenyl group (particularly an m-terphenyl-5' -group) substituted with at least one substituent group selected from the group consisting of a triphenylene group, a pyrenyl group and a group represented by the formula (A).
The "heteroaryl group which may be substituted" may include a group represented by the formula (A). In addition, specific examples of the "aryl group which may be substituted" and the "heteroaryl group which may be substituted" include dibenzofuranyl group, naphthobenzofuranyl group, phenyl-substituted dibenzofuranyl group, and the like.
At least one hydrogen in the compound represented by formula (3-H2) may be substituted with halogen, cyano, or deuterium. Examples of the "halogen" in the above case include: fluorine, chlorine, bromine, and iodine. Particularly preferred is a compound represented by the formula (3-H2) wherein all hydrogens in the compound are replaced with deuterium.
In the formula (3-H2), R c Is hydrogen, alkyl, or cycloalkyl, preferably hydrogen, methyl, or t-butyl, more preferably hydrogen.
In the formula (3-H2), ar is preferred 11 ～Ar 18 At least two of which are aryl or heteroaryl groups 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 an aryl group which may be substituted and a heteroaryl group which may be substituted are bonded to an anthracene ring.
Among the anthracene compounds represented by the formula (3-H2), ar is more preferable 11 ～Ar 18 Two of (a) are aryl which may be substituted or heteroaryl which may be substituted, and the other six are hydrogen, alkyl which may be substituted, cycloalkyl which may be substituted, alkenyl which may be substituted or alkoxy which may be substituted. 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 an aryl group which may be substituted and a heteroaryl group which may be substituted are bonded to an anthracene ring.
Among the anthracene compounds represented by the formula (3-H2), ar is more preferable 11 ～Ar 18 Any two of which are optionally substituted aryl or optionally substituted heteroaryl, and the other six of which are hydrogen, methyl, or tert-butyl.
Furthermore, in the formula (3-H2), R is preferable c Is hydrogen, and Ar 11 ～Ar 18 Any six of which are 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).
[ solution 79]
In 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), ar c' 、Ar 11' 、Ar 12' 、Ar 13' 、Ar 14' 、Ar 15' 、Ar 17' And Ar 18' Each independently is phenyl, biphenyl, terphenyl, quaterphenyl, naphthyl, phenanthryl, fluorenyl, benzofluorenyl, or the like,
A group, a triphenylene group, a pyrenyl group, or a group represented by the formula (A), at least one hydrogen in these groups may be substituted by phenyl, biphenyl, terphenyl, quaterphenyl, naphthyl, phenanthryl, fluorenyl, benzofluorenyl, or the like,
A group represented by the formula (A). Here, when the hydrogens of the methylene groups in the fluorenyl and benzofluorenyl groups are both substituted by phenyl groups, these phenyl groups may be bonded to each other by a single bond. Not bonding Ar c' 、Ar 11' 、Ar 12' 、Ar 13' 、Ar 14' 、Ar 15' 、Ar 17' And Ar 18' The carbon atom of the anthracene ring of (a) may be bonded with a methyl group or a tert-butyl group instead of hydrogen.
When Ar is c' 、Ar 11' 、Ar 12' 、Ar 13' 、Ar 14' 、Ar 15' 、Ar 17' And Ar 18' In the case of a substituted or unsubstituted phenyl group or a substituted or unsubstituted naphthyl group, respectively, a group represented by any one of the above-mentioned formulae (3-H2-X1) to (3-H2-X8) is preferred.
Ar c' 、Ar 11' 、Ar 12' 、Ar 13' 、Ar 14' 、Ar 15' 、Ar 17' And Ar 18' More preferably, each independently represents a phenyl group, a biphenyl group (particularly, biphenyl-2-yl group or biphenyl-4-yl group), a terphenyl group (particularly, m-terphenyl-5' -yl group), a naphthyl group, a phenanthryl group, a fluorenyl group, or any of the above formulas (A-1) to (A-4), and in this case, at least one hydrogen of these groups may be represented by a phenyl group, a biphenyl group, a naphthyl groupPhenanthryl, fluorenyl, or a group represented by any one of the formulae (A-1) to (A-4).
In addition, at least one hydrogen of the compound represented by formula (3-H2-A), formula (3-H2-B), formula (3-H2-C), formula (3-H2-D) or formula (3-H2-E) may be substituted with halogen, cyano, or deuterium. In addition, the compound is preferably in a deuterated form, and is preferably in a form in which all of the anthracyclines are deuterated, or in a form in which all of the hydrogen atoms are deuterated.
Particularly preferred anthracene compounds represented by the formula (3-H2) include anthracene compounds represented by the following formula (3-H2-Aa).
[ solution 80]
In the formula (3-H2-Aa), ar c' 、Ar 14' And Ar 15' Each independently is phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, fluorenyl, benzofluorenyl, or the like,
A group represented by a triphenylene group, a pyrenyl group or any one of the formulae (A-1) to (A-11), at least one hydrogen in these groups may be substituted by phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, fluorenyl, benzofluorenyl, fluorenyl,
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 by a phenyl group, the phenyl groups may be bonded to each other by a single bond. In addition, ar is not bonded c' 、Ar 14' And Ar 15' The carbon atom of the anthracene ring of (a) may be substituted with a methyl group or a tert-butyl group instead of hydrogen. At least one hydrogen in the compound represented by formula (3-H2-Aa) may be substituted with halogen or cyano, and at least one hydrogen in the compound represented by formula (3-H2-Aa) may be substituted with deuterium.
In the formula (3-H2-Aa), ar c' 、Ar 14' And Ar 15' Preferably, each of the groups is independently 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 formulae (A-1) to (A-4), and at least one hydrogen of these groups may be substituted by a phenyl group, a naphthyl group, a phenanthryl group, a fluorenyl group, or a group represented by any one of the formulae (A-1) to (A-4).
In the compound represented by the formula (3-H2-Aa), at least the carbon bonded to the 10-position of the anthracene ring (Ar is preferably bonded c' The bonded carbon is set to be in the 9-position) is replaced 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). Furthermore, in the formula (3-H2-Ab), D is deuterium, ar c' 、Ar 14' And Ar 15' The same as defined in formula (3-H2-Aa). D in the formula (3-H2-Ab) represents that at least the position is deuterium, any one or more hydrogen in the formula (3-H2-Ab) is deuterium at the same time, and it is also preferable that all the hydrogen in the formula (3-H2-Ab) is deuterium.
[ solution 81]
Specific examples of the anthracene compound include compounds represented by formulae (3-131-Y) to (3-182-Y), formulae (3-183-N), formulae (3-184-Y) to (3-284-Y), formulae (3-500) to (3-557), formulae (3-600) to (3-605), and formulae (3-606-Y) to (3-626-Y). The hydrogen atoms in these formulae may be partially or completely substituted by deuterium, but specific examples of the deuterium-substituted form are given individually. In which Y may be-O-, -S-, > N-R 29 (R 29 As defined above) or > C (-R) 30 ) 2 (R 30 Is any of an attachable aryl, or alkyl group), R 29 For example, phenyl, R 30 For example methyl. With respect to the formula number, for example, in the case where Y is O, formula (3-131-Y) is set to formula (3-131-O), and in the case where Y is-S-or > N-R 29 In the case of (2), the formula (3-131-S) or the formula (3-131-N) is used, respectively.
[ solution 82]
[ solution 83]
[ chemical formula 84]
[ solution 85]
[ solution 86]
[ solution 87]
[ solution 88]
[ solution 89]
[ solution 90]
[ solution 91]
[ solution 92]
[ solution 93]
[ solution 94]
[ solution 95]
[ solution 96]
[ solution 97]
[ solution 98]
[ solution 99]
[ solution 100]
[ solution 101]
In the above formula, D is deuterium.
Among the compounds, preferred are those of 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 (3-514-547), formula (3-521-538), formula (3-538) or formula (3-168-538) (3-605) and the formulae (3-606-Y) to (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 a compound having a reactive group at a desired position of an anthracene skeleton, or an anthracene compound represented by formula (3-H) may be X, ar 4 And a compound having a reactive group in a partial structure such as the structure of the formula (A) as a starting material, and produced by suzuki coupling, radicel coupling or other known coupling reaction. Examples of the reactive group of the reactive compound include halogen and boric acid. As specific production methods, for example, reference is made to: paragraph [0089 ] of International publication No. 2014/141725]Paragraph [0175 ]]The synthesis method of (1).
< fluorene Compound >
The compound represented by the formula (4-H) functions basically as a host.
[ solution 102]
In the formula (4-H),
R 1 to R 10 Each independently hydrogen, aryl, heteroaryl (the heteroaryl may be bonded to the fluorene skeleton in formula (4-H) via a linking group), diarylamino (two aryl may be bonded to each other via a linking group), diheteroarylamino (two heteroaryl may be bonded to each other via a linking group), arylheteroarylamino (aryl and heteroaryl may be bonded to each other via a linking group), alkyl, cycloalkyl, alkenyl, alkoxy, or aryloxy, at least one of which may be substituted by aryl, heteroaryl, alkyl, or cycloalkyl, and R 1 And R 2 、R 2 And R 3 、R 3 And R 4 、R 5 And R 6 、R 6 And R 7 、R 7 And R 8 Or R 9 And R 10 May be independently bonded to form a fused ring or a spiro ring, at least one hydrogen in the formed ring may be substituted by an aryl group, a heteroaryl group (the heteroaryl group may be bonded to the formed ring via a linking group), a diarylamino group (two aryl groups may be bonded to each other via a linking group), a diheteroarylamino group (two heteroaryl groups may be bonded to each other via a linking group), an arylheteroarylamino group (the aryl and the heteroaryl groups may be bonded to each other via a linking group), an alkyl group, a cycloalkyl group, an alkenyl group, an alkoxy group, or an aryloxy group, at least one hydrogen of which may be substituted by an aryl group, a heteroaryl group, an alkyl group, or a cycloalkyl group, and at least one hydrogen of the compounds represented by formula (4-H) may be substituted by a halogen, a cyano group, or deuterium.
The details of each group in the definition of the formula (4-H) may be referred to the description of the polycyclic aromatic compound of the formula (1) described above.
As R 1 To R 10 Examples of the alkenyl group in (b) 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, further 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.
Specific examples of the heteroaryl group include a monovalent group represented by a compound of the following formula (4-Ar 1), formula (4-Ar 2), formula (4-Ar 3), formula (4-Ar 4) or formula (4-Ar 5) in which any one hydrogen atom is removed.
[ solution 103]
In the formulae (4-Ar 1) to (4-Ar 5), Y 1 Each independently is O, S or N-R, R is phenyl, biphenyl, naphthyl, anthracenyl or hydrogen, and at least one hydrogen in the structures of formulae (4-Ar 1) to (4-Ar 5) may be substituted with phenyl, biphenyl, naphthyl, anthracenyl, phenanthrenyl, methyl, ethyl, propyl, or butyl.
These heteroaryl groups may be bonded to the fluorene skeleton in the formula (4-H) via a linking group. That is, the fluorene skeleton and the heteroaryl group in the formula (4-H) may be bonded not only directly but also via a linking group therebetween. 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-, etc.
In addition, R in the formula (4-H) 1 And R 2 、R 2 And R 3 、R 3 And R 4 、R 5 And R 6 、R 6 And R 7 Or R 7 And R 8 Each of which may independently be bonded to form a fused ring, R 9 And R 10 Can bond and form a spiro ring. From R 1 To R 8 The condensed ring to be formed is a ring condensed on the benzene ring in the formula (4-H), and is an aliphatic ring or an aromatic ring. An aromatic ring is preferable, and as a structure including a benzene ring in the formula (4-H), a naphthalene ring, a phenanthrene ring, or the like can be mentioned. From R 9 And R 10 The spiro ring formed is a ring spiro-bonded to the five-membered ring in the formula (4-H), and is an aliphatic ring or an aromatic ring. Preferred is an aromatic ring, and fluorene rings and the like can be mentioned.
The compound represented by the formula (4-H) is preferably a compound represented by the following formula (4-H-1), formula (4-H-2) or formula (4-H-3), and is R in the formula (4-H) 1 And R 2 A compound formed by condensation of bonded benzene rings, R in the formula (4-H) 3 And R 4 A compound formed by condensation of a bonded benzene ring, R in the formula (4-H) 1 To R 8 Is not bonded to any of them.
[ solution 104]
R in the formulae (4-H-1), (4-H-2) and (4-H-3) 1 To R 10 Is defined as R corresponding to formula (4-H) 1 To R 10 R in the same formulae (4-H-1) and (4-H-2) 11 To R 14 Is also defined as R in the formula (4) 1 To R 10 The same is true.
The compound represented by the formula (4-H) is more 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) is R 9 And R 10 A compound bonded to form a spiro-fluorene ring.
[ solution 105]
R in the formulae (4-H-1A), (4-H-2A) and (4-H-3A) 2 To R 7 R in the formulae (4-H-1), (4-H-2) and (4-H-3) 2 To R 7 Same, and R in the formula (4-H-1A) and the formula (4-H-2A) 11 To R 14 Is also defined as R in the formula (4-H-1) and the formula (4-H-2) 11 To R 14 The same is true.
In addition, all or a part of hydrogen in the compound represented by the formula (4-H) may be substituted by halogen, cyano or deuterium.
More specific examples of the fluorene compound as a main component of the present invention include compounds represented by the following structural formulae. Further, "Me" represents a methyl group.
[ chemical 106]
< Dibenzo
Compound (II)
Dibenzo as host
The compound is, for example, a compound represented by the following formula (5-H).
[ chemical No. 107]
In the formula (5-H), R 1 To R 16 Each independently hydrogen, aryl, heteroaryl (which heteroaryl may be linked to the dibenzo of formula (5-H) via a linking group
Backbone-bonded), diarylamino (two aryl groups may be bonded to each other via a linking group), diheteroarylamino (two heteroaryl groups may be bonded to each other via a linking group), arylheteroarylamino (aryl and heteroaryl groups may be bonded to each other via a linking group), alkyl, cycloalkyl, alkenyl, alkoxy, or aryloxy, at least one of which may be substituted with aryl, heteroaryl, alkyl, or cycloalkyl, and R is R 1 To R 16 May be bonded to each other to form a condensed ring, at least one hydrogen in the formed ring may be selected from an aryl group and a heteroaryl group (the heteroaryl group may be bonded to the formed ring through a linking group)Ring-bonded), diarylamino (two aryl groups may be bonded to each other via a linking group), diheteroarylamino (two heteroaryl groups may be bonded to each other via a linking group), arylheteroarylamino (aryl groups, heteroaryl groups may be bonded to each other via a linking group), alkyl, cycloalkyl, alkenyl, alkoxy, or aryloxy, at least one of which may be substituted with aryl, heteroaryl, alkyl, or cycloalkyl, at least one of which may be substituted with halogen, cyano, or deuterium in the compound represented by formula (5-H).
The details of each group in the definition of the formula (5-H) can be referred to the description of the polycyclic aromatic compound of the formula (1) described above.
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.
Specific examples of the heteroaryl group include a monovalent group represented by a compound of the following formula (5-Ar 1), formula (5-Ar 2), formula (5-Ar 3), formula (5-Ar 4) or formula (5-Ar 5) from which any one hydrogen atom has been removed.
[ solution 108]
In the formulae (5-Ar 1) to (5-Ar 5), Y 1 Each independently is O, S or N-R, R is phenyl, biphenyl, naphthyl, anthracenyl or hydrogen, and at least one hydrogen in the structures of formulas (5-Ar 1) through (5-Ar 5) may be substituted with 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 group
The skeleton is bonded. Namely, dibenzo in the formula (5-H)
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-, etc.
The compound represented by the formula (5-H) is preferably R 1 、R 4 、R 5 、R 8 、R 9 、R 12 、R 13 And R 16 Is hydrogen. In the case, R in the formula (5-H) 2 、R 3 、R 6 、R 7 、R 10 、R 11 、R 14 And R 15 Preferably, the monovalent group is a monovalent group having a structure represented by 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 represented by phenylene, biphenylene, naphthylene, anthrylene, methylene, ethylene, -OCH, or the like 2 CH 2 -、-CH 2 CH 2 O-, or-OCH 2 CH 2 O-and dibenzo in formula (5-H)
Backbone bond), 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 And R 16 Is hydrogen. In the case, R in the formula (5-H) 3 、R 6 、R 11 、R 14 At least one (preferably one or two, more preferably one) of (A) and (B) is a group having a single intervening bond, phenylene group, biphenylene group, naphthylene group, anthracenylene group, methylene group, ethylene groupRadical, -OCH 2 CH 2 -、-CH 2 CH 2 O-or-OCH 2 CH 2 O-is a monovalent group of the formula (5-Ar 1), formula (5-Ar 2), formula (5-Ar 3), formula (5-Ar 4) or formula (5-Ar 5), at least one other than (i.e., other than the position substituted by the monovalent group having the structure) is hydrogen, phenyl, biphenyl, naphthyl, anthracenyl, methyl, ethyl, propyl or butyl, and at least one of these hydrogens may be substituted by phenyl, biphenyl, naphthyl, anthracenyl, methyl, ethyl, propyl or butyl.
Further, R in the formula (5-H) 2 、R 3 、R 6 、R 7 、R 10 、R 11 、R 14 And R 15 In the case of selecting a monovalent group having a structure represented by formula (5-Ar 1) to formula (5-Ar 5), at least one hydrogen in the structure may react with R in formula (5-H) 1 To R 16 Any of which is bonded to form a single bond.
Dibenzo as subject of the invention
More specific examples of the compound include compounds represented by the following structural formulae. Further, "tBu" represents a tert-butyl group.
[ solution 109]
[ solution 110]
The material for the light-emitting layer (host material and dopant material) may be used as a polymer compound obtained by polymerizing a reactive compound obtained by substituting a reactive substituent in the material for the light-emitting layer (host material and dopant material) as a monomer, or a crosslinked polymer thereof obtained by reacting a main chain polymer with the reactive compound, or a pendant polymer compound obtained by substituting a reactive substituent in the material for the light-emitting layer (host material and dopant material) or a crosslinked pendant polymer thereof.
Luminescent layer comprising an auxiliary dopant and an emissive dopant
A light-emitting layer in an organic electroluminescent element may include a host compound as a first component, an auxiliary dopant (compound) as a second component, and an emitting dopant (compound) as a third component. The polycyclic aromatic compounds of the invention are also preferably used as emissive dopants. As the auxiliary dopant (compound), a thermally active type retardation phosphor can be used.
In the following description, an organic electroluminescent element using a Thermally active Delayed phosphor as an auxiliary dopant is sometimes referred to as a "TAF element" (Thermally active Delayed Fluorescence (TADF) assisted Fluorescence (assisted Fluorescence) element). The "host compound" in the TAF element is a compound having a higher lowest excited singlet energy level, which is determined from a shoulder on the short wavelength side of the peak of the fluorescence spectrum, than the thermally active delayed phosphor as the second component and the emissive dopant as the third component.
The "thermally active type delayed phosphor" refers to a compound that absorbs thermal energy, generates reverse intersystem crossing from a lowest excited triplet state to a lowest excited singlet state, and is radioactively inactivated from the lowest excited singlet state, thereby being capable of radioactively delaying fluorescence. The term "thermally active delayed fluorescence" includes the case where a higher-order triplet state passes through during excitation from a lowest excited triplet state to a lowest excited singlet state. For example, there may be cited a paper published by Monkman et al of the university of Durham (Durham) (Nature-COMMUNICATIONS, inc.; 13680; digital object identifier, DOI): 10.1038/ncomms 13680), a paper published by Fine Beebel et al (Hosokai et al), a Scientific progress (Science Advances, sci. Adv.) 2013, e1603282), a paper published by Zodiac et al of the university of Kyoto (Scientific Reports, 7 4820; DOI. In the present invention, regarding a sample containing a target compound, the target compound is judged to be a "thermally active type delayed phosphor" on the basis of the observation of a slow fluorescence component when the fluorescence lifetime is measured at 300K. The slow fluorescence component herein refers to a component having a fluorescence lifetime of 0.1 μ sec or more. The fluorescence lifetime can be measured, for example, using a fluorescence lifetime measuring apparatus (manufactured by Hamamatsu Photonics, inc., C11367-01).
The polycyclic aromatic compound of the present invention can function as an emitting dopant, and the "thermally active delayed phosphor" can function as an auxiliary dopant for assisting the luminescence 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 Emitting Dopant (ED). In the figure, the energy level of the ground state of the host (H) is set to E (1, g), the lowest excited singlet level of the host obtained from the shoulder at the short wavelength side of the fluorescence spectrum is set to E (1, s, sh), the lowest excited triplet level of the host obtained from the shoulder at the short wavelength side of the phosphorescence spectrum is set to E (1, t, sh), the energy level of the ground state of the Auxiliary Dopant (AD) as the second component is set to E (2, g), the lowest excited singlet level of the auxiliary dopant as the second component obtained from the shoulder at the short wavelength side of the fluorescence spectrum is set to E (2, s, sh), the lowest excited triplet level of the auxiliary dopant as the second component obtained from the shoulder at the short wavelength side of the phosphorescence spectrum is set to E (2, t, sh), the energy level of the ground state of the emissive dopant as the third component is set to E (3, g), the lowest excited singlet level of the emission dopant as the third component obtained from the shoulder at the short wavelength side of the phosphorescence spectrum is set to E (3, s), the emission dopant as the third component is set to E (3, sh), the emission dopant is set to E (3, sh) and the emission dopant at the third componentThe lowest excited triplet level obtained from the shoulder at the short wavelength side of the phosphorescence spectrum is E (3, T, sh), and the hole is h + Let electron be e - The fluorescence Resonance Energy Transfer is FRET (fluorescence Resonance Energy Transfer). In the TAF element, when a general fluorescent dopant is used as the Emitting Dopant (ED), the energy of Up-Conversion (Up Conversion) by the auxiliary dopant is transferred to the lowest excited singlet level E (3, s, sh) of the emitting dopant and light is emitted. However, a part of the lowest excited triplet level E (2, t, sh) on the auxiliary dopant moves to the lowest excited triplet level E (3, t, sh) of the emitting 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 emitting dopant, followed by thermal deactivation to the ground state E (3, g). Due to the path, a part of the energy is not used for emitting light, resulting in waste of energy.
In contrast, in the organic electroluminescent element of the present embodiment, energy efficiency in moving from the auxiliary dopant to the emitting dopant can be used for light emission, and thus high light emission efficiency can be achieved. The reason for this is presumed to be the following light emission mechanism.
Fig. 3 shows a preferable energy relationship in the organic electroluminescent element of this embodiment. In the organic electroluminescent element of this embodiment, the lowest excited triplet level E (3,t, sh) of the compound having a boron atom as the emission dopant is high. Therefore, in the case where the excited singlet energy up-converted by the auxiliary dopant is intersystem crossing to the lowest excited triplet level E (3,t, sh) by the emitting dopant, for example, the lowest excited triplet level E (2,t, sh) on the emitting dopant is also up-converted or recovered to the auxiliary dopant (thermally active type delayed phosphor). 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 kinds of molecules whose respective functions are highlighted, the retention time of high energy is reduced, and the load on the compound is reduced.
In this embodiment, a known compound can be used as the host compound, and examples thereof include a compound having at least one of a carbazole ring and a furan ring, and among them, a compound in which at least one of a furyl group and a carbazole group is bonded to at least one of an arylene group and a heteroarylene group is preferably used. Specific examples thereof include mCP and mCBP.
From the viewpoint of promoting but not inhibiting the generation of Thermally Active Delayed Fluorescence (TADF) in the light-emitting layer, the lowest excited triplet level E (1, t, sh) of the host compound determined from the shoulder on the short wavelength side of the peak of the phosphorescence spectrum is preferably higher than the lowest excited triplet level E (2, t, sh) and the lowest excited triplet level E (3, t, sh) of the emitting dopant or the assist 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 further preferably 0.1eV or more than E (2, t, sh) and E (3, t, sh). In addition, a compound having TADF activity may also be used as the host compound.
As the host compound, for example, a compound represented by any one of the above-described formulae (H1), (H2), and (H3) can be used.
< thermally active type delayed phosphor (auxiliary dopant) >)
The thermally active retardation phosphor (TADF compound) used in the TAF element is preferably a donor-acceptor type thermally active retardation phosphor (D-a type TADF compound) as follows: it is designed to localize the Highest Occupied Molecular Orbital (HOMO) and the Lowest Unoccupied Molecular Orbital (LUMO) within a molecule using an electron donating substituent called donor and an electron accepting substituent called acceptor to produce efficient reverse interbody crossing. Here, in the present specification, "electron donating substituent" (donor) refers to a substituent and a partial structure that locally exists in the HOMO orbital in the molecule of the thermally active retardation phosphor, and "electron accepting substituent" (acceptor) refers to a substituent and a partial structure that locally exists in the LUMO orbital in the molecule of the thermally active retardation phosphor.
In general, a thermally active retardation phosphor using a donor or acceptor has a large Spin Orbit Coupling (SOC) due to a structural reason, a small exchange interaction between HOMO and LUMO, and a small Δ E (ST), and thus can obtain a very fast reverse intersystem crossing rate. On the other hand, a thermally active type delayed phosphor using a donor or an acceptor has a large structural relaxation in an excited state (in a molecule, since a stable structure is different between a ground state and an excited state, when a transition from the ground state to the excited state occurs by an external stimulus, the structure is changed to the stable structure in the excited state thereafter), and provides a wide emission spectrum, and thus, when used as a light emitting material, there is a possibility that color purity may be lowered.
However, by using an appropriate emitting dopant such as the polycyclic aromatic compound of the present invention as an auxiliary dopant together with a thermally active type retardation phosphor using a donor or an acceptor, high color purity can be provided.
The thermally active retardation phosphor may be any compound having an emission spectrum at least partially overlapping with an absorption spectrum of the polycyclic aromatic compound of the present invention. The polycyclic aromatic compound of the present invention and the thermally active retardation phosphor may be contained in the same layer or may be contained in adjacent layers.
As the thermally active type retardation phosphor in the TAF device, for example, a compound in which a donor and an acceptor are bonded directly or via a spacer can be used. As the electron donating group (donor structure) and the electron accepting group (acceptor structure) used in the thermally active retardation phosphor of the present invention, for example, the structures described in Chemistry of Materials, 2017, 29, 1946-1963, can be used. Examples of the structure of the applicator include: carbazole, dimethylcarbazole, di-tert-butylcarbazole, dimethoxycarbazole, tetramethylcarbazole, benzofluorocarbazole, benzothienocarbazole, phenylindolinocarbazole, phenylbicarbazole, bicarbazole, tertcarbazole, diphenylcarbazylamine, tetraphenylcarbazolyldine, phenoxazine, dihydrophenazine, phenothiazine, dimethyldihydroacridine, diphenylamine, bis (tert-butylphenyl) amine, N 1 - (4- (diphenylamino) phenyl) -N 4 ,N 4 Diphenylbenzene-1, 4-diamine, dimethylatetraphenylacridinediamine, tetramethyl-dihydro-indenonacridine, diphenyl-dihydrodibenzoazasilane, and the like. Examples of acceptor structures include: sulfonyldibenzenes, benzophenones, phenylenebis (phenylmethanone), benzonitrile, isonicotinonitrile, phthalonitrile, isophthalonitrile, terephthalonitrile, benzenetricarboxylonitrile, triazole, oxazole, thiadiazole, benzothiazole, benzobis (thiazole), benzoxazole, benzobis (oxazole), quinoline, benzimidazole, dibenzoquinoxaline, heptaazaphenalene, thioxanthone dioxide, dimethylanthrone, anthracenedione, 5H-cyclopenta [1,2-b:5,4-b']Bipyridine, fluorenedicarbonitrile, triphenyltriazine, pyrazinedicarboxonitrile, pyrimidine, phenylpyrimidine, methylpyrimidine, pyridinedicarbonitrile, dibenzoquinoxalinedicarbonitrile, bis (phenylsulfonyl) benzene, dimethylthioxanthene dioxide, thianthrene tetraoxide, and tris (dimethylphenyl) borane. In particular, the compound having thermally active delayed fluorescence in the TAF element is preferably a compound having at least one partial structure selected from carbazole, phenoxazine, acridine, triazine, pyrimidine, pyrazine, thioxanthene, benzonitrile, phthalonitrile, isophthalonitrile, diphenylsulfone, triazole, oxadiazole, thiadiazole, and benzophenone.
The compound used as the second component of the light-emitting layer in the TAF element is a thermally active retardation phosphor, and is preferably a compound having an emission spectrum at least partially overlapping with an absorption peak of the emission dopant. Hereinafter, a compound which can be used as a second component (a thermally active retardation phosphor) of a light-emitting layer in a TAF device is exemplified. However, the compounds that can be used as the thermally active retardation phosphors in the TAF device are not to be construed as being limited to the following exemplified compounds. In the following formula, me represents a methyl group, tBu represents a t-butyl group, and a wavy line represents a bonding position.
[ solution 111]
[ chemical 112]
[ solution 113]
[ chemical formula 114]
[ solution 115]
Further, as the thermally active retardation phosphor, a compound represented by any one of the following formulae (AD 1), (AD 2), and (AD 3) may be used.
[ solution 116]
In the formulas (AD 1), (AD 2) and (AD 3), M is respectively and independently a single bond, -O-, > N-Ar or > CAr 2 From the viewpoint of the depth of HOMO of the partial structure to be formed and the heights of the lowest excited singlet level and the lowest excited triplet level, a single bond, -O-, or > N-Ar is preferable. J is a spacer structure for separating a donor partial structure from a receptor partial structure, and is each 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 a conjugate exuded between the donor partial structure and the receptor partial structure. More specifically, phenylene, methylphenylene and dimethylphenylene are exemplified. Q is independently = C (-H) -or = N-, respectively, with respect to the height of the lowest excited singlet level and the lowest excited triplet level and the height of the LUMO of the partial structure formedFrom the viewpoint of this, = N-is preferable. 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 from the viewpoints of the depth of the HOMO of the partial structure to be formed and the heights of the lowest excited singlet level and the lowest excited triplet level, 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 is preferable, and hydrogen, phenyl, tolyl, xylyl, mesityl, biphenyl, pyridyl, bipyridyl, triazinyl, carbazolyl, dimethylcarbazolyl, di-tert-butylcarbazolyl, benzimidazolyl or phenylbenzimidazolyl is more preferable, and hydrogen, phenyl or carbazolyl is further preferable. m is 1 or 2.n is an integer of not more than (6-m), and is preferably an integer of 4 to (6-m) from the viewpoint of steric hindrance. Further, at least one hydrogen in the compounds represented by each of the formulae may be substituted by halogen or deuterium.
More specifically, the compound used as the second component in this form is 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 in this form may be a donor-acceptor type TADF compound represented by D-a in which one donor D is directly bonded to one acceptor a or is 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 directly bonded or are bonded to one acceptor a via a linking group is preferable because the compound is more excellent in the 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 formulae (DAD 1) and (DAD 2), D 1 、D 2 And D 3 Each independently represents a donor group. As the donor group, a group having a donor group,the donor structure may be used. A. The 1 And A 2 Each independently represents a receptor group. The acceptor group may be a structure of the acceptor. L is a radical of an alcohol 1 、L 2 And L 3 Each independently represents a single bond or a conjugated linking group. The conjugated linking group has a spacer structure for separating the donor group and the acceptor group, and is preferably an arylene group having 6 to 18 carbon atoms, and more preferably an arylene group having 6 to 12 carbon atoms. L is 1 、L 2 And L 3 Further preferred are each independently phenylene, methylphenylene or dimethylphenylene. N in the formula (DAD 1) is 2 or more, and represents an integer of not more than the maximum number of substitutable A1. n may be selected, for example, in the range of 2 to 10, or in the range of 2 to 6. When n is 2, it is a compound represented by the formula (DAD 2). n number of D 1 N, which may be the same or different, L 1 May be the same or different. Preferred specific examples of the compounds represented by the formulae (DAD 1) and (DAD 2) include 2PXZ-TAZ and the following compounds, but the second component employable in the present invention is not limited to these compounds.
[ solution 117]
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 retardation phosphor, and the polycyclic aromatic compound of the present invention may be contained in the same layer, or may contain at least one component in each of a plurality of layers. The host compound, the thermally active retardation phosphor, and the polycyclic aromatic compound of the present invention contained in the light-emitting layer may be one kind or a combination of plural kinds. The auxiliary dopant and the emission dopant may be included in the entirety of the host compound as the host, or may be included in a portion of the host compound as the host. The light-emitting layer doped with the auxiliary dopant and the emission dopant can be formed by a method in which a host compound, the auxiliary dopant, and the emission dopant are formed into a film by a ternary co-evaporation method; a method of simultaneously vapor-depositing a host compound, an auxiliary dopant and an emitting dopant after they are mixed in advance; a wet film formation method for applying a composition (coating material) 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 kind of the host compound, and may be determined according to the characteristics of the host compound. The amount of the host compound used is preferably 40 to 99 mass%, more preferably 50 to 98 mass%, and still more preferably 60 to 95 mass% of the total mass of the material for the light-emitting layer. Within the above range, the dopant is preferably used, for example, in terms of efficient charge transport and efficient energy transfer to the dopant.
The amount of the auxiliary dopant (thermally active retardation phosphor) used varies depending on the kind of the auxiliary dopant, and may be determined depending on the characteristics of the auxiliary dopant. The amount of the auxiliary dopant used is preferably 1 to 60 mass%, more preferably 2 to 50 mass%, and still more preferably 5 to 30 mass%, based on the total mass of the material for the light-emitting layer. In the above range, it is preferable, for example, in terms of efficiently transferring energy to the emitting dopant.
The amount of the emitting dopant (compound having a boron atom) used varies depending on the kind of the emitting dopant, and may be determined according to the characteristics of the emitting dopant. The amount of the emitting dopant 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 total mass of the material for the light-emitting layer. The above range is preferable, for example, in terms of preventing the concentration quenching phenomenon.
In terms of preventing the concentration quenching phenomenon, it is preferable that the amount of the emitting dopant used is a low concentration. In terms of the efficiency of the thermally active delayed fluorescence mechanism, it is preferable that the amount of the auxiliary dopant used be high. Further, in terms of the efficiency of the thermally active delayed fluorescence mechanism of the auxiliary dopant, it is preferable that the amount of the emitting dopant used is lower than the amount of the auxiliary dopant used.
< 2-1-3. Substrate in organic electroluminescent element
The substrate 101 is a support of 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, a glass plate and a plate made of a transparent synthetic resin such as polyester, polymethacrylate, polycarbonate, polysulfone are preferable. In the case of a glass substrate, soda-lime glass, alkali-free glass, or the like can be used, and the thickness is sufficient to maintain mechanical strength, and therefore, for example, the thickness may be 0.2mm or more. The upper limit of the thickness is, for example, 2mm or less, preferably 1mm or less. The material of the glass is preferably alkali-free glass because it is preferable that the amount of eluted ions from the glass is small, and SiO is added 2 Etc. of barrier coating (barrier coat) are also commercially available, and therefore the soda-lime glass can be used. In addition, in order to improve the gas barrier property, a gas barrier film such as a fine silicon oxide film may be provided on at least one surface of the substrate 101, and in the case where a synthetic resin plate, film or sheet having low gas barrier property is used as the substrate 101, it is particularly preferable to provide a gas barrier film.
< 2-1-4 > anode in organic electroluminescent element
The anode 102 functions to inject holes into the light-emitting layer 105. When 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.
Examples of the material for forming the anode 102 include inorganic compounds and organic compounds. Examples of the inorganic compound include: metals (aluminum, gold, silver, nickel, palladium, chromium, etc.), metal oxides (Indium Oxide, tin Oxide, indium Tin Oxide (ITO), indium Zinc Oxide (IZO), etc.), metal halides (copper iodide, etc.), copper sulfide, carbon black, ITO glass, or NESA glass, etc. Examples of the organic compound include: polythiophene such as poly (3-methylthiophene), and conductive polymer such as polypyrrole and polyaniline. Further, it can be used by appropriately selecting from substances 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 preferably 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 is now available, so that a low-resistance product of, for example, 100 Ω/γ to 5 Ω/γ, preferably 50 Ω/γ to 5 Ω/γ is particularly preferably used. The thickness of ITO can be arbitrarily selected depending on the resistance value, but usually 50nm to 300nm is used in many cases.
< 2-1-5 > hole injection layer and hole transport layer in organic electroluminescent element
The hole injection layer 103 functions to efficiently inject holes transferred 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 through 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 laminating and mixing one or more kinds of hole injection/transport materials, or are formed by mixing a hole injection/transport material and a polymer binder. Further, an inorganic salt such as iron (III) chloride may be added to the hole injection/transport material to form a layer.
The hole injecting/transporting substance needs 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 in which impurities serving as traps are not easily generated during production and use, is preferable.
The materials for forming the hole injection layer 103 and the hole transport layer 104 include compounds conventionally used as charge transport materials for holes in photoconductive materials, p-type semiconductors, hole injection layers for organic EL devices, andany compound is selected from known compounds used in the hole transport layer. Specific examples of these compounds include carbazole derivatives (e.g., N-phenylcarbazole, polyvinylcarbazole, etc.), bis-carbazole derivatives such as bis (N-arylcarbazole) and bis (N-alkylcarbazole), triarylamine derivatives (4, 4' -tris (N-carbazolyl) triphenylamine, polymers having an aromatic tertiary amino group in the main chain or side chain, 1-bis (4-di-p-tolylaminophenyl) cyclohexane, N, N ' -diphenyl-N, N ' -di (3-methylphenyl) -4,4' -diaminobiphenyl, N ' -diphenyl-N, N ' -dinaphthyl-4, 4' -diaminobiphenyl, N ' -diphenyl-N, N ' -di (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' -tetrakis [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-based compounds, benzofuran derivatives or thiophene derivatives, oxadiazole derivatives, quinoxaline derivatives (for example, 1,4,5,8,9, 12-hexaazatriphenylene-2, 3,6,7,10, 11-hexacarbonitrile, etc.), heterocyclic compounds such as porphyrin derivatives, polysilanes, etc. In the polymer system, polycarbonate or styrene derivative, polyvinylcarbazole, polysilane, or the like having the monomer in the side chain is preferable, but there is no particular limitation as long as it is a compound which forms a thin film necessary for manufacturing a light-emitting element, and which can inject holes from an anode and can further transport holes.
Further, it is also known that the conductivity of an organic semiconductor is strongly affected by doping. Such an organic semiconductor matrix material contains a compound having a good electron donating property or a compound having a good electron accepting property. For the doping of electron-donating substances, strong electron acceptors such as Tetracyanoquinodimethane (TCNQ) or 2,3,5, 6-tetrafluorotetracyanoquinodimethane-1, 4-benzoquinodimethane (2, 3,5,6-tetrafluoro taurocyano-1, 4-benzoquinodimethane, F4 TCNQ) are known (see, for example, documents "m. Faffy, a. Bayer, t. Frietz, k. Rio (m. Pfeiffer, a. Beyer, t. Fritz, k.leo)," applied physics article (app. Phys. Lett), 73 (22), 3202-3204 (1998) "and documents" j. Bulokutz, m. Faffy, t. Friez, k. Richitz (j. Schwitt), pff. 731, t. Pp. Pfeiffei, t, p. Tez, r. Leutz) ", and documents" j. Bulokutz "," k. Bewez, k. Bewefty, p. Bewez, p. Pi. They generate so-called holes by an electron transfer process in an electron-donating base substance (hole-transporting substance). The conductivity of the base material varies considerably depending on the number and mobility of holes. As a matrix material having a hole transporting property, for example, a benzidine derivative (N, N ' -bis (3-methylphenyl) -N, N ' -bis (phenyl) benzidine (N, N ' -bis (3-methylphenylamino) -N, N ' -bis (phenyl) benzidine, TPD), etc.) or a starburst amine derivative (4,4 ',4 ″ -tris (N, N-diphenylamino) triphenylamine, TDATA, etc.), or a specific metal phthalocyanine (particularly zinc phthalocyanine (ZnPc), etc.) is known (japanese patent laid-open No. 2005-167175). The polycyclic aromatic compound of the present invention can also be used as a material for forming a hole injection layer or a material for forming a hole transport layer.
< 2-1-6. Electron blocking layer in organic electroluminescent element
An electron blocking layer for preventing diffusion of electrons from the light-emitting layer may 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 formulae (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 functions to efficiently inject electrons transferred 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 transporting layer 106 and the electron injecting layer 107 are formed by laminating and mixing one or more kinds of electron transporting/injecting materials, or are formed by mixing an electron transporting/injecting material and a polymer binder.
The electron injection/transport layer is a layer that is responsible for injecting electrons from the cathode and transporting the electrons, and is preferably a layer that has high electron injection efficiency and transports the injected electrons with good efficiency. Therefore, a substance having a high electron affinity, a high electron mobility, and excellent stability is preferable, and impurities that become traps are less likely to be generated during production and use. However, when the balance between the transport of holes and electrons is considered, if the effect of efficiently preventing holes from the anode from flowing to the cathode side without being recombined is mainly exerted, the effect of improving the light emission efficiency is obtained as in the case of 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 may also include a function of a layer capable of efficiently preventing hole transfer.
The material (electron transport material) for forming the electron transport layer 106 or the electron injection layer 107 can be selected and used as desired from compounds conventionally used as electron transport compounds in photoconductive materials, and known compounds used in electron injection layers and electron transport layers of organic EL devices.
The material used for the electron transport layer or the electron injection layer preferably contains 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 carbon, hydrogen, oxygen, sulfur, silicon, and phosphorus; pyrrole derivatives and fused ring derivatives thereof; and a metal complex having electron-accepting nitrogen. Specifically, the following are listed: fused ring system aromatic ring derivatives such as naphthalene and anthracene, styrene-based aromatic ring derivatives represented by 4,4' -bis (diphenylvinyl) biphenyl, perinone derivatives, coumarin derivatives, naphthalimide derivatives, quinone derivatives such as anthraquinone and diphenoquinone, phosphorus oxide derivatives, arylnitrile derivatives, and indole derivatives. Examples of the metal complex having electron-accepting nitrogen include: and hydroxyoxazole complexes such as hydroxyphenyl oxazole 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 transport compound include: pyridine derivatives, naphthalene derivatives, fluoranthene derivatives, BO derivatives, anthracene derivatives, phenanthroline derivatives, perinone derivatives, coumarin derivatives, naphthalimide derivatives, anthraquinone derivatives, diphenoquinone derivatives, diphenylquinone derivatives, perylene derivatives, oxadiazole derivatives (1, 3-bis [ (4-tert-butylphenyl) 1,3, 4-oxadiazolyl ] phenylene, etc.), thiophene derivatives, triazole derivatives (N-naphthyl-2, 5-diphenyl-1, 3, 4-triazole, etc.), thiadiazole derivatives, metal complexes of 8-hydroxyquinoline (oxine) derivatives, hydroxyquinoline-based metal complexes, quinoxaline derivatives, polymers of quinoxaline derivatives, indole (benzazole) based compounds, gallium complexes, pyrazole derivatives, perfluorinated phenylene derivatives, triazine derivatives, pyrazine derivatives, benzoquinoline derivatives (2, 2 '-bis (benzo [ h ] quinolin-2-yl) -9,9' -spirobifluorene, etc.), imidazopyridine derivatives, borane derivatives, benzimidazole derivatives (tris (N-phenylbenzimidazole-2-yl) benzene, etc.), pyridine derivatives (2 '-bis (benzothiazole-2-pyridyl) derivatives, 3-bis (benzothiazole derivatives, 3-terpyridyl) derivatives, etc.: 6',2 '-terpyridin-4' -yl) benzene, etc.), naphthyridine derivatives (bis (1-naphthyl) -4- (1, 8-naphthyridin-2-yl) phenylphosphine oxide, etc.) Aldazine derivatives, pyrimidine derivatives, arylnitrile derivatives, indole derivatives, phosphine oxide derivatives, bisstyryl derivatives, silole derivatives, oxazoline derivatives, and the like.
In addition, a metal complex having electron-accepting nitrogen may also be used, and examples thereof include: hydroxyoxazole complexes such as hydroxyquinoline metal complexes and hydroxyphenyl oxazole complexes, azomethine complexes, tropolone metal complexes, flavonol metal complexes, and benzoquinoline metal complexes.
The materials can be used alone or in admixture with different materials.
Among the above materials, preferred are borane derivatives, pyridine derivatives, fluoranthene derivatives, BO derivatives, anthracene derivatives, benzofluorene derivatives, phosphine oxide derivatives, pyrimidine derivatives, arylnitrile derivatives, triazine derivatives, benzimidazole derivatives, phenanthroline derivatives, hydroxyquinoline metal complexes, thiazole derivatives, benzothiazole derivatives, thiaole derivatives, and oxazoline derivatives.
The polycyclic aromatic compound of the present invention can also be used as a material for forming an electron injection layer or a material for forming an electron transport layer.
The electron transport layer or the electron injection layer may further contain a substance capable of reducing a material forming the electron transport layer or the electron injection layer. As the reducing substance, various substances can be used as long as they have 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 can 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), and Cs (work function 1.95 eV), and alkaline earth metals such as Ca (work function 2.9 eV), sr (work function 2.0 to 2.5 eV), and Ba (work function 2.52 eV), and particularly preferable substances have a work function of 2.9eV or less. Among these, the reducing substance is more preferably K, rb or Cs as an alkali metal, still more preferably Rb or Cs, and most preferably Cs. These alkali metals have particularly high reducing power, and by adding a relatively small amount of the alkali metals to a material forming the electron transporting layer or the electron injecting layer, improvement in light emission luminance or prolongation in life in the organic EL element can be achieved. In addition, as the reducing substance having a work function of 2.9eV or less, a combination of two or more of these alkali metals is also preferable, and a combination including Cs, for example, a combination of Cs and Na, cs and K, cs and Rb, or Cs and Na and K is particularly preferable. By including Cs, the reducing ability can be efficiently exerted, and by adding Cs to a material for forming an electron transporting layer or an electron injecting layer, improvement in light emission luminance or prolongation in life of the organic EL element can be achieved.
< 2-1-8. Cathode in organic electroluminescent element
The cathode 108 functions to inject electrons into the light-emitting layer 105 through the electron injection layer 107 and the electron transport layer 106.
The material forming the cathode 108 is not particularly limited as long as it can efficiently inject electrons into the organic layer, and the same material as the material forming the anode 102 can be used. Among them, metals such as tin, indium, calcium, aluminum, silver, copper, nickel, chromium, gold, platinum, iron, zinc, lithium, sodium, potassium, cesium, and magnesium, and alloys thereof (e.g., magnesium-silver alloys, magnesium-indium alloys, and aluminum-lithium alloys such as lithium fluoride and aluminum) 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 most often unstable in the atmosphere. In order to improve this, for example, a method of doping a small amount of lithium, cesium, or magnesium into an organic layer and using an electrode having high stability is known. As other dopant, inorganic salts such as lithium fluoride, cesium fluoride, lithium oxide, and cesium oxide can also be used. However, the present invention is not limited to these examples.
Further, the following are preferable examples: metals such as platinum, gold, silver, copper, iron, tin, aluminum, and indium, alloys using these metals, inorganic substances such as silicon dioxide, titanium dioxide, and silicon nitride, polyvinyl alcohol, vinyl chloride, and hydrocarbon-based polymer compounds are laminated to protect the electrodes. The method for producing these electrodes is not particularly limited as long as conduction can be achieved by resistance heating, electron beam evaporation, sputtering, ion plating, coating, or the like.
< 2-1-9. Binders usable 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 used individually or may be dispersed in a solvent-soluble resin such as polyvinyl chloride, polycarbonate, polystyrene, poly (N-vinylcarbazole), polymethyl methacrylate, polybutyl methacrylate, polyester, polysulfone, polyphenylene oxide, polybutadiene, a hydrocarbon resin, a ketone resin, a phenoxy resin, polyamide, ethyl cellulose, a vinyl acetate resin, an Acrylonitrile-Butadiene-Styrene (ABS) resin, or a polyurethane resin, or a curable resin such as a phenol resin, a xylene resin, a petroleum resin, a urea resin, a melamine resin, an unsaturated polyester resin, an alkyd resin, an epoxy resin, or a silicone resin, which is a polymer binder.
< 2-1-10. Method for manufacturing organic electroluminescent element
Each layer constituting the organic EL element can be formed by forming a material constituting each layer into a thin film by a method such as vapor deposition, resistance heating vapor deposition, electron beam vapor deposition, sputtering, molecular lamination, printing, ink jet, spin coating, casting, or coating. The film thickness of each layer formed in the above-described manner is not particularly limited, and may be appropriately set according to the properties of the material, but is usually in the range of 2nm to 5000 nm. The film thickness can be measured by a crystal oscillation film thickness measuring apparatus or the like. When a thin film is formed by a vapor deposition method, the vapor deposition conditions vary depending on the type of material, the target crystal structure and the association structure of the film, and the like. The deposition conditions are preferably set to +50 ℃ to +400 ℃ in the boat heating temperature and 10 degrees of vacuum -6 Pa～10 -3 Pa, a deposition rate of 0.01 nm/sec to 50 nm/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 formed by forming a thin film of an anode material on an appropriate substrate by an evaporation method or the like, and then a thin film of a hole injection layer and a hole transport layer is formed on the anode. A thin film is formed on the thin film by co-evaporation of a host material and a dopant material to form a light-emitting layer, an electron-transporting layer and an electron-injecting layer are formed on the light-emitting layer, and a thin film containing a substance for a cathode is formed by an evaporation method or the like to form a cathode, thereby obtaining a target organic EL element. In the production of the organic EL element, the order of production 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.
When a dc voltage is applied to the organic EL element obtained as described above, the anode may be applied with a + polarity and the cathode may be applied with a-polarity, and when a voltage of about 2V to 40V is applied, light emission can be observed from the transparent or translucent 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.
< 2-1-11. Application example of organic electroluminescent element
The organic EL element is also applicable to a display device, an illumination device, or the like.
A display device or an illumination device including an 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 (see, for example, japanese patent laid-open No. 10-335066, japanese patent laid-open No. 2003-321546, and japanese patent laid-open No. 2004-281086). The display mode of the display may be, for example, a matrix mode or a segment mode. Further, the matrix display and the segment display may coexist in the same panel (panel).
In the matrix, pixels for display are two-dimensionally arranged in a lattice shape, a mosaic shape, or the like, and characters or images are displayed by a set of pixels. The shape or size of the pixel is determined according to the application. For example, in image and character display of a personal computer, a monitor, and a television, a rectangular pixel having a side of 300 μm or less is generally used, and in the case of a large-sized display such as a display panel, a pixel having a side of mm level is used. In the case of monochrome display, pixels of the same color may be arranged, and in the case of color display, pixels of red, green, and blue are arranged in parallel to perform display. In this case, a triangular shape and a striped shape are typical. Also, as a driving method of the matrix, any one of a line-sequential (line-sequential) driving method or an active matrix may be used. The line sequential driving has an advantage of a simple structure, but when the operating characteristics are taken into consideration, the active matrix may be more excellent, and therefore the driving method needs to be used separately depending on the application.
In the segment method (type), a pattern is formed so as to display information determined in advance, and the determined region is caused to emit light. Examples thereof include: time and temperature display in a digital clock or a thermometer, operation state display of an audio device or an induction cooker, panel display of an automobile, and the like.
Examples of the illumination device include an illumination device such as an indoor illumination, and a backlight of a liquid crystal display device (see, for example, japanese patent laid-open nos. 2003-257621, 2003-277741, and 2004-119211). Backlights are used mainly for improving visibility of display devices that do not emit light, and are used for liquid crystal display devices, clocks, audio devices, automobile panels, display panels, signs, and the like. In particular, as a backlight for personal computer applications in which thinning is becoming a problem in a liquid crystal display device, when it is considered that thinning is difficult in the conventional system including a fluorescent lamp or a light guide plate, a backlight using an organic EL element has characteristics of being thin and lightweight.
< 2-2. Other organic devices
The polycyclic aromatic compound of the present invention can be used for the production of an organic field effect transistor, an organic thin film solar cell, or the like, in addition to the organic electroluminescent element.
An organic field effect transistor is a transistor that controls current by an electric field generated by voltage input, and includes 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 the flow of electrons (or holes) flowing between the source electrode and the drain electrode can be arbitrarily blocked to control the current. A field effect transistor is easy to be miniaturized compared with a single transistor (bipolar transistor), and is often used as an element constituting an integrated circuit or the like.
In general, the organic field effect transistor may be configured 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 through an insulating layer (dielectric layer) in contact with the organic semiconductor active layer. Examples of the element structure include the following structures.
(1) Substrate, gate electrode, insulator layer, source electrode, drain electrode, and organic semiconductor active layer
(2) Substrate, gate electrode, insulator layer, organic semiconductor active layer, source electrode and drain electrode
(3) Substrate/organic semiconductor active layer/source electrode and drain electrode/insulator layer/gate electrode
(4) Substrate/source and drain electrodes/organic semiconductor active layer/insulator layer/gate electrode
The organic field effect transistor configured as described above can be used as a pixel driving switching element of an active matrix driving type liquid crystal display, an organic electroluminescence display, or the like.
An organic thin-film solar cell has a structure in which an anode such as ITO, a hole transport layer, a photoelectric conversion layer, an electron transport layer, and a cathode are stacked on a transparent substrate such as glass. The photoelectric conversion layer has a p-type semiconductor layer on the anode side and an n-type semiconductor layer on the cathode side. The 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, and 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 transport material or an electron transport 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 layers. In the organic thin film solar cell, known materials used in the organic thin film solar cell may be appropriately selected and used in combination.
< 3. Wavelength converting Material
The polycyclic aromatic compound of the present invention is useful as a wavelength converting material.
Now, studies are actively being made to apply a multicolor technology based on a color conversion scheme to a liquid crystal display or an organic EL display, illumination, and the like. Color conversion is to convert light emitted from the phosphor into light having a longer wavelength, and means, for example, converting ultraviolet light or blue light into green light or red light. The wavelength conversion material having the color conversion function is formed into a film, and for example, is combined with a blue light source, whereby 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 manufactured by using a white light source in which a blue light source and a wavelength conversion film having a color conversion function are combined as a light source unit, and combining the white light source with a liquid crystal driving portion and a color filter. In addition, without a liquid crystal driving portion, the liquid crystal display device can be used as a white light source as it is, and can be applied to a white light source such as a light-emitting diode (LED) lighting. Further, 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 and combining it with a wavelength conversion film that converts blue light into green light and red light. Further, a low-cost full-color micro LED display 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 is useful as the wavelength converting 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 high color purity suitable for use in a display device (a display device or a liquid crystal display device using an organic EL element). The color to be converted can be adjusted by appropriately selecting the substituent of the polycyclic aromatic compound of the present invention, a binder resin used in the wavelength converting composition described later, and the like. The wavelength converting material is prepared as a wavelength converting composition containing the polycyclic aromatic compound of the present invention. In addition, a wavelength conversion film can also be formed using the wavelength conversion composition.
The wavelength conversion composition may further 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, resins described in paragraphs 0173 to 0176 of International publication No. 2016/190283 can be used. As other additives, 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 curing the wavelength conversion composition. As a method for producing a wavelength conversion layer from the wavelength conversion composition, a known film formation method can be referred to. The wavelength conversion film may contain only a wavelength conversion layer formed from the composition containing the polycyclic aromatic compound of the present invention, or may contain another wavelength conversion layer (for example, a wavelength conversion layer that converts blue light into green light or red light, or a wavelength conversion layer that converts blue light or green light into red light). Further, the wavelength conversion film may include a base material layer or a barrier layer for preventing the color conversion layer from being deteriorated by oxygen, moisture, or heat.
[ examples ]
The present invention will be described more specifically with reference to the following examples, but the present invention is not limited to these examples.
Synthesis example (1):
synthesis of Compound (1-1)
[ chemical formula 118]
The intermediate (X-1) (52.1 g), 1-tert-butyl-3, 4, 5-trichlorobenzene (23.8 g), dichlorobis [ di-tert-butyl (4-dimethylaminophenyl) phosphino ] palladium (II) (Pd-132, 0.91g) as a palladium catalyst, sodium tert-butoxide (NaOtBu, 14.4 g) and toluene (500 ml) were placed in a flask and heated at 110 ℃ for 3 hours under a nitrogen atmosphere. After the reaction, water and ethyl acetate were added to the reaction mixture and stirred, and then the organic layer was separated and washed with water. Then, the crude product obtained by concentrating the organic layer was purified by means of a silica gel short column (eluent: heptane), whereby 69.2g of intermediate (X-2) was obtained.
[ solution 119]
Intermediate (X-2) (36.2 g), intermediate (X-3) (29.9 g), pd-132 (0.719 g) as a palladium catalyst, naOtBu (7.2 g) and toluene (300 ml) were placed in a flask and heated at 110 ℃ for 3 hours under a nitrogen atmosphere. After 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. Then, the crude product obtained by concentrating the organic layer was purified by a silica gel short path column (eluent: toluene/heptane =1/9 (volume ratio)), whereby 52.2g of intermediate (X-4) was obtained.
[ chemical formula 120]
Under nitrogen atmosphere, and at 0 deg.C, intermediate (X-4) (12.86 g) and tert-butyl benzene (T-butylbenzene) t Bu-benzene ( t Bu-benzene), 100 ml) was charged with 1.60M t-butyllithium pentane solution ( t BuLi,12.5 ml). After the completion of the dropwise addition, the temperature was raised to 70 ℃ and the mixture was stirred for 0.5 hour, and then a component having a boiling point lower than that of tert-butylbenzene was distilled off under reduced pressure. Cooled to-50 ℃ and boron tribromide (2.51 g) was added, warmed to room temperature and stirred for 0.5 h. Then, it was cooled again to 0 ℃ and N, N-diisopropyl was addedEthylamine (EtN) i Pr 2 1.29 g) was added thereto, and the mixture was stirred at room temperature until heat generation was completed, and then heated to 100 ℃ and stirred for 1 hour. The reaction solution was cooled to room temperature, and then an aqueous sodium acetate solution cooled with an ice bath and ethyl acetate were added in this order to separate the reaction solution. The organic layer was concentrated and purified by silica gel short path column chromatography (eluent: chlorobenzene). The obtained crude product was recrystallized from toluene, whereby 7.72g of compound (1-1) was obtained.
[ solution 121]
Ionization time-of-flight mass spectrometry (MALDI-TOF-MS) by matrix-assisted laser desorption ionization and nuclear magnetic resonance (MALDI-TOF-MS) 1 H-nuclear magnetic resonance， 1 H-NMR) confirmed the compound (1-1).
m/z(M+H)＝1259.83
1 H-NMR(CDCl 3 )：δ＝8.6(d,1H),8.0(d,2H),8.0(d,1H),7.8(s,1H),7.7(s,1H),7.6～7.5(m,5H),7.4(d,2H),7.2(d,1H),7.0(m,3H),6.9(d,1H),6.8(d,1H),6.7(s,1H),6.6(s,1H),6.5(d,2H),1.9～1.8(m,4H),1.8(s,4H),1.6(s,4H),1.5(s,3H),1.5(s,3H),1.4(s,6H),1.4(s,6H),1.3(s,3H),1.3(s,3H),1.2(s,9H),1.2(s,6H),1.2(s,6H),1.1(s,9H),0.9(s,18H).
Synthesis example (2): synthesis of Compound (1-2)
Compound (1-2) was obtained according to the same procedure as in Synthesis example 1, except that Compound (X-4) was changed to Compound (X-4-2).
The target compound was confirmed to be M/z (M + H) =1301.79 by MALDI-TOF-MS.
[ chemical formula 122]
Synthesis example (3): synthesis of Compound (1-5)
Compound (1-5) was obtained according to the same procedure as in Synthesis example 1, except that Compound (X-4) was changed to Compound (X-4-5).
The target compound was confirmed to be M/z (M + H) =1127.74 by MALDI-TOF-MS.
[ solution 123]
Synthesis example (4): synthesis of Compound (1-6)
Compound (1-6) was obtained according to the same procedure as in Synthesis example 1, except that Compound (X-4) was changed to Compound (X-4-6).
The target compound was confirmed to be M/z (M + H) =1255.80 by MALDI-TOF-MS.
[ chemical 124]
Synthesis example (5): synthesis of Compound (1-11)
Compound (1-11) was obtained according to the same procedure as in Synthesis example 1, except that Compound (X-4) was changed to Compound (X-4-11).
The compound of the target was confirmed to be M/z (M + H) =1457.88 by MALDI-TOF-MS.
[ 125]
Synthesis example (6): synthesis of Compound (1-15)
Compound (1-15) was obtained according to the same procedure as in Synthesis example 1, except that Compound (X-4) was changed to Compound (X-4-15).
The compound of the target was confirmed to be M/z (M + H) =1347.77 by MALDI-TOF-MS.
[ solution 126]
Synthesis example (7): synthesis of Compound (1-16)
Compound (1-16) was obtained according to the same procedure as in Synthesis example 1, except that Compound (X-4) was changed to Compound (X-4-16).
The target compound was confirmed to be M/z (M + H) =1239.73 by MALDI-TOF-MS.
[ solution 127]
Synthesis example (8): synthesis of Compound (1-17)
Compound (1-17) was obtained by following the same procedures as in Synthesis example 1, except that Compound (X-4) was changed to Compound (X-4-17).
The target compound was confirmed to be M/z (M + H) =1410.87 by MALDI-TOF-MS.
[ solution 128]
Synthesis example (9): synthesis of Compound (1-21)
Compound (1-21) was obtained according to the same procedure as in Synthesis example 1, except that Compound (X-4) was changed to Compound (X-4-21).
The target compound was confirmed to be M/z (M + H) =955.52 by MALDI-TOF-MS.
[ solution 129]
Synthesis example (10): synthesis of Compound (1-22)
Compound (1-22) was obtained according to the same procedure as in Synthesis example 1, except that Compound (X-4) was changed to Compound (X-4-22).
The target compound was confirmed to be M/z (M + H) =1181.70 by MALDI-TOF-MS.
[ chemical formula 130]
Synthesis example (11): synthesis of Compound (1-23)
Compound (1-23) was obtained according to the same procedure as in Synthesis example 1, except that Compound (X-4) was changed to Compound (X-4-23).
The target compound was confirmed to be M/z (M + H) =1192.58 by MALDI-TOF-MS.
[ solution 131]
Synthesis example (12): synthesis of Compound (1-24)
Compound (1-24) was obtained according to the same procedure as in Synthesis example 1, except that Compound (X-4) was changed to Compound (X-4-24).
The target compound was confirmed to be M/z (M + H) =1387.76 by MALDI-TOF-MS.
[ solution 132]
Synthesis example (13): synthesis of Compound (1-26)
Compound (1-26) was obtained according to the same procedure as in Synthesis example 1, except that Compound (X-4) was changed to Compound (X-4-26).
The target compound (1-26) was confirmed to be M/z (M + H) =1385.88 by MALDI-TOF-MS.
[ solution 133]
Synthesis example (14): synthesis of Compound (1-30)
Compound (1-30) was obtained according to the same procedure as in Synthesis example 1, except that Compound (X-4) was changed to Compound (X-4-30).
The target compound was confirmed to be M/z (M + H) =1087.67 by MALDI-TOF-MS.
[ solution 134]
Synthesis example (15): synthesis of Compound (1-31)
Compound (1-31) was obtained according to the same procedure as in Synthesis example 1, except that Compound (X-4) was changed to Compound (X-4-31).
The target compound was confirmed to be M/z (M + H) =1232.72 by MALDI-TOF-MS.
[ solution 135]
Synthesis example (16): synthesis of Compound (1-35)
Compound (1-35) was obtained according to the same procedure as in Synthesis example 1, except that Compound (X-4) was changed to Compound (X-4-35).
The target compound was confirmed to be M/z (M + H) =1257.69 by MALDI-TOF-MS.
[ solution 136]
Synthesis example (17): synthesis of Compound (1-41)
Compound (1-41) was obtained according to the same procedure as in Synthesis example 1, except that Compound (X-4) was changed to Compound (X-4-41).
The compound of the target was confirmed to be M/z (M + H) =1392.70 by MALDI-TOF-MS.
[ solution 137]
Synthesis example (18): synthesis of Compound (1-46)
Compound (1-46) was obtained according to the same procedure as in Synthesis example 1, except that Compound (X-4) was changed to Compound (X-4-46).
The target compound was confirmed to be M/z (M + H) =1221.87 by MALDI-TOF-MS.
[ 138]
Synthesis example (19): synthesis of Compound (1-47)
Compound (1-47) was obtained by following the same procedures as in Synthesis example 1, except that Compound (X-4) was changed to Compound (X-4-47).
The target compound (1-4) was confirmed to be M/z (M + H) =1238.84 by MALDI-TOF-MS.
[ solution 139]
Synthesis example (20): synthesis of Compound (1-48)
Compound (1-48) was obtained according to the same procedure as in Synthesis example 1, except that Compound (X-4) was changed to Compound (X-4-48).
The target compound (1-4) was confirmed to be M/z (M + H) =1143.68 by MALDI-TOF-MS.
[ solution 140]
Synthesis example (21): synthesis of Compound (1-50)
Compound (1-50) was obtained according to the same procedure as in Synthesis example 1, except that Compound (X-4) was changed to Compound (X-4-50).
The target compound was confirmed to be M/z (M + H) =1282.98 by MALDI-TOF-MS.
[ solution 141]
Synthesis example (22): synthesis of Compound (1-52)
Compound (1-52) was obtained according to the same procedure as in Synthesis example 1, except that Compound (X-4) was changed to Compound (X-4-52).
The target compound was confirmed to be M/z (M + H) =1225.81 by MALDI-TOF-MS.
[ solution 142]
Synthesis example (23): synthesis of Compound (1-53)
Compound (1-53) was obtained by following the same procedures as in Synthesis example 1, except that Compound (X-4) was changed to Compound (X-4-53).
The target compound was confirmed to be M/z (M + H) =1049.56 by MALDI-TOF-MS.
[ solution 143]
Synthesis example (24): synthesis of Compound (1-54)
Compound (1-54) was obtained by following the same procedures as in Synthesis example 1, except that Compound (X-4) was changed to Compound (X-4-54).
The target compound was confirmed to be M/z (M + H) =1378.91 by MALDI-TOF-MS.
[ solution 144]
Synthesis example (25): synthesis of Compound (1-57)
Compound (1-57) was obtained according to the same procedure as in Synthesis example 1, except that Compound (X-4) was changed to Compound (X-4-57).
The target compound was confirmed to be M/z (M + H) =1314.78 by MALDI-TOF-MS.
[ solution 145]
Synthesis example (26): synthesis of Compound (1-58)
Compound (1-58) was obtained by following the same procedures as in Synthesis example 1, except that Compound (X-4) was changed to Compound (X-4-58).
The target compound was confirmed to be M/z (M + H) =1408.77 by MALDI-TOF-MS.
[ solution 146]
Synthesis example (27): synthesis of Compound (1-59)
Compound (1-59) was obtained according to the same procedure as in Synthesis example 1, except that Compound (X-4) was changed to Compound (X-4-59).
The target compound was confirmed to be M/z (M + H) =1501.85 by MALDI-TOF-MS.
[ solution 147]
Synthesis example (28): synthesis of Compound (1-61)
Compound (1-61) was obtained according to the same procedure as in Synthesis example 1, except that Compound (X-4) was changed to Compound (X-4-61).
The target compound was confirmed to be M/z (M + H) =1313.69 by MALDI-TOF-MS.
[ solution 148]
Synthesis example (29): synthesis of Compound (1-65)
Compound (1-65) was obtained by following the same procedure as in Synthesis example 1, except that Compound (X-4) was changed to Compound (X-4-65).
The target compound was confirmed to be M/z (M + H) =1243.86 by MALDI-TOF-MS.
[ 149]
Synthesis example (30): synthesis of Compound (1-66)
Compound (1-66) was obtained according to the same procedure as in Synthesis example 1, except that Compound (X-4) was changed to Compound (X-4-66).
The target compound was confirmed to be M/z (M + H) =1285.81 by MALDI-TOF-MS.
[ solution 150]
Synthesis example (31): synthesis of Compound (1-67)
Compound (1-67) was obtained according to the same procedure as in Synthesis example 1, except that Compound (X-4) was changed to Compound (X-4-67).
The target compound was confirmed to be M/z (M + H) =1239.82 by MALDI-TOF-MS.
[ solution 151]
Synthesis example (32): synthesis of Compound (1-71)
Compound (1-71) was obtained by following the same procedures as in Synthesis example 1, except that Compound (X-4) was changed to Compound (X-4-71).
The target compound was confirmed to be M/z (M + H) =993.52 by MALDI-TOF-MS.
[ 152]
Synthesis example (33): synthesis of Compound (1-72)
Compound (1-72) was obtained according to the same procedure as in Synthesis example 1, except that Compound (X-4) was changed to Compound (X-4-72).
The target compound was confirmed to be M/z (M + H) =1216.74 by MALDI-TOF-MS.
[ solution 153]
Synthesis example (34): synthesis of Compound (1-73)
Compound (1-73) was obtained according to the same procedure as in Synthesis example 1, except that Compound (X-4) was changed to Compound (X-4-73).
The target compound was confirmed to be M/z (M + H) =1270.81 by MALDI-TOF-MS.
[ chemical 154]
Synthesis example (35): synthesis of Compound (1-74)
Compound (1-74) was obtained by following the same procedures as in Synthesis example 1, except that Compound (X-4) was changed to Compound (X-4-74).
The target compound was confirmed to be M/z (M + H) =1123.71 by MALDI-TOF-MS.
[ solution 155]
Synthesis example (36): synthesis of Compound (1-75)
Compound (1-75) was obtained according to the same procedure as in Synthesis example 1, except that Compound (X-4) was changed to Compound (X-4-75).
The target compound was confirmed to be M/z (M + H) =1183.80 by MALDI-TOF-MS.
[ solution 156]
Synthesis example (37): synthesis of Compound (1-76)
Compound (1-76) was obtained according to the same procedure as in Synthesis example 1, except that Compound (X-4) was changed to Compound (X-4-76).
The target compound was confirmed to be M/z (M + H) =1311.86 by MALDI-TOF-MS.
[ chemical formula 157]
Synthesis example (38): synthesis of Compound (1-77)
Compound (1-77) was obtained according to the same procedure as in Synthesis example 1, except that Compound (X-4) was changed to Compound (X-4-77).
The target compound was confirmed to be M/z (M + H) =1229.79 by MALDI-TOF-MS.
[ solution 158]
Synthesis example (39): synthesis of Compound (1-78)
Compound (1-78) was obtained by following the same procedures as in Synthesis example 1, except that Compound (X-4) was changed to Compound (X-4-78).
The target compound was confirmed to be M/z (M + H) =1290.78 by MALDI-TOF-MS.
[ chemical formula 159]
Synthesis example (40): synthesis of Compound (1-79)
Compound (1-79) was obtained according to the same procedure as in Synthesis example 1, except that Compound (X-4) was changed to Compound (X-4-79).
The target compound was confirmed to be M/z (M + H) =1189.66 by MALDI-TOF-MS.
[ 160]
Synthesis example (41): synthesis of Compound (1-80)
Compound (1-80) was obtained according to the same procedure as in Synthesis example 1, except that Compound (X-4) was changed to Compound (X-4-80).
The target compound was confirmed to be M/z (M + H) =1183.80 by MALDI-TOF-MS.
[ chemical 161]
Synthesis example (42): synthesis of Compound (1-85)
Compound (1-85) was obtained by following the same procedure as in Synthesis example 1, except that Compound (X-4) was changed to Compound (X-4-85).
The target compound was confirmed to be M/z (M + H) =1254.84 by MALDI-TOF-MS.
[ chemical 162]
Synthesis example (43): synthesis of Compound (1-86)
Compound (1-86) was obtained according to the same procedure as in Synthesis example 1, except that Compound (X-4) was changed to Compound (X-4-86).
The target compound was confirmed to be M/z (M + H) =1107.73 by MALDI-TOF-MS.
[ chemical 163]
Synthesis example (44): synthesis of Compound (1-87)
Compound (1-87) was obtained by following the same procedure as in Synthesis example 1, except that Compound (X-4) was changed to Compound (X-4-87).
The target compound was confirmed to be M/z (M + H) =1167.82 by MALDI-TOF-MS.
[ 164]
Synthesis example (45): synthesis of Compound (1-88)
Compound (1-88) was obtained according to the same procedure as in Synthesis example 1, except that Compound (X-4) was changed to Compound (X-4-88).
The target compound was confirmed to be M/z (M + H) =1295.89 by MALDI-TOF-MS.
[ solution 165]
Synthesis example (46): synthesis of Compound (1-89)
Compound (1-89) was obtained according to the same procedure as in Synthesis example 1, except that Compound (X-4) was changed to Compound (X-4-89).
The compound of the target was confirmed to be M/z (M + H) =1213.81 by MALDI-TOF-MS.
[ solution 166]
Synthesis example (47): synthesis of Compound (1-90)
Compound (1-90) was obtained according to the same procedure as in Synthesis example 1, except that Compound (X-4) was changed to Compound (X-4-90).
The target compound was confirmed to be M/z (M + H) =1274.80 by MALDI-TOF-MS.
[ 167]
Synthesis example (48): synthesis of Compound (1-91)
Compound (1-91) was obtained according to the same procedure as in Synthesis example 1, except that Compound (X-4) was changed to Compound (X-4-91).
The target compound was confirmed to be M/z (M + H) =1173.68 by MALDI-TOF-MS.
[ solution 168]
Synthesis example (49): synthesis of Compound (1-92)
Compound (1-92) was obtained by following the same procedure as in Synthesis example 1, except that Compound (X-4) was changed to Compound (X-4-92).
The target compound was confirmed to be M/z (M + H) =1167.82 by MALDI-TOF-MS.
[ 169]
The other compounds of the present invention can be synthesized by the method according to the synthesis example by appropriately changing the compounds of the raw materials.
< evaluation method of basic Property >
< preparation of sample >
When the absorption characteristics and the emission characteristics (fluorescence and phosphorescence) of a compound to be evaluated are evaluated, there are a case where the compound to be evaluated is dissolved in a solvent and evaluated in the solvent, and a case where the compound to be evaluated is evaluated in a thin film state. Further, when the evaluation is performed in a thin film state, there are a case where only the compound to be evaluated is made thin and the evaluation is performed, and a case where the compound to be evaluated is dispersed in an appropriate matrix material and made thin and the evaluation is performed, depending on the use form of the compound to be evaluated in the organic EL element. Here, a thin film obtained by vapor deposition of only the compound to be evaluated is referred to as an "individual film", and a thin film obtained by applying and drying a coating liquid containing the compound to be evaluated and a matrix material is referred to as a "coating film".
As the matrix material, commercially available PMMA (polymethyl methacrylate) or the like can be used. In this example, PMMA and a compound to be evaluated were dissolved in toluene, and then a thin film was formed on a transparent support substrate (10 mm × 10 mm) made of quartz by a spin coating method to prepare a sample.
In addition, a film sample in which the host compound is a matrix material was prepared in the following manner. 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 industry, ltd.), a molybdenum vapor deposition boat containing a host compound and a molybdenum vapor deposition boat containing a dopant material were set, and then a vacuum chamber was depressurized to 5X 10 -4 Pa。Next, the evaporation boat containing the host compound and the evaporation boat containing the dopant material were heated at the same time, and co-evaporation was performed so that the host compound and the dopant material had an appropriate film thickness, thereby forming a mixed thin film (sample) of the host compound and the dopant material. Here, the deposition rate is controlled according to the set mass ratio of the host compound and the dopant material.
< evaluation of absorption Property and luminescence Property >
The absorption spectrum of the sample was measured using an ultraviolet-visible near-infrared spectrophotometer ((thigh) shimadzu corporation, UV-2600). The fluorescence spectrum or phosphorescence spectrum of the sample was measured using a spectrofluorometer (Hitachi High-Tech (manufactured by Hitachi High-Tech Co., ltd., F-7000)).
For measurement of fluorescence spectrum, photoluminescence (photoluminescence) was 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. In order to observe the phosphorescence spectrum, a delay time from irradiation of the excitation light to start of measurement was adjusted using a light chopper (optical chopper). With respect to the sample, photoluminescence is measured by excitation at an appropriate excitation wavelength.
In addition, fluorescence quantum yield (PLQY) was measured using an absolute PL quantum yield measuring device (manufactured by Hamamatsu Photonics (Inc.), C9920-02G).
Next, basic property evaluation of the polycyclic aromatic compound of the present invention will be described.
< evaluation of fluorescence lifetime (delayed fluorescence) >
The fluorescence lifetime was measured at 300K using a fluorescence lifetime measuring device (manufactured by 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 are observed at maximum emission wavelengths measured at appropriate excitation wavelengths. In the measurement of the fluorescence lifetime of a general organic EL material emitting fluorescence at room temperature, the triplet component is deactivated by heat, and thus a slow light emitting component in which the 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, it is observed that triplet energy indicating a long excitation lifetime is shifted to singlet energy by thermal activation, and delayed fluorescence is observed.
< calculation of energy gap (Eg) >)
From the long wavelength end a (nm) of the absorption spectrum obtained by the method, it was calculated by Eg = 1240/a.
< measurement of ionization potential (Ip) >
A transparent supporting 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 the Changzhou industry Co., ltd.), a molybdenum deposition boat containing a target compound was mounted, and then the pressure in a vacuum chamber was reduced to 5X 10 -4 Pa. Next, the evaporation boat was heated to evaporate the target compound, thereby forming a single film (undoped (new) film) of the target compound.
The ionization potential of the target compound was measured using a photoelectron spectrometer (PYS-201, sumitomo heavy machinery industry co., 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.
< measurement of excited singlet level E (S, sh) and excited triplet level E (T, sh) >
A fluorescence spectrum of an individual film of a target compound formed on a glass substrate is observed at 77K with a second absorption peak from the long wavelength side of the absorption spectrum as excitation light, and an excited singlet level E (S, sh) is obtained from a shoulder on the short wavelength side of the peak of the fluorescence spectrum. Further, a phosphorescence spectrum was observed at 77K with a second absorption peak from the long wavelength side of the absorption spectrum as excitation light for an individual film of the target compound formed on the glass substrate, and the excited triplet level E (T, sh) was obtained from a shoulder on the short wavelength side of the peak of the phosphorescence spectrum.
< evaluation of organic EL element >
Evaluation of the basic properties revealed that the compound of the present invention has appropriate energy gap (Eg) and triplet excitation energy (E) T ) High and Δ EST small. From these results, it is found that the compound of the present invention is expected to be applied to, for example, a light-emitting layer and a charge transport layer, and is particularly expected to be applied to a light-emitting layer.
Next, the production and evaluation of an organic EL device using the polycyclic aromatic compound of the present invention will be described.
< Structure of organic EL element >
An organic EL device is produced using the polycyclic aromatic compound of the present invention.
Table 1 below shows the material structures of the respective layers in the organic EL devices of examples 1 to 49 and comparative examples 1 to 15.
[ Table 1]
The chemical structures of "HI", "HAT-CN", "HT-1", "HT-2", "BH", "ET-1", "ET-2", "Liq", "comparative compound (1)", "comparative compound (2)", "comparative compound (3)", "comparative compound (4)", "comparative compound (5)", "comparative compound (6)", "comparative compound (7)", "comparative compound (8)", "comparative compound (9)", "comparative compound (10)", "comparative compound (11)", "comparative compound (12)", "comparative compound (13)", "comparative compound (14)" and "comparative compound (15)" in tables 1 and 2 are shown below.
[ solution 170]
[ solution 171]
(example 1)
A glass substrate (manufactured by Opto Science) having a thickness of 180nm formed by sputtering and having a thickness of 26mm by 28mm by 0.7mm 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 deposition (Strand)), and a molybdenum vapor deposition boat and an aluminum nitride vapor deposition boat were respectively charged with HI, HAT-CN, HT-1, HT-2, BH, the compounds (1-1), ET-1, and ET-2, and with Liq, liF, and aluminum.
The following layers are sequentially formed on the ITO film of the transparent support substrate. The vacuum vessel was depressurized to 5X 10 -4 Pa, HI was first heated and vapor-deposited so that the film thickness became 40nm, HAT-CN was heated and vapor-deposited so that the film thickness became 5nm, HT-1 was heated and vapor-deposited so that the film thickness became 45nm, 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) were heated simultaneously, and vapor deposition was performed so that the film thickness became 25nm to form a light-emitting layer. The deposition rate was adjusted so that the mass ratio of BH to the compound (1-1) became approximately 97 to 3. Further, ET-1 was heated and vapor-deposited so that the film thickness became 5nm, and then ET-2 was heated simultaneously with Liq and vapor-deposited so that the film thickness became 25nm, thereby forming an electron layer including two layers. The deposition rate was adjusted so that the mass ratio of ET-2 to Liq became approximately 50 to 50. The deposition rate of each layer is 0.01 nm/sec to 1 nm/sec. Then, liF was heated and vapor-deposited at a vapor deposition rate of 0.01 nm/second to 0.1 nm/second 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 49 and comparative examples 1 to 15)
Organic EL devices of examples 2 to 49 and comparative examples 1 to 15 were obtained in the same manner as in example 1, except that the respective materials described in table 2 were used instead of the compound (1-1).
< evaluation items and evaluation methods >
The evaluation items include a driving voltage (V), an emission wavelength (nm), CIE chromaticity (x, y), external quantum efficiency (%), a maximum wavelength (nm) and a half-value width (nm) of an emission spectrum, and the like. For example, 1000cd/m can be used as the evaluation items 2 Value when light is emitted.
The quantum efficiency of a light-emitting element includes internal quantum efficiency and external quantum efficiency, and the internal quantum efficiency indicates a proportion of external energy injected as electrons (or holes) into a light-emitting layer of the light-emitting element, which is converted into photons. On the other hand, the external quantum efficiency is calculated based on the amount of photons emitted to the outside of the light-emitting element, and since 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 emitted to the outside of the light-emitting element, the external quantum efficiency is lower than the internal quantum efficiency.
The measurement method of the spectral radiance (emission spectrum) and the external quantum efficiency is as follows. The luminance of the element was set to 1000cd/m by applying a voltage/current generator R6144 manufactured by Edwardten test (Advantest) 2 The element emits light by the voltage of (3). The spectral radiance in the visible light region was measured from the vertical direction of the light-emitting surface using a spectral radiance meter SR-3AR manufactured by Topycon (TOPCON). Assuming that the light-emitting surface is a perfect diffusion surface, the number obtained by dividing the value of the measured spectral emission luminance of each wavelength component by the wavelength energy and multiplying by pi is the number of photons at each wavelength. Next, the number of photons is integrated over the entire wavelength region to be observed, and the total number of photons emitted from the element is set. A value obtained by dividing an applied current value by an elementary charge (elementary charge) is set as a carrier number injected into the element, and a value obtained by dividing a total photon number released from the element by a carrier number injected into the element is an external quantum efficiency. The half-value width of the emission spectrum is determined as a width between upper and lower wavelengths at which the intensity becomes 50% with the maximum emission wavelength as the center.
In the organic EL devices of examples 1 to 49 and comparative examples 1 to 15, a dc voltage was applied to the ITO electrode as an anode and the LiF/aluminum electrode as a cathode, and 1000cd/m was measured 2 Characteristics in light emission and a luminance of 1000cd/m 2 And a time during which the voltage for light emission is continuously driven and the luminance is maintained at 95% or more of the initial luminance.
The results are shown in table 2.
[ Table 2]
[ Industrial Applicability ]
The polycyclic aromatic compound of the present invention is useful as a material for an organic device, particularly as a material for a light-emitting layer for forming a light-emitting layer of an organic electroluminescent element. By using the polycyclic aromatic compound of the present invention as a dopant for a light-emitting layer, an organic electroluminescent element having a low voltage and high light-emitting efficiency can be obtained.
Claims (17)
1. A polycyclic aromatic compound having one or more structures containing a structural unit represented by the following formula (1);
in the formula (1), the reaction mixture is,
the A ring and the B ring are respectively and independently substituted or unsubstituted aryl rings or substituted or unsubstituted heteroaryl rings;
the ring C is a ring represented by the formula (C),
in the formula (C), the compound represented by the formula (A),
X c is > O, > N-R, > C (-R) 2 、＞Si(-R) 2 S or Se, said > N-R, said > C (-R) 2 And said > Si (-R) 2 Each R of (A) is independently hydrogen, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted alkyl, or substituted or unsubstituted cycloalkyl, > C (-R) 2 And said > Si (-R) 2 Two R's may be bonded to each other to form a ring,
two Z's arbitrarily adjacent C Are each independently of Y 1 Or X 2 The carbon to which any one of them is directly bonded,
other Z C Are each independently N or C-R C ，R C Each independently hydrogen, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted diarylamino, substituted or unsubstituted diheteroarylamino, substituted or unsubstituted arylheteroarylamino, substituted or unsubstituted diarylboron, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkoxy, substituted or unsubstituted aryloxy, substituted or unsubstituted arylthio, or substituted silyl, the two aryl groups of the diarylamino being bondable to one another via a linking group, the two heteroaryl groups of the diheteroarylamino being bondable to one another via a linking group, the aryl and heteroaryl groups of the arylheteroarylamino being bondable to one another via a linking group, the two aryl groups of the diarylboron being bondable to one another via a single bond or a linking group,
two adjacent R C May be bonded to each other to form an aryl or heteroaryl ring, each of which is unsubstituted or substituted with at least one R C2 Substituted, R C2 And R C Are the same as each other, wherein R C2 Not being hydrogen, and two R being adjacent C2 Are not bonded to each other to form an aryl or heteroaryl ring,
in the ring represented by the formula (C), as R C Or R C2 And an aryl group substituted with at least a group represented by the formula (D-1) or (D-2) or at least a group represented by the formula(D-1) or a heteroaryl group substituted with a group represented by the formula (D-2);
the group represented by the formula (D-1) or (D-2) is bonded at two x-positions to two adjacent rings of the aryl or heteroaryl ring,
in the formulae (D-1) and (D-2), R D Each independently is substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted alkyl, or substituted or unsubstituted cycloalkyl, each independently is substituted or unsubstituted alkylene, substituted or unsubstituted alkenylene, substituted or unsubstituted arylene, or substituted or unsubstituted heteroarylene;
Y 1 is B, P = O, P = S, al, ga, as, si-R, or Ge-R, said Si-R and R of said Ge-R being a substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted alkyl, or substituted or unsubstituted cycloalkyl;
X 1 and X 2 Independently of each other > O, > N-R, > C (-R) 2 、＞Si(-R) 2 R > N-R is hydrogen, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted alkyl, or substituted or unsubstituted cycloalkyl, > C (-R) 2 And said > Si (-R) 2 Each R of (A) is independently hydrogen, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted alkyl, or substituted or unsubstituted cycloalkyl, > C (-R) 2 And said > Si (-R) 2 May bond to each other to form a ring, and further, the R > N-R and/or the > C (-R) 2 R of (2) may be bonded to the A ring and/or the B ring, or the A ring and/or the C ring via a connecting group or a single bond,
at least one hydrogen in the structure may be substituted with cyano, halogen, or deuterium.
2. The polycyclic aromatic compound of claim 1, wherein R is C Or R C2 The aryl group substituted with at least the group represented by the formula (D-1) or the formula (D-2) or the heteroaryl group substituted with at least the group represented by the formula (D-1) or the formula (D-2) may further contain, as a partial structure, at least one ring selected from the group consisting of an aryl ring substituted with at least the group represented by the formula (D-1) or the formula (D-2) and a heteroaryl ring substituted with at least the group represented by the formula (D-1) or the formula (D-2).
3. The polycyclic aromatic compound according to claim 1 or 2, wherein the structural unit represented by formula (1) is a structural unit represented by formula (2);
in the formula (2), the reaction mixture is,
z is each independently N or C-R 11 Or Z = Z is each independently > O, > N-R, > C (-R) 2 、＞Si(-R) 2 S or Se, said > N-R, said > C (-R) 2 And said > Si (-R) 2 Each R of (A) is independently hydrogen, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted alkyl, or substituted or unsubstituted cycloalkyl, > C (-R) 2 And said > Si (-R) 2 Two R's may be bonded to each other to form a ring,
the C-R 11 R of (A) 11 Each independently is hydrogen, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted diarylamino, substituted or unsubstituted diheteroarylamino, substituted or unsubstituted arylheteroarylamino, substituted or unsubstituted diarylboryl, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkoxy, substituted or unsubstituted aryloxy, substituted or unsubstituted arylthio, or substituted silyl,
the two aryl groups of the diarylamino group may be bonded to each other via a linking group, the two heteroaryl groups of the diheteroarylamino group may be bonded to each other via a linking group, the aryl group and the heteroaryl group of the arylheteroarylamino group may be bonded to each other via a linking group, the two aryl groups of the diarylboron group may be bonded to each other via a single bond or a linking group,
two adjacent R 11 May be bonded to each other and together with the a-ring or the b-ring form an aryl ring or heteroaryl ring, each unsubstituted or substituted with at least one R 11b Substituted, R 11b And R 11 Are of the same meaning, wherein R 11b Not being hydrogen, and two R being adjacent 11b Are not bonded to each other to form an aryl or heteroaryl ring,
the C ring is a ring represented by the formula (C);
Y 1 is B, P = O, P = S, al, ga, as, si-R, or Ge-R, said Si-R and R of said Ge-R being a substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted alkyl, or substituted or unsubstituted cycloalkyl;
X 1 and X 2 Independently of each other > O, > N-R, > C (-R) 2 、＞Si(-R) 2 R > N-R is hydrogen, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted alkyl, or substituted or unsubstituted cycloalkyl, > C (-R) 2 And said > Si (-R) 2 Each R of (A) is independently hydrogen, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted alkyl, or substituted or unsubstituted cycloalkyl, > C (-R) 2 And said > Si (-R) 2 May bond to each other to form a ring, and further, the R > N-R and/or the > C (-R) 2 R of (A) may be bonded to the a ring and/or the b ring, or the a ring and/or the C ring, through a linking group or a single bond;
at least one hydrogen in the structure may be substituted with cyano, halogen, or deuterium.
4. The polycyclic aromatic compound according to claim 3, wherein the structural unit represented by the formula (2) is a structural unit represented by the formula (2 a-1);
in the formula (2 a-1), Y 1 、X 1 、X 2 、X C And Y in formula (2) 1 、X 1 、X 2 、X C Are each the same as defined above, R 11b 、R C2 And R in the formula (2) 11b 、R C2 Are respectively the same as the above-mentioned definition,
n1 is an integer of 1 to 4, n2 is an integer of 0 to 4, n3 is an integer of 0 to 3,
at least one hydrogen in the structure may be substituted with cyano, halogen, or deuterium.
5. The polycyclic aromatic compound according to claim 4, represented by any one of the following formulae,
in the formula, me is methyl, tBu is tert-butyl, and D is deuterium.
6. The polycyclic aromatic compound according to claim 3, wherein the structural unit represented by the formula (2) is a structural unit represented by the formula (2 a-2);
in the formula (2 a-2), Y 1 、X 1 、X 2 、X C And Y in formula (2) 1 、X 1 、X 2 、X C Are each the same as R 11b 、R C2 And R in the formula (2) 11b 、R C2 Are respectively defined as the same meaning as that of each other,
X 3 and X 4 Independently of one another, a single bond, > O, > N-R, > C (-R) 2 Or > S, wherein X 3 And X 4 Is not a single bond at the same time,
n1 is an integer of 1 to 4, n2 is an integer of 0 to 4, n3 is an integer of 0 to 3, n4 is an integer of 0 to 2,
at least one hydrogen in the structure may be substituted with cyano, halogen, or deuterium.
7. The polycyclic aromatic compound according to claim 6, represented by any one of the following formulae;
in the formula, me is methyl, and tBu is tert-butyl.
8. The polycyclic aromatic compound according to claim 3, represented by the following formula;
9. a polycyclic aromatic compound having one or more structures containing a structural unit represented by the following formula (1');
in the formula (1'), in the presence of a catalyst,
the A ring and the B ring are respectively and independently substituted or unsubstituted aryl rings or substituted or unsubstituted heteroaryl rings;
the ring C is a ring represented by the formula (C),
in the formula (C), the compound represented by the formula (A),
X c is > O, > N-R, > C (-R) 2 、＞Si(-R) 2 S or Se, said > N-R, said > C (-R) 2 And said > Si (-R) 2 Each R of (A) is independently hydrogen, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted alkyl, or substituted or unsubstituted cycloalkyl, > C (-R) 2 And said > Si (-R) 2 Two R's may be bonded to each other to form a ring,
two Z's arbitrarily adjacent C Are each independently of Y 1 Or X 2 The carbon to which any one of them is directly bonded,
other Z C Are each independently N or C-R C ，R C Each independently is hydrogen, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted diarylamino, substituted or unsubstituted diheteroarylamino, substituted or unsubstituted arylheteroarylamino, substituted or unsubstituted diarylboronA group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted arylthio group, or a substituted silyl group, two aryl groups of the diarylamino group may be bonded to each other via a linking group, two heteroaryl groups of the diheteroarylamino group may be bonded to each other via a linking group, an aryl group and a heteroaryl group of the arylheteroarylamino group may be bonded to each other via a linking group, two aryl groups of the diarylboron group may be bonded to each other via a single bond or a linking group,
two adjacent R C May be bonded to each other to form an aryl or heteroaryl ring, each of which is unsubstituted or substituted with at least one R C2 Substituted, R C2 And R C Are the same as each other, wherein R C2 Not being hydrogen, and two R being adjacent C2 Are not bonded to each other to form an aryl or heteroaryl ring,
Y 1 is B, P = O, P = S, al, ga, as, si-R, or Ge-R, said Si-R and R of said Ge-R being a substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted alkyl, or substituted or unsubstituted cycloalkyl;
X 1 and X 2 Independently of each other > O, > N-R, > C (-R) 2 、＞Si(-R) 2 R > N-R is hydrogen, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted alkyl, or substituted or unsubstituted cycloalkyl, > C (-R) 2 And said > Si (-R) 2 Each R of (A) is independently hydrogen, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted alkyl, or substituted or unsubstituted cycloalkyl, > C (-R) 2 And said > Si (-R) 2 May bond to each other to form a ring, and further, the R > N-R and/or the > C (-R) 2 R of (A) may be bonded to the A ring and/or the B ring, or the A ring, through a connecting group or a single bondAnd/or a C ring bond;
the structure comprising at least one selected from the group consisting of an aryl ring substituted with at least a group represented by the formula (D-1) and a heteroaryl ring substituted with at least a group represented by the formula (D-1) as a partial structure,
the group represented by the formula (D-1) wherein R is bonded at two points to two adjacent rings in any one of the aryl or heteroaryl rings in the structure D Each independently is substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted alkyl, or substituted or unsubstituted cycloalkyl, each independently is substituted or unsubstituted alkylene, substituted or unsubstituted alkenylene, substituted or unsubstituted arylene, or substituted or unsubstituted heteroarylene;
at least one hydrogen in the structure may be substituted with cyano, halogen, or deuterium.
10. The polycyclic aromatic compound according to claim 9, wherein the group represented by the formula (D-1) is a group represented by the formula (D-1-1);
R D each independently substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted alkyl, or substituted or unsubstituted cycloalkyl.
11. The polycyclic aromatic compound according to claim 10, represented by any one of the following formulae;
12. a material for organic devices, comprising the polycyclic aromatic compound according to any one of claims 1 to 11.
13. 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 11.
14. The organic electroluminescent element according to claim 13, wherein the light-emitting layer contains a host and the polycyclic aromatic compound as a dopant.
15. The organic electroluminescent element according to claim 14, wherein the host is an anthracene compound, a fluorene compound, or a dibenzo
A compound is provided.
16. A display device comprising the organic electroluminescent element as claimed in any one of claims 13 to 15.
17. A lighting device comprising the organic electroluminescent element as claimed in any one of claims 13 to 15.
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| JP2021-143748 | 2021-09-03 | ||
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| JP2022113648A JP2023037571A (en) | 2021-09-03 | 2022-07-15 | Polycyclic aromatic compound |
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| CN115947747A (en) * | 2023-01-10 | 2023-04-11 | 冠能光电材料(深圳)有限责任公司 | Triptycene boron-nitrogen compound and application thereof |
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| JP6329754B2 (en) | 2013-11-22 | 2018-05-23 | 矢崎総業株式会社 | Parts with fastening members and their mounting methods |
| CN112105472B (en) | 2018-04-27 | 2023-04-18 | 株式会社博迈立铖 | Powder for magnetic core, magnetic core using same, and coil component |
| KR20220024468A (en) | 2019-06-14 | 2022-03-03 | 가꼬우 호징 관세이 가쿠잉 | polyaromatic compounds |
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| CN115947747A (en) * | 2023-01-10 | 2023-04-11 | 冠能光电材料(深圳)有限责任公司 | Triptycene boron-nitrogen compound and application thereof |
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