Compound, light-emitting material, delayed fluorescent material, and organic optical device

Abstract

Compounds represented by the general formula are useful as luminescent materials. R1 or R2 is Het-LA-* or CN-LA-*; one to three among R1-R5 are diarylamino groups, etc.; the remainder are hydrogen atoms or aryl groups; Het is a heteroaryl group; and LA is a single bond or an arylene group, etc.　

Description

[Technical Field]

[0001] The present invention relates to a compound having good luminescent properties, and also to a luminescent material, a delayed fluorescent material, and an organic optical device using the compound. [Background technology]

[0002] Research into improving the luminous efficiency of organic optical devices such as organic light-emitting diodes (OLEDs) is currently underway. For example, the use of compounds capable of reverse intersystem crossing from the triplet state to the singlet state has been actively pursued as a material for the emissive layer. Conventional fluorescent materials generate singlet and triplet excitons at a 25:75 ratio when excited by electric current at room temperature. Singlet excitons radiatively decay to the ground singlet state, emitting fluorescence. However, triplet excitons have a long lifetime and lose energy via thermal radiation before transitioning to the ground state, resulting in nonradiative decay. This prevents the energy of triplet excitons, which are likely to be generated, from being effectively utilized for luminescence. In contrast, compounds capable of reverse intersystem crossing from the triplet state to the singlet state also emit fluorescence upon transitioning to the ground singlet state. This allows the energy of triplet excitons, which are likely to be generated, to indirectly contribute to fluorescence. Therefore, a significantly higher luminous efficiency can be expected compared to when a normal fluorescent material that does not undergo reverse intersystem crossing is used. As organic optical devices utilizing compounds capable of causing such reverse intersystem crossing, many have been proposed that have a single light-emitting layer formed by co-evaporating a thermally activated delayed fluorescent material and a host material (see, for example, Patent Document 1). Here, a thermally activated delayed fluorescent material is a compound that causes reverse intersystem crossing from an excited triplet state to an excited singlet state upon absorption of thermal energy, and after fluorescent emission from singlet excitons directly excited from the ground singlet state is observed, fluorescent emission (delayed fluorescent emission) from singlet excitons generated via reverse intersystem crossing is observed with a delay. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] WO2018 / 237393 Summary of the Invention [Problem to be solved by the invention]

[0004] However, the light-emitting materials proposed to date still have room for improvement in terms of light-emitting efficiency. Therefore, the present inventors have conducted extensive research with the aim of finding a light-emitting material with good light-emitting properties and providing an organic optical device with high light-emitting efficiency. [Means for solving the problem]

[0005] As a result of extensive research, the present inventors have found that compounds having specific structures have excellent luminescence properties. The present invention has been proposed based on this finding and has the following configuration. [1] A compound represented by the following general formula (1): [ka] [R in general formula (1)] 1 ~R 5 Of these, R 1 and R 2 One of them is A, Remaining R 1 ~R 5 p of them are D, The remaining 4-p are R. Here A is Het-L A -* or CN-L A -*, where Het represents a substituted or unsubstituted heteroaryl group bonded via a carbon atom (provided that the heteroaryl group contains at least one nitrogen atom as a ring skeleton atom), and L A represents a single bond or a substituted or unsubstituted arylene group, and * represents the bonding position. D is a group represented by the following general formula (IIa), (IIb), (IIc) or (IId). [ka] where X' is NR D ', represents an oxygen atom or a sulfur atom, R D each independently represents a hydrogen atom, a deuterium atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted amino group, a cyano group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted heteroaryloxy group, or a silyl group, and two or more R D may be bonded to each other to form a cyclic structure, R D ' represents a hydrogen atom, a deuterium atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted amino group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group; R D ' is one or more R D may be bonded to form a cyclic structure, L D each independently represents a single bond, a substituted or unsubstituted arylene group, or a substituted or unsubstituted heteroarylene group; * indicates the bond position. R is a hydrogen atom, a deuterium atom, or a substituted or unsubstituted aryl group (excluding groups that can be A or D). p is an integer of 1 to 3. When p is 2 or 3, multiple Ds present in the molecule may be the same or different. When p is 1 or 2, multiple Rs present in the molecule may be the same or different. [2] R 2 The compound according to [1], wherein A is [3] R 1 The compound according to [1], wherein A is [4] R 1 ~R 5The compound according to any one of [1] to [3], wherein at least one of: [5] R 2 is A and R 1 and R 3 [2] The compound according to [2], wherein at least one of the groups is a hydrogen atom or a deuterium atom. [6] R 1 is A and R 2 is a hydrogen atom or a deuterium atom. [7] The compound according to any one of [1] to [6], wherein p is 3. [8] The compound according to [7], wherein R is a hydrogen atom or a deuterium atom. [9] The compound according to any one of [1] to [6], wherein p is 2.

[10] The compound according to [9], wherein one of the two Rs is a hydrogen atom or a deuterium atom, and the other is a substituted or unsubstituted aryl group (excluding groups that can be A or D).

[11] The compound according to [9], wherein each of the two Rs is independently a hydrogen atom or a deuterium atom.

[12] R 4 and R 5 and each independently represent D.

[13] R 4 and R 5 The compound according to any one of [1] to

[11] , wherein one of the groups is D and the other is a substituted or unsubstituted aryl group (excluding groups which can become A or D).

[14] A is Het-L A The compound according to any one of [1] to

[13] , wherein

[15] The compound according to

[14] , wherein A is represented by any one of the following general formulae (IIIa) to (IIIe): [ka] [In the general formulae (IIIa) to (IIIe), R 21 ~R 25R each independently represents a hydrogen atom or a substituent. 21 and R 22 , R 22 and R 23 , R 23 and R 24 , R 24 and R 25 may be bonded to each other to form a ring structure. A represents a single bond or a substituted or unsubstituted arylene group.

[16] The compound according to

[14] or

[15] , wherein Het is not a dialkylphenyl-1,3,5-triazinyl group.

[17] L A

[16] The compound according to

[16] , wherein

[18] The compound according to any one of [1] to

[17] , wherein D is a group represented by general formula (IIb):

[19] A light-emitting material comprising the compound according to any one of [1] to

[18] .

[20] A delayed fluorescent material comprising the compound according to any one of [1] to

[18] .

[21] An organic optical device comprising the compound according to any one of [1] to

[18] .

[22] The organic optical device according to

[21] , wherein the element has a layer containing the compound, the layer also containing a host material.

[23] The organic optical device of

[21] , wherein the element has a layer containing the compound, the layer also containing a light-emitting material.

[24] The organic optical device according to any one of

[21] to

[23] , wherein the compound emits the greatest amount of light among the materials contained in the element.

[25] The organic optical device according to

[23] , wherein the amount of light emitted from the light-emitting material is greater than the amount of light emitted from the compound.

[26] The organic optical device according to any one of

[21] to

[25] , which is an organic light-emitting diode (OLED).

[27] The organic optical device according to any one of

[21] to

[26] , which emits delayed fluorescence.

[0006]

[28] A compound represented by the following general formula (1'): [ka] [R in general formula (1')] 1 ~R 5 satisfies the following condition 1 or 2, (Condition 1) R 1 ~R 5 Of these, R 1 and R 2 one of the groups is a halogen atom, Remaining R 1 ~R 5 p of them are D, The remaining 4-p are R. (Condition 2) R 1 ~R 5 Of these, R 1 and R 2 One of them is A, Remaining R 1 ~R 5 p of the atoms are halogen atoms, The remaining 4-p are R. Here A is Het-L A -* or CN-L A -*, where Het represents a substituted or unsubstituted heteroaryl group bonded via a carbon atom (provided that the heteroaryl group contains at least one nitrogen atom as a ring skeleton atom), and L A represents a single bond or a substituted or unsubstituted arylene group, and * represents the bonding position. D is a group represented by the following general formula (IIa), (IIb), (IIc) or (IId). [ka] where X' is NR D ', represents an oxygen atom or a sulfur atom, R Deach independently represents a hydrogen atom, a deuterium atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted amino group, a cyano group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted heteroaryloxy group, or a silyl group, and two or more R D may be bonded to each other to form a cyclic structure, R D ' represents a hydrogen atom, a deuterium atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group; R D ' is one or more R D may be bonded to form a cyclic structure, L D each independently represents a single bond, a substituted or unsubstituted arylene group, or a substituted or unsubstituted heteroarylene group; * indicates the bond position. R is a hydrogen atom, a deuterium atom, or a substituted or unsubstituted aryl group (excluding groups that can be A or D). p is an integer of 1 to 3. When p is 2 or 3, multiple Ds present in the molecule may be the same or different. When p is 1 or 2, multiple Rs present in the molecule may be the same or different.

[29] The compound according to

[28] , which satisfies condition 1.

[30] The compound according to

[29] , wherein p is 2.

[31] The compound according to

[29] or

[30] , wherein D is a group represented by general formula (IIb).

[32] The compound according to any one of

[29] to

[31] , wherein the halogen atom is a chlorine atom or an iodine atom.

[33] The compound according to any one of

[29] to

[32] , wherein R is a substituted or unsubstituted aryl group.

[34] The compound according to

[33] , wherein R is an unsubstituted phenyl group.

[35] The compound according to

[28] , which satisfies condition 2.

[36] The compound according to

[35] , wherein p is 2 or 3.

[37] The compound according to

[35] or

[36] , wherein A has a substituted or unsubstituted triazinyl group.

[38] The compound according to any one of

[35] to

[37] , wherein the halogen atom is a fluorine atom. [Effects of the Invention]

[0007] According to the present invention, it is possible to provide a light-emitting material having good light-emitting properties, and also to provide an organic optical device having high light-emitting efficiency. DETAILED DESCRIPTION OF THE INVENTION

[0008] The contents of the present invention are described in detail below. The following description of the constituent elements may be based on representative embodiments and specific examples of the present invention, but the present invention is not limited to such embodiments and specific examples. In this specification, a numerical range expressed using "to" means a range that includes the numerical values ​​written before and after "to" as the lower and upper limits. The entire specification of Japanese Application No. 2020-017486, from which the priority of this application is claimed, is hereby incorporated by reference as part of the specification of this application.

[0009] The present invention provides a compound represented by the following general formula (1): [ka]

[0010] R in general formula (1) 1 ~R 5 Among them, R 1 and R 2 One of them is A and the other is R 1 ~R 5 Among them, p are D, and the remaining 4-p are R, where p is an integer of 1 to 3. In one embodiment, R 2 is A. In a preferred embodiment, R 2is A and R 1 and R 3 At least one of R is a hydrogen atom or a deuterium atom. 2 is A and R 1 is a hydrogen atom or a deuterium atom, and R 3 is D or a substituted or unsubstituted aryl group (excluding groups that can be A or D). For example, R 2 is A and R 3 is a hydrogen atom or a deuterium atom, and R 1 is D or a substituted or unsubstituted aryl group (excluding groups that can be A or D). For example, R 2 is A and R 1 and R 2 are each independently a hydrogen atom or a deuterium atom. In a preferred embodiment of the present invention, R 2 is A and R 4 and R 5 At least one of them is D. For example, R 2 is A and R 4 is D and R 5 is R [more preferably a substituted or unsubstituted aryl group (excluding groups that can be A or D)]. For example, R 2 is A and R 5 is D and R 4 is R [more preferably a substituted or unsubstituted aryl group (excluding groups that can be A or D)]. For example, R 2 is A and R 4 and R 5 are each independently D. In a preferred embodiment of the present invention, R 2 is A and R 1 and R 3 At least one of R is a hydrogen atom or a deuterium atom, 4 and R 5 At least one of them is D.

[0011] In one embodiment, R 1 is A. In a preferred embodiment, R 1 is A and R 2is a hydrogen atom or a deuterium atom. In another preferred embodiment, R 1 is A and R 4 and R 5 At least one of them is D. For example, R 1 is A and R 4 is D and R 5 is R [more preferably a substituted or unsubstituted aryl group (excluding groups that can be A or D)]. For example, R 1 is A and R 5 is D and R 4 is R [more preferably a substituted or unsubstituted aryl group (excluding groups that can be A or D)]. For example, R 1 is A and R 4 and R 5 are each independently D. In a preferred embodiment of the present invention, R 1 is A and R 2 is a hydrogen atom or a deuterium atom, and R 4 and R 5 At least one of R is D. 1 is A and R 3 is R. For example, R 1 is A and R 3 is a hydrogen atom or a deuterium atom. For example, R 1 is A and R 3 is a substituted or unsubstituted aryl group (excluding groups that can be A or D). 1 is A and R 3 is D.

[0012] In one embodiment, R 3 is a hydrogen atom or a deuterium atom. 3 is a substituted or unsubstituted aryl group (excluding groups that can be A or D). In one embodiment, R 3 is D.

[0013] In one embodiment, R 4 and R 5In a preferred embodiment of the present invention, at least one of R 4 and R 5 are each independently D. For example, R 4 and R 5 is the same D. For example, R 4 and R 5 are different D. In some embodiments, R 1 , R 4 and R 5 are each independently D. In some embodiments, R 2 , R 4 and R 5 are each independently D. In some embodiments, R 3 , R 4 and R 5 are each independently D. In one embodiment, R 3 and R 5 At least one of them is D. For example, R 3 and R 5 are each independently D. For example, R 3 is D and R 5 is R [more preferably a substituted or unsubstituted aryl group (excluding groups that can be A or D)]. For example, R 5 is D and R 3 is R [more preferably a substituted or unsubstituted aryl group (excluding groups that can be A or D)]. For example, R 3 is D and R 5 is a hydrogen atom or a deuterium atom. For example, R 5 is D and R 3 is a hydrogen atom or a deuterium atom. In one embodiment, R 1 and R 5 At least one of them is D. For example, R 1 and R 5 are each independently D. For example, R 1 is D and R 5 is R [more preferably a substituted or unsubstituted aryl group (excluding groups that can be A or D)]. For example, R 5 is D and R 1is R [more preferably a substituted or unsubstituted aryl group (excluding groups that can be A or D)]. For example, R 5 is D and R 1 is a hydrogen atom or a deuterium atom. For example, R 1 is D and R 5 is a hydrogen atom or a deuterium atom. In one embodiment, R 1 and R 4 At least one of them is D. For example, R 1 and R 4 are each independently D. For example, R 1 is D and R 4 is R [more preferably a substituted or unsubstituted aryl group (excluding groups that can be A or D)]. For example, R 4 is D and R 1 is R [more preferably a substituted or unsubstituted aryl group (excluding groups that can be A or D)]. For example, R 4 is D and R 1 is a hydrogen atom or a deuterium atom. For example, R 1 is D and R 4 is a hydrogen atom or a deuterium atom.

[0014] In one embodiment, R 1 , R 4 and R 5 At least one of R is a substituted or unsubstituted aryl group (excluding groups that can be A or D). 1 , R 4 and R 5 is a substituted or unsubstituted aryl group (excluding groups that can be A or D). For example, R 1 is a substituted or unsubstituted aryl group (excluding groups that can be A or D). For example, R 4 is a substituted or unsubstituted aryl group (excluding groups that can be A or D). For example, R 5 is a substituted or unsubstituted aryl group (excluding groups that can be A or D).

[0015] R 1 ~R 5 As a group of combinations of (R 1 , R 2 , R 3 , R 4 , R 5 ) can be (H,A,D,D,D), (D,A,H,D,D) and (H,A,H,D,D). Another group is (R 1 , R 2 , R 3 , R 4 , R 5 ) can be (H,A,D,D,D), (H,A,Ar,D,D), (H,A,D,Ar,D) and (H,A,D,D,Ar). Another group is (R 1 , R 2 , R 3 , R 4 , R 5 ) can be (H,A,D,D,D), (H,A,Ar,Ar,D), (H,A,D,Ar,Ar) and (H,A,Ar,D,Ar). Another group is (R 1 , R 2 , R 3 , R 4 , R 5 ) can be (Ar,A,H,D,D), (D,A,H,Ar,D) and (D,A,H,D,Ar). Another group is (R 1 , R 2 , R 3 , R 4 , R 5 ) can be (Ar,A,H,Ar,D), (Ar,A,H,D,Ar) and (D,A,H,Ar,Ar). Another group is (R 1 , R 2 , R 3 , R 4 , R 5) are (H,A,H,D,D), (H,A,H,Ar,D) and (H,A,H,D,Ar). Another group can be the group where (A,D,D,D,H), (A,D,D,D,Ar), (A,D,D,Ar,D) and (A,D,Ar,D,D). Another group can be the group where (A,D,H,D,Ar) and (A,D,Ar,D,H). Another group can be the group where (A,D,D,H,Ar) and (A,D,D,Ar,H). Another group can be the group where (A,D,Ar,H,D) and (A,D,H,Ar,D). Another group can be (D,A,H,D,D), (D,A,H,H,D), (D,A,H,Ar,D), and (D,A,H,D,Ar). Another group can be (H,A,D,Ar,D). Here, H represents a hydrogen atom, and Ar represents a substituted or unsubstituted aryl group (excluding groups that can become A or D). In the present invention, R that does not belong to the groups exemplified here can be 1 ~R 5 A combination of the above may also be employed.

[0016] In the general formula (1), A is Het-L A -* or CN-L A -*, where Het is a substituted or unsubstituted heteroaryl group bonded via a carbon atom, and the heteroaryl group contains at least one nitrogen atom as a ring skeleton atom. A represents a single bond or a substituted or unsubstituted arylene group. * represents the bonding position. As A in the general formula (1), Het-L A -* can be preferably selected. A You can also select -*. Het has a heteroaryl ring containing a nitrogen atom as a ring skeleton atom, and the ring skeleton carbon atom of the heteroaryl ring is L A It is preferable that the L AWhen Het-L is a single bond, it is bonded to the carbon atom constituting the ring skeleton of the pyridine ring in general formula (1). A -* is preferably a group represented by any one of the following general formulae (IIIa), (IIIb), (IIIc), (IIId) and (IIIe). [ka]

[0017] R 21 ~R 25 Each of L independently represents a hydrogen atom or a substituent. A represents a single bond or a substituted or unsubstituted arylene group. 21 ~R 25 are each independently a hydrogen atom, a deuterium atom, a cyano group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group. The alkyl group referred to here may be substituted with one or more substituents selected from, for example, a deuterium atom, a substituted or unsubstituted aryl group, and a substituted or unsubstituted heteroaryl group. The aryl group and heteroaryl group referred to here may each independently be substituted with one or more substituents selected from, for example, a deuterium atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, and a substituted or unsubstituted heteroaryl group. Two or more of these substituents may be bonded to form a cyclic structure. In addition, R 21 and R 22 , R 22 and R 23 , R 23 and R 24 , R 24 and R 25 may be bonded to each other to form a cyclic structure. The cyclic structure may be a substituted or unsubstituted aromatic ring, or a substituted or unsubstituted aliphatic ring. It may also be a carbocyclic ring or a heterocyclic ring. In a preferred embodiment, R 21 ~R 25 are each independently a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group.21 ~R 24 In a more preferred embodiment, at least one of R 21 ~R 25 R is each independently a substituted or unsubstituted aryl group. 21 ~R 25 may be the same or different, but can be the same, for example. 21 and R 22 , R 22 and R 23 , R 23 and R 24 , R 24 and R 25 are bonded to each other to form a benzene ring. 21 and R 22 , R 22 and R 23 , R 23 and R 24 , R 24 and R 25 are linked together to form a benzofuran or benzothiophene ring. R 21 and L A , R 25 and L A do not bond to each other to form a ring structure. Het-L A -* can be, for example, a group represented by any one of general formulas (IIIa), (IIIb) or (IIIc). It can also be a group represented by any one of general formulas (IIIb) or (IIIc). It can also be a group represented by any one of general formulas (IIId) or (IIIe). In a preferred embodiment, Het-L A -* is a group represented by general formula (IIIa).

[0018] In one embodiment, L A is a single bond. In another embodiment of the present invention, L A is a substituted or unsubstituted arylene group. Amay be a linking group in which two or three substituted or unsubstituted arylene groups are linked together. A may consist of only one substituted or unsubstituted arylene group. A is an unsubstituted arylene group. A is a substituted arylene group. In this case, the arylene group may be substituted with one or more substituents selected from, for example, a deuterium atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, and a cyano group, and two or more of these substituents may combine to form a cyclic structure. The cyclic structure here may be a substituted or unsubstituted aromatic ring or a substituted or unsubstituted aliphatic ring. It may also be a carbocyclic ring or a heterocyclic ring. In addition, L A The arylene group represented by may be substituted with any of the groups represented by (IIIa) to (IIIe). In one embodiment of the present invention, A is Het-L A -* and L A is an arylene group optionally substituted with one or a combination of two or more groups selected from the group consisting of an alkyl group, an aryl group, and a cyano group. In one embodiment of the present invention, A is CN-L A -* and L A is an arylene group optionally substituted with an alkyl group or a cyano group. A is a single bond, an unsubstituted phenylene group, or a phenylene group substituted with at least one alkyl group. Examples of the phenylene group include a 1,4-phenylene group, a 1,3-phenylene group, and a 1,2-phenylene group, and the 1,4-phenylene group and the 1,3-phenylene group are preferred. In one embodiment, A is selected from the group consisting of A1 to A21 shown below. In one embodiment, A is selected from the group consisting of A1 to A5 and A12 to A21. In one embodiment, A is selected from the group consisting of A6 to A11. * represents a bonding position. [ka]

[0019] In general formula (1), D is a group represented by the following general formula (IIa), (IIb), (IIc), or (IId). In one embodiment, D is a group represented by general formula (IIa), (IIb), or (IId). In one embodiment, D is a group represented by general formula (IIa). In one embodiment, D is a group represented by general formula (IIb). In one embodiment, D is a group represented by general formula (IId). [ka]

[0020] R D each independently represents a hydrogen atom, a deuterium atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted amino group, a cyano group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted heteroaryloxy group, or a silyl group, and two or more R D may be linked together to form a ring structure. In one embodiment of the present invention, R D are each independently selected from the group consisting of a hydrogen atom, a deuterium atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted amino group, a cyano group, and a substituted or unsubstituted aryl group. D are each independently selected from the group consisting of a hydrogen atom, a deuterium atom, a substituted or unsubstituted alkyl group, a cyano group, and a substituted or unsubstituted aryl group. D are each independently selected from the group consisting of a hydrogen atom, a deuterium atom, a substituted or unsubstituted alkyl group, and a substituted or unsubstituted alkoxy group. D are each independently selected from the group consisting of a hydrogen atom, a deuterium atom, a substituted or unsubstituted aryl group, and a substituted or unsubstituted aryloxy group. Dare each independently selected from the group consisting of a hydrogen atom, a deuterium atom, a substituted or unsubstituted heteroaryl group, and a substituted or unsubstituted heteroaryloxy group. D are each independently a hydrogen atom or a deuterium atom. D In the formula (I), the number of substituents that are neither hydrogen atoms nor deuterium atoms is 3 or 4 in one embodiment, 2 in another embodiment of the present invention, and 1 in another embodiment.

[0021] X' is NR D ', an oxygen atom, or a sulfur atom. In one embodiment, X' is NR D In certain embodiments, X' is an oxygen atom. In certain embodiments, X' is a sulfur atom. R D ' represents a hydrogen atom, a deuterium atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group; R D ' is one or more R D In one embodiment of the present invention, R D Each R' is independently a hydrogen atom or a deuterium atom. D In one embodiment of the invention, R D ' is a substituted or unsubstituted aryl group. Two or more R's D , or R D ' and one or more R D The cyclic structure formed by bonding may be a substituted or unsubstituted aromatic ring, or a substituted or unsubstituted aliphatic ring. It may also be a carbocyclic ring or a heterocyclic ring. R D and L D , R D ' and L D do not bond to each other to form a ring structure.

[0022] L Deach independently represents a single bond, a substituted or unsubstituted arylene group, or a substituted or unsubstituted heteroarylene group. D is a single bond. In some embodiments, L D is a substituted or unsubstituted arylene group. D may be a linking group in which two or three groups selected from the group consisting of substituted or unsubstituted arylene groups and substituted or unsubstituted heteroarylene groups are linked to each other. D is a linking group formed by linking two or three substituted or unsubstituted arylene groups. D consists of only one substituted or unsubstituted arylene group. D is an unsubstituted arylene group. D is a substituted arylene group. In this case, the arylene group may be substituted with one or more substituents selected from, for example, a deuterium atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, and a substituted or unsubstituted heteroaryl group, and two or more of these substituents may combine to form a cyclic structure. The cyclic structure here may be a substituted or unsubstituted aromatic ring or a substituted or unsubstituted aliphatic ring. It may also be a carbocyclic ring or a heterocyclic ring. In one embodiment, L D is a single bond, an unsubstituted phenylene group, or a phenylene group substituted with at least one alkyl group. Examples of the phenylene group include a 1,4-phenylene group, a 1,3-phenylene group, and a 1,2-phenylene group, and the 1,4-phenylene group and the 1,3-phenylene group are preferred.

[0023] In one embodiment, D is selected from the group consisting of D1 to D96 shown below. In one embodiment, D is selected from the group consisting of D1 to D4, D41 to D43, D84, D86 to D88, and D94 to D96. In one embodiment, D is selected from the group consisting of D1 to D5, D16 to D19, and D21 to D24. In one embodiment, D is selected from the group consisting of D32 to D38, D40 to D43, and D60 to D88. In one embodiment, D is selected from the group consisting of D89 to D91 and D93 to D96. * represents the bonding position. Ph represents an unsubstituted phenyl group. [ka] [ka] [ka] [ka] [ka]

[0024] In general formula (1), R is a hydrogen atom, a deuterium atom, or a substituted or unsubstituted aryl group (excluding groups that can be A or D). In one embodiment, R is a hydrogen atom. In one embodiment, R is a substituted or unsubstituted aryl group (excluding groups that can be A or D). For example, R is an unsubstituted aryl group. When R is a substituted aryl group, the aryl group may be substituted with one or more substituents selected from, for example, a deuterium atom, a substituted or unsubstituted alkyl group, and a substituted or unsubstituted aryl group. Two or more of these substituents may be bonded to form a cyclic structure. The cyclic structure may be a substituted or unsubstituted aromatic ring or a substituted or unsubstituted aliphatic ring. It may also be a carbocyclic ring or a heterocyclic ring. In a preferred embodiment, each R is independently a hydrogen atom or a substituted or unsubstituted aryl group. In a more preferred embodiment, each R is independently a hydrogen atom or an unsubstituted aryl group. For example, each R may be independently a hydrogen atom or a phenyl group.

[0025] In general formula (1), p is an integer of 1 to 3. When p is 2 or 3, multiple Ds present in the molecule may be the same or different. When p is 1 or 2, multiple Rs present in the molecule may be the same or different. In one embodiment, p is 3. In one embodiment, p is 2. In a preferred embodiment, R in general formula (1) 1 and R 2 , R 2 and R 3 , R 3 and R 4 , R 4 and R 5 None of the groups are bonded to each other to form a ring structure.

[0026] When it is intended to use an organic layer containing the compound represented by general formula (1) formed by vapor deposition, the molecular weight of the compound represented by general formula (1) is preferably 1500 or less, more preferably 1200 or less, even more preferably 1000 or less, and even more preferably 900 or less. The lower limit of the molecular weight is the molecular weight of the smallest compound represented by general formula (1). The compound represented by general formula (1) may be formed into a film by a coating method regardless of its molecular weight. If a coating method is used, it is possible to form a film even from a compound with a relatively large molecular weight.

[0027] The present invention may be applied to prepare a compound containing a plurality of structures represented by general formula (1) in the molecule, and such a compound may be used, for example, as a charge transport material. For example, a polymerizable group may be present in the structure represented by general formula (1) in advance, and the polymerizable group may be polymerized to obtain a polymer. 1 ~R 5 A polymer having repeating units can be obtained by polymerizing a monomer containing a polymerizable functional group in either one of the above or by copolymerizing it with other monomers. Alternatively, a dimer or trimer can be obtained by coupling compounds having the structure represented by general formula (1) together.

[0028] In some embodiments, the compound represented by general formula (1) does not contain a metal atom. In some embodiments, the compound represented by general formula (1) is composed only of hydrogen atoms, carbon atoms, and nitrogen atoms. In some embodiments, the compound represented by general formula (1) is composed only of atoms selected from the group consisting of hydrogen atoms, carbon atoms, nitrogen atoms, and oxygen atoms. In some embodiments, the compound represented by general formula (1) is composed only of atoms selected from the group consisting of hydrogen atoms, carbon atoms, nitrogen atoms, and sulfur atoms. In some embodiments, the compound represented by general formula (1) is composed only of atoms selected from the group consisting of hydrogen atoms, carbon atoms, nitrogen atoms, oxygen atoms, sulfur atoms, and silicon atoms. In some embodiments, the compound represented by general formula (1) is not composed of a cyano group. In some embodiments, the compound represented by general formula (1) is not composed of a diarylamino group (provided that the two aryl groups constituting the diarylamino group are not bonded to each other by a single bond or a linking group to form a cyclic structure).

[0029] Specific examples of the compound represented by general formula (1) are listed below, but the scope of the compounds of the present invention should not be construed as being limited by these specific examples. [Table 1-1] [Table 1-2] [Table 1-3] [Table 1-4] [Table 1-5] [Table 1-6] [Table 1-7] [Table 1-8] Table 1-9 Table 1-10 Table 1-11 Table 1-12 Table 1-13 Table 1-14 Table 1-15 Table 1-16 Table 1-17 Table 1-18 Table 1-19 Table 1-20 Table 1-21 Table 1-22 Table 1-23 Table 1-24 Table 1-25 [Table 1-26] [Table 1-27] [Table 1-28] [Table 1-29] [Table 1-30] [Table 1-31] [Table 1-32] [Table 1-33] [Table 1-34] [Table 1-35]

[0030] [Method for synthesizing the compound represented by general formula (1)] The compound represented by general formula (1) can be synthesized by combining known reactions. For example, R 1 , R 4 and R 5 is D1 and R 2 The compound in which is A1 can be synthesized via an intermediate according to the following reaction scheme. [ka]

[0031] In this reaction scheme, a halogenated pyridine is used as the starting material. A halogenated pyridine is prepared with a fluorine atom at the desired position for D1 and a chlorine atom at the desired position for A1. This halogenated pyridine is reacted with 4,4',4',5,5',5'-octamethyl-2,2'-bi(1,3,2-oxaborane) in the presence of a catalyst, followed by reaction with A1-Cl to obtain an intermediate in which the chlorine atom has been replaced with A1. This intermediate is then further reacted with D1-H in the presence of a catalyst to obtain the desired compound in which the fluorine atom has been replaced with D1. The first and second reactions of this two-step reaction can also be performed in reverse order. The above reaction is an application of a known reaction, and known reaction conditions can be appropriately selected and used. For details of the above reaction, the synthesis examples described below can be referenced. In addition, the compound represented by general formula (1) can also be synthesized by combining other known synthesis reactions.

[0032] The compound represented by the following general formula (1'), which is a synthetic intermediate of the compound represented by general formula (1), includes a novel compound. [ka]

[0033] R in general formula (1') 1 ~R 5 satisfies the following condition 1 or 2, (Condition 1) R 1 ~R 5 Of these, R 1 and R 2 one of the groups is a halogen atom, Remaining R 1 ~R 5 p of them are D, The remaining 4-p are R. (Condition 2) R 1 ~R 5 Of these, R 1 and R 2 One of them is A, Remaining R 1 ~R 5 p of the atoms are halogen atoms, The remaining 4-p are R. Here A is Het-L A -* or CN-L A -*, where Het represents a substituted or unsubstituted heteroaryl group bonded via a carbon atom (provided that the heteroaryl group contains at least one nitrogen atom as a ring skeleton atom), and L A represents a single bond or a substituted or unsubstituted arylene group, and * represents the bonding position. D is a group represented by the following general formula (IIa), (IIb), (IIc) or (IId). [ka] where X' is NR D ', represents an oxygen atom or a sulfur atom, R D each independently represents a hydrogen atom, a deuterium atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted amino group, a cyano group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted heteroaryloxy group, or a silyl group, and two or more R D may be bonded to each other to form a cyclic structure, R D ' represents a hydrogen atom, a deuterium atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group; R D ' is one or more R D may be bonded to form a cyclic structure, L D each independently represents a single bond, a substituted or unsubstituted arylene group, or a substituted or unsubstituted heteroarylene group; * indicates the bond position. R is a hydrogen atom, a deuterium atom, or a substituted or unsubstituted aryl group (excluding groups that can be A or D). p is an integer of 1 to 3. When p is 2 or 3, multiple Ds present in the molecule may be the same or different. When p is 1 or 2, multiple Rs present in the molecule may be the same or different.

[0034] For the explanation and preferred ranges of A, D, R, and p in general formula (1'), reference can be made to the corresponding descriptions in general formula (1). In one embodiment, condition 1 is satisfied. In one embodiment, p is 2. In one embodiment, D is a group represented by general formula (IIb). In one embodiment, the halogen atom is a chlorine atom. In one embodiment, the halogen atom is an iodine atom. In one embodiment, R is a substituted or unsubstituted aryl group. In one embodiment, R is an unsubstituted phenyl group. In some embodiments, condition 2 is satisfied. In some embodiments, p is 2 or 3. In some embodiments, A has a substituted or unsubstituted triazinyl group. In some embodiments, the halogen atom is a fluorine atom. Preferred examples include the synthetic intermediates of Synthesis Examples 1 to 3 described below.

[0035] The definitions of terms set forth in

[0039] to

[0101] of US2020 / 0168814A1 are hereby incorporated by reference in their entirety as part of this specification and serve to define the terms of the present invention.

[0036] In some embodiments, the compound represented by general formula (I) is a light-emitting material. In one embodiment, the compound represented by general formula (I) is a compound capable of emitting delayed fluorescence. In certain embodiments of the present disclosure, the compounds represented by general formula (I) can emit light in the UV region, the blue, green, yellow, orange, or red region of the visible spectrum (e.g., about 420 nm to about 500 nm, about 500 nm to about 600 nm, or about 600 nm to about 700 nm), or the near-infrared region when excited by thermal or electronic means. In certain embodiments of the present disclosure, the compounds represented by general formula (I) are capable of emitting light in the red or orange region of the visible spectrum (e.g., about 620 nm to about 780 nm, about 650 nm) when excited by thermal or electronic means. In certain embodiments of the present disclosure, the compounds represented by general formula (I) can emit light in the orange or yellow region of the visible spectrum (e.g., about 570 nm to about 620 nm, about 590 nm, about 570 nm) when excited by thermal or electronic means. In certain embodiments of the present disclosure, the compounds represented by general formula (I) are capable of emitting light in the green region of the visible spectrum (e.g., from about 490 nm to about 575 nm, about 510 nm) when excited by thermal or electronic means. In certain embodiments of the present disclosure, the compounds represented by general formula (I) are capable of emitting light in the blue region of the visible spectrum (e.g., about 400 nm to about 490 nm, about 475 nm) when excited by thermal or electronic means. In certain embodiments of the present disclosure, compounds represented by general formula (I) are capable of emitting light in the ultraviolet spectral region (e.g., 280-400 nm) when excited by thermal or electronic means. In certain embodiments of the present disclosure, compounds represented by general formula (I) are capable of emitting light in the infrared spectral region (eg, 780 nm to 2 μm) when excited by thermal or electronic means. In some embodiments of the present disclosure, the compound represented by general formula (I) is a charge transport material. In some embodiments of the present disclosure, the compound represented by general formula (I) is used in a charge transport layer. In some embodiments of the present disclosure, the compound represented by general formula (I) has high mobility and excellent durability as a charge transport material. In an embodiment of the present disclosure, an organic semiconductor device such as a CMOS (complementary metal oxide semiconductor) can be fabricated using a compound represented by general formula (I). In an embodiment of the present disclosure, an organic optical device such as an organic electroluminescence device or a solid-state imaging device (e.g., a CMOS image sensor) can be fabricated using a compound represented by general formula (I).

[0037] The electronic properties of small molecule chemical libraries can be calculated using well-known ab initio quantum chemical calculations. For example, the Hartree-Fock equations can be solved using time-dependent density functional theory (TD-DFT / B3LYP / 6-31G*) with a basis set known as 6-31G* and the Becke three-parameter Lee-Yang-Parr hybrid functional, to screen for molecular fragments (moieties) with a HOMO above a certain threshold and a LUMO below a certain threshold, and the calculated triplet state of the moieties is greater than 2.75 eV. Thus, the donor moiety ("D") can be selected for its HOMO energy (e.g., ionization potential) of, for example, -6.5 eV or greater, and the acceptor moiety ("A") can be selected for its LUMO energy (e.g., electron affinity) of, for example, -0.5 eV or less. The bridging moiety ("B") prevents overlap between the π-conjugated systems of the donor and acceptor moieties, for example, by providing a strongly conjugated system that tightly restricts the acceptor and donor moieties to specific configurations. In some embodiments, the compound library is screened using one or more of the following properties: 1. Emission around a specific wavelength 2. Calculated triplet states above a specific energy level 3. Delta E below a certain value ST value 4. Quantum yield above a certain value 5.HOMO level 6.LUMO level In one embodiment, the difference between the lowest singlet excited state and the lowest triplet excited state at 77 K (ΔE ST) is less than about 0.5 eV, less than about 0.4 eV, less than about 0.3 eV, less than about 0.2 eV, or less than about 0.1 eV. In some embodiments, ΔE ST The value is less than about 0.09 eV, less than about 0.08 eV, less than about 0.07 eV, less than about 0.06 eV, less than about 0.05 eV, less than about 0.04 eV, less than about 0.03 eV, less than about 0.02 eV, or less than about 0.01 eV. In certain embodiments, the compounds represented by general formula (I) exhibit a quantum yield of greater than 25%, e.g., about 30%, about 35%, about 40%, about 45%, about 50%, about 55%, about 60%, about 65%, about 70%, about 75%, about 80%, about 85%, about 90%, about 95% or more.

[0038] [Compositions using compounds of the present disclosure] In some embodiments, the compounds of formula (I) may be combined with one or more materials (e.g., small molecules, polymers, metals, metal complexes, etc.) that disperse, covalently bond, coat, support, or associate with the compounds to form a solid film or layer. For example, the compounds of formula (I) may be combined with an electroactive material to form a film. In some cases, the compounds of formula (I) may be combined with a hole transporting polymer. In some cases, the compounds of formula (I) may be combined with an electron transporting polymer. In some cases, the compounds of formula (I) may be combined with a hole transporting polymer and an electron transporting polymer. In some cases, the compounds of formula (I) may be combined with a copolymer having both a hole transporting moiety and an electron transporting moiety. In these embodiments, electrons and / or holes formed in the solid film or layer may interact with the compounds of formula (I).

[0039] [Film formation] In some embodiments, a film containing the compound of the present invention represented by general formula (I) can be formed by a wet process. In the wet process, a solution containing a composition containing the compound of the present invention is applied to a surface, and a film is formed after removing the solvent. Wet processes include, but are not limited to, spin coating, slit coating, inkjet printing (spraying), gravure printing, offset printing, and flexographic printing. In the wet process, an appropriate organic solvent capable of dissolving the composition containing the compound of the present invention is selected and used. In some embodiments, a substituent (e.g., an alkyl group) that increases the solubility in organic solvents can be introduced into the compound contained in the composition. In some embodiments, a film containing the compound of the present invention can be formed by a dry process. In some embodiments, the dry process can be a vacuum deposition process, but is not limited thereto. When a vacuum deposition process is used, the compounds constituting the film can be co-deposited from separate deposition sources, or from a single deposition source containing a mixture of compounds. When a single deposition source is used, a mixed powder of compound powders can be used, a compressed compact of the mixed powder can be used, or a mixture of the compounds can be used by heating, melting, and cooling. In some embodiments, co-deposition can be performed under conditions where the deposition rates (weight loss rates) of multiple compounds contained in a single deposition source are the same or nearly the same, thereby forming a film with a composition ratio corresponding to the composition ratio of the multiple compounds contained in the deposition source. By mixing multiple compounds in the same composition ratio as the composition ratio of the film to be formed and using the deposition source as a deposition source, a film with a desired composition ratio can be easily formed. In some embodiments, the temperature at which each of the co-deposited compounds has the same weight loss rate can be identified, and that temperature can be used as the temperature during co-deposition.

[0040] The descriptions of use examples, devices, displays, screens, etc. described in paragraphs

[0141] to

[0169] and

[0192] to

[0242] of US2020 / 0168814A1 are hereby incorporated by reference in their entirety as part of this specification and serve to describe the present invention.

[0041] In some embodiments of the present invention, the following compounds can be preferably used as the host material. [ka] [ka]

[0042] In some embodiments of the present invention, the following compounds can be preferably used as electron blocking materials. [ka]

[0043] In some embodiments of the present invention, the following compounds can be preferably used as hole-blocking materials. [ka]

[0044] Preferred examples of compounds that can be used as hole injection materials for organic electroluminescence devices are listed below. [ka]

[0045] Next, preferred examples of compounds that can be used as the electron injection material of an organic electroluminescence device will be listed. [ka]

[0046] Furthermore, examples of compounds that can be added to the organic layers of the organic electroluminescence device are as follows: For example, they can be added as stabilizing materials.

[0047] [ka] [Example]

[0048] The following synthesis examples and working examples will further illustrate the features of the present invention. The materials, processing details, processing procedures, etc. shown below can be modified as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the specific examples shown below. The following sample characteristics were evaluated using NMR (Bruker 500 MHz nuclear magnetic resonance), LC / MS (Waters liquid chromatography mass spectrometer), AC3 (Riken Keiki), high-performance UV / Vis / NIR spectrophotometer (PerkinElmer Lambda 950), fluorescence spectrophotometer (Horiba FluoroMax-4), photonic multichannel analyzer (Hamamatsu Photonics PMA-12 C10027-01), absolute PL quantum yield measurement system (Hamamatsu Photonics C11347), automatic current-voltage luminance measurement system (System Giken ETS-170), lifetime measurement system (System Giken EAS-26C), and streak camera (Hamamatsu Photonics Model C4334). PYD-2Cz was used as the host material in the examples, and mCBP was used for comparative compound A. The compounds in the examples of the present invention were purified by sublimation before being used in the production of devices and the like. [ka]

[0049] (Synthesis Example 1) Synthesis of Compound 939 [ka]

[0050] Synthesis of intermediate 1-1 Potassium acetate (2.93 g, 29.85 mmol), 4,4',4',5,5',5'-octamethyl-2,2'-bi(1,3,2-oxaborane) (3.34 g, 13.13 mmol), tris(dibenzylideneacetone)dipalladium(0) (0.22 g, 2 mol%), 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl (0.34 g, 6 mol%), and 3-chloro-2,5,6-trifluoropyridine (2.00 g, 11.94 mmol) were dissolved in 1,4-dioxane under a nitrogen atmosphere. The mixture was heated to 110 °C and stirred overnight. After the starting compound was no longer detected by thin-layer chromatography, the mixture was cooled to room temperature. To the flask containing the mixture, 2-chloro-4,6-diphenyl-1,3,5-triazine (3.97 g, 14.82 mmol), tetrakis(triphenylphosphine)palladium(0) (0.43 g, 3 mol%), and potassium carbonate (2.56 g, 18.53 mmol, 2 M aqueous solution) were added while maintaining a nitrogen atmosphere. The mixture was heated to 100 °C and stirred overnight under a nitrogen atmosphere. The reaction was quenched with brine solution at room temperature, and the mixture was extracted with chloroform, dried over MgSO4, and then concentrated using a vacuum evaporator system. The mixture was purified by silica gel column chromatography using n-hexane / chloroform as an eluent to obtain the powder product, 2,4-diphenyl-6-(2,5,6-trifluoropyridin-3-yl)-1,3,5-triazine (Intermediate 1-1) (yield: 2.30 g, 51.1%). 1 H NMR (500 M H Z , CDCl3) δ 7.59 (t, J = 8.0 H Z , 4H), 7.65 (t, J = 7.5 H Z , 2H), 8.73 (d, J= 8.0 H Z , 4H), 8.91 (q, J = 8.0 H Z , 1H), 19 F NMR (470 MH Z , CDCl3) δ -144.64 (t, J F = 29.1 H Z, 1F), -81.56 (t, J F = 13.63 H Z , 1F), -65.22 (t, J F = 19.74 H Z , 1F), MS (APCI) m / z 365.24 [(M+H) + ].

[0051] Synthesis of Compound 939 Potassium carbonate (1.90 g, 13.72 mmol), 2,4-diphenyl-6-(2,5,6-trifluoropyridin-3-yl)-1,3,5-triazine (Intermediate 1-1) (1.00 g, 2.74 mmol), and 9H-carbazole (1.84 g, 10.98 mmol) were placed in a three-necked round-bottom flask. The mixture was dried under vacuum, and then DMF (dimethylformamide) was added as a solvent under a nitrogen atmosphere. The reaction mixture was stirred overnight at 160 °C. The reaction was quenched with an aqueous solution of NH4Cl and extracted with chloroform. The organic layer separated after extraction was dried over MgSO4, and the solvent was concentrated using a vacuum evaporator system. The reaction product, 9,9′,9″-((2r,3r,6r)-5-(4,6-diphenyl-1,3,5-triazine-2,3,6-triyl)pyridine-2,3,6-triyl)tris(9H-carbazole) (Compound 939), was isolated by column chromatography using a mixture of toluene and hexane (1:4) as an eluent (yield: 2.20 g, 99.5%). 1 H NMR (500 M H Z , CDCl3) δ 6.99 (t, J = 6.5 H Z , 2H), 7.08 (t, J = 7.5 H Z , 2H), 7.13 (t, J= 7.0 H Z , 4H) 7.22-7.35 (m, 10H), 7.47-7.51 (m, 4H), 7.62 (d, J= 9.0 H Z , 2H), 7.78 (d, J = 8.5 H Z , 2H), 7.89 (d, J= 8.0 H Z, 2H), 8.01 (d, J = 7.5 H Z , 2H), 8.07 (d, J= 8.0 H Z , 2H), 9.42 (s, 1H), MS (APCI) m / z 806.50 [(M+H)+]

[0052] (Synthesis Example 2) Synthesis of Compound 962 [ka]

[0053] Synthesis of intermediate 2-1 Potassium carbonate (1.51 g, 10.89 mmol), 5-chloro-2,3-difluoro-4-iodopyridine (1.00 g, 3.63 mmol), and 9H-carbazole (1.82 g, 10.89 mmol) were placed in a three-necked round-bottom flask. The mixture was dried under vacuum, and then DMF was added as a solvent under a nitrogen atmosphere. The reaction mixture was stirred overnight at 160 °C, after which the reaction was quenched with aqueous NH4Cl and the mixture was extracted with chloroform. The organic layer separated after extraction was dried over MgSO4 and concentrated using a vacuum evaporator system. The reaction product, 9,9'-(((2r,3s)-5-chloro-4-iodopyridine-2,3-diyl)bis(9H-carbazole) (Intermediate 2-1), was isolated by column chromatography using a toluene / hexane mixture (1:4) as an eluent (yield 2.00 g, 96.7%). 1 H NMR (500 M H Z , CDCl3) δ 6.77-7.18 (m, 12H), 7.68 (d, J = 7.5 H Z , 2H), 7.75-7.77 (m, 2H) 8.83 (s, 1H), MS (APCI) m / z 570.28 [(M+H) + ]

[0054] Synthesis of intermediate 2-2 9'-((2r,3s)-5-chloro-4-iodopyridine-2,3-diyl)bis(9H-carbazole) (Intermediate 2-1) (2.50 g, 4.39 mmol), phenylboronic acid (0.64 g, 5.26 mmol), potassium carbonate (1.82 g, 13.16 mmol, 2 M in aqueous solution), and tetrakis(triphenylphosphine)palladium (0.15 g, 3 mol%) were dissolved in THF and distilled water (according to the amount of KCO). The resulting solution was refluxed under a nitrogen atmosphere for 12 h and then cooled to room temperature. After extraction with ethyl acetate and distilled water, the solvent of the organic layer was evaporated under vacuum. The residue was purified by column chromatography using toluene:hexane (1:1) as an eluent to obtain a white powder product, 9,9'-(((2r,3r)-5-chloro-4-phenylpyridine-2,3-diyl)bis(9H-carbazole) (Intermediate 2-2) (yield: 2.19 g, 96.1%). 1 H NMR (500 M H Z , CDCl3) δ 6.59-7.05 (m, 15H), 7.21 (d, J = 8.5 H Z , 2H), 7.58-7.59 (m, 2H) 7.72 (d, J = 7.5H Z , 2H), 9.00 (s, 1H), MS (APCI) m / z 520.42 [(M+H) + ]

[0055] Synthesis of Compound 962 Potassium acetate (1.13 g, 4,4',5',5'-octamethyl-2,2'-bi(1,3,2-dioxaborane) (2.93 g, 11.54 mmol), tris(dibenzylideneacetone)dipalladium (0.11 g, 3 mol%), 2-dicyclohexylphosphino-2',4'-triisopropylbiphenyl (0.11 g, (2r,3r)-5-chloro-4-phenylpyridine-2,3-di 2-chloro-4,6-diphenyl-1,3,5-triazine (1.58 g, 5.89 mmol) was added to the mixture in the flask. To the resulting mixture, tetrakis(triphenylphosphine)palladium(0) (0.14 g, 3 mol%), and potassium carbonate (1.63 g, 11.77 mmol, 2 M aqueous solution) were added while maintaining a nitrogen atmosphere. The mixture was heated to 100 °C and stirred overnight under a nitrogen atmosphere. The reaction was quenched at room temperature with brine solution, and the mixture was extracted with chloroform, dried over MgSO4, and then concentrated using a vacuum evaporator system. The mixture was purified by silica gel column chromatography using n-hexane / methylene chloride as an eluent to give the powder product 9,9'-((2r,3r)-5-(4,6-diphenyl-1,3,5-triazin-2-yl)-4-phenylpyridine-2,3-diyl)bis(9H-carbazole) (Compound 962) (yield: 0.37 g, 13.0%). 1 H NMR (500 M H Z , CDCl3) δ 6.84-7.05 (m, 16H), 7.26 (d, J = 8.0 H Z , 1H), 7.46 (t, J = 7.5 H Z , 4H), 7.57 (t, J = 7.0 H Z , 2H), 7.62-7.64 (m, 2H), 7.74 (d, J= 7.5 H Z , 2H), 8.35 (d, J = 8.0 H Z, 4H), 9.61 (s, 1H), MS (APCI) m / z 717.42 [(M+H) + ]

[0056] (Synthesis Example 3) Synthesis of Compound 950 [ka]

[0057] Synthesis of intermediate 3-1 Potassium acetate (5.06 g, 51.55 mmol), 4,4',4',4',5,5',5',5'-octamethyl-2,2'-bi(1,3,2-dioxaborane) (7.20 g, 28.35 mmol), [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II) (0.57 g, 3 mol%), and 5-bromo-2,3-difluoropyridine (5.00 g, 25.78 mmol) were dissolved in 1,4-dioxane under a nitrogen atmosphere. The mixture was heated to 100 °C and stirred overnight. After the starting compound was no longer detected by thin-layer chromatography, the mixture was cooled to room temperature. To the flask containing the mixture, 2-chloro-4,6-diphenyl-1,3,5-triazine (8.66 g, 32.36 mmol), tetrakis(triphenylphosphine)palladium(0) (0.93 g, 3 mol%), and potassium carbonate (5.59 g, 40.45 mmol, 2 M aqueous solution) were added while maintaining a nitrogen atmosphere. The mixture was heated to 100 °C and stirred overnight under a nitrogen atmosphere. The reaction was quenched with brine solution at room temperature, and the mixture was extracted with chloroform, dried over MgSO4, and then concentrated using a vacuum evaporator system. The mixture was purified by silica gel column chromatography using n-hexane / toluene as an eluent to obtain the powder product, 2-(5,6-difluoropyridin-3-yl)-4,6-diphenyl-1,3,5-triazine (Intermediate 3-1) (yield: 8.80 g, 94.2%). 1 H NMR (500 M H Z , CDCl3) δ 7.60 (t, J = 7.5 H Z, 4H), 7.66 (t,J = 7.5 H Z , 2H), 8.74 (d, J = 8.0 H Z , 4H), 8.86 (t, J = 9.0 H Z , 1H), 9.36 (s, 1H), MS (APCI) m / z 347.23 [(M+H) + ]

[0058] Synthesis of Compound 950 Potassium carbonate (1.20 g, 8.66 mmol), 2-(5,6-difluoropyridin-3-yl)-4,6-diphenyl-1,3,5-triazine (Intermediate 3-1) (1.00 g, 2.89 mmol), and 9H-carbazole (1.45 g, 8.66 mmol) were placed in a three-necked round-bottom flask. The mixture was dried under vacuum, and then DMF was added as a solvent under a nitrogen atmosphere. The reaction mixture was stirred overnight at 160 °C. The reaction was quenched with aqueous NH4Cl, and the mixture was extracted with chloroform. The organic layer separated after extraction was dried over MgSO4, and the solvent was concentrated using a vacuum evaporator system. The reaction product, 9,9'-(((2r,3r)-5-(4,6-diphenyl-1,3,5-triazine-2,3-diyl)pyridine-2,3-diyl)bis(9H-carbazole) (Compound 950), was isolated by column chromatography using a mixture of toluene and hexane (1:4) as the eluent (yield: 1.50 g, 81.1%). 1 H NMR (500 M H Z , CDCl3) δ 7.03 (t, J = 7.5 H Z , 2H), 7.07-7.15 (m, 6H), 7.19 (d, J = 7.5H Z , 2H), 7.36 (d, J = 8.0 H Z , 2H), 7.59 (t, J = 8.0 H Z , 4H), 7.65 (t, J = 7.5 H Z , 2H), 7.78 (d, J = 7.5 H Z , 2H), 7.87 (d, J = 7.5 HZ , 2H), 8.78 (d, J = 7.5 H Z , 4H), 9.48 (s, 1H), 10.19 (s, 1H), MS (APCI) m / z 641.52 [(M+H) + ] The synthesized compound 950 has better luminescence properties than its 4,6-di-p-tolyl substituted derivative, 9,9'-(((2r,3r)-5-(4,6-di-p-tolyl-1,3,5-triazine-2,3-diyl)pyridine-2,3-diyl)bis(9H-carbazole). The unsubstituted diphenyl-1,3,5-triazinyl derivative has better luminescence properties than the dialkylphenyl-1,3,5-triazinyl derivative.

[0059] (Synthesis Example 4) Synthesis of Compound 947 [ka] Synthesis of intermediate 4-1 Under a nitrogen stream, dichlorobis(triphenylphosphine)palladium(II) (0.13 g, 0.19 mmol) was added to a THF solution (20 mL) of 2,6-difluoro-3-pyridineboronic acid (1.00 g, 6.29 mmol), 2-chloro-4,6-diphenyl-1,3,5-triazine (1.77 g, 6.61 mmol), and 2 M aqueous sodium carbonate (6.3 mL, 12.6 mmol). The mixture was heated to reflux for 12 hours. After the reaction mixture was returned to room temperature, it was quenched by adding water and extracted with dichloromethane. The solvent was removed by evaporation, and the mixture was purified by silica gel column chromatography (hexane:toluene = 1:1) to obtain intermediate 4-1 (2.00 g, 5.77 mmol, 91.7% yield) as a white solid. 1 H NMR (400 MHZ, CDCl3) δ 7.05-7.07 (m, 1H), 7.57-7.64 (m, 6H), 8.74 (d, J = 6.8 HZ, 1H), 9.11 (dd, J = 9.2 HZ, J = 8.4 HZ, 1H) ASAP MS Spectral Analysis: C 20 H 12F2N4: theoretical value 346, observed value 347.

[0060] Synthesis of Compound 947 Under a nitrogen atmosphere, a dimethylformamide solution (10 mL) of 9H-carbazole (0.87 g, 5.20 mmol), potassium carbonate (0.72 g, 5.20 mmol), and intermediate 4-1 (0.60 g, 1.73 mmol) was stirred at 120 °C overnight. After returning the mixture to room temperature, it was quenched by adding saturated ammonium chloride solution and extracted with chloroform. The solvent was removed using an evaporator, and the residue was purified by silica gel column chromatography (toluene:hexane) to obtain compound 947 (1.10 g, 1.72 mmol, 99.1% yield). 1 H NMR (400 MHZ, CDCl3) δ 7.21 (t, J = 6.8 HZ, 2H), 7.27-7.38 (m, 13H), 8.00 (d, J = 8.4 HZ, 3H), 8.08 (d, J = 6.8 HZ, 3H), 8.12 (d, J = 6.8 HZ, 2H), 8.19 (d, J = 8.0 HZ, 2H), 9.13 (d, J = 8.8 HZ, 1H). ASAP MS Spectral Analysis: C 44 H 28 N6: Theoretical value 640, Observed value 640.

[0061] (Synthesis Example 5) Synthesis of Compound 5225 [ka] Synthesis of intermediate 5-1 Under a nitrogen stream, a dimethylformamide solution (20 mL) of 9H-carbazole (0.48 g, 2.89 mmol), potassium carbonate (0.51 g, 3.76 mmol), and compound 1 (1.0 g, 2.89 mmol) was stirred overnight at 70 °C. After returning the mixture to room temperature, it was quenched by adding saturated ammonium chloride solution and extracted with chloroform. The solvent was removed using an evaporator, and the residue was purified by silica gel column chromatography (toluene:hexane) to obtain intermediate 5-1 (1.08 g, 2.19 mmol, 75.7% yield). 1 H NMR (400 MHZ, CDCl3) δ 7.38 (t, J = 7.2 HZ, 2H), 7.51 (t, J = 8.4 HZ, 2H), 7.58-7.66 (m, 6H), 7.79 (d, J = 8.0 HZ, 1H), 8.12 (t, J = 8.0 HZ, 4H), 8.78 (d, J = 6.4 HZ, 4H), 9.20 (t, J = 9.6 HZ, 1H). ASAP MS Spectral Analysis: C 32 H 20 FN5: theoretical value 493, observed value 494.

[0062] Synthesis of compound 5225 Under a nitrogen atmosphere, a solution of 12H-[3,2-a]-benzofurocarbazole (0.76 g, 2.96 mmol), potassium carbonate (0.41 g, 2.96 mmol), and intermediate 5-1 (0.73 g, 1.48 mmol) in dimethylformamide (30 mL) was stirred overnight at 110 °C. After returning the mixture to room temperature, it was quenched by adding saturated ammonium chloride solution and extracted with chloroform. The solvent was removed using an evaporator, and the residue was purified by silica gel column chromatography (toluene:hexane) to obtain compound 5225 (0.91 g, 1.25 mmol, 84.1% yield). 1H NMR (400 MHZ, CDCl3) δ 6.21 (d, J = 7.6 HZ, 1H), 6.94 (t, J = 6.8 HZ, 1H), 7.23-7.47 (m, 15H), 7.55 (d, J = 7.6 HZ, 1H), 7.87 (d, J = 7.6 HZ, 4H), 8.02 (d, J = 8.8 HZ, 2H), 8.08 (t, J = 6.8 HZ, 4H), 8.22 (d, J = 8.4 HZ, 1H), 9.14 (d, J = 8.8 HZ, 1H). ASAP MS Spectral Analysis: C 50 H 30 N 6O : theoretical value 730, observed value 731.

[0063] (Synthesis Example 6) Synthesis of Compound 5223 [ka] Under a nitrogen atmosphere, a solution of 12H-[3,2-a]-benzofurocarbazole (0.93 g, 3.61 mmol), potassium carbonate (0.60 g, 4.33 mmol), and compound 1 (0.50 g, 1.44 mmol) in dimethylformamide (30 mL) was stirred overnight at 100 °C. After returning the mixture to room temperature, it was quenched by adding saturated ammonium chloride solution and extracted with chloroform. The solvent was removed using an evaporator, and the residue was purified by silica gel column chromatography (toluene:hexane) to obtain compound 5223 (0.70 g, 0.85 mmol, 59.2% yield). 1H NMR (400 MHZ, CDCl3)δ 6.34 (d, J = 8.0 HZ, 1H), 6.72 (d, J = 7.6 HZ, 1H), 6.90 (t, J = 6.8 HZ, 1H), 7.10 (t, J = 7.6 HZ, 1H), 7.18 (t, J = 6.8 HZ, 1H), 7.24-7.35 (m, 8H), 7.41-7.47 (m, 5H), 7.54-7.56 (m, 1H), 7.67-7.73 (m, 3 H), 7.88-7.91 (m, 4H), 7.95 (d, J = 8.4 HZ, 1H) 8.01 (d, J = 8.4 HZ, 1H), 8.05-8.11 (m, 2H), 8.24 (d, J = 8.0 HZ, 1H), 9.04 (d, J = 8.0 HZ, 1H). ASAP MSスペクトル Analysis: C 56 H 32 N6O2: theoretical value 820, experimental value 821.

[0064] (Synthesis Example 7) Synthesis of Compound 960

change

[0065] Synthesis of Compound 960 A dimethylformamide solution (10 mL) of 9H-carbazole (1.19 g, 7.10 mmol), potassium carbonate (1.31 g, 9.47 mmol), and compound 7-1 (1.0 g, 2.37 mmol) was stirred overnight at 120 °C under a nitrogen atmosphere. After the mixture was returned to room temperature, it was quenched by adding saturated ammonium chloride solution and extracted with chloroform. The solvent was removed using an evaporator, and the residue was purified by silica gel column chromatography (toluene:hexane) to obtain compound 960 (1.60 g, 2.23 mmol, 94.2% yield). 1 H NMR (400 MHZ, CDCl3) δ 6.56 (t, J = 7.6 HZ, 2H), 6.64 (t, J = 7.2 HZ, 1H), 6.74 (d, J = 7.2 HZ, 2H), 7.13 (t, J = 7.6 HZ, 4H), 7.19-7.24 (m, 4H), 7.30-7.35 (m, 8H), 7.48 (d, J = 7.2 HZ, 2H), 7.86 (d, J = 7.2 HZ, 2H), 8.00 (t, J = 8.4 HZ, 6 H), 9.71 (s, 1H). ASAP MS Spectral Analysis: C 50 H 32 N6: Theoretical value 716, Observed value 717.

[0066] Compounds 1 to 5231 other than the compounds synthesized in Synthesis Examples 1 to 7 can also be synthesized in the same manner.

[0067] Examples and Comparative Examples Vacuum deposition method on a quartz substrate at a vacuum level of 5 x 10 -5 Compound 939 and a host material were evaporated from different evaporation sources under conditions of 0.1 Pa or less to form a 100 nm-thick thin film containing 20 mass % of compound 939. This was designated as the doped thin film of Example 1. Furthermore, thin films were formed with the only change being that compound 939 was replaced with compound 947, compound 5225, compound 5223, compound 960, or the following comparative compound A, and these were designated as the doped thin films of Examples 2 to 5 and Comparative Example 1. Each of the doped thin films prepared was irradiated with 360 nm excitation light to measure the emission spectrum and the emission transient decay curve. Delayed fluorescence was observed from all of the thin films. Table 2 shows the maximum emission wavelength λmax, emission quantum yield PLQY, and delayed fluorescence lifetime τ d (unit: milliseconds). In addition, a quartz substrate was vacuum-deposited at a vacuum level of 5×10 -5Compound 939 was evaporated alone under conditions of 0.1 Pa or less to form a neat thin film of Example 1. Compounds 947, 5225, 5223, 960, and Comparative Compound A were evaporated alone under the same conditions to form neat thin films of Examples 2 to 5 and Comparative Example 1. The HOMO and LUMO energy levels of each compound were measured using each neat thin film, and the results are shown in Table 2.

[0068] [ka]

[0069] [Table 2]

[0070] The results in Table 2 show that the compound represented by general formula (1) has better luminescence efficiency and shorter delayed fluorescence lifetime than comparative compound A. It also shows that the compound represented by general formula (1) is useful as a blue luminescent material. The other compounds synthesized in the synthesis examples also exhibit excellent luminescence properties similar to compound 939. [Industrial Applicability]

[0071] The compound of the present invention has excellent luminescent properties and is also useful as a delayed fluorescent material. Therefore, the luminescent material of the present invention can be effectively used in organic optical devices such as organic electroluminescence elements. Therefore, the present invention has high industrial applicability.

Claims

1. A compound represented by the following general formula (1): 【Chemistry 1】 [R in general formula (1)] １ ~R ５ Of these, R 1 is a hydrogen atom or a deuterium atom; R ２ is A, R 3 and R 5 are D; R4 is R. Here A is a group represented by the following general formula (IIIa), where R ２２ and R ２４ each independently represents a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group; L Ａ represents a single bond, and * represents the bond position. 【Chemistry 2】 D is a group represented by the following general formula (IIb). 【Transformation 3】 Here, R Ｄ each independently represents a hydrogen atom, a deuterium atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted amino group, a cyano group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted heteroaryloxy group, or a silyl group; Ｄ may be bonded to each other to form a cyclic structure, L Ｄ represents a single bond, * indicates the bond position. R is a substituted or unsubstituted aryl group. Multiple Ds present in a molecule may be the same or different.]

2. A light-emitting material comprising the compound according to claim 1.

3. A delayed fluorescent material comprising the compound according to claim 1.

4. An organic optical device comprising the compound of claim 1.

5. 5. The organic optical device of claim 4, which is an organic light emitting diode (OLED).

6. A compound represented by the following general formula (1'): 【Chemistry 4】 [R in general formula (1')] １ ~R ５ satisfies the following condition 1 or 2, (Condition 1) R １ ~R ５ Of these, R 1 is a hydrogen atom or a deuterium atom; R ２ is a halogen atom, R 3 and R 5 are D; R4 is R. (Condition 2) R １ ~R ５ Of these, R 1 is a hydrogen atom or a deuterium atom; R ２ is A, R 3 and R 5 are halogen atoms; R4 is R. Here A is a group represented by the following general formula (IIIa), where R ２２ and R ２４ each independently represents a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group; L Ａ represents a single bond, and * represents the bond position. 【Transformation 5】 D is a group represented by the following general formula (IIb). 【Transformation 6】 Here, R Ｄ each independently represents a hydrogen atom, a deuterium atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted amino group, a cyano group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted heteroaryloxy group, or a silyl group; Ｄ may be bonded to each other to form a cyclic structure, L Ｄ represents a single bond, * indicates the bond position. R is a substituted or unsubstituted aryl group. Multiple Ds present in a molecule may be the same or different.]

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