Light-emitting member, light-emitting compound, and photoelectric conversion member

Abstract

This optical member contains a specific compound which has a squarylium ring at the center of the molecular structure thereof and has a molecular structure having an emission peak in a near-infrared long wavelength range, and in which a soluble group (a linear or branched alkyl group (a) having 4-12 carbon atoms, or a group (P) having a polyoxyethylene structure) is disposed on an outer group of the squarylium ring so as to extend in the direction toward the squarylium ring.

Description

[Technical field]

[0001] The present invention relates to a light-emitting component, a light-emitting compound, and a photoelectric conversion component, and more specifically to a light-emitting component and the like that is capable of emitting light in the long wavelength region of near-infrared light (hereinafter also referred to as "near-infrared long wavelength region") and that contains a light-emitting compound that can be incorporated into components at a high concentration, and that can achieve a high luminescence quantum yield in the near-infrared long wavelength region. [Background technology]

[0002] Near-infrared emitting materials have attracted attention because they allow the background effect of autofluorescence of living cells to be ignored under near-infrared excitation, and because near-infrared light is less scattered inside the body than visible light, they enable imaging deeper in the body, biometric authentication by vein imaging, biomeasurements such as pulse oximeters, etc. For this reason, compounds that emit light in the near-infrared region are being investigated.

[0003] However, it is generally known that the luminescence quantum yield drops drastically when a compound having an emission wavelength longer than the visible light region is used. This is because the excited state energy of near-infrared emission is low, and the effect of non-radiative deactivation due to molecular vibration is large. Furthermore, when the conjugated system of the dye is expanded to lengthen the emission wavelength, the intermolecular interaction increases, and the dye tends to aggregate in thin films or particles, resulting in concentration quenching. Therefore, even if a luminescent dye exhibits near-infrared emission with a high luminescence quantum yield in a solution, there is a problem that a high luminescence quantum yield cannot be maintained when the dye is dispersed in a solid matrix such as a resin.

[0004] Squarylium compounds are known as near-infrared absorbents (see, for example, Patent Document 1). It is also known that squarylium compounds are used in combination with delayed fluorescent materials or phosphorescent compounds in organic EL devices (see, for example, Patent Document 2). However, there have been no studies to date on the molecular structure of squarylium compounds from the viewpoint of obtaining high luminescence quantum yields even when contained at high concentrations for the purpose of application to light-emitting components. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] International Publication No. 2017 / 130825 [Patent Document 2] International Publication No. 2018 / 008721 Summary of the Invention [Problem to be solved by the invention]

[0006] The present invention has been made in consideration of the above problems and circumstances, and the problem to be solved is to provide a light-emitting component capable of achieving a high luminescence quantum yield in the long near-infrared wavelength region by containing a light-emitting compound that can emit light in the long near-infrared wavelength region and be blended into components at a high concentration. Another object is to provide a light-emitting compound that can emit light in the long near-infrared wavelength region and be blended into components at a high concentration. Furthermore, an object is to provide a photoelectric conversion component that can obtain a high external quantum efficiency by using a light-emitting compound that can emit light in the long near-infrared wavelength region and be blended into components at a high concentration. [Means for solving the problem]

[0007] In the course of investigating the causes of the above problems in order to solve the above problems, the present inventors discovered that in a compound having a squarylium ring at the center of its molecular structure, by forming a molecular structure having an emission peak in the long-wavelength near-infrared region and arranging soluble groups on the outer groups of the squarylium ring so that they extend in a direction toward the squarylium ring, the compound will emit light in the long-wavelength near-infrared region while mitigating concentration quenching, enabling it to be incorporated into a matrix at a high concentration, which led to the present invention. That is, the above-mentioned problems of the present invention are solved by the following means.

[0008] 1.The following general formula (T 2 A light-emitting member comprising a compound having a structure represented by the formula: [ka] [General formula (T 2 ) A to L each independently represent an aromatic hydrocarbon. Ring represent. n1 to n6 are each independently 0 or 1 Represents an integer. Ya and Yb each independently represent an OH group, an NHCORa group (wherein Ra represents a hydrocarbon group), or an NHSO 2 Rb (Rb represents a hydrocarbon group) group, or NHPO(ORf)(ORg) (Rf and Rg each represent a hydrocarbon group). Yc to Yl each independently represent a hydrogen atom or a substituent. However, Ya and Y b At least one of them is a linear or branched alkyl group (a) having 4 to 12 carbon atoms, or a group containing a group (P) having a structure represented by the following general formula (P). [ka] (In the general formula (P), * represents a substitution site. Q represents a single bond or a divalent linking group. n represents an integer of 1 to 9. R 51 represents a hydrogen atom or a methyl group.)]

[0010] 2 .The general formula (T 2 ) 、Y 2. The light-emitting member according to item 1, wherein at least one of e to Yl is a linear or branched alkyl group (a) having 4 to 12 carbon atoms, or a group containing a group (P) having a structure represented by general formula (P).

[0014] 3 . under The structure represented by the following general formula (1b) Contains a compound having the formula Illuminating components. [ka] (In general formula (1b), each Ra independently represents a hydrocarbon group. Each Rc independently represents a hydrogen atom or a substituent. Either of two Ra represents a linear or branched alkyl group (a) having 4 to 12 carbon atoms, or at least one of four Rc represents a linear or branched alkyl group (a) having 4 to 12 carbon atoms which may have -O- as a linking group, or a group (P) having a structure represented by general formula (P).)

[0016] 4. A light-emitting member containing a compound having a structure represented by the following general formula (1d): [ka] (In general formula (1d), each Ra independently represents a hydrocarbon group. Each Re independently represents a hydrogen atom or a substituent. Each Xa independently represents an alkyl group or an alkoxy group having 1 to 3 carbon atoms, or a substituted or unsubstituted phenyl group, and Xa bonded to the 4-position is, under It may be a group having a structure represented by the formula (D), and m represents an integer of 0 to 4. However, in the general formula (1d), either of the two Ra represents a linear or branched alkyl group (a) having 4 to 12 carbon atoms, or at least one of the four Re represents a linear or branched alkyl group (a) having 4 to 12 carbon atoms which may have -O- as a linking group, or a group (P) having a structure represented by the general formula (P), or Xa at the 4th position represents under A group having a structure represented by formula (D) is bonded. [ka] (In formula (D), * indicates the connection site. X 31 ~X 35 Each independently represents a hydrogen atom or a substituent. 31 and X 35 At least one of the above is a linear or branched alkyl group (a) having 4 to 12 carbon atoms, or a group (P) having a structure represented by the following general formula (P): 32 ~X 34 does not have a linear or branched alkyl group or a (poly)oxyalkylene group having 4 or more carbon atoms.)] [ka] (In the general formula (P), * represents a substitution site. Q represents a single bond or a divalent linking group. n represents an integer of 1 to 9. R 51 represents a hydrogen atom or a methyl group.)]

[0017] 5 The light-emitting member is a light-emitting thin film. 4 The light-emitting member according to any one of claims 1 to 5.

[0018] 6 The light-emitting member is a light-emitting particle. 4 The light-emitting member according to any one of claims 1 to 5.

[0019] 7 A light-emitting compound having a structure represented by the following general formula (1a): [ka] (In general formula (1a), each Rc independently represents a hydrogen atom or a substituent, and at least one of the four Rc represents a linear or branched alkyl group (a) having 4 to 12 carbon atoms which may have -O- as a linking group, or a group (P) having a structure represented by the following general formula (P).) [ka] (In the general formula (P), * represents a substitution site. Q represents a single bond or a divalent linking group. n represents an integer of 1 to 9. R 51 represents a hydrogen atom or a methyl group.

[0020] 8 A light-emitting compound having a structure represented by the following general formula (1b): [ka] (In general formula (1b), each Ra independently represents a hydrocarbon group. Each Rc independently represents a hydrogen atom or a substituent. Either of two Ra represents a linear or branched alkyl group (a) having 4 to 12 carbon atoms, or at least one of four Rc represents a linear or branched alkyl group (a) having 4 to 12 carbon atoms which may have -O- as a linking group, or a group (P) having a structure represented by the following general formula (P).) [ka] (In the general formula (P), * represents a substitution site. Q represents a single bond or a divalent linking group. n represents an integer of 1 to 9. R 51 represents a hydrogen atom or a methyl group.

[0024] 9 A photoelectric conversion member containing a compound having a structure represented by the following general formula (T): [ka] [In the general formula (T), A to L each independently represent an aromatic hydrocarbon ring or a heteroaromatic ring. n1 to n6 each independently represent an integer of 0 to 2. Ya and Yb each independently represent an OH group, an NHCORa group (wherein Ra represents a hydrocarbon group), or an NHSO 2 Rb (Rb represents a hydrocarbon group) group, or NHPO(ORf)(ORg) (Rf and Rg each represent a hydrocarbon group). Yc to Yl each independently represent a hydrogen atom or a substituent. However, at least one of Ya to Yl is a linear or branched alkyl group (a) having 4 to 12 carbon atoms, or a group containing a group (P) having a structure represented by the following general formula (P). [ka] (In the general formula (P), * represents a substitution site. Q represents a single bond or a divalent linking group. n represents an integer of 1 to 9. R 51represents a hydrogen atom or a methyl group.)] Effect of the Invention

[0025] According to the above-mentioned means of the present invention, it is possible to provide a light-emitting component that can achieve a high light emission quantum yield in the near-infrared long wavelength region, which contains a light-emitting compound that can emit light in the near-infrared long wavelength region and can be incorporated into a component at a high concentration. It is also possible to provide a light-emitting compound that can emit light in the near-infrared long wavelength region and can be incorporated into a component at a high concentration. Furthermore, it is possible to provide a photoelectric conversion component that can obtain a high external quantum efficiency by using a light-emitting compound that can emit light in the near-infrared long wavelength region and can be incorporated into a component at a high concentration.

[0026] Although the mechanism by which the effects of the present invention are expressed or the mechanism of action has not been clarified, it is speculated as follows.

[0027] A compound having a structure represented by general formula (T) (hereinafter also referred to as compound (T)) is a compound having a squarylium ring at the center of its molecular structure. Compound (T) has a structure in which nitrogen atoms are bonded to the left and right of a squarylium ring in the main skeleton via an aromatic hydrocarbon ring or a heteroaromatic ring, and two aromatic hydrocarbon rings or heteroaromatic rings are bonded to the nitrogen atoms. Note that these aromatic hydrocarbon rings or heteroaromatic rings also include a structure in which two or three are linked in a chain. In addition, compound (T) is a compound in which the aromatic hydrocarbon ring or heteroaromatic ring bonded to the squarylium ring has an OH group, an NHCORa group, an NHSO group, or a NHSO group at a predetermined position. 2 Rb group, or NHPO(ORf)(ORg) group. Furthermore, compound (T) has a structure in which a linear or branched alkyl group (a) having 4 to 12 carbon atoms, or a group (P) having a structure represented by the above general formula (P), as a solubilizing group, is bonded to the above aromatic hydrocarbon ring or heteroaromatic ring directly or via a linking group such that the group is positioned in a direction toward the central squarylium ring.

[0028] By giving the squarylium compound the above-mentioned molecular structure possessed by compound (T), the inventors have achieved a molecular structure having an emission peak in the long wavelength region of near-infrared light, while alleviating concentration quenching, thereby enabling incorporation into a matrix at a high concentration.

[0029] In the present invention, by incorporating the compound (T) into a light-emitting member, a light-emitting member capable of achieving a high light-emitting quantum yield in the near-infrared long wavelength region can be obtained. the below described A compound having a structure represented by general formula (1) (hereinafter also referred to as compound (1)) is preferred. In compound (1), a compound having the above specific molecular structure, that is, a compound represented by general formula (1a), (1b), or (1d) or the following general formula (1c) or (1e) The compound having the structure represented by the following formula (1) is a novel compound that has not been described in the literature so far. [ka] [In the general formula (1), L 1 represents a group having a structure represented by the following formula (L1), formula (L2) or formula (L3). 2 represents a group having a structure represented by the following formula (L4), formula (L5) or formula (L6). [ka] (In formulas (L1) to (L6), *1 and *4 respectively represent the sites of bonding to N in general formula (1). *2 and *3 respectively represent the sites of bonding to the carbon of the squarylium ring in general formula (1). R 1 、R 5 、R 21 and R 27 are each independently an OH group, an NHCORa group (wherein Ra represents a hydrocarbon group), or an NHSO 2 Rb (Rb represents a hydrocarbon group) group, or NHPO(ORf)(ORg) (Rf and Rg each represent a hydrocarbon group). R 2 ~R 4 、R 6 ~R 8 、R 11 ~R18 、R 22 ~R 26 and R 28 ~R 32 each independently represents a hydrogen atom or a substituent. Ar 1 ~Ar 4 each independently represents a group having a structure represented by the following formula (A), formula (B), or formula (C).

change

[0030] Furthermore, when compound (T) is used in a photoelectric conversion element, a photoelectric conversion element with high external quantum efficiency can be obtained. This is presumably because compound (T), especially compound (1), has the characteristic of having an emission peak in the long wavelength near infrared region and exhibiting a high emission quantum yield, which makes it difficult for excitons to pass through a quenching path such as non-radiative deactivation when the molecule is excited, resulting in such an effect. [Brief description of the drawings]

[0031] [Figure 1] This is the 1H-NMR spectrum (400 MHz, measurement solvent CDCl3) of compound (1a)-1. [Diagram 2]This is the 1H-NMR spectrum (400 MHz, measurement solvent CDCl3) of compound (1c)-1. [Diagram 3] This is the 1H-NMR spectrum (400 MHz, measurement solvent CDCl3) of compound (1d)-1. [Figure 4] FIG. 1 is a schematic cross-sectional view showing an example of the configuration of an infrared emitting surface light source using a wavelength conversion film having a light emitting member of the present invention. [Diagram 5] FIG. 1 is a schematic cross-sectional view showing an example of the configuration of a wavelength conversion film provided with a light emitting member of the present invention. [Figure 6] FIG. 1 is a schematic cross-sectional view showing an example of the configuration of an organic photoelectric conversion element including the photoelectric conversion member of the present invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0032] The light-emitting component of the present invention is characterized in that it contains a compound having a structure represented by the above general formula (T). This characteristic is a technical characteristic common to the following embodiments.

[0033] As an embodiment of the present invention, from the viewpoint of exerting the effects of the present invention, it is preferable that in the above general formula (T), A to L represent an aromatic hydrocarbon ring, n1 to n6 are each independently 0 or 1, and at least one of Ya and Yb is a linear or branched alkyl group (a) having 4 to 12 carbon atoms, or a group containing a group (P) having a structure represented by the above general formula (P).

[0034] As an embodiment of the present invention, from the viewpoint of exerting the effects of the present invention, it is preferable that in the above general formula (T), A to L represent an aromatic hydrocarbon ring, n1 to n6 each independently represent 0 or 1, and at least one of Ye to Yl represents a linear or branched alkyl group (a) having 4 to 12 carbon atoms, or a group containing a group (P) having a structure represented by the above general formula (P).

[0035] As an embodiment of the present invention, from the viewpoint of exerting the effects of the present invention, the structure represented by the above general formula (T) is preferably a structure represented by the above general formula (1).

[0036] A compound having a structure represented by general formula (1) (hereinafter also referred to as compound (1)) has a structure in which nitrogen atoms are bonded to the left and right of a squarylium ring via a benzene ring, a biphenyl ring, or a naphthalene ring, and two benzene rings or naphthalene rings are bonded to the nitrogen atom as a main skeleton. Compound (1) is a compound in which the bonding position of a linear or branched alkyl group (a) having 4 to 12 carbon atoms or a group (P) having a structure represented by the above general formula (P), which is contained in compound (T) as a soluble group, is specifically specified so that the group is bonded directly or via a linking group in a direction toward the central squarylium ring. Such compound (1) is a compound that particularly prominently has the characteristics of emitting light in the near-infrared long wavelength region that compound (T) has and being able to be incorporated into a component at a high concentration.

[0037] In an embodiment of the present invention, from the viewpoint of emitting light in the near infrared long wavelength region and being able to be incorporated into a component at a high concentration, in the above general formula (1), L 1 is a group having a structure represented by the above formula (L1), and L 2 is preferably a group having a structure represented by the above formula (L4).

[0038] As an embodiment of the present invention, from the viewpoint of emitting light in the near-infrared long wavelength region and being able to be incorporated into components at a high concentration, the structure represented by the above general formula (1) is preferably a structure represented by the above general formula (1a), general formula (1b), general formula (1c) or general formula (1d).

[0039] As an embodiment of the present invention, from the viewpoint of exerting the effects of the present invention, it is preferable that the light-emitting member is a light-emitting thin film or light-emitting particles.

[0040] Furthermore, the luminescent compound of the present invention having a structure represented by the above general formula (1a), general formula (1b), general formula (1c), general formula (1d) or general formula (1e) is a novel compound.

[0041] The photoelectric conversion member of the present invention is characterized by containing a compound having a structure represented by the above general formula (T), thereby providing a photoelectric conversion element with high external quantum efficiency.

[0042] The present invention, its components, and embodiments for carrying out the present invention will be described in detail below. In this application, the symbol "to" is used to mean that the numerical values ​​before and after the symbol "to" are included as the lower limit and upper limit.

[0043] In this specification, the compound having the structure represented by the general formula (T) is also referred to as the compound (T) as described above. In addition, the chemical structure may be indicated by adding the abbreviation of the compound having the structure represented by the chemical structure, such as compound (1a)-1. Furthermore, the group having the structure represented by the general formula (P) is also referred to as the group (P), and the group having the structure represented by the formula (L1) is also referred to as the group (L1). The same applies to other compounds and groups.

[0044] [Summary of the light-emitting member of the present invention] The light-emitting member of the present invention is characterized by containing a compound (T). In the light-emitting member of the present invention, the compound (T) acts as a near-infrared light-emitting agent. The light-emitting member of the present invention is a member having a predetermined shape, and may contain, in addition to the compound (T), a matrix material for uniformly dispersing the compound (T) in the light-emitting member and forming it into a predetermined shape. In addition to the compound (T), the light-emitting member of the present invention may contain various additives within a range that does not impair the effects of the present invention. The components of the light-emitting member of the present invention will be described in detail below.

[0045] <Compound (T)> The compound (T) is a compound having a structure represented by general formula (T).

[0046] [ka] In general formula (T), A to L each independently represent an aromatic hydrocarbon ring or a heteroaromatic ring. n1 to n6 each independently represent an integer of 0 to 2. Ya and Yb each independently represent an OH group, an NHCORa group (wherein Ra represents a hydrocarbon group), or an NHSO 2 Rb (Rb represents a hydrocarbon group) group, or NHPO(ORf)(ORg) (Rf and Rg each represent a hydrocarbon group). Yc to Yl each independently represent a hydrogen atom or a substituent. However, at least one of Ya to Yl is a linear or branched alkyl group (a) having 4 to 12 carbon atoms, or a group containing a group (P) having a structure represented by the following general formula (P). [ka] (In the general formula (P), * represents a substitution site. Q represents a single bond or a divalent linking group. n represents an integer of 1 to 9. R 51 represents a hydrogen atom or a methyl group.

[0047] In the general formula (T), A to L each independently represent an aromatic hydrocarbon ring or a heteroaromatic ring. The number of carbon atoms in the aromatic hydrocarbon ring or the heteroaromatic ring is preferably 4 to 10. Examples of heteroatoms in the heteroaromatic ring include an oxygen atom, a nitrogen atom, and a sulfur atom. Specific examples of the aromatic hydrocarbon ring or the heteroaromatic ring include a benzene ring, a naphthalene ring, a pyridine ring, a thiophene ring, a pyrrole ring, and a furan ring, and a benzene ring and a naphthalene ring are preferred.

[0048] In the general formula (T), n1 to n6 each independently represent an integer of 0 to 2, preferably 0 or 1. In the compound (T), the structure connecting the squarylium ring and the nitrogen atom is preferably a benzene ring, a biphenyl ring, or a naphthalene ring. Specifically, it is as described in the compound (1).

[0049] In compound (T), at least one of Ya to Yl is a linear or branched alkyl group (a) having 4 to 12 carbon atoms, or a group containing a group (P) having a structure represented by general formula (P) above (hereinafter also referred to as a substituent (E)). In compound (T), the position substituted with the substituent (E), that is, the position of Ya to Yl, is the position bonding toward the central squarylium ring.

[0050] In addition, Ya and Yb each independently represent an OH group, an NHCORa group (Ra represents a hydrocarbon group), or an NHSO 2 Rb (Rb represents a hydrocarbon group) group, or NHPO(ORf)(ORg) (Rf and Rg each represent a hydrocarbon group). When Ya and Yb have a substituent (E), Ra, Rb, Rf or Rg is the substituent (E). However, the substituent (E) in this case is limited to the substituent (E) containing an alkyl group (a).

[0051] The substituent (E) may be the alkyl group (a) or the group (P) itself, or may be a group in which the alkyl group (a) or the group (P) is bonded to the main skeleton via a divalent linking group. Examples of the linking group include a phenylene group, -O-, an ester bond (-C(=O)O- or -OC(=O)-), an amide bond (-NHCO-), and combinations thereof. Examples of the linking group include -O- and a phenylene group, and a 1,4-phenylene group is particularly preferred.

[0052] When Yc to Yl are the substituents (E), the substituents (E) are preferably the alkyl group (a) which may have -O- as a linking group or the group (P) itself. When Ra, Rb, Rf or Rg is the substituent (E), it is preferably the alkyl group (a).

[0053] The number of the substituents (E) in the compound (T) may be 1 or more, and is preferably in the range of 1 to 8, more preferably in the range of 2 to 8, and further preferably in the range of 2 to 4. The preferred position of the substituents (E) in the compound (T) will be described later in more specific compounds.

[0054] In the substituent (E), examples of the linear alkyl group (a) having 4 to 12 carbon atoms include n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, and n-dodecyl. Examples of the branched alkyl group (a) having 4 to 12 carbon atoms include isobutyl, s-butyl, t-butyl, 1-propylbutyl, 1-ethylpentyl, 2,4,4-trimethylpentyl, 2-ethylbutyl, 2,2-dimethylpropyl, 2-ethylhexyl, and 2-butyloctyl.

[0055] From the viewpoint of solubility, the alkyl group (a) is preferably a branched alkyl group (a) having 4 to 12 carbon atoms. The branched alkyl group (a) is preferably a group having a structure represented by any one of the following formulas (a1) to (a7). Here, the group (a1) is a 1-propylbutyl group, the group (a2) is a 1-ethylpentyl group, the group (a3) ​​is a 2,4,4-trimethylpentyl group, the group (a4) is an isobutyl group, the group (a5) is a 2-ethylbutyl group, the group (a6) is a 2-ethylhexyl group, and the group (a7) is a 2-butyloctyl group.

[0056] When Ra, Rb, Rf or Rg is a branched alkyl group (a), the alkyl group (a) is preferably the group (a1), the group (a2), the group (a3) ​​or the group (a4).When the branched alkyl group (a) is bonded to any other position, the branched alkyl group (a) is preferably the group (a4), the group (a5), the group (a6) or the group (a7).

[0057] [ka]

[0058] When the substituent (E) is a group (P), the number n, which indicates the number of repetitions of the oxyethylene group, may be within the range of 1 to 9. The number n is preferably 2, 3, 4, or 8 in terms of ease of production. In the group (P), Q is a single bond or a divalent linking group. When Q is a divalent linking group, examples of the linking group include an alkylene group having 1 to 4 carbon atoms, a carbonyl group (-C(=O)-), an arylene group having 6 to 12 carbon atoms, and combinations thereof. Q is preferably a single bond, an alkylene group having 1 to 2 carbon atoms, or a carbonyl group. When the group (P) is bonded to the main skeleton via a linking group, the linking group is preferably a phenylene group, and more preferably a 1,4-phenylene group, as described above.

[0059] In the compound (T), when they are not the substituent (E), Ra, Rb, Rf, Rg, and Yc to Yl each include an atom or group selected from a hydrogen atom, an alkyl group or alkoxy group having 1 to 3 carbon atoms, and an aryl group (not including any linear or branched alkyl group or (poly)oxyalkylene group having 4 or more carbon atoms), etc. Examples of the aryl group include a phenyl group, a tolyl group, and a xylyl group.

[0060] When Ra, Rb, Rf and Rg are not the substituent (E), they are preferably methyl groups.When Yc to Yl are not the substituent (E), they are preferably hydrogen atoms, alkyl groups having 1 to 3 carbon atoms or phenyl groups.

[0061] In A to L in compound (T), hydrogen atoms bonded to the aromatic hydrocarbon ring or heteroaromatic ring at positions other than Ya to Yl may be substituted. In A to L in compound (T), a substituent (E) may be further included at positions other than Ya to Yl, provided that the effects of the present invention are not impaired. Such positions are, for example, positions other than Ya to Yl that are bonded in the direction toward the central squarylium ring. Substituents other than the substituent (E) may be bonded to such positions, and examples of the substituent in this case include the same substituents as those when Ya to Yl are other than the substituent (E).

[0062] In the case where A to L of the compound (T) have a substituent at a position other than the above, the substituent is preferably a group that does not have a linear or branched alkyl group or a (poly)oxyalkylene group having 4 or more carbon atoms. Specific examples of such a substituent include an alkyl group or an alkoxy group having 1 to 3 carbon atoms, and an aryl group (however, the group does not have either a linear or branched alkyl group or a (poly)oxyalkylene group having 4 or more carbon atoms).

[0063] (Compound (1)) The compound (T) is preferably a compound (1) having a structure represented by the following general formula (1).

[0064] [ka]

[0065] In general formula (1), L 1 represents a group having a structure represented by the following formula (L1), formula (L2) or formula (L3). 2 represents a group having a structure represented by the following formula (L4), formula (L5) or formula (L6).

[0066] [ka]

[0067] In formulae (L1) to (L6), *1 and *4 each represent a site bonded to N in general formula (1). *2 and *3 each represent a site bonded to the carbon of the squarylium ring in general formula (1). R 1 , R 5 , R 21 and R 27 are each independently an OH group, an NHCORa group (wherein Ra represents a hydrocarbon group), or an NHSO 2 Rb (Rb represents a hydrocarbon group) group or NHPO(ORf)(ORg) (Rf and Rg each represent a hydrocarbon group). R 2 ~R 4 , R 6 ~R8 , R 11 ~R 18 , R 22 ~R 26 and R 28 ~R 32 each independently represents a hydrogen atom or a substituent.

[0068] In the general formula (1), Ar 1 ~Ar 4 each independently represents a group having a structure represented by the following formula (A), formula (B), or formula (C). [ka]

[0069] In the formulae (A) to (C), * indicates the connection site with the N atom. 1 ~X 27 each independently represents a hydrogen atom or a substituent.

[0070] In the general formula (1), L 1 , L 2 and Ar 1 ~Ar 4 has a linear or branched alkyl group (a) having 4 to 12 carbon atoms or a group (P) having a structure represented by the general formula (P) above at at least one of the following specified positions:

[0071] L 1 Or L 2 The predetermined position in R 1 , R 5 , R 21 and R 27 When is NHCORa group, Ra (excluding group (P)), R 1 , R 5 , R 21 and R 27 NHSO 2 Rb in the case of the Rb group (excluding the group (P)), R 1 , R 5 , R 21 and R 27Rf or Rg (excluding group (P)) when R is a NHPO(ORf)(ORg) group; 2 , R 11 , R 12 , R 6 , R 15 , R 16 , R 26 and R 32 It is. 1 ~Ar 4 The predetermined position in X 1 , X 5 , X 11 , X 21 and X 27 And X in the following formula (D) 31 and X 35 It is.

[0072] Furthermore, in the general formula (1), L 1 Or L 2 In R 3 , R 4 , R 13 , R 14 , R 23 , R 24 , R 25 , R 7 , R 8 , R 17 , R 18 , R 29 , R 30 and R 31 , Ar 1 ~Ar 4 In X 2 , X 3 , X 4 , X 12 , X 13 , X 14 , X 15 , X 22 , X 23 , X 24 and X 25 does not have a linear or branched alkyl group or a (poly)oxyalkylene group having 4 or more carbon atoms. 3 , X 13 and X 24 may be a group having a structure represented by the following formula (D).

[0073] [ka]

[0074] In formula (D), * indicates the connection site. X 31 ~X 35 Each independently represents a hydrogen atom or a substituent. 31 and X 35 At least one of the above is a linear or branched alkyl group (a) having 4 to 12 carbon atoms, or a group having a group (P) having a structure represented by the above general formula (P), and X 32 ~X 34 does not have a linear or branched alkyl group or a (poly)oxyalkylene group having 4 or more carbon atoms.

[0075] In compound (1), "L 1 , L 2 , Ar 1 ~Ar 4 has an alkyl group (a) or a group (P) at at least one of the predetermined positions" means that in compound (1), at least one of the predetermined positions is substituted with a substituent (substituent (E)) containing an alkyl group (a) or a group (P). In compound (1), the predetermined position substituted with a substituent (E) is a position that bonds toward the central squarylium ring.

[0076] Specifically, L 1 Or L 2 The given position in R 1 , R 5 , R 21 and R 27 When is NHCORa group, Ra (excluding group (P)), R 1 , R 5 , R 21 and R 27 NHSO 2 Rb in the case of the Rb group (excluding the group (P)), R 1 , R 5 , R 21 and R 27 Rf or Rg (excluding group (P)) when R is a NHPO(ORf)(ORg) group;2 , R 11 , R 12 , R 6 , R 15 , R 16 , R 26 and R 32 It is. 1 ~Ar 4 The predetermined position in X 1 , X 5 , X 11 , X 21 and X 27 And X 3 , X 13 and X 24 is a group having a structure represented by the above formula (D) (group (D)), 31 and X 35 It is.

[0077] That is, in compound (1), L 1 Or L 2 R 1 , R 5 , R 21 and R 27 When NHCORa is a group, Ra, NHSO 2 Rb in the case of the Rb group, Rf or Rg in the case of the NHPO(ORf)(ORg) group, R 2 , R 11 , R 12 , R 6 , R 15 , R 16 , R 26 and R 32 , Ar 1 ~Ar 4 X 1 , X 5 , X 11 , X 21 and X 27 And X 3 , X 13 and X 24 When X is a group (D), 31 and X 35 At least one of the groups is a substituent (E), provided that Ra, Rb, Rf and Rg are limited to the substituent (E) containing an alkyl group (a).

[0078] The substituent (E) is the same as the substituent (E) in the case of the above compound (T), including preferred embodiments. 2 , R 11 , R 12 , R 6 , R 15 , R 16 , R 26 or R 32 When R is a substituent (E), the substituent (E) is preferably an alkyl group (a) which may have -O- as a linking group or the group (P) itself. When R, Rb, Rf or Rg is a substituent (E), it is preferably an alkyl group (a). 1 Or L 2 When has a substituent (E), R 1 , R 5 , R 21 or R 27 is preferably NHCORa, where Ra is an alkyl group (a).

[0079] X 1 , X 5 , X 11 , X 21 and X 27 And X 3 , X 13 and X 24 When X is a group (D), 31 and X 35 is a substituent (E), the substituent (E) may be the alkyl group (a) or the group (P) itself, or the alkyl group (a) or the group (P) having a linking group. It is preferably the alkyl group (a) or the group (P) itself which may have -O- as a linking group.

[0080] Here, in addition to the above, compound (1) may optionally include L 1 Or L 2 R in 22 and R 28 , and Ar 1 ~Ar 4 X in 16 , X 17 and X 26 may have a substituent (E).

[0081] The number of the substituents (E) in the compound (1) is the same as that of the substituents (E) in the compound (T). The preferred position of the substituents (E) in the compound (1) will be described later in more specific compounds.

[0082] In the compound (1), when Ra, Rb, Rf and Rg are not the substituent (E), examples of them include an alkyl group having 1 to 3 carbon atoms, a linear or branched alkyl group having 4 or more carbon atoms, or an aryl group not having a polyoxyalkylene group. 2 , R 11 , R 12 , R 6 , R 15 , R 16 , R 22 , R 26 , R 28 , R 32 , X 1 , X 5 , X 11 , X 16 , X 17 , X 21 , X 26 , X 27 , X 31 and X 35 Examples of the aryl group include a hydrogen atom, an alkyl group or alkoxy group having 1 to 3 carbon atoms, a linear or branched alkyl group having 4 or more carbon atoms, and an aryl group not having a polyoxyalkylene group. Examples of the aryl group include a phenyl group, a tolyl group, and a xylyl group.

[0083] When Ra, Rb, Rf and Rg are not the substituent (E), they are preferably methyl groups. 2 , R 11 , R 12 , R 6 , R 15 , R 16 , R 22 , R 26 , R 28 and R 32 is preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and more preferably a hydrogen atom. 1 , X 5 , X11 , X 16 , X 17 , X 21 , X 26 , X 27 , X 31 and X 35 is preferably a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or a phenyl group, and more preferably a hydrogen atom, a methyl group, or a phenyl group.

[0084] In general formula (1), L 1 Or L 2 In R 3 , R 4 , R 13 , R 14 , R 23 , R 24 , R 25 , R 7 , R 8 , R 17 , R 18 , R 29 , R 30 and R 31 , Ar 1 ~Ar 4 In X 2 , X 3 , X 4 , X 12 , X 13 , X 14 , X 15 , X 22 , X 23 , X 24 and X 25 , and X 3 , X 13 and X 24 When X is a group (D), 32 ~X 34 represents an atom or group bonded to the main skeleton at a position other than the above-mentioned specified positions. These do not have a linear or branched alkyl group or polyoxyalkylene group having 4 or more carbon atoms.

[0085] L 1 Or L 2 In R 3 , R 4 , R 13 , R 14 , R 23 , R24 , R 25 , R 7 , R 8 , R 17 , R 18 , R 29 , R 30 and R 31 , Ar 1 ~Ar 4 In X 2 , X 3 , X 4 , X 12 , X 13 , X 14 , X 15 , X 22 , X 23 , X 24 and X 25 , and X 3 , X 13 and X 24 When X is a group (D), 32 ~X 34 Specific examples of R include a hydrogen atom, an alkyl group or alkoxy group having 1 to 3 carbon atoms, and an aryl group (however, the aryl group does not have a linear or branched alkyl group or a polyoxyalkylene group having 4 or more carbon atoms). 3 , R 4 , R 13 , R 14 , R 23 , R 24 , R 25 , R 7 , R 8 , R 17 , R 18 , R 29 , R 30 and R 31 is preferably a hydrogen atom, and X 2 , X 3 , X 4 , X 12 , X 13 , X 14 , X 15 , X 22 , X 23 , X 24 , X 25 and X 32 ~X 34 is preferably a hydrogen atom, a methyl group, or a phenyl group.

[0086] Compound (1) is preferably a compound having a symmetrical skeleton with respect to a central squarylium ring. Specific examples of such compounds include compounds (3) to (11) having structures represented by the following general formulas (3) to (11). The symbols in general formulas (3) to (11) represent the same categories as the symbols in general formula (1), including preferred embodiments.

[0087] Compounds (3) to (5) are the same as compound (1), except that L 1 is the group (L1), and L 2 Compounds (6) to (8) are compounds in which L 1 is the group (L2), and L 2 Compounds (9) to (11) are compounds in which L 1 is the group (L3), and L 2 In the embodiment of the present invention, from the viewpoints of emitting light in the long wavelength region of near infrared and being able to be incorporated into a component at a high concentration, compounds (3) to (5) are preferred, with compound (3) being more preferred.

[0088] Among the compounds (3), preferred compounds include compounds (1a) to (1d) having structures represented by the following general formulas (1a) to (1d). Among the compounds (1c) and (1d), the structure of a more preferred compound (1e) is shown in the following general formula (1e). The compounds (1a) to (1e) are novel compounds that have not been described in the literature. From the viewpoint of ease of production, it is preferred that the compounds (3) to (11) and (1a) to (1e) not only have a symmetrical skeleton with respect to the central squarylium ring, but also have symmetrical substituents.

[0089] As examples of compound (1), compounds (3) to (11) and compounds (1a) to (1e) will be explained below, but the present invention is not limited to these compounds.

[0090] Compound (3) having a structure represented by general formula (3) is compound (1), wherein L 1 is the group (L1), and L 2 is the group (L4), and Ar 1 ~Ar 4 are all groups (A).

[0091] [ka]

[0092] In compound (3), R 1 and R 5 is an OH group (the compound is also referred to as compound (31)), R 2 , R 6 and each X in the four groups (A) 1 and X 5 At least one of the groups is a substituent (E). Instead of or in addition to these, X 3 may be group (D). In compound (31), each X in the four groups (A) 1 and X 5 It is preferable that at least one of the groups is a substituent (E). Furthermore, it is preferable that one substituent (E) is present for each of the four groups (A).

[0093] That is, in the general formula (3), Ar 1 , Ar 2 , Ar 3 , Ar 4 Assuming that the groups (A) corresponding to the above are groups (A1), (A2), (A3) and (A4), respectively, the substituent (E) in the compound (31) is X of the group (A1). 1 Or X 5 , X in group (A2) 1 Or X 5 , X in group (A3) 1 Or X 5 and X in the group (A4) 1 Or X 5 In that case, R 2 , R 6, R 3 , R 4 , R 7 and R 8 is preferably a hydrogen atom. 1 and X 5 X that is not a substituent (E) 1 Or X 5 , X 2 , X 3 and X 4 is preferably a hydrogen atom, a methyl group, or a phenyl group. As the substituent (E) in the compound (31), the groups explained above can be applied without any particular limitation.

[0094] In compound (31), each X in the four groups (A) 1 and X 5 Examples of the compound in which at least one of the above is a substituent (E) include compound (1a) having a structure represented by the following general formula (1a) and compound (1c) having a structure represented by the following general formula (1c).

[0095] [ka]

[0096] In general formula (1a), each Rc independently represents a hydrogen atom or a substituent, and at least one of the four Rc is an alkyl group (a) or a group (P) which may have -O- as a linking group. The substituent (E) in compound (1a) is a group having a structure in which the alkyl group (a) or the group (P) is bonded to a 1,4-phenylene group which is a linking group. The substituent (E) may be a group having a 1,4-phenylene group and -O- in that order as linking groups, and the alkyl group (a) is bonded to the -O-.

[0097] Table I shows examples of compounds in which all four Rc in compound (1a) are the same alkyl group (a), alkyl group (a) having -O- as a linking group, or group (P). Table I lists the compound names and the types of Rc possessed by the compounds. In Table I, only abbreviations are shown for the compound names. Similarly, in the tables showing examples of other compounds shown below, only abbreviations are shown for the compound names.

[0098] In Table I, "n-butyl" refers to an n-butyl group, "n-pentyl" refers to an n-pentyl group, "n-hexyl" refers to an n-hexyl group, "n-heptyl" refers to an n-heptyl group, "n-octyl" refers to an n-octyl group, "n-nonyl" refers to an n-nonyl group, "n-decyl" refers to an n-decyl group, "n-undecyl" refers to an n-undecyl group, and "n-dodecyl" refers to an n-dodecyl group. An n-butyl group having -O- as a linking group is represented as "-On-butyl". Group (a1) is represented as (a1). The group (P) is represented by (P), for example, (P)(Q=-CH 2 -,n=2,R 51 =CH 3 ), the type of Q, the number of n, R 51 The type of is shown in parentheses after "(P)". However, when Q is a single bond, the notation of Q is omitted. The same applies to the descriptions in the tables for other compounds described later.

[0099] [Table 1]

[0100] [ka]

[0101] In the general formula (1c), each Rd independently represents a hydrogen atom or a substituent, and at least one of the four Rds is an alkyl group (a), an alkyl group (a) having -O- as a linking group, or a group (P). Each Xa independently represents an alkyl group or alkoxy group having 1 to 3 carbon atoms, or a substituted or unsubstituted phenyl group, and Xa bonded to the 4-position may be a group (D). In other cases, Xa does not have a linear or branched alkyl group or a (poly)oxyalkylene group having 4 or more carbon atoms as a substituent. m represents an integer of 0 to 4. The substituent (E) of the compound (1c) is the alkyl group (a) or the group (P) itself, or an alkyl group (a) having -O- as a linking group.

[0102] In compound (1c), in the four groups (A) bonded to the nitrogen atom, the hydrogen atoms at positions other than the position to which Rd is bonded may be substituted with a substituent Xa. When compound (1c) has a substituent Xa, it is preferable that the substituent Xa is bonded to a carbon atom other than the carbon atom adjacent to the carbon atom bonded to the nitrogen atom. Compound (1c) does not have a substituent Xa, or when it has a substituent Xa, the number of the substituent Xa is preferably 1 or 2, more preferably 1.

[0103] Table II shows an example of a compound (1c) in which all four groups (A) are the same. All Rd in the four groups (A) are the same alkyl group (a) or group (P). In Table II, the compound name, the type of Rd possessed by the compound, and the groups or atoms bonded to the carbon atom other than the carbon atom to which Rd is bonded in the group (A) are shown in order of X11, X12, X13, and X14, starting from the group bonded to the adjacent carbon atom on the opposite side of the nitrogen atom of the carbon atom to which Rd is bonded. In Table II, "-O-(a2)" indicates the group (a2) to which -O- is bonded as a linking group. In addition, "2,4,6-trimethoxyphenyl" indicates a 2,4,6-trimethoxyphenyl group, "Me" indicates a methyl group, and "Ph" indicates a phenyl group. The same applies to the descriptions in the tables relating to other compounds described later.

[0104] [Table 2]

[0105] In compound (3), R 1 and R 5 When is a NHCORa group (the compound is also referred to as compound (32)), Ra, R 2 , R 6 and each X in the four groups (A) 1 and X 5 At least one of the groups is a substituent (E). Instead of or in addition to these, X 3 may be a group (D). However, Ra is limited to a substituent (E) containing an alkyl group (a). In the compound (32), Ra and each X in the four groups (A) 1 and X 5 It is preferable that at least one of the groups is a substituent (E). Furthermore, it is preferable that one substituent (E) is present for each of the four groups (A).

[0106] That is, in the compound (32), as in the compound (31), the substituent (E) is X in the group (A1). 1 Or X 5 One as X in group (A2) 1 Or X 5 One as X in group (A3) 1 Or X 5 and one in group (A4) as X 1 Or X 5 In this case, it is preferable that Ra is an alkyl group (a) or a methyl group. 2 , R 6 , R 7 and R 8 is preferably a hydrogen atom. 1 and X 5 X that is not a substituent (E) 1 Or X 5 , X 2 , X 3 and X 4is preferably a hydrogen atom, a methyl group, or a phenyl group. As the substituent (E) in the compound (32), the groups explained above can be applied without any particular limitation.

[0107] In compound (32), each X in the four groups (A) 1 and X 5 Examples of the compound in which at least one of the above is a substituent (E) include compound (1b) having a structure represented by the following general formula (1b) and compound (1d) having a structure represented by the following general formula (1d).

[0108] [ka]

[0109] In the general formula (1b), each Ra independently represents a hydrocarbon group. Each Rc independently represents a hydrogen atom or a substituent. Either of the two Ra's represents a linear or branched alkyl group (a) having 4 to 12 carbon atoms, or at least one of the four Rc's represents a linear or branched alkyl group (a) having 4 to 12 carbon atoms which may have -O- as a linking group, or a group (P) having a structure represented by the general formula (P). Compound (1b) is a compound represented by the general formula (1) Ar 1 , Ar 2 , Ar 3 , Ar 4 The groups corresponding to the above are group (A), and the substituent (E) of group (A) is a group having a structure in which an alkyl group (a) or a group (P) is bonded to a 1,4-phenylene group as a linking group. The substituent (E) of group (A) may be a group having a 1,4-phenylene group and -O- in that order as linking groups, and an alkyl group (a) is bonded to the -O-. As Ra, an alkyl group (a) or an alkyl group having 1 to 3 carbon atoms is preferred.

[0110] In the compound (1b), two Ra are the same alkyl group, and all four Rc are the same alkyl group (a), alkyl group (a) having -O- as a linking group, or group (P), examples of the compound are shown in Table III. Table III lists the compound name and the type of Rc and Ra that the compound has.

[0111] [Table 3]

[0112] [ka]

[0113] In the general formula (1d), each Ra independently represents a hydrocarbon group. Each Re independently represents a hydrogen atom or a substituent. Each Xa independently represents an alkyl group or alkoxy group having 1 to 3 carbon atoms, or a substituted or unsubstituted phenyl group, and Xa bonded to the 4th position may be a group (D). In other cases, Xa does not have a linear or branched alkyl group or a (poly)oxyalkylene group having 4 or more carbon atoms as a substituent. m represents an integer of 0 to 4. However, in the general formula (1d), any of Ra represents an alkyl group (a), or at least one of the four Re is an alkyl group (a), an alkyl group (a) having -O- as a linking group, or a group (P), or a group (D) is bonded to the 4th position as Xa.

[0114] As described above, in compound (1d), in the four groups (A) bonded to the nitrogen atom, the hydrogen atoms at positions other than the position to which Re is bonded may be substituted with a substituent Xa. When compound (1d) has a substituent Xa, it is preferable that the substituent Xa is bonded to a carbon atom other than the carbon atom adjacent to the carbon atom bonded to the nitrogen atom. Compound (1d) does not have a substituent Xa, or when it has a substituent Xa, the number of the substituent Xa is preferably 1 or 2, and more preferably 1. In addition, when a group having a benzene ring skeleton that is the four groups (A) bonded to the nitrogen atom has Xa at the 4th position of the benzene ring, the Xa is preferably a group (D).

[0115] In compound (1d), Ra or Re corresponds to the substituent (E). Alternatively, Xa is bonded to the 4-position of the benzene ring having Re, and the Xa is a group (D). In compound (1d), only Ra may be a substituent (E), or only Re may be a substituent (E). Instead of Ra and Re being substituents (E), Xa may be bonded to the 4-position of the benzene ring having Re, and the Xa may be a group (D). Two or three of these may be a substituent (E) or have a substituent (E).

[0116] When Ra is a substituent (E), the substituent (E) is an alkyl group (a). When Ra is not a substituent (E), Ra is preferably an alkyl group having 1 to 3 carbon atoms. When Re is a substituent (E), the substituent (E) is an alkyl group (a), an alkyl group (a) having -O- as a linking group, or the group (P) itself. The group (D) is X 31 Or X 35 The substituent (E) in Re is preferably an alkyl group (a), an alkyl group (a) having -O- as a linking group, or the group (P) itself. 31 and X 35 When Re is not the substituent (E), it is preferably an alkyl group having 1 to 3 carbon atoms or a phenyl group. In the compound (1d), Re is preferably the substituent (E).

[0117] Table IV shows an example of a compound (1d) in which the two Ra and the four groups (A) are all the same. The two Ra are a methyl group, an ethyl group (shown as "Et" in the table), or an alkyl group (a). The Re in the four groups (A) are all the same alkyl group (a), group (P), methyl group, or phenyl group. Table IV shows the compound name, the type of Ra and Re that the compound has, and the groups or atoms bonded to the carbon atom other than the carbon atom to which Re is bonded in the group (A), as X11, X12, X13, and X14, in order from the group bonded to the adjacent carbon atom on the opposite side to the nitrogen atom of the carbon atom to which Re is bonded. X12 corresponds to the 4th position in the benzene ring of the group (A). "(D)-1" in Table IV shows a group having a structure represented by the following formula.

[0118] [ka]

[0119] [Table 4]

[0120] In the compounds (1c) and (1d), it is preferable that the 4-position of the benzene ring of the four groups (A) bonded to the nitrogen atom does not have a substituent. An example of such a compound is compound (1e) having a structure represented by the following general formula (1e).

[0121] [ka]

[0122] In the general formula (1e), Ya and Yb each independently represent an OH group or an NHCORa group (Ra represents a hydrocarbon group). Each Re each independently represents a hydrogen atom or a substituent. Each Xa each independently represents an alkyl group or an alkoxy group having 1 to 3 carbon atoms, or a substituted or unsubstituted phenyl group. However, Xa does not have a linear or branched alkyl group or a (poly)oxyalkylene group having 4 or more carbon atoms as a substituent. m represents an integer of 0 to 3. However, any of Ra represents an alkyl group (a), or at least one of the four Re represents an alkyl group (a), an alkyl group (a) having -O- as a linking group, or a group (P).

[0123] The same explanations can be applied to each group in compound (1e) as in the above compounds (1c) and (1d), except that the 4-position on the benzene ring of the four groups (A) bonded to the nitrogen atom does not have a substituent.

[0124] Specific examples of the compounds classified as compound (1e) include compounds (1c)-1 to (1c)-38 and compound (1c)-40 among the compounds shown in Table II above. Furthermore, examples of the compounds classified as compound (1e) include compounds (1c)-1 to (1d)-31, compound (1d)-33, compound (1d)-35, compound (1d)-37, compound (1d)-39 and compound (1d)-41 among the compounds shown in Table IV above.

[0125] Compound (4) having a structure represented by general formula (4) is a compound (1) having L 1 is the group (L1), and L 2 is the group (L4), and Ar 1 ~Ar 4 are all groups (B).

[0126] [ka]

[0127] In compound (4), R 1 and R 5 is an OH group, R 2 , R 6 and each X in the four groups (B) 11 At least one of the substituents (E) is a substituent. Alternatively, or in addition to these, X 13 may be a group (D). 16 and X 17 can be optionally substituted with a substituent (E). In the following description, in the compound (4) having the structure represented by the general formula (4), R 1 and R 5 The compound in which is an OH group is called compound (41).

[0128] In compound (41), each X in the four groups (B) 11 It is preferable that at least one of the groups is a substituent (E). Furthermore, it is preferable that one substituent (E) is present in each of the four groups (B).

[0129] That is, in the general formula (4), Ar 1 , Ar 2 , Ar 3 , Ar 4 Assuming that the groups (B) corresponding to the above are groups (B1), (B2), (B3) and (B4), respectively, the substituent (E) in the compound (41) is X of the group (B1). 11 , X in group (B2) 11 , X in group (B3) 11 and X in the group (B4) 11 In that case, R 2 , R 6 , R 7 and R 8 is preferably a hydrogen atom. 12 , X 13 , X 14 , X 15 , X 16 and X 17 is preferably a hydrogen atom, a methyl group, or a phenyl group. As the substituent (E) in the compound (41), the groups explained above can be applied without any particular limitation.

[0130] In the compound (4), R in the general formula (4) 1 and R 5 is the NHCORa group, NHSO 2 When it is an Rb group or an NHPO(ORf)(ORg) group, the compound is also called compound (42). In compound (42), Ra, Rb, Rf, Rg, R 2 , R 6 and each X in the four groups (B) 11 At least one of the substituents (E) is a substituent. Alternatively, or in addition to these, X 13 may be a group (D). 16 and X 17 can be optionally substituted with a substituent (E), provided that Ra, Rb, Rf and Rg are limited to the substituent (E) containing an alkyl group (a).

[0131] In the compound (42), Ra, Rb, Rf and Rg, each X in the four groups (B) 11 It is preferable that at least one of the groups (B) is a substituent (E). When four groups (B) have a substituent (E), it is preferable that one substituent (E) is present in each of the four groups (B).

[0132] Examples of Ra, Rb, Rf, and Rg that are not the substituents (E) include alkyl groups having 1 to 3 carbon atoms, and aryl groups such as a phenyl group, a tolyl group, and a xylyl group. 2 and R 6 Also, R 3 , R 4 , R 7 and R 8 is preferably a hydrogen atom. 12 , X 13 , X 14 , X 15 , X 16 and X 17 is preferably a hydrogen atom, a methyl group, or a phenyl group. As the substituent (E) in the compound (42), the groups explained above can be applied without any particular limitation.

[0133] Examples of compound (4) are shown in Table V. In the table, "tolyl" represents a tolyl group.

[0134] [Table 5]

[0135] Compound (5) having a structure represented by general formula (5) is a compound (1) having L 1 is the group (L1), and L 2 is the group (L4), and Ar 1 ~Ar 4 are all groups (C).

[0136] [ka]

[0137] In compound (5), R in general formula (5) 1 and R 5 When R is an OH group, the compound is also called compound (51). 2 , R 6 and each X in the four groups (C) 21 and X 27 At least one of the substituents (E) is a substituent. Alternatively, or in addition to these, X 24 may be a group (D). 26 can be optionally substituted with a substituent (E). In compound (51), each of X in the four groups (C) 21 and X 27 It is preferable that at least one of the groups is a substituent (E). Furthermore, it is preferable that one substituent (E) is present in each of the four groups (C).

[0138] That is, in the general formula (5), Ar 1 , Ar 2 , Ar 3 , Ar 4 Assuming that the groups (C) corresponding to the above are groups (C1), (C2), (C3) and (C4), respectively, the substituent (E) in the compound (51) is X of the group (C1). 21 Or X 27 , X in group (C2) 21 Or X 27 , X in group (C3) 21 Or X 27 and X in the group (C4) 21 Or X 27 In that case, R 2 and R 6 Also, R 3 , R 4 , R 7 and R 8 is preferably a hydrogen atom. 21 and X 27 X that is not a substituent (E) 21 and X27 , and X 22 , X 23 , X 24 , X 25 and X 26 is preferably a hydrogen atom, a methyl group, or a phenyl group. As the substituent (E) in the compound (51), the groups explained above can be applied without any particular limitation.

[0139] In compound (5), R in general formula (5) 1 and R 5 is the NHCORa group, NHSO 2 When it is an Rb group or an NHPO(ORf)(ORg) group, the compound is also called compound (52). In compound (52), Ra, Rb, Rf, Rg, R 2 , R 6 and each X in the four groups (C) 21 and X 27 At least one of the substituents (E) is a substituent. Alternatively, or in addition to these, X 24 may be a group (D). 26 can be optionally substituted with a substituent (E), provided that Ra, Rb, Rf and Rg are limited to the substituent (E) containing an alkyl group (a).

[0140] In the compound (52), Ra, Rb, Rf and Rg, each X in the four groups (C) 21 and X 27 It is preferable that at least one of the groups (C) is a substituent (E). When four groups (C) have a substituent (E), it is preferable that one substituent (E) is present in each of the four groups (C).

[0141] Examples of Ra, Rb, Rf, and Rg that are not the substituents (E) include alkyl groups having 1 to 3 carbon atoms, and aryl groups such as a phenyl group, a tolyl group, and a xylyl group. 2 and R 6 Also, R 3 , R 4 , R 7 and R 8is preferably a hydrogen atom. 21 and X 27 X that is not a substituent (E) 21 and X 27 , and X 22 , X 23 , X 24 , X 25 and X 26 is preferably a hydrogen atom, a methyl group, or a phenyl group. As the substituent (E) in the compound (52), the groups explained above can be applied without any particular limitation.

[0142] Examples of compound (5) are shown in Table VI.

[0143] [Table 6]

[0144] Compounds (6) to (8) having structures represented by general formulas (6) to (8) are compounds in which L 1 is the group (L2), and L 2 Compound (6) is a compound in which Ar 1 ~Ar 4 are both groups (A), and compound (7) is a compound represented by the formula (A). 1 ~Ar 4 are both groups (B), and compound (8) is a compound represented by the formula (1). 1 ~Ar 4 are all groups (C).

[0145] [ka]

[0146] In the compounds (6) to (8), Ar in the general formula (1) 1 ~Ar 4 The explanation for compounds (3) to (5) can be applied to the portion corresponding to the compound (6) to (8). 1 is the group (L2), and L2 In the compound (6), R in the general formula (6) is a group (L5). 1 and R 5 is an OH group, the compound is also called compound (61). 1 and R 5 When R in the general formula (8) is an OH group, the compound is also called compound (71). 1 and R 5 When is an OH group, the compound is also called compound (81).

[0147] In compound (61), R 2 , R 6 , R 11 , R 12 , R 15 , R 16 , each X in the four groups (A) 1 and X 5 At least one of R is a substituent (E). 2 , R 6 , R 11 , R 12 , R 15 , R 16 and each X in the four groups (B) 11 At least one of R is a substituent (E). 2 , R 6 , R 11 , R 12 , R 15 , R 16 , each X in the four groups (C) 21 and X 27 At least one of the groups is a substituent (E).

[0148] Alternatively or additionally, in compound (61), X 3 However, in compound (71), X 13 However, in compound (81), X 24 may each be a group (D). In the compound (71), each X 16 and X 17can be optionally substituted with a substituent (E). In addition, in compound (81), each X 26 can be optionally substituted with a substituent (E). In the compounds (61), (71) and (81), it is preferable that the substituent (E) is present in each of the four groups (A), (B) and (C).

[0149] In the compounds (61), (71) and (81), R other than the substituent (E) 2 , R 6 , R 11 , R 12 , R 15 and R 16 Also, R 3 , R 4 , R 7 , R 8 , R 13 , R 14 , R 17 and R 18 is preferably a hydrogen atom or a methyl group. In compound (61), X 1 ~X 5 X is not a substituent (E) or a group (D). 1 ~X 5 is preferably a hydrogen atom, a methyl group, or a phenyl group. In the compound (71), X 11 ~X 17 X is not a substituent (E) or a group (D). 11 ~X 17 is preferably a hydrogen atom, a methyl group, or a phenyl group. In the compound (81), X 21 ~X 27 X is not a substituent (E) or a group (D). 21 ~X 27 is preferably a hydrogen atom, a methyl group or a phenyl group.

[0150] In the compound (6), R in the general formula (6) 1 and R 5 is the NHCORa group, NHSO 2When R is an Rb group or an NHPO(ORf)(ORg) group, the compound is also called compound (62). 1 and R 5 is the NHCORa group, NHSO 2 When R is an Rb group or an NHPO(ORf)(ORg) group, the compound is also called compound (72). 1 and R 5 is the NHCORa group, NHSO 2 When it is an Rb group or an NHPO(ORf)(ORg) group, the compound is also referred to as compound (82).

[0151] In compound (62), Ra, Rb, Rf, Rg, R 2 , R 6 , R 11 , R 12 , R 15 , R 16 , each X in the four groups (A) 1 and X 5 At least one of Ra, Rb, Rf, Rg, and R 2 , R 6 , R 11 , R 12 , R 15 , R 16 and each X in the four groups (B) 11 At least one of Ra, Rb, Rf, Rg, and R 2 , R 6 , R 11 , R 12 , R 15 , R 16 , each X in the four groups (C) 21 and X 27 At least one of the groups is a substituent (E).

[0152] Alternatively or additionally, in compound (62), X 3 However, in compound (72), X 13 However, in compound (82), X 24may each be a group (D). In the compound (72), each X 16 and X 17 can be optionally substituted with a substituent (E). In addition, in compound (82), each X 26 can be optionally substituted with a substituent (E), provided that Ra, Rb, Rf and Rg are limited to the substituent (E) containing an alkyl group (a).

[0153] In the compounds (62), (72) and (82), it is preferable that the substituent (E) is present in each of the four groups (A), (B) and (C).

[0154] In the compounds (62), (72) and (82), R other than the substituent (E) 2 , R 6 , R 11 , R 12 , R 15 and R 16 Also, R 3 , R 4 , R 7 , R 8 , R 13 , R 14 , R 17 and R 18 In compound (62), X in four groups (A) is preferably a hydrogen atom. 1 ~X 5 X is not a substituent (E) or a group (D). 1 ~X 5 is preferably a hydrogen atom, a methyl group, or a phenyl group. In the compound (72), X 11 ~X 17 X is not a substituent (E) or a group (D). 11 ~X 17 is preferably a hydrogen atom, a methyl group, or a phenyl group. In the compound (82), X 21 ~X 27 X is not a substituent (E) or a group (D). 21 ~X 27 is preferably a hydrogen atom, a methyl group or a phenyl group.

[0155] Specific examples of compound (6), compound (7) and compound (8) are shown in Tables VII, VIII and IX, respectively. In Table IX, "-O-(a4)" means that -O- is bonded as a linking group. The group (a4) is shown.

[0156] [Table 7]

[0157] [Table 8]

[0158] [Table 9]

[0159] Compounds (9) to (11) having structures represented by general formulas (9) to (11) are the same as those in compound (1), except that L 1 is the group (L3), and L 2 Compound (9) is a compound in which Ar 1 ~Ar 4 are both groups (A), and compound (10) is a compound represented by the formula (A). 1 ~Ar 4 are both groups (B), and compound (11) is a compound represented by the formula (11) 1 ~Ar 4 are all groups (C).

[0160] [ka]

[0161] In the compounds (9) to (11), Ar 1 ~Ar 4 The explanation for compounds (3) to (5) can be applied to the portion corresponding to the compound (9) to (11). 1 is the group (L3), and L 2In the compound (9), R in the general formula (9) is a group (L6). 21 and R 27 is an OH group, the compound is also called compound (91). 21 and R 27 When R in the general formula (11) is an OH group, the compound is also called compound (101). 21 and R 27 When is an OH group, the compound is also called compound (111).

[0162] In compound (91), R 26 , R 32 , each X in the four groups (A) 1 and X 5 At least one of R is a substituent (E). 26 , R 32 and each X in the four groups (B) 11 At least one of R is a substituent (E). 26 , R 32 , each X in the four groups (C) 21 and X 27 At least one of the groups is a substituent (E).

[0163] Alternatively or additionally, in compound (91), X 3 However, in compound (101), X 13 However, in compound (111), X 24 may each be a group (D). In the compound (91), R 22 and R 28 can be optionally substituted with the substituent (E). In compound (101), R 22 , R 28 , each X 16 and X 17 can be optionally substituted with a substituent (E). In compound (111), R 22 , R 28 and each X 26can be optionally substituted with a substituent (E). In the compounds (91), (101) and (111), it is preferable that the substituent (E) is present in each of the four groups (A), (B) and (C).

[0164] In the compounds (91), (101) and (111), R which is not a substituent (E) 22 ~R 26 , R 28 ~R 32 is preferably a hydrogen atom or a methyl group. In compound (91), X 1 ~X 5 X is not a substituent (E) or a group (D). 1 ~X 5 is preferably a hydrogen atom, a methyl group, or a phenyl group. 11 ~X 17 X is not a substituent (E) or a group (D). 11 ~X 17 is preferably a hydrogen atom, a methyl group, or a phenyl group. In the compound (111), X 21 ~X 27 X is not a substituent (E) or a group (D). 21 ~X 27 is preferably a hydrogen atom, a methyl group or a phenyl group.

[0165] In the compound (9), R in the general formula (9) 21 and R 27 is the NHCORa group, NHSO 2 When R is an Rb group or an NHPO(ORf)(ORg) group, the compound is also called compound (92). 21 and R 27 is the NHCORa group, NHSO 2 When R is an Rb group or an NHPO(ORf)(ORg) group, the compound is also called compound (102). 21 and R 27 is the NHCORa group, NHSO 2When it is an Rb group or an NHPO(ORf)(ORg) group, the compound is also referred to as compound (112).

[0166] In compound (92), Ra, Rb, Rf, Rg, R 22 , R 26 , R 28 , R 32 , each X in the four groups (A) 1 and X 5 At least one of Ra, Rb, Rf, Rg, and R 22 , R 26 , R 28 , R 32 and each X in the four groups (B) 11 At least one of Ra, Rb, Rf, Rg, and R 22 , R 26 , R 28 , R 32 , each X in the four groups (C) 21 and X 27 At least one of the groups is a substituent (E).

[0167] Alternatively or additionally, in compound (92), X 3 However, in compound (102), X 13 However, in compound (112), X 24 may each be a group (D). In the compound (92), R 22 and R 28 can be optionally substituted with the substituent (E). In compound (102), R 22 , R 28 , each X 16 and X 17 can be optionally substituted with a substituent (E). In compound (112), R 22 , R 28 and each X 26 can be optionally substituted with a substituent (E), provided that Ra, Rb, Rf and Rg are limited to the substituent (E) containing an alkyl group (a).

[0168] In the compounds (92), (102) and (112), it is preferable that the substituent (E) is present in each of the four groups (A), (B) and (C).

[0169] In the compounds (92), (102) and (112), R which is not a substituent (E) 22 ~R 26 , R 28 ~R 32 In compound (92), X in four groups (A) is preferably a hydrogen atom. 1 ~X 5 X is not a substituent (E) or a group (D). 1 ~X 5 is preferably a hydrogen atom, a methyl group, or a phenyl group. In the compound (102), X 11 ~X 17 X is not a substituent (E) or a group (D). 11 ~X 17 is preferably a hydrogen atom, a methyl group, or a phenyl group. In the compound (112), X 21 ~X 27 X is not a substituent (E) or a group (D). 21 ~X 27 is preferably a hydrogen atom, a methyl group or a phenyl group.

[0170] Specific examples of compound (9), compound (10) and compound (11) are shown in Tables X, XI and XII, respectively.

[0171] [Table 10]

[0172] [Table 11]

[0173] [Table 12]

[0174] The above is an example of compound (1). Among compounds (1), as described above, compounds (1a) to (1d) are preferred. As compound (1a), compounds (1a)-1, (1a)-12 and (1a)-20 are preferred from the viewpoint of further exerting the effects of the present invention.

[0175] Similarly, as compound (1b), compound (1b)-14 and compound (1b)-18 are preferred. As compound (1c), compound (1c)-9, compound (1c)-12, compound (1c)-31 and compound (1c)-42 are preferred. As compound (1d), compound (1d)-1, compound (1d)-14, compound (1d)-36, compound (1d)-39 and compound (1d)-40 are preferred.

[0176] As the compound (4), the compounds (4)-5, (4)-6, (4)-9 and (4)-10 are preferable. As the compound (5), the compounds (5)-3, (5)-4 and (5)-9 are preferable.

[0177] As the compound (6), the compound (6)-3, the compound (6)-4 and the compound (6)-8 are preferable. As the compound (7), the compound (7)-4, the compound (7)-5, the compound (7)-6 and the compound (7)-8 are preferable. As the compound (8), the compound (8)-3, the compound (8)-4 and the compound (8)-10 are preferable.

[0178] As the compound (9), the compound (9)-4, the compound (9)-6, the compound (9)-7 and the compound (9)-10 are preferable. As the compound (10), the compound (10)-2, the compound (10)-4, the compound (10)-5 and the compound (10)-8 are preferable. As the compound (11), the compound (11)-2, the compound (11)-3 and the compound (11)-7 are preferable.

[0179] [Synthesis method] Compound (1) according to the present invention can be synthesized by referring to the methods described in, for example, Chemistry of Materials, Vol. 23, p. 4789 (2011) and The Journal of Physical Chemistry, Vol. 91, p. 5184 (1987), or the methods described in the references described in these documents. As an example, the synthesis examples of exemplary compounds (1a)-1, (1b)-1, (1c)-1, and (1d)-1 are shown below.

[0180] <Synthesis of exemplary compound (1a)-1> Compound (1a)-1 can be synthesized, for example, by the following scheme (A). In the following explanation, the amount of the compound used, the treatment temperature, the time, etc. are examples and can be appropriately adjusted. The same applies to the synthesis of other compounds.

[0181] [ka]

[0182] (Step 1) m-Anisidine (reagent 1-1), 1.5 equivalents of 1-bromo-2-iodobenzene (reagent 1-2), 5% tris(dibenzylideneacetone)dipalladium(0), 10% tris-tert-butylphosphonium tetrafluoroborate, and 3 equivalents of sodium tert-butoxide are refluxed in 30 mL of xylene. This is extracted, concentrated, and then purified by silica gel column chromatography to obtain intermediate 1-1.

[0183] (Step 2) Intermediate 1-1, 1.1 equivalents of 4-butylphenylboronic acid (reagent 1-3), 5% bis(dibenzylideneacetone)palladium(0), 10% 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl, and 6 equivalents of potassium phosphate are heated in a 10:1 mixture of 1,2-dimethoxyethane and water. This is extracted, concentrated, and then purified by silica gel chromatography to obtain intermediate 1-2.

[0184] (Step 3) Next, intermediate 1-2 is cooled to 0°C in methylene chloride, and a 1M solution of boron tribromide in methylene chloride is added dropwise using a dropping funnel and stirred for 1 hour at 0°C. Then, the mixture is returned to room temperature and stirred for 1 hour, after which water is added for extraction, concentration, and purification by silica gel chromatography to obtain intermediate 1-3.

[0185] (Step 4) Finally, the intermediate 1-3 and 3,4-dihydroxy-3-cyclobutene-1,2-dione obtained are heated in a 1:1 mixed solvent of toluene and butanol for 6 hours. After cooling, the green crystals that fall are collected by filtration to obtain compound (1a)-1. The structure of the compound is confirmed by mass spectrometry (MS) and 1 This can be confirmed by H-NMR. 1 The H-NMR spectrum (400 MHz, measurement solvent CDCl3) is shown.

[0186] <Synthesis of exemplary compound (1b)-1> Compound (1b)-1 can be synthesized, for example, according to the following scheme (B).

[0187] [ka]

[0188] (Step 1) 3-Nitroaniline (Reagent 2-1), 1-bromo-2-iodobenzene (Reagent 2-2), tris(dibenzylideneacetone)dipalladium(0), tris-tert-butylphosphonium tetrafluoroborate, sodium tert-butoxide, and reflux in 30 mL of xylene. This is extracted, concentrated, and then purified by silica gel column chromatography to obtain intermediate 2-1.

[0189] (Step 2) Intermediate 2-1, 4-butylphenylboronic acid (reagent 2-3), bis(dibenzylideneacetone)palladium(0), 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl, and potassium phosphate are heated in a 4:1 mixture of 1,2-dimethoxyethane and water. This is extracted, concentrated, and then purified by silica gel chromatography to obtain intermediate 2-2.

[0190] (Step 3) Next, add Pd-C (10%) catalyst to the intermediate 2-2 in a 1:1 ethanol-tetrahydrofuran mixed solvent and perform catalytic reduction with hydrogen. After 6 hours, confirm that the reaction is complete, remove Pd-C by filtration through Celite, and concentrate to obtain intermediate 2-3.

[0191] (Step 4) Next, intermediate 2-3 is reacted with valeryl chloride (reagent 2-4) to obtain intermediate 2-4.

[0192] (Step 5) Finally, the intermediate 2-4 and 3,4-dihydroxy-3-cyclobutene-1,2-dione (reagent 2-5) obtained are heated in a 1:1 toluene-butanol mixed solvent for 6 hours. After cooling, the mixture is extracted, concentrated, and purified by silica gel column chromatography to obtain compound (1b)-1. The structure of the compound is confirmed by MS and 1 This can be confirmed by H-NMR.

[0193] <Synthesis of exemplary compound (1c)-1> Compound (1c)-1 can be synthesized, for example, according to the following scheme (C).

[0194] [ka]

[0195] (Step 1) 2-Butylaniline (reagent 3-1), 3-bromoanisole (reagent 3-2) 2.1 equivalents, tris(dibenzylideneacetone)dipalladium(0) 0.05 equivalents, tris-tert-butylphosphonium tetrafluoroborate 0.15 equivalents, tert-butoxy sodium 1.5 equivalents, in toluene 20 mL, stir at 100° C. for 6 hours. Extract and concentrate, then purify by silica gel column chromatography to obtain intermediate 3-1.

[0196] (Step 1a) Separately, dissolve 3 equivalents of p-toluenesulfonic acid in 50 mL of acetonitrile for reagent 3-1, cool to 0°C, add dropwise a solution of 2 equivalents of sodium nitrite and 2.5 equivalents of potassium iodide in 20 mL of water over 30 minutes, and then stir at room temperature for 1 hour. This is extracted and purified by silica gel column chromatography to obtain intermediate 3-2.

[0197] (Step 2) Intermediate 3-1 is reacted with 1.3 equivalents of intermediate 3-2, 0.03 equivalents of tris(dibenzylideneacetone)dipalladium(0), 0.1 equivalents of tris-tert-butylphosphonium tetrafluoroborate, 1.5 equivalents of sodium tert-butoxide, and 30 mL of xylene at 135° C. for 16 hours. The mixture is extracted and concentrated, and then purified by silica gel column chromatography to obtain intermediate 3-3.

[0198] (Step 3) Dissolve intermediate 3-3 in 30 mL of dehydrated methylene chloride and cool to 0°C. Add 2 equivalents of a methylene chloride solution of boron tribromide (1 M) dropwise, then stir at room temperature for 8 hours. Extract, concentrate, and purify by silica gel column chromatography to obtain intermediate 3-4.

[0199] (Step 4) Finally, the obtained intermediate 3-4 and 0.4 equivalents of 3,4-dihydroxy-3-cyclobutene-1,2-dione (reagent 3-3) are heated in a 1:2 toluene-butanol mixed solvent at 115°C for 16 hours. After cooling, extraction, concentration, and purification by silica gel column chromatography are performed to obtain compound (1c)-1. The structure of the compound is confirmed by MS and 1 This can be confirmed by H-NMR. 1 The H-NMR spectrum (400 MHz, measurement solvent CDCl3) is shown.

[0200] <Synthesis of exemplary compound (1d)-1> Compound (1d)-1 can be synthesized, for example, according to the following scheme (D).

[0201] [ka]

[0202] (Step 1) o-Toluidine (reagent 4-1) is reacted with 1 equivalent of 2-bromotoluene (reagent 4-2), 0.03 equivalent of [1,1'-bis(diphenylphosphino)ferrocene]palladium(II) dichloride·methylene chloride adduct, 2 equivalents of sodium tert-butoxide, and 200 mL of toluene at 100°C for 6 hours. This is extracted and concentrated, and then purified by silica gel column chromatography to obtain intermediate 4-1.

[0203] (Step 2) Intermediate 4-1 is reacted with 1.2 equivalents of 3-bromonitrobenzene (reagent 4-3), 0.03 equivalents of tris(dibenzylideneacetone)dipalladium(0), 0.05 equivalents of tris-tert-butylphosphonium tetrafluoroborate, and 2 equivalents of sodium tert-butoxide in 150 mL of xylene at 130° C. for 16 hours. This is extracted and concentrated, and then purified by silica gel column chromatography to obtain intermediate 4-2.

[0204] (Step 3) Next, this intermediate 4-2 is dissolved in 250 mL of ethyl acetate and subjected to catalytic reduction reaction with hydrogen in the presence of 5 g of Pd-C (10%) catalyst at room temperature for 16 hours. The Pd-C is removed by filtration through Celite, and the mixture is concentrated to obtain intermediate 4-3.

[0205] (Step 4) Next, dissolve this intermediate 4-3 in 150 mL of methylene chloride, add 1.5 equivalents of triethylamine, cool to 0°C, add 1.2 equivalents of valeryl chloride (reagent 4-4), and stir at room temperature for 16 hours. After extraction and concentration, purify by silica gel column chromatography to obtain intermediate 4-4.

[0206] (Step 5) Finally, the intermediate 4-4 and 3,4-dihydroxy-3-cyclobutene-1,2-dione (reagent 4-5) obtained are heated in a 1:1 toluene-butanol mixed solvent for 6 hours. After cooling, the mixture is extracted, concentrated, and purified by silica gel column chromatography to obtain compound (1d)-1. The structure of the compound is confirmed by MS and 1 This can be confirmed by H-NMR. 1 The H-NMR spectrum (400 MHz, measurement solvent CDCl3) is shown.

[0207] <Optical properties of compound (T)> Compound (T) is a compound that absorbs red light and emits near-infrared fluorescent light. Among compounds (T), compound (1) is preferred in terms of its optical properties. The emission spectrum of compound (T) can be confirmed by the following method.

[0208] Compound (T) was dissolved in toluene for 10 -6 The emission spectrum of this sample is measured at room temperature (300 K) using a spectrofluorophotometer (Hitachi High-Technos Corporation, F7000).

[0209] Compound (T) is a near-infrared light-emitting compound that exhibits fluorescent emission with a maximum emission wavelength (wavelength at which the emission intensity is maximum; also referred to as "emission peak wavelength") exceeding 700 nm in the resulting emission spectrum. The emission peak wavelength of compound (T) is preferably 700 nm or more, more preferably 710 nm or more.

[0210] The absorption peak wavelength is 10 -6 The absorbance spectrum of this sample is measured at room temperature (300K). A spectrophotometer (Hitachi High-Technos Corporation, F7000) is used to measure the absorbance spectrum.

[0211] Furthermore, the luminescence quantum yield of a solution in which compound (T) is dissolved in toluene or the like, or the luminescence quantum yield of a thin film in which compound (T) is dispersed in a matrix material, can be measured, for example, by the following method and used for evaluation.

[0212] The luminescence quantum yield Φ (%) is expressed as the ratio of the number of absorbed photons to the number of emitted photons. If all excited molecules return to the ground state by fluorescence, the luminescence quantum yield Φ (%) will be 100%, but it will not be 100% if non-radiative deactivation occurs.

[0213] Nonradiative deactivation is a transition that returns to the ground state without emitting fluorescence. In addition to relaxation to the triplet state due to intersystem crossing, there are also internal conversions in which the energy of the electronic state is converted into vibrational energy or the like, which ultimately becomes thermal energy, and energy transfers in which energy is transferred to other molecules.

[0214] If the rate constants for the fluorescent transition and nonradiative transition of a molecule in an excited state are Kf and Knr, respectively, the luminescence quantum yield Φ (%) is expressed by the following equation. Φ(%)=(Kf / (Kf+Knr))×100

[0215] Therefore, in order to improve the luminescence quantum yield, it is necessary to suppress the non-radiative deactivation of molecules in an excited state.

[0216] [Light-emitting components] The light-emitting member of the present invention contains the above-mentioned compound (T), and thus has an emission peak in the long wavelength region of near infrared light and can achieve a high light emission quantum yield. Among the compounds (T), compound (1) is preferred because it can achieve the above characteristics at a higher level. Examples of the light-emitting member of the present invention include a light-emitting thin film and a light-emitting particle. The light-emitting thin film can also be used as a wavelength conversion film.

[0217] The light-emitting member of the present invention can be used for bioimaging, for example, as a label in biology and medicine as a dye for a new type of fluorescent probe. In addition, compound (T), which emits fluorescence as excess energy when excited electrons return to the ground state, has a wavelength conversion ability due to the difference in absorption and emission energy, and can be used as a color conversion filter in dyes, pigments, optical filters, agricultural films, etc.

[0218] Luminescent thin film The luminescent thin film, which is an embodiment of the luminescent member of the present invention, is characterized by containing a compound (T). The luminescent thin film can be produced by forming a composition obtained by adding a matrix material to compound (T) for film formation stability, etc., or a composition obtained by further adding a solvent to this, into a thin film.

[0219] Examples of the matrix material include (meth)acrylate resins, polyester resins, polyamide resins, polyimide resins, polystyrene resins, polyepoxy resins, polyester resins, amino resins, fluorine resins, phenol resins, polyurethane resins, polyethylene resins, polypropylene resins, polyvinyl chloride resins, polyvinyl alcohol resins, polyether resins, polyether ketone resins, polyphenylene sulfide resins, polycarbonate resins, and aramid resins, and are preferably polystyrene resins, polyethylene resins, polypropylene resins, polyvinyl chloride resins, and the like. Copolymers of these resins are also preferred.

[0220] A (meth)acrylate resin is synthesized by homopolymerizing or copolymerizing various methacrylate or acrylate monomers, and a desired (meth)acrylate resin can be obtained by changing the monomer type and monomer composition ratio. In the present invention, a (meth)acrylate monomer can be copolymerized with a copolymerizable monomer having an unsaturated double bond other than a (meth)acrylate monomer, and further, a poly(meth)acrylate resin can be mixed with a plurality of other resins.

[0221] Examples of monomer components forming the (meth)acrylate resin used in the present invention include (meth)acrylic acid, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, isopropyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, stearyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, acetoacetoxyethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, di(ethylene glycol) ethyl ether (meth)acrylate, ethylene glycol methyl ether (meth)acrylate, isobornyl (meth)acrylate, ethyltrimethylammonium chloride (meth)acrylate, trifluoroethyl (meth)acrylate, octafluoropentyl (meth)acrylate, 2-acetamidomethyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 2-dimethylamino ... ethylaminoethyl (meth)acrylate, 3-trimethoxysilanepropyl (meth)acrylate, benzyl (meth)acrylate, tridecyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, dodecyl (meth)acrylate, octadecyl (meth)acrylate, 2-diethylaminoethyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, phenyl (meth)acrylate Examples of the acrylates include ethyl (meth)acrylate and glycidyl (meth)acrylate, and preferred are (meth)acrylic acid, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, stearyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, acetoacetoxyethyl (meth)acrylate, benzyl (meth)acrylate, tridecyl (meth)acrylate, dodecyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate.

[0222] The polystyrene resin includes a homopolymer of a styrene monomer, or a random copolymer, block copolymer, or graft copolymer obtained by copolymerizing a monomer having another unsaturated double bond copolymerizable with the styrene monomer. In addition, a blend or polymer alloy obtained by blending such a polymer with another polymer is also included. Examples of the styrene monomer include styrene, α-methylstyrene, α-ethylstyrene, α-methylstyrene-p-methylstyrene, o-methylstyrene, m-methylstyrene, and p-methylstyrene, and other nuclear alkyl-substituted styrenes, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, p-bromostyrene, dichlorostyrene, dibromostyrene, trichlorostyrene, and tribromostyrene, and other nuclear halogenated styrenes. Among these, styrene and α-methylstyrene are preferred.

[0223] Examples of resins used in the present invention by homopolymerizing or copolymerizing these include copolymer resins such as benzyl methacrylate / ethyl acrylate or butyl acrylate, copolymer resins such as methyl methacrylate / 2-ethylhexyl methacrylate, copolymer resins such as methyl methacrylate / methacrylic acid / stearyl methacrylate / acetoacetoxyethyl methacrylate, copolymer resins of styrene / acetoacetoxyethyl methacrylate / stearyl methacrylate, copolymer resins of styrene / 2-hydroxyethyl methacrylate / stearyl methacrylate, and copolymer resins such as 2-ethylhexyl methacrylate / 2-hydroxyethyl methacrylate.

[0224] The weight average molecular weight of the resin is preferably within a range of 1,000 to 1,000,000, more preferably 5,000 to 800,000, and further preferably 10,000 to 600,000.

[0225] In the luminescent thin film, the compound (T) may be used alone or in combination of two or more. The content of the compound (T) in the luminescent thin film is preferably 0.001 parts by mass at the lower limit and 50 parts by mass at the upper limit relative to 100 parts by mass of the matrix material. When the content of the compound (T) is within this range, the luminescent thin film emits light in the long wavelength region of near infrared light and can achieve a high emission quantum yield. The more preferred lower limit of the content of the compound (T) is 0.01 parts by mass, the more preferred upper limit is 10 parts by mass, the even more preferred lower limit is 0.05 parts by mass, the even more preferred upper limit is 8 parts by mass, the particularly preferred lower limit is 0.1 parts by mass, and the particularly preferred upper limit is 5 parts by mass. The luminescent thin film can be used appropriately within a thickness range of 0.1 nm to 1 mm.

[0226] Luminous Particles The luminescent particles, which are an embodiment of the luminescent member of the present invention, are characterized by containing a compound (T). The luminescent particles may be luminescent particles having the compound (T) adsorbed on the particle surface, or may be luminescent particles having the compound (T) encapsulated therein.

[0227] For example, the compound (T) can be aggregated in a polymer particle dispersion to produce luminescent particles. Alternatively, the luminescent particles may contain the compound (T) by using a swelling polymer that absorbs the solvent and expands in volume when the polymer particles are immersed in the solvent.

[0228] The polymer particles may be commercially available or may be synthesized by a conventionally known method. The conventionally known method is not particularly limited, but may include dispersion polymerization, suspension polymerization, emulsion polymerization, etc., and emulsion polymerization is preferred. Specifically, the polymer is preferably a thermoplastic resin such as melamine resin or polystyrene resin. The monomers that are the raw materials for the polymer may be any of the various monomers listed as the monomers of the matrix material in the above-mentioned light-emitting thin film.

[0229] The solvent used for aggregating the compound (T) in the polymer particle dispersion is not particularly limited, and any known solvent can be used.

[0230] The volume average particle size of the polymer particles is preferably within a range of 0.01 to 50 μm, more preferably 0.02 to 1 μm, and even more preferably 0.04 to 0.5 μm.

[0231] When the volume average particle diameter is within the above range, the obtained luminescent particles can be applied to various applications. Specifically, the volume average particle diameter can be measured using a laser diffraction / scattered light particle size distribution measuring device, LS13320 model.

[0232] The weight average molecular weight of the polymer particles is preferably within a range of 1,000 to 1,000,000, more preferably 5,000 to 800,000, and further preferably 10,000 to 600,000.

[0233] The polymer particles contained in the luminescent particles may be of one type or of two or more types, but are usually of one type.

[0234] Furthermore, the compound (T) can be added to a solution of a resin raw material, and then the polymerization reaction can be carried out to produce luminescent particles. For example, when a thermosetting resin such as a melamine resin is used as the base resin, the reaction mixture containing the raw material of the resin (monomer, oligomer, or prepolymer, for example, methylolmelamine, which is a condensate of melamine and formaldehyde), the compound (T), and preferably further a surfactant and a polymerization reaction accelerator (such as an acid) is heated, and the polymerization reaction is carried out by emulsion polymerization to produce luminescent particles encapsulating the compound (T).

[0235] Furthermore, when a thermoplastic resin such as a styrene-based copolymer is used as the base resin, a reaction mixture containing the raw material of the resin, compound (T) (a monomer to which compound (T) has been bonded in advance by a covalent bond or the like may be used as the raw material monomer of the resin), and a polymerization initiator (benzoyl peroxide, azobisisobutyronitrile, etc.) can be heated and a polymerization reaction can be caused to proceed by radical polymerization or ionic polymerization, thereby producing luminescent particles encapsulating compound (T).

[0236] Alternatively, for example, luminescent particles can be produced by using silica as a base material and encapsulating compound (T) therein. In this case, a solution in which inorganic semiconductor nanoparticles, compound (T) and a silica precursor such as tetraethoxysilane are dissolved is dropped into a solution in which ethanol and ammonia are dissolved, and the silica precursor is hydrolyzed to produce the luminescent particles.

[0237] In the luminescent particles, the compound (T) may be used alone or in combination of two or more. The content of the compound (T) in the luminescent particles is preferably 0.001 parts by mass at the lower limit and 50 parts by mass at the upper limit relative to 100 parts by mass of the polymer particles. When the content of the compound (T) is within this range, the luminescent thin film emits light in the long wavelength region of near infrared light and can achieve a high luminescence quantum yield. The more preferred lower limit of the content of the compound (T) is 0.01 parts by mass, the more preferred upper limit is 10 parts by mass, and the even more preferred lower limit is 0.1 parts by mass.

[0238] Wavelength conversion film and infrared emitting surface light source The above-mentioned light-emitting thin film as a light-emitting member can be used as a wavelength conversion film to prepare an infrared-emitting surface light source. The wavelength conversion film can be applied to an infrared-emitting surface light source because it has a light-emitting thin film containing compound (T) and emits infrared light (near-infrared light). The wavelength conversion film may be composed of only the above-mentioned light-emitting thin film, or may be a laminated film laminated with other layers.

[0239] The infrared-emitting surface light source preferably comprises a surface light source that emits visible light and a wavelength conversion film that converts the visible light, particularly red light, emitted from the surface light source into near-infrared light, and has a maximum emission wavelength in the infrared wavelength range of more than 700 nm.

[0240] A basic configuration example of an infrared-emitting surface light source having a wavelength conversion film with a light-emitting thin film containing compound (T) is shown in Fig. 4. The infrared-emitting surface light source 1 shown in Fig. 4 has a configuration in which a wavelength conversion film 3 that converts the visible light of the surface light source 2 emitting red light (R) into near-infrared light (IR) is disposed on a surface light source 2 emitting visible light, for example, an organic EL element emitting red light (R).

[0241] The surface light source that emits visible light (red) is a light source that has the characteristic of emitting at least red light, and is preferably a surface light source that has a luminance uniformity of 70% or more when emitting uniform light. Specifically, the surface light source is preferably an organic EL element.

[0242] The infrared-emitting surface light source 1 may be configured in such a way that a wavelength conversion film 3 manufactured separately from the surface light source 2 emitting visible light (red) is superimposed on the surface light source 2 emitting visible light (red). Alternatively, the wavelength conversion film 3 may be laminated on the surface light source 2 emitting visible light (red).

[0243] The wavelength converting film 3 may be composed of a single layer of a luminescent thin film containing the compound (T), or may have a laminated structure including a luminescent thin film as shown in Fig. 5. The wavelength converting film 3 shown in Fig. 5 has a luminescent thin film 5 containing the compound (T), and a gas barrier film 4B is laminated to one surface of the luminescent thin film 5 via an adhesive layer 6, and a gas barrier film 4A is laminated to the other surface.

[0244] The thickness of the infrared emitting surface light source 1 is appropriately determined depending on the application, but is preferably 0.1 to 1000 μm from the viewpoint of flexibility and compactness, and more preferably in the range of 1 to 500 μm. Such an infrared emitting surface light source is suitable for use in biometric measuring devices and biometric authentication devices.

[0245] [Photoelectric conversion materials] The photoelectric conversion member of the present invention contains a compound (T). The photoelectric conversion member can be used as a member of a near-infrared photoelectric conversion element.

[0246] The near-infrared photoelectric conversion element to which the photoelectric conversion member of the present invention is applied is an element having a photoelectric conversion part between a pair of opposing electrodes, and light is incident on the photoelectric conversion part from above the electrodes. The photoelectric conversion part generates electrons and holes in response to the incident light, and a signal corresponding to the charge is read out by a semiconductor, and the element indicates the amount of incident light corresponding to the absorption wavelength of the photoelectric conversion part. A transistor for reading may be connected to the electrode on the side where light is not incident.

[0247] In such a near-infrared photoelectric conversion element, the photoelectric conversion member containing the compound (T) can be used as a member constituting the photoelectric conversion part, specifically, as a photoelectric conversion layer described below.

[0248] The photoelectric conversion part often comprises a photoelectric conversion layer and one or more organic thin film layers other than the photoelectric conversion layer selected from the group consisting of an electron transport layer, a hole transport layer, an electron blocking layer, a hole blocking layer, etc. The photoelectric conversion layer may be composed only of the compound (T), but may also contain a known infrared absorbing substance in addition to the compound (T).

[0249] The electrode film used in the near-infrared photoelectric conversion element plays a role of extracting holes from the photoelectric conversion layer and other organic thin film layers and collecting them when the photoelectric conversion layer included in the photoelectric conversion part described later has hole transport properties or when the organic thin film layer other than the photoelectric conversion layer is a hole transport layer having hole transport properties. Also, when the photoelectric conversion layer included in the photoelectric conversion part has electron transport properties or when the organic thin film layer is an electron transport layer having electron transport properties, the electrode film plays a role of extracting electrons from the photoelectric conversion layer and other organic thin film layers and discharging them.

[0250] Therefore, materials that can be used as the electrode film are not particularly limited as long as they have a certain degree of conductivity, but it is preferable to select the material taking into consideration the adhesion to the adjacent photoelectric conversion layer or other organic thin film layers, electron affinity, ionization potential, stability, etc.

[0251] Materials that can be used as the electrode film include, for example, conductive metal oxides such as tin oxide (NESA), indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); metals such as gold, silver, platinum, chromium, aluminum, iron, cobalt, nickel, and tungsten; inorganic conductive substances such as copper iodide and copper sulfide; conductive polymers such as polythiophene, polypyrrole, and polyaniline; and carbon.

[0252] These materials may be mixed and used as necessary, or may be laminated in two or more layers. The conductivity of the material used for the electrode film is not particularly limited as long as it does not unnecessarily hinder the light reception of the photoelectric conversion element, but it is preferable that it is as high as possible from the viewpoint of the signal strength and power consumption of the photoelectric conversion element. For example, an ITO film having a sheet resistance value of 300 Ω / □ or less functions sufficiently as an electrode film, but since substrates having an ITO film with a conductivity of about several Ω / □ are commercially available, it is desirable to use a substrate having such high conductivity.

[0253] The thickness of the ITO film (electrode film) can be selected arbitrarily in consideration of the electrical conductivity, but is usually about 5 to 500 nm, preferably about 10 to 300 nm. Methods for forming films such as ITO include the conventionally known deposition method, electron beam method, sputtering method, chemical reaction method, and coating method. The ITO film provided on the substrate may be subjected to UV-ozone treatment, plasma treatment, etc., as necessary.

[0254] The transparent electrode film used on at least one of the light-incident sides of the electrode film is made of ITO, IZO, SnO. 2 , ATO (antimony-doped tin oxide), ZnO, AZO (aluminum-doped zinc oxide), GZO (gallium-doped zinc oxide), TiO2 , FTO (fluorine-doped tin oxide), etc.

[0255] The photoelectric conversion part of the photoelectric conversion element includes at least a photoelectric conversion layer and an organic thin film layer other than the photoelectric conversion layer. An organic semiconductor film is generally used for the photoelectric conversion layer constituting the photoelectric conversion part, and the compound (T) of the present invention is contained in this organic semiconductor thin film. The organic semiconductor film may be a single layer or multiple layers, and in the case of a single layer, a P-type organic semiconductor film, an N-type organic semiconductor film, or a mixed film thereof (bulk heterostructure) is used. On the other hand, in the case of multiple layers, it is about 2 to 10 layers, and has a structure in which any of a P-type organic semiconductor film, an N-type organic semiconductor film, or a mixed film thereof (bulk heterostructure) is laminated, and a buffer layer may be inserted between the layers.

[0256] In the photoelectric conversion element according to the present invention, the organic thin film layer other than the photoelectric conversion layer constituting the photoelectric conversion part is also used as a layer other than the photoelectric conversion layer, for example, an electron transport layer, a hole transport layer, an electron blocking layer, a hole blocking layer, a crystallization prevention layer, an interlayer contact improving layer, etc. In particular, by using it as one or more thin film layers selected from the group consisting of an electron transport layer, a hole transport layer, an electron blocking layer, and a hole blocking layer, it is preferable because it is possible to obtain an element that efficiently converts even weak light energy into an electric signal.

[0257] The electron transport layer transports electrons generated in the photoelectric conversion layer to the electrode and blocks the movement of holes from the electrode to which the electrons are transported to the photoelectric conversion layer. The hole transport layer transports generated holes from the photoelectric conversion layer to the electrode and blocks the movement of electrons from the electrode to which the holes are transported to the photoelectric conversion layer. The electron blocking layer prevents the movement of electrons from the electrode to the photoelectric conversion layer, prevents recombination in the photoelectric conversion layer, and reduces dark current. The hole blocking layer has the function of preventing the movement of holes from the electrode to the photoelectric conversion layer, prevents recombination in the photoelectric conversion layer, and reduces dark current.

[0258] A typical element structure of a photoelectric conversion element is illustrated in FIG. 6. In the embodiment of FIG. 6, 11 represents an insulating part, 12 represents one electrode film, 13 represents an electron blocking layer, 14 represents a photoelectric conversion layer, 15 represents a hole blocking layer, 16 represents the other electrode, and 17 represents an insulating substrate or another organic photoelectric conversion element. Although a readout transistor is not illustrated in the figure, it is sufficient that it is connected to the electrode 12 or 16, and further, if the photoelectric conversion layer 14 is transparent, it may be formed on the outside of the electrode on the side opposite to the side where light is incident. The incidence of light on the organic photoelectric conversion element may be from either the top or bottom, as long as the components other than the photoelectric conversion layer 14 do not excessively inhibit the incidence of light of the main absorption wavelength of the photoelectric conversion layer. EXAMPLES

[0259] The present invention will be described in detail below with reference to examples, but the present invention is not limited thereto. In addition, unless otherwise specified, "%" and "parts" mean "% by mass" and "parts by mass", respectively.

[0260] Example 1 In the compound (1), the compounds (3), specifically, the compounds (1a) to (1d) and the compounds (4) to (11), each of which has the structure shown below, were prepared.

[0261] Compound (1a)-1, compound (1a)-12, and compound (1a)-20, which are classified as compound (1a), were produced according to the above scheme (A), and analyzed by MS and 1 The structure was confirmed by H-NMR.

[0262] [ka]

[0263] Compound (1b)-14, which is classified as compound (1b), was produced according to the above scheme (B) and analyzed by MS and 1 The structure was confirmed by H-NMR.

[0264] [ka]

[0265] Compound (1c)-9, compound (1c)-12, and compound (1c)-31, which are classified as compound (1c), were prepared according to the above scheme (C), and analyzed by MS and 1 The structure was confirmed by H-NMR.

[0266] [ka]

[0267] Compound (1d)-1, compound (1d)-14, compound (1d)-36, compound (1d)-39 and compound (1d)-40, which are classified as compound (1d), were produced according to the above scheme (D), and analyzed by MS and 1 The structure was confirmed by H-NMR.

[0268] [ka]

[0269] Regarding compound (4), compounds (4)-5, (4)-6, (4)-9 and (4)-10 were produced according to the methods of the above schemes (A) to (D), and MS and 1 The structure was confirmed by H-NMR.

[0270] [ka]

[0271] Regarding compound (5), compound (5)-3, compound (5)-4 and compound (5)-9 were produced by methods similar to the above schemes (A) to (D), and MS and 1 The structure was confirmed by H-NMR.

[0272] [ka]

[0273] Regarding compound (6), compound (6)-3, compound (6)-4 and compound (6)-8 were produced by methods similar to the above schemes (A) to (D), and MS and 1 The structure was confirmed by H-NMR.

[0274] [ka]

[0275] Regarding compound (7), compounds (7)-4, (7)-5, (7)-6 and (7)-8 were produced according to the methods of the above schemes (A) to (D), and MS and 1 The structure was confirmed by H-NMR.

[0276] [ka]

[0277] Regarding compound (8), compounds (8)-3, (8)-4 and (8)-10 were produced according to the methods of the above schemes (A) to (D), and MS and 1 The structure was confirmed by H-NMR.

[0278] [ka]

[0279] Regarding compound (9), compounds (9)-4, (9)-6, (9)-7 and (9)-10 were produced according to the methods of the above schemes (A) to (D), and MS and 1 The structure was confirmed by H-NMR.

[0280] [ka]

[0281] Regarding compound (10), compound (10)-2, compound (10)-4, compound (10)-5 and compound (10)-8 were produced by methods similar to the above schemes (A) to (D), and MS and 1 The structure was confirmed by H-NMR.

[0282] [ka]

[0283] Regarding compound (11), compound (11)-2, compound (11)-3 and compound (11)-7 were produced by methods similar to the above schemes (A) to (D), and MS and 1 The structure was confirmed by H-NMR.

[0284] [ka]

[0285] The compound obtained was dissolved in toluene at 10 -6 The fluorescence spectrum of the sample was measured at room temperature (300K). A spectrofluorophotometer (Hitachi High-Technos Corporation, F7000) was used to measure the emission spectrum. In addition, a similarly prepared sample was used to measure the absorption spectrum. A spectrophotometer (Hitachi High-Technos Corporation, F7000) was used to measure the absorption spectrum. For each compound obtained above, an emission peak was observed in the range of 700 to 900 nm.

[0286] Example 2 Among the compounds obtained in Example 1, the compounds shown in Table XIII below, comparative compound R-1 (a compound described in WO 2018 / 008721) and comparative compound R-2 (a compound described in Chem. Mater, 23, 4789, 2011) whose structures are shown below were evaluated for luminescence quantum yield in solution and in a thin film state by the following methods.

[0287] [ka]

[0288] (1) Evaluation of luminescence quantum yield in solution Each of the above compounds was dissolved in toluene for 10 -6 The absolute PL (light emission) quantum yield of the solution of this sample (hereinafter referred to as "PLQY solution") was measured at room temperature (300K) using an absolute PL quantum yield measurement device (Hamamatsu Photonics: C11347).

[0289] (2) Evaluation of the luminescence quantum yield in thin films The matrix material, polystyrene (manufactured by ACROS ORGANICS, weight average molecular weight Mw = 260,000) and the comparative compound R-1 were dissolved in toluene for 10 -2 These were placed in an eggplant flask, heated to 80° C., and stirred until fully dissolved.

[0290] The obtained solution was used to form a thin film on a PET (polyethylene terephthalate) film using an applicator, and then dried at room temperature for 10 minutes, further dried by heating at 80°C for 10 minutes, and peeled off from the PET film to prepare a luminescent thin film (comparative example) containing compound R-1. In addition, compound R-1 was replaced with comparative compound R-2 to prepare a luminescent thin film (comparative example) containing compound R-2. Furthermore, luminescent thin films of the present invention were prepared in the same manner except that compound R-1 was replaced with each compound according to the present invention shown in Table XIII. The absolute PL (luminescence) quantum yields (hereinafter referred to as "PLQY films") of these samples were measured at room temperature (300K). The absolute PL (luminescence) quantum yields were measured using an absolute PL quantum yield measurement device (manufactured by Hamamatsu Photonics KK: C11347).

[0291] The absolute PL (luminescence) quantum yield of the corresponding luminescent thin film is shown in Table XIII below as a relative value of the luminescence quantum yield, i.e., PLQY film / PLQY solution, when the absolute PL (luminescence) quantum yield of the luminescent thin film in a toluene solution is set to 1.00.

[0292] [Table 13]

[0293] From Table XIII, it was found that the luminescent thin film using the comparative compound R-1 and the luminescent thin film using the compound R-2 maintained the luminescence quantum yield of 0.19 and 0.13, respectively, from the solution state, while the luminescent thin films using each compound according to the present invention maintained the luminescence quantum yield of 0.50 or more from the solution state, and concentration quenching was significantly suppressed. Moreover, the luminescent thin films using each compound according to the present invention had a luminescence quantum yield at a level suitable for practical use.

[0294] Example 3 The luminescence quantum yields in solution and in luminescent particles were measured for the compounds shown in Table XIV below among the compounds obtained in Example 1 above, and for the comparative compounds R-1 and R-2.

[0295] (1) Evaluation of luminescence quantum yield in solution Each of the above compounds was dissolved in toluene for 10 -6 The absolute PL (light emission) quantum yield of the solution of this sample (hereinafter referred to as "PLQY solution") was measured at room temperature (300K) using an absolute PL quantum yield measurement device (Hamamatsu Photonics: C11347).

[0296] (2) Preparation of luminescent particles and evaluation of luminescence quantum yield To 96μL of polystyrene (PS) particle dispersion (solid content 5.2 mass%, volume average particle size of polystyrene particles 0.12μm, dispersion medium: water), 100μL of water, 50μL of 2% aqueous solution of nonionic surfactant (Kolliphor P407: Sigma-Aldrich), and 100μL of 0.01mmol / L THF solution of each of the above compounds were added to prepare a mixture of polystyrene particles and each compound. The mixture was stirred at 25℃ for 2 minutes to produce polystyrene particles containing each compound.

[0297] The obtained polystyrene particle dispersion was used to settle the particles by centrifugal purification, and the supernatant was removed, and then pure water was added to redisperse the particles. This operation (centrifugal purification and redispersion) was repeated four times to obtain luminescent particle dispersions 1 to 15 containing each compound.

[0298] The absolute PL (luminescence) quantum yields of the luminescent particle dispersions 1 to 15 obtained above were measured using an absolute PL quantum yield measurement device (C11347-01 manufactured by Hamamatsu Photonics). The absolute PL (luminescence) quantum yields of the corresponding luminescent particle dispersions when the absolute PL (luminescence) quantum yield of the luminescent thin film in a toluene solution is set to 1.00 are shown in Table XIV below as relative values ​​of the luminescence quantum yield, i.e., PLQY particles / PLQY solution.

[0299] [Table 14]

[0300] From Table XIV, it was found that the luminescent particles using the comparative compound R-1 and the luminescent particles using the compound R-2 maintained the luminescence quantum yield of 0.30 and 0.20, respectively, from the solution state, whereas the luminescent particles using each compound according to the present invention maintained the luminescence quantum yield of 0.50 or more from the solution state, and concentration quenching was significantly suppressed. Furthermore, the luminescent particles using each compound according to the present invention had a luminescence quantum yield at a level suitable for practical use.

[0301] Example 4 A wavelength converting film having a luminescent thin film containing compound (1a)-1 as the compound of the present invention was prepared according to the following method, and an infrared-emitting surface light source was prepared using the wavelength converting film. The prepared wavelength converting film was wavelength converting film 3 having the configuration shown in Fig. 5, and the infrared-emitting surface light source was infrared-emitting surface light source 1 having the configuration shown in Fig. 4.

[0302] (Preparation of wavelength conversion film 3) A matrix material, polystyrene (manufactured by ACROS ORGANICS, weight average molecular weight Mw=260000), and compound (1a)-1 were added to a solvent, toluene, in a mass ratio of 99:1, and the mixture was placed in an eggplant flask and heated to 80°C with stirring to fully dissolve.

[0303] Next, a SiO 2 film was applied to the entire surface of one side of a polyethylene naphthalate film (manufactured by Teijin DuPont) using an atmospheric pressure plasma discharge treatment device having the configuration described in JP-A-2004-68143. x The mixed solution obtained was applied by using an applicator onto a gas barrier film 4A having an inorganic gas barrier layer 4A formed to a thickness of 500 nm, which was made of the inorganic material. After drying at room temperature for 10 minutes, it was further dried by heating at 80°C for 10 minutes to form a light-emitting thin film 5.

[0304] Thereafter, a gas barrier film 4B with a sealing adhesive was prepared and laminated to the surface of the luminescent thin film 5 opposite to the gas barrier film 4A side, and sealing was performed using a vacuum laminator under a heating condition of 90° C. Then, a heat treatment was performed at 110° C. for 30 minutes to harden the adhesive and form an adhesive layer 6, thereby producing the wavelength conversion film 3. Although not shown, the wavelength conversion film 3 is configured to contain the polyethylene naphthalate film used as the base material.

[0305] (Production of infrared emitting surface light source) An infrared-emitting surface light source 1 as shown in Fig. 4 was produced by closely contacting the light-emitting surface of an organic EL element, which is a surface light source 2 emitting red light (R), with a wavelength conversion film 3. It was confirmed that by making the surface light source emitting red light (R), the red light of the surface light source emitting red light (R) was converted into near-infrared light.

[0306] Example 5 In this example, a photoelectric conversion element having a photoelectric conversion layer containing the compound (1d)-39 obtained above as a compound of the present invention was prepared as follows, and its performance was evaluated.

[0307] A 150 nm thick indium tin oxide (ITO) transparent conductive film was deposited on a glass substrate, and then patterned to a width of 2 mm using conventional photolithography and hydrochloric acid etching to form a transparent electrode. The patterned transparent electrode was then ultrasonically cleaned with a surfactant and ultrapure water, then ultrasonically cleaned with ultrapure water, dried with nitrogen blowing, and finally cleaned with ultraviolet light and ozone.

[0308] A 1 mg / mL chloroform solution of compound (1d)-39 was spin-coated on this transparent substrate to a thickness of 60 nm, and then heated and dried at 140°C in air for 10 minutes. After this, the substrate was brought into a glove box, and operations were carried out under a nitrogen atmosphere. First, the substrate was heat-treated at 140°C for 10 minutes under a nitrogen atmosphere. Next, the substrate on which the organic layer was formed was placed in a vacuum deposition apparatus. The element was set so that a 2 mm-wide shadow mask was perpendicular to the transparent electrode, and 10 -3 After reducing the pressure in the vacuum deposition apparatus to 40 Pa or less, fullerene C60 was deposited to 40 nm, bathocuproine to 10 nm, and Al to 100 nm. Finally, heating was performed at 120°C for 30 minutes to obtain a photoelectric conversion element 1 according to the present invention. The deposition rate was 2 nm / sec in each case, and the size was 2 mm square.

[0309] The obtained photoelectric conversion element 1 was sealed using an aluminum cap and a UV curing resin (UV RESIN XNR5570-B1, manufactured by Nagase ChemteX Corporation) under a nitrogen atmosphere. The photoelectric conversion element 1 thus produced was irradiated with 100 mW / cm 2 of a solar simulator (AM1.5G filter). 2 When light of an intensity of 1000 nm was irradiated onto the device, an electrical signal was confirmed, and it was confirmed that the device functioned satisfactorily as a photoelectric conversion element.

[0310] In the above, photoelectric conversion elements were similarly prepared and evaluated except that compound (1d)-39 was replaced with compound (4)-6, compound (5)-4, compound (6)-8, compound (7)-6, compound (8)-4, compound (9)-10, compound (10)-4, and compound (11)-2. As a result, it was confirmed that each of these elements produced an electrical signal and functioned satisfactorily as a photoelectric conversion element. [Industrial Applicability]

[0311] According to the present invention, it is possible to provide a light-emitting member capable of achieving a high light emission quantum yield in the near-infrared long wavelength region, which contains a light-emitting compound capable of emitting light in the near-infrared long wavelength region and being blended into a member at a high concentration. It is also possible to provide a light-emitting compound capable of emitting light in the near-infrared long wavelength region and being blended into a member at a high concentration. Furthermore, it is possible to provide a photoelectric conversion member capable of obtaining a high external quantum efficiency using a light-emitting compound capable of emitting light in the near-infrared long wavelength region and being blended into a member at a high concentration. [Explanation of symbols]

[0312] 1. Infrared emitting surface light source 2. Surface light source that emits visible light 3 Wavelength conversion film 4A, 4B Gas barrier film 5. Luminescent thin films 6 Adhesive layer IR Near infrared light R Red light 11 Insulation section 12 Upper electrode 13 Electron Block Layer 14 Photoelectric conversion layer 15 Hole blocking layer 16 Lower electrode 17 Insulating substrate or other photoelectric conversion element

Claims

1. A light-emitting member comprising a compound having a structure represented by the following general formula (T2): 【Chemistry 1】 [In the general formula (T2), A to L each independently represent an aromatic hydrocarbon ring. Each of n1 to n6 independently represents an integer of 0 or 1. Ya and Yb each independently represent an OH group, an NHCORa group (wherein Ra represents a hydrocarbon group), or an NHSO ２ Rb (Rb represents a hydrocarbon group) group, or NHPO(ORf)(ORg) (Rf and Rg each represent a hydrocarbon group). Yc to Yl each independently represent a hydrogen atom or a substituent. However, at least one of Ya and Yb is a linear or branched alkyl group (a) having 4 to 12 carbon atoms, or a group containing a group (P) having a structure represented by the following general formula (P): 【Chemistry 2】 (In formula (P), * represents a substitution site. Q represents a single bond or a divalent linking group. n represents an integer of 1 to 9. R ５１ represents a hydrogen atom or a methyl group.

2. The light-emitting member according to claim 1, wherein, in the general formula (T2), at least one of Ye to Yl is a linear or branched alkyl group having 4 to 12 carbon atoms, or a group containing a group (P) having a structure represented by the general formula (P).

3. A light emitting member comprising a compound having a structure represented by the following general formula (1b): 【Chemistry 3】 (In general formula (1b), each Ra independently represents a hydrocarbon group. Each Rc independently represents a hydrogen atom or a substituent. Either of two Ra's represents a linear or branched alkyl group (a) having 4 to 12 carbon atoms, or at least one of four Rc's represents a linear or branched alkyl group (a) having 4 to 12 carbon atoms which may have -O- as a linking group, or a group (P) having a structure represented by general formula (P).)

4. A light emitting member comprising a compound having a structure represented by the following general formula (1d): 【Chemistry 4】 (In general formula (1d), each Ra independently represents a hydrocarbon group. Each Re independently represents a hydrogen atom or a substituent. Each Xa independently represents an alkyl group or an alkoxy group having 1 to 3 carbon atoms, or a substituted or unsubstituted phenyl group, and Xa bonded to the 4th position may be a group having a structure represented by the following formula (D). m represents an integer of 0 to 4. However, in general formula (1d), either of two Ra represents a linear or branched alkyl group (a) having 4 to 12 carbon atoms, or at least one of four Re represents a linear or branched alkyl group (a) having 4 to 12 carbon atoms which may have -O- as a linking group, or a group (P) having a structure represented by the above general formula (P), or a group having a structure represented by the following formula (D) is bonded to the 4th position as Xa.) 【Chemistry 5】 (In formula (D), * denotes a connecting site; X 31 to X 35 each independently represent a hydrogen atom or a substituent; however, at least one of X 31 and X 35 is a linear or branched alkyl group (a) having 4 to 12 carbon atoms, or a group having a group (P) having a structure represented by the following general formula (P); and X 32 to X 34 do not have a linear or branched alkyl group having 4 or more carbon atoms, or a (poly)oxyalkylene group.) 【Chemistry 6】 (In formula (P), * represents a substitution site. Q represents a single bond or a divalent linking group. n represents an integer of 1 to 9. R 51 represents a hydrogen atom or a methyl group.)

5. The light-emitting member according to claim 1 , wherein the light-emitting member is a light-emitting thin film.

6. The light-emitting member according to claim 1 , wherein the light-emitting member is a light-emitting particle.

7. A light-emitting compound having a structure represented by the following general formula (1a): 【Chemistry 7】 (In general formula (1a), each Rc independently represents a hydrogen atom or a substituent, and at least one of the four Rc represents a linear or branched alkyl group (a) having 4 to 12 carbon atoms which may have -O- as a linking group, or a group (P) having a structure represented by the following general formula (P).) 【Chemistry 8】 (In formula (P), * represents a substitution site. Q represents a single bond or a divalent linking group. n represents an integer of 1 to 9. R ５１ represents a hydrogen atom or a methyl group.

8. A light-emitting compound having a structure represented by the following general formula (1b): 【Chemistry 9】 (In general formula (1b), each Ra independently represents a hydrocarbon group. Each Rc independently represents a hydrogen atom or a substituent. Either of two Ra's represents a linear or branched alkyl group (a) having 4 to 12 carbon atoms, or at least one of four Rc's represents a linear or branched alkyl group (a) having 4 to 12 carbon atoms which may have -O- as a linking group, or a group (P) having a structure represented by the following general formula (P).) 【Chemistry 10】 (In formula (P), * represents a substitution site. Q represents a single bond or a divalent linking group. n represents an integer of 1 to 9. R ５１ represents a hydrogen atom or a methyl group.

9. A photoelectric conversion member comprising a compound having a structure represented by the following general formula (T): 【Chemistry 11】 [In the general formula (T), A to L each independently represent an aromatic hydrocarbon ring or a heteroaromatic ring. n1 to n6 each independently represent an integer of 0 to 2. Ya and Yb each independently represent an OH group, an NHCORa group (wherein Ra represents a hydrocarbon group), or an NHSO ２ Rb (Rb represents a hydrocarbon group) group, or NHPO(ORf)(ORg) (Rf and Rg each represent a hydrocarbon group). Yc to Yl each independently represent a hydrogen atom or a substituent. However, at least one of Ya to Yl is a linear or branched alkyl group (a) having 4 to 12 carbon atoms, or a group containing a group (P) having a structure represented by the following general formula (P): 【Chemistry 12】 (In formula (P), * represents a substitution site. Q represents a single bond or a divalent linking group. n represents an integer of 1 to 9. R ５１ represents a hydrogen atom or a methyl group.

Images