JP7240653B2 - Emission color tone control method - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for controlling the emission color tone of a solution or solid composition.

Luminescent organic compounds are used in a wide range of fields such as biolabeling materials, organic electronic materials, chemical sensors, and organic lasers, and research and development of new luminescent materials is being actively conducted. In particular, fluorescent organic compounds that emit light when irradiated with X-rays, ultraviolet rays, or visible light can be used for organic fluorescent paints, etc., in addition to the above uses.
However, most of the molecules used as light-emitting organic materials are strong and have high planarity. Therefore, in a solution, there is little contact or mutual interference between molecules, and they emit light strongly. In many cases, the energy of the emitted electromagnetic wave is attenuated by the influence of nearby planar molecules, resulting in a marked decrease in luminous efficiency. Since luminescent organic materials are sometimes used in a solid state for some applications, the development of materials that exhibit strong luminescence not only in solution but also in the solid state is an important issue.

US Pat. No. 6,200,000 describes that boron complexes of 8-aminoquinoline derivatives can be used in electroluminescent assemblies. Patent document 2 describes that crystals of 4'-dimethylamino-N-methyl-4-stilbazolium tosylate have optical nonlinear properties. Furthermore, Patent Document 3 describes that a pyridine-N-oxide-difluoroboron compound emits light both in a solution state and a solid state. Non-Patent Document 1 describes that a solution containing 5-N-arylaminothiazole and a Lewis acid emits white light. Non-Patent Document 2 describes that a polymer to which a 2-(2'-hydroxyphenyl)imidazo[1,2-d]pyridine derivative is added emits light. Non-Patent Document 3 describes that the luminescent color is changed by changing the aggregation state of boron-dipyrin.

JP-A-2000-138096 Japanese Patent Publication No. 2000-504298 WO2014/132704

Murai, T. et. al., ChemistryOPEN 2016, 5, 434-438 Mutai, T.; Araki, K. et. al., ACS Appl. Mater. Inter., 2014, 6, 16065-16070 Yamamoto, Y. et al., ACS Nano, 2016, 10, 7058-7063

However, most of the compounds having the above-described luminescent properties do not emit light either in solution or in solid state, and even the compound described in Patent Document 3 cannot control the emission color.
An object of the present invention is to provide a means that exhibits excellent luminescence characteristics not only in a solution state but also in a solid state and that can control a wide range of luminescence color tones.

Therefore, the present inventor blended various fluorescent substances and compounds such as Lewis acids in a medium and examined the optical properties in the solution state and the solid state. However, it emits strong light not only in a solution state but also in a gel state, a solid state such as a film, a fiber, a molded body, etc., and various emission colors can be obtained by changing its content, etc., and a wide range of emission colors can be easily obtained. We found that it can be controlled, and completed the present invention.

That is, the present invention provides the following inventions [1] to [13].

[1] In a composition containing (a) a fluorescent substance, (b) a substance that non-covalently interacts with component (a), and (c) a medium, component (a) and component ( b) and the equilibrium constants of their complexes, or changing the content ratio of component (a) in component (c) or the weight ratio of component (a) and component (b) in component (c) A method for controlling emission color tone, characterized by:
[2] The method for controlling emission color tone according to [1], wherein the composition is a solution composition or a solid composition.
[3] The method for controlling emission color tone according to [1] or [2], wherein the fluorescent substance is a compound represented by formula (1).

(wherein Ar ¹ and Ar ² are the same or different and represent an aromatic hydrocarbon group or an aromatic heterocyclic group; R ¹ , R ² , R ³ and R ⁴ are the same or different and are hydrogen atoms; , indicates an aliphatic hydrocarbon group or an aromatic hydrocarbon)
[4] The method for controlling emission color tone according to any one of [1] to [3], wherein component (b) is Bronsted acid, Lewis acid or halogen bond donor.
[5] The emission color tone of any one of [1] to [4], wherein the equilibrium constants of the components (a), (b) and their complexes are changed from K = 0.1 to K = 10 ⁶ control method.
[6] The content ratio of component (a) in component (c) is 0.01 mM to 100 mM, or the weight ratio of component (a) and component (b) in component (c) is 0.01% to 100 The method for controlling emission color tone according to any one of [1] to [5], wherein
[7] A luminescent composition containing (a) a fluorescent substance, (b) a substance that non-covalently interacts with the component (a), and (c) a medium.
[8] The luminescent composition of [7], wherein the composition is a solution composition or a solid composition.
[9] The luminescent composition according to [7] or [8], wherein the fluorescent substance is a compound represented by formula (1).

(wherein Ar ¹ and Ar ² are the same or different and represent an aromatic hydrocarbon group or an aromatic heterocyclic group; R ¹ , R ² , R ³ and R ⁴ are the same or different and are hydrogen atoms; , indicates an aliphatic hydrocarbon group or an aromatic hydrocarbon)
[10] The luminescent composition according to any one of [7] to [9], wherein component (b) is a Bronsted acid, a Lewis acid or a halogen bond donor.
[11] The luminescent composition according to any one of [7] to [10], wherein the equilibrium constants of the components (a), (b) and their complexes are in the range of K = 0.1 to K = ¹⁰⁶ . thing.
[12] The content ratio of component (a) in component (c) is 0.01 mM to 100 mM in concentration, or the weight ratio of component (a) and component (b) in component (c) is 0.01%. to 100%, the luminescent composition according to any one of [7] to [11].
[13] The luminescent composition according to any one of [7] to [12], which is a white luminescent material exhibiting two peak wavelengths having complementary colors.

According to the method of the present invention, strong luminescence is exhibited in both the solution state and the solid state, and the luminescence color tone can be controlled in a wide range by easy means. Therefore, the composition capable of controlling the emission color tone according to the present invention includes a fluorescent light-emitting composition, a fluorescent coating composition, a wavelength conversion member composition, an organic EL member composition, an organic transistor member composition, an organic solar cell member composition, a chemical It is useful as an organic optical material contained in an optical composition selected from the composition group consisting of a sensor and an organic laser component composition.
In the present invention, the term "organic optical material" refers to all materials that utilize the conversion of the energy level of electrons constituting the material upon receiving light. Such materials can be used as organic EL, organic solid-state lasers, organic nonlinear optical materials, inks, etc., because they exhibit their functions upon receiving light, for example, they are colored or emit fluorescence. In addition, it can be used for organic solar cells, organic solid-state sensors, and the like. Furthermore, it can also be used in optoelectronic materials such as photo-activated electron transport layers, organic waveguides, diodes and transistors.

FIG. 1 shows emission color control by changing the ratio of component (a) (Michler's ketone derivative 1) and component (b) in a methylene chloride solution. FIG. 1 shows emission color control by changing the ratio of component (a) (Michler's ketone derivative 1) and component (b) in a methylene chloride solution. FIG. 1 shows emission color control by changing the concentration of component (a) (Michler's ketone derivative 1) and component (b) in a methylene chloride solution. FIG. 1 shows emission color control by changing the concentration of component (a) (Michler's ketone derivative 1) and component (b) in a methylene chloride solution. FIG. 1 shows emission color control by changing the concentration of component (a) (Michler's ketone derivative 1) and component (b) in a methylene chloride solution. FIG. 1 shows emission color control by changing the concentration of component (a) (Michler's ketone derivative 2) and component (b) in a methylene chloride solution. FIG. 1 shows emission color control by changing the concentration of component (a) (Michler's ketone derivative 2) and component (b) in a methylene chloride solution. FIG. 1 shows emission color control by changing the concentration of component (a) (Michler's ketone derivative 2) and component (b) in a methylene chloride solution. FIG. 1 shows emission color control by changing the mixed solvent ratio of component (a) (Michler's ketone derivative 2) and component (b) in a toluene-hexane mixed solvent. FIG. 1 shows emission color control by changing the mixed solvent ratio of component (a) (Michler's ketone derivative 2) and component (b) in a toluene-hexane mixed solvent. Fig. 3 shows emission color control (in solid state) in resin (polystyrene, PS) of component (a) and component (b). Fig. 2 shows emission color control (in solid state) in resins (polypropylene, PP) of component (a) and component (b). The emission color control in (solid state) in the resin (polyvinyl acetate, PVAc) of component (a) and component (b) is shown. The emission color control in (solid state) in the resin (polyvinyl chloride, PVC) of component (a) and component (b) is shown. Fig. 3 shows emission color control (in solid state) in resin (polymethyl methacrylate, PMMA) of component (a) and component (b). Fig. 2 shows emission color control (solid state) in resins (polyethylene glycol, PEG) of component (a) and component (b). The emission color control in (solid state) in the resin (polyvinyl alcohol, PVA) of component (a) and component (b) is shown. Fig. 3 shows emission color control (in a solid state) in a resin (polyvinylidene fluoride, PVDF) of component (a) and component (b). It shows that white color can be obtained by controlling the emission color (in the solid state) in the resin (PVAc) of components (a) and (b). IR spectra of component (a) alone and a complex of components (a) and (b) are shown.

As used herein, the term "medium" in the present invention means a substance that forms an environment in which a fluorescent substance or the like exists, and may also be described as a medium, a matrix, etc. Specifically, a solvent or a polymer point to
As used herein, the term "support" refers to a state in which components (a), (b) and their complexes are dispersed in component (c), and may or may not be homogenous.
In this specification, the terms "resin" and "polymer" are used synonymously.

The composition used in the method for controlling emission color tone of the present invention is a composition containing (a) a fluorescent substance, (b) a substance that non-covalently interacts with component (a), and (c) a medium. be.

(a) The fluorescent substance is not particularly limited as long as it absorbs light of a certain wavelength and emits light of another wavelength, but a substance that emits fluorescence in the visible region is preferable. Examples include fluorescein, eosin, rose bengal, acridine, phenazine, coumarin, benzophenone, fuchsine, alizarin, anthocyanin, anthraquinone, indigo, genistein, shikonin, piperidine, berberine, litmus, and rhodoxanthin.

Among the (a) fluorescent substances used in the present invention, the compound represented by formula (1) is preferred.

(wherein Ar ¹ and Ar ² are the same or different and represent an aromatic hydrocarbon group or an aromatic heterocyclic group; R ¹ , R ² , R ³ and R ⁴ are the same or different and are hydrogen atoms; , indicates an aliphatic hydrocarbon group or an aromatic hydrocarbon)

In formula (1), Ar ¹ and Ar ² are the same or different and represent an aromatic hydrocarbon group or an aromatic heterocyclic group. The aromatic hydrocarbon group includes monocyclic or condensed polycyclic aromatic hydrocarbon groups having 6 to 30 carbon atoms. Specifically, groups derived from monocyclic aromatic hydrocarbons such as benzene, cumene, mesitylene, styrene, toluene, and xylene; condensed polycyclic aromatic hydrocarbons such as indene, naphthalene, fluorene, phenanthrene, anthracene, pentacene, and hexacene; Groups derived from hydrogen can be mentioned. Among them, a group derived from a monocyclic aromatic hydrocarbon having 6 to 16 carbon atoms is more preferred, and a phenylene group is even more preferred.

Aromatic heterocyclic groups include monocyclic or condensed polycyclic heterocyclic groups having 1 to 4 nitrogen atoms, oxygen atoms or oxygen atoms. Specifically, heterocyclic groups such as pyrrole, furan, thiophene, imidazole, pyrazole, oxazole, thiazole, triazole, oxadiazole, thiadiazole, pyridine, pyrimidine, triazine, indole, indazole, quinoline, isoquinoline, carbazole, quinazoline, etc. derived groups.

R ¹ , R ² , R ³ and R ⁴ are the same or different and represent a hydrogen atom, an aliphatic hydrocarbon group or an aromatic hydrocarbon group. Aliphatic hydrocarbon groups include alkyl groups and alkenyl groups having 1 to 12 carbon atoms. Specifically, alkyl groups having 1 to 12 carbon atoms such as methyl group, ethyl group and isopropyl group; cycloalkyl groups having 3 to 8 carbon atoms such as cyclopropyl group, cyclopentyl group and cyclohexyl group; vinyl group, propenyl group and the like. alkenyl groups having 2 to 8 carbon atoms; and alkynyl groups having 2 to 6 carbon atoms such as ethynyl groups.
The aromatic hydrocarbon group includes aromatic hydrocarbon groups having 6 to 14 carbon atoms such as phenyl group, naphthyl group, cumenyl group and mesitylenenyl group.

(b) Bronsted acids, Lewis acids, and halogen bond donors are specifically known as substances that non-covalently interact with component (a).

Bronsted acids include carboxylic acid, sulfonic acid, phosphonic acid, phosphinic acid and the like. acetic acid, carboxylic acids such as trifluoroacetic acid, fluorosulfonic acid, methanesulfonic acid, ethylsulfonic acid, 4-dodecylbenzenesulfonic acid, heptadecafluorooctane sulfonic acid, camphorsulfonic acid, p-toluenesulfonic acid, 2,4- Sulfonic acids such as dinitrobenzenesulfonic acid, 1-naphthalenesulfonic acid and mesitylenesulfonic acid, phosphonic acids such as methylphosphonic acid, ethylphosphonic acid, propylphosphonic acid, tert-butylphosphonic acid, octylphosphonic acid and hexadecylphosphonic acid, dimethyl Phosphinic acid such as phosphinic acid, phenylphosphinic acid, diphenylphosphinic acid, diisooctylphosphinic acid, and the like.

Lewis acids include BF ₃ , BBr ₃ , B(NMe ₂ ) ₃ , tris(pyrrolidino)borane, tris(mesityl)borane, triethyl borate, tributyl borate, alpine borane, triphenylborane, B(C ₆ F ₅ ) ₃ , _AlCl3 , _FeCl3 , _FeBr3 , _ZnCl2 , _InCl3 , _TiCl4 , metal triflate salts.

As a halogen bond donor, a vacant orbital generated by the structure of the halogen bond donor itself can accept a lone pair of electrons of a Lewis base functional group. Specifically, perfluoroiodobenzene, halogen molecule, halogen cation, perfluoroiodoalkane, N-halogenodicarboxylic acid imide, 1,2,3-triazolinium-5-halide, N,N-dialkylimidazolinium -2-halide, 2-halogenoisoindolyl-1,3-dione, 2-halogenobenzo[d]isothiazol-3(2H)-one 1,1-dioxide, 2-halogeno-5-nitroisoindolyl -1,3-dione, 2-halogeno-3,4-dimethylthiazol-3-nium trifluorosulfonate and the like.

The non-covalent interaction in the present invention refers to a non-covalent bonding state, and includes coordinate bonding, ionic bonding, and the like. For example, a coordinate bond between a cyano group and a Lewis acid, an ionic bond between a nitrogen atom in an aromatic group (for example, a nitrogen atom in a pyridine ring) and a Bronsted acid, a Lewis acid, or a halogen bond donor, a coordinate bond, etc. are mentioned.

(c) medium includes both solvents and solid media. The solvent is not limited as long as it dissolves the components (a) and (b), and includes water and various organic solvents. Examples of organic solvents include alcohols such as methanol-ethanol, halogenated hydrocarbons such as dichloromethane and dichloroethane, ketone solvents such as acetone, hydrocarbons such as hexane, sulfoxide solvents such as dimethylsulfoxide, and ether solvents such as diethyl ether. Solvents include amide solvents such as N,N-dimethylformamide.

The solid medium may be any medium in which the component (a) and the component (b) or the combination of the component (a) and the component (b) can be uniformly dispersed. It does not matter if it is uneven or not. In the present specification, the case where they are uniformly dispersed will be described as an example. Examples of solid media include resin media such as thermosetting resins, thermoplastic resins, and photocurable resins, specifically polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyalkyl methacrylate, polyvinyl acetate, polyethylene glycol, polyvinyl alcohols, polyvinylidene fluoride, and mixtures of one or more of these. From the viewpoint of emission intensity, the resin used preferably has light transmittance. The resin medium also includes a monomer and a polymer precursor in addition to the resin medium.
When component (a) and component (b) or a combination of component (a) and component (b) are dissolved in a solvent, the composition of the present invention becomes a solution composition. On the other hand, when component (a) and component (b) or a combination of component (a) and component (b) are uniformly or non-uniformly dispersed in a solid medium, the composition of the present invention is a solid composition. become things.

The compositions of the present invention are highly luminous both in solution and in the solid state. Here, the composition (luminescent composition) of the present invention includes solutions, molded articles (films, fibers, molded articles), gel-like materials, materials coated on substrates, laminates, and the like.

The composition of the present invention changes the equilibrium constants of component (a), component (b) and their complexes in the composition, or the content ratio of component (a) in component (c) or component (c ) by changing the weight ratio of components (a) and (b) in ), the color tone of the emitted light changes over a wide range. Therefore, by using the composition of the present invention, it is possible to control (modulate) a wide range of emission color tones.

Components (a) and (b) form a complex in component (c), but are in equilibrium in medium (c). Assuming the equilibrium constant K,
K=[concentration of complex in component (c)]/{[concentration of component (a)]×[concentration of component (b)]
can be expressed as
The equilibrium constant K of component (a) and component (b) is preferably changed from K = 0.1 to K = ¹⁰⁶ , and the lower limit of equilibrium constant K is preferably 1 or more, more preferably 10 or more. , more preferably 10 ² , and the upper limit is more preferably 10 ⁵ and even more preferably 10 ⁴ . Emission in the blue to red range can be controlled by varying the equilibrium constant over this range.

In order to change the equilibrium constants of component (a), component (b) and their complexes within the above range, means for changing the polarity of the medium component (c), means for changing temperature, and means for changing pressure are mentioned. Here, means for changing the polarity of component (c), which is a medium, include means for selecting the type of functional group of component (c), which is a medium, the shape of the entire molecule, etc. When the medium is a solvent, Means of using a mixed solvent and changing the mixing ratio of two kinds of solvents can be mentioned. When the medium is a resin, the molecular weight, molecular weight distribution, melting point and glass transition point affect the medium, and other means include selecting the types of functional groups present in the main chain and side chains.

The content ratio of component (a) in component (c) is preferably changed from 0.01 mM to 100 mM, more preferably from 0.1 mM to 10 mM. The weight ratio of component (a) and component (b) in component (c) is preferably varied from 0.01% to 100%, more preferably from 0.1% to 50%. By varying these ranges, emission in the blue to red range can be controlled.

In the composition of the present invention, component (a) and component (b) are believed to be bound by non-covalent bonds such as coordinate bonds and ionic bonds. When the composition of the present invention is in a solid state, it is believed that the component (a) and the component (b) are dispersed in a bonded state in the matrix of the component (c).

In order to form a composition using the component (c) of the present invention as a medium, the components (a) and (b) may be dissolved in a solvent and then combined as they are, or isolated as a complex from the solution. You may mix the thing which carried out with the component (c). Further, when the component (c) is a polymer, when the components (a) and (b) are brought into contact with the component (c), a solvent may or may not be used, and either component may be dissolved in the solvent. It is also possible to contact Furthermore, component (c) may be heated and melted to dissolve components (a) and (b) in a solvent, or may be brought into contact without a solvent, or in the case of a thermosetting resin, the component before curing ( Components (a) and (b) may be added to c).

The composition of the present invention has the property of emitting strong fluorescence not only in a solution state but also in a solid state. As used herein, the term "fluorescence" refers to a form of light emission, in which electrons are excited by absorbing the energy when irradiated with X-rays, ultraviolet rays, and/or visible light, and then enter the ground state. It means the phenomenon of releasing excess energy as electromagnetic waves when returning, and should not be interpreted restrictively in any sense, but should be interpreted in the broadest sense. Fluorescence measurement in a solid state can generally be performed using an absolute PL quantum yield measurement device C-9920-02 (multichannel detector PMA-11, Hamamatsu Photonics Co., Ltd.). is not limited to the apparatus and method of

Specifically, the composition of the present invention can be used as an organic EL, an organic solid-state laser, an organic nonlinear optical material, an ink, and the like, and can also be used in an organic solar cell, an organic solid-state sensor, and the like. Further, it can be used in optoelectronic materials such as photo-activated electron transport layers, organic waveguides (including optical fibers), diodes, transistors and the like.

EXAMPLES Next, the present invention will be described in more detail with reference to Examples.

(reagent)
Additives: B(C ₆ F ₅ ) ₃ manufactured by Tokyo Chemical Industry Co., Ltd. was used.
Polymers: PVAc, PVC, PVDF, PAN (manufactured by Sigma-Aldrich), PMMA, PS (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), PEG (Kishida Chemical), PVA (Okenshoji) are those of the chemical companies indicated respectively. used.
Michler's ketone derivative 1: N,N,N',N'-tetramethyl-4,4'-diaminobenzophenone (Michler's ketone derivative 1, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)
Michler's ketone derivative 2: N,N,N',N'-tetraphenyl-4,4'-diaminobenzophenone (Michler's ketone derivative 2) was synthesized according to the following reaction scheme. Materials and reagents manufactured by Tokyo Chemical Industry Co., Ltd. were used.

4,4'-Difluorobenzophenone (655 mg, 3.0 mmol) was dissolved in 50 mL of N,N-dimethylformamide in a nitrogen atmosphere, and diphenylamine (1.18 g, 7.0 mmol) was added. Potassium t-butoxy (1.01 g, 9.0 mmol) was added thereto, and the solution was heated under reflux for 12 hours. After evaporating the solvent, methylene chloride was added to the residue and it was washed three times with aqueous ammonium chloride solution. The organic layer was dried over sodium sulfate and evaporated. The residue was purified by silica gel column chromatography. 580 mg (yield 38%) of the desired Michler's ketone derivative 2 was obtained.

(Used equipment)
Absorption spectrum measurement (solution):
Ultraviolet-visible absorption spectrometer V650 (JASCO Corporation)
Absorption spectrum measurement (solid/powder):
Ultraviolet-visible absorption spectrometer UV-3150 (Shimadzu Corporation)
Emission spectrum measurement (solution):
Emission spectrum measuring device FP-6000 (JASCO Corporation)
Or absolute PL quantum yield measurement device C9920-02
(multichannel detector PMA-11,
and solution measurement jig A10104-01 attached, Hamamatsu Photonics K.K.)
Emission spectrum measurement (solid/thin film):
Absolute PL quantum yield measurement device C9920-02
(Attached to multi-channel detector PMA-11, Hamamatsu Photonics K.K.)
Quantum yield measurement:
Absolute PL quantum yield measurement device C9920-02
(Attached to multi-channel detector PMA-11, Hamamatsu Photonics K.K.)

Example 1
Michler's ketone derivative 1, N,N,N',N'-tetramethyl-4,4'-diaminobenzophenone (2.7 mg, 0.01 mmol) was added to 10 mL of methylene chloride and dissolved in air. This was designated as solution A. Tris(pentafluorophenyl)borane (5.1 mg, 0.01 mmol) was added to 10 mL of methylene chloride and dissolved. This solution was designated as solution B. 0.9 mL from solution A and 0.1 mL from solution B were taken out and mixed. The color of the solution and the color of light emitted under irradiation with an ultraviolet lamp (λ=365 nm) were visually observed. The absorption spectrum, emission spectrum and absolute quantum yield of the solution were measured.

The results are shown in FIGS. 1, 2 and Table 2. By changing the content ratio of component (a) and component (b), strong luminescence in a wide range from blue to red was observed.

Example 2
N,N,N',N'-tetramethyl-4,4'-diaminobenzophenone (26.8 mg, 0.1 mmol), which is Michler's ketone derivative 1, and tris(pentafluorophenyl) borane (51.2 mg) in air. , 0.1 mmol) was added to 10 mL of methylene chloride and dissolved to prepare a solution with a concentration of 10 mM of Michler's ketone derivative 1 (solution C). The color of the solution and the color of light emitted under irradiation with an ultraviolet lamp (λ=365 nm) were visually observed. The absorption spectrum, emission spectrum and absolute quantum yield of the solution were measured. The color of the solution and the color of light emitted under irradiation with an ultraviolet lamp (λ=365 nm) were visually observed. The absorption spectrum, emission spectrum and absolute quantum yield of the solution were measured. 1 mL was taken out from solution C and diluted to 2 mL to prepare a solution having a concentration of Michler's ketone derivative 1 of 5 mM (solution D). The color of the solution and the color of light emitted under irradiation with an ultraviolet lamp (λ=365 nm) were visually observed. The absorption spectrum, emission spectrum and absolute quantum yield of the solution were measured. 1 mL was taken out from solution D and diluted to 2 mL to prepare a solution having a concentration of Michler's ketone derivative 1 of 2.5 mM (solution E). The color of the solution and the color of light emitted under irradiation with an ultraviolet lamp (λ=365 nm) were visually observed. The absorption spectrum, emission spectrum and absolute quantum yield of the solution were measured. 0.4 mL was taken out from the solution D and diluted to 2 mL to prepare a solution having a Michler ketone derivative 1 concentration of 1 mM (solution F). Thus, 0.75, 0.50, 0.25, 0.10, 0.05 and 0.01 mM solutions were prepared by successively diluting the solutions. The colors of these solutions and the color of light emitted under irradiation with an ultraviolet lamp (λ=365 nm) were visually observed. The absorption spectrum, emission spectrum and absolute quantum yield of the solution were measured.

The results are shown in FIGS. 3-5 and Table 4. As a result, by changing the concentration of component (a) (Michler's ketone derivative 1) (or the concentration of component (b) (borane)) in methylene chloride, strong luminescence in a wide range from blue to red was observed.

Example 3
N,N,N',N'-tetraphenyl-4,4'-diaminobenzophenone (51.6 mg, 0.1 mmol), which is Michler's ketone derivative 2, and tris(pentafluorophenyl)borane (51.2 mg) in air. , 0.1 mmol) was added to 10 mL of methylene chloride and dissolved to prepare a solution with a concentration of 10 mM of Michler's ketone derivative 2 (solution G). The color of the solution and the color of light emitted under irradiation with an ultraviolet lamp (λ=365 nm) were visually observed. The absorption spectrum, emission spectrum and absolute quantum yield of the solution were measured. The color of the solution and the color of light emitted under irradiation with an ultraviolet lamp (λ=365 nm) were visually observed. The absorption spectrum, emission spectrum and absolute quantum yield of the solution were measured. 1 mL was removed from the solution G and diluted to 2 mL to prepare a solution having a Michler's ketone derivative 2 concentration of 5 mM (solution H). The color of the solution and the color of light emitted under irradiation with an ultraviolet lamp (λ=365 nm) were visually observed. The absorption spectrum, emission spectrum and absolute quantum yield of the solution were measured. 1 mL was taken out from solution H and diluted to 2 mL to prepare a solution having a concentration of Michler's ketone derivative 2 of 2.5 mM (solution I). The color of the solution and the color of light emitted under irradiation with an ultraviolet lamp (λ=365 nm) were visually observed. The absorption spectrum, emission spectrum and absolute quantum yield of the solution were measured. 0.4 mL was taken out from solution D and diluted to 2 mL to prepare a solution having a concentration of Michler's ketone derivative 2 of 1 mM (solution J). Thus, 0.75, 0.50, 0.25, 0.10, 0.05 and 0.01 mM solutions were prepared by successively diluting the solutions. The colors of these solutions and the color of light emitted under irradiation with an ultraviolet lamp (λ=365 nm) were visually observed. The absorption spectrum, emission spectrum and absolute quantum yield of the solution were measured.

The results are shown in FIGS. 6-8 and Table 6. As a result, by changing the concentration of component (a) (Michler's ketone derivative 2) (or the concentration of component (b) (borane)) in methylene chloride, strong luminescence in a wide range from blue to red was observed.

Example 4
Michler's ketone derivative 2, N,N,N',N'-tetraphenyl-4,4'-diaminobenzophenone (5.2 mg, 0.01 mmol) and tris(pentafluorophenyl)borane (5.1 mg, 0.01 mmol). 01 mmol) was added to 5 mL of methylene chloride and dissolved to prepare a solution with a concentration of 2.0 mM of Michler's ketone derivative 2 (solution K). 0.25 mL was taken from there and diluted with 4.75 mL of toluene. The colors of these solutions and the color of light emitted under irradiation with an ultraviolet lamp (λ=365 nm) were visually observed. The absorption spectrum, emission spectrum and absolute quantum yield of the solution were measured. Similarly, by changing the ratio of diluting solvents, solutions were prepared in which the ratio of the mixed solvent was toluene:hexane=10:0 to 9.5:0.5.

The results are shown in FIGS. 9, 10 and Table 8. As a result, by varying the concentrations of component (a) and component (b) in component (c), strong luminescence in a wide range from blue to red was observed.

Example 5
Michler's ketone derivative N,N,N',N'-tetraphenyl-4,4'-diaminobenzophenone (5.2 mg, 0.01 mmol) and tris(pentafluorophenyl)borane (5.1 mg, 0.01 mmol) ) was added to 5 mL of methylene chloride and dissolved to prepare a solution with a Michler ketone derivative concentration of 2 mM (solution L). The weight concentration of solution L is ((N,N,N',N'-tetraphenyl-4,4'-diaminobenzophenone+tris(pentafluorophenyl)borane)/volume of methylene chloride)=10.3/5 mL= 2.06 mg/mL. Polystyrene (1000 mg) was added to 10 mL of methylene chloride and dissolved (solution M). 0.01 mL from solution L and 0.2 mL from solution M were taken out and diluted with methylene chloride so that the total volume was 1.5 mL. This was stirred for 5 minutes. 0.01 mL was taken out from here and dropped onto a quartz substrate. It was air-dried to distill off the solvent, and further dried under reduced pressure to completely remove the solvent to form a film. The amount of Michler's ketone and the borane compound supported on the polymer was calculated from the weight concentrations of solution L and solution M by ((2.06×amount of solution G taken out)/(100×amount of solution H taken out)). The color of this thin film and the emission color under irradiation with an ultraviolet lamp (λ=365 nm) were visually observed. The absorption spectrum, emission spectrum and absolute quantum yield of the thin film were measured.

In addition, PP (Example 6), PVAc (Example 7), PVC (Example 8), PMMA (Example 9), PEG (Example 10), PVA (Example 11), PVDF (Example 12) Also, a 100 mg/mL methylene chloride solution was prepared, and a polymer film was prepared in the same manner.

The results are shown in FIGS. 11-18 and Tables 10 and 11. As a result, the solid composition containing component (a) and component (b) in component (c) showed strong luminescence in a wide range from blue to red depending on the concentration change of component (a).

FIG. 13 shows that white light emission can be obtained when the concentration of components (a) and (b) is 5.0% by weight to 7.5% by weight. In FIG. 13, the spectrum indicates dichroic luminescence, in which blue and red luminescence are mixed, and 5.0 when their luminescence intensities are exactly 1:1. ~7.5% by weight. Although an example of a blue emission peak and a red emission peak is shown here, other emission peak wavelengths may be used as long as they have two wavelength peaks in a color relationship in the fluorescence spectrum.

Example 13
Preparation of white film Michler's ketone derivative 2 N,N,N',N'-tetraphenyl-4,4'-diaminobenzophenone (5.2 mg, 0.01 mmol) and tris(pentafluorophenyl)borane (5. 1 mg, 0.01 mmol) was added to 5 mL of methylene chloride and dissolved to prepare a solution with a concentration of 2 mM of Michler's ketone derivative 2 (solution L). The weight concentration of solution L is ((N,N,N',N'-tetraphenyl-4,4'-diaminobenzophenone+tris(pentafluorophenyl)borane)/volume of methylene chloride)=10.3/5 mL= 2.06 mg/mL. Polyvinyl acetate (1000 mg) was added to 10 mL of methylene chloride and dissolved (solution N). The weight concentration of the polymer in solution N was set to 100 mg/mL. 1.166 mL from solution L and 0.2 mL from solution N were taken out, mixed, and diluted with methylene chloride so that the total volume was 1.5 mL. This was stirred for 5 minutes. 0.01 mL was taken out from here and dropped onto a quartz substrate. It was air-dried to distill off the solvent, and further dried under reduced pressure to completely remove the solvent to form a film. The amounts of Michler's ketone 2 and the borane compound supported on the polymer were calculated from the weight concentrations of solution L and solution N by ((2.06×amount of solution L taken out)/(100×amount of solution N taken out)). The color of this thin film and the emission color under irradiation with an ultraviolet lamp (λ=365 nm) were visually observed. The absorption spectrum, emission spectrum and absolute quantum yield of the thin film were measured. When this emission color was expressed in the CIE coordinate system, it was (0.33, 0.32). (Comparison: If it is white, it is (0.33, 0.33))

The results are shown in FIG. 19 and Table 13. From FIG. 19 and Table 13, it was found that white light emission can also be obtained by changing the concentration of (PVAc) in the resin of component (a).

Example 14
(IR spectrum measurement)
Powders of complexes of component (a) (Michler's ketone derivative 2) and component (b) (borane) were prepared, and their IR spectra were measured. It is shown in FIG. 20 together with the simulation from the theoretical calculation. The results show good agreement with the simulation, and the results support the fact that the complex is formed by the interaction between the components (a) and (b).

Claims (7)

(a) a fluorescent substance, (b) a substance that non-covalently interacts with component (a), and (c ) a medium selected from solvents and resins , wherein changing the equilibrium constants of component (a), component (b) and their complexes in the composition, or changing the content ratio of component (a) in component (c) in the composition or in component (c) A method for controlling emission color tone, characterized by changing the weight ratio of component (a) and component (b) of
(a) the fluorescent substance is a compound represented by formula (1),

(wherein Ar ¹ and Ar ² are the same or different and represent an aromatic hydrocarbon group or an aromatic heterocyclic group; R ¹ , R ² , R ³ and R ⁴ are the same or different and are hydrogen atoms; , indicates an aliphatic hydrocarbon group or an aromatic hydrocarbon)
(b) The method for controlling emission color tone, wherein the substance that non-covalently interacts with component (a) is a Lewis acid. 2. The method of controlling emission color tone according to claim 1, wherein the equilibrium constant of said components (a) and (b) is changed from K=0.1 to K=10 ^<6> . Change the content ratio of component (a) in component (c) from 0.01 mM to 100 mM or change the weight ratio of component (a) and component (b) in component (c) from 0.01% to 100% 2. The method for controlling emission color tone according to claim 1 . (a) a fluorescent substance, (b) a substance that non-covalently interacts with component (a), and (c) a medium selected from solvents and resins , a solution or solid luminescent composition comprising ,
(a) the fluorescent substance is a compound represented by formula (1),

(wherein Ar ¹ and Ar ² are the same or different and represent an aromatic hydrocarbon group or an aromatic heterocyclic group; R ¹ , R ² , R ³ and R ⁴ are the same or different and are hydrogen atoms; , indicates an aliphatic hydrocarbon group or an aromatic hydrocarbon)
The luminescent composition, wherein (b) the substance that non-covalently interacts with component (a) is a Lewis acid. 5. The luminescent composition according to claim 4, wherein said components (a), (b) and their complexes have equilibrium constants in the range of K=0.1 to K=10 ^<6> . The content ratio of component (a) in component (c) is from 0.01 mM to 100 mM, or the weight ratio of component (a) and component (b) in component (c) is from 0.01% to 100%. A luminescent composition according to claim 4 . 7. The luminescent composition according to any one of claims 4 to 6 , which is a white luminescent material exhibiting two peak wavelengths having a complementary color relationship.

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