WO2022250087A1 - 有機シンチレーション材料 - Google Patents

有機シンチレーション材料 Download PDF

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WO2022250087A1
WO2022250087A1 PCT/JP2022/021418 JP2022021418W WO2022250087A1 WO 2022250087 A1 WO2022250087 A1 WO 2022250087A1 JP 2022021418 W JP2022021418 W JP 2022021418W WO 2022250087 A1 WO2022250087 A1 WO 2022250087A1
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compound
ring
group
condensed
scintillation material
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French (fr)
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健一郎 伊丹
亜樹子 岩田
綾人 佐藤
亮平 杉田
慶太朗 田野井
真一 山下
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国立大学法人東海国立大学機構
国立大学法人 東京大学
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C15/00—Cyclic hydrocarbons containing only six-membered aromatic rings as cyclic parts
    • C07C15/12—Polycyclic non-condensed hydrocarbons
    • C07C15/14—Polycyclic non-condensed hydrocarbons all phenyl groups being directly linked
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C15/00—Cyclic hydrocarbons containing only six-membered aromatic rings as cyclic parts
    • C07C15/20—Polycyclic condensed hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/02—Ethers
    • C07C43/20—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/56—Ring systems containing three or more rings
    • C07D209/80—[b, c]- or [b, d]-condensed
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/06—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
    • C07D213/22—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom containing two or more pyridine rings directly linked together, e.g. bipyridyl
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D307/78—Benzo [b] furans; Hydrogenated benzo [b] furans
    • C07D307/79—Benzo [b] furans; Hydrogenated benzo [b] furans with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the hetero ring
    • C07D307/81—Radicals substituted by nitrogen atoms not forming part of a nitro radical
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
    • C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
    • C07D471/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01T—MEASUREMENT OF NUCLEAR OR X-RADIATION
    • G01T1/00—Measuring X-radiation, gamma radiation, corpuscular radiation, or cosmic radiation
    • G01T1/16—Measuring radiation intensity
    • G01T1/20—Measuring radiation intensity with scintillation detectors
    • G01T1/203—Measuring radiation intensity with scintillation detectors the detector being made of plastics

Definitions

  • the present invention relates to organic scintillation materials.
  • the group of compounds (scintillation materials) having the property of being excited by radiation to emit light includes, for example, organic scintillation materials such as organic crystal scintillation materials typified by anthracene and organic liquid scintillation materials typified by diphenyloxazole (PPO).
  • organic scintillation materials such as organic crystal scintillation materials typified by anthracene and organic liquid scintillation materials typified by diphenyloxazole (PPO).
  • PPO diphenyloxazole
  • Other examples include inorganic scintillation materials such as inorganic crystal scintillation materials represented by sodium iodide and cesium iodide. These scintillation materials are incorporated in radiation measuring instruments such as Geiger counters and used for measuring radiation.
  • An object of the present invention is to provide an organic scintillation material with improved sensitivity to radiation and improved scintillator performance.
  • the present inventors have found that by adopting a specific polycyclic aromatic compound, even a small amount can improve the sensitivity to radiation and improve the scintillator performance. It has been found that scintillation materials can be provided. Specifically, the following inventions are included.
  • the polycyclic aromatic compound is (1) a catenane compound, (2) a carbon nanoring compound, (3A-1) a condensed ring planar compound (1) having a condensed ring other than a peryleneimide ring, in which 5 or more (hetero)aromatic rings are condensed; (3A-2) a condensed cyclic planar compound (2) in which one or more heteroaromatic rings and three aromatic rings are condensed; (3A-3) a triphenylene compound substituted with one or more aryl groups and containing no halogen atoms; (3A-4) a pyrene compound substituted with one or more hydrocarbon groups, (3B-1) at least one compound selected from the group consisting of a phenanthrene compound substituted with one or more aryl groups and containing no halogen atoms, and (3C) a warped nanographene compound; Organic scin
  • Item 1 The organic scintillation material according to Item 1, which is a solution in an organic solvent.
  • Item 3 An organic scintillation material containing a solution in which a polycyclic aromatic compound having 4 or more (hetero)aromatic rings is present in a solvent,
  • the polycyclic aromatic compound is (1) a catenane compound, (2) a carbon nanoring compound; and (3) a condensed ring having a condensed ring other than an anthracene ring in which three or more (hetero)aromatic rings are combined, and having four or more (hetero)aromatic rings.
  • the condensed ring compound is (3A) a condensed ring planar compound having a condensed ring in which 4 or more (hetero)aromatic rings are condensed; Item 3.
  • the fused ring planar compound is (3A-1) a condensed ring planar compound (1) having a condensed ring other than a peryleneimide ring, in which 5 or more (hetero)aromatic rings are condensed; (3A-2) a condensed cyclic planar compound (2) in which one heteroaromatic ring and three aromatic rings are condensed, (3A-3) triphenylene compounds substituted with one or more aryl groups and containing no halogen atoms, and (3A-4) at least one selected from the group consisting of pyrene compounds substituted with one or more hydrocarbon groups Item 5.
  • the phenanthrene compound is (3B-1)
  • the warped nanographene compound is (3C-1)
  • the organic scintillation material according to Item 1 or 4 which is a warped nanographene compound containing no hydrophilic group.
  • the catenane compound is (1A) The organic scintillation material according to item 1 or 3, wherein the two or more cycloparaphenylene compounds are entangled and geometrically connected interlock compounds.
  • the carbon nanoring compound is from the group consisting of (2A) a cycloparaphenylene compound having 8 to 30 benzene rings, and (2B) a hetero element-containing carbon nanoring compound in which 9 to 30 (hetero)aromatic rings are cyclically bonded by single bonds 4.
  • Item 10. The organic scintillation material according to Item 2 or 3, wherein the content of the polymer compound is 0 to 40 mol %, based on the total amount of solids contained in the organic scintillation material being 100 mol %.
  • Item 11 A radiation meter containing the organic scintillation material according to Item 1 or 3.
  • organic scintillation materials are capable of molecular design at the atomic level, and the design of organic scintillation materials specific to particle radiation such as ⁇ -rays, ⁇ -rays and proton beams, and electromagnetic radiation such as ⁇ -rays and X-rays. , can be synthesized and supplied.
  • Example 10 shows emission spectra of the organic scintillation material of Example 9 when irradiated with various electron beams.
  • the organic scintillation material of the present invention contains a polycyclic aromatic compound having 4 or more (hetero)aromatic rings
  • the polycyclic aromatic compound is (1) a catenane compound, (2) a carbon nanoring compound; and (3) a condensed ring having a condensed ring other than an anthracene ring in which three or more (hetero)aromatic rings are combined, and having four or more (hetero)aromatic rings. It is at least one compound selected from the group consisting of compounds.
  • the polycyclic aromatic compound is (1) a catenane compound, (2) a carbon nanoring compound, (3A-1) a condensed ring planar compound (1) having a condensed ring other than a peryleneimide ring, in which 5 or more (hetero)aromatic rings are condensed; (3A-2) a condensed cyclic planar compound (2) in which one heteroaromatic ring and three aromatic rings are condensed, (3A-3) a triphenylene compound substituted with one or more aryl groups and containing no halogen atoms; (3A-4) a pyrene compound substituted with one or more hydrocarbon groups, (3B-1) at least one compound selected from the group consisting of a phenanthrene compound substituted with one or more aryl groups and containing no halogen atoms, and (3C) a warped nanographene compound.
  • 3A-1 a condensed ring planar compound (1) having a condensed ring other than a perylene
  • the content of the polycyclic aromatic compound is 1.00 ⁇ 10 ⁇ 4 to 5% by mass based on 100% by mass of the total amount of the organic scintillation material.
  • Catenane compound The catenane compound is not particularly limited, and means an interlock compound in which two or more cyclic compounds are entangled and geometrically connected. From the viewpoint of (1A) An interlock compound in which two or more cycloparaphenylene compounds are entangled and geometrically connected is preferred.
  • catenane compounds include general formula (1A):
  • n and n are the same or different and represent an integer of 4 to 100. Two cycloparaphenylene molecules are entangled and geometrically connected. ] The catenane compound represented by is mentioned.
  • m and n are not particularly limited, and from the viewpoint of scintillator performance, spatial resolution of measurement, etc., an integer of 4 to 100 is preferable, an integer of 5 to 50 is more preferable, and 6 to An integer of 30 is more preferred, and an integer of 7-20 is particularly preferred.
  • n and n may be the same or different, they can be easily synthesized when they are the same.
  • a known or commercially available product can be used for such a catenane compound, and it can also be synthesized, for example, according to the method described in a previous report (Science 2019, 365, 272-276.).
  • the carbon nanoring compound is not particularly limited, and is a compound in which a (hetero)aromatic ring, that is, an aromatic ring or a heteroaromatic ring is cyclically bonded via a single bond.
  • a (hetero)aromatic ring that is, an aromatic ring or a heteroaromatic ring is cyclically bonded via a single bond.
  • 2A A cycloparaphenylene compound having 8 to 30 benzene rings
  • cycloparaphenylene compound is, for example, the general formula (2A):
  • k represents an integer of 3 to 25.
  • a cycloparaphenylene compound represented by is mentioned.
  • k is not particularly limited, and is preferably an integer of 3 to 25, more preferably an integer of 4 to 20, more preferably an integer of 5 to 15, from the viewpoint of scintillator performance, spatial resolution of measurement, etc. Integers are more preferred.
  • cycloparaphenylene compounds examples include
  • each is a cycloparaphenylene consisting of 15, 12, 11, 10, 9 and 8 benzene rings. ] etc.
  • cycloparaphenylene compounds known or commercially available products can be used. 2009, 48, 6112-6116., Chem. Sci. 2012, 3, 2340-2345.).
  • hetero-element-containing carbon nanoring compound for example, general formula (2B):
  • Ar is the same or different and represents a divalent aromatic hydrocarbon group or a divalent heterocyclic group. However, at least one of Ar represents a divalent heterocyclic group. j represents an integer of 9-15. ] etc.
  • Ar is a divalent aromatic hydrocarbon group or a divalent heterocyclic group. That is, Ar is a divalent group having an organic ring selected from an aromatic ring and a heteroaromatic ring (hereinafter sometimes referred to as a "divalent organic ring group”), and two It is a group in which hydrogen atoms bonded to carbon atoms are eliminated one by one.
  • each Ar may be the same or different. However, at least one of Ar represents a divalent heterocyclic group.
  • Examples of the aromatic ring include not only a benzene ring, but also a ring obtained by condensing a plurality of benzene rings (benzene condensed ring), a ring obtained by condensing a benzene ring and another ring, and the like (hereinafter referred to as a ring obtained by condensing a plurality of benzene rings A ring and a ring obtained by condensing a benzene ring and another ring may be collectively referred to simply as a “fused ring”).
  • condensed ring examples include pentalene ring, indene ring, naphthalene ring, anthracene ring, tetracene ring, pentacene ring, pyrene ring, perylene ring, triphenylene ring, azulene ring, heptalene ring, biphenylene ring, indacene ring, acenaphthylene ring, A fluorene ring, a phenalene ring, a phenanthrene ring and the like can be mentioned.
  • Heteroaromatic rings include, for example, heteroaromatic rings having at least one atom selected from a nitrogen atom, an oxygen atom, a boron atom, a phosphorus atom, a silicon atom and a sulfur atom.
  • Specific examples of heteroaromatic rings include furan ring, thiophene ring, pyrrole ring, silole ring, borole ring, phosphole ring, imidazole ring, pyrazole ring, oxazole ring, thiazole ring, pyridine ring, pyridazine ring, pyrimidine ring, A pyrazine ring etc. are mentioned.
  • heterocondensed ring thienothiophene ring, quinoline ring, benzofuran ring, benzothiophene ring, etc.
  • a heterocondensed ring between them or between them and a benzene ring or the above condensed ring can also be used.
  • Ar is preferably a group having a divalent 6-membered aromatic ring or a divalent 6-membered heteroaromatic ring and having a bond at the para position.
  • the organic ring forming Ar is preferably a monocyclic ring or a condensed ring, more preferably a monocyclic ring.
  • Ar has the general formula (4):
  • N represents a nitrogen-containing heteroaromatic ring.
  • a pyridylene group represented by is more preferable.
  • hetero-element-containing carbon nanoring compound for example,
  • hetero-element-containing carbon nanoring compounds are composed of two pyridine rings and eight and six benzene rings, respectively. ] etc.
  • the condensed ring compound having a condensed ring other than an anthracene ring in which three or more (hetero)aromatic rings are combined and having four or more (hetero)aromatic rings is not particularly limited, (Hetero)aromatic ring, that is, as long as it has a condensed ring other than an anthracene ring in which three or more aromatic rings or heteroaromatic rings are condensed, and has four or more aromatic rings or heteroaromatic rings
  • the condensed ring planar compound having a condensed ring is not particularly limited as long as it is a planar compound in which four or more (hetero)aromatic rings, that is, four or more aromatic rings or heteroaromatic rings form a condensed ring. Although there is no limitation, from the viewpoint of scintillator performance, spatial resolution of measurement, etc.
  • (3A-1) a condensed ring planar compound (1) having a condensed ring other than a peryleneimide ring, in which 5 or more (hetero)aromatic rings are condensed; (3A-2) a condensed cyclic planar compound (2) in which one heteroaromatic ring and three aromatic rings are condensed, (3A-3) Triphenylene compounds substituted with one or more aryl groups and containing no halogen atoms, (3A-4) Pyrene compounds substituted with one or more hydrocarbon groups, and the like are preferred.
  • the "condensed ring planar compound having a condensed ring of four or more (hetero)aromatic rings” includes the above-described (3A-1) to (3A-4 ) is essential.
  • a condensed ring planar compound (1) having a condensed ring other than a peryleneimide ring, in which 5 or more (hetero)aromatic rings are condensed A condensed cyclic planar compound (1) having a condensed ring other than a peryleneimide ring, to which five or more (hetero)aromatic rings are condensed, has five or more (hetero)aromatic rings, i.e., five or more aromatic It is a planar compound in which a ring or a heteroaromatic ring forms a condensed ring (condensed ring other than a peryleneimide ring), but from the viewpoint of scintillator performance, spatial resolution of measurement, etc., it is preferable that the molecule does not contain a sulfur atom.
  • the aromatic ring includes a benzene ring.
  • the heteroaromatic ring includes, for example, a heteroaromatic ring having at least one atom selected from a nitrogen atom, an oxygen atom, a boron atom, a phosphorus atom, a silicon atom and a sulfur atom.
  • a heteroaromatic ring having at least one atom selected from a nitrogen atom, an oxygen atom, a boron atom, a phosphorus atom, a silicon atom and a sulfur atom As described above, from the viewpoint of scintillator performance, spatial resolution of measurement, etc., it is preferable that the molecule does not contain a sulfur atom.
  • Heteroaromatic rings having at least one atom selected from silicon atoms are preferred.
  • heteroaromatic rings include furan ring, pyrrole ring, silole ring, borole ring, phosphole ring, imidazole ring, pyrazole ring, oxazole ring, thiazole ring, pyridine ring, pyridazine ring, pyrimidine ring, A pyrazine ring etc. are mentioned.
  • This condensed ring planar compound (1) may also have a substituent.
  • substituents include alkyl groups, alkoxy groups, aryl groups, heteroaryl groups, boronic acid or its ester groups, cyano groups and the like.
  • the alkyl group as a substituent is not particularly limited, and may be a chain having 1 to 10 carbon atoms (especially 1 to 6) such as methyl group, ethyl group, n-propyl group, n-butyl group and n-pentyl group.
  • alkyl groups branched chain alkyl groups having 3 to 10 carbon atoms (especially 3 to 6 carbon atoms) such as isopropyl group, isobutyl group, sec-butyl group and tert-butyl group are also included.
  • the alkyl group can also have a substituent.
  • substituents when the alkyl group is substituted include halogen atoms (fluorine atom, chlorine atom, bromine atom, iodine atom, etc.), alkoxy groups described later, aryl groups described later, heteroaryl groups described later, and or an ester group thereof, a cyano group, and the like.
  • the number thereof can be, for example, 1 to 5.
  • the alkoxy group as a substituent is not particularly limited, and may be a methoxy group, ethoxy group, n-propyloxy group, n-butyloxy group, n-pentyloxy group or the like having 1 to 10 carbon atoms (particularly 1 to 6).
  • branched chain alkoxy groups having 3 to 10 carbon atoms (especially 3 to 6) such as isopropyloxy, isobutyloxy, sec-butyloxy and tert-butyloxy groups are also included.
  • the alkoxy group can also have a substituent.
  • substituents when the alkoxy group is substituted include halogen atoms (fluorine atom, chlorine atom, bromine atom, iodine atom, etc.), the above alkoxy groups, the aryl groups described later, the heteroaryl groups described later, and the or an ester group thereof, a cyano group, and the like.
  • the number thereof can be, for example, 1 to 5.
  • An aryl group as a substituent is a monovalent group having an aromatic ring, and is a group formed by removing one hydrogen atom bonded to one carbon atom constituting this aromatic ring.
  • Examples of the aromatic ring include not only a benzene ring, but also a ring obtained by condensing a plurality of benzene rings (benzene condensed ring), a ring obtained by condensing a benzene ring and another ring, and the like (hereinafter referred to as a ring obtained by condensing a plurality of benzene rings A ring and a ring obtained by condensing a benzene ring and another ring may be collectively referred to simply as a “fused ring”).
  • condensed ring examples include pentalene ring, indene ring, naphthalene ring, anthracene ring, tetracene ring, pentacene ring, pyrene ring, perylene ring, triphenylene ring, azulene ring, heptalene ring, biphenylene ring, indacene ring, acenaphthylene ring, A fluorene ring, a phenalene ring, a phenanthrene ring and the like can be mentioned.
  • aryl groups include, for example, phenyl group, pentalenyl group, indenyl group, naphthyl group, anthracenyl group, tetracenyl group, pentacenyl group, pyrenyl group, perylenyl group, triphenylenyl group, azulenyl group, heptalenyl group, biphenylenyl group and indacenyl group. , acenaphthyl group, fluorenyl group, phenalenyl group, phenanthrenyl group and the like.
  • the aryl group can also have a substituent.
  • substituents when the aryl group is substituted include halogen atoms (fluorine atom, chlorine atom, bromine atom, iodine atom, etc.), the above alkyl groups, the above alkoxy groups, the above aryl groups, and the following A heteroaryl group, a boronic acid or its ester group described later, a cyano group, and the like can be mentioned.
  • the number thereof can be, for example, 1 to 5.
  • a heteroaryl group as a substituent is a monovalent group having a heteroaromatic ring, and is a group obtained by removing one hydrogen atom bonded to one carbon atom constituting the heteroaromatic ring.
  • Heteroaromatic rings include, for example, heteroaromatic rings having at least one atom selected from a nitrogen atom, an oxygen atom, a boron atom, a phosphorus atom, a silicon atom and a sulfur atom. As described above, from the viewpoint of scintillator performance, spatial resolution of measurement, etc., it is preferable that the molecule does not contain a sulfur atom. Heteroaromatic rings having at least one atom selected from silicon atoms are preferred.
  • heteroaromatic rings include furan ring, pyrrole ring, silole ring, borole ring, phosphole ring, imidazole ring, pyrazole ring, oxazole ring, thiazole ring, pyridine ring, pyridazine ring, pyrimidine ring, A pyrazine ring etc. are mentioned.
  • a heterocondensed ring thienothiophene ring, quinoline ring, benzofuran ring, etc.
  • no peryleneimide ring is formed.
  • aryl groups include, for example, phenyl group, pentalenyl group, indenyl group, naphthyl group, anthracenyl group, tetracenyl group, pentacenyl group, pyrenyl group, perylenyl group, triphenylenyl group, azulenyl group, heptalenyl group, biphenylenyl group and indacenyl group. , acenaphthyl group, fluorenyl group, phenalenyl group, phenanthrenyl group and the like.
  • the aryl group can also have a substituent.
  • substituents when the aryl group is substituted include halogen atoms (fluorine atom, chlorine atom, bromine atom, iodine atom, etc.), the above alkyl groups, the above alkoxy groups, the above aryl groups, and the following A heteroaryl group, a boronic acid or its ester group described later, a cyano group, and the like can be mentioned.
  • the number thereof can be, for example, 1 to 5.
  • R 1s are the same or different and represent a hydrogen atom or an alkyl group. Two R 1 's may combine with each other to form a ring together with adjacent —O—B—O—. ] A group represented by is preferred.
  • R1 of the above boronic acid or its ester group is a hydrogen atom or an alkyl group.
  • R 1 is an alkyl group
  • the carbon atoms constituting each alkyl group may be bonded to each other to form a ring together with the adjacent --O--B--O--.
  • the two oxygen atoms are bonded via an alkylene group (an alkylene group having 1 to 10 carbon atoms such as a methylene group, ethylene group, trimethylene group, tetramethylene group, etc.).
  • R 2 and R 3 are the same or different and represent a hydrogen atom or an alkyl group.
  • the group represented by is mentioned.
  • R 2 and R 3 above are hydrogen atoms or alkyl groups.
  • the boronic acid or its ester group can also have a substituent.
  • substituents when the boronic acid or ester group thereof is substituted include, for example, a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom, etc.), the above alkoxy group, the above aryl group, the above boron
  • a halogen atom fluorine atom, chlorine atom, bromine atom, iodine atom, etc.
  • the number thereof can be, for example, 1 to 5.
  • condensed ring planar compound (1) having a condensed ring other than a peryleneimide ring, in which five or more (hetero)aromatic rings are condensed, for example,
  • Me represents a methyl group.
  • t Bu represents a tert-butyl group.
  • Bpin represents a pinacolateboryl group.
  • Bn represents a benzyl group.
  • condensed ring planar compound (1) having a condensed ring other than a peryleneimide ring, in which five or more (hetero)aromatic rings are condensed known or commercially available products can be used. 2017, 56, 12224-12228. Angew. ncomms7251)., Chem. Sci. 2018, 9, 7556-7561.).
  • (3A-2) Condensed cyclic planar compound (2) in which one heteroaromatic ring and three aromatic rings are condensed
  • a condensed ring planar compound (2) in which one heteroaromatic ring and three aromatic rings are condensed has one heteroaromatic ring and three aromatic rings condensed.
  • the heteroaromatic ring includes, for example, a heteroaromatic ring having at least one atom selected from nitrogen, oxygen, boron, phosphorus, silicon and sulfur atoms. mentioned.
  • Specific examples of the heteroaromatic ring include, for example, furan ring, thiophene ring, pyrrole ring, silole ring, borole ring, phosphole ring, thiol ring, imidazole ring, pyrazole ring, oxazole ring, thiazole ring, pyridine ring, pyridazine ring, A pyrimidine ring, a pyrazine ring, etc. are mentioned.
  • a heterocondensed ring (thienothiophene ring, quinoline ring, benzofuran ring, benzothiophene ring, etc.) between them or between them and a benzene ring or the above condensed ring can also be used.
  • pyrrole rings are preferable from the viewpoint of scintillator performance, spatial resolution of measurement, and the like.
  • the aromatic ring includes a benzene ring.
  • This condensed ring planar compound (2) may also have a substituent.
  • substituents include alkyl groups, alkoxy groups, aryl groups, heteroaryl groups, boronic acid or its ester groups, cyano groups and the like. As these substituents, those described above can be adopted. In the present invention, from the viewpoint of scintillator performance, spatial resolution of measurement, etc., it is preferable that the condensed ring planar compound (2) does not contain a halogen atom.
  • Et represents an ethyl group.
  • Me represents a methyl group.
  • triphenylene compounds substituted with one or more aryl groups and containing no halogen atoms triphenylene compounds substituted with one or more aryl groups and containing no halogen atoms, wherein triphenylene contains one or more aryl groups; and does not contain a halogen atom.
  • An aryl group is a monovalent group having an aromatic ring, and is a group formed by removing one hydrogen atom bonded to one carbon atom constituting the aromatic ring.
  • Examples of the aromatic ring include not only a benzene ring, but also a ring obtained by condensing a plurality of benzene rings (benzene condensed ring), a ring obtained by condensing a benzene ring and another ring, and the like (hereinafter referred to as a ring obtained by condensing a plurality of benzene rings A ring and a ring obtained by condensing a benzene ring and another ring may be collectively referred to simply as a “fused ring”).
  • condensed ring examples include pentalene ring, indene ring, naphthalene ring, anthracene ring, tetracene ring, pentacene ring, pyrene ring, perylene ring, triphenylene ring, azulene ring, heptalene ring, biphenylene ring, indacene ring, acenaphthylene ring, A fluorene ring, a phenalene ring, a phenanthrene ring and the like can be mentioned.
  • aryl groups include, for example, phenyl group, pentalenyl group, indenyl group, naphthyl group, anthracenyl group, tetracenyl group, pentacenyl group, pyrenyl group, perylenyl group, triphenylenyl group, azulenyl group, heptalenyl group, biphenylenyl group and indacenyl group. , acenaphthyl group, fluorenyl group, phenalenyl group, phenanthrenyl group and the like.
  • the aryl group can also have a substituent.
  • substituents when the aryl group is substituted include the above alkyl group, the above alkoxy group, the above aryl group, the above heteroaryl group, the above boronic acid or its ester group, and a cyano group. mentioned. When having these substituents, the number thereof can be, for example, 1 to 5.
  • This triphenylene compound may further have a substituent.
  • substituents include alkyl groups, alkoxy groups, heteroaryl groups, boronic acid or its ester groups, and cyano groups. As these substituents, those described above can be adopted.
  • triphenylene compounds substituted with one or more aryl groups and containing no halogen atoms include:
  • triphenylene compound substituted with one or more aryl groups and containing no halogen atom can be a known or commercially available product.
  • (3A-4) Pyrene compound substituted with one or more hydrocarbon groups
  • the pyrene compound is substituted with one or more hydrocarbon groups.
  • Hydrocarbon groups as such substituents include, for example, alkyl groups and aryl groups. The above-described hydrocarbon groups can be used as these substituents.
  • Such a pyrene compound can be a known or commercially available product, and can be synthesized according to the method described in, for example, a previous report (Nature Commun. 2015, 6, 6251 (doi: 10.1038/ncomms7251).) can be done.
  • the phenanthrene compound has 4 or more (hetero)aromatic rings, that is, 4 or more aromatic rings. It has a ring or heteroaromatic ring. Since phenanthrene is formed by condensing three benzene rings, a phenanthrene compound having four or more (hetero)aromatic rings has, in addition to the phenanthrene skeleton, one or more (hetero)aromatic rings, That is, it is a compound having one or more aromatic or heteroaromatic rings.
  • Such phenanthrene compounds are not particularly limited, but from the viewpoint of scintillator performance, spatial resolution of measurement, etc., (3B-1) A phenanthrene compound substituted with one or more aryl groups and containing no halogen atoms is preferred.
  • a phenanthrene compound substituted with one or more aryl groups and containing no halogen atoms has phenanthrene substituted with one or more aryl groups and contains no halogen atoms.
  • An aryl group is a monovalent group having an aromatic ring, and is a group formed by removing one hydrogen atom bonded to one carbon atom constituting the aromatic ring.
  • Examples of the aromatic ring include not only a benzene ring, but also a ring obtained by condensing a plurality of benzene rings (benzene condensed ring), a ring obtained by condensing a benzene ring and another ring, and the like (hereinafter referred to as a ring obtained by condensing a plurality of benzene rings A ring and a ring obtained by condensing a benzene ring and another ring may be collectively referred to simply as a “fused ring”).
  • condensed ring examples include pentalene ring, indene ring, naphthalene ring, anthracene ring, tetracene ring, pentacene ring, pyrene ring, perylene ring, triphenylene ring, azulene ring, heptalene ring, biphenylene ring, indacene ring, acenaphthylene ring, A fluorene ring, a phenalene ring, a phenanthrene ring and the like can be mentioned.
  • aryl groups include, for example, phenyl group, pentalenyl group, indenyl group, naphthyl group, anthracenyl group, tetracenyl group, pentacenyl group, pyrenyl group, perylenyl group, triphenylenyl group, azulenyl group, heptalenyl group, biphenylenyl group and indacenyl group. , acenaphthyl group, fluorenyl group, phenalenyl group, phenanthrenyl group and the like.
  • the aryl group can also have a substituent.
  • substituents when the aryl group is substituted include the above alkyl group, the above alkoxy group, the above aryl group, the above heteroaryl group, the above boronic acid or its ester group, and a cyano group. mentioned. When having these substituents, the number thereof can be, for example, 1 to 5.
  • This phenanthrene compound may further have a substituent.
  • substituents include alkyl groups, alkoxy groups, heteroaryl groups, boronic acid or its ester groups, and cyano groups. As these substituents, those described above can be adopted.
  • phenanthrene compound substituted with one or more aryl groups and containing no halogen atoms for example,
  • Ph represents a phenyl group.
  • Me represents a methyl group.
  • tBu represents a tert-butyl group.
  • a phenanthrene compound substituted with one or more aryl groups and containing no halogen atoms known or commercially available products can be used. .) can be synthesized according to the method described in .
  • Warped nanographene compound A warped nanographene compound is a nanocarbon having a “wavy” (curved) structure derived from five heptagonal structures, unlike fullerenes, carbon nanotubes, graphene, and the like. .
  • the warped nanographene compound is not particularly limited, but from the viewpoint of scintillator performance, spatial resolution of measurement, etc. (3C-1) Hydrophilic group-free warped nanographene compounds and the like are preferred.
  • hydrophilic groups that the hydrophilic group-free warped nanographene compound does not contain include a hydroxyl group, a carboxyl group, a sulfonic acid group, a hydroxyalkyl group, an amide group, an alkylene oxide group, an ammonium group, etc., and general formula (6):
  • TEG represents a tetraethylene glycol group.
  • the group represented by is mentioned.
  • hydrophilic group-free warped nanographene compound for example,
  • Bpin represents a pinacolateboryl group.
  • hydrophilic group-free warped nanographene compound known or commercially available products can be used. It can be synthesized according to the method.
  • organic scintillation material of the present invention contains the above-described compound, it is based on nanocarbon molecular design by precise organic synthesis, and has improved fluorescence wavelength, solubility, scintillation performance, etc. and can be adjusted.
  • the organic scintillation material of the present invention can be suspended or dissolved in a solvent and used as a suspension or solution.
  • Solvents that can be used include, but are not limited to, water, toluene, N,N-dimethylformamide (DMF), and the like.
  • the organic scintillation material of the present invention can be dissolved in a solvent that is not toxic to living organisms, so it can be the first scintillation material that can be applied to living organisms.
  • it is essential to use a solution in which the above-described polycyclic aromatic compound is present in a solvent.
  • the organic scintillation material of the present invention can contain additives other than the polycyclic aromatic compounds described above, which can be contained in the organic scintillation material.
  • the total amount of solids is set to 100 mol%, and the content of the polymer compound that is the matrix that is normally used is reduced to 0 to 40 mol%, In particular, it can be 0 to 20 mol %, more preferably 0 to 10 mol %.
  • Such an organic scintillation material of the present invention can be used for measuring radioactive substances with a liquid scintillation counter, and can be used in various situations for detecting radioactive substances, such as being incorporated into a radiation detector. can.
  • the organic scintillation material of the present invention can also be used as materials for research using living organisms, such as pharmaceuticals.
  • the content of the polycyclic aromatic compound is not particularly limited, but even a very small amount can exhibit excellent scintillation performance. Therefore, when the organic scintillation material of the present invention is a solution, the content of the polycyclic aromatic compound is preferably 0.005 to 10 mmol/L, more preferably 0.1 to 1 mmol/L.
  • the organic scintillation material of the present invention is a solution, excellent scintillation performance can be exhibited even if the content of the polycyclic aromatic compound is very small. Therefore, when the organic scintillation material of the present invention is a solution, the content of the polycyclic aromatic compound is preferably 1.00 ⁇ 10 ⁇ 4 to 5% by mass, more preferably 1.50 ⁇ 10 ⁇ 4 to 1.5% by mass. More preferably 2.00 ⁇ 10 ⁇ 4 to 1.00 ⁇ 10 ⁇ 2 mass %. In addition, in the second aspect of the present invention, it is essential that the content of the polycyclic aromatic compound is 1.00 ⁇ 10 ⁇ 4 to 5% by mass.
  • the radiation meter of the present invention can be the same as conventional radiation meters except that it contains the organic scintillation material of the present invention. In this case, even a very small amount of the organic scintillation material of the present invention can exhibit excellent scintillation performance.
  • Examples 1 to 53 The organic scintillation material of Example 1 was synthesized according to the method described in a previous report (Science 2019, 365, 272-276.).
  • Example 2 The organic scintillation material of Example 2 was synthesized according to the method described in a previous report (Angew. Chem. Int. Ed. 2010, 49, 10202-10205.).
  • Example 4 The organic scintillation material of Example 4 was synthesized according to the method described in a previous report (Angew. Chem. Int. Ed. 2009, 48, 6112-6116.).
  • the organic scintillation material of Example 10 was synthesized according to the method described in the previous report (Org. Lett. 2012, 14, 1888-1991.).
  • Example 39 The organic scintillation material of Example 39 was synthesized according to the method described in a previous report (Angew. Chem. Int. Ed. 2018, 57, 2874-2878.).
  • the organic scintillation material of Example 7 was synthesized by the following method.
  • Me represents a methyl group.
  • DMF stands for dimethylformamide.
  • DCE stands for 1,2-dichloroethane.
  • MicroBeta 2 is a device for measuring luminescence by the coincidence counting method with photomultiplier tubes installed above and below the sample, and one sample was measured once per minute. In order to prevent luminescence due to the phosphorescence of the compound itself, the plate was set in the apparatus and placed in a dark environment, and measurement was started 1 hour later.
  • each organic scintillation material is measured to be equivalent to 0.2 mM, 0.5 mM or 1 mM. (cpm) was corrected. This measured value is the number of counts per minute, and the higher the number, the stronger the light.
  • Anthracene has a measured value (cpm) of about 71 at 7.8 mM, which is much higher than the organic scintillation material of each example. Furthermore, by dividing the value of each organic scintillation material by the value of anthracene, it was converted into a value as an anthracene relative ratio (cpm/cpm).

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