WO2008041331A1 - complexe fluorescent à base de métal du groupe des terres rares - Google Patents

complexe fluorescent à base de métal du groupe des terres rares Download PDF

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Publication number
WO2008041331A1
WO2008041331A1 PCT/JP2006/319848 JP2006319848W WO2008041331A1 WO 2008041331 A1 WO2008041331 A1 WO 2008041331A1 JP 2006319848 W JP2006319848 W JP 2006319848W WO 2008041331 A1 WO2008041331 A1 WO 2008041331A1
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WO
WIPO (PCT)
Prior art keywords
group
rare earth
earth metal
complex
metal complex
Prior art date
Application number
PCT/JP2006/319848
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English (en)
Japanese (ja)
Inventor
Masatoshi Kanesato
Kenta Sugaya
Masashi Segawa
Naoya Tsukada
Original Assignee
National Institute Of Advanced Industrial Science And Technology
Sanvic Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by National Institute Of Advanced Industrial Science And Technology, Sanvic Inc. filed Critical National Institute Of Advanced Industrial Science And Technology
Priority to PCT/JP2006/319848 priority Critical patent/WO2008041331A1/fr
Publication of WO2008041331A1 publication Critical patent/WO2008041331A1/fr

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    • 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
    • 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

Definitions

  • the present invention relates to a fluorescent rare earth metal complex and a method for producing the same.
  • Rare earth metals are actively used as components of various chemical reaction catalysts, fluorescent materials, and magnetic materials. It is also used as a raw material for reacting with other metal compounds to form composite materials.
  • high-density sintered bodies of yttrium-aluminum-garnet (YAG) are attracting attention as an alternative to Nd-doped YAG single crystals for lasers and are positioned as one of the important materials in the advanced technology field.
  • YAG yttrium-aluminum-garnet
  • rare earth metals are mainly used in the state of compounds composed of metal materials.
  • the combination of organic structures and metal ions and their use will also increase. Research is underway and the results are drawing attention.
  • Examples of the structure in which the organic structure and the metal ion are combined include a shift reagent that is a paramagnetic metal ion reagent added for the purpose of expanding the NMR chemical shift without increasing the external magnetic field.
  • Rare earth compounds are mainly used for this reagent, and metal complexes consisting of rare earth metal ions and organic ligands are known (JP2002-20358A).
  • rare earth metal complexes are useful as fluorescent probes and fluorescent labeling agents, and are also used as RNA cleavage catalysts.
  • rare earth metal complexes are used as aqueous solutions with a large amount of water-soluble compounds because the central metal ions have a high positive charge (3 +), but they are soluble in organic solvents. Because of this, there was a problem that its use was limited.
  • rare earth metal complexes have the characteristics of ⁇ and ⁇ ⁇ that facilitate a highly coordinated state, and in addition to the desired ligand, ligands such as solvent molecules are bound. Expected properties were hindered, and in some cases hydrolysis occurred, making it difficult to fully exploit the functions inherent to the complex.
  • the subject of the present invention is a fluorescent rare earth that is soluble in an organic solvent and that suppresses the incorporation of an inhibitor such as a solvent and maintains the original properties of the complex.
  • An object of the present invention is to provide a metal complex and a method for easily producing the same.
  • the present inventors have found that the rare earth metal salt and the alkali metal salt or alkaline earth of the specific carboxylic acid or its derivative are used.
  • a rare earth metal complex having a charge obtained by reacting a metal salt with the rare earth metal salt so that the positive charge of the rare earth metal ion in the rare earth metal salt is neutralized, a neutral organic ligand having a dipyridyl nucleus By reacting, it was found that a fluorescent rare earth metal complex coordinated with a specific acid that neutralizes the positive charge of a specific ligand and a rare earth metal ion can be obtained. It came to an eggplant.
  • the present invention provides a general formula
  • R is an alkyl group, a alkenyl group or an optionally substituted phenyl group, naphthyl group or quinolyl group
  • Ln is a rare earth metal
  • n is 0 or 1
  • Fluorescent rare earth metal complexes represented by the general formula
  • R has the same meaning as above, and M is a hydrogen atom, an alkali metal or a half-valent alkali earth metal
  • the present invention provides a method for producing the fluorescent rare earth complex represented by the general formula (I).
  • the rare earth complex of the general formula (I) there are no particular restrictions on the rare earth element of the central metal element, scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, samarium, sucrose, gadolinium, terbium, Can be arbitrarily selected from dysprosium, holmium, erbium, thulium, ytterbium, lutetium, etc. Preference is given to Palladium, samarium whose complex exhibits red fluorescence, terbium whose complex exhibits green fluorescence, etc. .
  • the rare earth metal is derived from a carboxylic acid represented by RCO H.
  • One neutral organic ligand represented by the formula is coordinated.
  • the neutral organic ligand when n is 1 is 1,10 phenanthrene
  • the neutral organic ligand when n force SO is 2, 2 , —Bibiridyl.
  • the fluorescent rare earth metal complex of the present invention requires a ligand having a negative charge that neutralizes the positive charge of the rare earth metal ion.
  • the carboxylic acid represented by the general formula (II) includes aliphatic saturated carboxylic acid, aliphatic unsaturated carboxylic acid, naphthoic acid, benzoic acid, quinoline carboxylic acid and the like.
  • the naphthoic acid may be either 1-naphthoic acid or 2-naphthoic acid.
  • the above naphthoic acid, benzoic acid, and quinolinecarboxylic acid are a phenol group, a naphthyl group, or a quinolyl group.
  • the nucleus group may be a nucleus-substituted derivative having a substituent! /.
  • substituents in this case include an alkyl group, an alkenyl group, an alkoxy group, a halogen atom, a hydroxyl group, a mercapto group, an alkylthio group, and a trifluoromethyl group. A plurality of such substituents may be present.
  • the alkyl group or alkenyl group in the ligand derived from the carboxylic acid force of the general formula (II) has a large number of carbon atoms in order to give a fluorescent rare earth metal complex soluble in an organic solvent. preferable. In addition, it is bulky and preferred to suppress coordination of solvent molecules that inhibit the binding of the target ligand.
  • the carboxylic acids represented by the general formula (II) include 1 naphthoic acid, 2 naphthoic acid, and their nuclear substitutes such as 4-methyl-1 naphthoic acid, p-t-butyl. It is preferable to use til benzoic acid, t-butyl acetic acid, higher fatty acids having 8 or more carbon atoms, and the like.
  • the fluorescent rare earth metal complex of the present invention can be produced according to the steps shown in the following reaction formula.
  • R, M, and Ln have the same meanings as described above, X is an anion, and L is 2,2′-bibilidinole or 1,10-phenantorin)
  • the rare earth metal salt (IV) and the carboxylic acid or the alkali metal or alkaline earth metal salt thereof are reacted at a ratio at which the positive charge of the rare earth metal ion is substantially neutralized.
  • the rare earth metal complex (V) and the alkali metal or alkali earth metal salt (VI) are formed.
  • the fluorescent rare earth metal complex (I) of the present invention is produced by reacting V) with 2,2′-bibilidyl or 1,10-phenantine phosphorus at a substantially chemical equivalent ratio.
  • the rare earth metal salt (IV) used in the first step includes, for example, rare earth metal triflates such as samarium triflate, europium triflate, terbium triflate, samarium, europium or terbium halides, There are nitrates and sulfates.
  • the fluorescent rare earth metal complex of the present invention is a carboxylic acid represented by the general formula (II) in an amount that neutralizes the positive charge of the rare earth metal ion, instead of reacting stepwise in two steps as described above.
  • it can also be produced by a one-step method in which an alkali metal or alkaline earth metal salt thereof is reacted with 2,2′-bibilidyl or 1,10-phenantorin simultaneously.
  • M in the general formula (II) is a hydrogen atom, that is, carboxylic acid is used
  • a rare earth metal salt can be used instead of the rare earth metal salt.
  • reaction solvent organic solvents commonly used as reaction solvents, such as methanol, ethanol, acetonitrile, dimethylformamide, tetrahydrofuran, acetone, chloroform, methylene, are used. Chloride, ethyl acetate, butyl acetate, dimethyl sulfoxide and the like are used.
  • the white powder 2.4 mmol was dissolved in 50 ml of dimethylformamide and heated, and this solution was dissolved in 20 ml of dehydrated ethanol by heating 2.4 ml of 1,10-phenantine phosphorus.
  • the mixture was refluxed for 5 hours while heated at 160 ° C, filtered while hot, and then allowed to stand for one month, but no precipitate was obtained. Therefore, 150 ml of 2-propanol and 2 ml of water were added thereto and allowed to stand for 5 days to obtain a white precipitate.
  • the precipitate was filtered and then dried under reduced pressure to obtain the desired yuguchipium complex as a white powder. The yield was 55%.
  • rare earth metal complexes were dissolved only in water or polar solvents, and were not soluble in organic solvents, so their fields of use were limited. However, according to the present invention, new rare earth metal complexes soluble in organic solvents were used. Fluorescent rare earth metal complexes have been provided and the range of use has been significantly expanded.
  • the fluorescent rare earth metal complex of the present invention is useful as various fluorescent materials as well as the fluorescent substances known so far.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)

Abstract

La présente invention concerne un complexe fluorescent à base de métal du groupe des terres rares qui est soluble dans des solvants organiques, présente une inclusion réduite des facteurs inhibant les propriétés attendues, notamment un solvant, et peut conserver les propriétés inhérentes au complexe ; et un procédé de fabrication facile du complexe. Le complexe est représenté par la formule (RCO2)3LnL (dans laquelle R est au moins un groupe choisi parmi les groupes alkyle, alcényle, et 1-naphtyle, 2-naphtyle, phényle, et quinolyle qui peuvent comporter un certain type de substituant ; Ln est un élément du groupe des terres rares ; et L est un ligand organique neutre). Il est produit en soumettant un sel de métal du groupe des terres rares et RCO2M (dans laquelle R est tel que défini ci-dessus et M est l'hydrogène ou un métal donné) à une réaction de neutralisation afin d'obtenir un complexe à base de métal du groupe des terres rares et en faisant réagir le complexe avec un ligand organique neutre.
PCT/JP2006/319848 2006-10-04 2006-10-04 complexe fluorescent à base de métal du groupe des terres rares WO2008041331A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/JP2006/319848 WO2008041331A1 (fr) 2006-10-04 2006-10-04 complexe fluorescent à base de métal du groupe des terres rares

Applications Claiming Priority (1)

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PCT/JP2006/319848 WO2008041331A1 (fr) 2006-10-04 2006-10-04 complexe fluorescent à base de métal du groupe des terres rares

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WO2008041331A1 true WO2008041331A1 (fr) 2008-04-10

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003347061A (ja) * 2001-08-20 2003-12-05 Tdk Corp 有機ｅｌ素子およびその製造方法
JP2006298777A (ja) * 2005-04-15 2006-11-02 National Institute Of Advanced Industrial & Technology 蛍光希土類金属錯体及びその製造方法
JP2006303033A (ja) * 2005-04-18 2006-11-02 National Institute Of Advanced Industrial & Technology 太陽電池モジュール
JP2006298974A (ja) * 2005-04-15 2006-11-02 National Institute Of Advanced Industrial & Technology エチレン−酢酸ビニル共重合体組成物

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003347061A (ja) * 2001-08-20 2003-12-05 Tdk Corp 有機ｅｌ素子およびその製造方法
JP2006298777A (ja) * 2005-04-15 2006-11-02 National Institute Of Advanced Industrial & Technology 蛍光希土類金属錯体及びその製造方法
JP2006298974A (ja) * 2005-04-15 2006-11-02 National Institute Of Advanced Industrial & Technology エチレン−酢酸ビニル共重合体組成物
JP2006303033A (ja) * 2005-04-18 2006-11-02 National Institute Of Advanced Industrial & Technology 太陽電池モジュール

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
DATABASE CA [online] LI Y. ET AL.: "The photofluorescence of Eu (III) and long chain fatty acid complexes", Database accession no. (137:192189) *
DATABASE CA [online] YANG H. ET AL.: "IR and Raman spectra of ternary solid complexes of rare earth with alpha-naphthoic acid and 1,10-phenanthroline", Database accession no. (140:66828) *
GUANGPUXUE YU GUANGPU FENXI, vol. 22, no. 3, 2002, pages 353 - 356 *
GUANGPUXUE YU GUANGPU FENXI, vol. 23, no. 3, 2003, pages 522 - 524 *

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